TW201339222A - Resin composition for optical material - Google Patents

Abstract

To provide a resin composition for optical materials that has a low viscosity even if large quantities of zirconium oxide particles and an organic silicon compound are compounded therewith, can inhibit yellowing, and forms a resin having a high refractive index and exhibiting excellent transparency and heat resistance. The resin composition for optical materials comprises zirconium oxide particles having an average particle size of 1-30 nm, a dispersant comprising a compound represented by formula (1), an organosilicon compound, and a compound having a polymerizable unsaturated group. In formula (1), R is a 3-24C alkyl and/or alkenyl group having a branched chain; AO is a 1-4C oxyalkylene group; n is a numerical value within the range of 3-30 expressing the average number of moles of alkylene oxide added; and X is a linking group comprising carbon, hydrogen and/or oxygen.

Description

Resin composition for optical materials

The present invention relates to a resin composition for an optical material, and more particularly to a resin composition for a low-viscosity optical material, wherein a refractive index and an Abbe number of the resin obtained by hardening are large and Can inhibit yellowing.

Resin-made lenses are widely used in cameras, office automation equipment (OA), glasses, and the like. For such a resin lens, it is required to have a high refractive index. In order to increase the refractive index of the resin, for example, Patent Document 1 discloses a dispersion in which a large amount of metal oxide fine particles such as zirconia which have been surface-treated with an organic acid are dispersed in a resin. Further, Patent Document 2 discloses a dispersion in which a large amount of metal oxide fine particles are treated with an organic cerium compound and dispersed in a large amount in a resin.

However, when the zirconia particles are dispersed in the resin as described above, there is a problem that the resin is susceptible to yellowing over time. The yellowing of this resin is like This can be solved by adding an organic ruthenium compound as shown in Citation 2. However, in the case of a resin composition for an optical material, it is necessary to increase the blending amount of the zirconia particles in order to increase the refractive index. However, if the amount of zirconia blended is increased, the viscosity of the dispersion itself is greatly increased, and in some cases, there is a problem that stirring cannot be performed.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-191167

Patent Document 2: Japanese Laid-Open Patent Publication No. 2008-120605

The present invention has been made in view of such problems in the prior art, and an object thereof is to provide a resin composition for an optical material which has a low viscosity even though a large amount of zirconia particles and an organic cerium compound are blended. Further, the yellowing of the obtained cured resin can be suppressed, and a resin having a high refractive index excellent in transparency and heat resistance can be formed.

The resin composition for an optical material of the present invention, which comprises a zirconia particle having an average particle diameter of 1 to 30 nm, a dispersing agent composed of a compound represented by the following formula (1), an organic cerium compound, and a polymerization. Sex-unsaturated compound;

Wherein R of the formula (1) is an alkyl group and/or an alkenyl group having a branched chain and having a carbon number of 3 to 24, AO is an oxyalkylene group having a carbon number of 1 to 4, and n is an epoxy group; The average addition mole number of the alkylene oxide is a value in the range of 3 to 30, and X is a linking group composed of a carbon atom, a hydrogen atom and/or an oxygen atom.

Here, in the above dispersant, X of the above formula (1) is preferably an alkylene group having a carbon number of 1 to 15.

Further, in the above dispersant, X of the above formula (1) is preferably a linking group represented by the following formula (2):

Wherein Y of the formula (2) is any one selected from the group consisting of an alkylene group having 1 to 15 carbon atoms, a vinyl group extending, a phenylene group, and a phenyl group having a carboxyl group.

In the present invention, the resin composition for the optical material is set to 100. When the weight % is used, the amount of the zirconia particles blended is preferably from 0.5 to 80% by weight.

[Formation of the Invention] Zirconia particles

In the resin composition for an optical material of the present invention, the zirconia particles as the dispersed particles are particles having an average particle diameter of 1 to 30 nm. This zirconia particle can be partially stabilized by the addition of other metal oxides. Further, it may be crystalline or amorphous. Further, the dispersed particles dispersed by the dispersing agent of the present invention may be isotropy particles or anisotropic particles or may be fibrous.

In the present invention, as the dispersed zirconia particles, those obtained by a conventional method can be used. As a method of preparing the fine particles, there is a top-down method in which coarse particles are mechanically pulverized and refined, and a group in which a plurality of unit particles are formed and agglomerated may be used. There are two ways of forming a bottom-up method of particles in a cluster state, but those prepared by any method are suitable for use. Further, these may be any one of the wet method and the dry method. In addition, there are physical methods and chemical methods from the bottom up. Can be used according to any method.

The dispersing agent in the present invention may be used in a step of mechanically pulverizing and refining coarse particles, and may be used in a cluster state in which a plurality of unit particles are formed and agglomerated. And the step of forming a particle in a bottom-up manner; or a particle may be used, and after the microparticle is prepared in advance by the foregoing method, in order to stably take out the microparticle from the medium, it is called a surface modifier or a surface protective agent. The protective agent is removed by coating or impregnation. As a protective agent, it can be used instead of the above-mentioned conventional dispersing agent.

