WO2015029846A1 - Sealant for display element, and oxime ester initiator - Google Patents

Sealant for display element, and oxime ester initiator Download PDF

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WO2015029846A1
WO2015029846A1 PCT/JP2014/071714 JP2014071714W WO2015029846A1 WO 2015029846 A1 WO2015029846 A1 WO 2015029846A1 JP 2014071714 W JP2014071714 W JP 2014071714W WO 2015029846 A1 WO2015029846 A1 WO 2015029846A1
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group
carbon atoms
groups
alkyl
carbon
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PCT/JP2014/071714
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French (fr)
Japanese (ja)
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和志 伊藤
山口　真史
島岡　淳一
卓夫 鈴木
山本　拓也
由季 小林
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積水化学工業株式会社
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Priority to KR1020157032281A priority Critical patent/KR20160048031A/en
Priority to JP2014542428A priority patent/JPWO2015029846A1/en
Publication of WO2015029846A1 publication Critical patent/WO2015029846A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • 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
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
    • C08G2650/24—Polymeric initiators
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to a sealant for a display element that can suppress generation of outgas and contamination of other materials, and is excellent in adhesiveness and transparency of a cured product. Moreover, this invention relates to the oxime ester initiator which can be used suitably for this sealing agent for display elements.
  • liquid crystal display elements In recent years, liquid crystal display elements, organic EL display elements, and the like are widely used as display elements having features such as thinness, light weight, and low power consumption.
  • a sealant for a display element is usually used for sealing a liquid crystal or a light emitting layer, bonding a substrate, an optical film, or a protective film.
  • Patent Document 1 discloses a pressure-sensitive adhesive for a polarizing film made of an acrylic resin composition.
  • Patent Document 2 discloses a method of forming a resin film made of an acrylic resin composition on an inorganic material film.
  • the acrylic sealant for display elements as disclosed in Patent Document 1 and Patent Document 2 generates a large amount of outgas due to the acrylic resin remaining in the manufacturing process of the display elements, and exhibits adhesion and curing. There was a problem that the transparency of things was inferior.
  • An object of the present invention is to provide a sealant for a display element that can suppress generation of outgas and contamination of other materials and is excellent in adhesiveness and transparency of a cured product. Moreover, an object of this invention is to provide the oxime ester initiator which can be used suitably for this sealing agent for display elements.
  • the present invention comprises a polythiol monomer having two or more thiol groups in one molecule, a polyene monomer having two or more carbon-carbon double bonds in one molecule, and a radical polymerization initiator,
  • the polymerization initiator is a sealant for a display element, which is a compound having a functional group that generates radicals by light irradiation or heating and a reactive functional group.
  • the present inventor uses a polythiol monomer having two or more thiol groups in one molecule instead of an acrylic resin as a sealant for a display element that is excellent in adhesiveness and transparency of a cured product, and in one molecule. It was investigated to use a resin composition containing a polyene monomer having two or more carbon-carbon double bonds. However, even when such a resin composition is used, the problem of outgas generation cannot be completely solved. In addition, when the obtained sealant for display element comes into contact with the liquid crystal of the liquid crystal display element, the liquid crystal is contaminated, or when it comes into contact with the organic light emitting material layer of the organic EL display element, the organic light emitting material layer is damaged. Sometimes happened.
  • the sealant for a display element of the present invention includes, as a polymerizable compound, a polythiol monomer having two or more thiol groups in one molecule (hereinafter also simply referred to as “polythiol monomer”) and two or more in one molecule. And a polyene monomer having a carbon-carbon double bond (hereinafter also simply referred to as “polyene monomer”).
  • the sealant for display elements of the present invention containing these components is excellent in adhesiveness and transparency of the cured product.
  • the “carbon-carbon double bond” means an ethylenically unsaturated bond.
  • polythiol monomer examples include aliphatic polythiols such as ethanedithiol, propanedithiol, hexamethylenedithiol and decamethylenedithiol, aromatic polythiols such as tolylene-2,4-dithiol and xylenedithiol, and the following formula (1)
  • a cyclic sulfide compound such as a 1,4-dithiane ring-containing polythiol compound, an ester bond-containing polythiol compound, diglycol dimercaptan, triglycol dimercaptan, tetraglycol dimercaptan, thiodiglycol dimercaptan, thiotril Glycol dimercaptan, thiotetraglycol dimercaptan, tris- (3-mercaptopropionyloxy) -ethyl isocyanurate, tetraethylene glycol-bis (3-mercaptop) Pionate), tri
  • l represents an integer of 1 to 5.
  • 1,4-dithiane ring-containing polythiol compound represented by the above formula (1) examples include 2,5-dimercaptomethyl-1,4-dithiane and 2,5-dimercaptoethyl-1 , 4-dithiane, 2,5-dimercaptopropyl-1,4-dithiane, 2,5-dimercaptobutyl-1,4-dithiane and the like.
  • an ester bond-containing polythiol monomer is preferable because the obtained sealant for display elements is excellent in transparency.
  • ester bond-containing polythiol monomer examples include trimethylolpropane tris (3-mercaptopropionate), tris-((3-mercaptopropionyloxy) -ethyl) -isocyanurate, pentaerythritol tetrakisthioglycol. Rate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.
  • trimethylolpropane tris (3-mercaptopropionate), pentaerythritol-tetrakis (3-mercaptopropionate), dipentaerythritol-hexakis (3-mercaptopropionate), 1,4-dithiane ring included Polythiol compounds are preferred, and trimethylolpropane tris (3-mercaptopropionate) and dipentaerythritol-hexakis (3-mercaptopropionate) are more preferred.
  • the said polythiol monomer contains the monomer (trifunctional or more polythiol monomer) which has a 3 or more thiol group in 1 molecule.
  • the tri- or higher functional polythiol monomer is preferably a monomer having 3 to 20 thiol groups in one molecule, and more preferably a monomer having 3 to 8 thiol groups in one molecule.
  • the preferable lower limit of the content of the polythiol monomer in 100 parts by weight of the whole polymerizable compound is 1 part by weight, and the preferable upper limit is 89 parts by weight.
  • the content of the polythiol monomer is less than 1 part by weight, coatability may be deteriorated.
  • the content of the polythiol monomer exceeds 89 parts by weight generation of outgas may not be sufficiently suppressed.
  • the minimum with more preferable content of the said polythiol monomer is 5 weight part, and a more preferable upper limit is 69 weight part.
  • polyene monomer examples include (meth) allyl compounds, (meth) acrylic compounds, divinylbenzene, and the like. These polyene monomers may be used alone or in combination of two or more.
  • the “(meth) allyl” means allyl or methallyl
  • the “(meth) acryl” means acryl or methacryl.
  • Examples of the (meth) allyl compound include triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, diallyl maleate, diallyl adipate, diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, glyceryl diallyl Ether, trimethylolpropane diallyl ether, pentaerythritol, diallyl ether, 1,3-diallyl-5-glycidyl isocyanurate, 1,3,4,6-tetraallylglycoluril, 1,3,4,6-tetraallyl-3a -Methyl glycoluril, 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril and the like. Of these, triallyl cyanurate, triallyl isocyanurate, and 1,3,4,6-tetraallylglycoluril are preferable.
  • the (meth) acrylic compound is not particularly limited as long as it is a compound having two or more acryloyl groups or methacryloyl groups in one molecule.
  • the “(meth) acrylate” means acrylate or methacrylate
  • the “epoxy (meth) acrylate” refers to all the epoxy groups in the epoxy compound and (meth) acrylic acid. It represents the reacted compound.
  • the epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth) acrylic acid and an epoxy compound in the presence of a basic catalyst according to a conventional method.
  • examples of the epoxy compound used as a raw material for the epoxy (meth) acrylate include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2′-diallyl bisphenol A type epoxy compound, and hydrogenated bisphenol.
  • Type epoxy compound propylene oxide-added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound , Orthocresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl novolac type epoxy Xyl compounds, naphthalenephenol novolac type epoxy compounds, glycidylamine type epoxy compounds, alkyl polyol type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, bisphenol A type episulfide compounds, and the like.
  • ester compounds obtained by reacting the (meth) acrylic acid with a compound having a hydroxyl group examples of the bifunctional compounds include 1,4-butanediol di (meth) acrylate and 1,3-butanediol.
  • those having three or more functional groups include, for example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added tri Methylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene N'okishido added glycer
  • the polyene monomer preferably contains a monomer having three or more carbon-carbon double bonds in one molecule (a polyene monomer having three or more functions).
  • the trifunctional or higher polyene monomer is preferably a monomer having 3 to 20 carbon-carbon double bonds in one molecule, and a monomer having 3 to 8 carbon-carbon double bonds in one molecule. More preferred.
  • the preferable lower limit of the content of the polyene monomer in 100 parts by weight of the total polymerizable compound is 1 part by weight, and the preferable upper limit is 89 parts by weight.
  • the content of the polyene monomer is less than 1 part by weight, coatability may be deteriorated.
  • the content of the polyene monomer exceeds 89 parts by weight unreacted polyene monomer may remain and outgas may be generated.
  • a more preferable lower limit of the content of the polyene monomer is 5 parts by weight, a more preferable upper limit is 79 parts by weight, and a still more preferable upper limit is 69 parts by weight.
  • the cured product of the obtained sealant for display elements has a high elastic modulus and is excellent in transparency and adhesiveness, those having a siloxane bond as the polythiol monomer and / or the polyene monomer are also suitable. Used for.
  • the siloxane bond is preferably derived from silsesquioxane. That is, the polythiol monomer having a siloxane bond is preferably a silsesquioxane resin having two or more thiol groups in one molecule (hereinafter also referred to as “thiol group-containing silsesquioxane resin”).
  • the polyene monomer having a siloxane bond is preferably a silsesquioxane resin having two or more reactive functional groups in one molecule (hereinafter also referred to as “reactive functional group-containing silsesquioxane resin”).
  • the thiol group-containing silsesquioxane resin used as the polythiol monomer is a hydrolysis condensate of a thiol group-containing silane compound represented by the following formula (2) (hereinafter also referred to as “hydrolysis condensate (a)”). Preferably there is.
  • hydrolysis condensate (a) is used as the polythiol monomer, the transparency, elastic modulus, and adhesiveness of the cured product of the obtained resin composition can be further increased.
  • R 1 represents a C 1-8 organic group having a thiol group and no aromatic ring, or an organic group having a thiol group and an aromatic ring
  • R 2 represents a hydrogen atom, an organic group having 1 to 8 carbon atoms having no aromatic ring, or an organic group having an aromatic ring.
  • R 1 examples include, for example, an aliphatic hydrocarbon group having 1 to 8 carbon atoms having a thiol group, an alicyclic hydrocarbon group having 1 to 8 carbon atoms having a thiol group, and an aromatic having a thiol group.
  • Group hydrocarbon group and the like The hydrocarbon group in R 1 is a group containing not only a carbon atom and a hydrogen atom but also a sulfur atom derived from a thiol group.
  • R 2 include a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 1 to 8 carbon atoms, and an aromatic hydrocarbon group.
  • the R 2 may be the same or different.
  • a hydrolysis-condensation product (a) can be obtained by hydrolyzing and condensing the thiol group-containing silane compound represented by the above formula (2). That is, a hydrolysis-condensation product (a) can be obtained by a hydrolysis reaction and a condensation reaction.
  • Examples of the thiol group-containing silane compound represented by the above formula (2) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, and 3-mercaptopropyltributoxysilane.
  • thiol group-containing silane compound represented by the above formula (2) may be used alone or in combination of two or more.
  • Examples of the other crosslinkable compounds include trialkylalkoxysilane, dialkyldialkoxysilane, alkyltrialkoxysilane, tetraalkoxysilane, tetraalkoxytitanium, tetraalkoxyzirconium and the like.
  • a trialkylalkoxysilane, a dialkyldialkoxysilane, or a tetraalkoxysilane is used as the other crosslinkable compound, the crosslink density of the hydrolysis condensate (a) can be easily adjusted.
  • alkyltrialkoxysilane is used as the other crosslinkable compound
  • the number of thiol groups contained in the hydrolysis condensate (a) can be easily adjusted.
  • tetraalkoxytitanium or tetraalkoxyzirconium is used as the other crosslinkable compound, the refractive index of the cured product of the resulting resin composition can be increased.
  • Said other crosslinking compound may be used independently and 2 or more types may be used together.
  • trialkylalkoxysilane examples include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and the like.
  • dialkyl dialkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3- Examples include mercaptopropylmethyldimethoxysilane.
  • alkyltrialkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
  • examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
  • examples of the tetraalkoxy titanium examples include tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, and tetrabutoxy titanium.
  • examples of the tetraalkoxyzirconium examples include tetraethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxyzirconium.
  • a catalyst In the hydrolysis reaction for obtaining the hydrolysis condensate (a), it is preferable to use a catalyst.
  • a conventionally known catalyst can be used as the catalyst, and is not particularly limited, but formic acid is preferable because it has high catalytic activity and functions as a catalyst for the condensation reaction.
  • the content of the catalyst is preferably 0.1 parts by weight with respect to 100 parts by weight of the thiol group-containing silane compound or 100 parts by weight of the thiol group-containing silane compound and the other crosslinkable compound.
  • the preferred upper limit is 25 parts by weight.
  • the content of the catalyst is less than 0.1 parts by weight, the catalytic effect may not be sufficiently exhibited.
  • the content of the catalyst exceeds 25 parts by weight, the storage stability of the silsesquioxane resin containing a thiol group may be lowered, or the catalyst may not be easily removed in a subsequent step.
  • a more preferable lower limit of the content of the catalyst is 1 part by weight, and a more preferable upper limit is 10 parts by weight.
  • the reaction temperature and reaction time of the hydrolysis reaction can be arbitrarily set according to the reactivity of the thiol group-containing silane compound or the reactivity of the thiol group-containing silane compound and the other crosslinkable compound.
  • the reaction temperature is usually 0 to 100 ° C., preferably 20 to 60 ° C., and the reaction time is about 1 minute to 2 hours.
  • a solvent may be used in the hydrolysis reaction.
  • the kind of said solvent is not specifically limited, It is preferable that it is the same as the solvent used for the condensation reaction mentioned later.
  • the reactivity of the thiol group-containing silane compound or the reactivity of the thiol group-containing silane compound and the other crosslinkable compound is low, it is preferable not to use a solvent during the hydrolysis reaction.
  • the hydrolysis reaction is [number of moles of hydroxyl groups generated by the hydrolysis reaction] / [above
  • the total number of alkoxy groups in the thiol group-containing silane compound or the composition containing the thiol group-containing silane compound and the other crosslinkable compound] (hereinafter also referred to as “molar ratio A”) is 0.5. It is preferable to make it progress so that it may become the above.
  • the molar ratio A is more preferably 0.8 or more.
  • condensation reaction water is generated between the hydroxyl groups generated by hydrolysis, and further, alcohol is generated between the hydroxyl group and the alkoxy group.
  • the hydrolysis condensate (a) is vitrified.
  • condensation catalyst In the condensation reaction, a conventionally known condensation catalyst can be used.
  • Formic acid has high catalytic activity and acts not only as a catalyst for hydrolysis reaction but also as a catalyst for condensation reaction. Therefore, the condensation catalyst is preferably formic acid.
  • the reaction temperature and reaction time in the condensation reaction can be arbitrarily set according to the reactivity of the thiol group-containing silane compound or the reactivity of the thiol group-containing silane compound and the other crosslinkable compound.
  • the reaction temperature is usually about 40 to 150 ° C., preferably 60 to 100 ° C., and the reaction time is about 30 minutes to 12 hours.
  • the reaction is included in [the total number of moles of unreacted hydroxyl group and unreacted alkoxy group] / [the thiol group-containing silane compound, or the composition containing the thiol group-containing silane compound and the other crosslinkable compound.
  • the total number of moles of alkoxy groups] (hereinafter also referred to as “molar ratio B”) is preferably 0.3 or less.
  • the molar ratio B is more preferably 0.2 or less.
  • the preferable lower limit of the total concentration of the thiol group-containing silane compound or the thiol group-containing silane compound and the other crosslinkable compound is 2% by weight, and the preferable upper limit is 80% by weight.
  • concentration is within the above range, gelation becomes difficult during the reaction, the molecular weight of the hydrolysis condensate (a) does not become too large, and the storage stability of the hydrolysis condensate (a) is further enhanced.
  • a more preferred lower limit of the concentration is 15% by weight, and a more preferred upper limit is 60% by weight.
  • the condensation reaction it is preferable to use a solvent having a boiling point higher than that of water and alcohol produced by the condensation reaction.
  • the solvent can be easily removed from the reaction system.
  • the said solvent may be used independently and 2 or more types may be used together.
  • the said other crosslinkable compound can also be used as a solvent.
  • the catalyst it is preferable to remove the catalyst after the condensation reaction.
  • the storage stability of the hydrolysis-condensation product (a) can be enhanced.
  • a known method can be appropriately selected according to the type of catalyst, and examples thereof include a method of heating above the boiling point of the catalyst and a method of reducing the pressure.
  • the catalyst is formic acid, formic acid can be easily removed by these methods.
  • Examples of the reactive functional group-containing silsesquioxane resin that serves as the polyene monomer include those having the thiol group of the thiol group-containing silsesquioxane resin as a group having a carbon-carbon double bond.
  • a hydrolytic condensate of a reactive functional group-containing silane compound in which R 1 in the above formula (2) is the reactive functional group or a group containing the reactive functional group (hereinafter referred to as “hydrolytic condensation”). (It is also referred to as a product (b) ”).
  • the hydrolysis condensate (b) is used as the polyene monomer, the transparency, elastic modulus, and adhesiveness of the cured product of the resin composition obtained can be further increased.
  • the hydrolysis condensate (b) can be produced in the same manner as the hydrolysis condensate (a) except that the thiol group-containing silane compound is a reactive functional group-containing silane compound.
  • polyene monomers having a siloxane bond include, for example, 1,3-divinyltetramethyldisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclo Tetrasiloxane, 1,3-divinylpropanedisiloxane, 1,5-bis [2- (2,3-epoxynorbornane-5-yl) ethyl] -1,1,3,3,5,5-hexamethylpentane Trisiloxane, 1,3,5,7,9,11,13,15-octakis [2- (triallylsilyl) ethyl] pentacyclo [9.5.1.13, 9.15, 15.17, 13] Icosan octasiloxane, 1,2-epoxy-4-vinylcyclohexane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 2,4,6,8-tetra 1,3-
  • Examples of commercially available polyene monomers having a siloxane bond include AC-SQ series (manufactured by Toagosei Co., Ltd.).
  • the sealing agent for display elements of this invention contains a polyene oligomer as said polymeric compound in addition to the said polyene monomer.
  • a polyene oligomer as said polymeric compound in addition to the said polyene monomer.
  • polyene monomer derived from the polyene oligomer examples include the (meth) allyl compound (meth) acrylic compound and divinylbenzene described above.
  • Examples of the method for producing the polyene oligomer include a method of reacting the polyene monomer in the presence of a radical polymerization initiator or the like described later.
  • Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator, and a thermal radical polymerization initiator is preferably used.
  • the minimum with a preferable weight average molecular weight of the said polyene oligomer is 300, and a preferable upper limit is 20,000. If the weight average molecular weight of the polyene oligomer is less than 300, the effect of suppressing the generation of outgas may not be sufficiently improved. When the weight average molecular weight of the polyene oligomer is more than 20,000, the viscosity of the obtained sealant for a display element may be too high and the coatability may be deteriorated.
  • the minimum with a more preferable weight average molecular weight of the said polyene oligomer is 400, and a more preferable upper limit is 4000.
  • the “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
  • the minimum with preferable content of the said polyene oligomer in 100 weight part of the said whole polymeric compound is 30 weight part, and a preferable upper limit is 90 weight part. If the content of the polyene oligomer is less than 30 parts by weight, the effect of further suppressing the generation of outgas may not be exhibited sufficiently. When content of the said polyene oligomer exceeds 90 weight part, the viscosity of the sealing agent for display elements obtained will become high too much, and coating property may deteriorate.
  • the minimum with more preferable content of the said thioether oligomer is 35 weight part, and a more preferable upper limit is 80 weight part.
  • the sealing agent for display elements of this invention contains the thioether oligomer formed by reaction of a polythiol monomer and a polyene monomer.
  • the thioether oligomer By forming the thioether oligomer, outgassing can be suppressed. Furthermore, by containing the thioether oligomer, the viscosity of the sealant for display elements is appropriately increased, and unevenness is less likely to occur during coating.
  • the thioether oligomer is obtained by adding the polythiol monomer and the polyene monomer in a molar ratio of 3: 1 to 1: 3 with respect to the polythiol monomer by light irradiation or heating in the presence of a radical polymerization initiator. By carrying out the polymerization reaction, it is obtained as a polymer in the reaction mixture.
  • the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator, and a thermal radical polymerization initiator is preferably used.
  • the thioether oligomer may contain an unreacted thiol group or an unreacted carbon-carbon double bond or may not contain an unreacted thiol group or an unreacted carbon-carbon double bond. That is, it may be an oligomer that does not contain an unreacted thiol group or an unreacted carbon-carbon double bond obtained by sufficiently proceeding an addition polymerization reaction between the polythiol monomer and the polyene monomer. It may be an oligomer containing an unreacted thiol group or an unreacted carbon-carbon double bond obtained by stopping the reaction in the middle.
  • thermal radical polymerization initiator what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
  • the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, and the like.
  • the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
  • radical photopolymerization initiator the thing similar to the radical photopolymerization initiator contained in the sealing agent for display elements of this invention mentioned later can be used.
  • the number of moles of thiol group of polythiol monomer to the number of moles of carbon-carbon double bond of polyene monomer (number of moles of thiol group / mol of carbon-carbon double bond)
  • the number is 0.15 or less, the polyene monomer usually remains as an unreacted component in the resulting reaction mixture.
  • the sealing agent for display elements of the present invention includes a polythiol monomer, a polyene monomer, and a thioether oligomer obtained by stopping the reaction during the addition polymerization reaction in the addition polymerization reaction of the polythiol monomer and the polyene monomer described above.
  • the mixture may contain a radical polymerization initiator.
  • the thioether oligomer may be prepared in advance with a polythiol monomer and a polyene monomer.
  • the polythiol monomer and polyene monomer that are the raw materials of the thioether oligomer are the same as the polythiol monomer and polyene monomer contained in the display element sealing agent of the present invention described above. It may be different or different.
  • a preferable lower limit of the weight average molecular weight of the thioether oligomer is 500.
  • the weight average molecular weight of the thioether oligomer is less than 500, the effect of preventing unevenness during application of the obtained sealant for display element may not be sufficiently exhibited.
  • the weight average molecular weight of the said thioether oligomer it is more preferable to exceed 1500, and it is still more preferable that it is 2000 or more.
  • the preferable upper limit of the weight average molecular weight of the thioether oligomer is 40,000.
  • the weight average molecular weight of the thioether oligomer is more than 40,000, the resulting sealant for a display element is too high in viscosity and inferior in coatability.
  • a more preferable upper limit of the weight average molecular weight of the thioether oligomer is 10,000, and a more preferable upper limit is 8,000.
  • the minimum with preferable content of the said thioether oligomer in 100 weight part of the said whole polymeric compound is 30 weight part.
  • the minimum with more preferable content of the said thioether oligomer is 35 weight part, and a still more preferable minimum is 40 weight part.
  • the upper limit with preferable content of the said thioether oligomer in 100 weight part of the said whole polymeric compound is 90 weight part.
  • the upper limit with more preferable content of the said thioether oligomer is 80 weight part.
  • the content of the polythiol monomer is 5 to 40% by weight, the content of the polyene monomer is 5 to 40% by weight, and the content of the thioether oligomer is 30 to 90% in the whole sealant for display elements of the present invention. It is preferable that it is weight%.
  • the sealing agent for display elements of the present invention may contain other polymerizable compounds other than the polythiol monomer, the polyene monomer, the polyene oligomer, and the thioether oligomer, as long as the object of the present invention is not impaired. Good.
  • the other polymerizable compound is not particularly limited as long as it undergoes a curing reaction with light or heat.
  • an epoxy compound or a partially (meth) acryl-modified epoxy compound that is a raw material for the above-described epoxy (meth) acrylate. Etc.
  • the “partially (meth) acryl-modified epoxy compound” means a compound having one or more epoxy groups and one (meth) acryloyl group in one molecule.
  • the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
  • the partial (meth) acryl-modified epoxy compound can be obtained, for example, by reacting one epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid.
  • the sealing agent for display elements of this invention contains a radical polymerization initiator.
  • the radical polymerization initiator is a compound having a functional group that generates radicals upon light irradiation or heating and a reactive functional group (hereinafter also referred to as “radical polymerization initiator according to the present invention”).
  • the radical polymerization initiator according to the present invention is incorporated into the cured product by having the reactive functional group while exhibiting the performance as an initiator by the functional group that generates radicals by light irradiation or heating. Outgas generation can be sufficiently suppressed.
  • the radical polymerization initiator is preferably a compound having a functional group that generates radicals upon irradiation with light and a reactive functional group.
  • the sealing agent for display elements of the present invention contains a photopolymerization initiator, and the photopolymerization initiator has a functional group that generates radicals upon irradiation with light and a reactive functional group. It is more preferable to contain.
  • Examples of the functional group that generates radicals upon light irradiation or heating include, for example, acylphosphine oxide functional groups, ⁇ -aminoalkylphenone functional groups, benzyl ketal functional groups, ⁇ -hydroxyalkylphenone functional groups, and benzoin functional groups.
  • Examples thereof include a functional group, an oxime ester functional group, a titanocene functional group, an organic peroxide functional group, and an azo compound functional group.
  • acylphosphine oxide functional group ⁇ -aminoalkylphenone functional group, benzyl ketal functional group, ⁇ -hydroxyalkylphenone functional group, benzoin functional group, oxime ester functional group It is preferably at least one selected from the group consisting of a group and a titanocene functional group, more preferably an acylphosphine oxide functional group.
  • these functional groups may be used independently and 2 or more types may be used in combination.
  • the acylphosphine oxide functional group means a group having a structure in which acylphosphine oxide or a part thereof is substituted with another group.
  • the ⁇ -aminoalkylphenone functional group means a group having a structure in which ⁇ -aminoalkylphenone or a part thereof is substituted with another group.
  • the benzyl ketal functional group means a group having a structure in which ⁇ -dihydroxyacetophenone or a part thereof is substituted with another group.
  • the ⁇ -hydroxyalkylphenone functional group means ⁇ -monohydroxyalkylphenone or a group having a structure in which a part other than the hydroxyl group is substituted with another group.
  • the benzoin functional group means a group having a structure in which benzoin or a part thereof is substituted with another group.
  • the oxime ester functional group means a group having a structure in which N-acetyldimethyloxime or a part thereof is substituted with another group.
  • the titanocene functional group means a group having a structure in which titanocene or a part thereof is substituted with another group.
  • the organic peroxide functional group means a group having a peroxy group.
  • the azo compound functional group means a group having an azo group.
  • Examples of the acylphosphine oxide functional group include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like.
  • Examples of the ⁇ -aminoalkylphenone functional group include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butanone, 1,2- (dimethylamino) -2-((4-methylphenyl) methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone and the like.
  • Examples of the benzyl ketal functional group include 2,2-dimethoxy-1,2-diphenylethane-1-one.
  • Examples of the ⁇ -hydroxyalkylphenone functional group include 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) phenyl) -2-methyl-propane-1 -ON and the like.
  • Examples of the benzoin functional group include benzoin isopropyl ether.
  • Examples of the oxime ester functional group include 1,2-octanedione-1- (4- (phenylthio) -2- (O-benzoyloxime)), ethanone-1- (9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl) -1- (O-acetyloxime) and the like.
  • Examples of the titanocene functional group include bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, and the like. Is mentioned.
  • the reactive functional group is preferably a thiol group and / or a carbon-carbon double bond.
  • the radical polymerization initiator according to the present invention is easily incorporated into the cured product.
  • the radical polymerization initiator according to the present invention preferably has the reactive functional group in the side chain. By having the reactive functional group in the side chain, the radical polymerization initiator according to the present invention is more easily incorporated into the cured product.
  • the radical polymerization initiator according to the present invention preferably has two or more of the reactive functional groups in one molecule. By having two or more of the reactive functional groups in one molecule, the radical polymerization initiator according to the present invention is more easily taken into the cured product.
  • the compound having a functional group capable of generating a radical upon irradiation with light or heating and having two or more functional groups having a carbon-carbon double bond as the reactive functional group in one molecule is the polyene. It is not a monomer but a radical polymerization initiator according to the present invention.
  • the sealing agent for display elements of the present invention is excellent in photoreactivity and can suppress adverse effects such as outgassing
  • the compound represented by the following formula (3) as a radical polymerization initiator according to the present invention It is preferable to contain the oxime ester initiator which is.
  • the oxime ester initiator which is a compound represented by the following formula (3) is also one aspect of the present invention.
  • R 3 is selected from the group consisting of a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR 10 group, —SR 11 group, and —NR 12 R 13 group).
  • R 4 and R 7 are each independently a reactive functional group, a group having a hydrogen bonding functional group, a hydrogen atom, a carboalkoxyalkyl group having 3 to 20 carbon atoms (interrupted by one or more oxygen atoms, and / Or optionally substituted with one or more hydroxyl groups), a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (—OR 10 group, —SR 11 group, and A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 12 carbon atoms, which may be substituted with at least one selected from the group consisting of —NR 12 R 13 groups) (interrupted by one or more oxygen atoms, and / or may be substituted by one or more hydroxyl groups), a phenoxy
  • R 4 and R 7 are a reactive functional group.
  • R 5 , R 6 , R 8 , and R 9 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (—OR 10 group, — SR 11 group, or optionally substituted by —NR 12 R 13 group), benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms (one or more Optionally interrupted by an oxygen atom and / or substituted by one or more hydroxyl groups), a phenoxycarbonyl group, a —OR 10 group, a —SR 11 group, a —SOR 11 group, a —SO 2 R 11 group, or a -NR 12 R 13 groups, 10 groups -OR, -SR, atom,
  • R 10 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 6 carbon atoms (—OH group, —SH group, —CN group, alkoxy group having 1 to 4 carbon atoms, 3 to 3 carbon atoms).
