WO2013077219A1

WO2013077219A1 - Resin composition for optical material

Info

Publication number: WO2013077219A1
Application number: PCT/JP2012/079318
Authority: WO
Inventors: 真徳大本; 直樹池
Original assignee: 第一工業製薬株式会社
Priority date: 2011-11-25
Filing date: 2012-11-13
Publication date: 2013-05-30
Also published as: JP2013112707A; TW201339222A; KR20140092850A; KR101606303B1; CN103987781A; CN103987781B; JP5795949B2; TWI488898B

Abstract

Provided is a resin composition for an optical material. The resin composition has a low viscosity even if formulated having high quantities of zirconium oxide particles and an organic silicon compound, is capable of inhibiting yellowing, and forms a resin having a high refractive index and exhibiting excellent transparency and heat resistance. The resin composition for an optical material is characterized by including zirconium oxide particles having an average particle size in the range of 1-30nm, a dispersant comprising a compound represented by formula (1), an organic silicon compound, and a compound having polymerizable unsaturated groups. In formula (1), R is a branched-chain C3-24 alkyl and/or alkenyl group, AO is a C1-4 oxyalkylene group, n is a value in 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 optical materials, and more particularly to a resin composition for optical materials having a low refractive index and an Abbe number of a resin obtained by curing and capable of suppressing yellowing.

Resin lenses are widely used in cameras, office automation equipment, and glasses. Such a resin lens is required to have a high refractive index. In order to increase the refractive index of the resin, for example, Patent Document 1 discusses a dispersion in which a large amount of metal oxide fine particles such as zirconium oxide surface-treated with an organic acid are dispersed in the resin. In Patent Document 2, a dispersion in which metal oxide fine particles are treated with an organosilicon compound and dispersed in a large amount in a resin is studied.

However, when the zirconium oxide particles are dispersed in the resin as described above, there arises a problem that the resin is easily yellowed over time. The problem of yellowing of the resin can be solved by adding an organosilicon compound as in Reference 2. However, in the resin composition for optical materials, it is necessary to increase the amount of zirconium oxide particles to increase the refractive index. However, when the amount of zirconium oxide is increased, the viscosity of the dispersion itself greatly increases, and in some cases, it becomes impossible to stir.

Japanese Unexamined Patent Publication No. 2009-191167 Japanese Unexamined Patent Publication No. 2008-120605

The present invention has been made in view of such problems of the prior art, and the object thereof is a low viscosity despite the large amount of the zirconium oxide particles and the organosilicon compound, and the resulting cured product. An object of the present invention is to provide a resin composition for an optical material that can suppress yellowing of a resin over time and can form a resin having a high refractive index that is excellent in transparency and heat resistance.

The resin composition for optical materials of the present invention comprises zirconium oxide particles having an average particle size of 1 to 30 nm, a dispersant comprising a compound represented by the following formula (1), an organosilicon compound, a polymerizable unsaturated group It contains the compound which has this.

In the formula (1), R is a branched chain alkyl group and / or alkenyl group having 3 to 24 carbon atoms, AO is an oxyalkylene group having 1 to 4 carbon atoms, and n is an alkylene group It is a numerical value in the range of 3 to 30 indicating the average number of moles of oxide added, and X is a linking group consisting of a carbon atom, a hydrogen atom and / or an oxygen atom.

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

In the dispersant, X in the formula (1) is preferably a linking group represented by the following formula (2).

However, Y in the formula (2) is any selected from an alkylene group having 1 to 15 carbon atoms, a vinylene group, a phenylene group, and a carboxyl group-containing phenylene group.

In the present invention, the blending amount of the zirconium oxide particles when the resin composition for optical materials is 100% by weight is preferably 0.5 to 80% by weight.

The resin composition for an optical material of the present invention has a low viscosity despite a large amount of zirconium oxide particles and an organosilicon compound, can suppress yellowing of the resulting cured resin over time, and is transparent. Resin having a high refractive index and excellent heat resistance and heat resistance and a low haze value can be formed.

