TWI708803B - Curable composition and optical member - Google Patents

Abstract

The present invention provides a curable composition with a high refractive index and a low viscosity, a cured product thereof, and an optical member using the curable composition. The present invention is a curable composition, a cured product thereof, and an optical member using the curable composition. The curable composition is characterized by containing: zirconia particles (A) and (meth)acrylic acid (B), and the above-mentioned (meth)acryloyl group-containing compound (B) contains phenyl benzyl (meth)acrylate (B1) as an essential component. The above-mentioned curable composition has a characteristic of low viscosity even if it contains zirconia particles (A).

Description

Curable composition and optical member

The present invention relates to a curable composition with high refractive index and low viscosity, its cured product, and an optical component.

The backlight device such as the liquid crystal display device is provided with a brightness-enhancing sheet such as a thin film or a micro-lens film for enhancing the brightness. The brightness-enhancing film is mainly manufactured by shaping the resin material with a mold. Therefore, the resin material for the brightness-enhancing film must contain no solvent and have a low viscosity suitable for shaping. In addition, in order to enhance the brightness improvement effect, the cured product has a high refractive index, high transparency, and resistance to damage.

As a resin material for a brightness enhancement film, a curable composition containing zirconia fine particles, phenylphenol polyethoxyacrylate, and the like is known (see Patent Document 1). This type of inorganic fine particle blended resin material has the characteristic of high refractive index. On the other hand, due to the blending of inorganic fine particles, there is a tendency to increase the viscosity. Therefore, it is required to develop a resin material that contains inorganic fine particles but has a lower viscosity.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] JP 2013-249439 A

Therefore, the problem to be solved by the present invention is to provide a curable composition with a high refractive index and low viscosity, a cured product thereof, and an optical member.

The inventors of the present invention conducted intensive research to solve the above-mentioned problems and found that by combining zirconia particles with phenylbenzyl (meth)acrylate, a curable composition with a very good balance of viscosity and refractive index can be obtained. , Thereby completing the present invention.

That is, the present invention relates to a curable composition characterized by containing: zirconium oxide particles (A) and a (meth)acryloyl group-containing compound (B), and the (meth)acryloyl group-containing compound (B) Phenyl benzyl (meth)acrylate (B1) is used as an essential component.

The present invention further relates to a cured product obtained by curing the above-mentioned curable composition, and an optical member.

According to the present invention, it is possible to provide a curable composition having a high refractive index and a low viscosity, a cured product thereof, and an optical member.

Hereinafter, the present invention will be described in detail.

The curable composition of the present invention is characterized by containing zirconium oxide particles (A) and a (meth)acryloyl group-containing compound (B), and the (meth)acryloyl group-containing compound (B) is Phenyl benzyl meth)acrylate (B1) is an essential component.

The zirconia particles (A) contained in the curable composition of the present invention are obtained by dispersing the raw material zirconia particles (a) in a dispersion medium containing a (meth)acryloyl group-containing compound (B) as an essential component obtain. In terms of becoming a cured product with a high refractive index and excellent light transmittance, the average particle diameter of the zirconia particles (A) in the curable composition is preferably in the range of 20 to 100 nm.

Furthermore, in the present invention, the average particle diameter of the zirconia particles (A) is a value obtained by measuring the particle diameter in the curable composition under the following conditions.

Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.

Particle size measurement sample: The curable composition is made into a non-volatile 0.6 mass% methyl isobutyl ketone solution.

The zirconium oxide particles (a) used as a raw material can be generally known ones such as commercially available ones. The particle shape is not particularly limited, and may be, for example, a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an amorphous shape. Among them, in terms of obtaining a cured product having excellent dispersion stability and a high refractive index, a spherical shape is preferred. In terms of obtaining a cured product having excellent dispersion stability and relatively high light transmittance and refractive index, the average primary particle size of the above-mentioned zirconia particles (a) is preferably 1 to 50 nm, particularly preferably 1 to 30 nm. The crystal structure of the zirconium oxide particles (a) is also not particularly limited. In terms of obtaining a cured product having excellent dispersion stability and a high refractive index, a monoclinic system is preferred. Moreover, in the present invention, various silane coupling agents (C) and the like can also be used to remove the functional group It is introduced to the surface of the fine particles of the zirconia particles (a).

Examples of the above-mentioned silane coupling agent (C) include the following.

Examples of the (meth)acryloxy silane coupling agent include: 3-(meth)acryloxypropyltrimethylsilane, 3-(meth)acryloxypropylmethyldimethyldimethyl Oxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane Group propyl triethoxy silane. As the acryloxy-based silane coupling agent, 3-propenoxypropyltrimethoxysilane can be exemplified.

Examples of the vinyl silane coupling agent include: allyl trichlorosilane, allyl triethoxy silane, allyl trimethoxy silane, diethoxy methyl vinyl silane, trichloro vinyl silane , Vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane.