In order to more specifically describe the bottom-up manner, a method of preparing metal nanoparticles in the aforementioned zirconia particles is exemplified. In the bottom-up mode, a representative example of a physical method is a method in which a bulk metal is evaporated in an inert gas and cooled and condensed by collision with a gas to form a nanoparticle. Evaporation method. In addition, the chemical method has a liquid phase reduction method or a metal error in which a metal ion is reduced in a liquid phase in the presence of a protective agent, and the formed zero-valent metal is stabilized at a nanometer size. The thermal decomposition method of the compound. As the liquid phase reduction method, a chemical reduction method, an electrochemical reduction method, a photoreduction method, a combination chemical reduction method, a light irradiation method, or the like can be used.

Further, the zirconia particles which are suitably used in the present invention may be obtained by any of the top-down method and the bottom-up method as described above, and these may also be in the water system. Any environment other than water or gas The next modulation. Further, when such zirconia particles are used, it is also possible to use a dispersion of zirconia particles in various solvents in advance.

In the present invention, since zirconia particles are used, the refractive index of the resin obtained by curing is increased, and the Abbe number can also be increased.

In the resin composition for an optical material of the present invention, the preferable blending amount of the zirconia particles is from 0.5 to 80% by weight based on the entire composition (100% by weight) from the viewpoint of the refractive index and the viscosity. It is preferably from 30 to 70% by weight, still more preferably from 35 to 60% by weight.

2. About the hydrophobic group of the dispersant (R)

The hydrophobic group (R) of the dispersing agent in the present invention is an alkyl group and/or an alkenyl group having a branched chain and having a carbon number of 3 to 24. The content of the alkyl group and/or the alkenyl group having a branched chain and having a carbon number of 3 to 24 is preferably 70% by weight or more based on the total of R.

The carbon number of the starting alcohol used to form R may be a mixture of alcohols of a single or different carbon number. Further, the starting material alcohol may be a mixture derived from synthesis or derived from nature, and its chemical structure may be a single composition or a complex isomer. The starting alcohol which can be used is a conventional one, and specific examples thereof are butanol, isobutanol, pentanol and/or its isomer, hexanol and/or its isomer, heptanol derived from synthesis. And / or its isomer, octanol and / or its isomer, 3,5,5-trimethyl-1-hexanol, will be mixed with or from propylene or butene The higher olefin derived from the olefin by the oxo process, isodecyl alcohol, isodecyl alcohol, is undecyl alcohol, isododecyl alcohol, isotridecyl alcohol, manufactured by Shell Chemicals Corp. NEODOL 23, 25, 45, SAFOL 23 manufactured by Sasol Corp., EXXAL 7, EXXAL 8N, EXXAL 9, EXXAL 10, EXXAL 11, and EXXAL 13 manufactured by Exxon Mobil Corporation Also an example of a higher alcohol suitable for use. Also, derived from natural octanol, decyl alcohol, lauryl alcohol (1-dodecanol), myristyl alcohol (1-tetradecanol), cetyl alcohol (1-hexadecanol), stearyl alcohol (1- Octadecanol), oleyl alcohol (cis-9-octadecen-1-ol) and the like are also examples of higher alcohols that can be used. Further, a single composition of a Guerbet Alcohol type having a chemical structure of a 2-alkyl-1-alkanol type, or a mixture thereof, etc., is also an example of a higher alcohol which is suitable for use, and these are in addition to 2 -ethyl-1-hexanol, 2-propyl-1-hexanol, 2-butyl-1-hexanol, 2-ethyl-1-heptanol, 2-propyl-1-heptanol, 2 -ethyl-1-octanol, 2-hexyl-1-nonanol, 2-heptyl-1-undecyl alcohol, 2-octyl-1-dodecanol, 2-mercapto-1-undecyl alcohol In addition to the isostearyl alcohol derived from the branched alcohol, etc. Further, the above various alcohols may be used in combination of two or more kinds. However, in the dispersant of the present invention, as described above, the hydrophobic group (R) is a branched alkyl group and/or alkenyl group having a carbon number of 3 to 24.

Further, the hydrophobic group (R) is in the case of hydrogen or a hydrocarbon group having 1 to 2 carbon atoms, when the carbon number is more than 25, and the carbon number of the hydrophobic group (R) is in the range of 3 to 24. In the case where the content of the linear alkyl group and/or the alkenyl group is more than 30% by weight, there is a possibility that the zirconia particles are not present. The method is stably dispersed in a disperse medium, or the range of choice of the dispersing medium that can be used is limited, or replacement or mixing of the dispersing medium for dispersing occurs in the preparation step of the dispersion. As a result, the stability of the dispersion is remarkably lowered, and the precipitate is immediately generated, or the stability with time is remarkably lowered to lower the added value of the final product, the productivity is lowered, the processing property is lowered, and the quality is deteriorated. In order to avoid such problems and to make the action of the dispersant particularly effective in the present invention, the hydrophobic group (R) is more preferably a branched alkyl group having a carbon number of 8 to 18.