1. Zirconium oxide particles The zirconium oxide particles that are dispersoid particles in the resin composition for optical materials of the present invention have an average particle diameter of 1 to 30 nm. The zirconium oxide particles may be partially stabilized by adding other metal oxides. Further, it may be crystalline or amorphous. Further, the dispersoid particles dispersed by the dispersant in the present invention may be isotropic particles, anisotropic particles, or fibrous.

As the zirconium oxide particles to be dispersed in the present invention, those obtained by a known method can be used. As a method for preparing fine particles, a top-down method in which coarse particles are mechanically pulverized and refined, and a bottom in which particles are formed through a cluster state in which several unit particles are generated and aggregated. Although there are two types of up systems, any one prepared by any method can be suitably used. Further, they may be either a wet method or a dry method. The bottom-up method includes a physical method and a chemical method, and any method may be used. The dispersant in the present invention may be used in a top-down process in which coarse particles are mechanically pulverized and refined to form several unit particles, which pass through a cluster state in which they are aggregated. May be used in a bottom-up process in which particles are formed, or after preparing fine particles in advance by the above-described method, a surface modifier or surface protective agent is used to stably remove the fine particles from the medium. It is also possible to use particles taken out after being coated or impregnated with a known protective agent. As the protective agent, the above-mentioned known dispersants can be substituted.

In order to more specifically explain the bottom-up method, a method for preparing metal nanoparticles among the zirconium oxide particles will be exemplified. Among the bottom-up methods, a representative example of a physical method is an in-gas evaporation method in which bulk metal is evaporated in an inert gas and cooled and condensed by collision with the gas to generate nanoparticles. Chemical methods include a liquid phase reduction method in which metal ions are reduced in the liquid phase in the presence of a protective agent, and the generated zero-valent metal is stabilized at the nanosize, and a metal complex thermal decomposition method. is there. As the liquid phase reduction method, a chemical reduction method, an electrochemical reduction method, a photoreduction method, a method combining a chemical reduction method and a light irradiation method, or the like can be used.

Further, as described above, the zirconium oxide particles that can be suitably used in the present invention may be those obtained by any of the top-down method and the bottom-up method, and they are aqueous, non-aqueous, and in the gas phase. It may be prepared in any environment. In addition, when using these zirconium oxide particles, you may use what disperse | distributed the zirconium oxide particles previously in various solvents.

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

A preferable blending amount of the zirconium oxide particles in the resin composition for an optical material of the present invention is 0.5 to 80% by weight with respect to the whole composition (100% by weight), more preferably from the viewpoint of refractive index and viscosity. Is 30 to 70% by weight, more preferably 35 to 60% by weight.

2. About the hydrophobic group (R) of the dispersant
The hydrophobic group (R) of the dispersant in the present invention is a branched chain alkyl group and / or alkenyl group having 3 to 24 carbon atoms. The content of the branched alkyl group having 3 to 24 carbon atoms and / or alkenyl is preferably 70% by weight or more based on the entire R.

The raw material alcohol that can be used to generate R may have a single carbon number or a mixture of alcohols having different carbon numbers. The raw material alcohol may be synthetically or naturally derived, and the chemical structure may be a single composition or a mixture of a plurality of isomers. As the raw material alcohol that can be used, known alcohols can be selected. Specific examples include butanol, isobutanol, pentanol and / or its isomer, hexanol and / or its isomer, heptanol and / or its isomer derived from synthesis. , Octanol and / or its isomer, 3,5,5-trimethyl-1-hexanol, isononanol, isodecanol, isounol produced by the oxo process via higher olefins derived from propylene or butene, or mixtures thereof Decanol, isododecanol, isotridecanol, Neodol 23, 25, 45 manufactured by Shell Chemicals, SAFOL23 manufactured by Sasol, EXXAL7, EXXAL8N, EXXAL9, EXXAL10, EXXXAL11 and EXXXA manufactured by Exxon Mobil 13 illustrates another example of a higher alcohol which can be suitably used. Furthermore, natural octyl alcohol, decyl alcohol, lauryl alcohol (1-dodecanol), myristyl alcohol (1-tetradecanol), cetyl alcohol (1-hexadecanol), stearyl alcohol (1-octadecanol), oleyl alcohol (Cis-9-octadecene-1-ol) and the like are also examples of higher alcohols that can be used. A single composition of Guerbet alcohol having a 2-alkyl-1-alkanol type chemical structure (Guerbet Alcohol) or a mixture thereof is also an example of a higher alcohol that can be suitably used. 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-decanol, 2 In addition to heptyl-1-undecanol, 2-octyl-1-dodecanol, 2-decyl-1-tetradecanol, there are isostearyl alcohols derived from branched alcohols. Moreover, it is also possible to mix | blend and use 2 or more types of said various alcohol. However, in the dispersant in the present invention, as described above, the hydrophobic group (R) contains a branched alkyl group and / or alkenyl group having 3 to 24 carbon atoms.

