WO2016182007A1 - Polymerizable composition containing zirconium oxide particles and (meth)acrylate, and method for producing same - Google Patents

Polymerizable composition containing zirconium oxide particles and (meth)acrylate, and method for producing same Download PDF

Info

Publication number
WO2016182007A1
WO2016182007A1 PCT/JP2016/064075 JP2016064075W WO2016182007A1 WO 2016182007 A1 WO2016182007 A1 WO 2016182007A1 JP 2016064075 W JP2016064075 W JP 2016064075W WO 2016182007 A1 WO2016182007 A1 WO 2016182007A1
Authority
WO
WIPO (PCT)
Prior art keywords
zirconium oxide
oxide particles
meth
weight
polymerizable composition
Prior art date
Application number
PCT/JP2016/064075
Other languages
French (fr)
Japanese (ja)
Inventor
敦樹 寺部
木村　真一
育実 加藤
Original Assignee
レジノカラー工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by レジノカラー工業株式会社 filed Critical レジノカラー工業株式会社
Publication of WO2016182007A1 publication Critical patent/WO2016182007A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials

Definitions

  • the present invention relates to a polymerizable composition containing zirconium oxide particles and (meth) acrylates and a method for producing the same.
  • the present invention is a polymerizable composition having high transparency, high refractive index, and high fluidity containing zirconium oxide particles and (meth) acrylates, and is produced by light or heat in the presence of a polymerization initiator.
  • the present invention relates to a polymerizable composition that gives a cured product having high transparency and a high refractive index, and a method for producing the same.
  • a plastic substrate such as a liquid crystal display (LCD), a resin material for sealing a semiconductor element in a light emitting diode (LED), a transparent resin material or an adhesive for an optical material such as an optical lens, etc.
  • Various polymerizable compositions having high transparency and high refractive index obtained by dispersing various zirconium oxide particles in a dispersion medium composed of (meth) acrylates have been proposed and put into practical use.
  • the polymerizable composition is applied on an appropriate base material or injected into a molding die according to the use, and then heated or irradiated with light such as ultraviolet rays, and the above ( By polymerizing and curing (meth) acrylates, it is possible to obtain a resin film or a resin molded body having high transparency and a high refractive index.
  • the zirconium oxide particles have a hydroxy group on the surface and are inherently hydrophilic, when dispersed in an organic solvent or (meth) acrylates, the zirconium oxide particles are sufficient for the organic solvent or (meth) acrylate. In the absence of such affinity, the zirconium oxide particles can easily agglomerate, the resulting mixture can become cloudy, and sometimes thicken significantly, even losing fluidity.
  • the zirconium oxide particles are usually surface-treated so as to have an affinity for organic solvents and (meth) acrylates and dispersed in organic solvents and (meth) acrylates.
  • zirconium oxide particles are surface-treated with an organic acid, the hydroxyl groups on the surface of the zirconium oxide particles and the organic acid are hydrogen-bonded, and the organic acid is adsorbed on the surface of the zirconium oxide particles. It has been proposed to disperse the oxidized zirconium particles in an organic solvent or (meth) acrylate to obtain a polymerizable composition containing the zirconium oxide particles (see Patent Document 1).
  • a method of surface-treating zirconium oxide particles with a silane coupling agent is also well known.
  • a polymerizable composition containing zirconium oxide particles by adding a silane coupling agent to an organic solvent dispersion of zirconium oxide particles, surface-treating the zirconium oxide particles, removing the dispersion medium, and then adding (meth) acrylates has been proposed to obtain a product (see Patent Document 2).
  • the present inventors have combined a predetermined ratio of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant under the above-described circumstances of the polymerizable composition containing zirconium oxide particles and (meth) acrylates.
  • Is used as a dispersant and is used in a predetermined ratio with respect to the zirconium oxide particles, so that the (meth) acrylates as a dispersion medium contain zirconium oxide particles at a high concentration as a dispersoid and have a high refractive index.
  • a polymerizable composition having high transparency and high fluidity can be obtained, and according to a preferred embodiment, by using a small amount of the dispersant, zirconium oxide particles having an average particle diameter of 10 nm or less can be obtained at a high concentration. It is found that a polymerizable composition having high transparency, high fluidity and high refractive index can be obtained while including Te in which the present invention has been completed.
  • the present invention preferably contains zirconium oxide particles as a dispersoid in (meth) acrylates as a dispersion medium, preferably in a high concentration, and thus has high transparency and high fluidity while having a high refractive index.
  • An object of the present invention is to provide a polymerizable composition. According to a preferred embodiment, the average particle size is 10 nm or less, and particularly according to a preferred embodiment, zirconium oxide particles having an average particle size of 1 to 10 nm are contained at a high concentration.
  • An object of the present invention is to provide a polymerizable composition having high transparency, high fluidity and high refractive index. Furthermore, an object of this invention is to provide the manufacturing method which can obtain such a polymeric composition easily.
  • a polymerizable composition comprising (meth) acrylates
  • the dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anion surfactant, and in the dispersant, the weight of the silane coupling agent relative to the polyoxyethylene alkyl ether phosphate anion surfactant
  • a polymerizable composition is provided having a ratio in the range of 85/15 to 30/70.
  • the polymerizable composition contains zirconium oxide particles, a dispersant, and (meth) acrylates as essential components, and other components in the range of 10% by weight or less, preferably in the range of 5% by weight or less. And all ingredients make up 100% by weight.
  • the polymerizable composition is most preferably composed of zirconium oxide particles, a dispersant, and residual (meth) acrylates, and these components constitute 100% by weight in total.
  • the zirconium oxide particles usually have an average particle size of 100 nm or less, and preferably in the range of 1 to 10 nm.
  • the polymerizable composition according to the present invention preferably contains the dispersant in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the zirconium oxide particles.
  • the manufacturing method of the said polymeric composition is provided. That is, according to the present invention, (A) Add (b) a dispersant and (c) (meth) acrylates to an organic solvent dispersion of zirconium oxide particles, The obtained mixture is heated with stirring to remove the organic solvent from the mixture, and a polymerizable composition containing 10 to 70% by weight of the zirconium oxide particles, a dispersant, and (meth) acrylates.
  • a manufacturing method of The dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant,
  • the weight ratio of the silane coupling agent to the polyoxyethylene alkyl ether phosphate anionic surfactant is in the range of 85/15 to 30/70,
  • a method for producing a polymerizable composition using the dispersant in the range of 8 to 40 parts by weight based on 100 parts by weight of zirconium oxide particles.
  • the average particle diameter of the zirconium oxide particles in the organic solvent dispersion of the zirconium oxide particles to be used is usually 100 nm or less, and preferably in the range of 1 to 10 nm.
  • the dispersant is used in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the zirconium oxide particles.
  • the polymerizable composition according to the present invention contains 10 to 70% by weight of zirconium oxide particles, a dispersant and (meth) acrylates, and the zirconium oxide particles preferably have an average particle diameter of 100 nm or less, particularly preferably 1 It is in the range of ⁇ 10 nm and has high transparency and high fluidity while having a high refractive index.
  • it contains fine zirconium oxide particles having an average particle diameter of 1 to 10 nm in a concentration of 30% by weight or more, has a high refractive index, and has high transparency and high fluidity. And can be suitably used as transparent resin materials and adhesives for various optical materials.
  • the zirconium oxide particles are fine or the concentration of the zirconium oxide particles is high, the above-described high transparency can be achieved without aggregation, white turbidity, gelation, etc. of the zirconium oxide particles.
  • a polymerizable composition having a high refractive index and high fluidity can be obtained easily and stably.
  • the polymerizable composition according to the present invention comprises: (A) 10 to 70% by weight of zirconium oxide particles, (B) 8 to 40 parts by weight of a dispersant with respect to 100 parts by weight of the zirconium oxide particles, (C) a polymerizable composition comprising (meth) acrylates,
  • the dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anion surfactant, and in the dispersant, the weight of the silane coupling agent relative to the polyoxyethylene alkyl ether phosphate anion surfactant The ratio is in the range of 85/15 to 30/70.
  • the average particle size of the zirconium oxide particles is usually 100 nm or less, preferably 10 nm or less, more preferably in the range of 1 to 10 nm, and most preferably It is in the range of 1 to 5 nm.
  • the average particle diameter of the zirconium oxide particles in the polymerizable composition is a value obtained by diluting the polymerizable composition and measuring the obtained dilution by a dynamic light scattering method.
  • the average particle diameter of the zirconium oxide particles in the organic solvent dispersion of zirconium oxide particles used in the production of the polymerizable composition according to the present invention is also dynamic light scattering for the organic solvent dispersion of zirconium oxide particles. It is a value measured by the method.
  • the zirconium oxide particles may contain a rare earth element such as yttrium as a stabilizing element in addition to aluminum, magnesium and titanium.
  • the zirconium oxide particles may be obtained by neutralizing a zirconium salt with an alkali in an appropriate solvent.
  • zirconium oxide particles having an average particle diameter of 10 nm or less can be obtained.
  • the zirconium oxide particles may be produced by a so-called top-down method. That is, coarse zirconium oxide particles may be mechanically pulverized to have an average particle diameter of 100 nm or less.
  • the polymerizable composition according to the present invention contains a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate ester anionic surfactant as a dispersing agent together with zirconium oxide particles, and in this dispersing agent, the silane coupling agent Of the polyoxyethylene alkyl ether phosphate anion surfactant, ie, the silane coupling agent / polyoxyethylene alkyl ether phosphate anion surfactant weight ratio is in the range of 85/15 to 30/70.
  • the ratio of such a dispersant to 100 parts by weight of the zirconium oxide particles is 8 to 40 parts by weight.
  • Range preferably in the range of 10 to 30 parts by weight, More preferably, by including in the range of 10 to 20 parts by weight, in the (meth) acrylates in which the zirconium oxide particles are a dispersion medium, they are finely and stably dispersed without causing white turbidity, aggregation or gelation.
  • the polymerizable composition has high transparency and high fluidity.
  • the polymerizable composition according to the present invention contains zirconium oxide particles in the range of 10 to 70% by weight.
  • the proportion of zirconium oxide particles in the polymerizable composition is less than 10% by weight, it is difficult to obtain a polymerizable composition having a high refractive index.
  • the proportion of the zirconium oxide particles in the polymerizable composition is more than 70% by weight, not only the stability of the polymerizable composition is impaired, but also the fluidity is lowered, and the required film or molded product can be obtained. It becomes difficult to obtain.
  • the lower limit value of the zirconium oxide particle concentration is 10% by weight, preferably 20% by weight, more preferably 25% by weight, particularly preferably. Is 30% by weight.
  • the upper limit value of the zirconium oxide particle concentration is 70% by weight, preferably 65% by weight, more preferably 60% by weight, as described above. Particularly preferred is 55% by weight.
  • the polymerizable composition according to the present invention preferably contains the zirconium oxide particles in a high concentration in this way, and yet the zirconium oxide particles do not aggregate, become cloudy, or gel in (meth) acrylates. It is stably dispersed and has high transparency and high fluidity.
  • the concentration of the zirconium oxide particles in the polymerizable composition is preferably in the range of 20 to 65% by weight, considering its stability, transparency, fluidity and refractive index. More preferably, it is in the range of 25 to 60% by weight, and most preferably in the range of 30 to 55% by weight.
  • the silane coupling agent used in the present invention is usually represented by the following general formula (I) R n —Si—X 4-n (I) (In the formula, R represents a non-reactive group or a group containing a reactive functional group, X represents a hydrolyzable group or a hydroxy group, and n is 1, 2 or 3.) It is represented by
  • non-reactive group examples include an alkyl group, a cycloalkyl group, a halogenated alkyl group, a phenyl group, and an alkylphenyl group.
  • group containing the reactive functional group examples include an amino group. , Epoxy group, vinyl group, mercapto group, halogen atom, (meth) acryloyl group and the like.
  • non-reactive silane coupling agents having non-reactive groups include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane.
  • reactive silane coupling agents having a group containing a reactive functional group include, for example, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane.
  • a silane coupling agent having a high refractive index for example, 1.45 or more is used.
  • the silane coupling agent having such a high refractive index include p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis (triethoxy And silylpropyl) tetrasulfide.
  • silane coupling agents are used in combination of two or more as required.
  • polyoxyethylene alkyl ether phosphate anionic surfactant used in the present invention is preferably the following general formula (II)
  • R is an alkyl or alkenyl group having 4 to 18 carbon atoms
  • M is a hydrogen atom or metal ion, ammonium ion or organic base ion
  • n is a number in the range of 1 to 20, k is 1 or 2.
  • the metal ion is preferably an alkali metal ion such as sodium ion or potassium ion, or an alkaline earth metal ion such as magnesium ion, and the organic base ion includes, for example, an alkanolamine ion such as triethanolamine ion. It is an amine ion.
  • polyoxyethylene alkyl ether phosphate anionic surfactants examples include phosphanol RA-600, ML-220, ML-240, RD-510Y, RS available from Toho Chemical Industry Co., Ltd. -410, RS-610, RS-710 and the like.
  • the polymerizable composition according to the present invention includes a combination of the silane coupling agent and the polyoxyethylene alkyl ether phosphate anionic surfactant as a dispersant for zirconium oxide particles, and in this dispersant, the silane coupling agent
  • the weight ratio of the agent / polyoxyethylene alkyl ether phosphate anionic surfactant is in the range of 85/15 to 30/70, preferably in the range of 75/25 to 40/60, and such dispersion
  • the agent is contained in a ratio of 8 to 40 parts by weight, preferably 10 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the zirconium oxide particles. Includes (meth) acrylates.
  • the above (meth) acrylates means methacrylates and / or acrylates having a polymerization property by light or heat.
  • Examples of such (meth) acrylates include monofunctional (meth) acrylates having one (meth) acryloyl group in the molecule and polyfunctional (meta) having two or more (meth) acryloyl groups in the molecule. ) Acrylates.
  • Examples of the monofunctional methacrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth).
  • Polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di ( (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexa Methylene di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Over DOO, dipentaerythritol hexa (meth) acrylate and
  • the polymerizable composition according to the present invention contains such (meth) acrylates together with the above-described zirconium oxide particles, and when thermally polymerized, it is heated in the presence of a thermal polymerization initiator, and when photopolymerized.
  • the monofunctional and / or polyfunctional (meth) acrylates are polymerized by irradiating light, for example, ultraviolet rays or electron beams in the presence of a photopolymerization initiator, and thus have high transparency and high refractive index. Heat or photocured product is provided.
  • the cured product refers to a polymer of monofunctional (meth) acrylates containing zirconium oxide when the polymerizable composition according to the present invention contains only monofunctional (meth) acrylates as (meth) acrylates.
  • the polymerizable composition according to the present invention contains polyfunctional (meth) acrylates and (monofunctional (meth) acrylates) as (meth) acrylates, polyfunctional (meta) containing zirconium oxide.
  • Solidified product (usually insoluble and infusible) having a crosslinked structure formed by (co) polymerization of acrylates (and monofunctional (meth) acrylates).
  • the polymerizable composition according to the present invention contains zirconium oxide particles, a dispersant, and (meth) acrylates as essential components, and the other components in the range of 10% by weight or less, preferably 5% by weight.
  • the total amount of zirconium oxide particles, dispersant, (meth) acrylates and other components constitutes 100% by weight.
  • the polymerizable composition according to the present invention comprises zirconium oxide particles, a dispersant, and residual (meth) acrylates, in which case these components constitute 100% by weight.
  • the amount of (meth) acrylates is preferably in the range of 10 to 89% by weight, preferably in the range of 15 to 75% by weight, more preferably in the range of 20 to It is in the range of 70% by weight, and particularly preferably in the range of 25 to 65% by weight.
  • the polymerizable composition preferably comprises 10 to 70% by weight of zirconium oxide particles, a dispersant and 10 to 89% by weight of (meth) acrylates, more preferably zirconium oxide particles 20 Containing 65 to 65% by weight of a dispersant and 15 to 75% by weight of (meth) acrylates, more preferably 25 to 60% by weight of zirconium oxide particles, 20 to 70% by weight of a dispersant and (meth) acrylates, Most preferably, it contains 30 to 55% by weight of zirconium oxide particles, a dispersant and 25 to 65% by weight of (meth) acrylates.
  • the dispersant is in the range of 8 to 40 parts by weight, preferably in the range of 10 to 30 parts by weight, and more preferably in the range of 10 to 20 parts per 100 parts by weight of the zirconium oxide particles.
  • the range is parts by weight.
  • the polymerizable composition according to the present invention has not only excellent stability and transparency, but also low viscosity and excellent fluidity even when zirconium oxide particles are contained in a high concentration.
  • the viscosity of the polymerizable composition according to the present invention is in the range of 100 to 40000 mPa ⁇ s at 25 ° C., preferably in the range of 150 to 30000 mPa ⁇ s, depending on the concentration of the zirconium oxide particles.
  • the polymerizable composition according to the present invention usually has a refractive index in the range of 1.55 to 1.75, although it depends on the refractive index of the silane coupling agent and (meth) acrylate used. According to the present invention, a cured product having a refractive index of 1.65 or more is obtained according to a more preferable embodiment.
  • the polymerizable composition according to the present invention can be suitably used as an optical resin material having high transparency and a high refractive index.
  • the above-described polymerizable composition according to the present invention can be obtained by the following production method according to the present invention.
  • the method for producing a polymerizable composition according to the present invention includes: (A) Add (b) a dispersant and (c) (meth) acrylates to an organic solvent dispersion of zirconium oxide particles, The obtained mixture is heated under stirring to remove the organic solvent from the mixture, and a polymerizable composition containing 10 to 70% by weight of zirconium oxide particles, a dispersant, and polymerizable (meth) acrylates.
  • the dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant,
  • the weight ratio of the silane coupling agent to the polyoxyethylene alkyl ether phosphate anionic surfactant is in the range of 85/15 to 30/70,
  • the dispersant is used in the range of 8 to 40 parts by weight with respect to 100 parts by weight of the zirconium oxide particles.
  • the organic solvent dispersion of zirconium oxide particles used in the present invention preferably has an average particle diameter of zirconium oxide particles of 100 nm or less, preferably 10 nm or less, more preferably in the range of 1 to 10 nm. Most preferably, it is in the range of 1 to 5 nm.
  • the dispersion medium in the organic solvent dispersion of zirconium oxide particles preferably has a boiling point that can be removed by heating under normal pressure, for example, a boiling point of about 60 to 200 ° C.
  • a boiling point for example, methanol, methyl ethyl ketone, toluene and the like are typical examples.
  • a dispersion of fine zirconium oxide particles having an average particle diameter of 10 nm or less is often initially produced as a dispersion using water as a dispersion medium.
  • water which is the dispersion medium of the zirconium oxide particle dispersion in which such a dispersion medium is water, is replaced with a water-miscible or hydrophilic organic solvent, and the water-miscibility is further changed as necessary.
  • it is often produced by replacing a hydrophilic organic solvent with a hydrophobic or lipophilic organic solvent.
  • a methanol dispersion produced by replacing water, which is a dispersion medium of a zirconium oxide particle dispersion, in which the dispersion medium is water, with a water-miscible organic solvent, for example, methanol can be preferably used.
  • a dispersion obtained by replacing this methanol with methyl ethyl ketone or toluene can also be preferably used.
  • methyl ethyl ketone is more lipophilic than methanol, since both hydrophilicity and lipophilicity are relative, in the present invention, methyl ethyl ketone is also included in the hydrophilic organic solvent for convenience.
  • the organic solvent dispersion of zirconium oxide particles used may be a top-down type as described above. That is, coarse zirconium oxide particles may be pulverized and dispersed as fine particles in an appropriate organic solvent.
  • the organic solvent that is a dispersion medium in the organic solvent dispersion of zirconium oxide particles is not particularly limited, but in the case of the water-miscible or hydrophilic organic solvent, such water is used.
  • the miscible organic solvent is not particularly limited, and examples thereof include aliphatic alcohols such as methanol, ethanol, 2-propanol and t-butyl alcohol, aliphatic carboxylic acid esters such as ethyl acetate and methyl formate, acetone , Aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, polyhydric alcohols such as ethylene glycol and glycerin, and mixtures of two or more thereof, particularly preferably methanol, methyl ethyl ketone, methyl isobutyl ketone or these It is a mixture of
  • an organic solvent dispersion of zirconium oxide particles is obtained by, for example, converting the hydrophilic organic solvent into a lipophilic organic solvent by a distillation substitution method or an ultrafiltration substitution method that is already well known.
  • An organic solvent dispersion of zirconium oxide particles substituted with may be used.
  • the organic solvent dispersion of zirconium oxide particles is, for example, ketones such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, butyl acetate, propylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate.
  • ketones such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, butyl acetate, propylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate.
  • Esters such as methyl acrylate and methyl methacrylate, ethers such as dibutyl ether and dioxane, hydrocarbons such as n-hexane, cyclohexane, toluene, xylene and solvent naphtha, halogens such as carbon tetrachloride, dichloroethane and chlorobenzene
  • carboxylic acid amides such as carbohydrides, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
  • the dispersion of zirconium oxide particles in the organic solvent is dispersed in the organic solvent dispersion of zirconium oxide particles of polymerizable (meth) acrylates.
  • the organic dispersion is miscible with methanol and more lipophilic than methanol.
  • a solvent such as methyl ethyl ketone may be added.
  • the organic solvent dispersion of the zirconium oxide particles described above includes various additives such as acids, bases, silane coupling agents, surfactants, and the like from the beginning, depending on the production method. May be. However, when the organic solvent dispersion of zirconium oxide particles used in the present invention contains these additives from the beginning as described above, these additives are not included in the dispersant in the present invention. That is, these additives are not included in the calculation as a dispersant in the present invention.
  • a combination of a silane coupling agent and the polyoxyethylene alkyl ether phosphate ester anionic surfactant is used as a dispersant in the organic solvent dispersion of the zirconium oxide particles described above.
  • the weight ratio of silane coupling agent / polyoxyethylene alkyl ether phosphate ester anionic surfactant is in the range of 85/15 to 30/70, and such a dispersant is added to the organic particles of zirconium oxide particles.
  • silane coupling agent and polyoxyethylene alkyl ether phosphate ester anionic surfactant are as described above.
  • a silane coupling agent having a high refractive index is preferably used.
  • the (meth) acrylates used for the production of the polymerizable composition according to the present invention are also as described above, and monofunctional (meth) acrylates and / or polyfunctional (meth) acrylates are used.
  • the silane coupling agent described above as a dispersing agent together with (meth) acrylates in an organic solvent dispersion of zirconium oxide particles having an average particle diameter of 100 nm or less, preferably 10 nm or less is thus obtained.
  • a combination of polyoxyethylene alkyl ether phosphate ester anionic surfactant in a predetermined ratio with respect to the zirconium oxide particles, and heating the resulting mixture to remove the organic solvent from the mixture The above-mentioned zirconium oxide particles can be stably dispersed in (meth) acrylates without causing cloudiness, aggregation, gelation, etc., and a polymerizable composition having high transparency and high fluidity can be obtained. .
  • a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant is added to the organic solvent dispersion of the zirconium oxide particles, and then polymerizable.
  • (Meth) acrylates are added, and the organic solvent is removed from the mixture by heating to a temperature not lower than the boiling point of the dispersion medium of the organic solvent dispersion of the zirconium oxide particles while stirring the resulting mixture.
  • the polymerizable composition according to the present invention can be obtained.
  • the temperature at which the mixture is heated to remove the organic solvent from the mixture depends on the boiling point of the organic solvent that is the dispersion medium to be used, but is usually in the range of 40 to 100 ° C., preferably 50 to 70. It is in the range of ° C. Moreover, when the said mixture is heated and the dispersion medium of the organic solvent dispersion liquid of a zirconium oxide particle is removed from a mixture, you may heat a mixture under pressure reduction as needed.
  • the polymerizable composition according to the present invention uses an organic solvent dispersion of zirconium oxide particles as a starting material in the production thereof, the resulting polymerizable composition has a range of 10% by weight or less, that is, It is permissible to contain the above organic solvent in the range of 0 to 10% by weight. That is, the polymerizable composition according to the present invention contains 10 to 70% by weight of zirconium oxide particles, the dispersant and the (meth) acrylate, and the organic solvent is in the range of 0 to 10% by weight, preferably 0 to You may contain in 5 weight% of range.
  • the polymerizable composition according to the present invention contains zirconium oxide particles in the range of 10% by weight or more, and according to a preferred embodiment, the zirconium oxide particles contain in the range of 30% by weight or more, while still containing zirconium oxide.
  • the particles are stably dispersed in the polymerizable (meth) acrylates and have high transparency and high fluidity.
  • a polymerizable composition having excellent transparency and fluidity can be obtained by using a small amount of a dispersant for the zirconium oxide particles.
  • the polymerizable composition thus obtained usually has a refractive index in the range of 1.55 to 1.75, depending on the refractive index of the silane coupling agent used, as described above.
  • a cured product having a refractive index of 1.60 or more, and more preferably 1.65 or more is provided.
  • the polymerizable composition according to the present invention is mixed with an appropriate amount of a photopolymerization initiator that generates radicals by irradiation with active energy rays such as ultraviolet rays and electron beams, or a thermal polymerization initiator that generates radicals by heating, Since the (meth) acrylates are polymerized by the action of such a polymerization initiator, a photopolymerizable composition or a thermally polymerizable composition is provided, respectively.
  • a photopolymerization initiator that generates radicals by irradiation with active energy rays such as ultraviolet rays and electron beams
  • a thermal polymerization initiator that generates radicals by heating
  • photopolymerization initiator examples include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphide. A fin oxide etc. can be mentioned. These photopolymerization initiators are used alone or in admixture of two or more.
  • thermal polymerization initiator examples include hydroperoxides such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t- Dialkyl peroxides such as butyl peroxide and dicumyl peroxide, peroxy esters such as t-butyl peroxybenzoate and t-butyl peroxy (2-ethylhexanoate), and diacyl peroxides such as benzoyl peroxide And peroxides such as diisopropyl peroxycarbonate, peroxides such as peroxyketal and ketone peroxide. These polymerization initiators are also used alone or in admixture of two or more.
  • part means “part by weight” unless otherwise specified.
  • the following were used as the methanol dispersion of zirconium oxide, the silane coupling agent, the polyoxyethylene alkyl ether phosphate ester anionic surfactant, and the (meth) acrylates.
  • Zirconium oxide particle methanol dispersion Zirconium oxide particle methanol dispersion manufactured by Sakai Chemical Industry Co., Ltd., SZR-M, zirconium oxide particle concentration 30% by weight, average particle diameter of zirconium oxide by dynamic light scattering method 3 nm
  • Silane coupling agent A P-styryltrimethoxysilane, KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Silane coupling agent B Phenyltrimethoxysilane, KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd. Polyoxyethylene alkyl ether phosphate anionic surfactant A Toho Chemical Co., Ltd.
  • Phosphanol, RS-710 Polyoxyethylene alkyl ether phosphate anionic surfactant B Phosphanol manufactured by Toho Chemical Industry Co., Ltd., RA-600 (Meth) acrylate Nippon Kayaku Co., Ltd. o-phenylphenol monoethoxy acrylate, KAYARAD OPP-1
  • Example 1 Zirconium oxide methanol dispersion (Zircon Chemical Industry Co., Ltd. Zirconium oxide methanol dispersion, SZR-M, zirconium oxide concentration 30% by weight, average particle diameter of zirconium oxide by dynamic light scattering method 3 nm, hereinafter the same) 100 parts P-styryltrimethoxysilane (p-styryltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1403, hereinafter the same) 4.20 parts, polyoxyethylene alkyl ether phosphate anionic surfactant (Toho Chemical) 1.05 part of phosphanol RS-710 manufactured by Kogyo Co., Ltd.
  • P-styryltrimethoxysilane p-styryltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1403, hereinafter the same
  • o-phenylphenol monoethoxy acrylate (KAYARAD OPP-1 manufactured by Nippon Kayaku Co., Ltd.) were added to the mixture. Prepared. While stirring the mixture, the mixture was heated to a temperature of 55 to 70 ° C. to remove methanol, and the composition was 50.0 parts of zirconium oxide, 7.00 parts of p-styryltrimethoxysilane, as shown in Table 1. A polymerizable composition comprising 1.75 parts of a polyoxyethylene alkyl ether phosphate anionic surfactant and 41.25 parts of o-phenylphenol monoethoxy acrylate was obtained.
  • Examples 2 to 19 Mixtures were prepared with the compositions shown in Tables 1 to 3, and polymerizable compositions having the compositions shown in Tables 1 to 3 were obtained in the same manner as in Example 1.
  • Comparative Example 1 A mixture is prepared by adding 4.50 parts of p-styryltrimethoxysilane and 25.50 parts of o-phenylphenol monoethoxyacrylate to 100 parts of zirconium oxide methanol dispersion, and stirring the mixture at a temperature of 55-70. When heated to 0 ° C., the zirconium oxide particles aggregated, the resulting mixture became cloudy and the viscosity increased. As a result, the obtained polymerizable composition did not have fluidity.
  • Comparative Examples 2-4 A mixture was prepared with the composition shown in Table 3, and a polymerizable composition having the composition shown in Table 3 was obtained in the same manner as in Example 1.
  • Tables 1 to 3 show the transparency, fluidity, viscosity, and average particle diameter determined by the dynamic light scattering method, together with the component composition (parts) of the polymerizable compositions obtained in Examples 1 to 19 above. Some polymerizable compositions exhibit a refractive index. Table 3 shows the composition (parts) of the polymerizable compositions obtained in Comparative Examples 1 to 4 together with the transparency, fluidity, viscosity, and average particle size by dynamic light scattering.