3. Oxidation alkenyl (AO) _{n of the} dispersant

In the present invention, an alkylene oxide species as a dispersing agent is suitably selected, and AO in the formula (1) is an oxyalkylene group having a carbon number of 1 to 4, specifically, the carbon number is The alkylene oxide of 2 is ethylene oxide. The alkylene oxide having a carbon number of 3 is propylene oxide. The alkylene oxide having a carbon number of 4 is tetrahydrofuran or butylene oxide, preferably 1,2-butylene oxide or 2,3-butylene oxide. The oxyalkylene chain (-(AO) _n -) in the dispersing agent is introduced for the purpose of adjusting the dispersing agent affinity of the dispersing agent, and the alkylene oxide may be a single polymeric chain or two or more. A random polymeric chain or a block polymeric chain of alkylene oxides, and combinations thereof can also be used. The n of the average addition mole number of the alkylene oxide of the formula (1) is in the range of 3 to 30, preferably in the range of 5 to 20.

4. The linking group of the dispersing agent (X)

The linking group (X) can be composed of carbon atoms, hydrogen atoms, and oxygen atoms. The structure is conventionally selected from the group consisting of a saturated hydrocarbon group, an unsaturated hydrocarbon group, an ether group, a carbonyl group, and an ester group, and may have an alicyclic structure or an aromatic ring structure, and may also have a repeating unit. . When the linking group X contains a nitrogen atom and/or a sulfur atom and/or a phosphorus atom or the like, it has an effect of weakening the affinity of the carboxyl group for the dispersoid, and is not suitable as a dispersing agent in the present invention. Structural factor.

Further, X of the formula (1) is preferably an alkylene group having a carbon number of 1 to 15, more preferably an alkylene group having a carbon number of 1 to 8.

Further, X of the formula (1) is preferably a substance represented by the above formula (2). Among them, Y in the formula (2) is any one selected from the group consisting of an alkylene group having 1 to 15 carbon atoms, a vinyl group extending, a phenylene group, and a phenyl group having a carboxyl group.

5. Better dispersant

In the present invention, it is more preferred to use a dispersing agent of the following formula (3).

Wherein R in the formula (3) is preferably a branched alkyl group having a carbon number of 8 to 18, and n is an average addition molar number of ethylene oxide, and preferably in the range of 5 to 20. . Since the composition of the dispersing agent is within this range, the selection range of the dispersing medium for the preparation of the dispersion can be expanded, and for heterogeneous The applicability of mixing and replacement of dispersing media is improved. As described above, by limiting the composition range of the dispersant, it is more suitable for the stability of the dispersion over time, and as a result, the added value of the final product can be improved, the productivity can be improved, the processing characteristics can be improved, and the quality can be stabilized.

6. Dispersant blending amount

In the present invention, the blending amount of the dispersing agent is not particularly limited, and may be 0.5% by weight or more and 25% by weight or less, preferably 0.5% to 20% by weight, and more preferably 1.25% by weight or more based on the zirconia particles. And 10% by weight or less.

7. Method for producing dispersant

The dispersant in the present invention can be produced by a known method. For example, a conventional nonionic surfactant compound in which an alkylene oxide is added to an alcohol, an amine, or a mercaptan is used as a raw material by a conventional method, and a monohalogenated lower carboxylic acid or a salt thereof is used in the presence of a base. A method of reacting with a hydroxyl group at the end of an alkylene oxide; or using an acid anhydride, and is produced by a ring-opening reaction with a hydroxyl group at the terminal of an alkylene oxide, but is not limited thereto.

Further, since the optimum composition is selected by specifically limiting the type of the hydrophobic group, the alkylene species and the addition form thereof, the amount of addition moles, the linking group, and the like in the above range, it is more dispersible than the conventional dispersant. A wide variety of dispersoids, and can disperse the dispersion in a wider variety of dispersion media. As a result, the value of utilization in the industry is large.

Further, the dispersing agent used in the present invention can reduce the ion species contained in the conventional refining method, particularly the contents of ions of alkali metal ions, alkaline earth metal ions, heavy metal ions, and halogen ions. use. Ionic species in the dispersant, dispersion stability, corrosion resistance, oxidation resistance, electrical properties of the dispersed coating film (conductive properties, insulating properties), stability over time, heat resistance, low humidity The properties and weather resistance have a large influence, and the content of the above ions can be appropriately determined, but it is preferably less than 10 ppm in the dispersant.