  • alkeneoxy groups —OCH 2 CH 2 CN groups, —OCH 2 CH 2 (CO) O-alkyl groups having 4 to 7 carbon atoms, —O (CO) -alkyl groups having 2 to 5 carbon atoms, —O (CO) -phenyl group,-(CO) OH group, or a-(CO) O-alkyl group having 2 to 5 carbon atoms), an alkyl group having 2 to 6 carbon atoms (one or more Interrupted by an oxygen atom), — (CH 2 CH 2 O) n H group, alkanoyl group having 2 to 8 carbon atoms, alkenyl group having 3 to 12 carbon atoms, alkenoyl group having 3 to 6 carbon atoms, cyclohexyl group , Phenyl group (halogen atom, alkyl group having 1 to 12 carbon atoms, May be substituted with an alkoxy group having 1 to 4 carbon atoms), a phenylalkyl group
  • R 11 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, an alkyl group having 2 to 6 carbon atoms (—OH group, —SH group, —CN group, carbon C 1-4 alkoxy group, C 3-6 alkeneoxy group, —OCH 2 CH 2 CN group, C 4-7 —OCH 2 CH 2 (CO) O-alkyl group, C 2-5 -O (CO) -alkyl group, -O (CO) -phenyl group,-(CO) OH group, or-(CO) O-alkyl group having 2 to 5 carbon atoms), carbon An alkyl group of 2 to 12 (interrupted by one or more oxygen or sulfur atoms), a phenyl group (a halogen atom, an alkyl group of 1 to 12 carbon atoms, or an alk
  • R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkyl group having 3 to 5 carbon atoms.
  • R 12 is a hydrogen atom
  • R 13 may be a group represented by the following formula (6)
  • R 3 and R 4 are the same as those in formula (3).
  • M 1 is a bond or an alkyleneoxy group having 1 to 12 carbon atoms (which may be interrupted by 1 to 5 oxygen atoms, sulfur atoms, and / or —NR 12 — groups).
  • R 3 and R 4 may be the same as those in formula (3).
  • M 2 is a bond or an alkylene-S— group having 1 to 12 carbon atoms (which may be interrupted by 1 to 5 oxygen atoms, sulfur atoms and / or —NR 12 — groups). is there.
  • R 3 and R 4 are the same as those in formula (3).
  • M 3 represents a bond, a piperazino group, or an alkylene-NH— group having 1 to 12 carbon atoms (even if interrupted by 1 to 5 oxygen atoms, sulfur atoms, and / or —NR 12 — groups. Good).
  • the oxime ester initiator of the present invention is a compound represented by the above formula (3).
  • the description of the substituent is common to the corresponding ones of R 3 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13. It is an explanation about the matter.
  • the phenyl group When the phenyl group is substituted, the phenyl group is substituted with 1 to 4 substituents, preferably 1 to 3 substituents, more preferably 2 substituted. preferable.
  • Substituents on the phenyl ring are in the 4-position, 3,4-position, 3,4,5-position, 2,6-position, 2,4-position, or 2,4,6-position of the phenyl ring. It is preferably located, more preferably in the 4-position or 3,4-position.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2,4 1,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, icosyl, etc. Is mentioned.
  • examples of the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms include —CH 2 — CH 2 —O—CH 2 CH 3 group, — (CH 2 CH 2 O) y —CH 3 group (where y is 1 to 9), — (CH 2 —CH 2 O) 7 —CH 2 CH 3 groups, —CH 2 CH (CH 3 ) —O—CH 2 CH 2 CH 3 groups, —CH 2 CH (CH 3 ) —O—CH 2 CH 3 groups, —CH 2 CH (CH 3 ) —O—CH 2 CH 3 groups, —CH 2 —CH 2 —O— CH 2 —CH 2 —O—CH 2 CH 3 group, —CH 2 —CH 2 —O—CH 2 CH 3 group and the like can be mentioned.
  • alkyl group having 2 to 20 carbon atoms When the alkyl group having 2 to 20 carbon atoms is substituted with one or more hydroxyl groups, examples of the alkyl group having 2 to 20 carbon atoms substituted with one or more hydroxyl groups include 2-hydroxyethyl Group, 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 4-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, Examples include 2,3-dihydroxypropyl group and 2,4-dihydroxybutyl group.
  • cycloalkyl group examples include those corresponding to the number of carbon atoms among a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and the like. Of these, a cyclopentyl group and a cyclohexyl group are preferable, and a cyclohexyl group is more preferable.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butyloxy group, a sec-butyloxy group, an isobutyloxy group, and a tert-butyloxy group. Things.
  • alkoxyalkyl group having 2 to 10 carbon atoms examples include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a propoxymethyl group, a propoxyethyl group, and a propoxypropyl group.
  • alkanoyl group examples include an acetyl group, a propionyl group, a butanoyl group, an isobutanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a dodecanoyl group, a tetradecanoyl group, and a pentadecanoyl group.
  • alkanoyloxy group having 2 to 4 carbon atoms examples include acetyloxy group, propionyloxy group, butanoyloxy group, isobutanoyloxy group, and the like. Of these, an acetyloxy group is preferable.
  • alkoxycarbonyl group having 2 to 12 carbon atoms examples include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butyloxyocarbonyl group, isobutyloxycarbonyl group, 1,1-dimethylpropoxycarbonyl group, pentyl.
  • Examples include oxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group and the like.
  • a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butyloxycarbonyl group, and an isobutyloxycarbonyl group are preferable, and a methoxycarbonyl group is more preferable.
  • the phenoxycarbonyl group is substituted with 1 to 4 substituents, preferably 1 to 3 are substituted, and 2 are substituted. Is more preferable.
  • Substituents on the phenyl ring are the 4-position, 3,4-position, 3,4,5-position, 2,6-position, 2,4-position, or 2,4,6-position of the phenyl ring. It is preferably located, more preferably in the 4-position or 3,4-position.
  • phenylalkyl group having 7 to 9 carbon atoms examples include benzyl group, phenylethyl group, ⁇ -methylbenzyl group, ⁇ , ⁇ -dimethylbenzyl group and the like. Of these, a benzyl group is preferable.
  • alkenyl group examples include allyl group, methallyl group, 1,1-dimethylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, 7 -Of the octenyl group, dodecyl group, etc., the corresponding number of carbon atoms can be mentioned. Of these, an allyl group is preferable.
  • alkeneoxy group having 3 to 6 carbon atoms examples include allyloxy group, methallyloxy group, butenyloxy group, penteneoxy group, 1,3-pentadienyloxy group, and 5-hexenyloxy group.
  • alkenoyl group having 3 to 6 carbon atoms examples include propenoyl group, 2-methyl-propenoyl group, butenoyl group, pentenoyl group, 1,3-pentadienoyl group, 5-hexenoyl group and the like.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example. Of these, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom and a chlorine atom are more preferable.
  • aryl group examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like corresponding to the number of carbon atoms. Of these, a phenyl group is preferred.
  • R 3 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Moreover, in said formula (3), it is preferable that R ⁇ 5 >, R ⁇ 6 >, R ⁇ 8 > and R ⁇ 9 > are hydrogen atoms.
  • R 4 and R 7 are each independently a reactive functional group, a group having a hydrogen bonding functional group, a hydrogen atom, a carboalkoxyalkyl group having 3 to 20 carbon atoms (one or more Optionally substituted by one or more hydroxyl groups), halogen atom, alkyl group having 1 to 12 carbon atoms, cyclopentyl group, cyclohexyl group, phenyl group (—OR 10 group) , -SR 11 group, and -NR 12 R 13 group, which may be substituted with at least one selected from the group consisting of a group, benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, carbon number 2 to 12 alkoxycarbonyl groups (which may be interrupted by one or more oxygen atoms and / or substituted by one or more hydroxyl groups), phenoxycarbo Nyl group, —OR 10 group, —SR 11 group, —SOR 11 group,
  • the reactive functional group possessed by the oxime ester initiator of the present invention means a functional group capable of reacting with the polymerizable compound.
  • R 4 and R 7 are preferably both reactive functional groups.
  • a vinyl group, a thiol group, an acryloyl group, a methacryloyl group, an epoxy group etc. are mentioned, for example.
  • a vinyl group and a thiol group are preferable, and a vinyl group is more preferable.
  • the other when one of R 4 and R 7 is a reactive functional group, the other may be a group having a hydrogen bonding functional group.
  • the hydrogen bonding functional group means a functional group having hydrogen bonding properties.
  • the compatibility with the polymerizable compound is increased, and contamination due to elution into liquid crystal or the like is sufficiently suppressed. can do.
  • the hydrogen bonding functional group include an —OH group, —NH 2 group, —NHR group (R represents an aromatic, aliphatic hydrocarbon, or derivative thereof), —COOH group, —CONH.
  • functional groups such as two groups and —NHOH group, and residues such as —NHCO— bond, —NH— bond, —CONHCO— bond, and —NH—NH— bond. Of these, —OH group is preferable.
  • R 4 or R 7 is a carboalkoxyalkyl group having 3 to 20 carbon atoms
  • examples of the carboalkoxyalkyl group include a carbomethoxymethyl group, a carboethoxymethyl group, a carbomethoxyethyl group, a carboxyethoxyethyl group, Carboxymethoxypropyl group, carboxymethoxyoctyl group, carboxymethoxylauryl group, carboxymethoxystearyl group, carboxypropoxymethyl group, carboxypropoxyethyl group, carboxypropoxypropyl group, carboxyoctoxymethyl group, carboxylauroxymethyl group, carboxymyrist Examples thereof include a xymethyl group, a carboxyoctoxyethyl group, a carboxylauroxyethyl group, and a carboxy stearoxyethyl group.
  • oxime ester initiator of the present invention compounds represented by the following formulas (7) to (11) are preferable because they are excellent in photoreactivity and particularly excellent in suppressing adverse effects such as outgassing.
  • Compounds represented by the following formulas (7) to (10) are more preferable.
  • Examples of the method for producing the oxime ester initiator of the present invention are the same as those in the above formula (3) except for the ⁇ N—OC ( ⁇ O) —R 4 group and R 7 in the above formula (3).
  • ⁇ N—OC ( ⁇ O) —R 4 oxime is converted to an acyl compound in which the portion of the 4 group is a hydrogen atom to obtain an oxime compound, and then the portion of R 7 in the above formula (3) is formed.
  • Examples include a method of reacting acyl chloride having R 4 .
  • the compound represented by the above formula (7) can be produced by the following method or the like.
  • 2-phenylthiomethanol was reacted with acetyl chloride in dichloromethane in the presence of triethylamine to obtain 2-phenylthioethyl acetate, and then 2-phenylthioethyl acetate was obtained in dichloromethane.
  • Reaction with octanoic acid chloride in the presence of aluminum chloride produces an acyl compound represented by the following formula (12-1).
  • the obtained acyl compound was reacted with isoamyl nitrite in tetrahydrofuran in the presence of concentrated hydrochloric acid to prepare an oxime compound represented by the following formula (12-2).
  • the obtained oxime compound was converted into tetrahydrofuran.
  • the compound represented by the above formula (7) can be produced by reacting with 3-allyloxypropionic acid chloride in the presence of triethylamine.
  • the radical polymerization initiator according to the present invention has a preferable lower limit of molecular weight of 250 and a preferable upper limit of 1500.
  • the sealant for display element of the present invention is further excellent in the effect of suppressing the generation of outgas.
  • the molecular weight of the radical polymerization initiator according to the present invention is less than 250, outgas may be generated.
  • the molecular weight of the radical polymerization initiator according to the present invention exceeds 1500, curing may be insufficient.
  • the more preferable lower limit of the molecular weight of the radical polymerization initiator according to the present invention is 300, the more preferable upper limit is 1050, the still more preferable lower limit is 348, and the further preferable upper limit is 790. .
  • a preferable lower limit is 0.1 part by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the entire polymerizable compound.
  • the content of the radical polymerization initiator according to the present invention is less than 0.1 parts by weight, polymerization of the obtained sealant for display element may not sufficiently proceed.
  • the content of the radical polymerization initiator according to the present invention exceeds 5 parts by weight, the curing reaction becomes too fast, the workability is lowered, or the cured product of the obtained sealant for display elements becomes non-uniform.
  • the more preferable lower limit of the content of the radical polymerization initiator according to the present invention is 0.5 parts by weight, and the more preferable upper limit is 3 parts by weight.
  • the sealing agent for display elements of this invention may contain another polymerization initiator in addition to the radical polymerization initiator concerning this invention.
  • the sealant for display elements of the present invention may contain an adhesion promoter.
  • the adhesion-imparting agent include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N- (aminoethyl) aminopropyltrimethoxy
  • silane coupling agents such as silane and mercaptopropyltrimethoxysilane, titanium coupling agents, and aluminum coupling agents. These adhesiveness imparting agents may be used alone or in combination of two or more.
  • the sealing agent for display elements of the present invention may contain a stabilizer for the purpose of preventing oxidation or the like.
  • the stabilizer include 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2 Examples include '-methylenebis- (4-ethyl-6-t-butylphenol). These stabilizers may be used independently and 2 or more types may be used together.
  • the sealant for display element of the present invention further includes a filler, a curing accelerator, a plasticizer, a surfactant, a flame retardant, an antistatic agent, an antifoaming agent, and a leveling agent as long as the object of the present invention is not impaired. Further, additives such as an ultraviolet absorber and an organic solvent may be contained.
  • Examples of the method for producing the sealant for a display element of the present invention include stirring a polythiol monomer, a polyene monomer, a radical polymerization initiator according to the present invention, and an adhesiveness imparting agent added as necessary. The method etc. which mix uniformly using a machine are mentioned.
  • the sealing agent for display elements of the present invention has a preferred lower limit of viscosity of 0.4 Pa ⁇ s and a preferred upper limit of 40 Pa ⁇ s measured using a cone rotor viscometer under the conditions of 20 ° C. and 20 rpm.
  • the viscosity is less than 0.4 Pa ⁇ s, compositional unevenness occurs in the obtained sealant for display element, coating becomes difficult, or display characteristics of the obtained display element are deteriorated. There is.
  • the viscosity exceeds 40 Pa ⁇ s, coating may be difficult.
  • the more preferred lower limit of the viscosity is 0.5 Pa ⁇ s
  • the more preferred upper limit is 10 Pa ⁇ s
  • the still more preferred lower limit is 1 Pa ⁇ s
  • the still more preferred upper limit is 6 Pa ⁇ s
  • the particularly preferred lower limit is 2 Pa ⁇ s
  • the particularly preferred upper limit is 4 Pa. -S.
  • the sealant for display element of the present invention preferably has an average visible light transmittance of 80% or more in a region of a cured product having a wavelength of 380 to 780 nm.
  • the average transmittance of visible light is 80% or more, it can be suitably used for applications requiring transparency.
  • the average transmittance of the visible light is more preferably 95% or more.
  • permeability of the said visible light can be obtained by the method of irradiating a 2000mJ / cm ⁇ 2 > ultraviolet-ray with respect to the sealing agent for display elements of this invention.
  • the sealant for a display element of the present invention preferably has a weight reduction rate of 0.15% or less when a 100 ⁇ m thick cured product is heated to 130 ° C. at a temperature rising rate of 10 ° C./min. Since the weight reduction rate can be regarded as an outgas generation amount, an adverse effect on the display element can be suppressed by being 0.15% or less.
  • the weight reduction rate is more preferably 0.1% or less.
  • cured material which measures the said weight decreasing rate can be obtained by the method of irradiating 2000 mJ / cm ⁇ 2 > of ultraviolet-rays with respect to the sealing agent for display elements of this invention apply
  • the sealant for display elements of the present invention can be cured by light irradiation or heating, and is preferably cured by light irradiation.
  • Examples of the method for photocuring the sealant for display elements of the present invention include a method of irradiating light having a wavelength of 300 to 400 nm and an integrated light amount of 300 to 3000 mJ / cm 2 .
  • Examples of the light source for irradiating the sealing agent for display element of the present invention with light include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, and a microwave excitation mercury lamp. , Metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices, and the like. These light sources may be used independently and 2 or more types may be used together.
  • Examples of light irradiation means for the sealant for display elements of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. Irradiation means may be used.
  • the sealant for display element of the present invention is a sealant for sealing the entire surface, front surface, rear surface, or periphery of the display element, or a seal for sealing an opening provided in the display element. It can be used as an agent, and is particularly preferably used for sealing the entire surface of the display element.
  • the “entire surface” does not necessarily mean 100% of the surface having the display element, but means a necessary sealing surface required for the display element.
  • the “front surface” means a surface from which light is extracted, that is, a surface on the viewing side.
  • the sealant for display elements of the present invention can be used, for example, as a sealant for organic EL display elements, a sealant for liquid crystal display elements, a sealant for electrochromic substrates, a sealant for electronic paper, and the like. .
  • the sealing agent for display elements which is excellent in adhesiveness and transparency of hardened
  • the oxime ester initiator which can be used suitably for this sealing agent for display elements can be provided.
  • 1 is a 1 H-NMR spectrum of a compound represented by formula (7).
  • 1 is a 1 H-NMR spectrum of a compound represented by formula (8).
  • 1 is a 1 H-NMR spectrum of a compound represented by formula (9).
  • 1 is a 1 H-NMR spectrum of a compound represented by formula (10).
  • 1 is a 1 H-NMR spectrum of a compound represented by formula (11).
  • the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) using Shodex LF-804 (manufactured by Showa Denko KK) as a column.
  • GPC gel permeation chromatography
  • Shodex LF-804 manufactured by Showa Denko KK
  • Examples 1 to 7, Comparative Example 1 According to the blending ratio described in Table 1, each material was mixed using a stirrer (manufactured by Shinto Kagaku Co., Ltd., “Three One Motor HEIDON BLH300”), so that the display elements of Examples 1 to 7 and Comparative Example 1 A sealing agent was prepared.
  • the radical polymerization initiator according to the present invention in Examples 1 to 3, 6, and 7, the initiator A is a compound having an ⁇ -hydroxyalkylphenone functional group and an acryloyl group in the molecule (manufactured by KSM Co., Ltd.).
  • the initiator B is represented by the following formula (13) having an ⁇ -aminoalkylphenone functional group and a thiol group: “UV-H-4000”, weight average molecular weight 850).
  • a compound (molecular weight 353) was used, and as initiator C, 50 parts by weight of initiator A and 50 parts by weight of trimethylolpropane tris (3-mercaptopropionate) Gradually add 0.2 parts by weight of '-azobis (2,4-dimethylvaleronitrile), pour the resulting reaction mixture into a poor solvent, collect the precipitate, and vacuum the solvent In the compound obtained by removing the (weight-average molecular weight 98,000) was used.
  • Adhesiveness 0.05 g of each display element sealant obtained in Examples 1 to 7 and Comparative Example 1 was applied onto a glass substrate using a micropipette. This substrate was bonded to another glass substrate on which a spacer was disposed so as to have a thickness of 50 ⁇ m, and irradiated with 2000 mJ / cm 2 of ultraviolet rays using a high-pressure mercury lamp, to prepare a sample for adhesion test. The obtained adhesion test sample was subjected to a peel test using EZ GRAPH (manufactured by Shimadzu Corporation) at a peel rate of 5 mm / min to measure the adhesive force. The adhesiveness was evaluated as “ ⁇ ” when the adhesive strength was 1.0 N / cm or more, and “X” when the adhesive strength was less than 1.0 N / cm.
  • Transparency (transmittance) of the cured product Each display element sealant obtained in Examples 1 to 7 and Comparative Example 1 is sandwiched between PET resin films and irradiated with 2000 mJ / cm 2 of ultraviolet light to produce a 100 ⁇ m thick sample for transmittance measurement. did.
  • the obtained transmittance measurement sample was measured for light transmittance at a wavelength of 380 to 780 nm using a spectrophotometer (manufactured by Hitachi, Ltd., “U-3000”, conditions 300 to 800 nm).
  • a glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the substrate.
  • the substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.). The last treatment was performed with “NL-UV253”).
  • this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -NPD) is put into an unglazed crucible and other different types.
  • 200 mg of tris (8-hydroxyquinola) aluminum (Alq 3 ) was put in an unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 ⁇ 10 ⁇ 4 Pa. Thereafter, the crucible containing ⁇ -NPD was heated, and ⁇ -NPD was deposited on the substrate at a deposition rate of 15 s / s to form a 600 ⁇ ⁇ hole transport layer.
  • the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 ⁇ at a deposition rate of 15 ⁇ / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added.
  • the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 ⁇ 10 ⁇ 4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did.
  • the inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and the substrate on which the laminate including the organic light emitting material layer of 10 mm ⁇ 10 mm was arranged was taken out.
  • a mask having an opening of 13 mm ⁇ 13 mm is installed so as to cover the entire laminate of the substrate on which the laminate including the obtained organic light emitting material layer is disposed, and the inorganic material film A is formed by plasma CVD. Formed.
  • SiH 4 gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and chamber pressure is 0. The test was performed at 9 Torr.
  • the formed inorganic material film A had a thickness of about 0.2 ⁇ m.
  • Vacuum deposition was performed so that Thereafter, ultraviolet rays having a wavelength of 365 nm were irradiated using a high-pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm 2 to cure the sealant for display elements to form a resin protective film.
  • a mask having an opening of 12 mm ⁇ 12 mm is installed so as to cover the entire 11 mm ⁇ 11 mm resin protective film of the substrate on which the resin protective film is formed, and an inorganic material film B is formed by plasma CVD and displayed.
  • An element organic EL display element
  • SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
  • the formed inorganic material film B had a thickness of about 1 ⁇ m.
  • the prepared organic EL display elements were exposed for 100 hours under conditions of 60 ° C. and 90% RH, respectively, and then a voltage of 3 V was applied, and the light emission state (light emission and dark spots, presence / absence of pixel peripheral quenching) was visually observed. Evaluation was made with “ ⁇ ” when the light was emitted uniformly without dark spots or peripheral quenching, “ ⁇ ” when the dark spots or peripheral quenching was observed, and “X” when the non-light emitting portion was significantly enlarged.
  • FIG. 1 shows the 1 H-NMR spectrum of the obtained compound represented by the formula (7).
  • FIG. 5 shows the 1 H-NMR spectrum of the obtained compound represented by the formula (11).
  • Examples 8 to 14, Comparative Examples 2 and 3 According to the compounding ratio described in Table 2, each material was heated and mixed at 70 ° C. for 3 hours using a stirrer (manufactured by Shinto Kagaku Co., Ltd., “Three-One Motor HEIDON BLH300”) for 3 hours. Was prepared.
  • Display performance of display element (4-1) Display performance of liquid crystal display element (production of liquid crystal display element) Prepare two glass substrates (length 25mm, width 25mm, thickness 0.7mm) on which an ITO electrode with a thickness of 1000mm is formed on the surface and then an orientation film with a thickness of 800mm is applied on the surface by spin coating. Then, using a thermosetting epoxy resin (peripheral sealant) on one substrate, printing of a pattern in which a liquid crystal injection port was provided was performed by screen printing. Next, the substrate on which the pattern was printed was kept at 80 ° C. for 3 minutes to perform preliminary drying and fusion of the peripheral sealant to the substrate, and then returned to room temperature.
  • a thermosetting epoxy resin peripheral sealant
  • each substrate was bonded, and the peripheral sealant was cured by hot pressing heated to 130 ° C. for 2 hours to obtain an empty cell. .
  • the obtained empty cell was vacuumed, and liquid crystal (“ZLI-4792” manufactured by Merck & Co., Inc.) was injected from the injection port.
  • the injection port was obtained in each of Examples 8 to 14 and Comparative Examples 2 and 3.
  • Sealing was performed using a sealant for display elements, and the sealant was cured by irradiating with 3000 mJ / cm 2 ultraviolet rays using a high-pressure mercury lamp. Thereafter, the liquid crystal was annealed at 120 ° C. for 1 hour to produce a liquid crystal display element.
  • the obtained liquid crystal display element was driven in a halftone display state at a voltage of AC 3.5 V, and the alignment disorder of the liquid crystal near the inlet was observed with a polarizing microscope.
  • the case where no alignment disorder is confirmed is “ ⁇ ”
  • the case where alignment disorder less than 1 mm is confirmed is “ ⁇ ”
  • the case where there is a clear alignment disorder (dark color unevenness) of 1 mm or more is “X”.
  • the display performance of the liquid crystal display element was evaluated.
  • this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine ( ⁇ -NPD) is put into an unglazed crucible and other different types.
  • 200 mg of tris (8-hydroxyquinola) aluminum (Alq 3 ) was put in an unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 ⁇ 10 ⁇ 4 Pa. Thereafter, the crucible containing ⁇ -NPD was heated, and ⁇ -NPD was deposited on the substrate at a deposition rate of 15 s / s to form a 600 ⁇ ⁇ hole transport layer.
  • the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 ⁇ at a deposition rate of 15 ⁇ / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added.
  • the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 ⁇ 10 ⁇ 4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did.
  • the inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and the substrate on which the laminate including the organic light emitting material layer of 10 mm ⁇ 10 mm was arranged was taken out.
  • a mask having an opening of 13 mm ⁇ 13 mm is installed so as to cover the entire laminate of the substrate on which the laminate including the obtained organic light emitting material layer is disposed, and the inorganic material film A is formed by plasma CVD. Formed.
  • SiH 4 gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and chamber pressure is 0.
  • the test was performed at 9 Torr.
  • the thickness of the formed inorganic material film A of silicon nitride was about 0.2 ⁇ m.
  • ultraviolet rays having a wavelength of 365 nm were irradiated using a high-pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm 2 to cure the sealant for display elements to form a resin protective film.
  • a mask having an opening of 12 mm ⁇ 12 mm is installed so as to cover the entire 11 mm ⁇ 11 mm resin protective film of the substrate on which the resin protective film is formed, and an inorganic material film B is formed by plasma CVD and displayed.
  • An element organic EL display element
  • SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
  • the thickness of the formed inorganic material film B of silicon nitride was about 1 ⁇ m.
  • the sealing agent for display elements which is excellent in adhesiveness and transparency of hardened
  • the oxime ester initiator which can be used suitably for this sealing agent for display elements can be provided.

Abstract

A purpose of the present invention is to provide a sealant for a display element, with which production of outgas and contamination of other materials can be minimized, and which has exceptional adhesion and transparency of the cured article. Another purpose of the present invention is to provide an oxime ester initiator suitable for use in the sealant for a display element. The present invention is a sealant for a display element, containing a polythiol monomer having two or more thiol groups per molecule, a polyene monomer having two or more carbon-carbon double bonds per molecule, and a radical polymerization initiator, the radical polymerization initiator being a compound which has a functional group that produces a radical upon heating or irradiation with light, and a reactive functional group.

Description

表示素子用封止剤及びオキシムエステル開始剤Sealant for display element and oxime ester initiator
本発明は、アウトガスの発生や他材料の汚染を抑制することができ、接着性、及び、硬化物の透明性に優れる表示素子用封止剤に関する。また、本発明は、該表示素子用封止剤に好適に用いることができるオキシムエステル開始剤に関する。 The present invention relates to a sealant for a display element that can suppress generation of outgas and contamination of other materials, and is excellent in adhesiveness and transparency of a cured product. Moreover, this invention relates to the oxime ester initiator which can be used suitably for this sealing agent for display elements.
近年、薄型、軽量、低消費電力等の特徴を有する表示素子として、液晶表示素子や有機ＥＬ表示素子等が広く利用されている。これらの表示素子では、通常、液晶や発光層の封止、基板や光学フィルムや保護フィルムの接着等に表示素子用封止剤が用いられる。 In recent years, liquid crystal display elements, organic EL display elements, and the like are widely used as display elements having features such as thinness, light weight, and low power consumption. In these display elements, a sealant for a display element is usually used for sealing a liquid crystal or a light emitting layer, bonding a substrate, an optical film, or a protective film.
液晶表示素子では、基板の表面に接着剤を介して偏光フィルム等の光学フィルムや保護フィルムが貼着されている。例えば、特許文献１には、アクリル系の樹脂組成物からなる偏光フィルム用の粘着剤が開示されている。
また、有機ＥＬ表示素子では、有機発光材料層や電極が外気に曝されると、その性能が急激に劣化してしまうため、有機ＥＬ表示素子の安定性や耐久性を高めるために、有機発光材料層と電極とを、無機材料膜を介して樹脂膜で被覆して封止する方法が提案されている。例えば、特許文献２には、無機材料膜の上にアクリル系の樹脂組成物からなる樹脂膜を形成する方法が開示されている。 In a liquid crystal display element, an optical film such as a polarizing film or a protective film is attached to the surface of a substrate via an adhesive. For example, Patent Document 1 discloses a pressure-sensitive adhesive for a polarizing film made of an acrylic resin composition.
In addition, in the organic EL display element, when the organic light emitting material layer and the electrode are exposed to the outside air, the performance of the organic EL display element deteriorates rapidly. Therefore, in order to increase the stability and durability of the organic EL display element, There has been proposed a method in which a material layer and an electrode are covered with a resin film via an inorganic material film and sealed. For example, Patent Document 2 discloses a method of forming a resin film made of an acrylic resin composition on an inorganic material film.
しかしながら、特許文献１や特許文献２に開示されているようなアクリル系の表示素子用封止剤は、表示素子の製造過程で残存するアクリル樹脂により多量のアウトガスを発生させたり、接着性や硬化物の透明性に劣るものであったりするという問題があった。 However, the acrylic sealant for display elements as disclosed in Patent Document 1 and Patent Document 2 generates a large amount of outgas due to the acrylic resin remaining in the manufacturing process of the display elements, and exhibits adhesion and curing. There was a problem that the transparency of things was inferior.
特開２０１０－１９６００１号公報JP 2010-196001 A 特開２００１－３０７８７３号公報JP 2001-307873 A
本発明は、アウトガスの発生や他材料の汚染を抑制することができ、接着性、及び、硬化物の透明性に優れる表示素子用封止剤を提供することを目的とする。また、本発明は、該表示素子用封止剤に好適に用いることができるオキシムエステル開始剤を提供することを目的とする。 An object of the present invention is to provide a sealant for a display element that can suppress generation of outgas and contamination of other materials and is excellent in adhesiveness and transparency of a cured product. Moreover, an object of this invention is to provide the oxime ester initiator which can be used suitably for this sealing agent for display elements.
本発明は、１分子中に２個以上のチオール基を有するポリチオールモノマー、１分子中に２個以上の炭素－炭素二重結合を有するポリエンモノマー、及び、ラジカル重合開始剤を含有し、前記ラジカル重合開始剤は、光照射又は加熱によりラジカルを発生する官能基と、反応性官能基とを有する化合物である表示素子用封止剤である。
以下に本発明を詳述する。 The present invention comprises a polythiol monomer having two or more thiol groups in one molecule, a polyene monomer having two or more carbon-carbon double bonds in one molecule, and a radical polymerization initiator, The polymerization initiator is a sealant for a display element, which is a compound having a functional group that generates radicals by light irradiation or heating and a reactive functional group.
The present invention is described in detail below.