When the hydrophobic group (R) is hydrogen or a hydrocarbon group having 1 to 2 carbon atoms, when the carbon number exceeds 25, and when the hydrophobic group (R) has a carbon number in the range of 3 to 24 However, when the content of the linear alkyl group and / or alkenyl group exceeds 30% by weight, the zirconium oxide particles cannot be stably dispersed in the dispersion medium, or the selection range of the dispersion medium that can be used. May be limited, or substitution or mixing with a different type of dispersion medium may occur in the dispersion preparation process. As a result, the stability of the dispersion is significantly reduced, resulting in immediate sedimentation, and the stability over time is significantly reduced, resulting in problems such as a decrease in added value, productivity, processing characteristics, and quality deterioration of the final product. . In order to avoid these problems and make the action of the dispersant particularly effective in the present invention, the hydrophobic group (R) is more preferably a branched alkyl group having 8 to 18 carbon atoms. .

3. Dispersant oxyalkylene group (AO) n
In the present invention, the alkylene oxide species suitably selected as the dispersant in the formula (1) is that AO represents an oxyalkylene group having 1 to 4 carbon atoms, specifically, an alkylene oxide having 2 carbon atoms is ethylene oxide. It is. The alkylene oxide having 3 carbon atoms is propylene oxide. The alkylene oxide having 4 carbon atoms is tetrahydrofuran or butylene oxide, and is preferably 1,2-butylene oxide or 2,3-butylene oxide. In the dispersant, the oxyalkylene chain (-(AO) n-) is blocked by either a homopolymer chain or a random polymer chain of two or more alkylene oxides for the purpose of adjusting the dispersion medium affinity of the dispersant. It may be a polymer chain or a combination thereof. N representing the average number of added moles of the alkylene oxide of the formula (1) is in the range of 3 to 30, but is preferably in the range of 5 to 20.

4). Dispersing agent linking group (X)
The linking group (X) can be selected from a known structure consisting of a carbon atom, a hydrogen atom, and an oxygen atom, preferably a saturated hydrocarbon group, an unsaturated hydrocarbon group, an ether group, a carbonyl group, or an ester group. It may have an alicyclic structure or an aromatic ring structure, and may have a repeating unit. When the linking group X contains a nitrogen atom and / or a sulfur atom and / or a phosphorus atom, it has an action of weakening the affinity effect of the carboxyl group on the dispersoid, and thus is not suitable as a structural factor of the dispersant in the present invention. .

Further, X in the formula (1) is preferably an alkylene group having 1 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms.

Further, X in the formula (1) is preferably a substance represented by the above formula (2). However, Y in Formula (2) is any selected from an alkylene group having 1 to 15 carbon atoms, a vinylene group, a phenylene group, and a carboxyl group-containing phenylene group.

5. More preferable dispersant In the present invention, it is more preferable to use a dispersant described in the following formula (3).

However, in formula (3), R is preferably a branched alkyl group having 8 to 18 carbon atoms, and n is the average number of moles of ethylene oxide added, preferably in the range of 5 to 20. By limiting the composition of the dispersant to this range, the applicability to expansion of the selection range of the dispersion medium that can be used for preparation of the dispersion, mixing of different types of dispersion medium, and substitution is improved. In this way, by limiting the composition range of the dispersant, it works more favorably with respect to the stability of the dispersion over time. Can be achieved.

6). The blending amount of the dispersant in the present invention is not particularly limited, but is 0.5 wt% or more and 25 wt% or less, and 0.5 to 20 wt% with respect to the zirconium oxide particles. Is preferable, and more preferably 1.25 wt% or more and 10 wt% or less.