Abstract

According to the present invention, a polymerizable composition comprising (a) 10-70 wt% zirconium oxide particles, (b) 8-40 parts by weight of dispersant with respect to 100 parts by weight of the zirconium oxide particles, and (c) (meth)acrylate is provided, wherein the aforementioned dispersant comprises a combination of a silane coupling agent and polyoxyethylene alkyl ether phosphate ester anionic surfactant, and in the dispersant, the proportion by weight of the silane coupling agent with respect to the polyoxyethylene alkyl ether phosphate ester anionic surfactant falls within the range of 85/15 to 30/70. Also provided is a method for producing said polymerizable composition.

Description

酸化ジルコニウム粒子と（メタ）アクリレート類を含む重合性組成物とその製造方法Polymerizable composition containing zirconium oxide particles and (meth) acrylates and method for producing the same
　本発明は酸化ジルコニウム粒子と（メタ）アクリレート類を含む重合性組成物とその製造方法に関する。詳しくは、本発明は、酸化ジルコニウム粒子と（メタ）アクリレート類を含む高透明性と高屈折率と高流動性を有する重合性組成物であって、重合開始剤の存在下に光や熱によって高透明性と高屈折率を有する硬化物を与える重合性組成物とその製造方法に関する。 The present invention relates to a polymerizable composition containing zirconium oxide particles and (meth) acrylates and a method for producing the same. Specifically, the present invention is a polymerizable composition having high transparency, high refractive index, and high fluidity containing zirconium oxide particles and (meth) acrylates, and is produced by light or heat in the presence of a polymerization initiator. The present invention relates to a polymerizable composition that gives a cured product having high transparency and a high refractive index, and a method for producing the same.
　液晶ディスプレイ（ＬＣＤ）のようなプラスチック基板、発光ダイオード（ＬＥＤ）における半導体素子の封止用樹脂材料、光学レンズ等の光学材料用の透明樹脂材料や接着剤等として、近年、屈折率の高い微細な酸化ジルコニウム粒子を（メタ）アクリレート類からなる分散媒に分散させてなる高透明性と高屈折率を有する重合性組成物が種々、提案され、また、実用化されている。 In recent years, as a plastic substrate such as a liquid crystal display (LCD), a resin material for sealing a semiconductor element in a light emitting diode (LED), a transparent resin material or an adhesive for an optical material such as an optical lens, etc. Various polymerizable compositions having high transparency and high refractive index obtained by dispersing various zirconium oxide particles in a dispersion medium composed of (meth) acrylates have been proposed and put into practical use.
　上記重合性組成物は、これを用途に応じて、適宜の基材上に塗布し、又は成形用の金型内に注入した後、加熱し、又は紫外線等の光を照射して、上記（メタ）アクリレート類を重合、硬化させることによって、高透明性と高屈折率を有する樹脂被膜や樹脂成形体を得ることができる。 The polymerizable composition is applied on an appropriate base material or injected into a molding die according to the use, and then heated or irradiated with light such as ultraviolet rays, and the above ( By polymerizing and curing (meth) acrylates, it is possible to obtain a resin film or a resin molded body having high transparency and a high refractive index.
　しかし、酸化ジルコニウム粒子は、表面にヒドロキシ基を有して、本来、親水性であるので、これを有機溶媒や（メタ）アクリレート類に分散させる場合に、その有機溶媒や（メタ）アクリレートに十分な親和性をもたないときは、酸化ジルコニウム粒子が容易に凝集したり、また、得られた混合物が白濁したり、時には、著しく増粘して、流動性を失うことさえある。 However, since the zirconium oxide particles have a hydroxy group on the surface and are inherently hydrophilic, when dispersed in an organic solvent or (meth) acrylates, the zirconium oxide particles are sufficient for the organic solvent or (meth) acrylate. In the absence of such affinity, the zirconium oxide particles can easily agglomerate, the resulting mixture can become cloudy, and sometimes thicken significantly, even losing fluidity.
　そこで、酸化ジルコニウム粒子は、通常、有機溶媒や（メタ）アクリレート類に親和性を有するように表面処理して、有機溶媒や（メタ）アクリレート類に分散させることが提案されている。 Therefore, it has been proposed that the zirconium oxide particles are usually surface-treated so as to have an affinity for organic solvents and (meth) acrylates and dispersed in organic solvents and (meth) acrylates.
　例えば、酸化ジルコニウム粒子を有機酸にて表面処理して、酸化ジルコニウム粒子の表面のヒドロキシ基と有機酸を水素結合させて、有機酸を酸化ジルコニウム粒子の表面に吸着させ、このように、表面修飾した酸化ジルコニウム粒子を有機溶媒や（メタ）アクリレートに分散させて、酸化ジルコニウム粒子を含む重合性組成物を得ることが提案されている（特許文献１参照）。 For example, zirconium oxide particles are surface-treated with an organic acid, the hydroxyl groups on the surface of the zirconium oxide particles and the organic acid are hydrogen-bonded, and the organic acid is adsorbed on the surface of the zirconium oxide particles. It has been proposed to disperse the oxidized zirconium particles in an organic solvent or (meth) acrylate to obtain a polymerizable composition containing the zirconium oxide particles (see Patent Document 1).
　酸化ジルコニウム粒子をシランカップリング剤で表面処理する方法もよく知られている。例えば、酸化ジルコニウム粒子の有機溶媒分散液にシランカップリング剤を加え、酸化ジルコニウム粒子を表面処理し、分散媒を除去した後、（メタ）アクリレート類を加えて、酸化ジルコニウム粒子を含む重合性組成物を得ることが提案されている（特許文献２参照）。 A method of surface-treating zirconium oxide particles with a silane coupling agent is also well known. For example, a polymerizable composition containing zirconium oxide particles by adding a silane coupling agent to an organic solvent dispersion of zirconium oxide particles, surface-treating the zirconium oxide particles, removing the dispersion medium, and then adding (meth) acrylates. It has been proposed to obtain a product (see Patent Document 2).
　更に、シランカップリング剤と界面活性剤を併用する酸化ジルコニウム粒子の表面処理も提案されている。例えば、酸化ジルコニウム粒子を湿式粉砕攪拌機を用いて、有機溶媒中、リン酸エステル系界面活性剤とシランカップリング剤にて順次に湿式分散処理した後、これに（メタ）アクリレート類を加え、上記有機溶媒を除去して、酸化ジルコニウム粒子を含む重合性組成物を得ることが提案されている（特許文献３参照）。　　　　　　　　　　 Furthermore, surface treatment of zirconium oxide particles using a silane coupling agent and a surfactant in combination is also proposed. For example, after the zirconium oxide particles are wet-dispersed sequentially with a phosphate ester surfactant and a silane coupling agent in an organic solvent using a wet pulverization stirrer, (meth) acrylates are added thereto, and the above It has been proposed to obtain a polymerizable composition containing zirconium oxide particles by removing the organic solvent (see Patent Document 3). .
　本発明者らは、酸化ジルコニウム粒子と（メタ）アクリレート類を含む重合性組成物の上述した状況の下、シランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の所定割合の組み合わせを分散剤とし、これを酸化ジルコニウム粒子に対して所定の割合で用いることによって、分散媒である（メタ）アクリレート類中に分散質として酸化ジルコニウム粒子を高濃度で含み、高屈折率を有しながら、高透明性と高流動性を有する重合性組成物を得ることができ、好ましい態様によれば、上記分散剤を少量を用いることによって、平均粒子径１０ｎｍ以下の酸化ジルコニウム粒子を高濃度で含みながら、それでいて、高透明性と高流動性と高屈折率を有する重合性組成物を得ることができることを見出して本発明を完成したものである。 The present inventors have combined a predetermined ratio of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant under the above-described circumstances of the polymerizable composition containing zirconium oxide particles and (meth) acrylates. Is used as a dispersant, and is used in a predetermined ratio with respect to the zirconium oxide particles, so that the (meth) acrylates as a dispersion medium contain zirconium oxide particles at a high concentration as a dispersoid and have a high refractive index. However, a polymerizable composition having high transparency and high fluidity can be obtained, and according to a preferred embodiment, by using a small amount of the dispersant, zirconium oxide particles having an average particle diameter of 10 nm or less can be obtained at a high concentration. It is found that a polymerizable composition having high transparency, high fluidity and high refractive index can be obtained while including Te in which the present invention has been completed.
特開２００９－１９１１６７号公報JP 2009-191167 A 特開２０１１－２０１７４０号公報JP 2011-201740 A 特開２０１０－１８９５０６号公報JP 2010-189506 A
　従って、本発明は、分散媒である（メタ）アクリレート類中に分散質として酸化ジルコニウム粒子を好ましくは高濃度で含み、従って、高屈折率を有しながら、高透明性と高流動性を有する重合性組成物を提供することを目的とし、好ましい態様によれば、平均粒子径１０ｎｍ以下、特に、好ましい態様によれば、平均粒子径１～１０ｎｍの範囲の酸化ジルコニウム粒子を高濃度で含みながら、高透明性と高流動性と高屈折率を有する重合性組成物を提供することを目的とする。更に、本発明は、そのような重合性組成物を容易に得ることができる製造方法を提供することを目的とする。 Therefore, the present invention preferably contains zirconium oxide particles as a dispersoid in (meth) acrylates as a dispersion medium, preferably in a high concentration, and thus has high transparency and high fluidity while having a high refractive index. An object of the present invention is to provide a polymerizable composition. According to a preferred embodiment, the average particle size is 10 nm or less, and particularly according to a preferred embodiment, zirconium oxide particles having an average particle size of 1 to 10 nm are contained at a high concentration. An object of the present invention is to provide a polymerizable composition having high transparency, high fluidity and high refractive index. Furthermore, an object of this invention is to provide the manufacturing method which can obtain such a polymeric composition easily.
　本発明によれば、
（ａ）酸化ジルコニウム粒子１０～７０重量％と、
（ｂ）上記酸化ジルコニウム粒子１００重量部に対して８～４０重量部の分散剤と、
（ｃ）（メタ）アクリレート類と
を含む重合性組成物であって、
　上記分散剤がシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせからなり、上記分散剤において、シランカップリング剤のポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比が８５／１５～３０／７０の範囲にある重合性組成物が提供される。 According to the present invention,
(A) 10 to 70% by weight of zirconium oxide particles,
(B) 8 to 40 parts by weight of a dispersant with respect to 100 parts by weight of the zirconium oxide particles,
(C) a polymerizable composition comprising (meth) acrylates,
The dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anion surfactant, and in the dispersant, the weight of the silane coupling agent relative to the polyoxyethylene alkyl ether phosphate anion surfactant A polymerizable composition is provided having a ratio in the range of 85/15 to 30/70.
　本発明において、上記重合性組成物は、酸化ジルコニウム粒子と分散剤と（メタ）アクリレート類を必須成分として含み、その他の成分を１０重量％以下の範囲で、好ましくは、５重量％以下の範囲で含んでよく、すべての成分は合計で１００重量％を構成する。 In the present invention, the polymerizable composition contains zirconium oxide particles, a dispersant, and (meth) acrylates as essential components, and other components in the range of 10% by weight or less, preferably in the range of 5% by weight or less. And all ingredients make up 100% by weight.
　本発明において、上記重合性組成物は、最も好ましくは、酸化ジルコニウム粒子と分散剤と残余（メタ）アクリレート類からなり、これらの成分が合計で１００重量％を構成する。 In the present invention, the polymerizable composition is most preferably composed of zirconium oxide particles, a dispersant, and residual (meth) acrylates, and these components constitute 100% by weight in total.
　本発明による重合性組成物において、酸化ジルコニウム粒子は、通常、平均粒子径が１００ｎｍ以下であり、好ましくは、１～１０ｎｍの範囲である。 In the polymerizable composition according to the present invention, the zirconium oxide particles usually have an average particle size of 100 nm or less, and preferably in the range of 1 to 10 nm.
　本発明による重合性組成物は、好ましくは、上記分散剤を酸化ジルコニウム粒子１００重量部に対して１０～３０重量部の範囲で含む。 The polymerizable composition according to the present invention preferably contains the dispersant in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the zirconium oxide particles.
　また、本発明によれば、上記重合性組成物の製造方法が提供される。即ち、本発明によれば、
（ａ）酸化ジルコニウム粒子の有機溶媒分散液に
（ｂ）分散剤と
（ｃ）（メタ）アクリレート類を加え、
　得られた混合物を攪拌下に加熱して、この混合物から上記有機溶媒を除去して、上記酸化ジルコニウム粒子１０～７０重量％と、分散剤と、（メタ）アクリレート類とを含む重合性組成物の製造方法であって、
　上記分散剤がシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせからなり、
　上記分散剤において、シランカップリング剤のポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比が８５／１５～３０／７０の範囲にあり、
　上記分散剤を酸化ジルコニウム粒子１００重量部に対して８～４０重量部の範囲で用いる重合性組成物の製造方法が提供される。 Moreover, according to this invention, the manufacturing method of the said polymeric composition is provided. That is, according to the present invention,
(A) Add (b) a dispersant and (c) (meth) acrylates to an organic solvent dispersion of zirconium oxide particles,
The obtained mixture is heated with stirring to remove the organic solvent from the mixture, and a polymerizable composition containing 10 to 70% by weight of the zirconium oxide particles, a dispersant, and (meth) acrylates. A manufacturing method of
The dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant,
In the dispersant, the weight ratio of the silane coupling agent to the polyoxyethylene alkyl ether phosphate anionic surfactant is in the range of 85/15 to 30/70,
There is provided a method for producing a polymerizable composition using the dispersant in the range of 8 to 40 parts by weight based on 100 parts by weight of zirconium oxide particles.
　本発明の方法においては、用いる酸化ジルコニウム粒子の有機溶媒分散液における酸化ジルコニウム粒子の平均粒子径は、通常、１００ｎｍ以下であり、好ましくは、１～１０ｎｍの範囲である。 In the method of the present invention, the average particle diameter of the zirconium oxide particles in the organic solvent dispersion of the zirconium oxide particles to be used is usually 100 nm or less, and preferably in the range of 1 to 10 nm.
　また、本発明の方法においては、好ましくは、上記分散剤を上記酸化ジルコニウム粒子１００重量部に対して１０～３０重量部の範囲で用いる。 In the method of the present invention, preferably, the dispersant is used in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the zirconium oxide particles.
　本発明による重合性組成物は、酸化ジルコニウム粒子１０～７０重量％と分散剤と（メタ）アクリレート類を含み、上記酸化ジルコニウム粒子は、好ましくは、平均粒子径１００ｎｍ以下、特に、好ましくは、１～１０ｎｍの範囲であり、高屈折率を有しながら、高透明性と高流動性を有している。 The polymerizable composition according to the present invention contains 10 to 70% by weight of zirconium oxide particles, a dispersant and (meth) acrylates, and the zirconium oxide particles preferably have an average particle diameter of 100 nm or less, particularly preferably 1 It is in the range of ˜10 nm and has high transparency and high fluidity while having a high refractive index.