本発明者は、接着性、及び、硬化物の透明性に優れる表示素子用封止剤として、アクリル樹脂に代えて、１分子中に２個以上のチオール基を有するポリチオールモノマーと、１分子中に２個以上の炭素－炭素二重結合を有するポリエンモノマーとを含有する樹脂組成物を用いることを検討した。しかしながら、このような樹脂組成物を用いた場合でも、アウトガス発生の問題は完全には解決できなかった。また、得られた表示素子用封止剤が液晶表示素子の液晶と接触した場合に液晶を汚染したり、有機ＥＬ表示素子の有機発光材料層と接触した場合に有機発光材料層にダメージを与えたりすることがあった。
本発明者は、アウトガスの発生を充分に抑制できなかったり、他材料を汚染したりする原因が、表示素子用封止剤に含有されるラジカル重合開始剤にあると考えた。そこで本発明者は、ポリチオールモノマーとポリエンモノマーとを含有する表示素子用封止剤に特定のラジカル重合開始剤を用いることにより、アウトガスの発生や他材料の汚染を抑制することができ、接着性、及び、硬化物の透明性に優れる表示素子用封止剤を得ることができることを見出し、本発明を完成させるに至った。 The present inventor uses a polythiol monomer having two or more thiol groups in one molecule instead of an acrylic resin as a sealant for a display element that is excellent in adhesiveness and transparency of a cured product, and in one molecule. It was investigated to use a resin composition containing a polyene monomer having two or more carbon-carbon double bonds. However, even when such a resin composition is used, the problem of outgas generation cannot be completely solved. In addition, when the obtained sealant for display element comes into contact with the liquid crystal of the liquid crystal display element, the liquid crystal is contaminated, or when it comes into contact with the organic light emitting material layer of the organic EL display element, the organic light emitting material layer is damaged. Sometimes happened.
The inventor considered that the radical polymerization initiator contained in the sealant for a display element has a cause that the generation of outgas cannot be sufficiently suppressed or the other material is contaminated. Therefore, the present inventor can suppress generation of outgas and contamination of other materials by using a specific radical polymerization initiator for the sealant for a display element containing a polythiol monomer and a polyene monomer, and adhesion. And it discovered that the sealing agent for display elements excellent in transparency of hardened | cured material could be obtained, and came to complete this invention.
本発明の表示素子用封止剤は、重合性化合物として、１分子中に２個以上のチオール基を有するポリチオールモノマー（以下、単に「ポリチオールモノマー」ともいう）と、１分子中に２個以上の炭素－炭素二重結合を有するポリエンモノマー（以下、単に「ポリエンモノマー」ともいう）とを含有する。これらの成分を含有する本発明の表示素子用封止剤は、接着性、及び、硬化物の透明性に優れるものとなる。
なお、本明細書において上記「炭素－炭素二重結合」は、エチレン性不飽和結合を意味する。 The sealant for a display element of the present invention includes, as a polymerizable compound, a polythiol monomer having two or more thiol groups in one molecule (hereinafter also simply referred to as “polythiol monomer”) and two or more in one molecule. And a polyene monomer having a carbon-carbon double bond (hereinafter also simply referred to as “polyene monomer”). The sealant for display elements of the present invention containing these components is excellent in adhesiveness and transparency of the cured product.
In the present specification, the “carbon-carbon double bond” means an ethylenically unsaturated bond.
上記ポリチオールモノマーとしては、例えば、エタンジチオール、プロパンジチオール、ヘキサメチレンジチオール、デカメチレンジチオール等の脂肪族ポリチオールや、トリレン－２，４－ジチオール、キシレンジチオール等の芳香族ポリチオールや、下記式（１）で表される１，４－ジチアン環含有ポリチオール化合物等の環状スルフィド化合物や、エステル結合含有ポリチオール化合物や、ジグリコールジメルカプタン、トリグリコールジメルカプタン、テトラグリコールジメルカプタン、チオジグリコールジメルカプタン、チオトリグリコールジメルカプタン、チオテトラグリコールジメルカプタン、トリス－（３－メルカプトプロピオニルオキシ）－エチルイソシアヌレート、テトラエチレングリコール－ビス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトール－テトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトール－ヘキサキス（３－メルカプトプロピオネート）、４－（メルカプトメチル）－３，６－ジチアオクタン－１，８－ジチオール、４，８－ビス（メルカプトメチル）－３，６，９－トリチアウンデカン－１，１１－ジチオール、１，３，４，６－テトラメルカプトプロピオニルグリコールウリル等のその他のポリチオールモノマー等が挙げられる。これらのポリチオールモノマーは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the polythiol monomer include aliphatic polythiols such as ethanedithiol, propanedithiol, hexamethylenedithiol and decamethylenedithiol, aromatic polythiols such as tolylene-2,4-dithiol and xylenedithiol, and the following formula (1) A cyclic sulfide compound such as a 1,4-dithiane ring-containing polythiol compound, an ester bond-containing polythiol compound, diglycol dimercaptan, triglycol dimercaptan, tetraglycol dimercaptan, thiodiglycol dimercaptan, thiotril Glycol dimercaptan, thiotetraglycol dimercaptan, tris- (3-mercaptopropionyloxy) -ethyl isocyanurate, tetraethylene glycol-bis (3-mercaptop) Pionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol-tetrakis (3-mercaptopropionate), dipentaerythritol-hexakis (3-mercaptopropionate), 4- (mercaptomethyl)- 3,6-dithiaoctane-1,8-dithiol, 4,8-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol, 1,3,4,6-tetramercaptopropionyl glycol Examples include other polythiol monomers such as uril. These polythiol monomers may be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
式（１）中、ｌは、１～５の整数を表す。 In the formula (1), l represents an integer of 1 to 5.
上記式（１）で表される１，４－ジチアン環含有ポリチオール化合物としては、具体的には例えば、２，５－ジメルカプトメチル－１，４－ジチアン、２，５－ジメルカプトエチル－１，４－ジチアン、２，５－ジメルカプトプロピル－１，４－ジチアン、２，５－ジメルカプトブチル－１，４－ジチアン等が挙げられる。 Specific examples of the 1,4-dithiane ring-containing polythiol compound represented by the above formula (1) include 2,5-dimercaptomethyl-1,4-dithiane and 2,5-dimercaptoethyl-1 , 4-dithiane, 2,5-dimercaptopropyl-1,4-dithiane, 2,5-dimercaptobutyl-1,4-dithiane and the like.
上記ポリチオールモノマーのなかでも、得られる表示素子用封止剤が透明性に優れるものとなるため、エステル結合含有ポリチオールモノマーが好ましい。 Among the polythiol monomers, an ester bond-containing polythiol monomer is preferable because the obtained sealant for display elements is excellent in transparency.
上記エステル結合含有ポリチオールモノマーとしては、具体的には例えば、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリス－（（３－メルカプトプロピオニルオキシ）－エチル）－イソシアヌレート、ペンタエリスリトールテトラキスチオグリコレート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、テトラエチレングリコールビス（３－メルカプトプロピオネート）等が挙げられる。
なかでも、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトール－テトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトール－ヘキサキス（３－メルカプトプロピオネート）、１，４－ジチアン環含有ポリチオール化合物が好ましく、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ジペンタエリスリトール－ヘキサキス（３－メルカプトプロピオネート）がより好ましい。 Specific examples of the ester bond-containing polythiol monomer include trimethylolpropane tris (3-mercaptopropionate), tris-((3-mercaptopropionyloxy) -ethyl) -isocyanurate, pentaerythritol tetrakisthioglycol. Rate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.
Among them, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol-tetrakis (3-mercaptopropionate), dipentaerythritol-hexakis (3-mercaptopropionate), 1,4-dithiane ring included Polythiol compounds are preferred, and trimethylolpropane tris (3-mercaptopropionate) and dipentaerythritol-hexakis (3-mercaptopropionate) are more preferred.
また、上記ポリチオールモノマーは、１分子中に３個以上のチオール基を有するモノマー（３官能以上のポリチオールモノマー）を含有することが好ましい。
上記３官能以上のポリチオールモノマーとしては、１分子中に３～２０個のチオール基を有するモノマーが好ましく、１分子中に３～８個のチオール基を有するモノマーを含有がより好ましい。 Moreover, it is preferable that the said polythiol monomer contains the monomer (trifunctional or more polythiol monomer) which has a 3 or more thiol group in 1 molecule.
The tri- or higher functional polythiol monomer is preferably a monomer having 3 to 20 thiol groups in one molecule, and more preferably a monomer having 3 to 8 thiol groups in one molecule.
上記重合性化合物全体１００重量部中における上記ポリチオールモノマーの含有量の好ましい下限は１重量部、好ましい上限は８９重量部である。上記ポリチオールモノマーの含有量が１重量部未満であると、塗工性が悪化することがある。上記ポリチオールモノマーの含有量が８９重量部を超えると、アウトガスの発生を充分に抑制できなくなることがある。上記ポリチオールモノマーの含有量のより好ましい下限は５重量部、より好ましい上限は６９重量部である。 The preferable lower limit of the content of the polythiol monomer in 100 parts by weight of the whole polymerizable compound is 1 part by weight, and the preferable upper limit is 89 parts by weight. When the content of the polythiol monomer is less than 1 part by weight, coatability may be deteriorated. When the content of the polythiol monomer exceeds 89 parts by weight, generation of outgas may not be sufficiently suppressed. The minimum with more preferable content of the said polythiol monomer is 5 weight part, and a more preferable upper limit is 69 weight part.
上記ポリエンモノマーとしては、例えば、（メタ）アリル化合物、（メタ）アクリル化合物、ジビニルベンゼン等が挙げられる。これらのポリエンモノマーは、単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
なお、本明細書において、上記「（メタ）アリル」とはアリル又はメタリルを意味し、上記「（メタ）アクリル」とは、アクリル又はメタクリルを意味する。 Examples of the polyene monomer include (meth) allyl compounds, (meth) acrylic compounds, divinylbenzene, and the like. These polyene monomers may be used alone or in combination of two or more.
In the present specification, the “(meth) allyl” means allyl or methallyl, and the “(meth) acryl” means acryl or methacryl.
上記（メタ）アリル化合物としては、例えば、トリアリルシアヌレート、トリアリルイソシアヌレート、トリメタリルイソシアヌレート、ジアリルマレエート、ジアリルアジペート、ジアリルフタレート、トリアリルトリメリテート、テトラアリルピロメリテート、グリセリンジアリルエーテル、トリメチロールプロパンジアリルエーテル、ペンタエリスリトール、ジアリルエーテル、１，３－ジアリル－５－グリシジルイソシアヌレート、１，３，４，６－テトラアリルグリコールウリル、１，３，４，６－テトラアリル－３ａ－メチルグリコールウリル、１，３，４，６－テトラアリル－３ａ，６ａ－ジメチルグリコールウリル等が挙げられる。なかでも、トリアリルシアヌレート、トリアリルイソシアヌレート、１，３，４，６－テトラアリルグリコールウリルが好ましい。 Examples of the (meth) allyl compound include triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate, diallyl maleate, diallyl adipate, diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate, glyceryl diallyl Ether, trimethylolpropane diallyl ether, pentaerythritol, diallyl ether, 1,3-diallyl-5-glycidyl isocyanurate, 1,3,4,6-tetraallylglycoluril, 1,3,4,6-tetraallyl-3a -Methyl glycoluril, 1,3,4,6-tetraallyl-3a, 6a-dimethylglycoluril and the like. Of these, triallyl cyanurate, triallyl isocyanurate, and 1,3,4,6-tetraallylglycoluril are preferable.
上記（メタ）アクリル化合物としては、アクリロイル基又はメタクリロイル基を１分子中に２個以上有する化合物であれば特に限定されず、例えば、（メタ）アクリル酸とエポキシ化合物との反応により得られるエポキシ（メタ）アクリレート、（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られるエステル化合物、イソシアネートに水酸基を有する（メタ）アクリル酸誘導体を反応させることにより得られるウレタン（メタ）アクリレート等が挙げられる。
なお、本明細書において、上記「（メタ）アクリレート」とは、アクリレート又はメタクリレートを意味し、上記「エポキシ（メタ）アクリレート」とは、エポキシ化合物中の全てのエポキシ基を（メタ）アクリル酸と反応させた化合物のことを表す。 The (meth) acrylic compound is not particularly limited as long as it is a compound having two or more acryloyl groups or methacryloyl groups in one molecule. For example, an epoxy obtained by reaction of (meth) acrylic acid and an epoxy compound ( (Meth) acrylate, ester compound obtained by reacting a compound having a hydroxyl group with (meth) acrylic acid, urethane (meth) acrylate obtained by reacting a (meth) acrylic acid derivative having a hydroxyl group with isocyanate, etc. It is done.
In the present specification, the “(meth) acrylate” means acrylate or methacrylate, and the “epoxy (meth) acrylate” refers to all the epoxy groups in the epoxy compound and (meth) acrylic acid. It represents the reacted compound.
上記エポキシ（メタ）アクリレートは特に限定されず、例えば、（メタ）アクリル酸とエポキシ化合物とを、常法に従って塩基性触媒の存在下で反応させることにより得られるものが挙げられる。
上記エポキシ（メタ）アクリレートの原料となるエポキシ化合物としては、例えば、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールＳ型エポキシ化合物、２，２’－ジアリルビスフェノールＡ型エポキシ化合物、水添ビスフェノール型エポキシ化合物、プロピレンオキシド付加ビスフェノールＡ型エポキシ化合物、レゾルシノール型エポキシ化合物、ビフェニル型エポキシ化合物、スルフィド型エポキシ化合物、ジフェニルエーテル型エポキシ化合物、ジシクロペンタジエン型エポキシ化合物、ナフタレン型エポキシ化合物、フェノールノボラック型エポキシ化合物、オルトクレゾールノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、ナフタレンフェノールノボラック型エポキシ化合物、グリシジルアミン型エポキシ化合物、アルキルポリオール型エポキシ化合物、ゴム変性型エポキシ化合物、グリシジルエステル化合物、ビスフェノールＡ型エピスルフィド化合物等が挙げられる。 The epoxy (meth) acrylate is not particularly limited, and examples thereof include those obtained by reacting (meth) acrylic acid and an epoxy compound in the presence of a basic catalyst according to a conventional method.
Examples of the epoxy compound used as a raw material for the epoxy (meth) acrylate include bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, 2,2′-diallyl bisphenol A type epoxy compound, and hydrogenated bisphenol. Type epoxy compound, propylene oxide-added bisphenol A type epoxy compound, resorcinol type epoxy compound, biphenyl type epoxy compound, sulfide type epoxy compound, diphenyl ether type epoxy compound, dicyclopentadiene type epoxy compound, naphthalene type epoxy compound, phenol novolac type epoxy compound , Orthocresol novolac type epoxy compound, dicyclopentadiene novolac type epoxy compound, biphenyl novolac type epoxy Xyl compounds, naphthalenephenol novolac type epoxy compounds, glycidylamine type epoxy compounds, alkyl polyol type epoxy compounds, rubber-modified epoxy compounds, glycidyl ester compounds, bisphenol A type episulfide compounds, and the like.
上記（メタ）アクリル酸に水酸基を有する化合物を反応させることにより得られるエステル化合物のうち、２官能のものとしては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、２－ｎ－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコール（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＦジ（メタ）アクリレート、ジメチロールジシクロペンタジエンルジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド変性イソシアヌル酸ジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、カーボネートジオールジ（メタ）アクリレート、ポリエーテルジオールジ（メタ）アクリレート、ポリエステルジオールジ（メタ）アクリレート、ポリカプロラクトンジオールジ（メタ）アクリレート、ポリブタジエンジオールジ（メタ）アクリレート等が挙げられる。 Among the ester compounds obtained by reacting the (meth) acrylic acid with a compound having a hydroxyl group, examples of the bifunctional compounds include 1,4-butanediol di (meth) acrylate and 1,3-butanediol. Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n-butyl-2- Ethyl-1,3-propanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, tet Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, dimethylol di Cyclopentadiene didi (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyl Roxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) acrylate, polyester diol (Meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene di (meth) acrylate.
また、上記エステル化合物のうち、３官能以上のものとしては、例えば、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加イソシアヌル酸トリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、プロピレンオキシド付加グリセリントリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート等が挙げられる。 Among the above ester compounds, those having three or more functional groups include, for example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, and ethylene oxide-added tri Methylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, ethylene oxide-added isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane Tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene N'okishido added glycerin tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, and the like.
また、上記ポリエンモノマーは、１分子中に３個以上の炭素－炭素二重結合を有するモノマー（３官能以上のポリエンモノマー）を含有することが好ましい。
上記３官能以上のポリエンモノマーとしては、１分子中に３～２０個の炭素－炭素二重結合を有するモノマーが好ましく、１分子中に３～８個の炭素－炭素二重結合を有するモノマーがより好ましい。 The polyene monomer preferably contains a monomer having three or more carbon-carbon double bonds in one molecule (a polyene monomer having three or more functions).
The trifunctional or higher polyene monomer is preferably a monomer having 3 to 20 carbon-carbon double bonds in one molecule, and a monomer having 3 to 8 carbon-carbon double bonds in one molecule. More preferred.
上記重合性化合物全体１００重量部中における上記ポリエンモノマーの含有量の好ましい下限は１重量部、好ましい上限は８９重量部である。上記ポリエンモノマーの含有量が１重量部未満であると、塗工性が悪化することがある。上記ポリエンモノマーの含有量が８９重量部を超えると、ポリエンモノマーの未反応物が残りアウトガスが発生することがある。上記ポリエンモノマーの含有量のより好ましい下限は５重量部、より好ましい上限は７９重量部、更に好ましい上限は６９重量部である。 The preferable lower limit of the content of the polyene monomer in 100 parts by weight of the total polymerizable compound is 1 part by weight, and the preferable upper limit is 89 parts by weight. When the content of the polyene monomer is less than 1 part by weight, coatability may be deteriorated. When the content of the polyene monomer exceeds 89 parts by weight, unreacted polyene monomer may remain and outgas may be generated. A more preferable lower limit of the content of the polyene monomer is 5 parts by weight, a more preferable upper limit is 79 parts by weight, and a still more preferable upper limit is 69 parts by weight.
得られる表示素子用封止剤の硬化物が高い弾性率を有し、透明性や接着性に優れるものとなることから、上記ポリチオールモノマー及び／又は上記ポリエンモノマーとして、シロキサン結合を有するものも好適に用いられる。 Since the cured product of the obtained sealant for display elements has a high elastic modulus and is excellent in transparency and adhesiveness, those having a siloxane bond as the polythiol monomer and / or the polyene monomer are also suitable. Used for.
上記シロキサン結合は、シルセスキオキサン由来のものであることが好ましい。
即ち、上記シロキサン結合を有するポリチオールモノマーは、１分子中に２個以上のチオール基を有するシルセスキオキサン樹脂（以下、「チオール基含有シルセスキオキサン樹脂」ともいう）であることが好ましく、上記シロキサン結合を有するポリエンモノマーは、反応性官能基を１分子中に２個以上有するシルセスキオキサン樹脂（以下、「反応性官能基含有シルセスキオキサン樹脂」ともいう）であることが好ましい。 The siloxane bond is preferably derived from silsesquioxane.
That is, the polythiol monomer having a siloxane bond is preferably a silsesquioxane resin having two or more thiol groups in one molecule (hereinafter also referred to as “thiol group-containing silsesquioxane resin”). The polyene monomer having a siloxane bond is preferably a silsesquioxane resin having two or more reactive functional groups in one molecule (hereinafter also referred to as “reactive functional group-containing silsesquioxane resin”). .
上記ポリチオールモノマーとなるチオール基含有シルセスキオキサン樹脂は、下記式（２）で表されるチオール基含有シラン化合物の加水分解縮合物（以下、「加水分解縮合物（ａ）」ともいう）であることが好ましい。上記ポリチオールモノマーとして、上記加水分解縮合物（ａ）を用いる場合、得られる樹脂組成物の硬化物の透明性や、弾性率や、接着性を更に高めることができる。 The thiol group-containing silsesquioxane resin used as the polythiol monomer is a hydrolysis condensate of a thiol group-containing silane compound represented by the following formula (2) (hereinafter also referred to as “hydrolysis condensate (a)”). Preferably there is. When the hydrolysis condensate (a) is used as the polythiol monomer, the transparency, elastic modulus, and adhesiveness of the cured product of the obtained resin composition can be further increased.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
式（２）中、Ｒ１は、チオール基を有しかつ芳香環を有さない炭素数１～８の有機基、又は、チオール基を有しかつ芳香環を有する有機基を表し、Ｒ２は、水素原子、芳香環を有さない炭素数１～８の有機基、又は、芳香環を有する有機基を表す。 In Formula (2), R 1 represents a C 1-8 organic group having a thiol group and no aromatic ring, or an organic group having a thiol group and an aromatic ring, and R 2 Represents a hydrogen atom, an organic group having 1 to 8 carbon atoms having no aromatic ring, or an organic group having an aromatic ring.
上記Ｒ１としては、具体的には例えば、チオール基を有する炭素数１～８の脂肪族炭化水素基、チオール基を有する炭素数１～８の脂環式炭化水素基、チオール基を有する芳香族炭化水素基等が挙げられる。なお、上記Ｒ１における炭化水素基は、炭素原子と水素原子とだけでなく、チオール基に由来する硫黄原子も含む基である。
上記Ｒ２としては、具体的には例えば、水素原子、炭素数１～８の脂肪族炭化水素基、炭素数１～８の脂環式炭化水素基、芳香族炭化水素基等が挙げられる。
上記Ｒ２は、それぞれ同一であってもよいし、異なっていてもよい。 Specific examples of R 1 include, for example, an aliphatic hydrocarbon group having 1 to 8 carbon atoms having a thiol group, an alicyclic hydrocarbon group having 1 to 8 carbon atoms having a thiol group, and an aromatic having a thiol group. Group hydrocarbon group and the like. The hydrocarbon group in R 1 is a group containing not only a carbon atom and a hydrogen atom but also a sulfur atom derived from a thiol group.
Specific examples of R 2 include a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 1 to 8 carbon atoms, and an aromatic hydrocarbon group.
The R 2 may be the same or different.
上記式（２）で表されるチオール基含有シラン化合物を加水分解及び縮合させることにより、加水分解縮合物（ａ）を得ることができる。すなわち、加水分解反応及び縮合反応により、加水分解縮合物（ａ）を得ることができる。 A hydrolysis-condensation product (a) can be obtained by hydrolyzing and condensing the thiol group-containing silane compound represented by the above formula (2). That is, a hydrolysis-condensation product (a) can be obtained by a hydrolysis reaction and a condensation reaction.
上記式（２）で表されるチオール基含有シラン化合物としては、例えば、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、３－メルカプトプロピルトリプロポキシシラン、３－メルカプトプロピルトリブトキシシラン、１，４－ジメルカプト－２－（トリメトキシシリル）ブタン、１，４－ジメルカプト－２－（トリエトキシシリル）ブタン、１，４－ジメルカプト－２－（トリプロポキシシリル）ブタン、１，４－ジメルカプト－２－（トリブトキシシリル）ブタン、２－メルカプトメチル－３－メルカプトプロピルトリメトキシシラン、２－メルカプトメチル－３－メルカプトプロピルトリエトキシシラン、２－メルカプトメチル－３－メルカプトプロピルトリプロポキシシラン、２－メルカプトメチル－３－メルカプトプロピルトリブトキシシラン、１，２－ジメルカプトエチルトリメトキシシラン、１，２－ジメルカプトエチルトリエトキシシラン、１，２－ジメルカプトエチルトリプロポキシシラン、１，２－ジメルカプトエチルトリブトキシシラン等が挙げられる。なかでも、加水分解反応の反応性が高く、かつ入手が容易であるため、３－メルカプトプロピルトリメトキシシランが好ましい。上記式（２）で表されるチオール基含有シラン化合物は、単独で用いられてもよいし、２種以上が併用されてもよい。 Examples of the thiol group-containing silane compound represented by the above formula (2) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, and 3-mercaptopropyltributoxysilane. 1,4-dimercapto-2- (trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane, 1,4- Dimercapto-2- (tributoxysilyl) butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2-Merka Tomethyl-3-mercaptopropyltributoxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyl A tributoxysilane etc. are mentioned. Of these, 3-mercaptopropyltrimethoxysilane is preferred because of its high reactivity of hydrolysis reaction and easy availability. The thiol group-containing silane compound represented by the above formula (2) may be used alone or in combination of two or more.
また、上記加水分解縮合物（ａ）を得るに際し、上記チオール基含有シラン化合物に加えて、他の架橋性化合物を用いてもよい。 In obtaining the hydrolysis-condensation product (a), other crosslinkable compounds may be used in addition to the thiol group-containing silane compound.
上記他の架橋性化合物としては、トリアルキルアルコキシシラン、ジアルキルジアルコキシシラン、アルキルトリアルコキシシラン、テトラアルコキシシラン、テトラアルコキシチタン、テトラアルコキシジルコニウム等が挙げられる。
上記他の架橋性化合物として、トリアルキルアルコキシシラン、ジアルキルジアルコキシシラン、テトラアルコキシシランを使用した場合、加水分解縮合物（ａ）の架橋密度を容易に調整できる。
また、上記他の架橋性化合物としてアルキルトリアルコキシシランを使用した場合、加水分解縮合物（ａ）に含まれるチオール基の数を容易に調整できる。
上記他の架橋性化合物としてテトラアルコキシチタン又はテトラアルコキシジルコニウムを使用した場合、得られる樹脂組成物の硬化物の屈折率を高めることができる。
上記他の架橋性化合物は、単独で用いられてもよいし、２種以上が併用されてもよい。 Examples of the other crosslinkable compounds include trialkylalkoxysilane, dialkyldialkoxysilane, alkyltrialkoxysilane, tetraalkoxysilane, tetraalkoxytitanium, tetraalkoxyzirconium and the like.
When a trialkylalkoxysilane, a dialkyldialkoxysilane, or a tetraalkoxysilane is used as the other crosslinkable compound, the crosslink density of the hydrolysis condensate (a) can be easily adjusted.
In addition, when alkyltrialkoxysilane is used as the other crosslinkable compound, the number of thiol groups contained in the hydrolysis condensate (a) can be easily adjusted.
When tetraalkoxytitanium or tetraalkoxyzirconium is used as the other crosslinkable compound, the refractive index of the cured product of the resulting resin composition can be increased.
Said other crosslinking compound may be used independently and 2 or more types may be used together.
上記トリアルキルアルコキシシランとしては、例えば、トリメチルメトキシシラン、トリメチルエトキシシラン、トリエチルメトキシシラン、トリエチルエトキシシラン、トリフェニルメトキシシラン、トリフェニルエトキシシラン等が挙げられる。
上記ジアルキルジアルコキシシランとしては、例えば、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、メチルフェニルジメトキシシラン、メチルフェニルジエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン等が挙げられる。
上記アルキルトリアルコキシシランとしては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン等が挙げられる。
上記テトラアルコキシシランとしては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等が挙げられる。
上記テトラアルコキシチタンとしては、例えば、テトラメトキシチタン、テトラエトキシチタン、テトラプロポキシチタン、テトラブトキシチタン等が挙げられる。
上記テトラアルコキシジルコニウムとしては、例えば、テトラエトキシジルコニウム、テトラプロポキシジルコニウム、テトラブトキシジルコニウム等が挙げられる。 Examples of the trialkylalkoxysilane include trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and the like.
Examples of the dialkyl dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3- Examples include mercaptopropylmethyldimethoxysilane.
Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
Examples of the tetraalkoxy titanium include tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, and tetrabutoxy titanium.
Examples of the tetraalkoxyzirconium include tetraethoxyzirconium, tetrapropoxyzirconium, and tetrabutoxyzirconium.
上記加水分解縮合物（ａ）を得るための加水分解反応では、触媒を用いることが好ましい。
上記触媒としては、従来公知の触媒を用いることができ、特に限定されないが、触媒活性が高く、縮合反応の触媒としても機能するので、ギ酸であることが好ましい。 In the hydrolysis reaction for obtaining the hydrolysis condensate (a), it is preferable to use a catalyst.
A conventionally known catalyst can be used as the catalyst, and is not particularly limited, but formic acid is preferable because it has high catalytic activity and functions as a catalyst for the condensation reaction.
上記触媒の含有量は、上記チオール基含有シラン化合物１００重量部、又は、上記チオール基含有シラン化合物と上記他の架橋性化合物との合計１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が２５重量部である。上記触媒の含有量が０．１重量部未満であると、触媒効果が充分に発揮されないことがある。上記触媒の含有量が２５重量部を超えると、チオール基を含有するシルセスキオキサン樹脂の保存安定性が低くなったり、後工程で触媒を容易に除去でなかったりすることがある。上記触媒の含有量のより好ましい下限は１重量部、より好ましい上限は１０重量部である。 The content of the catalyst is preferably 0.1 parts by weight with respect to 100 parts by weight of the thiol group-containing silane compound or 100 parts by weight of the thiol group-containing silane compound and the other crosslinkable compound. The preferred upper limit is 25 parts by weight. When the content of the catalyst is less than 0.1 parts by weight, the catalytic effect may not be sufficiently exhibited. When the content of the catalyst exceeds 25 parts by weight, the storage stability of the silsesquioxane resin containing a thiol group may be lowered, or the catalyst may not be easily removed in a subsequent step. A more preferable lower limit of the content of the catalyst is 1 part by weight, and a more preferable upper limit is 10 parts by weight.
上記加水分解反応の反応温度及び反応時間は、上記チオール基含有シラン化合物の反応性、又は、上記チオール基含有シラン化合物及び上記他の架橋性化合物の反応性に応じて任意に設定できる。
上記反応温度は、通常０～１００℃、好ましくは２０～６０℃であり、上記反応時間は、１分～２時間程度である。 The reaction temperature and reaction time of the hydrolysis reaction can be arbitrarily set according to the reactivity of the thiol group-containing silane compound or the reactivity of the thiol group-containing silane compound and the other crosslinkable compound.
The reaction temperature is usually 0 to 100 ° C., preferably 20 to 60 ° C., and the reaction time is about 1 minute to 2 hours.
上記加水分解反応の際には、溶剤を用いてもよい。
上記溶剤の種類は特に限定されないが、後述する縮合反応に用いられる溶剤と同じであることが好ましい。
上記チオール基含有シラン化合物の反応性、又は、上記チオール基含有シラン化合物及び上記他の架橋性化合物の反応性が低い場合は、上記加水分解反応の際に、溶剤を用いないことが好ましい。 A solvent may be used in the hydrolysis reaction.
Although the kind of said solvent is not specifically limited, It is preferable that it is the same as the solvent used for the condensation reaction mentioned later.
When the reactivity of the thiol group-containing silane compound or the reactivity of the thiol group-containing silane compound and the other crosslinkable compound is low, it is preferable not to use a solvent during the hydrolysis reaction.
上記加水分解により生じた水酸基間だけでなく、該水酸基と残存アルコキシ基との間でも縮合反応が進行するため、上記加水分解反応は、［加水分解反応により生じた水酸基のモル数］／［上記チオール基含有シラン化合物、又は、上記チオール基含有シラン化合物と上記他の架橋性化合物を含む組成物に含まれるアルコキシ基の合計モル数］（以下、「モル比Ａ」ともいう）が０．５以上となるように進行させることが好ましい。上記モル比Ａは０．８以上であることがより好ましい。 Since the condensation reaction proceeds not only between the hydroxyl groups generated by the hydrolysis, but also between the hydroxyl groups and the remaining alkoxy groups, the hydrolysis reaction is [number of moles of hydroxyl groups generated by the hydrolysis reaction] / [above The total number of alkoxy groups in the thiol group-containing silane compound or the composition containing the thiol group-containing silane compound and the other crosslinkable compound] (hereinafter also referred to as “molar ratio A”) is 0.5. It is preferable to make it progress so that it may become the above. The molar ratio A is more preferably 0.8 or more.