7). Dispersant Production Method The dispersant in the present invention can be produced by a known method. For example, using a general nonionic surfactant compound obtained by adding an alkylene oxide to an alcohol, amine, or thiol by a known method as a raw material, a monohalogenated lower carboxylic acid or a salt thereof is used. Although it can manufacture by the method of making it react with a hydroxyl group, or the method of ring-opening reaction with the hydroxyl group of the alkylene oxide terminal using an acid anhydride, it is not limited to these methods.

In addition, the types of hydrophobic groups, alkylene oxide types and addition forms thereof, addition molar amounts, linking groups, etc. are particularly limited within the above-mentioned range, so that a wider range of types than known dispersants can be selected. The industrial utility value is great in that it can disperse various dispersoids and can disperse and stabilize the dispersoids in a wider variety of dispersion media.

In addition, the dispersant used in the present invention should be used by reducing the content of ionic species, particularly alkali metal ions, alkaline earth metal ions, heavy metal ions, and halogen ions, contained by a known purification method. Can do. The ionic species in the dispersant is greatly affected by the dispersion stability, touch resistance, oxidation resistance, electrical properties (conductive properties, insulation properties), aging stability, heat resistance, low humidity, and weather resistance of the dispersion. However, it is desirable that the content of the ions is less than 10 ppm in the dispersant.

The resin composition for an optical material of the present invention can be prepared using a known stirring means, homogenizing means, and dispersing means. Examples of dispersers that can be used include roll mills such as two rolls and three rolls, ball mills such as ball mills and vibration ball mills, paint shakers, continuous disk type bead mills, bead mills such as continuous annular type bead mills, sand mills, and jets. Mill etc. are mentioned. Further, the dispersion treatment can be performed in an ultrasonic wave generation bath.

8). Organosilicon compound As the organosilicon compound in the resin composition for an optical material of the present invention, when the surface of the zirconium oxide particles is modified, the reactivity with respect to a chemical reaction such as oxidation or reduction reaction is low or non-reactive. In addition, those having high affinity for a dispersion medium such as water, an organic solvent, and a resin are preferable. Among these, one or more selected from the group of modified silicone, silicone resin, alkoxysilane compound, chlorosilane compound, silanol compound, and silazane compound are particularly preferable.

Examples of the modified silicone include alkoxy-modified silicone, epoxy-modified silicone, epoxy-polyether-modified silicone, carbinol-modified silicone, silanol-modified silicone, mercapto-modified silicone, aralkyl-modified silicone, methacryl-modified silicone, methacrylate-modified silicone, and carboxyl-modified silicone. Phenol-modified silicone, methylstyryl-modified silicone, acrylic-modified silicone, mercapto-modified silicone, amino-modified silicone, methyl hydrogen silicone, phenylmethyl hydrogen silicone, and the like. The modified silicone includes vinyl group and / or silicon as long as it does not affect the surface activity of the zirconium oxide particles and does not impair the optical and mechanical properties of the resin when forming a composite with the resin. Those having a functional group bonded to an atom may be used.

Examples of the silicone resin include methyl silicone resin, phenylmethyl silicone resin, diphenyl silicone resin, and the like.

Examples of the alkoxysilane compound include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, hexyltrimethoxysilane, and hexyltriethoxy. Examples include silane, decyltrimethoxysilane, phenyltrimethoxysilane, diphenyltrimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, and trifluoropropyltrimethoxysilane.

Examples of the chlorosilane compound include alkylchlorosilane, and examples of the alkylchlorosilane include methyltrichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, trimethylchlorosilane, and triethylchlorosilane.

Examples of silanol compounds include trimethylsilanol and triethylsilanol.

These alkoxysilane compounds, chlorosilane compounds, and silanol compounds are in a range that does not affect the surface activity of the zirconium oxide particles, and in a range that does not impair the optical properties and mechanical properties of the resin when forming a composite with the resin. You may use together with the silane coupling agent containing reactive functional groups, such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, an isocyanate group, a mercapto group.

Examples of the silazane compound include hexamethyldisilazane.