　特に、本発明の好ましい態様によれば、平均粒子径１～１０ｎｍの範囲の微細な酸化ジルコニウム粒子を３０重量％以上の濃度で含み、高屈折率を有しながら、高透明性と高流動性を有し、種々の光学材料用の透明樹脂材料や接着剤等として好適に用いることができる。 In particular, according to a preferred embodiment of the present invention, it contains fine zirconium oxide particles having an average particle diameter of 1 to 10 nm in a concentration of 30% by weight or more, has a high refractive index, and has high transparency and high fluidity. And can be suitably used as transparent resin materials and adhesives for various optical materials.
　また、本発明の方法によれば、酸化ジルコニウム粒子が微細であっても、また、酸化ジルコニウム粒子濃度が高くとも、酸化ジルコニウム粒子の凝集、白濁、ゲル化等なしに、上述した高透明性と高屈折率と高流動性を有する重合性組成物を容易に且つ安定して得ることができる。 Further, according to the method of the present invention, even if the zirconium oxide particles are fine or the concentration of the zirconium oxide particles is high, the above-described high transparency can be achieved without aggregation, white turbidity, gelation, etc. of the zirconium oxide particles. A polymerizable composition having a high refractive index and high fluidity can be obtained easily and stably.
　本発明による重合性組成物は、
（ａ）酸化ジルコニウム粒子１０～７０重量％と、
（ｂ）上記酸化ジルコニウム粒子１００重量部に対して８～４０重量部の分散剤と、
（ｃ）（メタ）アクリレート類と
を含む重合性組成物であって、
　上記分散剤がシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせからなり、上記分散剤において、シランカップリング剤のポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比が８５／１５～３０／７０の範囲にあるものである。 The polymerizable composition according to the present invention comprises:
(A) 10 to 70% by weight of zirconium oxide particles,
(B) 8 to 40 parts by weight of a dispersant with respect to 100 parts by weight of the zirconium oxide particles,
(C) a polymerizable composition comprising (meth) acrylates,
The dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anion surfactant, and in the dispersant, the weight of the silane coupling agent relative to the polyoxyethylene alkyl ether phosphate anion surfactant The ratio is in the range of 85/15 to 30/70.
　本発明による重合性組成物において、上記酸化ジルコニウム粒子の平均粒子径は、通常、１００ｎｍ以下であり、好ましくは、１０ｎｍ以下であり、より好ましくは、１～１０ｎｍの範囲であり、最も好ましくは、１～５ｎｍの範囲である。ここに、重合性組成物における酸化ジルコニウム粒子の平均粒子径は、重合性組成物を希釈し、得られた希釈物について動的光散乱法にて測定した値である。 In the polymerizable composition according to the present invention, the average particle size of the zirconium oxide particles is usually 100 nm or less, preferably 10 nm or less, more preferably in the range of 1 to 10 nm, and most preferably It is in the range of 1 to 5 nm. Here, the average particle diameter of the zirconium oxide particles in the polymerizable composition is a value obtained by diluting the polymerizable composition and measuring the obtained dilution by a dynamic light scattering method.
　また、後述するように、本発明による重合性組成物の製造において用いる酸化ジルコニウム粒子の有機溶媒分散液における酸化ジルコニウム粒子の平均粒子径も、上記酸化ジルコニウム粒子の有機溶媒分散液について動的光散乱法にて測定した値である。 Further, as will be described later, the average particle diameter of the zirconium oxide particles in the organic solvent dispersion of zirconium oxide particles used in the production of the polymerizable composition according to the present invention is also dynamic light scattering for the organic solvent dispersion of zirconium oxide particles. It is a value measured by the method.
　本発明による重合性組成物においては、上記酸化ジルコニウム粒子は、アルミニウム、マグネシウム、チタンのほか例えば、イットリウムのような希土類元素を安定化元素として含んでいてもよい。 In the polymerizable composition according to the present invention, the zirconium oxide particles may contain a rare earth element such as yttrium as a stabilizing element in addition to aluminum, magnesium and titanium.
　また、本発明による重合性組成物において、上記酸化ジルコニウム粒子は、適宜の溶媒中でジルコニウム塩をアルカリで中和して得られたものでもよく、このような方法によれば、好ましい態様によれば、平均粒子径１０ｎｍ以下の酸化ジルコニウム粒子を得ることができる。しかし、本発明においては、上記酸化ジルコニウム粒子は、所謂トップダウン方式によって製造されたものでもよい。即ち、粗大な酸化ジルコニウム粒子を機械的に粉砕して、平均粒子径１００ｎｍ以下としたものでもよい。 Further, in the polymerizable composition according to the present invention, the zirconium oxide particles may be obtained by neutralizing a zirconium salt with an alkali in an appropriate solvent. For example, zirconium oxide particles having an average particle diameter of 10 nm or less can be obtained. However, in the present invention, the zirconium oxide particles may be produced by a so-called top-down method. That is, coarse zirconium oxide particles may be mechanically pulverized to have an average particle diameter of 100 nm or less.
　本発明による重合性組成物においては、酸化ジルコニウム粒子と共に、分散剤としてシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせを含み、この分散剤において、上記シランカップリング剤の上記ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比、即ち、シランカップリング剤／ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤重量比は８５／１５～３０／７０の範囲であり、好ましくは、７５／２５～４０／６０の範囲であり、しかも、本発明による重合性組成物は、このような分散剤を上記酸化ジルコニウム粒子１００重量部に対する割合が８～４０重量部の範囲、好ましくは、１０～３０重量部の範囲、より好ましくは、１０～２０重量部の範囲で含むことによって、上記酸化ジルコニウム粒子が分散媒である（メタ）アクリレート類において、白濁、凝集、ゲル化等を起こすことなく、微細且つ安定に分散しており、重合性組成物は、高透明性と高流動性を有している。 The polymerizable composition according to the present invention contains a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate ester anionic surfactant as a dispersing agent together with zirconium oxide particles, and in this dispersing agent, the silane coupling agent Of the polyoxyethylene alkyl ether phosphate anion surfactant, ie, the silane coupling agent / polyoxyethylene alkyl ether phosphate anion surfactant weight ratio is in the range of 85/15 to 30/70. Yes, preferably in the range of 75/25 to 40/60, and in the polymerizable composition according to the present invention, the ratio of such a dispersant to 100 parts by weight of the zirconium oxide particles is 8 to 40 parts by weight. Range, preferably in the range of 10 to 30 parts by weight, More preferably, by including in the range of 10 to 20 parts by weight, in the (meth) acrylates in which the zirconium oxide particles are a dispersion medium, they are finely and stably dispersed without causing white turbidity, aggregation or gelation. The polymerizable composition has high transparency and high fluidity.
　本発明による重合性組成物は、酸化ジルコニウム粒子を１０～７０重量％の範囲で含む。本発明において、重合性組成物における酸化ジルコニウム粒子の割合が１０重量％よりも少ないときは、高屈折率を有する重合性組成物を得ることが困難である。しかし、重合性組成物における酸化ジルコニウム粒子の割合が７０重量％よりも多いときは、重合性組成物の安定性が損なわれるのみならず、流動性が低下して、所要の被膜や成形物を得ることが困難になる。 The polymerizable composition according to the present invention contains zirconium oxide particles in the range of 10 to 70% by weight. In the present invention, when the proportion of zirconium oxide particles in the polymerizable composition is less than 10% by weight, it is difficult to obtain a polymerizable composition having a high refractive index. However, when the proportion of the zirconium oxide particles in the polymerizable composition is more than 70% by weight, not only the stability of the polymerizable composition is impaired, but also the fluidity is lowered, and the required film or molded product can be obtained. It becomes difficult to obtain.
　本発明による重合性組成物において、酸化ジルコニウム粒子濃度の下限値は、上述したように、１０重量％であり、好ましくは、２０重量％であり、より好ましくは、２５重量％であり、特に好ましくは、３０重量％である。 In the polymerizable composition according to the present invention, as described above, the lower limit value of the zirconium oxide particle concentration is 10% by weight, preferably 20% by weight, more preferably 25% by weight, particularly preferably. Is 30% by weight.
　一方、本発明による重合性組成物において、酸化ジルコニウム粒子濃度の上限値は、上述したように、７０重量％であり、好ましくは、６５重量％であり、より好ましくは、６０重量％であり、特に好ましくは、５５重量％である。 On the other hand, in the polymerizable composition according to the present invention, the upper limit value of the zirconium oxide particle concentration is 70% by weight, preferably 65% by weight, more preferably 60% by weight, as described above. Particularly preferred is 55% by weight.
　本発明による重合性組成物は、好ましくは、このように酸化ジルコニウム粒子を高濃度で含みながら、それでいて、酸化ジルコニウム粒子が（メタ）アクリレート類中において、凝集、白濁、ゲル化することなしに、安定に分散していると共に、高透明性と高流動性を有している。 The polymerizable composition according to the present invention preferably contains the zirconium oxide particles in a high concentration in this way, and yet the zirconium oxide particles do not aggregate, become cloudy, or gel in (meth) acrylates. It is stably dispersed and has high transparency and high fluidity.
　特に、本発明によれば、重合性組成物は、その安定性、透明性、流動性及び屈折率を考慮すれば、酸化ジルコニウム粒子濃度は、好ましくは、２０～６５重量％の範囲であり、より好ましくは、２５～６０重量％の範囲であり、最も好ましくは、３０～５５重量％の範囲である。 In particular, according to the present invention, the concentration of the zirconium oxide particles in the polymerizable composition is preferably in the range of 20 to 65% by weight, considering its stability, transparency, fluidity and refractive index. More preferably, it is in the range of 25 to 60% by weight, and most preferably in the range of 30 to 55% by weight.
　本発明において用いるシランカップリング剤は、通常、次の一般式(Ｉ)
　　　　　　　　　　　　　　Ｒn－Ｓｉ－Ｘ4-n
　　　　　　　　　　　　　　　　　　　（Ｉ）
（式中、Ｒは非反応性基又は反応性官能基を含む基を示し、Ｘは加水分解性基又はヒドロキシ基を示し、ｎは１、２又は３である。）
で表される。 The silane coupling agent used in the present invention is usually represented by the following general formula (I)
R n —Si—X 4-n
(I)
(In the formula, R represents a non-reactive group or a group containing a reactive functional group, X represents a hydrolyzable group or a hydroxy group, and n is 1, 2 or 3.)
It is represented by
　上記非反応性基としては、例えば、アルキル基、シクロアルキル基、ハロゲン化アルキル基、フェニル基、アルキルフェニル基等を挙げることができ、上記反応性官能基を含む基としては、例えば、アミノ基、エポキシ基、ビニル基、メルカプト基、ハロゲン原子、（メタ）アクリロイル基等を含む基を挙げることができる。 Examples of the non-reactive group include an alkyl group, a cycloalkyl group, a halogenated alkyl group, a phenyl group, and an alkylphenyl group. Examples of the group containing the reactive functional group include an amino group. , Epoxy group, vinyl group, mercapto group, halogen atom, (meth) acryloyl group and the like.
　従って、非反応性基を有する所謂非反応性シランカップリング剤の具体例として、例えば、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ブチルトリメトキシシラン、ヘキシルトリメトキシシラン、デシルトリメトキシシラン、ブチルトリエトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリエトキシシラン、３，３，３－トリフルオロプロピルトリメトキシシラン、メチル－３，３，３－トリフルオロプロピルジメトキシシラン、パーフルオロオクチルエチルトリメトキシシラン、パーフルオロオクチルエチルトリエトキシシラン、パーフルオロオクチルエチルトリイソプロポキシシラン、トリフルオロプロピルトリメトキシシラン、ジメチルメトキシヒドロキシシラン等を挙げることができる。 Therefore, specific examples of so-called non-reactive silane coupling agents having non-reactive groups include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane. , Phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane , Decyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, perful B octyl ethyltrimethoxysilane, perfluorooctyl ethyl triethoxysilane, perfluorooctylethyl triisopropoxysilane, trifluoropropyl trimethoxysilane, and dimethyl methoxy hydroxy silane.
　反応性官能基を含む基を有する所謂反応性シランカップリング剤の具体例としては、例えば、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β－メトキシエトキシ）シラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、γ－グリシドキシメチルトリメトキシシラン、γ－グリシドキシメチルトリエキシシラン、γ－グリシドキシエチルトリメトキシシラン、γ－グリシドキシエチルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－（β－グリシドキシエトキシ)プロピルトリメトキシシラン、γ－（メタ）アクリロイルオキシメチルトリメトキシシラン、γ－（メタ）アクリロイルオキシメチルトリエトキシシラン、γ－（メタ）アクリロイルオキシエチルトリメトキシシラン、γ－（メタ）アクリロイルオキシエチルトリエトキシシラン、γ－（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ－（メタ）アクリロイルオキシプロピルトリエトキシシラン、γ-メルカプトプロピルトリメトキシシラン、ｐ－スチリルトリメトキシシラン、メチルトリクロロシラン等を挙げることができる。 Specific examples of so-called reactive silane coupling agents having a group containing a reactive functional group include, for example, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. , Vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriexylsilane, γ-glycidoxy Ethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (Meth) acryloyloxymethyltrimethoxy Γ- (meth) acryloyloxymethyltriethoxysilane, γ- (meth) acryloyloxyethyltrimethoxysilane, γ- (meth) acryloyloxyethyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, Examples include γ- (meth) acryloyloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, and methyltrichlorosilane.
　本発明においては、特に、高屈折率を有する重合性組成物を得る場合には、同様に、高屈折率 、例えば、１．４５以上を有するシランカップリング剤が用いられる。そのよう
な高屈折率を有するシランカップリング剤としては、例えば、ｐ－スチリルトリメトキシシラン、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、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド等を挙げることができる。これらのシランカップリング剤は必要に応じて、２種以上を組み合わせて用いられる。 In the present invention, in particular, when obtaining a polymerizable composition having a high refractive index, a silane coupling agent having a high refractive index, for example, 1.45 or more is used. Examples of the silane coupling agent having such a high refractive index include p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis (triethoxy And silylpropyl) tetrasulfide. These silane coupling agents are used in combination of two or more as required.
　本発明において用いるポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤は、好ましくは、次の一般式（II） The polyoxyethylene alkyl ether phosphate anionic surfactant used in the present invention is preferably the following general formula (II)