上記縮合反応では、加水分解により生じた水酸基間で水が生成し、更に、水酸基とアルコキシ基間でアルコールが生成する。この縮合反応により、加水分解縮合物（ａ）はガラス化する。 In the condensation reaction, water is generated between the hydroxyl groups generated by hydrolysis, and further, alcohol is generated between the hydroxyl group and the alkoxy group. By this condensation reaction, the hydrolysis condensate (a) is vitrified.
上記縮合反応では、従来公知の縮合触媒を用いることができる。ギ酸は、触媒活性が高く、加水分解反応の触媒としてだけでなく、縮合反応の触媒としても作用する。従って、上記縮合触媒は、ギ酸であることが好ましい。 In the condensation reaction, a conventionally known condensation catalyst can be used. Formic acid has high catalytic activity and acts not only as a catalyst for hydrolysis reaction but also as a catalyst for condensation reaction. Therefore, the condensation catalyst is preferably formic acid.
上記縮合反応での反応温度及び反応時間はそれぞれ、上記チオール基含有シラン化合物の反応性、又は、上記チオール基含有シラン化合物及び上記他の架橋性化合物の反応性に応じて任意に設定できる。
上記反応温度は、通常４０～１５０℃程度、好ましくは６０～１００℃であり、上記反応時間は、３０分～１２時間程度である。 The reaction temperature and reaction time in the condensation reaction can be arbitrarily set according to the reactivity of the thiol group-containing silane compound or the reactivity of the thiol group-containing silane compound and the other crosslinkable compound.
The reaction temperature is usually about 40 to 150 ° C., preferably 60 to 100 ° C., and the reaction time is about 30 minutes to 12 hours.
未反応の水酸基とアルコキシ基とが、樹脂組成物の保管中に縮合反応してゲル化し難くなり、更に、硬化物において縮合反応が進行し難くなり、クラックが発生し難くなることから、上記縮合反応は、［未反応の水酸基と未反応のアルコキシ基との合計モル数］／［上記チオール基含有シラン化合物、又は、上記チオール基含有シラン化合物と上記他の架橋性化合物を含む組成物に含まれるアルコキシ基の合計モル数］（以下、「モル比Ｂ」ともいう）が０．３以下となるように進行させることが好ましい。上記モル比Ｂは０．２以下であることがより好ましい。 Since the unreacted hydroxyl group and the alkoxy group are difficult to gel by condensation reaction during storage of the resin composition, and further, the condensation reaction is difficult to proceed in the cured product, and cracks are less likely to occur. The reaction is included in [the total number of moles of unreacted hydroxyl group and unreacted alkoxy group] / [the thiol group-containing silane compound, or the composition containing the thiol group-containing silane compound and the other crosslinkable compound. The total number of moles of alkoxy groups] (hereinafter also referred to as “molar ratio B”) is preferably 0.3 or less. The molar ratio B is more preferably 0.2 or less.
上記縮合反応における、上記チオール基含有シラン化合物、又は、上記チオール基含有シラン化合物及び上記他の架橋性化合物の合計の濃度の好ましい下限は２重量％、好ましい上限は８０重量％である。上記濃度が上記範囲内にある場合には、反応中にゲル化し難くなり、加水分解縮合物（ａ）の分子量が大きくなりすぎず、加水分解縮合物（ａ）の保存安定性がより一層高くなる。上記濃度のより好ましい下限は１５重量％、より好ましい上限は６０重量％である。 In the condensation reaction, the preferable lower limit of the total concentration of the thiol group-containing silane compound or the thiol group-containing silane compound and the other crosslinkable compound is 2% by weight, and the preferable upper limit is 80% by weight. When the concentration is within the above range, gelation becomes difficult during the reaction, the molecular weight of the hydrolysis condensate (a) does not become too large, and the storage stability of the hydrolysis condensate (a) is further enhanced. Become. A more preferred lower limit of the concentration is 15% by weight, and a more preferred upper limit is 60% by weight.
上記縮合反応においては、上記縮合反応によって生成する水及びアルコールよりも沸点が高い溶剤を用いることが好ましい。この場合には、反応系中から、溶剤を容易に除去できる。上記溶剤は、単独で用いられてもよいし、２種以上が併用されてもよい。また、上記他の架橋性化合物を溶剤として用いることもできる。 In the condensation reaction, it is preferable to use a solvent having a boiling point higher than that of water and alcohol produced by the condensation reaction. In this case, the solvent can be easily removed from the reaction system. The said solvent may be used independently and 2 or more types may be used together. Moreover, the said other crosslinkable compound can also be used as a solvent.
上記縮合反応の後に、触媒を除去することが好ましい。触媒の除去により、加水分解縮合物（ａ）の保存安定性を高めることができる。上記触媒の除去方法は、触媒の種類に応じて公知方法を適宜に選択でき、触媒の沸点以上に加熱する方法、減圧する方法等が挙げられる。上記触媒がギ酸である場合には、これらの方法によりギ酸を容易に除去できる。 It is preferable to remove the catalyst after the condensation reaction. By removing the catalyst, the storage stability of the hydrolysis-condensation product (a) can be enhanced. As the method for removing the catalyst, a known method can be appropriately selected according to the type of catalyst, and examples thereof include a method of heating above the boiling point of the catalyst and a method of reducing the pressure. When the catalyst is formic acid, formic acid can be easily removed by these methods.
上記ポリエンモノマーとなる反応性官能基含有シルセスキオキサン樹脂としては、上記チオール基含有シルセスキオキサン樹脂のチオール基を炭素－炭素二重結合を有する基としたもの等が挙げられる。
具体的には、上記式（２）におけるＲ１を、上記反応性官能基又は上記反応性官能基を含む基とした反応性官能基含有シラン化合物の加水分解縮合物（以下、「加水分解縮合物（ｂ）」ともいう）であることが好ましい。上記ポリエンモノマーとして、上記加水分解縮合物（ｂ）を用いる場合、得られる樹脂組成物の硬化物の透明性や、弾性率や、接着性を更に高めることができる。
上記加水分解縮合物（ｂ）は、上記チオール基含有シラン化合物を反応性官能基含有シラン化合物とすること以外は、上記加水分解縮合物（ａ）と同様にして作製することができる。 Examples of the reactive functional group-containing silsesquioxane resin that serves as the polyene monomer include those having the thiol group of the thiol group-containing silsesquioxane resin as a group having a carbon-carbon double bond.
Specifically, a hydrolytic condensate of a reactive functional group-containing silane compound in which R 1 in the above formula (2) is the reactive functional group or a group containing the reactive functional group (hereinafter referred to as “hydrolytic condensation”). (It is also referred to as a product (b) ”). When the hydrolysis condensate (b) is used as the polyene monomer, the transparency, elastic modulus, and adhesiveness of the cured product of the resin composition obtained can be further increased.
The hydrolysis condensate (b) can be produced in the same manner as the hydrolysis condensate (a) except that the thiol group-containing silane compound is a reactive functional group-containing silane compound.
上記シロキサン結合を有するポリエンモノマーのうち、その他のものとしては、例えば、１，３－ジビニルテトラメチルジシロキサン、２，４，６，８－テトラメチル－２，４，６，８－テトラビニルシクロテトラシロキサン、１，３－ジビニルプロパンジシロキサン、１，５－ビス［２－（２，３－エポキシノルボルナン－５－イル）エチル］－１，１，３，３，５，５－ヘキサメチルペンタントリシロキサン、１，３，５，７，９，１１，１３，１５－オクタキス［２－（トリアリルシリル）エチル］ペンタシクロ［９．５．１．１３，９．１５，１５．１７，１３］イコサンオクタシロキサン、１，２－エポキシ－４－ビニルシクロヘキサンと１，３－ジビニル－１，１，３，３－テトラメチルジシロキサンと２，４，６，８－テトラメチルシクロテトラシロキサンの１，３－ビス（２－｛４，６，８－トリス［２－（３，４－エポキシシクロヘキシル）エチル］－２，４，６，８－テトラメチルシクロテトラシロキサン－２－イル｝エチル）－１，１，３，３－テトラメチルジシロキサン、ビスメタクリル酸オキシビス［ジメチルシリレン（３，１－プロパンジイル）］、１，５－ジメタクリロキシヘキサメチルトリシロキサン等が挙げられる。 Other polyene monomers having a siloxane bond include, for example, 1,3-divinyltetramethyldisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclo Tetrasiloxane, 1,3-divinylpropanedisiloxane, 1,5-bis [2- (2,3-epoxynorbornane-5-yl) ethyl] -1,1,3,3,5,5-hexamethylpentane Trisiloxane, 1,3,5,7,9,11,13,15-octakis [2- (triallylsilyl) ethyl] pentacyclo [9.5.1.13, 9.15, 15.17, 13] Icosan octasiloxane, 1,2-epoxy-4-vinylcyclohexane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 2,4,6,8-tetra 1,3-bis (2- {4,6,8-tris [2- (3,4-epoxycyclohexyl) ethyl] -2,4,6,8-tetramethylcyclotetrasiloxane-2 of tilcyclotetrasiloxane -Yl} ethyl) -1,1,3,3-tetramethyldisiloxane, bisbismethacrylic acid oxybis [dimethylsilylene (3,1-propanediyl)], 1,5-dimethacryloxyhexamethyltrisiloxane, etc. It is done.
上記シロキサン結合を有するポリエンモノマーのうち市販されているものとしては、例えば、ＡＣ－ＳＱシリーズ（東亞合成社製）等が挙げられる。 Examples of commercially available polyene monomers having a siloxane bond include AC-SQ series (manufactured by Toagosei Co., Ltd.).
上記ポリチオールモノマーと上記ポリエンモノマーとの配合割合としては、上記ポリチオールモノマーのチオール基と、上記ポリエンモノマーの炭素－炭素二重結合とのモル比がチオール基：炭素－炭素二重結合＝３：１～１：３となる範囲で配合することが好ましく、チオール基：炭素－炭素二重結合＝２：１～１：２となる範囲で配合することがより好ましい。 The blending ratio of the polythiol monomer and the polyene monomer is such that the molar ratio between the thiol group of the polythiol monomer and the carbon-carbon double bond of the polyene monomer is thiol group: carbon-carbon double bond = 3: 1. It is preferably blended in a range of ˜1: 3, and more preferably in a range of thiol group: carbon-carbon double bond = 2: 1 to 1: 2.
本発明の表示素子用封止剤は、上記重合性化合物として、上記ポリエンモノマーに加えて、ポリエンオリゴマーを含有することが好ましい。上記ポリエンオリゴマーを含有することにより、アウトガスの発生を抑制する効果や塗布性を向上させることができる。
なお、本明細書において、上記「ポリエンオリゴマー」は、上記「ポリエンモノマー」には含まれない。 It is preferable that the sealing agent for display elements of this invention contains a polyene oligomer as said polymeric compound in addition to the said polyene monomer. By containing the said polyene oligomer, the effect and coating property which suppress generation | occurrence | production of outgas can be improved.
In the present specification, the “polyene oligomer” is not included in the “polyene monomer”.
上記ポリエンオリゴマーに由来するポリエンモノマーとしては、上述した、（メタ）アリル化合物（メタ）アクリル化合物、ジビニルベンゼン等が挙げられる。 Examples of the polyene monomer derived from the polyene oligomer include the (meth) allyl compound (meth) acrylic compound and divinylbenzene described above.
上記ポリエンオリゴマーを製造する方法としては、例えば、上記ポリエンモノマーを、後述するラジカル重合開始剤等の存在下で反応させる方法等が挙げられる。上記ラジカル重合開始剤としては、光ラジカル重合開始剤、熱ラジカル重合開始剤が挙げられ、熱ラジカル重合開始剤が好ましく用いられる。 Examples of the method for producing the polyene oligomer include a method of reacting the polyene monomer in the presence of a radical polymerization initiator or the like described later. Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator, and a thermal radical polymerization initiator is preferably used.
上記ポリエンオリゴマーの重量平均分子量の好ましい下限は３００、好ましい上限は２万である。上記ポリエンオリゴマーの重量平均分子量が３００未満であると、アウトガスの発生を抑制する効果を充分に向上させることができないことがある。上記ポリエンオリゴマーの重量平均分子量が２万を超えると、得られる表示素子用封止剤の粘度が高くなりすぎて塗工性が悪化することがある。上記ポリエンオリゴマーの重量平均分子量のより好ましい下限は４００、より好ましい上限は４０００である。
なお、本明細書において、上記「重量平均分子量」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際に用いるカラムとしては、例えば、Ｓｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）等が挙げられる。 The minimum with a preferable weight average molecular weight of the said polyene oligomer is 300, and a preferable upper limit is 20,000. If the weight average molecular weight of the polyene oligomer is less than 300, the effect of suppressing the generation of outgas may not be sufficiently improved. When the weight average molecular weight of the polyene oligomer is more than 20,000, the viscosity of the obtained sealant for a display element may be too high and the coatability may be deteriorated. The minimum with a more preferable weight average molecular weight of the said polyene oligomer is 400, and a more preferable upper limit is 4000.
In the present specification, the “weight average molecular weight” is a value determined by polystyrene conversion after measurement by gel permeation chromatography (GPC). Examples of the column used when measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko).
上記重合性化合物全体１００重量部中における上記ポリエンオリゴマーの含有量の好ましい下限は３０重量部、好ましい上限は９０重量部である。上記ポリエンオリゴマーの含有量が３０重量部未満であると、アウトガスの発生を更に抑制する効果が充分に発揮されなかったりする。上記ポリエンオリゴマーの含有量が９０重量部を超えると、得られる表示素子用封止剤の粘度が高くなりすぎて塗工性が悪化することがある。上記チオエーテルオリゴマーの含有量のより好ましい下限は３５重量部、より好ましい上限は８０重量部である。 The minimum with preferable content of the said polyene oligomer in 100 weight part of the said whole polymeric compound is 30 weight part, and a preferable upper limit is 90 weight part. If the content of the polyene oligomer is less than 30 parts by weight, the effect of further suppressing the generation of outgas may not be exhibited sufficiently. When content of the said polyene oligomer exceeds 90 weight part, the viscosity of the sealing agent for display elements obtained will become high too much, and coating property may deteriorate. The minimum with more preferable content of the said thioether oligomer is 35 weight part, and a more preferable upper limit is 80 weight part.
本発明の表示素子用封止剤は、ポリチオールモノマーとポリエンモノマーとの反応により形成されるチオエーテルオリゴマーを含有することが好ましい。上記チオエーテルオリゴマーを形成することにより、アウトガスの発生を抑制することができる。更に、上記チオエーテルオリゴマーを含有することにより、表示素子用封止剤の粘度が適度に高くなり、塗工時にムラが生じにくくなる。 It is preferable that the sealing agent for display elements of this invention contains the thioether oligomer formed by reaction of a polythiol monomer and a polyene monomer. By forming the thioether oligomer, outgassing can be suppressed. Furthermore, by containing the thioether oligomer, the viscosity of the sealant for display elements is appropriately increased, and unevenness is less likely to occur during coating.
上記チオエーテルオリゴマーは、上記ポリチオールモノマーと、上記ポリチオールモノマーに対してモル比で３：１～１：３となる範囲の上記ポリエンモノマーとを、ラジカル重合開始剤の存在下で光照射や加熱により付加重合反応させることにより重合体として反応混合物中に得られる。上記ラジカル重合開始剤としては、光ラジカル重合開始剤、熱ラジカル重合開始剤が挙げられ、熱ラジカル重合開始剤が好ましく用いられる。
なお、上記チオエーテルオリゴマーは、未反応チオール基や未反応炭素－炭素二重結合を含んでいてもよいし、未反応チオール基や未反応炭素－炭素二重結合を含んでいなくてもよい。即ち、上記ポリチオールモノマーと上記ポリエンモノマーとの付加重合反応を充分に進めて得られる未反応チオール基や未反応炭素－炭素二重結合を含まないオリゴマーであってもよいし、該付加重合反応の途中で反応を停止させることにより得られる未反応チオール基や未反応炭素－炭素二重結合を含むオリゴマーであってもよい。 The thioether oligomer is obtained by adding the polythiol monomer and the polyene monomer in a molar ratio of 3: 1 to 1: 3 with respect to the polythiol monomer by light irradiation or heating in the presence of a radical polymerization initiator. By carrying out the polymerization reaction, it is obtained as a polymer in the reaction mixture. Examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal radical polymerization initiator, and a thermal radical polymerization initiator is preferably used.
The thioether oligomer may contain an unreacted thiol group or an unreacted carbon-carbon double bond or may not contain an unreacted thiol group or an unreacted carbon-carbon double bond. That is, it may be an oligomer that does not contain an unreacted thiol group or an unreacted carbon-carbon double bond obtained by sufficiently proceeding an addition polymerization reaction between the polythiol monomer and the polyene monomer. It may be an oligomer containing an unreacted thiol group or an unreacted carbon-carbon double bond obtained by stopping the reaction in the middle.
上記熱ラジカル重合開始剤としては、例えば、アゾ化合物、有機過酸化物等からなるものが挙げられる。
上記アゾ化合物としては、例えば、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、アゾビスイソブチロニトリル等が挙げられる。
上記有機過酸化物としては、例えば、過酸化ベンゾイル、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシエステル、ジアシルパーオキサイド、パーオキシジカーボネート等が挙げられる。
また、上記光ラジカル重合開始剤としては、後述する本発明の表示素子用封止剤に含有される光ラジカル重合開始剤と同様のものを用いることができる。 As said thermal radical polymerization initiator, what consists of an azo compound, an organic peroxide, etc. is mentioned, for example.
Examples of the azo compound include 2,2′-azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, and the like.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, and peroxydicarbonate.
Moreover, as said radical photopolymerization initiator, the thing similar to the radical photopolymerization initiator contained in the sealing agent for display elements of this invention mentioned later can be used.
上述したポリチオールモノマーとポリエンモノマーとの付加重合反応において、ポリエンモノマーの炭素－炭素二重結合のモル数に対するポリチオールモノマーのチオール基のモル数（チオール基のモル数／炭素－炭素二重結合のモル数）が０．１５以下である場合は、通常、得られる反応混合物中にポリエンモノマーが未反応成分として残る。 In the above addition polymerization reaction of polythiol monomer and polyene monomer, the number of moles of thiol group of polythiol monomer to the number of moles of carbon-carbon double bond of polyene monomer (number of moles of thiol group / mol of carbon-carbon double bond) When the number) is 0.15 or less, the polyene monomer usually remains as an unreacted component in the resulting reaction mixture.
なお、本発明の表示素子用封止剤は、上述したポリチオールモノマーとポリエンモノマーとの付加重合反応において、付加重合反応の途中で反応を停止させることにより得られるポリチオールモノマーとポリエンモノマーとチオエーテルオリゴマーの混合物にラジカル重合開始剤を含有させたものであってもよい。
また、上記チオエーテルオリゴマーは、予め作製したものをポリチオールモノマー及びポリエンモノマーと混合してもよい。
上記チオエーテルオリゴマーを予め作製する場合、上記チオエーテルオリゴマーの原料となるポリチオールモノマー及びポリエンモノマーは、上述した、本発明の表示素子用封止剤に含有されるポリチオールモノマー及びポリエンモノマーと同一のものであってもよいし、異なるものであってもよい。 In addition, the sealing agent for display elements of the present invention includes a polythiol monomer, a polyene monomer, and a thioether oligomer obtained by stopping the reaction during the addition polymerization reaction in the addition polymerization reaction of the polythiol monomer and the polyene monomer described above. The mixture may contain a radical polymerization initiator.
The thioether oligomer may be prepared in advance with a polythiol monomer and a polyene monomer.
When the thioether oligomer is prepared in advance, the polythiol monomer and polyene monomer that are the raw materials of the thioether oligomer are the same as the polythiol monomer and polyene monomer contained in the display element sealing agent of the present invention described above. It may be different or different.
上記チオエーテルオリゴマーの重量平均分子量の好ましい下限は５００である。上記チオエーテルオリゴマーの重量平均分子量が５００未満であると、得られる表示素子用封止剤の塗工時のムラを防止する効果が充分に発揮されないことがある。上記チオエーテルオリゴマーの重量平均分子量は１５００を超えることがより好ましく、２０００以上であることが更に好ましい。
また、上記チオエーテルオリゴマーの重量平均分子量の好ましい上限は４万である。上記チオエーテルオリゴマーの重量平均分子量が４万を超えると、得られる表示素子用封止剤が、粘度が高くなりすぎて塗工性に劣るものとなる。上記チオエーテルオリゴマーの重量平均分子量のより好ましい上限は１万、更に好ましい上限は８０００である。 A preferable lower limit of the weight average molecular weight of the thioether oligomer is 500. When the weight average molecular weight of the thioether oligomer is less than 500, the effect of preventing unevenness during application of the obtained sealant for display element may not be sufficiently exhibited. As for the weight average molecular weight of the said thioether oligomer, it is more preferable to exceed 1500, and it is still more preferable that it is 2000 or more.
Moreover, the preferable upper limit of the weight average molecular weight of the thioether oligomer is 40,000. When the weight average molecular weight of the thioether oligomer is more than 40,000, the resulting sealant for a display element is too high in viscosity and inferior in coatability. A more preferable upper limit of the weight average molecular weight of the thioether oligomer is 10,000, and a more preferable upper limit is 8,000.
上記重合性化合物全体１００重量部中における上記チオエーテルオリゴマーの含有量の好ましい下限は３０重量部である。上記チオエーテルオリゴマーの含有量が３０重量部未満であると、アウトガスの発生を充分に抑制することができなかったり、得られる表示素子用封止剤の塗工時のムラを防止する効果が充分に発揮されなかったりする。上記チオエーテルオリゴマーの含有量のより好ましい下限は３５重量部、更に好ましい下限は４０重量部である。
また、上記重合性化合物全体１００重量部中における上記チオエーテルオリゴマーの含有量の好ましい上限は９０重量部である。上記チオエーテルオリゴマーの含有量が９０重量部を超えると、得られる表示素子用封止剤の粘度が高くなりすぎて塗工性が悪化することがある。上記チオエーテルオリゴマーの含有量のより好ましい上限は８０重量部である。 The minimum with preferable content of the said thioether oligomer in 100 weight part of the said whole polymeric compound is 30 weight part. When the content of the thioether oligomer is less than 30 parts by weight, it is not possible to sufficiently suppress the generation of outgas, or the effect of preventing unevenness at the time of coating the obtained sealant for display element is sufficiently obtained. It may not be demonstrated. The minimum with more preferable content of the said thioether oligomer is 35 weight part, and a still more preferable minimum is 40 weight part.
Moreover, the upper limit with preferable content of the said thioether oligomer in 100 weight part of the said whole polymeric compound is 90 weight part. When content of the said thioether oligomer exceeds 90 weight part, the viscosity of the sealing agent for display elements obtained will become high too much, and coating property may deteriorate. The upper limit with more preferable content of the said thioether oligomer is 80 weight part.
本発明の表示素子用封止剤全体中における、ポリチオールモノマーの含有量は５～４０重量％であり、ポリエンモノマーの含有量は５～４０重量％であり、チオエーテルオリゴマーの含有量は３０～９０重量％であることが好ましい。上記ポリチオールモノマー、上記ポリエンモノマー、及び、上記チオエーテルオリゴマーの含有量がこの範囲であることにより、アウトガスの発生を抑制する効果、塗工性、接着性、及び、硬化物の透明性の全てにおいて、充分な効果を発揮できるものとなる。 The content of the polythiol monomer is 5 to 40% by weight, the content of the polyene monomer is 5 to 40% by weight, and the content of the thioether oligomer is 30 to 90% in the whole sealant for display elements of the present invention. It is preferable that it is weight%. By the content of the polythiol monomer, the polyene monomer, and the thioether oligomer within this range, the effect of suppressing the generation of outgas, coating properties, adhesiveness, and transparency of the cured product, A sufficient effect can be exhibited.
本発明の表示素子用封止剤は、本発明の目的を阻害しない範囲において、上記ポリチオールモノマー、上記ポリエンモノマー、上記ポリエンオリゴマー、及び、上記チオエーテルオリゴマー以外のその他の重合性化合物を含有してもよい。
上記その他の重合性化合物としては、光又は熱で硬化反応するものであれば特に限定されず、例えば、上述したエポキシ（メタ）アクリレートの原料となるエポキシ化合物や、部分（メタ）アクリル変性エポキシ化合物等が挙げられる。
なお、本明細書において上記「部分（メタ）アクリル変性エポキシ化合物」とは、１分子中に１個以上のエポキシ基と１個の（メタ）アクリロイル基とを有する化合物を意味する。また、本明細書において上記「（メタ）アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味する。
上記部分（メタ）アクリル変性エポキシ化合物は、例えば、１分子中に２個以上のエポキシ基を有するエポキシ化合物の１個のエポキシ基を（メタ）アクリル酸と反応させることによって得ることができる。 The sealing agent for display elements of the present invention may contain other polymerizable compounds other than the polythiol monomer, the polyene monomer, the polyene oligomer, and the thioether oligomer, as long as the object of the present invention is not impaired. Good.
The other polymerizable compound is not particularly limited as long as it undergoes a curing reaction with light or heat. For example, an epoxy compound or a partially (meth) acryl-modified epoxy compound that is a raw material for the above-described epoxy (meth) acrylate. Etc.
In the present specification, the “partially (meth) acryl-modified epoxy compound” means a compound having one or more epoxy groups and one (meth) acryloyl group in one molecule. In the present specification, the “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
The partial (meth) acryl-modified epoxy compound can be obtained, for example, by reacting one epoxy group of an epoxy compound having two or more epoxy groups in one molecule with (meth) acrylic acid.
本発明の表示素子用封止剤は、ラジカル重合開始剤を含有する。
上記ラジカル重合開始剤は、光照射又は加熱によりラジカルを発生する官能基と、反応性官能基とを有する化合物（以下、「本発明にかかるラジカル重合開始剤」ともいう）である。本発明にかかるラジカル重合開始剤は、上記光照射又は加熱によりラジカルを発生する官能基により開始剤としての性能を発揮しつつ、上記反応性官能基を有することにより硬化物中に取り込まれるため、アウトガスの発生を充分に抑制することができる。
上記ラジカル重合開始剤は、光照射によりラジカルを発生する官能基と、反応性官能基とを有する化合物であることが好ましい。
また、本発明の表示素子用封止剤は、光重合開始剤を含有することが好ましく、該光重合開始剤として、光照射によりラジカルを発生する官能基と、反応性官能基とを有する化合物を含有することがより好ましい。 The sealing agent for display elements of this invention contains a radical polymerization initiator.
The radical polymerization initiator is a compound having a functional group that generates radicals upon light irradiation or heating and a reactive functional group (hereinafter also referred to as “radical polymerization initiator according to the present invention”). The radical polymerization initiator according to the present invention is incorporated into the cured product by having the reactive functional group while exhibiting the performance as an initiator by the functional group that generates radicals by light irradiation or heating. Outgas generation can be sufficiently suppressed.
The radical polymerization initiator is preferably a compound having a functional group that generates radicals upon irradiation with light and a reactive functional group.
Moreover, it is preferable that the sealing agent for display elements of the present invention contains a photopolymerization initiator, and the photopolymerization initiator has a functional group that generates radicals upon irradiation with light and a reactive functional group. It is more preferable to contain.
上記光照射又は加熱によりラジカルを発生する官能基としては、例えば、アシルホスフィンオキサイド系官能基、α－アミノアルキルフェノン系官能基、ベンジルケタール系官能基、α－ヒドロキシアルキルフェノン系官能基、ベンゾイン系官能基、オキシムエステル系官能基、チタノセン系官能基、有機過酸化物系官能基、アゾ化合物系官能基等が挙げられる。なかでも、光硬化性の観点から、アシルホスフィンオキサイド系官能基、α－アミノアルキルフェノン系官能基、ベンジルケタール系官能基、α－ヒドロキシアルキルフェノン系官能基、ベンゾイン系官能基、オキシムエステル系官能基、チタノセン系官能基からなる群より選択される少なくとも一種であることが好ましく、アシルホスフィンオキサイド系官能基であることがより好ましい。これらの官能基は単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。
ここで、上記アシルホスフィンオキサイド系官能基とは、アシルホスフィンオキサイド又はその一部が別の基に置換した構造を有する基を意味する。上記α－アミノアルキルフェノン系官能基とは、α－アミノアルキルフェノン又はその一部が別の基に置換した構造を有する基を意味する。上記ベンジルケタール系官能基とは、α－ジヒドロキシアセトフェノン又はその一部が別の基に置換した構造を有する基を意味する。上記α－ヒドロキシアルキルフェノン系官能基とは、α－モノヒドロキシアルキルフェノン又はその水酸基以外の一部が別の基に置換した構造を有する基を意味する。上記ベンゾイン系官能基とは、ベンゾイン又はその一部が別の基に置換した構造を有する基を意味する。上記オキシムエステル系官能基とは、Ｎ－アセチルジメチルオキシム又はその一部が別の基に置換した構造を有する基を意味する。上記チタノセン系官能基とは、チタノセン又はその一部が別の基に置換した構造を有する基を意味する。上記有機過酸化物系官能基とは、ペルオキシ基を有する基を意味する。上記アゾ化合物系官能基とは、アゾ基を有する基を意味する。 Examples of the functional group that generates radicals upon light irradiation or heating include, for example, acylphosphine oxide functional groups, α-aminoalkylphenone functional groups, benzyl ketal functional groups, α-hydroxyalkylphenone functional groups, and benzoin functional groups. Examples thereof include a functional group, an oxime ester functional group, a titanocene functional group, an organic peroxide functional group, and an azo compound functional group. Among these, from the viewpoint of photocurability, acylphosphine oxide functional group, α-aminoalkylphenone functional group, benzyl ketal functional group, α-hydroxyalkylphenone functional group, benzoin functional group, oxime ester functional group It is preferably at least one selected from the group consisting of a group and a titanocene functional group, more preferably an acylphosphine oxide functional group. These functional groups may be used independently and 2 or more types may be used in combination.
Here, the acylphosphine oxide functional group means a group having a structure in which acylphosphine oxide or a part thereof is substituted with another group. The α-aminoalkylphenone functional group means a group having a structure in which α-aminoalkylphenone or a part thereof is substituted with another group. The benzyl ketal functional group means a group having a structure in which α-dihydroxyacetophenone or a part thereof is substituted with another group. The α-hydroxyalkylphenone functional group means α-monohydroxyalkylphenone or a group having a structure in which a part other than the hydroxyl group is substituted with another group. The benzoin functional group means a group having a structure in which benzoin or a part thereof is substituted with another group. The oxime ester functional group means a group having a structure in which N-acetyldimethyloxime or a part thereof is substituted with another group. The titanocene functional group means a group having a structure in which titanocene or a part thereof is substituted with another group. The organic peroxide functional group means a group having a peroxy group. The azo compound functional group means a group having an azo group.