9. Compound having a polymerizable unsaturated group The compound having a polymerizable unsaturated group that can be used in the present invention is not particularly limited as long as it has a polymerizable functional group capable of undergoing a curing reaction after formation of a coating film. Although not intended, carboxylic acid group-containing unsaturated polymerizable monomers, alkyl esters of carboxylic acid group-containing unsaturated polymerizable monomers, vinyl compounds and urethane acrylates can be preferably used.

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

Examples of alkyl esters of carboxylic acid group-containing unsaturated polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth ) Decyl acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid-t-butylcyclohexyl, (meth) acrylic acid Isobornyl, adamantyl (meth) acrylate, (meth) acrylic Bicyclo [3,3,1] nonyl, 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, diethylamino (meth) acrylate Ethyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, methoxyethylene glycol ( (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxyethylene glycol (meth) acrylate, propoxypolyethylene glycol (Meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypropylene glycol (meth) acrylate and propoxypolypropylene glycol (meth) Mono (meth) acrylic esters such as acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and triethylene glycol di (meth) Di (meth) acrylate compounds such as acrylate, trimethylol group Tri (meth) acrylate compounds such as pantri (meth) acrylate and glycerol tri (meth) acrylate, tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and sorbitol hexa (meth) ) Hexa (meth) acrylate compounds such as acrylate. In addition, (meth) acrylate means an acrylate or a methacrylate.

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

Urethane acrylate is obtained by reacting polyisocyanate and hydroxyl group-containing (meth) acrylate.

Although it does not specifically limit as polyisocyanate which can be used for urethane acrylate, Tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, phenylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hexamethylene diisocyanate, trimethyl Examples include hexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, norbornene diisocyanate, and modified products thereof.

Further, an isocyanate group-terminated urethane prepolymer obtained by reacting a polyisocyanate and a polyol can also be used as the polyisocyanate. Examples of such polyols include, but are not limited to, polyol compounds such as alkylene glycol, trimethylol alkane, glycerin and pentaerythritol, as well as polyether polyols, polyester polyols, polycaprolactone polyols, polyolefin polyols, polybutadiene polyols, and polycarbonates. A polyol etc. are also mentioned.

The hydroxyl group-containing (meth) acrylate that can be used for urethane acrylate is a (meth) acrylate 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, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethylacryloyl. Phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipenta Examples include erythritol penta (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate.

The resin composition for an optical material of the present invention can be polymerized by a known polymerization reaction such as a photopolymerization reaction or a thermal polymerization reaction. At that time, a known 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 anthraquinone photopolymerization initiator.

As thermal polymerization initiators, in addition to azo polymerization initiators and substituted ethane polymerization initiators, peroxide initiators such as persulfates and peroxides, sulfites, hydrogen sulfites and metal salts, etc. And redox polymerization initiators in combination with other reducing agents.

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

As the polymerization method, a known method such as emulsion polymerization is used.

The polymerization temperature is adjusted depending on the kind of the polymerization initiator, and is preferably 20 ° C. to 100 ° C., for example.

In the present invention, among the compounds having a polymerizable unsaturated group, those having three or more polymerizable functional groups in one molecule are preferable from the viewpoint of increasing hardness and preventing damage.

Furthermore, the resin composition for an optical material in which the compound having a polymerizable unsaturated group having three or more polymerizable functional groups in one molecule and zirconium oxide as the dispersoid particle are used together has a higher refractive index. It becomes possible to provide the coating film which has a rate, and the utilization in a various field | area becomes possible.

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

10. Optional components In addition to the above components, the resin composition for optical materials of the present invention also includes various resins, oligomers, and monomers used for ordinary paints, adhesives, and moldings. Can be used without restriction. Specifically, acrylic resin, polyester resin, alkyd resin, urethane resin, silicone resin, fluorine resin, epoxy resin, polycarbonate resin, polyvinyl chloride resin, polyvinyl alcohol, or the like may be added. Moreover, you may add the organic solvent whose boiling point in 1 atmosphere is less than 100 degreeC.