Further, the resin composition for an optical material of the present invention can be prepared by a conventional stirring method, a homogenization method, or a dispersion method. Examples of the dispersing machine that can be used include a roll mill of a two-roll type roll, a three roll type roll, a ball mill of a ball mill, a vibratory ball mill, a paint shaker, a continuous disc type ball mill, and a continuous ring type. A ball mill or the like, a beads-mill, a sand mill, a jet mill, or the like. Further, dispersion treatment can also be carried out in an ultrasonic generation bath.

8. Organic germanium compounds

In the resin composition for an optical material of the present invention, the organic ruthenium compound preferably has low reactivity or no reactivity with respect to a chemical reaction such as oxidation or reduction reaction when the zirconia particles are surface-modified. Further, the affinity for a dispersion medium such as water, an organic solvent or a resin is high. among them, Particularly preferred is a modified silicone, a silicone resin, an alkoxydecane compound, a chlorosilane compound, a silanol compound, a silazane compound. One or more of the groups of compounds).

Examples of the modified anthrone include alkoxy modified fluorenone, epoxy modified fluorenone, and epoxy. Polyether modified fluorenone, methanol modified fluorenone, stanol modified fluorenone, thiol modified fluorenone, aralkyl modified fluorenone, methacrylic modified fluorenone, methacrylate modified矽 ketone, carboxy modified fluorenone, phenol modified fluorenone, methyl styrene modified fluorenone, acrylic modified fluorenone, thiol modified fluorenone, amine modified fluorenone, methyl Hydroquinone, phenylmethylhydroquinone, and the like. The modified anthrone can also be used in a range that does not affect the surface activity of the zirconia particles and does not impair the optical or mechanical properties of the resin when the composite is formed with the resin. And / or the functional group of the atom.

Examples of the fluorenone resin include a methyl fluorenone resin, a phenylmethyl fluorenone resin, and a diphenyl fluorenone resin.

Examples of the alkoxydecane compound include methyltrimethoxydecane, methyltriethoxydecane, dimethyldimethoxydecane, dimethyltriethoxydecane, and ethyltrimethoxydecane. , propyl trimethoxy decane, butyl trimethoxy decane, hexyl trimethoxy decane, hexyl triethoxy decane, decyl trimethoxy decane, phenyl trimethoxy decane, diphenyl trimethyl Oxydecane, phenyltriethoxydecane, diphenyldiethoxydecane, trifluoropropyltrimethoxydecane, and the like.

Examples of the chlorodecane compound include alkyl chlorodecane; and examples of the alkyl chlorodecane include methyltrichlorodecane, ethyltrichlorodecane, phenyltrichlorodecane, dimethyldichlorodecane, and diethyl. Dichlorodecane, trimethylchlorodecane, triethylchlorodecane, and the like.

Examples of the stanol compound include trimethyl stanol and triethyl decyl alcohol.

These alkoxydecane compounds, chlorodecane compounds and stanol compounds can also not impair the optical properties or mechanical properties of the resin insofar as they do not affect the surface activity of the zirconia particles and form a composite with the resin. The range of properties is used in combination with a decane coupling agent containing a reactive functional group such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amine group, an isocyanate group or a thiol group.

Examples of the decane alkane compound include hexamethyldiazane and the like.

9. A compound having a polymerizable unsaturated group

A compound having a polymerizable unsaturated group which can be used in the present invention as long as it is a polymerizable functional group which can undergo a hardening reaction after formation of a coating film In the case of the base, there is no particular limitation, and it is suitable to use an unsaturated polymerizable monomer containing a carboxylic acid group, an alkyl ester of a carboxylic acid group-containing unsaturated polymerizable monomer, a vinyl compound, and a urethane. Acrylate.

Examples of the unsaturated polymerizable monomer containing a carboxylic acid group include (meth)acrylic acid, crotonic acid, maleic acid, and itaconic acid.

Examples of the alkyl ester of the unsaturated polymerizable monomer containing a carboxylic acid group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Propyl ester, butyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ( Octyl methacrylate, decyl (meth) acrylate, decyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauric (meth) acrylate, ( Cyclohexyl methacrylate, butyl cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, bicyclo [methyl] acrylate [3, 3, 1] decyl ester, 2-methoxyethyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, (meth) acrylate Diethylaminoethyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Ester, methoxy (meth) acrylate Ethylene glycol ester, methoxypolyethylene glycol (meth)acrylate, ethoxyethylene glycol (meth)acrylate, ethoxylated (meth)acrylate Ethylene glycol ester, propoxyethylene glycol (meth)acrylate, propoxy polyethylene glycol (meth)acrylate, methoxypropyl glycol (meth)acrylate, methoxy (meth)acrylate Polypropylene glycol ester, ethoxypropyl glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, propoxypropylene glycol (meth)acrylate, and propoxylated polypropylene glycol (meth)acrylate One (meth) acrylate such as ester; ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, poly(meth)acrylic acid poly a bis(meth) acrylate compound such as propylene glycol ester or triethylene glycol di(meth)acrylate; trimethylolpropane tris(meth)acrylate; and tris(meth)acrylate a (meth) acrylate compound; a tetra(meth) acrylate compound such as tetrakis(meth)acrylic acid pentaerythritol ester, dipentaerythritol hexa(meth)acrylate, and hexa(meth)acrylic acid; A hexa(meth) acrylate compound such as sorbitol ester. In addition, the term "(meth)acrylate" means "acrylate" or "methacrylate".