上記アシルホスフィンオキサイド系官能基としては、例えば、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）フェニルホスフィンオキサイド等が挙げられる。
上記α－アミノアルキルフェノン系官能基としては、例えば、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン、１，２－（ジメチルアミノ）－２－（（４－メチルフェニル）メチル）－１－（４－（４－モルホリニル）フェニル）－１－ブタノン等が挙げられる。
上記ベンジルケタール系官能基としては、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン等が挙げられる。
上記α－ヒドロキシアルキルフェノン系官能基としては、例えば、２－ヒロドキシ－１－（４－（４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル）フェニル）－２－メチル－プロパン－１－オン等が挙げられる。
上記ベンゾイン系官能基としては、例えば、ベンゾインイソプロピルエーテル等が挙げられる。
上記オキシムエステル系官能基としては、例えば、１，２－オクタンジオン－１－（４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム））、エタノン－１－（９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル）－１－（Ｏ－アセチルオキシム）等が挙げられる。
上記チタノセン系官能基としては、例えば、ビス（η５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウム等が挙げられる。 Examples of the acylphosphine oxide functional group include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like.
Examples of the α-aminoalkylphenone functional group include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butanone, 1,2- (dimethylamino) -2-((4-methylphenyl) methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone and the like.
Examples of the benzyl ketal functional group include 2,2-dimethoxy-1,2-diphenylethane-1-one.
Examples of the α-hydroxyalkylphenone functional group include 2-hydroxy-1- (4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) phenyl) -2-methyl-propane-1 -ON and the like.
Examples of the benzoin functional group include benzoin isopropyl ether.
Examples of the oxime ester functional group include 1,2-octanedione-1- (4- (phenylthio) -2- (O-benzoyloxime)), ethanone-1- (9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl) -1- (O-acetyloxime) and the like.
Examples of the titanocene functional group include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, and the like. Is mentioned.
上記反応性官能基としては、チオール基及び／又は炭素－炭素二重結合であることが好ましい。上記反応性官能基としてチオール基及び／又は炭素－炭素二重結合を有することにより、本発明にかかるラジカル重合開始剤は、硬化物中に取り込まれやすいものとなる。 The reactive functional group is preferably a thiol group and / or a carbon-carbon double bond. By having a thiol group and / or a carbon-carbon double bond as the reactive functional group, the radical polymerization initiator according to the present invention is easily incorporated into the cured product.
本発明にかかるラジカル重合開始剤は、側鎖に上記反応性官能基を有することが好ましい。側鎖に上記反応性官能基を有することにより、本発明にかかるラジカル重合開始剤は、より硬化物中に取り込まれやすいものとなる。 The radical polymerization initiator according to the present invention preferably has the reactive functional group in the side chain. By having the reactive functional group in the side chain, the radical polymerization initiator according to the present invention is more easily incorporated into the cured product.
本発明にかかるラジカル重合開始剤は、上記反応性官能基を１分子中に２個以上有することが好ましい。上記反応性官能基を１分子中に２個以上有することにより、本発明にかかるラジカル重合開始剤は、より硬化物中に取り込まれやすいものとなる。
なお、上記光照射又は加熱によりラジカルを発生する官能基を有し、かつ、上記反応性官能基として炭素－炭素二重結合を有する官能基を１分子中に２個以上有する化合物は、上記ポリエンモノマーではなく、本発明にかかるラジカル重合開始剤とする。 The radical polymerization initiator according to the present invention preferably has two or more of the reactive functional groups in one molecule. By having two or more of the reactive functional groups in one molecule, the radical polymerization initiator according to the present invention is more easily taken into the cured product.
The compound having a functional group capable of generating a radical upon irradiation with light or heating and having two or more functional groups having a carbon-carbon double bond as the reactive functional group in one molecule is the polyene. It is not a monomer but a radical polymerization initiator according to the present invention.
本発明の表示素子用封止剤は、光反応性に優れ、アウトガスの発生等の悪影響を抑制することができることから、本発明にかかるラジカル重合開始剤として下記式（３）で表される化合物であるオキシムエステル開始剤を含有することが好ましい。下記式（３）で表される化合物であるオキシムエステル開始剤もまた、本発明の１つである。 Since the sealing agent for display elements of the present invention is excellent in photoreactivity and can suppress adverse effects such as outgassing, the compound represented by the following formula (3) as a radical polymerization initiator according to the present invention It is preferable to contain the oxime ester initiator which is. The oxime ester initiator which is a compound represented by the following formula (3) is also one aspect of the present invention.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
式（３）中、Ｒ３は、フェニル基（炭素数１～６のアルキル基、フェニル基、ハロゲン原子、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、炭素数１～２０のアルキル基、炭素数２～２０のアルキル基（１個以上の酸素原子により中断、及び／若しくは、１個以上のヒドロキシル基により置換されていてもよい）、炭素数５～８のシクロアルキル基、炭素数２～２０のアルカノイル基、ベンゾイル基（炭素数１～６のアルキル基、フェニル基、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、炭素数２～１２のアルコキシカルボニル基（１個以上の酸素原子により中断、及び／若しくは、１個以上のヒドロキシル基により置換されていてもよい）、フェノキシカルボニル基（炭素数１～６のアルキル基、フェニル基、ハロゲン原子、－ＯＲ１０基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、－ＣＯＮＲ１２Ｒ１３基、－ＣＮ基、－ＮＯ２基、炭素数１～４のハロアルキル基、炭素数１～６の－Ｓ（Ｏ）ｍ－アルキル基、炭素数６～１２の－Ｓ（Ｏ）ｍ－アリール基（炭素数１～１２のアルキル基により置換されていてもよい）、炭素数１～６の－ＳＯ２Ｏ－アルキル基、炭素数６～１０の－ＳＯ２Ｏ－アリール基、又は、ジフェニルホスフィノイル基であり、ｍは、１又は２である。
Ｒ４及びＲ７は、それぞれ独立して、反応性官能基、水素結合性官能基を有する基、水素原子、炭素数３～２０のカルボアルコキシアルキル基（１個以上の酸素原子により中断、及び／又は、１個以上のヒドロキシル基により置換されていてもよい）、ハロゲン原子、炭素数１～１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基（－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、ベンジル基、ベンゾイル基、炭素数２～１２のアルカノイル基、炭素数２～１２のアルコキシカルボニル基（１個以上の酸素原子により中断、及び／又は、１個以上のヒドロキシル基により置換されていてもよい）、フェノキシカルボニル基、－ＯＲ１０基、－ＳＲ１１基、－ＳＯＲ１１基、－ＳＯ２Ｒ１１基、或いは、－ＮＲ１２Ｒ１３基（ここで、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基は、フェニル環の有する置換基若しくはフェニル環の炭素原子の一つと、Ｒ１０、Ｒ１１、Ｒ１２、及び／若しくは、Ｒ１３を介して５員環又は６員環を形成していてもよい）である。ただし、Ｒ４及びＲ７の少なくとも一方は、反応性官能基である。
Ｒ５、Ｒ６、Ｒ８、及び、Ｒ９は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基（－ＯＲ１０基、－ＳＲ１１基、若しくは、－ＮＲ１２Ｒ１３基により置換されていてもよい）、ベンジル基、ベンゾイル基、炭素数２～１２のアルカノイル基、炭素数２～１２のアルコキシカルボニル基（１個以上の酸素原子により中断、及び／若しくは、１個以上のヒドロキシル基により置換されていてもよい）、フェノキシカルボニル基、－ＯＲ１０基、－ＳＲ１１基、－ＳＯＲ１１基、－ＳＯ２Ｒ１１基、又は、－ＮＲ１２Ｒ１３基であり、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基は、フェニル環の有する置換基又はフェニル環の炭素原子の一つと、Ｒ１０、Ｒ１１、Ｒ１２、及び／又は、Ｒ１３を介して５員環又は６員環を形成していてもよい。
Ｒ１０は、水素原子、炭素数１～１２のアルキル基、炭素数２～６のアルキル基（－ＯＨ基、－ＳＨ基、－ＣＮ基、炭素数１～４のアルコキシ基、炭素数３～６のアルケンオキシ基、－ＯＣＨ２ＣＨ２ＣＮ基、炭素数４～７の－ＯＣＨ２ＣＨ２（ＣＯ）Ｏ－アルキル基、炭素数２～５の－Ｏ（ＣＯ）－アルキル基、－Ｏ（ＣＯ）－フェニル基、－（ＣＯ）ＯＨ基、若しくは、炭素数２～５の－（ＣＯ）Ｏ－アルキル基で置換されている）、炭素数２～６のアルキル基（１個以上の酸素原子により中断されている）、－（ＣＨ２ＣＨ２Ｏ）ｎＨ基、炭素数２～８のアルカノイル基、炭素数３～１２のアルケニル基、炭素数３～６のアルケノイル基、シクロヘキシル基、フェニル基（ハロゲン原子、炭素数１～１２のアルキル基、若しくは、炭素数１～４のアルコキシ基で置換されていてもよい）、炭素数７～９のフェニルアルキル基、－Ｓｉ（炭素数１～８のアルキル）ｒ（フェニル）３－ｒ基、又は、下記式（４）で表される基のいずれかである。ｎは、１～２０であり、ｒは、１～３である。
Ｒ１１は、水素原子、炭素数１～１２のアルキル基、炭素数３～１２のアルケニル基、シクロヘキシル基、炭素数２～６のアルキル基（－ＯＨ基、－ＳＨ基、－ＣＮ基、炭素数１～４のアルコキシ基、炭素数３～６のアルケンオキシ基、－ＯＣＨ２ＣＨ２ＣＮ基、炭素数４～７の－ＯＣＨ２ＣＨ２（ＣＯ）Ｏ－アルキル基、炭素数２～５の－Ｏ（ＣＯ）－アルキル基、－Ｏ（ＣＯ）－フェニル基、－（ＣＯ）ＯＨ基、若しくは、炭素数２～５の－（ＣＯ）Ｏ－アルキル基で置換されている）、炭素数２～１２のアルキル基（１個以上の酸素原子若しくは硫黄原子により中断されている）、フェニル基（ハロゲン原子、炭素数１～１２のアルキル基、若しくは、炭素数１～４のアルコキシ基で置換されていてもよい）、炭素数７～９のフェニルアルキル基、又は、下記式（５）で表される基のいずれかである。
Ｒ１２及びＲ１３は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～４のヒドロキシアルキル基、炭素数２～１０のアルコキシアルキル基、炭素数３～５のアルケニル基、炭素数５～１２のシクロアルキル基、炭素数７～９のフェニルアルキル基、フェニル基（炭素数１～１２のアルキル基若しくは炭素数１～４のアルコキシ基により置換されている）、炭素数２～３のアルカノイル基、炭素数３～６のアルケノイル基、ベンゾイル基、或いは、Ｒ１２及びＲ１３が１つの基となった炭素数２～６のアルキレン基（酸素原子若しくは－ＮＲ１０－基により中断、及び／又は、ヒドロキシル基、炭素数１～４のアルコキシ基、炭素数２～４のアルカノイルオキシ基、若しくは、ベンゾイルオキシ基で置換されていてもよい）である。Ｒ１２が水素原子である場合、Ｒ１３は、下記式（６）で表される基であってもよい。 In the formula (3), R 3 is selected from the group consisting of a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR 10 group, —SR 11 group, and —NR 12 R 13 group). Optionally substituted by at least one selected), an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms (interrupted by one or more oxygen atoms, and / or one or more Optionally substituted with a hydroxyl group), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, an —OR 10 group, -SR 11 groups, and, -NR 12 may be substituted by at least one selected from the group consisting of R 13 groups), the alkoxycarbonyl group (one or more oxygen atoms of 2 to 12 carbon atoms Interruption, and / or may be substituted by one or more hydroxyl groups), a phenoxycarbonyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, -OR 10 groups, and, -NR 12 Optionally substituted by at least one selected from the group consisting of R 13 groups), —CONR 12 R 13 group, —CN group, —NO 2 group, haloalkyl group having 1 to 4 carbon atoms, carbon number 1 -S (O) m -alkyl group having 6 to 6, -S (O) m -aryl group having 6 to 12 carbon atoms (which may be substituted with an alkyl group having 1 to 12 carbon atoms), 1 to carbon atoms 6 —SO 2 O-alkyl group, 6 to 10 carbon atoms —SO 2 O-aryl group, or diphenylphosphinoyl group, and m is 1 or 2.
R 4 and R 7 are each independently a reactive functional group, a group having a hydrogen bonding functional group, a hydrogen atom, a carboalkoxyalkyl group having 3 to 20 carbon atoms (interrupted by one or more oxygen atoms, and / Or optionally substituted with one or more hydroxyl groups), a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (—OR 10 group, —SR 11 group, and A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 12 carbon atoms, which may be substituted with at least one selected from the group consisting of —NR 12 R 13 groups) (interrupted by one or more oxygen atoms, and / or may be substituted by one or more hydroxyl groups), a phenoxycarbonyl group, -OR 0 group, -SR 11 group, -SOR 11 group, -SO 2 R 11 group, or, -NR 12 R 13 group (herein, 10 group -OR, -SR 11 groups, and, -NR 12 R 13 group May form a 5-membered or 6-membered ring with R 10 , R 11 , R 12 , and / or R 13 with one of the substituents of the phenyl ring or the carbon atom of the phenyl ring. ). However, at least one of R 4 and R 7 is a reactive functional group.
R 5 , R 6 , R 8 , and R 9 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (—OR 10 group, — SR 11 group, or optionally substituted by —NR 12 R 13 group), benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms (one or more Optionally interrupted by an oxygen atom and / or substituted by one or more hydroxyl groups), a phenoxycarbonyl group, a —OR 10 group, a —SR 11 group, a —SOR 11 group, a —SO 2 R 11 group, or a -NR 12 R 13 groups, 10 groups -OR, -SR 11 groups, and, -NR 12 R 13 groups, the substituent or the phenyl ring with a phenyl ring And one atom, R 10, R 11, R 12, and / or may form a 5- or 6-membered ring via the R 13.
R 10 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 6 carbon atoms (—OH group, —SH group, —CN group, alkoxy group having 1 to 4 carbon atoms, 3 to 3 carbon atoms). 6 alkeneoxy groups, —OCH 2 CH 2 CN groups, —OCH 2 CH 2 (CO) O-alkyl groups having 4 to 7 carbon atoms, —O (CO) -alkyl groups having 2 to 5 carbon atoms, —O (CO) -phenyl group,-(CO) OH group, or a-(CO) O-alkyl group having 2 to 5 carbon atoms), an alkyl group having 2 to 6 carbon atoms (one or more Interrupted by an oxygen atom), — (CH 2 CH 2 O) n H group, alkanoyl group having 2 to 8 carbon atoms, alkenyl group having 3 to 12 carbon atoms, alkenoyl group having 3 to 6 carbon atoms, cyclohexyl group , Phenyl group (halogen atom, alkyl group having 1 to 12 carbon atoms, May be substituted with an alkoxy group having 1 to 4 carbon atoms), a phenylalkyl group having 7 to 9 carbon atoms, -Si (alkyl having 1 to 8 carbon atoms) r (phenyl) 3-r groups, or Or any one of groups represented by the following formula (4). n is 1 to 20, and r is 1 to 3.
R 11 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, an alkyl group having 2 to 6 carbon atoms (—OH group, —SH group, —CN group, carbon C 1-4 alkoxy group, C 3-6 alkeneoxy group, —OCH 2 CH 2 CN group, C 4-7 —OCH 2 CH 2 (CO) O-alkyl group, C 2-5 -O (CO) -alkyl group, -O (CO) -phenyl group,-(CO) OH group, or-(CO) O-alkyl group having 2 to 5 carbon atoms), carbon An alkyl group of 2 to 12 (interrupted by one or more oxygen or sulfur atoms), a phenyl group (a halogen atom, an alkyl group of 1 to 12 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms) Which may be substituted), Niruarukiru group, or any one of groups represented by the following formula (5).
R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkyl group having 3 to 5 carbon atoms. An alkenyl group, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a phenyl group (substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms), An alkanoyl group having 2 to 3 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a benzoyl group, or an alkylene group having 2 to 6 carbon atoms in which R 12 and R 13 form one group (oxygen atom or —NR 10 -Interrupted by a group and / or substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkanoyloxy group having 2 to 4 carbon atoms, or a benzoyloxy group It is also may). When R 12 is a hydrogen atom, R 13 may be a group represented by the following formula (6).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
式（４）中、Ｒ３及びＲ４は、式（３）と同じものが挙げられる。Ｍ１は、結合手、又は、炭素数１～１２のアルキレンオキシ基（１～５個の酸素原子、硫黄原子、及び／若しくは、－ＮＲ１２－基により中断されていてもよい）である。 In formula (4), R 3 and R 4 are the same as those in formula (3). M 1 is a bond or an alkyleneoxy group having 1 to 12 carbon atoms (which may be interrupted by 1 to 5 oxygen atoms, sulfur atoms, and / or —NR 12 — groups).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
式（５）中、Ｒ３及びＲ４は、式（３）と同じものが挙げられる。Ｍ２は、結合手、又は、炭素数１～１２のアルキレン－Ｓ－基（１～５個の酸素原子、硫黄原子、及び／若しくは、－ＮＲ１２－基により中断されていてもよい）である。 In formula (5), R 3 and R 4 may be the same as those in formula (3). M 2 is a bond or an alkylene-S— group having 1 to 12 carbon atoms (which may be interrupted by 1 to 5 oxygen atoms, sulfur atoms and / or —NR 12 — groups). is there.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
式（６）中、Ｒ３及び、Ｒ４は、式（３）と同じものが挙げられる。Ｍ３は、結合手、ピペラジノ基、又は、炭素数１～１２のアルキレン－ＮＨ－基（１～５個の酸素原子、硫黄原子、及び／若しくは、－ＮＲ１２－基により中断されていてもよい）である。 In formula (6), R 3 and R 4 are the same as those in formula (3). M 3 represents a bond, a piperazino group, or an alkylene-NH— group having 1 to 12 carbon atoms (even if interrupted by 1 to 5 oxygen atoms, sulfur atoms, and / or —NR 12 — groups. Good).
本発明のオキシムエステル開始剤は、上記式（３）で表される化合物である。
以下、置換基についての説明は、特に指定しない限り、Ｒ３、Ｒ５、Ｒ６、Ｒ８、Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２、及び、Ｒ１３のそれぞれ該当するものに共通する事項についての説明である。 The oxime ester initiator of the present invention is a compound represented by the above formula (3).
Hereinafter, unless otherwise specified, the description of the substituent is common to the corresponding ones of R 3 , R 5 , R 6 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13. It is an explanation about the matter.
上記フェニル基が置換されている場合、該フェニル基は、１～４個の置換基にて置換されており、１～３個置換されていることが好ましく、２個置換されていることがより好ましい。フェニル環の置換基は、フェニル環の４－位、３，４－位、３，４，５－位、２，６－位、２，４－位、又は、２，４，６－位に位置することが好ましく、４－位又は３，４－位に位置することがより好ましい。 When the phenyl group is substituted, the phenyl group is substituted with 1 to 4 substituents, preferably 1 to 3 substituents, more preferably 2 substituted. preferable. Substituents on the phenyl ring are in the 4-position, 3,4-position, 3,4,5-position, 2,6-position, 2,4-position, or 2,4,6-position of the phenyl ring. It is preferably located, more preferably in the 4-position or 3,4-position.
上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、２，４，４－トリメチルペンチル基、２－エチルヘキシル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、オクタデシル基、イコシル基等のうち、炭素原子の相当する数のものが挙げられる。 Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2,4 1,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, icosyl, etc. Is mentioned.
上記炭素数２～２０のアルキル基が１個以上の酸素原子により中断されている場合、１個以上の酸素原子により中断された炭素数２～２０のアルキル基としては、例えば、－ＣＨ２－ＣＨ２－Ｏ－ＣＨ２ＣＨ３基、－（ＣＨ２ＣＨ２Ｏ）ｙ－ＣＨ３基（ここで、ｙは、１～９である）、－（ＣＨ２－ＣＨ２Ｏ）７－ＣＨ２ＣＨ３基、－ＣＨ２ＣＨ（ＣＨ３）－Ｏ－ＣＨ２ＣＨ２ＣＨ３基、－ＣＨ２ＣＨ（ＣＨ３）－Ｏ－ＣＨ２ＣＨ３基、－ＣＨ２－ＣＨ２－Ｏ－ＣＨ２－ＣＨ２－Ｏ－ＣＨ２ＣＨ３基、－ＣＨ２－ＣＨ２－Ｏ－ＣＨ２ＣＨ３基等が挙げられる。 When the alkyl group having 2 to 20 carbon atoms is interrupted by one or more oxygen atoms, examples of the alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms include —CH 2 — CH 2 —O—CH 2 CH 3 group, — (CH 2 CH 2 O) y —CH 3 group (where y is 1 to 9), — (CH 2 —CH 2 O) 7 —CH 2 CH 3 groups, —CH 2 CH (CH 3 ) —O—CH 2 CH 2 CH 3 groups, —CH 2 CH (CH 3 ) —O—CH 2 CH 3 groups, —CH 2 —CH 2 —O— CH 2 —CH 2 —O—CH 2 CH 3 group, —CH 2 —CH 2 —O—CH 2 CH 3 group and the like can be mentioned.
上記炭素数２～２０のアルキル基が１個以上のヒドロキシル基により置換されている場合、１個以上のヒドロキシル基により置換された炭素数２～２０のアルキル基としては、例えば、２－ヒドロキシエチル基、１－ヒドロキシエチル基、１－ヒドロキシプロピル基、２－ヒドロキシプロピル基、３－ヒドロキシプロピル基、１－ヒドロキシブチル基、４－ヒドロキシブチル基、２－ヒドロキシブチル基、３－ヒドロキシブチル基、２，３－ジヒドロキシプロピル基、２，４－ジヒドロキシブチル基等が挙げられる。 When the alkyl group having 2 to 20 carbon atoms is substituted with one or more hydroxyl groups, examples of the alkyl group having 2 to 20 carbon atoms substituted with one or more hydroxyl groups include 2-hydroxyethyl Group, 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 4-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, Examples include 2,3-dihydroxypropyl group and 2,4-dihydroxybutyl group.
上記シクロアルキル基としては、例えば、シクロペンチル基、シクロヘキシル基、シクロオクチル基、シクロドデシル基等のうち、炭素原子の相当する数のものが挙げられる。なかでも、シクロペンチル基、シクロヘキシル基が好ましく、シクロヘキシル基がより好ましい。 Examples of the cycloalkyl group include those corresponding to the number of carbon atoms among a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and the like. Of these, a cyclopentyl group and a cyclohexyl group are preferable, and a cyclohexyl group is more preferable.
上記アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ｎ－ブチルオキシ基、ｓｅｃ－ブチルオキシ基、イソブチルオキシ基、ｔｅｒｔ－ブチルオキシ基等のうち、炭素原子の相当する数のものが挙げられる。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butyloxy group, a sec-butyloxy group, an isobutyloxy group, and a tert-butyloxy group. Things.
上記炭素数２～１０のアルコキシアルキル基としては、例えば、メトキシメチル基、メトキシエチル基、メトキシプロピル基、エトキシメチル基、エトキシエチル基、エトキシプロピル基、プロポキシメチル基、プロポキシエチル基、プロポキシプロピル基等が挙げられる。 Examples of the alkoxyalkyl group having 2 to 10 carbon atoms include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, a propoxymethyl group, a propoxyethyl group, and a propoxypropyl group. Etc.
上記アルカノイル基としては、例えば、アセチル基、プロピオニル基、ブタノイル基、イソブタノイル基、ペンタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ドデカノイル基、テトラデカノイル基、ペンタデカノイル基、ヘキサデカノイル基、オクタデカノイル基、イコサノイル基等のうち、炭素原子の相当する数のものが挙げられる。なかでも、アセチル基が好ましい。 Examples of the alkanoyl group include an acetyl group, a propionyl group, a butanoyl group, an isobutanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a dodecanoyl group, a tetradecanoyl group, and a pentadecanoyl group. , Hexadecanoyl group, octadecanoyl group, icosanoyl group, and the like. Of these, an acetyl group is preferable.
上記炭素数２～４のアルカノイルオキシ基としては、例えば、アセチルオキシ基、プロピオニルオキシ基、ブタノイルオキシ基、イソブタノイルオキシ基等が挙げられる。なかでも、アセチルオキシ基が好ましい。 Examples of the alkanoyloxy group having 2 to 4 carbon atoms include acetyloxy group, propionyloxy group, butanoyloxy group, isobutanoyloxy group, and the like. Of these, an acetyloxy group is preferable.
上記炭素数２～１２のアルコキシカルボニル基としては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｎ－ブチルオキシオカルボニル基、イソブチルオキシカルボニル基、１，１－ジメチルプロポキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基、ヘプチルオキシカルボニル基、オクチルオキシカルボニル基、ノニルオキシカルボニル基、デシルオキシカルボニル基、ウンデシルオキシカルボニル基等が挙げられる。なかでも、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｎ－ブチルオキシカルボニル基、イソブチルオキシカルボニル基が好ましく、メトキシカルボニル基がより好ましい。 Examples of the alkoxycarbonyl group having 2 to 12 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butyloxyocarbonyl group, isobutyloxycarbonyl group, 1,1-dimethylpropoxycarbonyl group, pentyl. Examples include oxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, undecyloxycarbonyl group and the like. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butyloxycarbonyl group, and an isobutyloxycarbonyl group are preferable, and a methoxycarbonyl group is more preferable.
上記フェノキシカルボニル基が置換されている場合、該フェノキシカルボニル基は、１～４個の置換基にて置換されており、１～３個置換されていることが好ましく、２個置換されていることがより好ましい。フェニル環の置換基は、フェニル環の４－位、３，４－位、３，４，５－位、２，６－位、２，４－位、又は、２，４，６－位に位置することが好ましく、４－位又は３，４－位に位置することがより好ましい。 When the phenoxycarbonyl group is substituted, the phenoxycarbonyl group is substituted with 1 to 4 substituents, preferably 1 to 3 are substituted, and 2 are substituted. Is more preferable. Substituents on the phenyl ring are the 4-position, 3,4-position, 3,4,5-position, 2,6-position, 2,4-position, or 2,4,6-position of the phenyl ring. It is preferably located, more preferably in the 4-position or 3,4-position.
上記炭素数７～９のフェニルアルキル基としては、例えば、ベンジル基、フェニルエチル基、α－メチルベンジル基、α，α－ジメチルベンジル基等が挙げられる。なかでも、ベンジル基が好ましい。 Examples of the phenylalkyl group having 7 to 9 carbon atoms include benzyl group, phenylethyl group, α-methylbenzyl group, α, α-dimethylbenzyl group and the like. Of these, a benzyl group is preferable.
上記アルケニル基としては、例えば、アリル基、メタリル基、１，１－ジメチルアリル基、１－ブテニル基、３－ブテニル基、２－ブテニル基、１，３－ペンタジエニル基、５－ヘキセニル基、７－オクテニル基、ドデシル基等のうち、炭素原子の相当する数のものが挙げられる。なかでも、アリル基が好ましい。 Examples of the alkenyl group include allyl group, methallyl group, 1,1-dimethylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, 7 -Of the octenyl group, dodecyl group, etc., the corresponding number of carbon atoms can be mentioned. Of these, an allyl group is preferable.
上記炭素数３～６のアルケンオキシ基としては、例えば、アリルオキシ基、メタリルオキシ基、ブテニルオキシ基、ペンテンオキシ基、１，３－ペンタジエニルオキシ基、５－ヘキセニルオキシ基等が挙げられる。 Examples of the alkeneoxy group having 3 to 6 carbon atoms include allyloxy group, methallyloxy group, butenyloxy group, penteneoxy group, 1,3-pentadienyloxy group, and 5-hexenyloxy group.
上記炭素数３～６のアルケノイル基としては、例えば、プロペノイル基、２－メチル－プロペノイル基、ブテノイル基、ペンテノイル基、１，３－ペンタジエノイル基、５－ヘキセノイル基等が挙げられる。 Examples of the alkenoyl group having 3 to 6 carbon atoms include propenoyl group, 2-methyl-propenoyl group, butenoyl group, pentenoyl group, 1,3-pentadienoyl group, 5-hexenoyl group and the like.
上記ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。なかでも、フッ素原子、塩素原子、臭素原子が好ましく、フッ素原子、塩素原子がより好ましい。 As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example. Of these, a fluorine atom, a chlorine atom and a bromine atom are preferable, and a fluorine atom and a chlorine atom are more preferable.
上記アリール基としては、例えば、フェニル基、１－ナフチル基、２－ナフチル基等のうち、炭素原子の相当する数のものが挙げられる。なかでも、フェニル基が好ましい。 Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like corresponding to the number of carbon atoms. Of these, a phenyl group is preferred.
Ｒ３は、炭素数１～２０のアルキル基であることが好ましく、炭素数１～６のアルキル基であることがより好ましい。
また、上記式（３）中、Ｒ５、Ｒ６、Ｒ８、及び、Ｒ９は、水素原子であることが好ましい。 R 3 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Moreover, in said formula (3), it is preferable that R < 5 >, R < 6 >, R < 8 > and R < 9 > are hydrogen atoms.
上記式（３）中、Ｒ４及びＲ７は、それぞれ独立して、反応性官能基、水素結合性官能基を有する基、水素原子、炭素数３～２０のカルボアルコキシアルキル基（１個以上の酸素原子により中断、及び／又は、１個以上のヒドロキシル基により置換されていてもよい）、ハロゲン原子、炭素数１～１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基（－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、ベンジル基、ベンゾイル基、炭素数２～１２のアルカノイル基、炭素数２～１２のアルコキシカルボニル基（１個以上の酸素原子により中断、及び／又は、１個以上のヒドロキシル基により置換されていてもよい）、フェノキシカルボニル基、－ＯＲ１０基、－ＳＲ１１基、－ＳＯＲ１１基、－ＳＯ２Ｒ１１基、或いは、－ＮＲ１２Ｒ１３基（ここで、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基は、フェニル環の有する置換基若しくはフェニル環の炭素原子の一つと、Ｒ１０、Ｒ１１、Ｒ１２、及び／若しくは、Ｒ１３を介して５員環又は６員環を形成していてもよい）である。ただし、Ｒ４及びＲ７の少なくとも一方は、反応性官能基である。 In the above formula (3), R 4 and R 7 are each independently a reactive functional group, a group having a hydrogen bonding functional group, a hydrogen atom, a carboalkoxyalkyl group having 3 to 20 carbon atoms (one or more Optionally substituted by one or more hydroxyl groups), halogen atom, alkyl group having 1 to 12 carbon atoms, cyclopentyl group, cyclohexyl group, phenyl group (—OR 10 group) , -SR 11 group, and -NR 12 R 13 group, which may be substituted with at least one selected from the group consisting of a group, benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, carbon number 2 to 12 alkoxycarbonyl groups (which may be interrupted by one or more oxygen atoms and / or substituted by one or more hydroxyl groups), phenoxycarbo Nyl group, —OR 10 group, —SR 11 group, —SOR 11 group, —SO 2 R 11 group, or —NR 12 R 13 group (here, —OR 10 group, —SR 11 group, and — The NR 12 R 13 group forms a 5-membered or 6-membered ring with R 10 , R 11 , R 12 , and / or R 13 with one of the substituents of the phenyl ring or the carbon atom of the phenyl ring. You may have). However, at least one of R 4 and R 7 is a reactive functional group.