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（式中、Ｒは炭素原子数４～１８のアルキル基又はアルケニル基であり、Ｍは水素原子又は金属イオン、アンモニウムイオン又は有機塩基イオンであり、ｎは１～２０の範囲の数であり、ｋは１又は２である。）
で表されるモノエステル、ジエステル又はこれらの混合物である。 Wherein R is an alkyl or alkenyl group having 4 to 18 carbon atoms, M is a hydrogen atom or metal ion, ammonium ion or organic base ion, and n is a number in the range of 1 to 20, k is 1 or 2.)
A monoester, a diester or a mixture thereof.
　上記金属イオンは、好ましくは、ナトリウムイオン、カリウムイオン等のアルカリ金属イオン、マグネシウムイオン等のアルカリ土類金属イオンであり、有機塩基イオンは、例えば、トリエタノールアミンイオンのようなアルカノールアミンイオンを含むアミンイオンである。 The metal ion is preferably an alkali metal ion such as sodium ion or potassium ion, or an alkaline earth metal ion such as magnesium ion, and the organic base ion includes, for example, an alkanolamine ion such as triethanolamine ion. It is an amine ion.
　このようなポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤としては、例えば、東邦化学工業（株）から入手し得るフォスファノールＲＡ－６００、ＭＬ－２２０、ＭＬ－２４０、ＲＤ－５１０Ｙ、ＲＳ－４１０、ＲＳ－６１０、ＲＳ－７１０等を挙げることができる。 Examples of such polyoxyethylene alkyl ether phosphate anionic surfactants include phosphanol RA-600, ML-220, ML-240, RD-510Y, RS available from Toho Chemical Industry Co., Ltd. -410, RS-610, RS-710 and the like.
　本発明による重合性組成物は、酸化ジルコニウム粒子のための分散剤として上記シランカップリング剤と上記ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせを含み、この分散剤において、シランカップリング剤／ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤重量比は８５／１５～３０／７０の範囲であり、好ましくは、７５／２５～４０／６０の範囲であり、しかも、このような分散剤を酸化ジルコニウム粒子１００重量部に対する割合が８～４０重量部の範囲、好ましくは、１０～３０重量部の範囲、より好ましくは、１０～２０重量部の範囲にて含み、重合性成分として（メタ）アクリレート類を含む。 The polymerizable composition according to the present invention includes a combination of the silane coupling agent and the polyoxyethylene alkyl ether phosphate anionic surfactant as a dispersant for zirconium oxide particles, and in this dispersant, the silane coupling agent The weight ratio of the agent / polyoxyethylene alkyl ether phosphate anionic surfactant is in the range of 85/15 to 30/70, preferably in the range of 75/25 to 40/60, and such dispersion The agent is contained in a ratio of 8 to 40 parts by weight, preferably 10 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the zirconium oxide particles. Includes (meth) acrylates.
　本発明において、上記（メタ）アクリレート類とは、光又は熱による重合性を有するメタアクリレート類及び／又はアクリレート類を意味する。 In the present invention, the above (meth) acrylates means methacrylates and / or acrylates having a polymerization property by light or heat.
　そのような（メタ）アクリレート類としては、分子内に１個の（メタ）アクリロイル基を有する単官能（メタ）アクリレート類と分子内に２個以上の（メタ）アクリロイル基を有する多官能（メタ）アクリレート類を挙げることができる。 Examples of such (meth) acrylates include monofunctional (meth) acrylates having one (meth) acryloyl group in the molecule and polyfunctional (meta) having two or more (meth) acryloyl groups in the molecule. ) Acrylates.
　上記単官能メタクリレート類としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、フェニルグリシジル（メタ）アクリレート、ジメチルアミノメチル（メタ）アクリレート、フェニルセロソルブ（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ビフェニル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリロイルフォスフェート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシプロピル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシルメタクリレート等を挙げることができる。 Examples of the monofunctional methacrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenylglycidyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, phenyl cello Rub (meth) acrylate, dicyclopentenyl (meth) acrylate, biphenyl (meth) acrylate, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate , Benzyl (meth) acrylate, cyclohexyl methacrylate and the like.
　また、多官能（メタ）アクリレート類としては、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、トリ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、ノナエチレングリコールジ（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、１，４ブタンジオールジ（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、ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサメチレンジ（メタ）アクリレート、ヒドロキシピバリン酸エステルネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（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、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリス（メタ）アクリロキシエチルイソシアヌレート等を挙げることができる。 Polyfunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di ( (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexa Methylene di (meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Over DOO, dipentaerythritol hexa (meth) acrylate and tris (meth) acryloxy ethyl isocyanurate.
　本発明による重合性組成物は、前述した酸化ジルコニウム粒子と共に、このような（メタ）アクリレート類を含み、熱重合させるときは熱重合開始剤の存在下に加熱し、また、光重合させるときは、光重合開始剤の存在下に光、例えば、紫外線や電子線を照射することによって、上記単官能及び／又は多官能（メタ）アクリレート類が重合し、かくして、高透明性と高屈折率を有する熱又は光硬化物を与える。 The polymerizable composition according to the present invention contains such (meth) acrylates together with the above-described zirconium oxide particles, and when thermally polymerized, it is heated in the presence of a thermal polymerization initiator, and when photopolymerized. The monofunctional and / or polyfunctional (meth) acrylates are polymerized by irradiating light, for example, ultraviolet rays or electron beams in the presence of a photopolymerization initiator, and thus have high transparency and high refractive index. Heat or photocured product is provided.
　本発明において、硬化物とは、本発明による重合性組成物が（メタ）アクリレート類として単官能（メタ）アクリレート類のみを含むときは、酸化ジルコニウムを含む単官能（メタ）アクリレート類のポリマーからなる固化物をいい、本発明による重合性組成物が（メタ）アクリレート類として多官能（メタ）アクリレート類と（単官能（メタ）アクリレート類）を含むときは、酸化ジルコニウムを含む多官能（メタ）アクリレート類（と単官能（メタ）アクリレート類）が（共）重合してなる架橋構造を有する（通常、不溶不融の）固化物をいう。 In the present invention, the cured product refers to a polymer of monofunctional (meth) acrylates containing zirconium oxide when the polymerizable composition according to the present invention contains only monofunctional (meth) acrylates as (meth) acrylates. When the polymerizable composition according to the present invention contains polyfunctional (meth) acrylates and (monofunctional (meth) acrylates) as (meth) acrylates, polyfunctional (meta) containing zirconium oxide. ) Solidified product (usually insoluble and infusible) having a crosslinked structure formed by (co) polymerization of acrylates (and monofunctional (meth) acrylates).
　本発明による重合性組成物は、前述したように、酸化ジルコニウム粒子と分散剤と（メタ）アクリレート類を必須成分として含み、その他の成分を１０重量％以下の範囲で、好ましくは、５重量％以下の範囲で含んでよく、この場合、酸化ジルコニウム粒子、分散剤、（メタ）アクリレート類及びその他の成分の合計量が１００重量％を構成する。 As described above, the polymerizable composition according to the present invention contains zirconium oxide particles, a dispersant, and (meth) acrylates as essential components, and the other components in the range of 10% by weight or less, preferably 5% by weight. In this case, the total amount of zirconium oxide particles, dispersant, (meth) acrylates and other components constitutes 100% by weight.
　最も好ましくは、本発明による重合性組成物は、酸化ジルコニウム粒子と分散剤と残余（メタ）アクリレート類からなり、この場合、これらの成分で１００重量％を構成する。本発明による重合性組成物において、（メタ）アクリレート類の量は、好ましくは、１０～８９重量％の範囲であり、好ましくは、１５～７５重量％の範囲であり、より好ましくは、２０～７０重量％の範囲であり、特に好ましくは、２５～６５重量％の範囲である。 Most preferably, the polymerizable composition according to the present invention comprises zirconium oxide particles, a dispersant, and residual (meth) acrylates, in which case these components constitute 100% by weight. In the polymerizable composition according to the present invention, the amount of (meth) acrylates is preferably in the range of 10 to 89% by weight, preferably in the range of 15 to 75% by weight, more preferably in the range of 20 to It is in the range of 70% by weight, and particularly preferably in the range of 25 to 65% by weight.
　かくして、本発明によれば、重合性組成物は、好ましくは、酸化ジルコニウム粒子１０～７０重量％と分散剤と（メタ）アクリレート類１０～８９重量％を含み、より好ましくは、酸化ジルコニウム粒子２０～６５重量％と分散剤と（メタ）アクリレート類１５～７５重量％を含み、更に好ましくは、酸化ジルコニウム粒子２５～６０重量％と分散剤と（メタ）アクリレート類２０～７０重量％を含み、最も好ましくは、酸化ジルコニウム粒子３０～５５重量％と分散剤と（メタ）アクリレート類２５～６５重量％を含む。上記のいずれにおいても、分散剤は、酸化ジルコニウム粒子１００重量部に対して、８～４０重量部の範囲であり、好ましくは、１０～３０重量部の範囲であり、より好ましくは、１０～２０重量部の範囲である。 Thus, according to the present invention, the polymerizable composition preferably comprises 10 to 70% by weight of zirconium oxide particles, a dispersant and 10 to 89% by weight of (meth) acrylates, more preferably zirconium oxide particles 20 Containing 65 to 65% by weight of a dispersant and 15 to 75% by weight of (meth) acrylates, more preferably 25 to 60% by weight of zirconium oxide particles, 20 to 70% by weight of a dispersant and (meth) acrylates, Most preferably, it contains 30 to 55% by weight of zirconium oxide particles, a dispersant and 25 to 65% by weight of (meth) acrylates. In any of the above, the dispersant is in the range of 8 to 40 parts by weight, preferably in the range of 10 to 30 parts by weight, and more preferably in the range of 10 to 20 parts per 100 parts by weight of the zirconium oxide particles. The range is parts by weight.
　本発明による重合性組成物は、酸化ジルコニウム粒子を高濃度に含む場合であっても、安定性と透明性にすぐれているのみならず、粘度が低く、流動性にもすぐれている。 The polymerizable composition according to the present invention has not only excellent stability and transparency, but also low viscosity and excellent fluidity even when zirconium oxide particles are contained in a high concentration.
　即ち、本発明による重合性組成物の粘度は、酸化ジルコニウム粒子の濃度にもよるが、２５℃において、１００～４００００ｍＰａ・ｓの範囲であり、好ましくは、１５０～３００００ｍＰａ・ｓの範囲である。 That is, the viscosity of the polymerizable composition according to the present invention is in the range of 100 to 40000 mPa · s at 25 ° C., preferably in the range of 150 to 30000 mPa · s, depending on the concentration of the zirconium oxide particles.
　また、本発明による重合性組成物は、用いるシランカップリング剤や（メタ）アクリレート類の屈折率にもよるが、通常、１．５５～１．７５の範囲の屈折率を有し、好ましい態様によれば、１．６０以上、より好ましい態様によれば、１．６５以上の屈折率を有する硬化物を与える。 The polymerizable composition according to the present invention usually has a refractive index in the range of 1.55 to 1.75, although it depends on the refractive index of the silane coupling agent and (meth) acrylate used. According to the present invention, a cured product having a refractive index of 1.65 or more is obtained according to a more preferable embodiment.
　かくして、本発明による重合性組成物は、高い透明性と高い屈折率を有する光学樹脂材料として好適に用いることができる。 Thus, the polymerizable composition according to the present invention can be suitably used as an optical resin material having high transparency and a high refractive index.
　本発明による上述した重合性組成物は、本発明による下記の製造方法によって得ることができる。 The above-described polymerizable composition according to the present invention can be obtained by the following production method according to the present invention.
　即ち、本発明による重合性組成物の製造方法は、
（ａ）酸化ジルコニウム粒子の有機溶媒分散液に
（ｂ）分散剤と
（ｃ）（メタ）アクリレート類を加え、
　得られた混合物を攪拌下に加熱して、この混合物から上記有機溶媒を除去して、酸化ジルコニウム粒子１０～７０重量％と、分散剤と、重合性（メタ）アクリレート類とを含む重合性組成物の製造方法であって、
　上記分散剤がシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせからなり、
　上記分散剤において、シランカップリング剤のポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比が８５／１５～３０／７０の範囲にあり、
　上記分散剤を酸化ジルコニウム粒子１００重量部に対して８～４０重量部の範囲で用いるものである。 That is, the method for producing a polymerizable composition according to the present invention includes:
(A) Add (b) a dispersant and (c) (meth) acrylates to an organic solvent dispersion of zirconium oxide particles,
The obtained mixture is heated under stirring to remove the organic solvent from the mixture, and a polymerizable composition containing 10 to 70% by weight of zirconium oxide particles, a dispersant, and polymerizable (meth) acrylates. A method for manufacturing a product,
The dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant,
In the dispersant, the weight ratio of the silane coupling agent to the polyoxyethylene alkyl ether phosphate anionic surfactant is in the range of 85/15 to 30/70,
The dispersant is used in the range of 8 to 40 parts by weight with respect to 100 parts by weight of the zirconium oxide particles.
　本発明において用いる酸化ジルコニウム粒子の有機溶媒分散液は、好ましくは、酸化ジルコニウム粒子の平均粒径が１００ｎｍ以下であり、好ましくは、１０ｎｍ以下であり、より好ましくは、１～１０ｎｍの範囲であり、最も好ましくは、１～５ｎｍの範囲である。 The organic solvent dispersion of zirconium oxide particles used in the present invention preferably has an average particle diameter of zirconium oxide particles of 100 nm or less, preferably 10 nm or less, more preferably in the range of 1 to 10 nm. Most preferably, it is in the range of 1 to 5 nm.
　本発明において、酸化ジルコニウム粒子の有機溶媒分散液における分散媒、即ち、上記有機溶媒は、常圧下、加熱によって除去し得る程度の沸点、例えば、６０～２００℃程度の沸点を有するものが好ましい。後述するように、例えば、メタノール、メチルエチルケトン、トルエン等がその代表的な例である。 In the present invention, the dispersion medium in the organic solvent dispersion of zirconium oxide particles, that is, the organic solvent preferably has a boiling point that can be removed by heating under normal pressure, for example, a boiling point of about 60 to 200 ° C. As will be described later, for example, methanol, methyl ethyl ketone, toluene and the like are typical examples.
　即ち、例えば、平均粒子径が１０ｎｍ以下の微粒子の酸化ジルコニウム粒子の分散液は、最初、分散媒を水とした分散液として製造されることが多く、分散媒が有機溶媒である酸化ジルコニウム粒子の有機溶媒分散液は、このような分散媒が水である酸化ジルコニウム粒子分散液の分散媒である水を水混和性又は親水性有機溶媒で置換し、更に、必要に応じて、この水混和性又は親水性有機溶媒を疎水性乃至親油性有機溶媒に置換して製造されることが多い。 That is, for example, a dispersion of fine zirconium oxide particles having an average particle diameter of 10 nm or less is often initially produced as a dispersion using water as a dispersion medium. In the organic solvent dispersion, water, which is the dispersion medium of the zirconium oxide particle dispersion in which such a dispersion medium is water, is replaced with a water-miscible or hydrophilic organic solvent, and the water-miscibility is further changed as necessary. Alternatively, it is often produced by replacing a hydrophilic organic solvent with a hydrophobic or lipophilic organic solvent.