Examples of the vinyl compound include vinyl acetate, vinyl propionate, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, butadiene, and isoprene.

The urethane acrylate is obtained by reacting a polyisocyanate with a hydroxyl group-containing (meth) acrylate.

As a polyisocyanate which can be used for urethane acrylate, However, there are no particular restrictions, but examples thereof include: tolyl diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, phenyl diisocyanate, naphthalene diisocyanate, decyl diisocyanate, tetramethyl Didecyl diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tolidine diisocyanate, tolidine triisocyanate, dicyclohexylmethane diisocyanate, hydrogenated deuterated diisocyanate, different Carbaryl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, norbornene diisocyanate and the like.

Further, an isocyanate-terminated urethane prepolymer obtained by reacting a polyisocyanate with a polyhydric alcohol can also be used as the polyisocyanate. Such a polyol is not particularly limited, and examples thereof include a polyether polyol, a polyester polyol, and a polyhydric alcohol compound such as an alkyl diol, a trimethylol alkane, glycerin, and neopentyl alcohol. Caprolactone polyol, polyolefin polyol, polybutadiene polyol, polycarbonate polyol, and the like.

The hydroxyl group-containing (meth) acrylate which can be used for the urethane acrylate is a (meth) acrylate type compound having one or more hydroxyl groups in the molecule. Examples of such a compound include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Ester, 2-hydroxyethyl propylene phthalate phosphate, 2-(meth) propylene oxiranyl ethyl hydroxypropyl phthalate, glyceryl di(meth) acrylate, (meth) acrylate 2 -hydroxy-3-propenyloxypropyl ester, neopentaerythritol tri(meth)acrylate Ester, di-n-pentaerythritol penta(meth)acrylate, caprolactone modified 2-hydroxyethyl (meth)acrylate, mono(meth)acrylate cyclohexanedimethanol ester, and the like.

The resin composition for an optical material of the present invention can be polymerized by a known polymerization reaction such as photopolymerization or thermal polymerization. Here, a conventional polymerization initiator such as a photopolymerization initiator or a thermal polymerization initiator can be used.

Examples of the photopolymerization initiator include a benzophenone polymerization initiator, an acetophenone polymerization initiator, and an oxime photopolymerization initiator.

Examples of the thermal polymerization initiator include, in addition to the azo polymerization initiator and the substituted ethane polymerization initiator, a peroxide initiator such as a persulfate or a peroxide, and a sulfite. A redox reaction initiator produced by a combination of a reducing agent such as a hydrogen sulfite salt and a metal salt.

The amount of the polymerization initiator to be used is usually 0.005 to 10 parts by weight, based on 100 parts by weight of the compound having a polymerizable unsaturated group.

Further, as the polymerization method, a conventional method such as emulsion polymerization is used.

The polymerization temperature is adjusted according to the kind of the polymerization initiator described above, preferably It is, for example, 20 ° C to 100 ° C.

In the present invention, in the case of the compound having the above polymerizable unsaturated group, it is preferred to have three or more polymerizable functional groups in one molecule, from the viewpoint that the hardness is increased to prevent further scratching.

In addition, a resin composition for an optical material having a polymerizable unsaturated group having three or more polymerizable functional groups in one molecule and a zirconia as a dispersion particle as described above may be used. A coating film having a higher refractive index is provided and can be used in various fields.

The blending amount of the compound having a polymerizable unsaturated group is preferably from 1 to 80% by weight, more preferably from 30 to 70% by weight based on the total of the resin composition for an optical material of the present invention.

10. Optional ingredients

In the resin composition for an optical material of the present invention, the above-mentioned respective components may be further added, and various resins, oligomers, and monomers which are generally used for coating, adhesion, and molding may be used without particular limitation. class. Specifically, an acrylic resin, a polyester resin, an alkyd resin, a urethane resin, an anthrone resin, a fluororesin, an epoxy resin, a polycarbonate resin, a polyvinyl chloride resin, a polyvinyl alcohol, or the like may be added. . Further, an organic solvent having a boiling point of less than 100 ° C at 1 atm may also be added.