本発明のオキシムエステル開始剤の有する反応性官能基は、上記重合性化合物と反応し得る官能基を意味する。
上記式（３）中、Ｒ４及びＲ７の少なくとも一方が反応性官能基であることにより、本発明のオキシムエステル開始剤を重合性化合物の重合反応に用いた際に、該重合反応を開始させるとともに、重合性化合物と反応して硬化物中に取り込まれるため、アウトガスの発生や、液晶等へ溶出することによる汚染を充分に抑制することができる。
Ｒ４及びＲ７は、両方が反応性官能基であることが好ましい。 The reactive functional group possessed by the oxime ester initiator of the present invention means a functional group capable of reacting with the polymerizable compound.
In the above formula (3), when at least one of R 4 and R 7 is a reactive functional group, the polymerization reaction starts when the oxime ester initiator of the present invention is used for the polymerization reaction of the polymerizable compound. In addition, since it reacts with the polymerizable compound and is taken into the cured product, it is possible to sufficiently suppress the occurrence of outgas and contamination due to elution into the liquid crystal.
R 4 and R 7 are preferably both reactive functional groups.
本発明のオキシムエステル開始剤の有する反応性官能基としては、例えば、ビニル基、チオール基、アクリロイル基、メタクリロイル基、エポキシ基等が挙げられる。なかでも、ビニル基、チオール基が好ましく、ビニル基がより好ましい。 As a reactive functional group which the oxime ester initiator of this invention has, a vinyl group, a thiol group, an acryloyl group, a methacryloyl group, an epoxy group etc. are mentioned, for example. Of these, a vinyl group and a thiol group are preferable, and a vinyl group is more preferable.
上記式（３）中、Ｒ４及びＲ７の一方が反応性官能基である場合、もう一方は水素結合性官能基を有する基であってもよい。
上記水素結合性官能基は、水素結合性を有する官能基を意味する。
上記式（３）中、Ｒ４及びＲ７の一方が水素結合性官能基を有する基である場合、重合性化合物との相溶性が高くなり、液晶等へ溶出することによる汚染を充分に抑制することができる。
上記水素結合性官能基としては、例えば、－ＯＨ基、－ＮＨ２基、－ＮＨＲ基（Ｒは、芳香族、脂肪族炭化水素、又は、これらの誘導体を表す）、－ＣＯＯＨ基、－ＣＯＮＨ２基、－ＮＨＯＨ基等の官能基や、－ＮＨＣＯ－結合、－ＮＨ－結合、－ＣＯＮＨＣＯ－結合、－ＮＨ－ＮＨ－結合等の残基が挙げられる。なかでも、－ＯＨ基が好ましい。 In the above formula (3), when one of R 4 and R 7 is a reactive functional group, the other may be a group having a hydrogen bonding functional group.
The hydrogen bonding functional group means a functional group having hydrogen bonding properties.
In the above formula (3), when one of R 4 and R 7 is a group having a hydrogen bondable functional group, the compatibility with the polymerizable compound is increased, and contamination due to elution into liquid crystal or the like is sufficiently suppressed. can do.
Examples of the hydrogen bonding functional group include an —OH group, —NH 2 group, —NHR group (R represents an aromatic, aliphatic hydrocarbon, or derivative thereof), —COOH group, —CONH. And functional groups such as two groups and —NHOH group, and residues such as —NHCO— bond, —NH— bond, —CONHCO— bond, and —NH—NH— bond. Of these, —OH group is preferable.
Ｒ４又はＲ７が炭素数３～２０のカルボアルコキシアルキル基である場合、該カルボアルコキシアルキル基としては、例えば、カルボメトキシメチル基、カルボエトキシメチル基、カルボメトキシエチル基、カルボキシエトキシエチル基、カルボキシメトキシプロピル基、カルボキシメトキシオクチル基、カルボキシメトキシラウリル基、カルボキシメトキシステアリル基、カルボキシプロポキシメチル基、カルボキシプロポキシエチル基、カルボキシプロポキシプロピル基、カルボキシオクトキシメチル基、カルボキシラウロキシメチル基、カルボキシミリストキシメチル基、カルボキシオクトキシエチル基、カルボキシラウロキシエチル基、カルボキシステアロキシエチル基等が挙げられる。 When R 4 or R 7 is a carboalkoxyalkyl group having 3 to 20 carbon atoms, examples of the carboalkoxyalkyl group include a carbomethoxymethyl group, a carboethoxymethyl group, a carbomethoxyethyl group, a carboxyethoxyethyl group, Carboxymethoxypropyl group, carboxymethoxyoctyl group, carboxymethoxylauryl group, carboxymethoxystearyl group, carboxypropoxymethyl group, carboxypropoxyethyl group, carboxypropoxypropyl group, carboxyoctoxymethyl group, carboxylauroxymethyl group, carboxymyrist Examples thereof include a xymethyl group, a carboxyoctoxyethyl group, a carboxylauroxyethyl group, and a carboxy stearoxyethyl group.
本発明のオキシムエステル開始剤としては、光反応性に優れ、かつ、アウトガスの発生等の悪影響を抑制する効果に特に優れることから、下記式（７）～（１１）で表される化合物が好ましく、下記式（７）～（１０）で表される化合物がより好ましい。 As the oxime ester initiator of the present invention, compounds represented by the following formulas (7) to (11) are preferable because they are excellent in photoreactivity and particularly excellent in suppressing adverse effects such as outgassing. Compounds represented by the following formulas (7) to (10) are more preferable.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
本発明のオキシムエステル開始剤を製造する方法としては、例えば、上記式（３）における＝Ｎ－ＯＣ（＝Ｏ）－Ｒ４基及びＲ７以外の部分が上記式（３）と同様であり、＝Ｎ－ＯＣ（＝Ｏ）－Ｒ４基の部分が水素原子であるアシル化合物をオキシム化して、オキシム化合物を得た後、上記式（３）におけるＲ７の部分を形成し、更に、Ｒ４を有するアシルクロリドを反応させる方法等が挙げられる。
具体的には例えば、上記式（７）で表される化合物は、以下の方法等により製造することができる。即ち、まず、２－フェニルチオメタノールを、ジクロロメタン中、トリエチルアミンの存在下で塩化アセチルと反応させて酢酸２－フェニルチオエチルを得た後、得られた酢酸２－フェニルチオエチルを、ジクロロメタン中、塩化アルミニウムの存在下でオクタン酸クロリドと反応させて下記式（１２－１）で表されるアシル化合物を作製する。次いで、得られたアシル化合物を、テトラヒドロフラン中、濃塩酸の存在下でイソアミルナイトライトと反応させて下記式（１２－２）で表されるオキシム化合物を作製し、得られたオキシム化合物を、テトラヒドロフラン中、トリエチルアミンの存在下で３－アリルオキシプロピオン酸クロリドと反応させることにより、上記式（７）で表される化合物を製造することができる。 Examples of the method for producing the oxime ester initiator of the present invention are the same as those in the above formula (3) except for the ═N—OC (═O) —R 4 group and R 7 in the above formula (3). , ═N—OC (═O) —R 4 oxime is converted to an acyl compound in which the portion of the 4 group is a hydrogen atom to obtain an oxime compound, and then the portion of R 7 in the above formula (3) is formed. Examples include a method of reacting acyl chloride having R 4 .
Specifically, for example, the compound represented by the above formula (7) can be produced by the following method or the like. That is, first, 2-phenylthiomethanol was reacted with acetyl chloride in dichloromethane in the presence of triethylamine to obtain 2-phenylthioethyl acetate, and then 2-phenylthioethyl acetate was obtained in dichloromethane. Reaction with octanoic acid chloride in the presence of aluminum chloride produces an acyl compound represented by the following formula (12-1). Next, the obtained acyl compound was reacted with isoamyl nitrite in tetrahydrofuran in the presence of concentrated hydrochloric acid to prepare an oxime compound represented by the following formula (12-2). The obtained oxime compound was converted into tetrahydrofuran. The compound represented by the above formula (7) can be produced by reacting with 3-allyloxypropionic acid chloride in the presence of triethylamine.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
本発明にかかるラジカル重合開始剤は、分子量の好ましい下限が２５０、好ましい上限が１５００である。分子量が２５０～１５００のラジカル重合開始剤を用いることにより、本発明の表示素子用封止剤は、アウトガスの発生を抑制する効果に更に優れるものとなる。本発明にかかるラジカル重合開始剤の分子量が２５０未満であると、アウトガス発生の原因となることがある。本発明にかかるラジカル重合開始剤の分子量が１５００を超えると、硬化が不充分となることがある。なかでも、アウトガスの発生を低減する等の観点から、本発明にかかるラジカル重合開始剤の分子量のより好ましい下限は３００、より好ましい上限は１０５０、更に好ましい下限は３４８、更に好ましい上限は７９０である。 The radical polymerization initiator according to the present invention has a preferable lower limit of molecular weight of 250 and a preferable upper limit of 1500. By using a radical polymerization initiator having a molecular weight of 250 to 1500, the sealant for display element of the present invention is further excellent in the effect of suppressing the generation of outgas. When the molecular weight of the radical polymerization initiator according to the present invention is less than 250, outgas may be generated. When the molecular weight of the radical polymerization initiator according to the present invention exceeds 1500, curing may be insufficient. Among these, from the viewpoint of reducing the generation of outgas, the more preferable lower limit of the molecular weight of the radical polymerization initiator according to the present invention is 300, the more preferable upper limit is 1050, the still more preferable lower limit is 348, and the further preferable upper limit is 790. .
本発明にかかるラジカル重合開始剤の含有量は、上記重合性化合物全体１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が５重量部である。本発明にかかるラジカル重合開始剤の含有量が０．１重量部未満であると、得られる表示素子用封止剤の重合が充分に進行しないことがある。本発明にかかるラジカル重合開始剤の含有量が５重量部を超えると、硬化反応が速くなりすぎて、作業性が低下したり、得られる表示素子用封止剤の硬化物が不均一となったりすることがある。本発明にかかるラジカル重合開始剤の含有量のより好ましい下限は０．５重量部、より好ましい上限は３重量部である。 With respect to the content of the radical polymerization initiator according to the present invention, a preferable lower limit is 0.1 part by weight and a preferable upper limit is 5 parts by weight with respect to 100 parts by weight of the entire polymerizable compound. When the content of the radical polymerization initiator according to the present invention is less than 0.1 parts by weight, polymerization of the obtained sealant for display element may not sufficiently proceed. When the content of the radical polymerization initiator according to the present invention exceeds 5 parts by weight, the curing reaction becomes too fast, the workability is lowered, or the cured product of the obtained sealant for display elements becomes non-uniform. Sometimes. The more preferable lower limit of the content of the radical polymerization initiator according to the present invention is 0.5 parts by weight, and the more preferable upper limit is 3 parts by weight.
本発明の表示素子用封止剤は、本発明の目的を阻害しない範囲において、本発明にかかるラジカル重合開始剤に加えて、その他の重合開始剤を含有してもよい。 In the range which does not inhibit the objective of this invention, the sealing agent for display elements of this invention may contain another polymerization initiator in addition to the radical polymerization initiator concerning this invention.
本発明の表示素子用封止剤は、接着性付与剤を含有してもよい。
上記接着性付与剤としては、例えば、３－メタクリロキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、Ｎ－（アミノエチル）アミノプロピルトリメトキシシラン、メルカプトプロピルトリメトキシシラン等のシランカップリング剤や、チタンカップリング剤や、アルミニウムカップリング剤等が挙げられる。これらの接着性付与剤は単独で用いられてもよいし、２種以上が併用されてもよい。 The sealant for display elements of the present invention may contain an adhesion promoter.
Examples of the adhesion-imparting agent include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N- (aminoethyl) aminopropyltrimethoxy Examples include silane coupling agents such as silane and mercaptopropyltrimethoxysilane, titanium coupling agents, and aluminum coupling agents. These adhesiveness imparting agents may be used alone or in combination of two or more.
本発明の表示素子用封止剤は、酸化防止等を目的として安定剤を含有してもよい。
上記安定剤としては、例えば、２，２’－メチレンビス－（４－メチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデンビス－（６－ｔ－ブチル－３－メチルフェノール）、２，２’－メチレンビス－（４－エチル－６－ｔ－ブチルフェノール）等が挙げられる。これらの安定剤は単独で用いられてもよいし、２種以上が併用されてもよい。 The sealing agent for display elements of the present invention may contain a stabilizer for the purpose of preventing oxidation or the like.
Examples of the stabilizer include 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis- (6-tert-butyl-3-methylphenol), 2,2 Examples include '-methylenebis- (4-ethyl-6-t-butylphenol). These stabilizers may be used independently and 2 or more types may be used together.
本発明の表示素子用封止剤は、更に、本発明の目的を阻害しない範囲において、充填剤、硬化促進剤、可塑剤、界面活性剤、難燃剤、帯電防止剤、消泡剤、レベリング剤、紫外線吸収材、有機溶剤等の添加剤を含有してもよい。 The sealant for display element of the present invention further includes a filler, a curing accelerator, a plasticizer, a surfactant, a flame retardant, an antistatic agent, an antifoaming agent, and a leveling agent as long as the object of the present invention is not impaired. Further, additives such as an ultraviolet absorber and an organic solvent may be contained.
本発明の表示素子用封止剤を製造する方法としては、例えば、ポリチオールモノマー、ポリエンモノマー、本発明にかかるラジカル重合開始剤、及び、必要に応じて添加される接着性付与剤等を、撹拌機を用いて均一に混合する方法等が挙げられる。 Examples of the method for producing the sealant for a display element of the present invention include stirring a polythiol monomer, a polyene monomer, a radical polymerization initiator according to the present invention, and an adhesiveness imparting agent added as necessary. The method etc. which mix uniformly using a machine are mentioned.
本発明の表示素子用封止剤は、コーンローター式粘度計を用いて、２０℃、２０ｒｐｍの条件で測定した粘度の好ましい下限が０．４Ｐａ・ｓ、好ましい上限が４０Ｐａ・ｓである。上記粘度が０．４Ｐａ・ｓ未満であると、得られる表示素子用封止剤に組成ムラが発生したり、塗工が困難になったり、得られる表示素子の表示特性が悪くなったりすることがある。上記粘度が４０Ｐａ・ｓを超えると、塗工が困難となることがある。上記粘度のより好ましい下限は０．５Ｐａ・ｓ、より好ましい上限は１０Ｐａ・ｓ、更に好ましい下限は１Ｐａ・ｓ、更に好ましい上限は６Ｐａ・ｓ、特に好ましい下限は２Ｐａ・ｓ、特に好ましい上限は４Ｐａ・ｓである。 The sealing agent for display elements of the present invention has a preferred lower limit of viscosity of 0.4 Pa · s and a preferred upper limit of 40 Pa · s measured using a cone rotor viscometer under the conditions of 20 ° C. and 20 rpm. When the viscosity is less than 0.4 Pa · s, compositional unevenness occurs in the obtained sealant for display element, coating becomes difficult, or display characteristics of the obtained display element are deteriorated. There is. When the viscosity exceeds 40 Pa · s, coating may be difficult. The more preferred lower limit of the viscosity is 0.5 Pa · s, the more preferred upper limit is 10 Pa · s, the still more preferred lower limit is 1 Pa · s, the still more preferred upper limit is 6 Pa · s, the particularly preferred lower limit is 2 Pa · s, and the particularly preferred upper limit is 4 Pa. -S.
本発明の表示素子用封止剤は、硬化物の波長３８０～７８０ｎｍの領域での可視光の平均透過率が８０％以上であることが好ましい。上記可視光の平均透過率が８０％以上であることにより、透明性が求められる用途に好適に用いることができる。上記可視光の平均透過率は、９５％以上であることがより好ましい。
なお、上記可視光の平均透過率を測定する硬化物は、本発明の表示素子用封止剤に対して、２０００ｍＪ／ｃｍ２の紫外線を照射する方法により得ることができる。 The sealant for display element of the present invention preferably has an average visible light transmittance of 80% or more in a region of a cured product having a wavelength of 380 to 780 nm. When the average transmittance of visible light is 80% or more, it can be suitably used for applications requiring transparency. The average transmittance of the visible light is more preferably 95% or more.
In addition, the hardened | cured material which measures the average transmittance | permeability of the said visible light can be obtained by the method of irradiating a 2000mJ / cm < 2 > ultraviolet-ray with respect to the sealing agent for display elements of this invention.
本発明の表示素子用封止剤は、厚さ１００μｍの硬化物を、昇温速度１０℃／ｍｉｎで１３０℃まで加熱したときの重量減少率が０．１５％以下であることが好ましい。上記重量減少率は、アウトガス発生量とみなすことができるため、０．１５％以下であることにより、表示素子への悪影響を抑制できるものとなる。上記重量減少率は、０．１％以下であることがより好ましい。
なお、上記重量減少率を測定する硬化物は、厚さ１００μｍとなるように塗布した本発明の表示素子用封止剤に対して、２０００ｍＪ／ｃｍ２の紫外線を照射する方法により得ることができる。 The sealant for a display element of the present invention preferably has a weight reduction rate of 0.15% or less when a 100 μm thick cured product is heated to 130 ° C. at a temperature rising rate of 10 ° C./min. Since the weight reduction rate can be regarded as an outgas generation amount, an adverse effect on the display element can be suppressed by being 0.15% or less. The weight reduction rate is more preferably 0.1% or less.
In addition, the hardened | cured material which measures the said weight decreasing rate can be obtained by the method of irradiating 2000 mJ / cm < 2 > of ultraviolet-rays with respect to the sealing agent for display elements of this invention apply | coated so that it may become thickness 100 micrometers. .
本発明の表示素子用封止剤は、光照射又は加熱により硬化させることができ、光照射により硬化させることが好ましい。
本発明の表示素子用封止剤を光硬化させる方法としては、例えば、３００～４００ｎｍの波長及び３００～３０００ｍＪ／ｃｍ２の積算光量の光を照射する方法等が挙げられる。 The sealant for display elements of the present invention can be cured by light irradiation or heating, and is preferably cured by light irradiation.
Examples of the method for photocuring the sealant for display elements of the present invention include a method of irradiating light having a wavelength of 300 to 400 nm and an integrated light amount of 300 to 3000 mJ / cm 2 .
本発明の表示素子用封止剤に光を照射するための光源としては、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、エキシマレーザ、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、ナトリウムランプ、ハロゲンランプ、キセノンランプ、ＬＥＤランプ、蛍光灯、太陽光、電子線照射装置等が挙げられる。これらの光源は単独で用いられてもよいし、２種以上が併用されてもよい。 Examples of the light source for irradiating the sealing agent for display element of the present invention with light include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, and a microwave excitation mercury lamp. , Metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices, and the like. These light sources may be used independently and 2 or more types may be used together.
本発明の表示素子用封止剤への光の照射手段としては、例えば、各種光源の同時照射、時間差をおいての逐次照射、同時照射と逐次照射との組み合わせ照射等が挙げられ、いずれの照射手段を用いてもよい。 Examples of light irradiation means for the sealant for display elements of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc. Irradiation means may be used.
本発明の表示素子用封止剤は、表示素子の全面、前面、後面、若しくは、周囲を封止するための封止剤、又は、表示素子に設けられた開口部を封止するための封口剤として用いることができ、なかでも、表示素子の全面を封止するために好適に用いられる。
なお、本明細書において上記「全面」とは、表示素子を有する面の必ずしも１００％を意味するものではなく、表示素子に求められる必要な封止面を意味する。また、上記「前面」とは、光線を取り出す側、即ち、視認側の面を意味する The sealant for display element of the present invention is a sealant for sealing the entire surface, front surface, rear surface, or periphery of the display element, or a seal for sealing an opening provided in the display element. It can be used as an agent, and is particularly preferably used for sealing the entire surface of the display element.
In the present specification, the “entire surface” does not necessarily mean 100% of the surface having the display element, but means a necessary sealing surface required for the display element. The “front surface” means a surface from which light is extracted, that is, a surface on the viewing side.
本発明の表示素子用封止剤は、例えば、有機ＥＬ表示素子用封止剤、液晶表示素子用封止剤、エレクトロクロミック基板用封止剤、電子ペーパー用封止剤等に用いることができる。 The sealant for display elements of the present invention can be used, for example, as a sealant for organic EL display elements, a sealant for liquid crystal display elements, a sealant for electrochromic substrates, a sealant for electronic paper, and the like. .
本発明によれば、アウトガスの発生や他材料の汚染を抑制することができ、接着性、及び、硬化物の透明性に優れる表示素子用封止剤を提供することができる。また、本発明によれば、該表示素子用封止剤に好適に用いることができるオキシムエステル開始剤を提供することができる。 According to this invention, generation | occurrence | production of outgas and contamination of other materials can be suppressed, and the sealing agent for display elements which is excellent in adhesiveness and transparency of hardened | cured material can be provided. Moreover, according to this invention, the oxime ester initiator which can be used suitably for this sealing agent for display elements can be provided.
式（７）で表される化合物の１Ｈ－ＮＭＲスペクトルである。 1 is a 1 H-NMR spectrum of a compound represented by formula (7). 式（８）で表される化合物の１Ｈ－ＮＭＲスペクトルである。 1 is a 1 H-NMR spectrum of a compound represented by formula (8). 式（９）で表される化合物の１Ｈ－ＮＭＲスペクトルである。 1 is a 1 H-NMR spectrum of a compound represented by formula (9). 式（１０）で表される化合物の１Ｈ－ＮＭＲスペクトルである。 1 is a 1 H-NMR spectrum of a compound represented by formula (10). 式（１１）で表される化合物の１Ｈ－ＮＭＲスペクトルである。 1 is a 1 H-NMR spectrum of a compound represented by formula (11).
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（チオエーテルオリゴマーの作製）
ポリチオールモノマーとしてトリメチロールプロパントリス（３－メルカプトプロピオネート）６３重量部と、ポリエンモノマーとしてトリアリルイソシアヌレート３７重量部とを加熱撹拌しながら、熱ラジカル重合開始剤として２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．２重量部を徐々に添加し、得られた反応混合物を貧溶媒に流し、沈殿したオリゴマーを集め、溶媒を真空下で除去することにより、チオエーテルオリゴマーを得た。
得られたチオエーテルオリゴマーについて、カラムとしてＳｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）を用いたゲルパーミエーションクロマトグラフィー（ＧＰＣ）にてポリスチレン換算による重量平均分子量を測定した。その結果、チオエーテルオリゴマーの重量平均分子量は５０００であった。 (Production of thioether oligomer)
While heating and stirring 63 parts by weight of trimethylolpropane tris (3-mercaptopropionate) as a polythiol monomer and 37 parts by weight of triallyl isocyanurate as a polyene monomer, 2,2′-azobis ( 2,4-dimethylvaleronitrile) is gradually added, the resulting reaction mixture is poured into a poor solvent, the precipitated oligomer is collected, and the solvent is removed under vacuum to obtain a thioether oligomer. It was.
For the obtained thioether oligomer, the weight average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) using Shodex LF-804 (manufactured by Showa Denko KK) as a column. As a result, the weight average molecular weight of the thioether oligomer was 5000.
（ポリエンオリゴマーの作製）
ポリエンモノマーとしてトリアリルイソシアヌレート１００重量部を加熱撹拌しながら、熱ラジカル重合開始剤として２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．２重量部を徐々に添加し、得られた反応混合物を貧溶媒に流し、沈殿したオリゴマーを集め、溶媒を真空下で除去することにより、ポリエンオリゴマーを得た。
得られたポリエンオリゴマーについて、カラムとしてＳｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）を用いたゲルパーミエーションクロマトグラフィー（ＧＰＣ）にてポリスチレン換算による重量平均分子量を測定した。その結果、チオエーテルオリゴマーの重量平均分子量は１２５０であった。 (Preparation of polyene oligomer)
While heating and stirring 100 parts by weight of triallyl isocyanurate as a polyene monomer, 0.2 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) is gradually added as a thermal radical polymerization initiator. The reaction mixture was poured into a poor solvent, the precipitated oligomer was collected, and the solvent was removed under vacuum to obtain a polyene oligomer.
About the obtained polyene oligomer, the weight average molecular weight by polystyrene conversion was measured with the gel permeation chromatography (GPC) using Shodex LF-804 (made by Showa Denko KK) as a column. As a result, the weight average molecular weight of the thioether oligomer was 1250.
（実施例１～７、比較例１）
表１に記載された配合比に従い、各材料を、撹拌機（新東科学社製、「スリーワンモーター　ＨＥＩＤＯＮ　ＢＬＨ３００」）を用いて混合することにより、実施例１～７及び比較例１の表示素子用封止剤を調製した。
なお、本発明にかかるラジカル重合開始剤として、実施例１～３、６、７では、開始剤Ａとして、分子内にα－ヒドロキシアルキルフェノン系官能基とアクリロイル基とを有する化合物（ケーエスエム社製、「ＵＶ－Ｈ－４０００」、重量平均分子量８５０）を用い、実施例４では、開始剤Ｂとして、α－アミノアルキルフェノン系官能基とチオール基とを有する下記式（１３）で表される化合物（分子量３５３）を用い、実施例５では、開始剤Ｃとして、開始剤Ａ５０重量部とトリメチロールプロパントリス（３－メルカプトプロピオネート）５０重量部とに熱ラジカル重合開始剤として２，２’－アゾビス（２，４－ジメチルバレロニトリル）０．２重量部を徐々に添加し、得られた反応混合物を貧溶媒に流し、沈殿物を集め、溶媒を真空下で除去することにより得られた化合物（重量平均分子量９万８０００）を用いた。また、その他の光重合開始剤として、比較例１では、開始剤Ｄとして、１－（４－（２－ヒドロキシエトキシ）－フェニル）－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（ＢＡＳＦ　Ｊａｐａｎ社製、「ＩＲＧＡＣＵＲＥ２９５９」）を用いた。 (Examples 1 to 7, Comparative Example 1)
According to the blending ratio described in Table 1, each material was mixed using a stirrer (manufactured by Shinto Kagaku Co., Ltd., “Three One Motor HEIDON BLH300”), so that the display elements of Examples 1 to 7 and Comparative Example 1 A sealing agent was prepared.
As the radical polymerization initiator according to the present invention, in Examples 1 to 3, 6, and 7, the initiator A is a compound having an α-hydroxyalkylphenone functional group and an acryloyl group in the molecule (manufactured by KSM Co., Ltd.). In Example 4, the initiator B is represented by the following formula (13) having an α-aminoalkylphenone functional group and a thiol group: “UV-H-4000”, weight average molecular weight 850). In Example 5, a compound (molecular weight 353) was used, and as initiator C, 50 parts by weight of initiator A and 50 parts by weight of trimethylolpropane tris (3-mercaptopropionate) Gradually add 0.2 parts by weight of '-azobis (2,4-dimethylvaleronitrile), pour the resulting reaction mixture into a poor solvent, collect the precipitate, and vacuum the solvent In the compound obtained by removing the (weight-average molecular weight 98,000) was used. As another photopolymerization initiator, in Comparative Example 1, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one was used as the initiator D. ("IRGACURE2959" manufactured by BASF Japan) was used.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
＜評価＞
実施例１～７及び比較例１で得られた各表示素子用封止剤について、以下の方法により評価を行った。結果を表１に示した。 <Evaluation>
The sealants for display elements obtained in Examples 1 to 7 and Comparative Example 1 were evaluated by the following methods. The results are shown in Table 1.
（１）粘度
コーンローター式粘度計（東機産業社製、「ＴＶ－２２型」）を用いて、２０℃、２０ｒｐｍの条件で実施例１～７及び比較例１で得られた各表示素子用封止剤の粘度を測定した。 (1) Each display element obtained in Examples 1 to 7 and Comparative Example 1 under the conditions of 20 ° C. and 20 rpm using a viscosity cone rotor viscometer (“TV-22 type” manufactured by Toki Sangyo Co., Ltd.) The viscosity of the sealing agent was measured.
（２）塗工性
ディスペンサー（武蔵エンジニアリング社製、「ＳＨＯＴＭＡＳＴＥＲ３００」）を用いて、ガラス基板上に実施例１～７及び比較例１で得られた各表示素子用封止剤を塗工した際の塗工性を評価した。ディスペンスノズルを４００μｍ、ノズルギャップを３０μｍ、塗出圧を３００ｋＰａに固定して塗工したとき、かすれやダレがなく塗工できた場合「○」、かすれやダレが生じた場合「△」、大きな塗工切れや塗工ムラが生じたり、全く塗工できなかったりした場合「×」として塗工性を評価した。 (2) When the sealants for display elements obtained in Examples 1 to 7 and Comparative Example 1 were applied on a glass substrate using a coatable dispenser (manufactured by Musashi Engineering Co., Ltd., “SHOTMASTER300”) The coating property was evaluated. When coating with a dispensing nozzle of 400 μm, a nozzle gap of 30 μm, and a coating pressure of 300 kPa, it was possible to apply without fading or sagging, “◯”, when fading or sagging occurred, “△”, large The coating property was evaluated as “×” when the coating was cut off, coating unevenness occurred, or coating could not be performed at all.
（３）アウトガス発生量
実施例１～７及び比較例１で得られた各表示素子用封止剤を、バーコーターを用いて塗工後の厚さが１００μｍとなるように塗工し、超高圧水銀灯を用いて２０００ｍＪ／ｃｍ２の紫外線を照射してフィルムを形成した。
得られたフィルムを熱分析装置（Ｓｅｉｋｏ　Ｉｎｓｔｒｕｍｅｎｔｓ社製、「ＴＧ／ＤＴＡ６２００」）を用いて、昇温速度１０℃／ｍｉｎで１５０℃まで加熱したときの重量減少率を測定し、これをアウトガス発生量とした。 (3) Outgas generation amount Each sealant for display element obtained in Examples 1 to 7 and Comparative Example 1 was applied using a bar coater so that the thickness after coating was 100 μm. A film was formed by irradiating ultraviolet light of 2000 mJ / cm 2 using a high-pressure mercury lamp.
Using a thermal analyzer (“TG / DTA6200” manufactured by Seiko Instruments, Inc.), the resulting film was measured for weight loss rate when heated to 150 ° C. at a rate of temperature increase of 10 ° C./min, and this was generated as outgas. The amount.