　本発明においても、分散媒が水である酸化ジルコニウム粒子分散液の分散媒である水を水混和性有機溶媒、例えば、メタノールで置換して製造されたメタノール分散液を好ましく用いることができる。また、本発明においては、このメタノールをメチルエチルケトンやトルエンで置換した分散液も好ましく用いることができる。但し、メチルエチルケトンはメタノールよりは親油性であるが、親水性も親油性も相対的なものであるので、本発明においては、便宜上、メチルエチルケトンも親水性有機溶媒に含めている。 Also in the present invention, a methanol dispersion produced by replacing water, which is a dispersion medium of a zirconium oxide particle dispersion, in which the dispersion medium is water, with a water-miscible organic solvent, for example, methanol, can be preferably used. In the present invention, a dispersion obtained by replacing this methanol with methyl ethyl ketone or toluene can also be preferably used. However, although methyl ethyl ketone is more lipophilic than methanol, since both hydrophilicity and lipophilicity are relative, in the present invention, methyl ethyl ketone is also included in the hydrophilic organic solvent for convenience.
　しかし、本発明による重合性組成物の製造においては、用いる酸化ジルコニウム粒子の有機溶媒分散液は、前述したように、トップダウン方式によるものでもよい。即ち、粗大な酸化ジルコニウム粒子を粉砕し、適宜の有機溶媒中に微粒子として分散させてなるものでもよい。 However, in the production of the polymerizable composition according to the present invention, the organic solvent dispersion of zirconium oxide particles used may be a top-down type as described above. That is, coarse zirconium oxide particles may be pulverized and dispersed as fine particles in an appropriate organic solvent.
　従って、本発明においては、酸化ジルコニウム粒子の有機溶媒分散液における分散媒である有機溶媒は、特に限定されるものではないが、上記水混和性又は親水性有機溶媒である場合、そのような水混和性有機溶媒は、特に限定されるものではなく、例えば、メタノール、エタノール、２－プロパノール、ｔ－ブチルアルコール等の脂肪族アルコール類、酢酸エチル、ギ酸メチル等の脂肪族カルボン酸エステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等の脂肪族ケトン類、エチレングリコール、グリセリン等の多価アルコール類や、これらの２種以上の混合物であるが、特に、好ましくは、メタノール、メチルエチルケトン、メチルイソブチルケトン又はこれらの混合物である。 Accordingly, in the present invention, the organic solvent that is a dispersion medium in the organic solvent dispersion of zirconium oxide particles is not particularly limited, but in the case of the water-miscible or hydrophilic organic solvent, such water is used. The miscible organic solvent is not particularly limited, and examples thereof include aliphatic alcohols such as methanol, ethanol, 2-propanol and t-butyl alcohol, aliphatic carboxylic acid esters such as ethyl acetate and methyl formate, acetone , Aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, polyhydric alcohols such as ethylene glycol and glycerin, and mixtures of two or more thereof, particularly preferably methanol, methyl ethyl ketone, methyl isobutyl ketone or these It is a mixture of
　本発明においては、酸化ジルコニウム粒子の有機溶媒分散液は、例えば、方法としてはそれ自体、既によく知られている蒸留置換法や限外濾過置換法によって、上記親水性有機溶媒を親油性有機溶媒に置換した酸化ジルコニウム粒子の有機溶媒分散液であってもよい。 In the present invention, an organic solvent dispersion of zirconium oxide particles is obtained by, for example, converting the hydrophilic organic solvent into a lipophilic organic solvent by a distillation substitution method or an ultrafiltration substitution method that is already well known. An organic solvent dispersion of zirconium oxide particles substituted with may be used.
　従って、本発明においては、酸化ジルコニウム粒子の有機溶媒分散液は、例えば、ジエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン等のケトン類、酢酸ブチル、プロピレングリコールメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、アクリル酸メチル、メタクリル酸メチル等のエステル類、ジブチルエーテル、ジオキサン等のエーテル類、ｎ－ヘキサン、シクロヘキサン、トルエン、キシレン、ソルベントナフサ等の炭化水素類、四塩化炭素、ジクロロエタン、クロロベンゼン等のハロゲン化炭素水素類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ－メチルピロリドン等のカルボン酸アミドを挙げることができる。これらの有機溶媒は、単独で、又は２種以上の混合物として用いられる。 Accordingly, in the present invention, the organic solvent dispersion of zirconium oxide particles is, for example, ketones such as diethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, butyl acetate, propylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate. , Esters such as methyl acrylate and methyl methacrylate, ethers such as dibutyl ether and dioxane, hydrocarbons such as n-hexane, cyclohexane, toluene, xylene and solvent naphtha, halogens such as carbon tetrachloride, dichloroethane and chlorobenzene And carboxylic acid amides such as carbohydrides, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These organic solvents are used alone or as a mixture of two or more.
　更に、本発明においては、酸化ジルコニウム粒子の有機溶媒分散液は、当初の分散媒が、例えば、メタノ－ルである場合、重合性（メタ）アクリレート類の酸化ジルコニウム粒子の有機溶媒分散液への溶解を助けるために、酸化ジルコニウム粒子の有機溶媒分散液に重合性（メタ）アクリレート類を加える前に、酸化ジルコニウム粒子のメタノール分散液にメタノールと混和性を有すると共にメタノールよりも親油性である有機溶媒、例えば、メチルエチルケトンを加えてもよい。 Furthermore, in the present invention, when the initial dispersion medium is, for example, methanol, the dispersion of zirconium oxide particles in the organic solvent is dispersed in the organic solvent dispersion of zirconium oxide particles of polymerizable (meth) acrylates. Before adding polymerizable (meth) acrylates to the organic solvent dispersion of zirconium oxide particles to aid dissolution, the organic dispersion is miscible with methanol and more lipophilic than methanol. A solvent such as methyl ethyl ketone may be added.
　上述した酸化ジルコニウム粒子の有機溶媒分散液は、その製造方法にもよるが、当初から、種々の添加剤、例えば、酸や塩基類、シランカップリング剤や界面活性剤等の分散剤を含んでいてもよい。しかし、このように、本発明において用いる酸化ジルコニウム粒子の有機溶媒分散液が当初からこれらの添加剤を含んでいる場合、これらの添加剤は、本発明における分散剤に含めない。即ち、これらの添加剤は、本発明において、分散剤として、その量を計算に含めない。 The organic solvent dispersion of the zirconium oxide particles described above includes various additives such as acids, bases, silane coupling agents, surfactants, and the like from the beginning, depending on the production method. May be. However, when the organic solvent dispersion of zirconium oxide particles used in the present invention contains these additives from the beginning as described above, these additives are not included in the dispersant in the present invention. That is, these additives are not included in the calculation as a dispersant in the present invention.
　本発明による重合性組成物の製造においては、上述した酸化ジルコニウム粒子の有機溶媒分散液に分散剤としてシランカップリング剤と上記ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせ用いる。この分散剤において、シランカップリング剤／ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤重量比は８５／１５～３０／７０の範囲にあり、しかも、このような分散剤を酸化ジルコニウム粒子の有機溶媒分散液における酸化ジルコニウム粒子１００重量部に対して８～４０重量部の範囲で含み、好ましくは、１０～３０重量部の範囲で含み、より好ましくは、１０～２０重量部の範囲で含むように用いる。 In the production of the polymerizable composition according to the present invention, a combination of a silane coupling agent and the polyoxyethylene alkyl ether phosphate ester anionic surfactant is used as a dispersant in the organic solvent dispersion of the zirconium oxide particles described above. In this dispersant, the weight ratio of silane coupling agent / polyoxyethylene alkyl ether phosphate ester anionic surfactant is in the range of 85/15 to 30/70, and such a dispersant is added to the organic particles of zirconium oxide particles. It is contained in the range of 8 to 40 parts by weight, preferably in the range of 10 to 30 parts by weight, more preferably in the range of 10 to 20 parts by weight with respect to 100 parts by weight of the zirconium oxide particles in the solvent dispersion. Used for.
　上記シランカップリング剤及びポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤については、前述したとおりである。 The above silane coupling agent and polyoxyethylene alkyl ether phosphate ester anionic surfactant are as described above.
　前述したように、特に、高屈折率を有する重合性組成物を得る場合には、同様に、高屈折率を有するシランカップリング剤が好ましく用いられる。 As described above, in particular, when a polymerizable composition having a high refractive index is obtained, similarly, a silane coupling agent having a high refractive index is preferably used.
　また、本発明による重合性組成物の製造に用いる（メタ）アクリレート類についても、前述したとおりであり、単官能（メタ）アクリレート類及び／又は多官能（メタ）アクリレート類が用いられる。 The (meth) acrylates used for the production of the polymerizable composition according to the present invention are also as described above, and monofunctional (meth) acrylates and / or polyfunctional (meth) acrylates are used.
　本発明によれば、このようにして、平均粒子径が１００ｎｍ以下、好ましくは、１０ｎｍ以下である酸化ジルコニウム粒子の有機溶媒分散液に（メタ）アクリレート類と共に、分散剤として上述したシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせを上記酸化ジルコニウム粒子に対して所定の割合にて加え、得られた混合物を加熱して、上記有機溶媒を混合物から除去することによって、上記酸化ジルコニウム粒子が（メタ）アクリレート類中において白濁、凝集、ゲル化等を起こすことなく、安定に分散していると共に、高透明性と高流動性を有する重合性組成物を得ることができる。 According to the present invention, the silane coupling agent described above as a dispersing agent together with (meth) acrylates in an organic solvent dispersion of zirconium oxide particles having an average particle diameter of 100 nm or less, preferably 10 nm or less is thus obtained. And a combination of polyoxyethylene alkyl ether phosphate ester anionic surfactant in a predetermined ratio with respect to the zirconium oxide particles, and heating the resulting mixture to remove the organic solvent from the mixture, The above-mentioned zirconium oxide particles can be stably dispersed in (meth) acrylates without causing cloudiness, aggregation, gelation, etc., and a polymerizable composition having high transparency and high fluidity can be obtained. .
　好ましい態様によれば、本発明によれば、上記酸化ジルコニウム粒子の有機溶媒分散液に先ず、シランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせを加え、次いで、重合性（メタ）アクリレート類を加え、かくして、得られた混合物を攪拌しながら、上記酸化ジルコニウム粒子の有機溶媒分散液の分散媒の沸点以上の温度に加熱して、上記有機溶媒を混合物から除去することによって、本発明による重合性組成物を得ることができる。 According to a preferred embodiment, according to the present invention, first, a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant is added to the organic solvent dispersion of the zirconium oxide particles, and then polymerizable. (Meth) acrylates are added, and the organic solvent is removed from the mixture by heating to a temperature not lower than the boiling point of the dispersion medium of the organic solvent dispersion of the zirconium oxide particles while stirring the resulting mixture. Thus, the polymerizable composition according to the present invention can be obtained.
　上記混合物を加熱して、上記有機溶媒を混合物から除去する際の温度は、用いる分散媒である上記有機溶媒の沸点によるが、通常、４０～１００℃の範囲であり、好ましくは、５０～７０℃の範囲である。また、上記混合物を加熱して、酸化ジルコニウム粒子の有機溶媒分散液の分散媒を混合物から除去する際に、必要に応じて、混合物を減圧下に加熱してもよい。 The temperature at which the mixture is heated to remove the organic solvent from the mixture depends on the boiling point of the organic solvent that is the dispersion medium to be used, but is usually in the range of 40 to 100 ° C., preferably 50 to 70. It is in the range of ° C. Moreover, when the said mixture is heated and the dispersion medium of the organic solvent dispersion liquid of a zirconium oxide particle is removed from a mixture, you may heat a mixture under pressure reduction as needed.
　本発明による重合性組成物は、上述したように、その製造に際して、出発物質として、酸化ジルコニウム粒子の有機溶媒分散液を用いるので、得られる重合性組成物が１０重量％以下の範囲、即ち、０～１０重量％の範囲の上記有機溶媒を含むことは許容される。即ち、本発明による重合性組成物は、酸化ジルコニウム粒子１０～７０重量％と前記分散剤と前記（メタ）アクリレート類を含み、上記有機溶媒を０～１０重量％の範囲、好ましくは、０～５重量％の範囲で含んでいてもよい。 As described above, since the polymerizable composition according to the present invention uses an organic solvent dispersion of zirconium oxide particles as a starting material in the production thereof, the resulting polymerizable composition has a range of 10% by weight or less, that is, It is permissible to contain the above organic solvent in the range of 0 to 10% by weight. That is, the polymerizable composition according to the present invention contains 10 to 70% by weight of zirconium oxide particles, the dispersant and the (meth) acrylate, and the organic solvent is in the range of 0 to 10% by weight, preferably 0 to You may contain in 5 weight% of range.
　このように、本発明による重合性組成物は、酸化ジルコニウム粒子を１０重量％以上の範囲で含み、好ましい態様によれば、酸化ジルコニウム粒子を３０重量％以上の範囲で含みながら、それでいて、酸化ジルコニウム粒子が重合性（メタ）アクリレート類中において、安定に分散していると共に、高透明性と高流動性を有している。 Thus, the polymerizable composition according to the present invention contains zirconium oxide particles in the range of 10% by weight or more, and according to a preferred embodiment, the zirconium oxide particles contain in the range of 30% by weight or more, while still containing zirconium oxide. The particles are stably dispersed in the polymerizable (meth) acrylates and have high transparency and high fluidity.
　従って、本発明によれば、好ましい態様においては、酸化ジルコニウム粒子に対して、少量の分散剤を用いることによって、透明性と流動性にすぐれる重合性組成物を得ることができる。 Therefore, according to the present invention, in a preferred embodiment, a polymerizable composition having excellent transparency and fluidity can be obtained by using a small amount of a dispersant for the zirconium oxide particles.
　このようにして得られる重合性組成物は、前述したように、用いるシランカップリング剤の屈折率にもよるが、通常、１．５５～１．７５の範囲の屈折率を有し、従って、好ましい場合には、１．６０以上、より好ましい場合には、１．６５以上の屈折率を有する硬化物を与える。 The polymerizable composition thus obtained usually has a refractive index in the range of 1.55 to 1.75, depending on the refractive index of the silane coupling agent used, as described above. When preferable, a cured product having a refractive index of 1.60 or more, and more preferably 1.65 or more is provided.