11. How to use

The hard coat coating of the present invention can be obtained by applying the resin composition for an optical material of the present invention to a substrate, evaporating the solvent, and curing the solvent. Examples of the substrate to be coated include resin films such as glass and polyethylene terephthalate (PET); glass composites, ceramics, metals, and steel sheets. Further, the coating method may be exemplified by spin coating, bar coating, spraying, screen, gravure, offset, relief printing, intaglio, inkjet, etc. These can be carried out using a device, an apparatus, or the like which is usually used without any particular limitation. Further, the hardening of the coated film is a known one that can use heat, ultraviolet rays, radiation, or the like.

Further, an optical material such as a lens can be produced by using the resin composition for an optical material of the present invention and molding it with a molding die.

In the resin composition for an optical material of the present invention, although the amount of the zirconia particles and the organic cerium compound is large, the resin composition is low in viscosity, and the yellowing of the obtained cured resin can be suppressed, and transparency can be formed. A resin having a high refractive index which is excellent in heat resistance and has a low haze value.

"Embodiment"

Hereinafter, examples and comparative examples of the invention will be described. another In addition, hereinafter, "parts" indicating the blending amount means "parts by weight", and "%" means "% by weight". It is needless to say that the present invention is not limited to the embodiments described below, and may be appropriately modified or modified without departing from the technical scope of the invention.

<Synthesis of Dispersant> [Production Example 1 (Synthesis of Dispersant A)]

In a toluene solvent, a branched C11-14 alkyl alcohol (product name: EXXAL 13, manufactured by ExxonMobil) ethylene oxide 10 molar addition product 640 g (1 mol) and sodium monochloroacetate 152 Gram (1.3 mol), fed to the reactor and stirred to homogeneity. Then, 52 g of sodium hydroxide was added under the conditions of a reaction system temperature of 60 °C. Next, the temperature of the reaction system was raised to 80 ° C and allowed to mature for 3 hours. After the ripening, a white suspension solution was obtained by dropwise adding 117 g (1.2 mol) of 98% sulfuric acid under the condition that the reaction system was 50 °C. Next, the white suspension solution was washed with distilled water, and the solvent was removed by distillation under reduced pressure to obtain a dispersant A (R: branched C11-14 alkyl group, AO: ethylene oxide, n: 10, X) :CH ₂ ).

[Production Example 2 (Synthesis of Dispersant B)]

In addition to the branched C11-14 alkyl alcohol oxide 10 molar addition product in Production Example 1, instead of the hetero-sterol ethylene oxide 10 molar addition product 598 g (1 mol), The rest were carried out in the same manner as in Production Example 1, to obtain a dispersant B (R: isodecyl group, AO: ethylene oxide, n: 10, X: CH ₂ ).

[Production Example 3 (Synthesis of Dispersant C)]

In addition to the branched C11-14 alkyl alcohol oxide 10 molar addition in the manufacturing example 1, instead of the branched C11-14 alkyl alcohol ethylene oxide 5 molar addition 420 grams (1 Mo Other than the ear, the rest was carried out in the same manner as in Production Example 1, to obtain a dispersant C (R: a branched C11-14 alkyl group, AO: ethylene oxide, n:5, X:CH ₂ ).

[Production Example 4 (Synthesis of Dispersant D)]

The reaction was carried out at 120 ° C for 2 hours by dispersing 640 g (1 mol) of a branched C11-14 alkyl alcohol oxide 10 mol extract and 100 g (1 mol) of succinic anhydride to obtain a dispersant D. (R: branched C11-14 alkyl, AO: ethylene oxide, n: 10, X: COCH ₂ CH ₂ ).

[Production Example 5 (Synthesis of Dispersant E)]

In addition to the branched C11-14 alkyl alcohol oxide 10 molar addition in Production Example 1, instead of 2-ethylhexanol ethylene oxide 10 molar addition 570 grams (1 mole) The rest were carried out in the same manner as in Production Example 1 to obtain a dispersant E (R: 2-ethylhexyl group, AO: ethylene oxide, n: 10, X: CH ₂ ).

[Production Example 6 (Synthesis of Dispersant a)]

Except for the branched C11-14 alkyl alcohol oxide 10 molar addition product in Production Example 1, instead of the methanol ethylene oxide 10 molar addition product 472 g (1 mol), the rest The same procedure as in Production Example 1 was carried out to obtain a dispersant a (R: methyl group, AO: ethylene oxide, n: 10, X: CH ₂ ).

[Production Example 7 (Synthesis of urethane acrylate A)]

504 g (1 mol) of a trimer of hexamethylene diisocyanate (HMDI), neopentyl glycol triacrylate (trade name: PET-3, Dai-ichi Kogyo Seiyaku Co.) , Ltd.) 894 g (3 mol) and hydroquinone monomethyl ether 0.8 g were added, and the reaction was carried out at 70 ° C to 80 ° C until the residual isocyanate concentration became 0.1% by weight or less to obtain an amine group. Acid ester acrylate A.