（４）接着性
実施例１～７及び比較例１で得られた各表示素子用封止剤をマイクロピペットを用いてガラス基板上に０．０５ｇ塗工した。この基板を、スペーサーを配置した別のガラス基板と５０μｍの厚みとなるように貼り合わせ、高圧水銀灯を用いて２０００ｍＪ／ｃｍ２の紫外線を照射して、接着力試験用試料を作製した。得られた接着力試験用試料について、ＥＺ　ＧＲＡＰＨ（島津製作所社製）を用いて、剥離速度５ｍｍ／ｍｉｎの条件で剥離試験を行い、接着力を測定した。接着力が１．０Ｎ／ｃｍ以上であったものを「○」、接着力が１．０Ｎ／ｃｍ未満であったものを「×」として接着性を評価した。　 (4) Adhesiveness 0.05 g of each display element sealant obtained in Examples 1 to 7 and Comparative Example 1 was applied onto a glass substrate using a micropipette. This substrate was bonded to another glass substrate on which a spacer was disposed so as to have a thickness of 50 μm, and irradiated with 2000 mJ / cm 2 of ultraviolet rays using a high-pressure mercury lamp, to prepare a sample for adhesion test. The obtained adhesion test sample was subjected to a peel test using EZ GRAPH (manufactured by Shimadzu Corporation) at a peel rate of 5 mm / min to measure the adhesive force. The adhesiveness was evaluated as “◯” when the adhesive strength was 1.0 N / cm or more, and “X” when the adhesive strength was less than 1.0 N / cm.
（５）硬化物の透明性（透過率）
実施例１～７及び比較例１で得られた各表示素子用封止剤を、ＰＥＴ樹脂フィルムに挟み、２０００ｍＪ／ｃｍ２の紫外線を照射して、厚さ１００μｍの透過率測定用サンプルを作製した。得られた透過率測定用サンプルについて、分光光度計（日立製作所社製、「Ｕ－３０００」、条件３００～８００ｎｍ）を用いて、波長３８０～７８０ｎｍにおける光線透過率を測定した。 (5) Transparency (transmittance) of the cured product
Each display element sealant obtained in Examples 1 to 7 and Comparative Example 1 is sandwiched between PET resin films and irradiated with 2000 mJ / cm 2 of ultraviolet light to produce a 100 μm thick sample for transmittance measurement. did. The obtained transmittance measurement sample was measured for light transmittance at a wavelength of 380 to 780 nm using a spectrophotometer (manufactured by Hitachi, Ltd., “U-3000”, conditions 300 to 800 nm).
（６）表示素子の表示性能
（有機発光材料層を含む積層体が配置された基板の作製）
ガラス基板（長さ２５ｍｍ、幅２５ｍｍ、厚さ０．７ｍｍ）にＩＴＯ電極を１０００Åの厚さで成膜したものを基板とした。上記基板をアセトン、アルカリ水溶液、イオン交換水、イソプロピルアルコールにてそれぞれ１５分間超音波洗浄した後、煮沸させたイソプロピルアルコールにて１０分間洗浄し、更に、ＵＶ－オゾンクリーナ（日本レーザー電子社製、「ＮＬ－ＵＶ２５３」）にて直前処理を行った。
次に、この基板を真空蒸着装置の基板フォルダに固定し、素焼きの坩堝にＮ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニルベンジジン（α－ＮＰＤ）を２００ｍｇ、他の異なる素焼き坩堝にトリス（８－ヒドロキシキノリラ）アルミニウム（Ａｌｑ３）を２００ｍｇ入れ、真空チャンバー内を、１×１０－４Ｐａまで減圧した。その後、α－ＮＰＤの入った坩堝を加熱し、α－ＮＰＤを蒸着速度１５Å／ｓで基板に堆積させ、膜厚６００Åの正孔輸送層を成膜した。次いで、Ａｌｑ３の入った坩堝を加熱し、１５Å／ｓの蒸着速度で膜厚６００Åの有機発光材料層を成膜した。その後、正孔輸送層及び有機発光材料層が形成された基板を別の真空蒸着装置に移し、この真空蒸着装置内のタングステン製抵抗加熱ボートにフッ化リチウム２００ｍｇを、別のタングステン製ボートにアルミニウム線１．０ｇを入れた。その後、真空蒸着装置の蒸着器内を２×１０－４Ｐａまで減圧してフッ化リチウムを０．２Å／ｓの蒸着速度で５Å成膜した後、アルミニウムを２０Å／ｓの速度で１０００Å成膜した。窒素により蒸着器内を常圧に戻し、１０ｍｍ×１０ｍｍの有機発光材料層を含む積層体が配置された基板を取り出した。 (6) Display performance of display element (production of a substrate on which a laminate including an organic light emitting material layer is disposed)
A glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.). The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into an unglazed crucible and other different types. 200 mg of tris (8-hydroxyquinola) aluminum (Alq 3 ) was put in an unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa. Thereafter, the crucible containing α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 ｓ / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added. After that, the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 × 10 −4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did. The inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and the substrate on which the laminate including the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.
（無機材料膜Ａによる被覆）
得られた有機発光材料層を含む積層体が配置された基板の、該積層体の全体を覆うように、１３ｍｍ×１３ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ａを形成した。
プラズマＣＶＤ法は、原料ガスとしてＳｉＨ４ガス及び窒素ガスを用い、各々の流量を１０ｓｃｃｍ及び２００ｓｃｃｍとし、ＲＦパワーを１０Ｗ（周波数２．４５ＧＨｚ）、チャンバー内温度を１００℃、チャンバー内圧力を０．９Ｔｏｒｒとする条件で行った。
形成された無機材料膜Ａの厚さは、約０．２μｍであった。 (Coating with inorganic material film A)
A mask having an opening of 13 mm × 13 mm is installed so as to cover the entire laminate of the substrate on which the laminate including the obtained organic light emitting material layer is disposed, and the inorganic material film A is formed by plasma CVD. Formed.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and chamber pressure is 0. The test was performed at 9 Torr.
The formed inorganic material film A had a thickness of about 0.2 μm.
（樹脂保護膜の形成）
真空装置内に、無機材料膜Ａで被覆された積層体が配置された基板を設置し、真空装置の中に設置された加熱ボートに実施例１～７及び比較例１で得られた各表示素子用封止剤を０．５ｇ入れ、１０Ｐａに減圧して、積層体を含む１１ｍｍ×１１ｍｍの四角形の部分に、表示素子用封止剤を２００℃にて加熱し、厚さが０．５μｍになるように真空蒸着を行った。その後、真空環境下で高圧水銀灯を用いて波長３６５ｎｍの紫外線を照射量が３０００ｍＪ／ｃｍ２となるように照射して、表示素子用封止剤を硬化させて樹脂保護膜を形成した。 (Formation of resin protective film)
In the vacuum apparatus, a substrate on which a laminated body coated with the inorganic material film A is arranged, and each display obtained in Examples 1 to 7 and Comparative Example 1 is placed on a heating boat installed in the vacuum apparatus. 0.5 g of element sealant was put, pressure was reduced to 10 Pa, and the sealant for display element was heated at 200 ° C. to a 11 mm × 11 mm square portion including the laminate, and the thickness was 0.5 μm. Vacuum deposition was performed so that Thereafter, ultraviolet rays having a wavelength of 365 nm were irradiated using a high-pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm 2 to cure the sealant for display elements to form a resin protective film.
（無機材料膜Ｂによる被覆）
樹脂保護膜が形成された基板の１１ｍｍ×１１ｍｍの樹脂保護膜の全体を覆うように、１２ｍｍ×１２ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ｂを形成して表示素子（有機ＥＬ表示素子）を得た。
プラズマＣＶＤ法は、原料ガスとしてＳｉＨ４ガス及び窒素ガスを用い、各々の流量をＳｉＨ４ガス１０ｓｃｃｍ、窒素ガス２００ｓｃｃｍとし、ＲＦパワーを１０Ｗ（周波数２．４５ＧＨｚ）、チャンバー内温度を１００℃、チャンバー内圧力を０．９Ｔｏｒｒとする条件で行った。
形成された無機材料膜Ｂの厚さは、約１μｍであった。 (Coating with inorganic material film B)
A mask having an opening of 12 mm × 12 mm is installed so as to cover the entire 11 mm × 11 mm resin protective film of the substrate on which the resin protective film is formed, and an inorganic material film B is formed by plasma CVD and displayed. An element (organic EL display element) was obtained.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The formed inorganic material film B had a thickness of about 1 μm.
（有機ＥＬ表示素子の発光状態）
作製した有機ＥＬ表示素子をそれぞれ６０℃、９０％ＲＨの条件下に１００時間暴露した後、３Ｖの電圧を印加し、発光状態（発光及びダークスポット、画素周辺消光の有無）を目視で観察し、ダークスポットや周辺消光が無く均一に発光した場合を「○」、ダークスポットや周辺消光が認められた場合を「△」、非発光部が著しく拡大した場合を「×」として評価した。 (Light emission state of organic EL display element)
The prepared organic EL display elements were exposed for 100 hours under conditions of 60 ° C. and 90% RH, respectively, and then a voltage of 3 V was applied, and the light emission state (light emission and dark spots, presence / absence of pixel peripheral quenching) was visually observed. Evaluation was made with “◯” when the light was emitted uniformly without dark spots or peripheral quenching, “Δ” when the dark spots or peripheral quenching was observed, and “X” when the non-light emitting portion was significantly enlarged.
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
（製造例１（式（７）で表される化合物の製造））
（アシル化合物Ａの製造）
ジクロロメタン２００ｍＬとトリエチルアミン２９ｍＬとを含有する溶液に、２－フェニルチオエタノール１０４ｍｍｏｌ及び塩化アセチル８．２ｍＬを添加し、０℃で撹拌し、水洗浄した。次いで、ジクロロメタン２００ｍＬに溶解した塩化アルミニウム１２ｇを添加した後に、ジクロロメタン３６０ｍＬと塩化アルミニウム１４．８ｇとオクタン酸クロリド１８．４ｍＬとを含む溶液を０℃で滴下した。０℃で撹拌して反応を進行させた後、反応液を水で洗浄した。次いで、ジイソプロピルエチルエーテルで粉砕し、２１．６ｇのアシル化合物Ａを得た。 (Production Example 1 (Production of compound represented by formula (7)))
(Production of acyl compound A)
To a solution containing 200 mL of dichloromethane and 29 mL of triethylamine, 104 mmol of 2-phenylthioethanol and 8.2 mL of acetyl chloride were added, stirred at 0 ° C., and washed with water. Next, 12 g of aluminum chloride dissolved in 200 mL of dichloromethane was added, and then a solution containing 360 mL of dichloromethane, 14.8 g of aluminum chloride and 18.4 mL of octanoic acid chloride was added dropwise at 0 ° C. After stirring at 0 ° C. to advance the reaction, the reaction solution was washed with water. Then, it was pulverized with diisopropylethyl ether to obtain 21.6 g of acyl compound A.
（オキシム化合物Ａの製造）
上記「（アシル化合物Ａの製造）」で得られたアシル化合物Ａ１４ｇをテトラヒドロフラン２４０ｍＬに溶解し、濃塩酸７．２ｍＬ及びイソアミルナイトライト９．２ｍＬを室温下で加えた。５２時間撹拌して反応を進行させた後、反応液を水洗浄した。次いで、シリカゲルカラムで濾過して９．２ｇのオキシム化合物Ａを得た。 (Production of oxime compound A)
14 g of the acyl compound A obtained in the above “(production of acyl compound A)” was dissolved in 240 mL of tetrahydrofuran, and 7.2 mL of concentrated hydrochloric acid and 9.2 mL of isoamyl nitrite were added at room temperature. After stirring for 52 hours to allow the reaction to proceed, the reaction solution was washed with water. Next, the mixture was filtered through a silica gel column to obtain 9.2 g of oxime compound A.
（オキシム化合物Ａのオキシムエステル化）
トリエチルアミン１８．８ｍＬとテトラヒドロフラン２００ｍＬとを含有する溶液に、上記「（オキシム化合物Ａの製造）」で得られたオキシム化合物Ａ９．２ｇを加え、３－アリルオキシプロピオン酸クロリド９．６ｇを－１０℃の温度下で滴下し、撹拌した。得られた反応物を、０．５ｍｏｌ／Ｌの塩酸で洗浄し、シリカゲルカラムで濾過して上記式（７）で表される化合物を得た。得られた式（７）で表される化合物の１Ｈ－ＮＭＲスペクトルを図１に示す。 (Oxime esterification of oxime compound A)
To a solution containing 18.8 mL of triethylamine and 200 mL of tetrahydrofuran, 9.2 g of the oxime compound A obtained in the above-mentioned “(Preparation of oxime compound A)” was added, and 9.6 g of 3-allyloxypropionic acid chloride was added at −10 ° C. The solution was added dropwise at a temperature of and stirred. The obtained reaction product was washed with 0.5 mol / L hydrochloric acid and filtered through a silica gel column to obtain a compound represented by the above formula (7). FIG. 1 shows the 1 H-NMR spectrum of the obtained compound represented by the formula (7).
（製造例２（式（８）で表される化合物の製造））
（アシル化合物Ｂの製造）
ジクロロメタン４５０ｍＬと塩化アルミニウム２５．８ｇとオクタン酸クロリド３１．７ｍＬとを含有する溶液に、０℃で、ジクロロメタン２５０ｍＬとフェニルチオ酢酸２５ｇと塩化アルミニウム１９．８ｇとを含む溶液を加えて撹拌した。水で洗浄した後、ジエチルエーテルで粉砕して３８．５ｇのアシル化合物Ｂを得た。 (Production Example 2 (Production of Compound Represented by Formula (8)))
(Production of acyl compound B)
To a solution containing 450 mL of dichloromethane, 25.8 g of aluminum chloride and 31.7 mL of octanoic acid chloride, a solution containing 250 mL of dichloromethane, 25 g of phenylthioacetic acid and 19.8 g of aluminum chloride was added and stirred at 0 ° C. After washing with water, the mixture was triturated with diethyl ether to obtain 38.5 g of acyl compound B.
（オキシム化合物Ｂ－１の製造）
上記「（アシル化合物Ｂの製造）」で得られたアシル化合物Ｂ１０ｇをテトラヒドロフラン１００ｍＬに溶解し、濃塩酸５．７ｍＬに溶解したイソアミルナイトライト７．２ｍＬを室温下で加え、１２時間撹拌して反応を進行させた。次いで、水で洗浄した後、トルエンにて再結晶化して５．２ｇの反応物を得た。次いで、得られた反応物３．５ｇに１８ｍｏｌ／Ｌの硫酸０．１７ｍＬ及びアリルアルコール１７ｍＬを加え、室温で１２時間撹拌し、反応液を得た。得られた反応液を水洗浄した後、シリカゲルカラムで濾過し、３．３ｇのオキシム化合物Ｂ－１を得た。 (Production of oxime compound B-1)
10 g of the acyl compound B obtained in the above “(Production of acyl compound B)” was dissolved in 100 mL of tetrahydrofuran, 7.2 mL of isoamyl nitrite dissolved in 5.7 mL of concentrated hydrochloric acid was added at room temperature, and the reaction was stirred for 12 hours. Made progress. Subsequently, after washing with water, recrystallization was performed with toluene to obtain 5.2 g of a reaction product. Next, 0.17 mL of 18 mol / L sulfuric acid and 17 mL of allyl alcohol were added to 3.5 g of the obtained reaction product, and the mixture was stirred at room temperature for 12 hours to obtain a reaction solution. The resulting reaction solution was washed with water and then filtered through a silica gel column to obtain 3.3 g of oxime compound B-1.
（オキシム化合物Ｂ－１のオキシムエステル化）
トリエチルアミン３．１５ｍＬとテトラヒドロフラン５０ｍＬとを含有する溶液に、－１０℃にて上記「（オキシム化合物Ｂ－１の製造）」で得られたオキシム化合物Ｂ－１を３．３ｇ加え、３－アリルオキシプロピオン酸クロリド１．７ｇを－１０℃の温度下で滴下し撹拌した。得られた反応物を、０．５ｍｏｌ／Ｌの塩酸で洗浄し、シリカゲルカラムで濾過して上記式（８）で表される化合物を得た。得られた式（８）で表される化合物の１Ｈ－ＮＭＲスペクトルを図２に示す。 (Oxime esterification of oxime compound B-1)
To a solution containing 3.15 mL of triethylamine and 50 mL of tetrahydrofuran was added 3.3 g of oxime compound B-1 obtained in the above “(Production of oxime compound B-1)” at −10 ° C. 1.7 g of propionic acid chloride was added dropwise at a temperature of −10 ° C. and stirred. The obtained reaction product was washed with 0.5 mol / L hydrochloric acid and filtered through a silica gel column to obtain a compound represented by the above formula (8). FIG. 2 shows the 1 H-NMR spectrum of the obtained compound represented by the formula (8).
（製造例３（式（９）で表される化合物及び式（１０）で表される化合物の製造））
（オキシム化合物Ｂ－２及びオキシム化合物Ｂ－３の製造）
上記製造例２における「（アシル化合物Ｂの製造）」と同様にして得られたアシル化合物Ｂ２８．３ｇをテトラヒドロフラン２８０ｍＬに溶解し、濃塩酸１６．２ｍＬ及びイソアミルナイトライト２０．４ｍＬを室温下で加え、１２時間撹拌して反応を進行させ、水で洗浄した後、トルエンにて再結晶化して１１．６ｇの反応物を得た。次いで、１８ｍｏｌ／Ｌの硫酸０．５７ｍＬ及び１，３－ブタンジオール５５ｍＬを加え撹拌し、反応液を得た。得られた反応液を水洗浄後、シリカゲルカラムで濾過し、オキシム化合物Ｂ－２とオキシム化合物Ｂ－３との混合物８．６ｇを得た。 (Production Example 3 (Production of Compound Represented by Formula (9) and Compound Represented by Formula (10)))
(Production of oxime compound B-2 and oxime compound B-3)
28.3 g of the acyl compound B obtained in the same manner as “(Production of acyl compound B)” in the above Production Example 2 was dissolved in 280 mL of tetrahydrofuran, and 16.2 mL of concentrated hydrochloric acid and 20.4 mL of isoamyl nitrite were added at room temperature. The reaction was allowed to proceed with stirring for 12 hours, washed with water, and recrystallized with toluene to obtain 11.6 g of a reaction product. Next, 0.57 mL of 18 mol / L sulfuric acid and 55 mL of 1,3-butanediol were added and stirred to obtain a reaction solution. The resulting reaction solution was washed with water and then filtered through a silica gel column to obtain 8.6 g of a mixture of oxime compound B-2 and oxime compound B-3.
（オキシム化合物Ｂ－２及びオキシム化合物Ｂ－３のオキシムエステル化）
トリエチルアミン９．１ｍＬとテトラヒドロフラン１７０ｍＬとを含有する溶液に、上記「（オキシム化合物Ｂ－２及びオキシム化合物Ｂ－３の製造）」で得られたオキシム化合物Ｂ－２とオキシム化合物Ｂ－３との混合物８．６ｇを加え、３－アリルオキシプロピオン酸クロリド４．８５ｇを－１０℃の温度下で滴下し、撹拌した。得られた反応物を水洗浄後、カラム濾過により式（９）で表される化合物と式（１０）で表される化合物とを分離した。得られた上記式（９）で表される化合物及び上記式（１０）で表される化合物の１Ｈ－ＮＭＲスペクトルをそれぞれ図３及び図４に示す。 (Oxime esterification of oxime compound B-2 and oxime compound B-3)
In a solution containing 9.1 mL of triethylamine and 170 mL of tetrahydrofuran, a mixture of the oxime compound B-2 and the oxime compound B-3 obtained in the above “(Production of oxime compound B-2 and oxime compound B-3)” 8.6 g was added, and 4.85 g of 3-allyloxypropionic acid chloride was added dropwise at a temperature of −10 ° C. and stirred. The obtained reaction product was washed with water, and the compound represented by formula (9) and the compound represented by formula (10) were separated by column filtration. FIGS. 3 and 4 show the 1 H-NMR spectra of the compound represented by the above formula (9) and the compound represented by the above formula (10), respectively.
（製造例４（式（１１）で表される化合物の製造））
（アシル化合物Ｃの製造）
ジクロロメタン１００ｍＬと塩化アルミニウム９．２ｇとプロピオン酸クロリド５．８ｍＬとを含有する溶液に、フェニルチオ酢酸１０ｇ、塩化アルミニウム８ｇとジクロロメタン１８０ｍＬとを含有する溶液を０℃で加え、撹拌して反応を進行させた後、水洗浄し、１０．６ｇのアシル化合物Ｃを得た。 (Production Example 4 (Production of Compound Represented by Formula (11)))
(Production of acyl compound C)
To a solution containing 100 mL of dichloromethane, 9.2 g of aluminum chloride and 5.8 mL of propionic acid chloride, a solution containing 10 g of phenylthioacetic acid, 8 g of aluminum chloride and 180 mL of dichloromethane was added at 0 ° C., and the reaction was allowed to proceed by stirring. And then washed with water to obtain 10.6 g of acyl compound C.
（オキシム化合物Ｃの製造）
上記「（アシル化合物Ｃの製造）」で得られたアシル化合物Ｃ１０．６ｇをテトラヒドロフラン１０ｍＬに溶解し、濃塩酸５．６４ｍＬ及びイソアミルナイトライト０．９６ｍＬを室温下で加え、１２時間撹拌して反応を進行させた。次いで、水洗浄後、トルエンにて再結晶化して７．２ｇのオキシム化合物Ｃを得た。 (Production of oxime compound C)
10.6 g of the acyl compound C obtained in the above “(Production of acyl compound C)” is dissolved in 10 mL of tetrahydrofuran, 5.64 mL of concentrated hydrochloric acid and 0.96 mL of isoamyl nitrite are added at room temperature, and the reaction is stirred for 12 hours. Made progress. Then, after washing with water, recrystallization from toluene yielded 7.2 g of oxime compound C.
（オキシム化合物Ｃのオキシムエステル化）
上記「（オキシム化合物Ｃの製造）」で得られたオキシム化合物Ｃ７．２ｇを、エタノール７２ｍＬと濃硫酸２．８ｍＬとを含有する溶液に添加して溶解させた。室温で１２時間撹拌後、水洗浄した後にシリカゲルカラムで濾過して７．２ｇのエステル化合物を得た。
得られたエステル化合物７．２ｇをトリエチルアミン９ｍＬとテトラヒドロフラン１８０ｍＬとを含有する溶液に加え、テトラヒドロフラン１８ｍＬに溶解した３－アリルオキシプロピオン酸クロリド４．６８ｇを－５℃の温度下で滴下し、９０分撹拌した。得られた反応物を、０．５ｍｏｌ／Ｌの塩酸で洗浄し、シリカゲルカラムで濾過して、上記式（１１）で表される化合物を得た。得られた式（１１）で表される化合物の１Ｈ－ＮＭＲスペクトルを図５に示す。 (Oxime esterification of oxime compound C)
7.2 g of the oxime compound C obtained in the above “(Production of oxime compound C)” was added and dissolved in a solution containing 72 mL of ethanol and 2.8 mL of concentrated sulfuric acid. The mixture was stirred at room temperature for 12 hours, washed with water, and then filtered through a silica gel column to obtain 7.2 g of an ester compound.
7.2 g of the obtained ester compound was added to a solution containing 9 mL of triethylamine and 180 mL of tetrahydrofuran, and 4.68 g of 3-allyloxypropionic acid chloride dissolved in 18 mL of tetrahydrofuran was added dropwise at a temperature of −5 ° C. for 90 minutes. Stir. The obtained reaction product was washed with 0.5 mol / L hydrochloric acid and filtered through a silica gel column to obtain a compound represented by the above formula (11). FIG. 5 shows the 1 H-NMR spectrum of the obtained compound represented by the formula (11).
（実施例８～１４、比較例２、３）
表２に記載された配合比に従い、各材料を、攪拌機（新東科学社製、「スリーワンモーター　ＨＥＩＤＯＮ　ＢＬＨ３００」）を用いて７０℃にて３時間加熱混合することにより、表示素子用封止剤を調製した。 (Examples 8 to 14, Comparative Examples 2 and 3)
According to the compounding ratio described in Table 2, each material was heated and mixed at 70 ° C. for 3 hours using a stirrer (manufactured by Shinto Kagaku Co., Ltd., “Three-One Motor HEIDON BLH300”) for 3 hours. Was prepared.
＜評価＞
実施例８～１４及び比較例２、３で得られた各表示素子用封止剤について以下の評価を行った。結果を表２に示した。 <Evaluation>
The following evaluations were performed on the sealants for display elements obtained in Examples 8 to 14 and Comparative Examples 2 and 3. The results are shown in Table 2.
（１）光硬化性
実施例８～１４及び比較例２、３で得られた各表示素子用封止剤をガラス基板上に塗工し、波長３６５ｎｍのＬＥＤランプを用いて、積算光量が１０００ｍＪ／ｃｍ２となるように光を照射した。その後、ＦＴ－ＩＲを用いた分析方法により、アリル基の反応率を測定した。アリル基の反応率が７０％を超えた場合を「○」、５０～７０％であった場合を「△」、５０％未満であった場合を「×」として光硬化性を評価した。 (1) Photocurability Each sealant for display elements obtained in Examples 8 to 14 and Comparative Examples 2 and 3 was coated on a glass substrate, and the integrated light quantity was 1000 mJ using an LED lamp with a wavelength of 365 nm. Light was irradiated so as to be / cm 2 . Thereafter, the reaction rate of the allyl group was measured by an analysis method using FT-IR. Photocurability was evaluated by assuming that the reaction rate of the allyl group exceeded 70% as “◯”, the case of 50 to 70% as “Δ”, and the case of less than 50% as “X”.
（２）硬化物の透明性（透過率）
実施例８～１４及び比較例２、３で得られた各表示素子用封止剤を、ＰＥＴ樹脂フィルムに挟み、２０００ｍＪ／ｃｍ２の紫外線を照射して、厚さ１００μｍの透過率測定用サンプルを作製した。得られた透過率測定用サンプルについて、分光光度計（日立製作所社製、「Ｕ－３０００」、条件３００～８００ｎｍ）を用いて、波長３８０～７８０ｎｍにおける光線透過率を測定した。 (2) Transparency (transmittance) of the cured product
Samples for measuring transmittance having a thickness of 100 μm are obtained by sandwiching the sealants for display elements obtained in Examples 8 to 14 and Comparative Examples 2 and 3 between PET resin films and irradiating with 2000 mJ / cm 2 ultraviolet rays. Was made. The obtained transmittance measurement sample was measured for light transmittance at a wavelength of 380 to 780 nm using a spectrophotometer (manufactured by Hitachi, Ltd., “U-3000”, conditions 300 to 800 nm).
（３）アウトガス発生量
実施例８～１４及び比較例２、３で得られた各表示素子用封止剤を、バーコーターを用いて塗工後の厚さが１００μｍとなるように塗工し、超高圧水銀灯を用いて２０００ｍＪ／ｃｍ２の紫外線を照射してフィルムを形成した。得られたフィルムを熱分析装置（Ｓｅｉｋｏ　Ｉｎｓｔｒｕｍｅｎｔｓ社製、「ＴＧ／ＤＴＡ６２００」）を用いて、昇温速度１０℃／ｍｉｎで１５０℃まで加熱したときの重量減少率を測定し、これをアウトガス発生量とした。 (3) Outgas generation amount Each sealant for display element obtained in Examples 8 to 14 and Comparative Examples 2 and 3 was coated using a bar coater so that the thickness after coating was 100 μm. A film was formed by irradiating ultraviolet rays of 2000 mJ / cm 2 using an ultrahigh pressure mercury lamp. Using a thermal analyzer (“TG / DTA6200” manufactured by Seiko Instruments, Inc.), the resulting film was measured for weight loss rate when heated to 150 ° C. at a rate of temperature increase of 10 ° C./min, and this was generated as outgas. The amount.
（４）表示素子の表示性能
（４－１）液晶表示素子の表示性能
（液晶表示素子の作製）
厚さ１０００ÅのＩＴＯ電極を表面に成膜した後、更にスピンコートにて厚さ８００Åの配向膜を表面に塗布したガラス基板（長さ２５ｍｍ、幅２５ｍｍ、厚さ０．７ｍｍ）を２枚用意し、一方の基板に熱硬化性エポキシ樹脂（周辺シール剤）を用いて、液晶注入口部を設けるようにしたパターンの印刷をスクリーン印刷にて行った。次に、パターンの印刷を行った基板を８０℃で３分間保持することにより予備乾燥と基板への周辺シール剤の融着とを行った後、室温に戻した。次いで、もう一方の基板に５μｍのスペーサーを散布した後、それぞれの基板を貼り合わせ、１３０℃に加熱した熱プレスで２時間の圧着を行って周辺シール剤を硬化させ、空のセルを得た。得られた空のセルを真空吸引した後、注入口より液晶（メルク社製、「ＺＬＩ－４７９２」）を注入し、注入口を実施例８～１４及び比較例２、３で得られた各表示素子用封止剤を用いて封止し、高圧水銀灯を用いて３０００ｍＪ／ｃｍ２の紫外線を照射して封止剤を硬化させた。その後、１２０℃で１時間液晶のアニールを行い、液晶表示素子を作製した。 (4) Display performance of display element (4-1) Display performance of liquid crystal display element (production of liquid crystal display element)
Prepare two glass substrates (length 25mm, width 25mm, thickness 0.7mm) on which an ITO electrode with a thickness of 1000mm is formed on the surface and then an orientation film with a thickness of 800mm is applied on the surface by spin coating. Then, using a thermosetting epoxy resin (peripheral sealant) on one substrate, printing of a pattern in which a liquid crystal injection port was provided was performed by screen printing. Next, the substrate on which the pattern was printed was kept at 80 ° C. for 3 minutes to perform preliminary drying and fusion of the peripheral sealant to the substrate, and then returned to room temperature. Next, after spraying a spacer of 5 μm on the other substrate, each substrate was bonded, and the peripheral sealant was cured by hot pressing heated to 130 ° C. for 2 hours to obtain an empty cell. . The obtained empty cell was vacuumed, and liquid crystal (“ZLI-4792” manufactured by Merck & Co., Inc.) was injected from the injection port. The injection port was obtained in each of Examples 8 to 14 and Comparative Examples 2 and 3. Sealing was performed using a sealant for display elements, and the sealant was cured by irradiating with 3000 mJ / cm 2 ultraviolet rays using a high-pressure mercury lamp. Thereafter, the liquid crystal was annealed at 120 ° C. for 1 hour to produce a liquid crystal display element.
（液晶表示素子の配向乱れ）
得られた液晶表示素子を、ＡＣ３．５Ｖの電圧にて中間調の表示状態で駆動させ、注入口近傍の液晶の配向乱れを偏光顕微鏡で観察した。配向乱れが確認されなかった場合を「○」、１ｍｍ未満の配向乱れが確認された場合を「△」、１ｍｍ以上のはっきりとした配向乱れ（濃い色むら）があった場合を「×」として液晶表示素子の表示性能を評価した。 (Liquid crystal orientation disorder)
The obtained liquid crystal display element was driven in a halftone display state at a voltage of AC 3.5 V, and the alignment disorder of the liquid crystal near the inlet was observed with a polarizing microscope. The case where no alignment disorder is confirmed is “◯”, the case where alignment disorder less than 1 mm is confirmed is “Δ”, and the case where there is a clear alignment disorder (dark color unevenness) of 1 mm or more is “X”. The display performance of the liquid crystal display element was evaluated.