11. Method of Use The hard coat coating of the present invention is obtained by applying the resin composition for an optical material of the present invention on a substrate, evaporating the solvent, and then curing. Examples of the base material to be coated include glass, resin films such as polyethylene terephthalate (PET), glass composites, ceramics, metals, and steel plates. Examples of the coating method include spin coating, bar coating, spraying, screen, gravure, offset, letterpress, intaglio, and ink jet, but are not limited to these, and generally used apparatuses and instruments. Can be used. For curing the coated film, known materials such as heat, ultraviolet rays and radiation can be used.

Also, an optical material such as a lens can be produced by molding with a mold using the resin composition for optical material of the present invention.

Hereinafter, examples and comparative examples of the present invention will be described. In the following, “part” indicating the blending amount indicates “part by weight” and “%” indicates “% by weight”. Needless to say, the present invention is not limited to the following examples, and appropriate changes and modifications can be made without departing from the technical scope of the present invention.

<Synthesis of dispersant>
[Production Example 1 (Synthesis of Dispersant A)]
Into a toluene solvent, 640 g (1 mol) of ethylene oxide 10 mol adduct and 152 g (1.3 mol) of sodium monochloroacetate, branched C11-14 alkyl alcohol (product name: EXXAL13, manufactured by Exxon Mobil Co., Ltd.) were uniformly added. It stirred until it became. Thereafter, 52 g of sodium hydroxide was added under the condition that the temperature of the reaction system was 60 ° C. Subsequently, the temperature of the reaction system was raised to 80 ° C. and aged for 3 hours. After aging, 117 g (1.2 mol) of 98% sulfuric acid was added dropwise with the reaction system at 50 ° C. to obtain a white suspension. Next, the white suspension is washed with distilled water, and the solvent is distilled off under reduced pressure to obtain a dispersant A (R: branched C11-14 alkyl, AO: ethylene oxide, n: 10, X: CH ₂ ). It was.

[Production Example 2 (Synthesis of Dispersant B)]
In Production Example 1, the same method as in Production Example 1 was carried out except that 598 g (1 mol) of isodecyl alcohol ethylene oxide 10 mol adduct was used instead of the branched C11-14 alkyl alcohol ethylene oxide 10 mol adduct. Agent B (R: isodecyl, AO: ethylene oxide, n: 10, X: CH ₂ ) was obtained.

[Production Example 3 (Synthesis of Dispersant C)]
In Production Example 1, the same method as in Production Example 1 was carried out, except that 420 g (1 mol) of a branched C11-14 alkyl alcohol ethylene oxide 5 mol adduct was used instead of the branched C11-14 alkyl alcohol ethylene oxide 10 mol adduct. Dispersant C (R: branched C11-14 alkyl, AO: ethylene oxide, n: 5, X: CH ₂ ) was obtained.

[Production Example 4 (Synthesis of Dispersant D)]
By reacting 640 g (1 mol) of branched C11-14 alkyl alcohol ethylene oxide 10 mol adduct and 100 g (1 mol) of succinic anhydride at 120 ° C. for 2 hours, 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 Production Example 1, the same method as in Production Example 1 was carried out except that 570 g (1 mol) of 2-ethylhexyl alcohol ethylene oxide 10 mol adduct was used instead of the branched C11-14 alkyl alcohol ethylene oxide 10 mol adduct, Dispersant E (R: 2-ethylhexyl, AO: ethylene oxide, n: 10, X: CH ₂ ) was obtained.

[Production Example 6 (Synthesis of Dispersant a)]
The same procedure as in Production Example 1 was carried out except that 472 g (1 mol) of methanol ethylene oxide 10 mol adduct was used in place of the branched C11-14 alkyl alcohol ethylene oxide 10 mol adduct in Production Example 1, and dispersant a (R: methyl, AO: ethylene oxide, n: 10, X: CH ₂ ) was obtained.

[Production Example 7 (Synthesis of urethane acrylate A)]
504 g (1 mol) of hexamethylene diisocyanate (HMDI) trimer, 894 g (3 mol) of pentaerythritol triacrylate (trade name: PET-3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 0.8 g of hydroquinone monomethyl ether The resultant was added and reacted at 70 ° C. to 80 ° C. until the residual isocyanate concentration became 0.1% by weight or less to obtain urethane acrylate A.