Examples of epoxy-based silane coupling agents include diethoxy (glycidoxypropyl) methyl silane, 2-(3,4 epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy Propyl propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl triethoxy silane. As the styrene-based silane coupling agent, p-styryltrimethoxysilane can be exemplified.

Examples of the amino-based silane coupling agent include: N-2 (aminoethyl) 3-aminopropylmethyl dimethoxy silane, N-2 (aminoethyl) 3-aminopropyl trimethyl Oxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N-(1,3-dimethylbutylene) propylamine, N-phenyl-3-aminopropyl trimethoxysilane.

As the ureido silane coupling agent, 3-ureidopropyl triethoxy silane can be exemplified. As the chloropropyl silane coupling agent, 3-chloropropyltrimethoxysilane can be exemplified. As the mercapto-based silane coupling agent, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane can be exemplified. As the sulfur-based silane coupling agent, bis(triethoxysilylpropyl) tetrasulfide can be exemplified. As the isocyanato-based silane coupling agent, 3-isocyanatopropyltriethoxysilane can be exemplified. As the aluminum-based coupling agent, acetoxy aluminum diisopropoxide can be exemplified.

These silane coupling agents (C) may be used individually by 1 type, and may use 2 or more types together. Among them, those having a (meth)acryloxy group, glycidyl group, and epoxycyclohexyl group are preferred, and 3-(meth)acryloxypropyltrimethoxysilane is particularly preferred.

In the present invention, in order to further improve the dispersion stability of the zirconia particles (A), a dispersant (D) may also be used. The dispersant (D) is not particularly limited as long as it is a compound containing a functional group having affinity with the zirconia particles (A), and examples thereof include carboxylic acid, sulfuric acid, sulfonic acid, phosphoric acid, and these acid compounds Anionic dispersing agents with acid groups such as salts. Among them, in terms of becoming a curable composition with higher dispersion stability, a phosphate ester-based dispersant is preferred, and one having a structural part derived from a lactone compound is more preferred. Moreover, the acid value is more preferably in the range of 100 to 300 mgKOH/g, and the weight average molecular weight (Mw) is more preferably in the range of 1,000 to 3,000.

Furthermore, in the present invention, the weight average molecular weight (Mw) is a value measured using a gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Co., Ltd.

Column: protection column HXL-H manufactured by Tosoh Co., Ltd.

+TSkgel G5000HXL manufactured by Tosoh Co., Ltd.

+TSkgel G4000HXL manufactured by Tosoh Co., Ltd.

+TSkgel G3000HXL manufactured by Tosoh Co., Ltd.

+TSkgel G2000HXL manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data processing: SC-8010 manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40℃

Solvent: Tetrahydrofuran

Flow rate: 1.0ml/min

Standard: Polystyrene

Sample: Use a micro filter to filter a 0.4% by mass tetrahydrofuran solution converted to resin solid content (100μl)

In the preparation of the curable composition of the present invention, the amount of the dispersant (D) used is not particularly limited, and it is preferably in the range of 0.1-30% by mass relative to the total mass of the zirconia particles (a), More preferably, it is the range of 0.5-15 mass %.

The (meth)acryloyl group-containing compound (B) contained in the curable composition of the present invention contains phenylbenzyl (meth)acrylate (B1) as an essential component. Phenyl benzyl (meth)acrylate (B1) can be o-phenylbenzyl (meth)acrylate, m-phenylbenzyl (meth)acrylate, or p-phenylbenzyl (meth)acrylate. It can also be used as a mixture of two or more kinds. Among them, o-phenylbenzyl (meth)acrylate and m-phenylbenzyl (meth)acrylate are preferred in the following aspects, that is, the refractive index of the liquid at 25°C is 1.57 or more, and the viscosity is 30mPa‧s or less , Is a relatively high refractive index, and also exhibits low viscosity. In addition, p-phenylbenzyl acrylate is preferable in that although it is a solid at room temperature, the refractive index of a liquid at 40°C is 1.59 The above is a very high value.

In particular, it is preferable to combine ortho-phenylbenzyl (meth)acrylate, m-phenylbenzyl (meth)acrylate, and (methyl) ) P-phenylbenzyl acrylate is used in combination, and the blending ratio at this time is preferably the sum of o-phenylbenzyl (meth)acrylate and m-phenylbenzyl (meth)acrylate and p-phenyl(meth)acrylate The molar ratio of benzyl ester [{[(meth) phenyl benzyl acrylate] + [(meth) phenyl benzyl acrylate])/[(meth) phenyl benzyl acrylate]] becomes 55 Use in the range of /45~10/90.

In addition, o-phenylbenzyl (meth)acrylate and p-phenylbenzyl (meth)acrylate are also preferable in terms of ease of production. In the case of using these two components, the blending ratio becomes a curable composition with high refractive index and low viscosity, preferably o-phenylbenzyl (meth)acrylate and (methyl) The molar ratio of p-phenyl benzyl acrylate [[(meth) phenyl benzyl acrylate]/[(meth) phenyl benzyl acrylate]] is in the range of 55/45 to 10/90.