（４－２）有機ＥＬ表示素子の表示性能
（有機発光材料層を含む積層体が配置された基板の作製）
ガラス基板（長さ２５ｍｍ、幅２５ｍｍ、厚さ０．７ｍｍ）にＩＴＯ電極を１０００Åの厚さで成膜したものを基板とした。上記基板をアセトン、アルカリ水溶液、イオン交換水、イソプロピルアルコールにてそれぞれ１５分間超音波洗浄した後、煮沸させたイソプロピルアルコールにて１０分間洗浄し、更に、ＵＶ－オゾンクリーナ（日本レーザー電子社製、「ＮＬ－ＵＶ２５３」）にて直前処理を行った。
次に、この基板を真空蒸着装置の基板フォルダに固定し、素焼きの坩堝にＮ，Ｎ’－ジ（１－ナフチル）－Ｎ，Ｎ’－ジフェニルベンジジン（α－ＮＰＤ）を２００ｍｇ、他の異なる素焼き坩堝にトリス（８－ヒドロキシキノリラ）アルミニウム（Ａｌｑ３）を２００ｍｇ入れ、真空チャンバー内を、１×１０－４Ｐａまで減圧した。その後、α－ＮＰＤの入った坩堝を加熱し、α－ＮＰＤを蒸着速度１５Å／ｓで基板に堆積させ、膜厚６００Åの正孔輸送層を成膜した。次いで、Ａｌｑ３の入った坩堝を加熱し、１５Å／ｓの蒸着速度で膜厚６００Åの有機発光材料層を成膜した。その後、正孔輸送層及び有機発光材料層が形成された基板を別の真空蒸着装置に移し、この真空蒸着装置内のタングステン製抵抗加熱ボートにフッ化リチウム２００ｍｇを、別のタングステン製ボートにアルミニウム線１．０ｇを入れた。その後、真空蒸着装置の蒸着器内を２×１０－４Ｐａまで減圧してフッ化リチウムを０．２Å／ｓの蒸着速度で５Å成膜した後、アルミニウムを２０Å／ｓの速度で１０００Å成膜した。窒素により蒸着器内を常圧に戻し、１０ｍｍ×１０ｍｍの有機発光材料層を含む積層体が配置された基板を取り出した。 (4-2) Display performance of organic EL display device (production of a substrate on which a laminate including an organic light emitting material layer is disposed)
A glass substrate (length 25 mm, width 25 mm, thickness 0.7 mm) on which an ITO electrode was formed to a thickness of 1000 mm was used as the substrate. The substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes, respectively, then washed with boiled isopropyl alcohol for 10 minutes, and a UV-ozone cleaner (manufactured by Nippon Laser Electronics Co., Ltd.). The last treatment was performed with “NL-UV253”).
Next, this substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put into an unglazed crucible and other different types. 200 mg of tris (8-hydroxyquinola) aluminum (Alq 3 ) was put in an unglazed crucible, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa. Thereafter, the crucible containing α-NPD was heated, and α-NPD was deposited on the substrate at a deposition rate of 15 ｓ / s to form a 600 正 孔 hole transport layer. Next, the crucible containing Alq 3 was heated to form an organic light emitting material layer having a thickness of 600 で at a deposition rate of 15 Å / s. Thereafter, the substrate on which the hole transport layer and the organic light emitting material layer are formed is transferred to another vacuum vapor deposition apparatus, and 200 mg of lithium fluoride is added to a tungsten resistance heating boat in the vacuum vapor deposition apparatus, and aluminum is added to another tungsten boat. 1.0 g of wire was added. After that, the inside of the vapor deposition unit of the vacuum vapor deposition apparatus is depressurized to 2 × 10 −4 Pa to form a lithium fluoride film with a thickness of 5 mm at a deposition rate of 0.2 kg / s, and then aluminum with a film thickness of 1000 mm at a rate of 20 kg / s. did. The inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and the substrate on which the laminate including the organic light emitting material layer of 10 mm × 10 mm was arranged was taken out.
（無機材料膜Ａによる被覆）
得られた有機発光材料層を含む積層体が配置された基板の、該積層体の全体を覆うように、１３ｍｍ×１３ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ａを形成した。
プラズマＣＶＤ法は、原料ガスとしてＳｉＨ４ガス及び窒素ガスを用い、各々の流量を１０ｓｃｃｍ及び２００ｓｃｃｍとし、ＲＦパワーを１０Ｗ（周波数２．４５ＧＨｚ）、チャンバー内温度を１００℃、チャンバー内圧力を０．９Ｔｏｒｒとする条件で行った。
形成されたシリコンナイトライドの無機材料膜Ａの厚さは、約０．２μｍであった。 (Coating with inorganic material film A)
A mask having an opening of 13 mm × 13 mm is installed so as to cover the entire laminate of the substrate on which the laminate including the obtained organic light emitting material layer is disposed, and the inorganic material film A is formed by plasma CVD. Formed.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates are 10 sccm and 200 sccm, RF power is 10 W (frequency: 2.45 GHz), chamber temperature is 100 ° C., and chamber pressure is 0. The test was performed at 9 Torr.
The thickness of the formed inorganic material film A of silicon nitride was about 0.2 μm.
（樹脂保護膜の形成）
真空装置内に、無機材料膜Ａで被覆された積層体が配置された基板を設置し、真空装置の中に設置された加熱ボートに実施例８～１４及び比較例２、３で得られた各表示素子用封止剤を０．５ｇ入れ、１０Ｐａに減圧して、積層体を含む１１ｍｍ×１１ｍｍの四角形の部分に、表示素子用封止剤を２００℃にて加熱し、厚さが０．５μｍになるように真空蒸着を行った。その後、真空環境下で高圧水銀灯を用いて波長３６５ｎｍの紫外線を照射量が３０００ｍＪ／ｃｍ２となるように照射して、表示素子用封止剤を硬化させて樹脂保護膜を形成した。 (Formation of resin protective film)
The substrate on which the laminate coated with the inorganic material film A was placed in the vacuum device, and obtained in Examples 8 to 14 and Comparative Examples 2 and 3 on the heating boat installed in the vacuum device. 0.5 g of each sealant for display element is put in, reduced in pressure to 10 Pa, and the sealant for display element is heated at 200 ° C. to a 11 mm × 11 mm square part including the laminate, and the thickness is 0 Vacuum deposition was performed to a thickness of 5 μm. Thereafter, ultraviolet rays having a wavelength of 365 nm were irradiated using a high-pressure mercury lamp in a vacuum environment so that the irradiation amount was 3000 mJ / cm 2 to cure the sealant for display elements to form a resin protective film.
（無機材料膜Ｂによる被覆）
樹脂保護膜が形成された基板の１１ｍｍ×１１ｍｍの樹脂保護膜の全体を覆うように、１２ｍｍ×１２ｍｍの開口部を有するマスクを設置し、プラズマＣＶＤ法にて無機材料膜Ｂを形成して表示素子（有機ＥＬ表示素子）を得た。
プラズマＣＶＤ法は、原料ガスとしてＳｉＨ４ガス及び窒素ガスを用い、各々の流量をＳｉＨ４ガス１０ｓｃｃｍ、窒素ガス２００ｓｃｃｍとし、ＲＦパワーを１０Ｗ（周波数２．４５ＧＨｚ）、チャンバー内温度を１００℃、チャンバー内圧力を０．９Ｔｏｒｒとする条件で行った。
形成されたシリコンナイトライドの無機材料膜Ｂの厚さは、約１μｍであった。 (Coating with inorganic material film B)
A mask having an opening of 12 mm × 12 mm is installed so as to cover the entire 11 mm × 11 mm resin protective film of the substrate on which the resin protective film is formed, and an inorganic material film B is formed by plasma CVD and displayed. An element (organic EL display element) was obtained.
In the plasma CVD method, SiH 4 gas and nitrogen gas are used as source gases, the flow rates of each are SiH 4 gas 10 sccm, nitrogen gas 200 sccm, RF power 10 W (frequency 2.45 GHz), chamber temperature 100 ° C., chamber The test was performed under the condition that the internal pressure was 0.9 Torr.
The thickness of the formed inorganic material film B of silicon nitride was about 1 μm.
（有機ＥＬ表示素子の発光状態）
作製した有機ＥＬ表示素子をそれぞれ６０℃、９０％ＲＨの条件下に１００時間暴露した後、３Ｖの電圧を印加し、発光状態（発光及びダークスポット、画素周辺消光の有無）を目視で観察し、ダークスポットや周辺消光が無く均一に発光した場合を「○」、ダークスポットや周辺消光が認められた場合を「△」、非発光部が著しく拡大した場合を「×」として有機ＥＬ表示素子の表示性能を評価した。 (Light emission state of organic EL display element)
The prepared organic EL display elements were exposed for 100 hours under conditions of 60 ° C. and 90% RH, respectively, and then a voltage of 3 V was applied, and the light emission state (light emission and dark spots, presence / absence of pixel peripheral quenching) was visually observed. Organic light emitting diode display element where “○” indicates that there is no dark spot or peripheral quenching, “◯” indicates that dark spot or peripheral quenching is observed, and “X” indicates that the non-light emitting portion is significantly enlarged. The display performance of was evaluated.
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
本発明によれば、アウトガスの発生や他材料の汚染を抑制することができ、接着性、及び、硬化物の透明性に優れる表示素子用封止剤を提供することができる。また、本発明によれば、該表示素子用封止剤に好適に用いることができるオキシムエステル開始剤を提供することができる。 According to this invention, generation | occurrence | production of outgas and contamination of other materials can be suppressed, and the sealing agent for display elements which is excellent in adhesiveness and transparency of hardened | cured material can be provided. Moreover, according to this invention, the oxime ester initiator which can be used suitably for this sealing agent for display elements can be provided.

Claims (9)

  1. １分子中に２個以上のチオール基を有するポリチオールモノマー、１分子中に２個以上の炭素－炭素二重結合を有するポリエンモノマー、及び、ラジカル重合開始剤を含有し、
    前記ラジカル重合開始剤は、光照射又は加熱によりラジカルを発生する官能基と、反応性官能基とを有する化合物である
    ことを特徴とする表示素子用封止剤。     A polythiol monomer having two or more thiol groups in one molecule, a polyene monomer having two or more carbon-carbon double bonds in one molecule, and a radical polymerization initiator,
    The sealing agent for a display element, wherein the radical polymerization initiator is a compound having a functional group that generates radicals by light irradiation or heating and a reactive functional group.
  2. ポリチオールモノマーは、１分子中に３個以上のチオール基を有するモノマーを含有することを特徴とする請求項１記載の表示素子用封止剤。 The polythiol monomer contains a monomer having three or more thiol groups in one molecule, and the sealant for display elements according to claim 1.
  3. ポリエンモノマーは、１分子中に３個以上の炭素－炭素二重結合を有するモノマーを含有することを特徴とする請求項１又は２記載の表示素子用封止剤。 3. The sealant for a display element according to claim 1, wherein the polyene monomer contains a monomer having 3 or more carbon-carbon double bonds in one molecule.
  4. ポリエンオリゴマーを含有することを特徴とする請求項１、２又は３記載の表示素子用封止剤。 The sealing agent for display elements according to claim 1, 2 or 3, characterized by containing a polyene oligomer.
  5. ポリチオールモノマーとポリエンモノマーとの反応により形成されるチオエーテルオリゴマーを含有する請求項１、２、３又は４記載の表示素子用封止剤。 The sealing agent for display elements of Claim 1, 2, 3, or 4 containing the thioether oligomer formed by reaction of a polythiol monomer and a polyene monomer.
  6. チオエーテルオリゴマーの重量平均分子量が５００～４万であることを特徴とする請求項５記載の表示素子用封止剤。 6. The sealant for a display element according to claim 5, wherein the thioether oligomer has a weight average molecular weight of 500 to 40,000.
  7. ラジカル重合開始剤の有する反応性官能基は、チオール基及び／又は炭素－炭素二重結合であることを特徴とする請求項１、２、３、４、５又は６記載の表示素子用封止剤。 7. The sealing for a display device according to claim 1, wherein the reactive functional group of the radical polymerization initiator is a thiol group and / or a carbon-carbon double bond. Agent.
  8. ラジカル重合開始剤は、反応性官能基を１分子中に２個以上有することを特徴とする請求項１、２、３、４、５、６又は７記載の表示素子用封止剤。 The sealing agent for display elements according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the radical polymerization initiator has two or more reactive functional groups in one molecule.
  9. 下記式（３）で表される化合物であることを特徴とするオキシムエステル開始剤。
    Figure JPOXMLDOC01-appb-C000001
     式（３）中、Ｒ３は、フェニル基（炭素数１～６のアルキル基、フェニル基、ハロゲン原子、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、炭素数１～２０のアルキル基、炭素数２～２０のアルキル基（１個以上の酸素原子により中断、及び／若しくは、１個以上のヒドロキシル基により置換されていてもよい）、炭素数５～８のシクロアルキル基、炭素数２～２０のアルカノイル基、ベンゾイル基（炭素数１～６のアルキル基、フェニル基、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、炭素数２～１２のアルコキシカルボニル基（１個以上の酸素原子により中断、及び／若しくは、１個以上のヒドロキシル基により置換されていてもよい）、フェノキシカルボニル基（炭素数１～６のアルキル基、フェニル基、ハロゲン原子、－ＯＲ１０基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、－ＣＯＮＲ１２Ｒ１３基、－ＣＮ基、－ＮＯ２基、炭素数１～４のハロアルキル基、炭素数１～６の－Ｓ（Ｏ）ｍ－アルキル基、炭素数６～１２の－Ｓ（Ｏ）ｍ－アリール基（炭素数１～１２のアルキル基により置換されていてもよい）、炭素数１～６の－ＳＯ２Ｏ－アルキル基、炭素数６～１０の－ＳＯ２Ｏ－アリール基、又は、ジフェニルホスフィノイル基であり、ｍは、１又は２である。
    Ｒ４及びＲ７は、それぞれ独立して、反応性官能基、水素結合性官能基を有する基、水素原子、炭素数３～２０のカルボアルコキシアルキル基（１個以上の酸素原子により中断、及び／又は、１個以上のヒドロキシル基により置換されていてもよい）、ハロゲン原子、炭素数１～１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基（－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基からなる群より選択される少なくとも１種により置換されていてもよい）、ベンジル基、ベンゾイル基、炭素数２～１２のアルカノイル基、炭素数２～１２のアルコキシカルボニル基（１個以上の酸素原子により中断、及び／又は、１個以上のヒドロキシル基により置換されていてもよい）、フェノキシカルボニル基、－ＯＲ１０基、－ＳＲ１１基、－ＳＯＲ１１基、－ＳＯ２Ｒ１１基、或いは、－ＮＲ１２Ｒ１３基（ここで、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基は、フェニル環の有する置換基若しくはフェニル環の炭素原子の一つと、Ｒ１０、Ｒ１１、Ｒ１２、及び／若しくは、Ｒ１３を介して５員環又は６員環を形成していてもよい）である。ただし、Ｒ４及びＲ７の少なくとも一方は、反応性官能基である。
    Ｒ５、Ｒ６、Ｒ８、及び、Ｒ９は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１～１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基（－ＯＲ１０基、－ＳＲ１１基、若しくは、－ＮＲ１２Ｒ１３基により置換されていてもよい）、ベンジル基、ベンゾイル基、炭素数２～１２のアルカノイル基、炭素数２～１２のアルコキシカルボニル基（１個以上の酸素原子により中断、及び／若しくは、１個以上のヒドロキシル基により置換されていてもよい）、フェノキシカルボニル基、－ＯＲ１０基、－ＳＲ１１基、－ＳＯＲ１１基、－ＳＯ２Ｒ１１基、又は、－ＮＲ１２Ｒ１３基であり、－ＯＲ１０基、－ＳＲ１１基、及び、－ＮＲ１２Ｒ１３基は、フェニル環の有する置換基又はフェニル環の炭素原子の一つと、Ｒ１０、Ｒ１１、Ｒ１２、及び／又は、Ｒ１３を介して５員環又は６員環を形成していてもよい。
    Ｒ１０は、水素原子、炭素数１～１２のアルキル基、炭素数２～６のアルキル基（－ＯＨ基、－ＳＨ基、－ＣＮ基、炭素数１～４のアルコキシ基、炭素数３～６のアルケンオキシ基、－ＯＣＨ２ＣＨ２ＣＮ基、炭素数４～７の－ＯＣＨ２ＣＨ２（ＣＯ）Ｏ－アルキル基、炭素数２～５の－Ｏ（ＣＯ）－アルキル基、－Ｏ（ＣＯ）－フェニル基、－（ＣＯ）ＯＨ基、若しくは、炭素数２～５の－（ＣＯ）Ｏ－アルキル基で置換されている）、炭素数２～６のアルキル基（１個以上の酸素原子により中断されている）、－（ＣＨ２ＣＨ２Ｏ）ｎＨ基、炭素数２～８のアルカノイル基、炭素数３～１２のアルケニル基、炭素数３～６のアルケノイル基、シクロヘキシル基、フェニル基（ハロゲン原子、炭素数１～１２のアルキル基、若しくは、炭素数１～４のアルコキシ基で置換されていてもよい）、炭素数７～９のフェニルアルキル基、－Ｓｉ（炭素数１～８のアルキル）ｒ（フェニル）３－ｒ基、又は、下記式（４）で表される基のいずれかである。ｎは、１～２０であり、ｒは、１～３である。
    Ｒ１１は、水素原子、炭素数１～１２のアルキル基、炭素数３～１２のアルケニル基、シクロヘキシル基、炭素数２～６のアルキル基（－ＯＨ基、－ＳＨ基、－ＣＮ基、炭素数１～４のアルコキシ基、炭素数３～６のアルケンオキシ基、－ＯＣＨ２ＣＨ２ＣＮ基、炭素数４～７の－ＯＣＨ２ＣＨ２（ＣＯ）Ｏ－アルキル基、炭素数２～５の－Ｏ（ＣＯ）－アルキル基、－Ｏ（ＣＯ）－フェニル基、－（ＣＯ）ＯＨ基、若しくは、炭素数２～５の－（ＣＯ）Ｏ－アルキル基で置換されている）、炭素数２～１２のアルキル基（１個以上の酸素原子若しくは硫黄原子により中断されている）、フェニル基（ハロゲン原子、炭素数１～１２のアルキル基、若しくは、炭素数１～４のアルコキシ基で置換されていてもよい）、炭素数７～９のフェニルアルキル基、又は、下記式（５）で表される基のいずれかである。
    Ｒ１２及びＲ１３は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数２～４のヒドロキシアルキル基、炭素数２～１０のアルコキシアルキル基、炭素数３～５のアルケニル基、炭素数５～１２のシクロアルキル基、炭素数７～９のフェニルアルキル基、フェニル基（炭素数１～１２のアルキル基若しくは炭素数１～４のアルコキシ基により置換されている）、炭素数２～３のアルカノイル基、炭素数３～６のアルケノイル基、ベンゾイル基、或いは、Ｒ１２及びＲ１３が１つの基となった炭素数２～６のアルキレン基（酸素原子若しくは－ＮＲ１０－基により中断、及び／又は、ヒドロキシル基、炭素数１～４のアルコキシ基、炭素数２～４のアルカノイルオキシ基、若しくは、ベンゾイルオキシ基で置換されていてもよい）である。Ｒ１２が水素原子である場合、Ｒ１３は、下記式（６）で表される基であってもよい。
    Figure JPOXMLDOC01-appb-C000002
     式（４）中、Ｒ３及びＲ４は、式（３）と同じものが挙げられる。Ｍ１は、結合手、又は、炭素数１～１２のアルキレンオキシ基（１～５個の酸素原子、硫黄原子、及び／若しくは、－ＮＲ１２－基により中断されていてもよい）である。
    Figure JPOXMLDOC01-appb-C000003
     式（５）中、Ｒ３及びＲ４は、式（３）と同じものが挙げられる。Ｍ２は、結合手、又は、炭素数１～１２のアルキレン－Ｓ－基（１～５個の酸素原子、硫黄原子、及び／若しくは、－ＮＲ１２－基により中断されていてもよい）である。
    Figure JPOXMLDOC01-appb-C000004
     式（６）中、Ｒ３及び、Ｒ４は、式（３）と同じものが挙げられる。Ｍ３は、結合手、ピペラジノ基、又は、炭素数１～１２のアルキレン－ＮＨ－基（１～５個の酸素原子、硫黄原子、及び／若しくは、－ＮＲ１２－基により中断されていてもよい）である。     An oxime ester initiator, which is a compound represented by the following formula (3).
    Figure JPOXMLDOC01-appb-C000001
     In the formula (3), R 3 is selected from the group consisting of a phenyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, —OR 10 group, —SR 11 group, and —NR 12 R 13 group). Optionally substituted by at least one selected), an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms (interrupted by one or more oxygen atoms, and / or one or more Optionally substituted with a hydroxyl group), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, a benzoyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, an —OR 10 group, -SR 11 groups, and, -NR 12 may be substituted by at least one selected from the group consisting of R 13 groups), the alkoxycarbonyl group (one or more oxygen atoms of 2 to 12 carbon atoms Interruption, and / or may be substituted by one or more hydroxyl groups), a phenoxycarbonyl group (an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, -OR 10 groups, and, -NR 12 Optionally substituted by at least one selected from the group consisting of R 13 groups), —CONR 12 R 13 group, —CN group, —NO 2 group, haloalkyl group having 1 to 4 carbon atoms, carbon number 1 -S (O) m -alkyl group having 6 to 6, -S (O) m -aryl group having 6 to 12 carbon atoms (which may be substituted with an alkyl group having 1 to 12 carbon atoms), 1 to carbon atoms 6 —SO 2 O-alkyl group, 6 to 10 carbon atoms —SO 2 O-aryl group, or diphenylphosphinoyl group, and m is 1 or 2.
    R 4 and R 7 are each independently a reactive functional group, a group having a hydrogen bonding functional group, a hydrogen atom, a carboalkoxyalkyl group having 3 to 20 carbon atoms (interrupted by one or more oxygen atoms, and / Or optionally substituted with one or more hydroxyl groups), a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (—OR 10 group, —SR 11 group, and A benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or an alkoxycarbonyl group having 2 to 12 carbon atoms, which may be substituted with at least one selected from the group consisting of —NR 12 R 13 groups) (interrupted by one or more oxygen atoms, and / or may be substituted by one or more hydroxyl groups), a phenoxycarbonyl group, -OR 0 group, -SR 11 group, -SOR 11 group, -SO 2 R 11 group, or, -NR 12 R 13 group (herein, 10 group -OR, -SR 11 groups, and, -NR 12 R 13 group May form a 5-membered or 6-membered ring with R 10 , R 11 , R 12 , and / or R 13 with one of the substituents of the phenyl ring or the carbon atom of the phenyl ring. ). However, at least one of R 4 and R 7 is a reactive functional group.
    R 5 , R 6 , R 8 , and R 9 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group (—OR 10 group, — SR 11 group, or optionally substituted by —NR 12 R 13 group), benzyl group, benzoyl group, alkanoyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms (one or more Optionally interrupted by an oxygen atom and / or substituted by one or more hydroxyl groups), a phenoxycarbonyl group, a —OR 10 group, a —SR 11 group, a —SOR 11 group, a —SO 2 R 11 group, or a -NR 12 R 13 groups, 10 groups -OR, -SR 11 groups, and, -NR 12 R 13 groups, the substituent or the phenyl ring with a phenyl ring And one atom, R 10, R 11, R 12, and / or may form a 5- or 6-membered ring via the R 13.
    R 10 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 6 carbon atoms (—OH group, —SH group, —CN group, alkoxy group having 1 to 4 carbon atoms, 3 to 3 carbon atoms). 6 alkeneoxy groups, —OCH 2 CH 2 CN groups, —OCH 2 CH 2 (CO) O-alkyl groups having 4 to 7 carbon atoms, —O (CO) -alkyl groups having 2 to 5 carbon atoms, —O (CO) -phenyl group,-(CO) OH group, or a-(CO) O-alkyl group having 2 to 5 carbon atoms), an alkyl group having 2 to 6 carbon atoms (one or more Interrupted by an oxygen atom), — (CH 2 CH 2 O) n H group, alkanoyl group having 2 to 8 carbon atoms, alkenyl group having 3 to 12 carbon atoms, alkenoyl group having 3 to 6 carbon atoms, cyclohexyl group , Phenyl group (halogen atom, alkyl group having 1 to 12 carbon atoms, May be substituted with an alkoxy group having 1 to 4 carbon atoms), a phenylalkyl group having 7 to 9 carbon atoms, -Si (alkyl having 1 to 8 carbon atoms) r (phenyl) 3-r groups, or Or any one of groups represented by the following formula (4). n is 1 to 20, and r is 1 to 3.
    R 11 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, a cyclohexyl group, an alkyl group having 2 to 6 carbon atoms (—OH group, —SH group, —CN group, carbon C 1-4 alkoxy group, C 3-6 alkeneoxy group, —OCH 2 CH 2 CN group, C 4-7 —OCH 2 CH 2 (CO) O-alkyl group, C 2-5 -O (CO) -alkyl group, -O (CO) -phenyl group,-(CO) OH group, or-(CO) O-alkyl group having 2 to 5 carbon atoms), carbon An alkyl group of 2 to 12 (interrupted by one or more oxygen or sulfur atoms), a phenyl group (a halogen atom, an alkyl group of 1 to 12 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms) Which may be substituted), Niruarukiru group, or any one of groups represented by the following formula (5).
    R 12 and R 13 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, or an alkyl group having 3 to 5 carbon atoms. An alkenyl group, a cycloalkyl group having 5 to 12 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, a phenyl group (substituted by an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 4 carbon atoms), An alkanoyl group having 2 to 3 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, a benzoyl group, or an alkylene group having 2 to 6 carbon atoms in which R 12 and R 13 form one group (oxygen atom or —NR 10 -Interrupted by a group and / or substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkanoyloxy group having 2 to 4 carbon atoms, or a benzoyloxy group It is also may). When R 12 is a hydrogen atom, R 13 may be a group represented by the following formula (6).
    Figure JPOXMLDOC01-appb-C000002
     In formula (4), R 3 and R 4 are the same as those in formula (3). M 1 is a bond or an alkyleneoxy group having 1 to 12 carbon atoms (which may be interrupted by 1 to 5 oxygen atoms, sulfur atoms, and / or —NR 12 — groups).
    Figure JPOXMLDOC01-appb-C000003
     In formula (5), R 3 and R 4 may be the same as those in formula (3). M 2 is a bond or an alkylene-S— group having 1 to 12 carbon atoms (which may be interrupted by 1 to 5 oxygen atoms, sulfur atoms and / or —NR 12 — groups). is there.
    Figure JPOXMLDOC01-appb-C000004
     In formula (6), R 3 and R 4 are the same as those in formula (3). M 3 represents a bond, a piperazino group, or an alkylene-NH— group having 1 to 12 carbon atoms (even if interrupted by 1 to 5 oxygen atoms, sulfur atoms, and / or —NR 12 — groups. Good).
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017040763A (en) * 2015-08-19 2017-02-23 積水化学工業株式会社 Sealant for display element
JP2017044969A (en) * 2015-08-28 2017-03-02 積水化学工業株式会社 Sealing agent for display element
WO2022048699A1 (en) * 2019-12-12 2022-03-10 Heliatek Gmbh Coating for an optoelectronic component, method for producing such a coating, and optoelectronic component comprising such a coating
WO2024090339A1 (en) * 2022-10-25 2024-05-02 デンカ株式会社 Photocurable resin composition for display device, and display device

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002285156A (en) * 2001-03-26 2002-10-03 Sharp Corp Liquid crystal display cell, agent for sealing liquid crystal injection opening and liquid crystal composition
JP2004107450A (en) * 2002-09-17 2004-04-08 Sekisui Chem Co Ltd Photocurable resin for sealing agent, liquid-crystal display element or organic electroluminescent element
JP2005015758A (en) * 2003-06-04 2005-01-20 Sekisui Chem Co Ltd Curable resin composition, sealing agent for liquid crystal display element, encapsulating agent for liquid crystal display element, vertical conduction material for liquid crystal display element, and liquid crystal display element
WO2006027982A1 (en) * 2004-09-06 2006-03-16 Nippon Kayaku Kabushiki Kaisha Liquid crystal sealing material and liquid crystal display cell using same
JP2007065349A (en) * 2005-08-31 2007-03-15 Sekisui Chem Co Ltd Liquid crystal injection hole sealing agent and liquid crystal cell
JP2007310317A (en) * 2006-05-22 2007-11-29 Fujifilm Corp Photopolymerization composition, color filter, and manufacturing method therefor
WO2012132558A1 (en) * 2011-03-25 2012-10-04 株式会社Adeka Oxime ester compound and photoinitiator containing said compound
JP5337293B1 (en) * 2012-11-13 2013-11-06 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002285156A (en) * 2001-03-26 2002-10-03 Sharp Corp Liquid crystal display cell, agent for sealing liquid crystal injection opening and liquid crystal composition
JP2004107450A (en) * 2002-09-17 2004-04-08 Sekisui Chem Co Ltd Photocurable resin for sealing agent, liquid-crystal display element or organic electroluminescent element
JP2005015758A (en) * 2003-06-04 2005-01-20 Sekisui Chem Co Ltd Curable resin composition, sealing agent for liquid crystal display element, encapsulating agent for liquid crystal display element, vertical conduction material for liquid crystal display element, and liquid crystal display element
WO2006027982A1 (en) * 2004-09-06 2006-03-16 Nippon Kayaku Kabushiki Kaisha Liquid crystal sealing material and liquid crystal display cell using same
JP2007065349A (en) * 2005-08-31 2007-03-15 Sekisui Chem Co Ltd Liquid crystal injection hole sealing agent and liquid crystal cell
JP2007310317A (en) * 2006-05-22 2007-11-29 Fujifilm Corp Photopolymerization composition, color filter, and manufacturing method therefor
WO2012132558A1 (en) * 2011-03-25 2012-10-04 株式会社Adeka Oxime ester compound and photoinitiator containing said compound
JP5337293B1 (en) * 2012-11-13 2013-11-06 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017040763A (en) * 2015-08-19 2017-02-23 積水化学工業株式会社 Sealant for display element
JP2017044969A (en) * 2015-08-28 2017-03-02 積水化学工業株式会社 Sealing agent for display element
WO2022048699A1 (en) * 2019-12-12 2022-03-10 Heliatek Gmbh Coating for an optoelectronic component, method for producing such a coating, and optoelectronic component comprising such a coating
WO2024090339A1 (en) * 2022-10-25 2024-05-02 デンカ株式会社 Photocurable resin composition for display device, and display device

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