[Example 1]

A commercially available zirconia dispersion (trade name SZR-M manufactured by Sakai Chemical Industry Co., Ltd., a primary particle diameter of 3 nm, and a methanol dispersion containing 30% by weight of zirconia) was 100 parts. 1.5 parts of Dispersant A produced in Production Example 1 and phenyltriethoxydecane (trade name: KBE-103, manufactured by Shin-Etsu Silicone Co., Ltd.) 1.5 parts, neopentyl glycol triacrylate (product name: NEW FRONTIER PET-3, manufactured by Dai-ichi Kogyo Co., Ltd.) 18.9 parts, and 8.1 parts of phenoxyethyl acrylate (trade name: NEW FRONTIER PHE, manufactured by Dai-ichi Kogyo Co., Ltd.) were mixed. This mixture was subjected to pressure reduction under reduced pressure by using a rotary evaporator to obtain a resin composition for an optical material of the present example.

[Example 2]

The resin composition for an optical material of the present example was obtained in the same manner as in Example 1 except that 1.5 parts of the dispersant B described in Production Example 2 was used instead of 1.5 parts of the dispersant A.

[Example 3]

The resin composition for an optical material of the present example was obtained in the same manner as in Example 1 except that 1.5 parts of the dispersant C described in Production Example 3 was used instead of 1.5 parts of the dispersant A.

[Example 4]

The resin composition for an optical material of the present example was obtained in the same manner as in Example 1 except that 1.5 parts of the dispersant A was used instead of 1.5 parts of the dispersant A.

[Example 5]

The resin composition for an optical material of the present example was obtained in the same manner as in Example 1 except that 1.5 parts of the dispersing agent E described in Production Example 5 was used instead of 1.5 parts of the dispersing agent A.

[Example 6]

In place of 1.5 parts of phenyltriethoxydecane, 1.5 parts of methyltriethoxydecane (trade name: KBE-13, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. The rest was carried out in the same manner as in Example 1 to obtain a resin composition for an optical material of the present example.

[Example 7]

In addition to 1.5 parts of phenyltriethoxydecane, 1.5 parts of 3-methylpropenyloxypropyltrimethoxydecane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of In the same manner as in Example 1, the resin composition for an optical material of the present example was obtained.

[Example 8]

Except that 8.1 parts of phenoxyethyl acrylate was used instead of 4 parts of phenoxyethyl acrylate and 4.1 parts of urethane acrylate A as disclosed in Production Example 7, the same as in Example 1. In the manner of the above, the resin composition for an optical material of the present Example was obtained.

[Example 9]

In addition to 18.9 parts of neopentyl triacrylate, 9.5 parts of neopentyl triacrylate and dimethylol tricyclodecyl diacrylate (manufactured by Nippon Kayaku Co., Ltd.) were used instead. In the same manner as in Example 1, except that 9.4 parts of KAYARAD R-684), the resin composition for an optical material of the present example was obtained.

[Example 10]

Use of methacrylic acid instead of replacing 8.1 parts of phenoxyethyl acrylate 4 parts of acid methoxy polyethylene glycol ester (trade name: NEW FRONTIER MPEM-400, manufactured by Dai-Il Pharmaceutical Co., Ltd.) and bisphenol A polyethylene glycol methacrylate (trade name: NEW FRONTIER BPEM-10, Other than 4.1 parts of the first industrial pharmaceutical company, the rest was carried out in the same manner as in Example 1, and the resin composition for an optical material of the present example was obtained.

[Example 11]

The resin composition for an optical material of the present example was obtained in the same manner as in Example 1 except that 8.1 parts of phenoxyethyl acrylate was used instead of 8.1 parts of phenylthioethyl acrylate.

[Example 12]

The same as in Example 1, except that 18.9 parts of pentaerythritol triacrylate and 8.1 parts of phenoxyethyl acrylate were replaced by 29.4 parts of pentaerythritol triacrylate and 12.6 parts of phenoxyethyl acrylate. In the manner of the above, the resin composition for an optical material of the present Example was obtained.

[Example 13]

The same as in Example 1, except that 18.9 parts of pentaerythritol triacrylate and 8.1 parts of phenoxyethyl acrylate were replaced by 17.2 parts of pentaerythritol triacrylate and 7.3 parts of phenoxyethyl acrylate. In the manner of the above, the resin composition for an optical material of the present Example was obtained.

[Comparative Example 1]

Except that the same amount of lauric acid was used instead of the dispersant A of Example 1, the rest was carried out in the same manner, and the composition of this comparative example was obtained.

[Comparative Example 2]

The composition of this comparative example was obtained by the same method except that the same amount of 2-ethylhexanoic acid was used instead of the dispersant A of Example 1.