The method for producing the above-mentioned phenyl benzyl (meth)acrylate (B1) includes, for example, a method of esterifying biphenylmethanol and (meth)acrylic acid (method 1), using chloromethyl biphenyl, bromine The method of reacting the halogenated methyl biphenyl like methyl biphenyl with the alkali metal salt of (meth)acrylic acid such as potassium, sodium, lithium (method 2), and using biphenyl, hydrogen halide, and formaldehyde derivatives The method of reacting the reaction mixture obtained by the reaction with acrylic acid or acrylic acid alkali metal salt (method 3), etc.

烷等任一形態而使用。上述鹵化氫可列舉濃鹽酸或氯化氫氣體等，且較佳為以相對於聯苯為過量之莫耳比而使用。反應較佳為於酸 觸媒條件下進行，所使用之酸觸媒例如可列舉：硫酸、磷酸、多磷酸、三氯乙酸、二氯乙酸、單氯乙酸、甲磺酸、對甲苯磺酸、氯化鋅等路易斯酸等。亦可視需要於二甲氧基乙烷、二

烷、環戊基甲醚、乙酸等有機溶劑中進行反應，且反應溫度較佳為60~180℃之範圍。 For the above method 3, the reaction ratio of biphenyl to formaldehyde is preferably to use formaldehyde in the range of 1-25 mol relative to 1 mol of biphenyl. Formaldehyde can be used as formalin aqueous solution, paraformaldehyde, three

Any form such as alkane is used. Examples of the above-mentioned hydrogen halide include concentrated hydrochloric acid, hydrogen chloride gas, and the like, and are preferably used in an excess molar ratio relative to biphenyl. The reaction is preferably carried out under acid catalyst conditions. Examples of acid catalysts used include: sulfuric acid, phosphoric acid, polyphosphoric acid, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, Lewis acids such as zinc chloride, etc. It can also be used in dimethoxyethane, two

The reaction is carried out in organic solvents such as alkane, cyclopentyl methyl ether, and acetic acid, and the reaction temperature is preferably in the range of 60 to 180°C.

When the above-mentioned phenylbenzyl (meth)acrylate (B1) is produced by this method, in addition to the phenylbenzyl (meth)acrylate (B1), bis[(methyl) Acrylic methyl] biphenyl (B1') and a biphenyl compound (B1") having a molecular structure in which a biphenyl structure is bonded via a methylene group. In this case, 100 parts by mass of the reaction product The content of phenyl benzyl (meth)acrylate (B1) is preferably in the range of 30 to 95 parts by mass, more preferably in the range of 35 to 85 parts by mass. In addition, the double [(former) in 100 parts by mass of the reaction product The content of (yl)acryloylmethyl]biphenyl (B1') is preferably in the range of 5 to 70 parts by mass, more preferably in the range of 15 to 65 parts by mass. Furthermore, the above-mentioned in 100 parts by mass of the reaction product The content of the biphenyl compound (B1") of a molecular structure having a biphenyl structure bonded via a methylene group is preferably in the range of 0.5 to 30 parts by mass, more preferably in the range of 1 to 25 parts by mass.

In addition, when the above-mentioned phenylbenzyl (meth)acrylate (B1) is produced by such a method, the unreacted biphenyl may remain in the reaction product. In this case, the content of biphenyl in 100 parts by mass of the reaction product is preferably 0.5-15 parts by mass in terms of the effect required by the present invention, that is, obtaining a composition with high refractive index and low viscosity. The range is more preferably a range of 1-10 parts by mass.

As a method of measuring the content rate of each component in the reaction product, for example, gas chromatography, liquid chromatography, gel permeation chromatography, etc. can be cited.

Examples of the above-mentioned bis[(meth)acryloylmethyl]biphenyl (B1') include: 2,2'- Bis(acryloylmethyl)-1,1'-biphenyl, 3,3'-bis(acryloylmethyl)-1,1'-biphenyl, 4,4'-bis(acryloylmethyl) Base)-1,1'-biphenyl, 2,4'-bis(acryloylmethyl)-1,1'-biphenyl, 2,4-bis(acryloylmethyl)-1,1' -Biphenyl, 2,6-bis(acryloylmethyl)-1,1'-biphenyl, etc.

The above-mentioned biphenyl compound (B1") having a molecular structure in which a biphenyl structure is bonded via a methylene group is preferably in the range of 2 to 5 in the number of biphenyl structural units contained in the molecular structure. Identification of the biphenyl compound The method for the degree of polymerization of (B1") can be, for example, the following methods: using gas chromatography mass spectrometry (GC-MS) or high-speed liquid chromatography mass spectrometry (LC-MS), and using silica gel column chromatography The reaction product was analyzed by removing the above-mentioned phenylbenzyl (meth)acrylate (B1) or the above-mentioned bis(acryloylmethyl)biphenyl (B1').