　本発明による重合性組成物は、これに紫外線、電子線等の活性エネルギー線の照射によりラジカルを発生する光重合開始剤又は加熱によりラジカルを発生する熱重合開始剤を適量、配合すれば、（メタ）アクリレート類がそのような重合開始剤の作用によって重合するので、それぞれ光重合性組成物又は熱重合性組成物を与える。 If the polymerizable composition according to the present invention is mixed with an appropriate amount of a photopolymerization initiator that generates radicals by irradiation with active energy rays such as ultraviolet rays and electron beams, or a thermal polymerization initiator that generates radicals by heating, Since the (meth) acrylates are polymerized by the action of such a polymerization initiator, a photopolymerizable composition or a thermally polymerizable composition is provided, respectively.
　本発明においては、そのような光重合開始剤及び熱重合開始剤としてはいずれも、従来から知られているものを適宜に用いることができる。 In the present invention, conventionally known photopolymerization initiators and thermal polymerization initiators can be appropriately used.
　光重合開始剤としては、例えば、ベンゾフェノン、ベンゾインメチルエーテル、ベンゾインプロピルエーテル、ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２，６－ジメチルベンゾイルジフェニルホスフィンオキシド、２，４，６－トリメチルベンゾイルジフェニルホシフィンオキシド等を挙げることができる。これらの光重合開始剤は、単独で、又は２種以上を混合して用いられる。 Examples of the photopolymerization initiator include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenyl phosphide. A fin oxide etc. can be mentioned. These photopolymerization initiators are used alone or in admixture of two or more.
　熱重合開始剤としては、例えば、ハイドロパーオキサイド、ｔ－ブチルハイドロパーキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド等のハイドロパーオキサイド類、ジｔ－ブチルパーオキサイド、ジクミルパーオキサイド等のジアルキルパーオキサイド類、ｔ－ブチルパーオキシベンゾエート、ｔ－ブチルパーオキシ（２－エチルヘキサノエート）等のパーオキシエステル類、ベンゾイルパーオキシド等のジアシルパーオキサイド類、ジイソプロピルパーオキシカーボネート等のパーオキシカーボネート類、パーオキシケタール、ケトンパーオキサイド等の過酸化物を挙げることができる。これらの重合開始剤も、単独で、又は２種以上を混合して用いられる。 Examples of the thermal polymerization initiator include hydroperoxides such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t- Dialkyl peroxides such as butyl peroxide and dicumyl peroxide, peroxy esters such as t-butyl peroxybenzoate and t-butyl peroxy (2-ethylhexanoate), and diacyl peroxides such as benzoyl peroxide And peroxides such as diisopropyl peroxycarbonate, peroxides such as peroxyketal and ketone peroxide. These polymerization initiators are also used alone or in admixture of two or more.
　以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。以下において、「部」は特に断りのない限り、「重量部」を意味する。また、以下において、酸化ジルコニウムのメタノール分散体、シランカップリング剤、ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤及び（メタ）アクリレート類は下記のものを用いた。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following, “part” means “part by weight” unless otherwise specified. In the following, the following were used as the methanol dispersion of zirconium oxide, the silane coupling agent, the polyoxyethylene alkyl ether phosphate ester anionic surfactant, and the (meth) acrylates.
酸化ジルコニウム粒子メタノール分散体
　堺化学工業（株）製酸化ジルコニウム粒子メタノール分散体、ＳＺＲ－Ｍ、酸化ジルコニウム粒子濃度３０重量％、動的光散乱法による酸化ジルコニウムの平均粒子径３ｎｍ
シランカップリング剤Ａ
　信越化学工業（株）製ｐ－スチリルトリメトキシシラン、ＫＢＭ－１４０３
シランカップリング剤Ｂ
　信越化学工業（株）製フェニルトリメトキシシラン、ＫＢＭ－１０３
ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤Ａ
　東邦化学工業（株）製フォスファノール、ＲＳ－７１０
ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤Ｂ
　東邦化学工業（株）製フォスファノール、ＲＡ－６００
（メタ）アクリレート
　日本化薬（株）製ｏ－フェニルフェノールモノエトキシアクリレート、ＫＡＹＡＲＡＤ　ＯＰＰ－１ Zirconium oxide particle methanol dispersion Zirconium oxide particle methanol dispersion manufactured by Sakai Chemical Industry Co., Ltd., SZR-M, zirconium oxide particle concentration 30% by weight, average particle diameter of zirconium oxide by dynamic light scattering method 3 nm
Silane coupling agent A
P-styryltrimethoxysilane, KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.
Silane coupling agent B
Phenyltrimethoxysilane, KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd.
Polyoxyethylene alkyl ether phosphate anionic surfactant A
Toho Chemical Co., Ltd. Phosphanol, RS-710
Polyoxyethylene alkyl ether phosphate anionic surfactant B
Phosphanol manufactured by Toho Chemical Industry Co., Ltd., RA-600
(Meth) acrylate Nippon Kayaku Co., Ltd. o-phenylphenol monoethoxy acrylate, KAYARAD OPP-1
　また、以下の実施例及び比較例において、酸化ジルコニウム粒子の有機溶媒分散液と重合性組成物の物性は下記のようにして測定した。 Further, in the following Examples and Comparative Examples, the physical properties of the organic solvent dispersion of the zirconium oxide particles and the polymerizable composition were measured as follows.
（酸化ジルコニウム粒子の有機溶媒分散液における酸化ジルコニウム粒子の平均粒子径）
　日機装（株）製粒度分布測定装置ＵＰＡ－ＥＸ１５０を用いて、動的光散乱法にて測定した。
（重合性組成物における酸化ジルコニウム粒子の平均粒子径）
　重合性組成物をメチルエチルケトンにて希釈し、得られた希釈物について、日機装（株）製粒度分布測定装置ＵＰＡ－ＥＸ１５０を用いて、動的光散乱法にて測定した。
（重合性組成物の透明性）
　重合性組成物を透明な容器に入れ、目視して、透明であるときを○、白濁しているときを×とした。
（流動性）
　重合性組成物を透明な容器に入れ、傾けたとき、流れが認められたときを○、流れが認められなかったときを×とした。
（粘度）
　Ｅ型回転粘度計（東機産業（株）製ＴＶ－２０）を用いて、液温２５℃、ローターの角度３°、半径９．７ｍｍ、回転数６０ｒｐｍにて測定した。
（屈折率）
　アッベ屈折計（（株）アタゴ製ＲＸ－７０００ｉ）によって、光源としてナトリウムスペクトルのＤ線を用いて、液温２０℃にて測定した。 (Average particle diameter of zirconium oxide particles in an organic solvent dispersion of zirconium oxide particles)
Measurement was performed by a dynamic light scattering method using a particle size distribution measuring apparatus UPA-EX150 manufactured by Nikkiso Co., Ltd.
(Average particle diameter of zirconium oxide particles in the polymerizable composition)
The polymerizable composition was diluted with methyl ethyl ketone, and the resulting dilution was measured by a dynamic light scattering method using a particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.
(Transparency of polymerizable composition)
The polymerizable composition was put in a transparent container and visually observed. The case where it was transparent was marked with ◯, and the time when it was cloudy was marked with ×.
(Liquidity)
When the polymerizable composition was placed in a transparent container and tilted, the flow was recognized as ◯, and the flow was not observed as x.
(viscosity)
Using an E-type rotational viscometer (TV-20 manufactured by Toki Sangyo Co., Ltd.), the liquid temperature was 25 ° C., the rotor angle was 3 °, the radius was 9.7 mm, and the rotation speed was 60 rpm.
(Refractive index)
Using an Abbe refractometer (RX-7000i, manufactured by Atago Co., Ltd.), measurement was performed at a liquid temperature of 20 ° C. using a D line of a sodium spectrum as a light source.
　以下の実施例及び比較例において、重合性組成物を調製するために用いた成分の仕込み組成と共に、得られた重合性組成物の成分組成と物性を表１及び表２に示す。 In the following Examples and Comparative Examples, the component composition and physical properties of the obtained polymerizable composition are shown in Tables 1 and 2 together with the charged compositions of the components used for preparing the polymerizable composition.
実施例１
　酸化ジルコニウムメタノール分散体（堺化学工業（株）製酸化ジルコニウムメタノール分散体、ＳＺＲ－Ｍ、酸化ジルコニウム濃度３０重量％、動的光散乱法による酸化ジルコニウムの平均粒子径３ｎｍ、以下、同じ）１００部にｐ－スチリルトリメトキシシラン（信越化学工業（株）製ｐ－スチリルトリメトキシシラン、ＫＢＭ－１４０３、以下、同じ）４．２０部、ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤（東邦化学工業（株）製フォスファノールＲＳ－７１０、以下、同じ）１．０５部及びｏ－フェニルフェノールモノエトキシアクリレート（日本化薬（株）製ＫＡＹＡＲＡＤ　ＯＰＰ－１）２４．７５部を加えて混合物を調製した。この混合物を攪拌しながら、温度５５～７０℃に加熱し、メタノールを除去して、その組成を表１に示すように、酸化ジルコニウム５０．０部、ｐ－スチリルトリメトキシシラン７．００部、ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤１．７５部及びｏ－フェニルフェノールモノエトキシアクリレート４１．２５部からなる重合性組成物を得た。 Example 1
Zirconium oxide methanol dispersion (Zircon Chemical Industry Co., Ltd. Zirconium oxide methanol dispersion, SZR-M, zirconium oxide concentration 30% by weight, average particle diameter of zirconium oxide by dynamic light scattering method 3 nm, hereinafter the same) 100 parts P-styryltrimethoxysilane (p-styryltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1403, hereinafter the same) 4.20 parts, polyoxyethylene alkyl ether phosphate anionic surfactant (Toho Chemical) 1.05 part of phosphanol RS-710 manufactured by Kogyo Co., Ltd. and the same below and 24.75 parts of o-phenylphenol monoethoxy acrylate (KAYARAD OPP-1 manufactured by Nippon Kayaku Co., Ltd.) were added to the mixture. Prepared. While stirring the mixture, the mixture was heated to a temperature of 55 to 70 ° C. to remove methanol, and the composition was 50.0 parts of zirconium oxide, 7.00 parts of p-styryltrimethoxysilane, as shown in Table 1. A polymerizable composition comprising 1.75 parts of a polyoxyethylene alkyl ether phosphate anionic surfactant and 41.25 parts of o-phenylphenol monoethoxy acrylate was obtained.
実施例２～１９
　表１から表３に示す仕込む組成にて混合物を調製し、実施例１と同様にして、表１から表３に示す組成を有する重合性組成物を得た。 Examples 2 to 19
Mixtures were prepared with the compositions shown in Tables 1 to 3, and polymerizable compositions having the compositions shown in Tables 1 to 3 were obtained in the same manner as in Example 1.
比較例１
　酸化ジルコニウムメタノール分散体１００部にｐ－スチリルトリメトキシシラン４．５０部及びｏ－フェニルフェノールモノエトキシアクリレート２５．５０部を加えて、混合物を調製し、この混合物を攪拌しながら、温度５５～７０℃に加熱したところ、酸化ジルコニウム粒子が凝集して、得られた混合物が白濁すると共に、粘度が上昇した。その結果、得られた重合性組成物は流動性を有しなかった。 Comparative Example 1
A mixture is prepared by adding 4.50 parts of p-styryltrimethoxysilane and 25.50 parts of o-phenylphenol monoethoxyacrylate to 100 parts of zirconium oxide methanol dispersion, and stirring the mixture at a temperature of 55-70. When heated to 0 ° C., the zirconium oxide particles aggregated, the resulting mixture became cloudy and the viscosity increased. As a result, the obtained polymerizable composition did not have fluidity.
比較例２～４
　表３に示す仕込む組成にて混合物を調製し、実施例１と同様にして、表３に示す組成を有する重合性組成物を得た。 Comparative Examples 2-4
A mixture was prepared with the composition shown in Table 3, and a polymerizable composition having the composition shown in Table 3 was obtained in the same manner as in Example 1.
　上記実施例１～１９において得られた重合性組成物の成分組成（部）と共に、透明性、流動性、粘度及び動的光散乱法による平均粒子径を表１から表３に示す。一部の重合性組成物については屈折率を示す。また、上記比較例１～４において得られた重合性組成物の成分組成（部）と共に、透明性、流動性、粘度及び動的光散乱法による平均粒子径を表３に示す。 Tables 1 to 3 show the transparency, fluidity, viscosity, and average particle diameter determined by the dynamic light scattering method, together with the component composition (parts) of the polymerizable compositions obtained in Examples 1 to 19 above. Some polymerizable compositions exhibit a refractive index. Table 3 shows the composition (parts) of the polymerizable compositions obtained in Comparative Examples 1 to 4 together with the transparency, fluidity, viscosity, and average particle size by dynamic light scattering.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１から表３に示す結果から明らかなように、微細な酸化ジルコニウム粒子が（メタ）アクリレート類中において、凝集、白濁、ゲル化等することなしに、安定に分散していると共に、高透明性と高屈折率と高流動性を有する重合性組成物を得ることができる。 As is clear from the results shown in Tables 1 to 3, fine zirconium oxide particles are stably dispersed in (meth) acrylates without aggregation, white turbidity, gelation, etc., and high transparency A polymerizable composition having high properties, high refractive index and high fluidity can be obtained.
　これに対して、比較例１によれば、分散剤としてシランカップリング剤のみを用いて、酸化ジルコニウムの有機溶媒分散液に（メタ）アクリレートであるｏ－フェニルフェノールモノエトキシアクリレートを加え、攪拌しながら加熱下にメタノールを除去したので、酸化ジルコニウム粒子が凝集して、得られた混合物は白濁し、更に、粘度も上昇した。その結果、流動性を有する組成物を得ることはできなかった。 On the other hand, according to Comparative Example 1, using only a silane coupling agent as a dispersant, o-phenylphenol monoethoxy acrylate (meth) acrylate was added to an organic solvent dispersion of zirconium oxide and stirred. However, since methanol was removed under heating, the zirconium oxide particles were agglomerated, the resulting mixture became cloudy, and the viscosity also increased. As a result, a composition having fluidity could not be obtained.
　比較例２及び３においては、シランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせからなる分散剤を用いたものの、シランカップリング剤の上記ポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比が本発明において規定する範囲外にあるために、酸化ジルコニウム粒子の有機溶媒分散液に重合性（メタ）アクリレートを加え、加熱下にメタノールを除去している間に、得られた混合物は増粘して、その結果、流動性を有する組成物を得ることはできなかった。 In Comparative Examples 2 and 3, although the dispersant comprising a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant was used, the polyoxyethylene alkyl ether phosphate ester of the silane coupling agent was used. Since the weight ratio to the anionic surfactant is outside the range specified in the present invention, while adding the polymerizable (meth) acrylate to the organic solvent dispersion of the zirconium oxide particles and removing methanol under heating, The resulting mixture thickened, and as a result, a composition having fluidity could not be obtained.
　比較例４においては、分散剤としてポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤のみを用いたので、酸化ジルコニウム粒子の有機溶媒分散液に重合性（メタ）アクリレートを加え、加熱下にメタノールを除去している間に、得られた混合物は著しく増粘し、その結果、流動性を有する組成物を得ることはできなかった。 In Comparative Example 4, since only the polyoxyethylene alkyl ether phosphate anionic surfactant was used as the dispersant, polymerizable (meth) acrylate was added to the organic solvent dispersion of zirconium oxide particles, and methanol was added under heating. During removal, the resulting mixture thickened significantly, and as a result it was not possible to obtain a fluid composition.