[Example 1]
100 parts of a commercially available zirconium oxide dispersion (trade name SZR-M, manufactured by Sakai Chemical Co., Ltd., a methanol dispersion containing zirconium oxide with a primary particle size of 3 nm and 30% by weight) and dispersant A produced in Production Example 1 1.5 parts, 1.5 parts of phenyltriethoxysilane (trade name: KBE-103, manufactured by Shin-Etsu Silicone) and pentaerythritol triacrylate (trade name: New Frontier PET-3, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 18.9 parts and 8.1 parts of phenoxyethyl acrylate (trade name: New Frontier PHE, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were mixed. By removing methanol from this mixture under reduced pressure using a rotary evaporator, the resin composition for optical materials of the present Example was obtained.

[Example 2]
A resin composition for optical materials of this example was obtained in the same manner as in Example 1 except that 1.5 parts of Dispersant B described in Production Example 2 was used instead of 1.5 parts of Dispersant A. It was.

[Example 3]
A resin composition for optical materials of this example was obtained in the same manner as in Example 1 except that 1.5 parts of dispersant C described in Production Example 3 was used instead of 1.5 parts of dispersant A. It was.

[Example 4]
A resin composition for optical materials of this example was obtained in the same manner as in Example 1 except that 1.5 parts of dispersant D described in Production Example 4 was used instead of 1.5 parts of dispersant A. It was.

[Example 5]
It replaced with 1.5 parts of dispersing agent A, and carried out similarly to Example 1 except having used 1.5 parts of dispersing agent E as described in manufacture example 5, and obtained the resin composition for optical materials of a present Example. .

[Example 6]
This example was carried out in the same manner as in Example 1 except that 1.5 parts of methyltriethoxysilane (trade name: KBE-13, manufactured by Shin-Etsu Silicone) was used instead of 1.5 parts of phenyltriethoxysilane. The resin composition for optical materials was obtained.

[Example 7]
Example 1 was repeated except that 1.5 parts of 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Silicone) was used instead of 1.5 parts of phenyltriethoxysilane. The resin composition for optical materials of the present Example was obtained.

[Example 8]
The optical material of this example was the same as that of Example 1 except that 4.1 parts of phenoxyethyl acrylate and 4.1 parts of urethane acrylate A described in Production Example 7 were used instead of 8.1 parts of phenoxyethyl acrylate. A resin composition was obtained.

[Example 9]
Instead of using 18.9 parts of pentaerythritol triacrylate, 9.5 parts of pentaerythritol triacrylate and 9.4 parts of tricyclodecane dimethylol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R-684) were used. It carried out like Example 1 and obtained the resin composition for optical materials of a present Example.

[Example 10]
In place of 8.1 parts of phenoxyethyl acrylate, 4 parts of methoxypolyethylene glycol methacrylate (trade name: New Frontier MPEM-400, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and bisphenol A polyethylene glycol methacrylate (trade name: New Frontier BPEM-10, No. 1) The same procedure as in Example 1 was carried out except that 4.1 parts by Ichi Kogyo Seiyaku Co., Ltd. were used to obtain a resin composition for optical materials of this example.

[Example 11]
A resin composition for optical materials of this example was obtained in the same manner as in Example 1 except that 8.1 parts of phenylthioethyl acrylate was used instead of 8.1 parts of phenoxyethyl acrylate.

[Example 12]
The same procedure as in Example 1 was carried out except that 18.9 parts of pentaerythritol triacrylate and 8.1 parts of phenoxyethyl acrylate were replaced with 29.4 parts of pentaerythritol triacrylate and 12.6 parts of phenoxyethyl acrylate. The resin composition for optical materials of the Example was obtained.

[Example 13]
The same procedure as in Example 1 was performed except that 17.2 parts of pentaerythritol triacrylate and 7.3 parts of phenoxyethyl acrylate were used instead of 18.9 parts of pentaerythritol triacrylate and 8.1 parts of phenoxyethyl acrylate. The resin composition for optical materials of the Example was obtained.

[Comparative Example 1]
A composition of this comparative example was obtained in the same manner as in Example 1 except that the same amount of lauric acid was used instead of the dispersant A.

[Comparative Example 2]
A composition of this comparative example was obtained in the same manner as in Example 1 except that the same amount of 2-ethylhexanoic acid was used instead of the dispersant A.