In the present invention, other (meth)acrylic acid group-containing compounds (B2) other than the above-mentioned phenyl benzyl (meth)acrylate (B1) may also be used in combination as the (meth)acrylic acid group-containing compound ( B). The above-mentioned other (meth)acrylic acid group-containing compounds (B2) include, for example, epoxy (meth)acrylate, (meth)acrylate amine ester, pyrene skeleton-containing (meth)acrylate, etc. Monofunctional or polyfunctional (meth)acrylate compounds, etc.

The epoxy (meth)acrylate is specifically obtained by reacting (meth)acrylic acid or its anhydride with an epoxy resin. Examples of the epoxy resin include hydroquinone, catechol, etc. Diglycidyl ether of diphenol; Diglycidyl ether of biphenol compounds such as 3,3'-biphenyldiol and 4,4'-biphenyldiol; bisphenol A type epoxy resin, bisphenol B type ring Oxygen resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins; 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, Polyglycidyl ether of naphthol compounds such as 2,6-naphthalenediol, 2,7-naphthalenediol, binaphthol, bis(2,7-dihydroxynaphthyl)methane; 4,4',4"- Triglycidyl ethers such as methine triphenol; Novolac epoxy resins such as phenol novolac type epoxy resins and cresol novolac resins; By the above-mentioned biphenol compound, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthol compound and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, The polyether obtained by the ring-opening polymerization of various cyclic ether compounds such as butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether is modified polyglycidyl ether of aromatic polyols; by the above-mentioned biphenyl Polyglycidol which is obtained by polycondensation of diphenol compound, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthol compound and lactone compounds such as ε-caprolactone, etc. Ether etc.

Among these, in terms that the finally obtained composition has a high refractive index, one having an aromatic ring skeleton in the molecular structure is preferable. In particular, in terms of obtaining a cured coating film that exhibits a higher refractive index and exhibits higher adhesion to the plastic film substrate even under high temperature and high humidity conditions, the above-mentioned bisphenol type is particularly preferred Epoxy resin.

Furthermore, in the bisphenol type epoxy resin, in terms of obtaining a cured product with a higher refractive index and high hardness, the epoxy equivalent is preferably in the range of 160 to 1000 g/eq, more preferably 165 to 600 g/ Those in the range of eq.

Examples of the (meth)acrylate amine ester include those obtained by reacting various polyisocyanate compounds, hydroxyl group-containing (meth)acrylate compounds, and optionally various polyol compounds. Examples of the polyisocyanate compound include: diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or the like Modified urate, modified adduct, and modified biuret. Examples of the above-mentioned hydroxyl-containing (meth)acrylate compound include: hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, trimethylolpropane diacrylate, neopenteritol tris(methyl) Base) acrylate, dineopentyl erythritol penta(meth)acrylate, and polyoxyalkylene modified products, polylactone modified products, etc. Examples of the above-mentioned polyol compounds include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, glycerin, trimethylolpropane, neopenteritol, biphenol, and bisphenol Wait.

The above-mentioned (meth)acrylic acid ester containing a stilbene skeleton has a particularly high refractive index. Specifically, the compound etc. which are represented by any one of following structural formula 1-4 are mentioned.

[In the formula, X is a hydrogen atom or a hydroxyl group, R ¹ and R ⁴ are each independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a direct bond or methylene Base, m is an integer of 0 or more]

[In the formula, two Xs are each independently a hydrogen atom or a hydroxyl group, two R ^1s are each independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, m and n are each independently Is an integer of 0 or more]

[In the formula, X is a hydrogen atom or a hydroxyl group, R ¹ is a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, R ² is a hydrogen atom or a methyl group, and R ³ is a direct bond. Junction or methylene, m and n are each independently an integer of 0 or 1 or more]

[In the formula, two Xs are each independently a hydrogen atom or a hydroxyl group, two R ¹ are each independently a hydrogen atom or an alkyl group with 1 to 3 carbon atoms, and two R ² are each independently a hydrogen atom or a methyl group, m And n are each independently an integer of 0 or 1 or more].

Examples of other monofunctional or polyfunctional (meth)acrylate compounds include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate , Pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate and other aliphatic mono(meth)acrylate compounds; (A Cyclohexyl acrylate, isobornyl (meth)acrylate, adamantyl mono(meth)acrylate and other alicyclic mono(meth)acrylate compounds; glycidyl(meth)acrylate, acrylic acid Heterocyclic mono(meth)acrylate compounds such as tetrahydrofurfuryl ester; benzyl(meth)acrylate, phenyl(meth)acrylate, phenoxy(meth)acrylate, phenoxy(meth)acrylate Ethyl ester, phenoxyethoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxybenzyl (meth)acrylate, (meth) Aromatic mono(meth)acrylate compounds such as benzyl benzyl acrylate and phenylphenoxyethyl (meth)acrylate; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth) Hydroxy-containing mono(meth)acrylate compounds such as hydroxybutyl acrylate; the following structural formula (5)