Claims (7)

  1. （ａ）酸化ジルコニウム粒子１０～７０重量％と、
    （ｂ）上記酸化ジルコニウム粒子１００重量部に対して８～４０重量部の分散剤と、
    （ｃ）（メタ）アクリレート類と
    を含む重合性組成物であって、
    　上記分散剤がシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせからなり、上記分散剤において、シランカップリング剤のポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比が８５／１５～３０／７０の範囲にある重合性組成物。     (A) 10 to 70% by weight of zirconium oxide particles,
    (B) 8 to 40 parts by weight of a dispersant with respect to 100 parts by weight of the zirconium oxide particles,
    (C) a polymerizable composition comprising (meth) acrylates,
    The dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anion surfactant, and in the dispersant, the weight of the silane coupling agent relative to the polyoxyethylene alkyl ether phosphate anion surfactant A polymerizable composition having a ratio in the range of 85/15 to 30/70.
  2. 　上記酸化ジルコニウム粒子が平均粒子径１００ｎｍ以下のものである請求項１に記載の重合性組成物。 The polymerizable composition according to claim 1, wherein the zirconium oxide particles have an average particle diameter of 100 nm or less.
  3. 　上記分散剤を酸化ジルコニウム粒子１００重量部に対して１０～３０重量部の範囲で含む請求項１に記載の重合性組成物。 The polymerizable composition according to claim 1, comprising the dispersant in an amount of 10 to 30 parts by weight with respect to 100 parts by weight of the zirconium oxide particles.
  4. 　１．５５～１．７５の範囲の屈折率を有する請求項１から３のいずれかに記載の重合性組成物。 The polymerizable composition according to any one of claims 1 to 3, which has a refractive index in the range of 1.55 to 1.75.
  5. （ａ）酸化ジルコニウム粒子の有機溶媒分散液に
    （ｂ）分散剤と
    （ｃ）（メタ）アクリレート類を加え、
    　得られた混合物を攪拌下に加熱して、この混合物から上記有機溶媒を除去して、上記酸化ジルコニウム粒子１０～７０重量％と、上記分散剤と、上記（メタ）アクリレート類とを含む重合性組成物の製造方法であって、
    　上記分散剤がシランカップリング剤とポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤の組み合わせからなり、
    　上記分散剤において、シランカップリング剤のポリオキシエチレンアルキルエーテルリン酸エステルアニオン界面活性剤に対する重量比が８５／１５～３０／７０の範囲にあり、
    　上記分散剤を酸化ジルコニウム粒子１００重量部に対して８～４０重量部の範囲で用いる重合性組成物の製造方法。     (A) Add (b) a dispersant and (c) (meth) acrylates to an organic solvent dispersion of zirconium oxide particles,
    The obtained mixture is heated with stirring to remove the organic solvent from the mixture, and the polymerizable composition contains 10 to 70% by weight of the zirconium oxide particles, the dispersant, and the (meth) acrylates. A method for producing a composition comprising:
    The dispersant comprises a combination of a silane coupling agent and a polyoxyethylene alkyl ether phosphate anionic surfactant,
    In the dispersant, the weight ratio of the silane coupling agent to the polyoxyethylene alkyl ether phosphate anionic surfactant is in the range of 85/15 to 30/70,
    A method for producing a polymerizable composition, wherein the dispersant is used in an amount of 8 to 40 parts by weight based on 100 parts by weight of zirconium oxide particles.
  6. 　上記酸化ジルコニウム粒子の有機溶媒分散液における上記酸化ジルコニウム粒子が平均粒子径１００ｎｍ以下のものである請求項５に記載の重合性組成物の製造方法。 The method for producing a polymerizable composition according to claim 5, wherein the zirconium oxide particles in the organic solvent dispersion of the zirconium oxide particles have an average particle diameter of 100 nm or less.
  7. 　上記分散剤を酸化ジルコニウム粒子１００重量部に対して１０～３０重量部の範囲で用いる請求項５に記載の重合性組成物の製造方法。 6. The method for producing a polymerizable composition according to claim 5, wherein the dispersant is used in an amount of 10 to 30 parts by weight based on 100 parts by weight of the zirconium oxide particles.
PCT/JP2016/064075 2015-05-13 2016-05-12 Polymerizable composition containing zirconium oxide particles and (meth)acrylate, and method for producing same WO2016182007A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-098646 2015-05-13
JP2015098646A JP6072134B2 (en) 2015-05-13 2015-05-13 Polymerizable composition containing zirconium oxide particles and (meth) acrylates and method for producing the same