[Comparative Example 3]

The composition of this comparative example was obtained by the same method except that the same amount of the dispersing agent a disclosed in Production Example 6 was used instead of the dispersing agent A of Example 1.

[Comparative Example 4]

The composition of this comparative example was obtained in the same manner except that the blending amount of the phenyltriethoxysilane of Example 1 was 3 parts, and the dispersant A was not used.

<Evaluation of characteristics of dispersion (dispersion)>

The dispersibility and viscosity of the resin compositions for optical materials of the above examples and comparative examples were evaluated, and the results are shown in Table 1. The evaluation method is as follows.

(dispersion)

The presence or absence of the precipitate was visually confirmed, and was ○ when there was no precipitate, and X when there was a precipitate.

(viscosity)

The viscosity of the dispersion at 25 ° C was measured according to JIS K5600-2-3 using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80R).

<Evaluation of characteristics of hardened materials>

To 5 g of the resin composition for an optical material prepared by the above-mentioned respective examples and the respective comparative examples, 0.15 g of Lucirin TPO (trade name, manufactured by BASF Japan, Ltd.) was added as a polymerization initiator. After it was dissolved, it was placed in a case made of a glass plate having a spacer of 25 μm, and cured by irradiation of UV (ultraviolet rays) of 400 mJ to obtain a cured product having a thickness of 25 μm. The appearance, the refractive index, the haze, and the degree of yellowing after the heat resistance test are shown in Table 1 for this cured product. The evaluation method is as follows.

(appearance of hardened material)

The appearance of the cured product was visually observed, and when no precipitate or crack was observed, it was ○, and when precipitates or cracks were observed, it was X.

(refractive index)

The refractive index at a wavelength of 589 nm was measured using a prism coupler (METRICON(TM) model manufactured by Metricon Corporation).

(Abbe number)

According to JIS K0062, the refractive index of the cured product at wavelengths of 405 nm, 532 nm, and 633 nm was measured using a 稜鏡 coupler (trade name: METRICON(稜鏡 coupler model 2010, manufactured by METRICON), and the obtained measurement was performed. The value calculates the Abbe number.

(haze)

The haze of the cured product was measured using a haze meter (manufactured by Suga Manufacturing Co., Ltd., HGM type) in accordance with JIS K7136.

(heat resistance test. yellowing degree)

The cured product was placed on a hot plate at 250 ° C, and ΔYI was calculated from the measured value of the yellowing degree before heating and after 5 minutes in accordance with JIS K7105.

<Result>

As is apparent from Table 1, the resin compositions for optical materials of the respective examples showed excellent results in any evaluation of dispersibility and viscosity. On the other hand, in the resin compositions of Comparative Examples 1 and 2, the evaluation of the dispersibility was poor, and the resin compositions of Comparative Examples 1 to 4 had an increased viscosity, so that it was difficult to uniformly mix and the cured product could not be formed.

Further, the cured product obtained from the resin composition for an optical material of each of the examples exhibited excellent results in any evaluation of appearance, refractive index, Abbe number, haze and yellowing degree.

[Industrial use possibility]

In the resin composition for an optical material of the present invention, although the amount of the zirconia particles and the organic cerium compound is large, the resin composition is low in viscosity, and the yellowing of the obtained cured resin can be suppressed, and transparency can be formed. Sex and A high refractive index resin excellent in heat resistance. Therefore, it can be used in the field of manufacturing of optical machines and the like. The present invention has been described in detail with reference to the preferred embodiments of the invention.

The present application is based on Japanese Patent Application No. 2011-257960, filed on Jan.

Claims (4)

A resin composition for an optical material, comprising: a zirconia particle having an average particle diameter of 1 to 30 nm, a dispersing agent composed of a compound represented by the following formula (1), an organic cerium compound, and a polymerizable property a compound of a saturated group; Wherein R of the formula (1) is an alkyl group and/or an alkenyl group having a branched chain and having a carbon number of 3 to 24, AO is an oxyalkylene group having a carbon number of 1 to 4, and n is an average addition of an alkylene oxide. The molar number is a value in the range of 3 to 30, and X is a linking group composed of a carbon atom, a hydrogen atom, and/or an oxygen atom. The resin composition for an optical material according to claim 1, wherein, in the dispersant, X in the above formula (1) is an alkylene group having 1 to 15 carbon atoms. The resin composition for an optical material according to claim 1, wherein, in the dispersant, X in the above formula (1) is a linking group represented by the following formula (2): Wherein Y of the formula (2) is any one selected from the group consisting of an alkylene group having 1 to 15 carbon atoms, a vinyl group, a phenylene group, and a phenyl group having a carboxyl group. The resin for optical materials according to any one of claims 1 to 3 In the composition, when the resin composition for an optical material is 100% by weight, the amount of the zirconia particles blended is 0.5 to 80% by weight.