Mono(meth)acrylate compounds such as the compounds shown: Polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains are introduced into the various mono(meth)acrylate monomers mentioned above. The polyoxyalkylene modified mono(meth)acrylate compound is formed in the molecular structure of the body; the (poly)lactone structure is introduced into the molecular structure of the above-mentioned various mono(meth)acrylate compounds. Ester modified mono(meth)acrylate compound; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate ) Aliphatic di(meth)acrylate compounds such as acrylate and neopentyl glycol di(meth)acrylate; 1,4-cyclohexanedimethanol di(meth)acrylate, norbornane bis(meth)acrylate Yl) acrylate, norbornane dimethanol di(meth)acrylate, dicyclopentyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate and other alicyclic di(meth) Acrylate compounds; aromatic di(meth)acrylate compounds such as biphenol di(meth)acrylate and bisphenol di(meth)acrylate; glycerol di(meth)acrylate, trimethylolpropane di (Meth) acrylate and other hydroxyl-containing di(meth)acrylate compounds; polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polyoxytetramethylene chains, etc. are introduced into the above-mentioned various bis(methyl) ) A polyoxyalkylene modified di(meth)acrylate compound formed from the molecular structure of an acrylate compound; the (poly)lactone structure is introduced into the molecular structure of the above-mentioned various di(meth)acrylate compounds Modified di(meth)acrylate compound by the lactone; aliphatic tri(meth)acrylate compound such as trimethylolpropane tri(meth)acrylate and glycerol tri(meth)acrylate; neopentyl Tetraol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dineopentaerythritol tri(meth)acrylate and other hydroxyl-containing tri(meth)acrylate compounds; Polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, and polyoxytetramethylene chains are introduced into the molecular structure of the above-mentioned various tri(meth)acrylate compounds. (Meth)acrylate compound; a lactone modified tri(meth)acrylate compound by introducing a (poly)lactone structure into the molecular structure of the above-mentioned various tri(meth)acrylate compounds; neopentaerythritol Tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dineopentaerythritol hexa(meth)acrylate and other aliphatic poly(meth)acrylate compounds with more than four functions ; Dineopentaerythritol tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate and other tetrafunctional or more hydroxyl-containing poly (meth) acrylate compounds; the polyoxyethylene chain, polyoxy Polyoxyalkylene chains such as propylene chain and polyoxytetramethylene chain are introduced into the molecular structure of the above-mentioned various poly(meth)acrylate compounds to form a polyoxyalkylene modified poly(meth) ) Acrylate compound; introducing the (poly)lactone structure into the molecular structure of the various poly(meth)acrylate compounds mentioned above Poly(meth)acrylate compound modified by lactone with more than four functions: the following structural formula (6)

(Where X ¹ and X ² are each independently a hydrogen atom or a (meth)acryloyl group) bicarbazole compound and the like represented by the formula.

Among the above-mentioned other (meth)acrylic acid group-containing compounds (B2), in terms of obtaining a curable composition with a higher refractive index, a compound having an aromatic ring in the molecular structure is preferable, and a molecular structure is more preferable Compounds with bisphenol structure.

In the case of using the above-mentioned other (meth)acryloyl group-containing compound (B2), regarding the (meth)acryloyl group-containing compound (B), the above-mentioned phenyl benzyl (meth)acrylate (B1) The ratio is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, and particularly preferably 50 parts by mass or more in terms of a curable composition having an excellent balance of refractive index and viscosity. On the other hand, when attaching importance to the flexibility of the hardened material and relatively more use of (meth)acrylates having a polyoxyalkylene structure in the molecular structure, compounds containing (meth)acryloyl groups The above-mentioned phenyl benzyl (meth)acrylate (B1) in (B) may be less than 20 parts by mass. Even in this case, by containing phenyl benzyl (meth)acrylate (B1), a curable composition with a high refractive index and a viscosity that is not too high can be obtained.

When using the above-mentioned epoxy (meth)acrylate as the above-mentioned other (meth)acryloyl group-containing compound (B2), it is preferably in the (meth)acryloyl group-containing compound (B). Use within the range of ~35 parts by mass. In the case of using the above-mentioned (meth)acrylic amine ester as the above-mentioned other (meth)acryloyl group-containing compound (B2), it is preferably 5~ in the (meth)acryloyl group-containing compound (B). Use within 35 parts by mass. In the case of using the above-mentioned (meth)acrylic acid ester containing a chlorophyll skeleton as the above-mentioned other (meth)acryloyl group-containing compound (B2), it is preferably in the (meth)acryloyl group-containing compound (B) Use within the range of 5~45 parts by mass. In the use of the above-mentioned monofunctional or multifunctional (meth)acrylic ester compound, the compound containing the (meth)acrylic acid group In the case of the compound (B2), it is preferably used in the range of 5 to 60 parts by mass in the (meth)acrylic acid group-containing compound (B).

When a (meth)acrylate having a polyoxyalkylene structure in the molecular structure is used as the (meth)acrylic acid group-containing compound (B2), it is preferably a (meth)acrylic acid group-containing compound (B2). Use within the range of 5 to 45 parts by mass in the compound (B). In addition, the number of repeating units of the oxyalkylene structure of the (meth)acrylate having a polyoxyalkylene structure in the molecular structure is preferably in the range of 10-30 per molecule. By using a (meth)acrylate having a polyoxyalkylene structure in the molecular structure as the above-mentioned (meth)acrylic acid group-containing compound (B2), a cured product with high flexibility and excellent recovery properties can be obtained .