Publications (1)

Publication Number Publication Date
WO2016182007A1 true WO2016182007A1 (en) 2016-11-17

Family

ID=57248866

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/064075 WO2016182007A1 (en) 2015-05-13 2016-05-12 Polymerizable composition containing zirconium oxide particles and (meth)acrylate, and method for producing same

Country Status (3)

Country Link
JP (1) JP6072134B2 (en)
TW (1) TW201704328A (en)
WO (1) WO2016182007A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210021447A (en) * 2018-06-15 2021-02-26 나가세케무텍쿠스가부시키가이샤 Dispersion of inorganic oxide fine particles
WO2023029381A1 (en) * 2021-09-02 2023-03-09 江苏大学 Method for preparing zirconium oxide composite adsorbent on basis of droplet confined space, and defluorination use of same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019052196A (en) * 2016-01-27 2019-04-04 Ａｇｃ株式会社 Curable composition, cured article, manufacturing method therefor and article
JPWO2022181302A1 (en) 2021-02-26 2022-09-01

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008242076A (en) * 2007-03-27 2008-10-09 Nippon Shokubai Co Ltd Antistatic hard coat composition and optical article
JP2010189506A (en) * 2009-02-17 2010-09-02 Dic Corp Resin composition containing inorganic oxide fine particle and cured product obtained from the composition
JP2011037957A (en) * 2009-08-07 2011-02-24 Asahi Kasei Chemicals Corp Thermoplastic composite material
JP2013136710A (en) * 2011-12-28 2013-07-11 Jgc Catalysts & Chemicals Ltd Substrate with transparent coloring film and coating solution for forming transparent coloring film
JP2015117157A (en) * 2013-12-18 2015-06-25 レジノカラー工業株式会社 Non-alcohol organic solvent dispersion of zirconium oxide particles and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008242076A (en) * 2007-03-27 2008-10-09 Nippon Shokubai Co Ltd Antistatic hard coat composition and optical article
JP2010189506A (en) * 2009-02-17 2010-09-02 Dic Corp Resin composition containing inorganic oxide fine particle and cured product obtained from the composition
JP2011037957A (en) * 2009-08-07 2011-02-24 Asahi Kasei Chemicals Corp Thermoplastic composite material
JP2013136710A (en) * 2011-12-28 2013-07-11 Jgc Catalysts & Chemicals Ltd Substrate with transparent coloring film and coating solution for forming transparent coloring film
JP2015117157A (en) * 2013-12-18 2015-06-25 レジノカラー工業株式会社 Non-alcohol organic solvent dispersion of zirconium oxide particles and method for producing the same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210021447A (en) * 2018-06-15 2021-02-26 나가세케무텍쿠스가부시키가이샤 Dispersion of inorganic oxide fine particles
US20210198513A1 (en) * 2018-06-15 2021-07-01 Nagase Chemtex Corporation Inorganic oxide microparticle dispersion
JPWO2019240154A1 (en) * 2018-06-15 2021-07-29 ナガセケムテックス株式会社 Inorganic oxide fine particle dispersion
JP7406485B2 (en) 2018-06-15 2023-12-27 ナガセケムテックス株式会社 Inorganic oxide fine particle dispersion
KR102647460B1 (en) 2018-06-15 2024-03-13 나가세케무텍쿠스가부시키가이샤 Inorganic oxide fine particle dispersion
WO2023029381A1 (en) * 2021-09-02 2023-03-09 江苏大学 Method for preparing zirconium oxide composite adsorbent on basis of droplet confined space, and defluorination use of same

Also Published As

Publication number Publication date
TW201704328A (en) 2017-02-01
JP6072134B2 (en) 2017-02-01
JP2016210948A (en) 2016-12-15

Similar Documents

Publication Publication Date Title
JP5466640B2 (en) Curable composition and cured product thereof
JP5167582B2 (en) Zirconia transparent dispersion, transparent composite, and method for producing transparent composite
JPWO2015019941A1 (en) Semiconductor nanoparticle-containing curable composition, cured product, optical material and electronic material
JP6072134B2 (en) Polymerizable composition containing zirconium oxide particles and (meth) acrylates and method for producing the same
JP2020019958A (en) Inorganic particle dispersion, inorganic particle-containing composition, coating film, plastic substrate with coating film, and display device
TW201625480A (en) Process for producing dispersion of fine inorganic particles, curable composition containing said dispersion, and cured object obtained therefrom
CN108368211B (en) Curable composition and cured product
TWI627190B (en) Hollow particle and use thereof
JPWO2016088646A1 (en) Semiconductor nanoparticle-containing curable composition, cured product, optical material and electronic material
JP6025701B2 (en) Non-alcohol organic solvent dispersion of zirconium oxide particles and production method thereof
US20120003502A1 (en) Organic solvent dispersion, resin composition, and optical device
JP2007171555A (en) Hard coat film and optical functional film, optical lens and optical component
TW201516082A (en) Silicone resin composition for optical semiconductor and cured product thereof
JP7415230B2 (en) Reactive silicone composition and cured product thereof
JP5374921B2 (en) Transparent fine particle dispersion, fine particle-containing transparent resin composition, fine particle-containing transparent resin, and optical member
JP2017002243A (en) Composition containing zirconium oxide particle and organopolysiloxane and method for producing the same
US10745508B2 (en) Surface-modified metal oxide particles, production method, dispersion liquid, curable composition, and cured product
JP2013194091A (en) Active energy ray-curing resin composition and method for producing the same, and coating agent, laminate
TW202337833A (en) Zro2 liquid dispersion
JP4974133B2 (en) Method for producing resin composition and resin composition
WO2017111094A1 (en) Dispersion, curable composition, cured product, surface-modified silica particles and method for producing same
TW202244156A (en) Zirconium element-containing resin composition
JP2009229805A (en) Photocuring type lens

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16792732

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16792732

Country of ref document: EP

Kind code of ref document: A1