[Comparative Example 3]
A composition of this comparative example was obtained in the same manner as in Example 1 except that the same amount of the dispersant a described in Production Example 6 was used instead of the dispersant A.

[Comparative Example 4]
A composition of this comparative example was obtained by carrying out the same method except that the amount of phenyltriethoxysilane in Example 1 was 3 parts and the dispersant A was not used.

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

(Dispersibility)
The presence or absence of precipitates was confirmed by visual observation.

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

<Characteristic evaluation of cured product>
After adding 0.15 g of Lucirin TPO (trade name, manufactured by BASF Japan) as a polymerization initiator to 5 g of the optical semiconductor encapsulant composition prepared in each of the above Examples and Comparative Examples, 25 μm A cured product with a thickness of 25 μm was obtained by placing in a case made of a glass plate with a spacer interposed between them and irradiating and curing with UV of 400 mJ. Table 1 shows the appearance, refractive index, haze, and degree of yellowing after the heat resistance test for this cured product. The evaluation method is as follows.

(Appearance of cured product)
The appearance of the cured product was observed with the naked eye, and the case where no precipitates and cracks were observed was evaluated as ◯, and the case where precipitates or cracks were observed was evaluated as x.

(Refractive index)
Using a prism coupler (METRICON prism coupler model 2010 manufactured by METRICON), the refractive index at a wavelength of 589 nm was measured.

(Abbe number)
According to JIS K0062, a prism coupler (trade name: METRICON prism coupler model 2010, manufactured by METRICON) was used to measure the refractive index of the cured product at wavelengths of 405 nm, 532 nm, and 633 nm, and the Abbe number was determined from the obtained measured values. Was calculated.

(Haze)
According to JIS K7136, the haze of the cured product was measured using a haze meter (HGM type manufactured by Suga Seisakusho).

(Heat resistance test / yellowing degree)
The cured product was placed on a hot plate at 250 ° C., and ΔYI was calculated from the measured values of yellowing before heating and after 5 minutes according to JIS K7105.

<Result>
As is clear from Table 1, the resin composition for optical material of each example shows excellent results in any evaluation of dispersibility and viscosity. On the other hand, the resin compositions of Comparative Examples 1 and 2 are inferior in evaluation of dispersibility, and the resin compositions of Comparative Examples 1 to 4 have a large viscosity, which makes it difficult to uniformly mix and cure. An object could not be formed.

Moreover, the cured product obtained from the resin composition for optical materials of each Example shows excellent results in any evaluation of appearance, refractive index, Abbe number, haze and yellowing degree.

The resin composition for an optical material of the present invention has a low viscosity despite a large amount of zirconium oxide particles and an organosilicon compound, can suppress yellowing of the resulting cured resin over time, and is transparent. Since the resin having a high refractive index and excellent in heat resistance and heat resistance can be formed, it can be used in the field of manufacturing optical equipment.

Claims

It contains zirconium oxide particles having an average particle diameter of 1 to 30 nm, a dispersant composed of a compound represented by the following formula (1), an organosilicon compound, and a compound having a polymerizable unsaturated group. A resin composition for optical materials.

In the formula (1), R is a branched chain alkyl group and / or alkenyl group having 3 to 24 carbon atoms, AO is an oxyalkylene group having 1 to 4 carbon atoms, and n is an alkylene group It is a numerical value in the range of 3 to 30 indicating the average number of moles of oxide added, and X is a linking group consisting of a carbon atom, a hydrogen atom and / or an oxygen atom.
2. The resin composition for an optical material according to claim 1, wherein X in the formula (1) in the dispersant is an alkylene group having 1 to 15 carbon atoms.
2. The resin composition for an optical material according to claim 1, wherein X in the formula (1) in the dispersant is a linking group represented by the following formula (2).

However, Y in the formula (2) is any selected from an alkylene group having 1 to 15 carbon atoms, a vinylene group, a phenylene group, and a carboxyl group-containing phenylene group.
4. The compounding amount of the zirconium oxide particles when the resin composition for optical materials is 100% by weight is 0.5 to 80% by weight. A resin composition for optical materials.