In the curable composition of the present invention, the blending ratio of the above-mentioned zirconia particles (A) and the above-mentioned (meth)acryloyl group-containing compound (B) can be appropriately adjusted according to the required viscosity and refractive index. In terms of a curable composition having excellent dispersion stability and sufficiently high refractive index, it is preferable that the mass ratio [(A)/(B)] of the two is in the range of 25/75 to 75/25, and more Preferably, it is in the range of 40/60~70/30.

及9-氧硫

衍生物、2,2'-二甲氧基-1,2-二苯乙烷-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁烷-1-酮等。 The curable composition of the present invention may also contain a radical polymerization initiator. Examples of the radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy (Yl)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 9-oxysulfur

And 9-oxysulfur

Derivatives, 2,2'-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4 ,6-Trimethylbenzyl)phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-propanone, 2-benzyl- 2-Dimethylamino-1-(4-morpholinylphenyl)-butan-1-one and the like.

Examples of commercially available products of these radical polymerization initiators include: "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure-369", "Irgacure-500", "Irgacure-651", "Irgacure-754", "Irgacure-784", "Irgacure" -819", "Irgacure-907", "Irgacure-1116", "Irgacure-1664", "Irgacure-1700", "Irgacure-1800", "Irgacure-1850", "Irgacure-2959", "Irgacure-4043" ", "Darocure-1173" (manufactured by Ciba Specialty Chemicals), "Lucirin TPO" (manufactured by BASF), "kayacure-DETX", "kayacure-MBP", "kayacure-DMBI", "kayacure-EPA", " kayacure-OA" (manufactured by Nippon Kayaku Co., Ltd.), "Vicure-10", "Vicure-55" (manufactured by Stouffer Chemical), "Tri gonal P1" (manufactured by Akzo), "Sandoray 1000" (manufactured by Sandoz) Manufacturing), "Deap" (manufactured by Apjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), etc.

In order to exhibit sufficient curability, the addition amount of the above radical polymerization initiator is preferably in the range of 0.05 to 20 parts by mass relative to 100 parts by mass of the curable composition of the present invention, more preferably 0.1 to 10 parts by mass The scope.

When curing the curable composition of the present invention by photopolymerization, various photosensitizers may be added to the above-mentioned radical polymerization initiator. Examples of the aforementioned photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, or other nitrogen-containing compounds. These may be used alone or in combination of two or more. When adding these photosensitizers, the addition amount is preferably in the range of 0.01 to 10 parts by mass relative to 100 parts by mass of the curable composition of the present invention.

The curable composition of the present invention may also contain other various additives as needed. Examples of various additives include: ultraviolet absorbers, antioxidants, silicone-based additives, fluorine-based Additives, rheology control agents, defoamers, antistatic agents, antifogging agents, etc. Regarding the addition amount in the case of adding these additives, within the range where the effect of the additives is fully exerted without hindering the ultraviolet curing, it is preferably 0.01-40 parts by mass relative to 100 parts by mass of the curable composition of the present invention range.

The viscosity of the curable composition of the present invention is preferably 6000 mPa in terms of being able to spread over the details of the mold without defects even under high-speed coating conditions when it is used for shaping purposes using a mold, for example. ‧S below.

The refractive index of the curable composition of the present invention is preferably 1.57 or more, more preferably 1.60 or more.

The production method of the curable composition of the present invention is not particularly limited. For example, it can be produced by the following method: the above-mentioned zirconia particles (a), the above-mentioned (meth)acryloyl group-containing compound (B), and the above Dispersant (D) or a method of dispersing raw materials containing other additives at one time (Method 1); or disperse the above-mentioned zirconia particles (a) in an organic solvent, and add other ingredients to it and mix, and then reduce as needed Method to remove organic solvents (Method 2), etc.

The dispersing machine used in the above-mentioned method 1 or 2 can be used without limitation, such as a medium-type wet dispersing machine and other commonly known ones, for example, a bead mill (Star Mill LMZ-015 manufactured by Ashizawa Finetech Co., Ltd., Stock) manufactured by Ultra Apex Mill UAM-015, etc.).

The medium used in the dispersing machine is not particularly limited as long as it is generally known particles, but preferably includes zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. The average particle size of the medium is preferably 50 to 500 μm, more preferably 100 to 200 μm. If the particle size is 50μm or more, the impact force on the raw material powder is appropriate, and the dispersion does not require much time. On the other hand, if the particle size of the medium is 500 μm or less, the impact force on the raw material powder is appropriate, so the increase in the surface energy of the dispersed particles can be suppressed, and re-aggregation can be prevented.

In addition, after the particle size of the dispersed particles becomes smaller due to the use of a medium with a large impact force in the initial step of the dispersion, a two-stage method is used to use a medium with a small particle size that is not easy to reagglomerate , It can also shorten the dispersion step time.

The curable composition of the present invention can be cured by irradiation with active energy rays, heating, etc., for example. In the case of curing by the above-mentioned active energy rays, examples of the active energy rays include electron beams, ultraviolet rays, and visible rays. When using electron beams as active energy rays, Cockcroft Walton type accelerator, Van de Graaff type electron accelerator, resonance transformer type accelerator, insulated core transformer type, high-frequency high-voltage accelerator type, Linear Filament type and high-frequency type can be used The electron beam generating device hardens the curable composition of the present invention. In addition, when ultraviolet rays are used as the active energy rays, mercury lamps such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, etc. can be used for curing. At this time, the exposure amount of ultraviolet rays is preferably in the range of 0.1 to 1000 mJ/cm ² .

On the other hand, when it is hardened by heating, it can be hardened by heating to a temperature range of 60~250℃.

The curable composition of the present invention exhibits high refraction and very low viscosity, which has not yet been seen. For example, it can be better used in spectacle lenses, digital camera lenses, Fresnel lenses, and Plastic lenses such as optical lenses, and optical protective coating agents, hard coating agents, anti-reflection coatings, optical fibers, optical waveguides, holographic images, optical lenses, LED sealing materials, solar cell coating materials for solar cells, etc. For component applications, among these, it is especially suitable for plastic lenses such as prism lenses for liquid crystal substrates.

The above-mentioned so-called liquid crystal substrate lens is a sheet-like molded body having a plurality of fine ridge shape parts on one side, and is usually arranged on the back surface of the liquid crystal display element (light source) with the ridge surface facing the element side. Side), and further, a sheet lens for arranging a light guide sheet on its back surface, or a sheet lens with the above-mentioned prism lens having the function of the light guide sheet.

Here, the shape of the ridge portion of the ridge lens is preferably in the range of 70~110°, especially 75~100°, in terms of excellent light-gathering performance and increased brightness. The range of 80~95° is particularly preferred.

In addition, the distance between the ridges is preferably 100 μm or less, especially in terms of preventing the occurrence of moiré on the screen and further improving the clarity of the screen, it is particularly preferably within the range of 70 μm. In addition, the height of the unevenness of the ridge is determined based on the value of the angle θ of the apex angle of the ridge and the distance between the ridge, and is preferably within a range of 50 μm or less. Furthermore, the thickness of the sheet of the prism lens is preferably thicker in terms of strength, but in order to suppress light absorption optically, it is preferably thinner. Therefore, in terms of the balance of these, It is preferably in the range of 50 μm to 1000 μm.

The method of manufacturing the above-mentioned scallop lens using the curable composition of the present invention may be, for example, the following method: apply the composition to a mold with scallop pattern or a resin mold, etc., to smooth the surface of the composition , Laminating the transparent substrates, and irradiating active energy rays from the transparent substrate side to harden them.

The transparent substrate used here may include: a plastic substrate composed of acrylic resin, polycarbonate resin, polyester resin, polystyrene resin, fluororesin, polyimide resin, or glass.

The prism sheet obtained by the above method can be used directly, or the transparent substrate can be peeled off and used as a separate prism lens. To form the stubble part directly on the transparent substrate and In the case of use, in order to improve the adhesion between the lens and the transparent substrate, it is preferable to perform an adhesion improvement treatment such as primer treatment on the surface of the transparent substrate in advance.

On the other hand, when the transparent substrate is peeled off and used, in order to make the transparent substrate easily peelable, it is preferable to treat the surface of the transparent substrate with a silicone or a fluorine-based release agent in advance.

[Example]

Hereinafter, the present invention will be described in more detail with examples and comparative examples.

The details of each component and dispersing machine used in production examples or examples are as follows.

Production Example 1 Production of zirconium dispersion (1)

50 g of zirconium oxide particles (a1), 7.5 g of silane coupling agent (C1), and 183.0 g of methyl ethyl ketone were mixed and stirred with a dispersion mixer for 30 minutes to perform coarse dispersion. Disperse the obtained mixed liquid using a medium type wet disperser using zirconia particles with a particle size of 100 μm. While confirming the particle size in the process, after performing the dispersion treatment for a residence time of 100 minutes, 5 g of the dispersant (D1) was added and mixed, and the zirconium dispersion liquid (1) was obtained by the dispersion treatment for 20 minutes.

Production Example 2 Production of phenyl benzyl acrylate composition

‧Synthesis of chlorine intermediates

709 g of biphenyl, 276 g of paraformaldehyde, 1381 g of acetic acid, and 958 g of concentrated hydrochloric acid were added to a 5L four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a hydrogen chloride gas introduction device, and the temperature was raised to 80°C. After confirming that the feed solution is 80°C, use a Kinoshita glass Bohr filter to introduce hydrogen chloride gas into the feed solution at a rate of 20 g/hr. After confirming that the hydrogen chloride gas is saturated in the feed solution, 1061 g of phosphoric acid was added dropwise for 1 hour, and the reaction was continued for 30 hours. After the reaction, the lower layer was immediately removed from the reaction solution, 2.3 kg of toluene was added to the organic layer, and 400 g of 12.5% sodium hydroxide aqueous solution, saturated sodium bicarbonate aqueous solution, and distilled water were used to wash the organic layer. After distilling off the organic layer, 908 g of the chlorine intermediate was obtained as a white solid.

‧Acrylation

908 g of the intermediate obtained above was dissolved in 1603 g of dimethylformamide as a reaction solvent, and 372 g of potassium carbonate and p-methoxyphenol were added so that the total amount reached 300 ppm. After the intermediate solution was heated to 40°C, 323 g of acrylic acid was added dropwise to the intermediate solution over 1.5 hours. After the dropwise addition, the temperature was raised to 80°C over 2 hours, and the mixture was heated and stirred at 80°C for 3 hours. After adding 3.4 kg of water and 1.8 kg of toluene to the obtained solution and performing extraction, the organic layer was washed until the water layer became neutral. Concentrate the organic layer to obtain liquid phenyl benzyl acrylate composition 物995g.

‧Analysis of phenyl benzyl acrylate composition

The liquid refractive index of the obtained phenyl benzyl acrylate composition at 25°C is 1.592, and the viscosity is 30 mPa·s. The content of each component contained in 100 parts by mass of the phenyl benzyl acrylate composition was measured using gas chromatograms. As a result, it was found that 65.2 parts by mass of phenyl benzyl acrylate was contained, and bis(acryloylmethyl) 18.6 parts by mass of benzene, 2.3 parts by mass of biphenyl compound having a biphenyl structure bonded via a methylene group, and 5.8 parts by mass of biphenyl, and the remaining 8.1 parts by mass contains unreacted other than biphenyl Raw materials, etc. In addition, the mass ratio of isomers of phenyl benzyl acrylate (the molar ratio is also the same) [[o-phenylbenzyl acrylate]/[m-phenylbenzyl acrylate]/[p-phenylbenzyl acrylate]] is 20/1/79.

The gas chromatogram analysis conditions of the phenylbenzyl acrylate composition are as follows.

Machine: "GC-2010" manufactured by Shimadzu Corporation

Pillar: "Zebron ZB-5" manufactured by Shimadzu Corporation

Conditions: He carrier gas, flow rate 1.47mL/min, column oven 50℃, gasification chamber 300℃, heating range 50℃ to 300℃ (25℃/min)

Example 1

◆Preparation of hardening composition (1)

The (meth)acrylate compound was added to the zirconium dispersion (1) obtained in Production Example 1 at the ratio shown in Table 2, and the volatile components were removed under reduced pressure using an evaporator. Furthermore, a polymerization initiator was added to prepare a curable composition (1).

◆Measurement of particle size of zirconia particles

The zirconia particles in the curable composition (1) obtained previously were measured under the following conditions: The average particle size.

Particle size measuring device: "ELSZ-2" manufactured by Otsuka Electronics Co., Ltd.

Particle size measurement sample: The curable composition is made into a non-volatile 0.6 mass% methyl isobutyl ketone solution.

◆Measurement of refractive index

An Abbe refractometer was used to measure the refractive index of the curable composition obtained previously. The results are shown in Table 2.

◆Measurement of viscosity

Using an E-type rotary viscometer ("RE80U" manufactured by Toki Sangyo Co., Ltd.), the viscosity of the curable composition was measured at 25°C.

Examples 2 to 8 and Comparative Examples 1 to 4

The curable composition and the cured product were produced with the same points as in Example 1, and various evaluations were performed. The results are shown in Table 2 or 3.

Claims (4)

A curable composition comprising: zirconium oxide particles (A) and a (meth)acryloyl group-containing compound (B), and the (meth)acryloyl group-containing compound (B) is a (meth)acryloyl group-containing compound (B) Phenyl benzyl acrylate (B1) is an essential component, and the above-mentioned phenyl benzyl (meth)acrylate (B1) contains o-phenylbenzyl (meth)acrylate, m-phenylbenzyl (meth)acrylate, And p-phenylbenzyl (meth)acrylate, the sum of the above-mentioned o-phenylbenzyl (meth)acrylate and the above-mentioned m-phenylbenzyl (meth)acrylate is the same as the above-mentioned p-phenylbenzyl (meth)acrylate The molar ratio [{[(meth)acrylic acid o-phenylbenzyl]+[(meth)acrylic acid m-phenylbenzyl]}/[(meth)acrylic acid p-phenylbenzyl]] is 55/45 ~10/90 range. For example, the curable composition of item 1 of the scope of patent application, wherein the particle diameter of the above-mentioned zirconia particles (A) in the curable composition is in the range of 20-100 nm. A hardened product, which is the hardened product of the hardenable composition of item 1 or 2 of the scope of patent application. An optical component which is formed by using the curable composition of item 1 or 2 of the scope of patent application.