JP2023156990A - Curable compositions, cured products, optical articles, lenses, and glasses - Google Patents

Abstract

To provide a curable composition which produces a cured product with a low specific gravity and high refractive index; a cured product derived from the curable composition; and an optical article, a lens, and spectacles, each comprising the cured product.SOLUTION: An embodiment of the present invention is a curable composition. The curable composition contains a sulfur-containing compound represented by formula (I) and a styrene compound. The styrene compound contains at least one selected from the group consisting of styrene and styrene derivatives. In formula (I), R1 represents a linear thiol alkylene group having one or more sulfur atoms. R2 and R3 independently represent a hydrogen atom, a methyl group, or an ethyl group.SELECTED DRAWING: Figure 1

Description

The present invention relates to a curable composition, a cured product, an optical article, a lens, and glasses.

Glass lenses include glass lenses and plastic lenses. The specific gravity of plastic lenses is lower than that of glass lenses, so plastic lenses are lighter. On the other hand, the refractive index of plastic lenses tends to be lower than that of glass lenses. In order to make lenses even thinner, plastic lenses with a high refractive index are required.

A plastic lens is manufactured, for example, by photopolymerizing a curable composition containing a monomer having a (meth)acryloyl group and a photopolymerization initiator.

Japanese Patent Application Publication No. 2004-269814 Japanese Patent Application Publication No. 2009-031796

An object of the present invention is to provide a curable composition that can realize a cured product with low specific gravity and a high refractive index, this cured product, and optical articles, lenses, and eyeglasses containing the cured product.

According to embodiments, a curable composition is provided. The curable composition contains a sulfur-containing compound represented by the following formula (I) and a styrene compound. The styrene compound includes at least one selected from the group consisting of styrene and styrene derivatives.

In formula (I), R ¹ is a chain thioalkylene group containing one or more sulfur atoms. R ² and R ³ are each independently a hydrogen atom, a methyl group, or an ethyl group.

According to an embodiment, a cured body is provided. The cured product is a cured product of the curable composition according to the embodiment.

According to embodiments, an optical article is provided. The optical article includes the cured product according to the embodiment.

According to embodiments, a lens is provided. The lens includes the optical article according to the embodiment.

According to embodiments, eyeglasses are provided. The glasses include lenses according to other embodiments.

According to the present invention, it is an object of the present invention to provide a curable composition capable of realizing a cured product having a low specific gravity and a high refractive index, this cured product, and optical articles, lenses, and eyeglasses containing the cured product.

FIG. 1 is a cross-sectional view schematically showing an example of a lens according to an embodiment. 1 is a cross-sectional view schematically showing an example of eyeglasses according to an embodiment.

[Curable composition]
The curable composition according to the embodiment includes a sulfur-containing compound represented by the following formula (I) and at least one styrene compound selected from the group consisting of styrene and styrene derivatives.

In formula (I), R ¹ is a chain thioalkylene group containing one or more sulfur atoms. R ² and R ³ are each independently a hydrogen atom, a methyl group, or an ethyl group.

As a result of intensive research, the present inventors found that the sulfur-containing compound represented by the above formula (I) is highly compatible with styrene compounds, and by combining them, a cured product with low specific gravity and high refractive index is realized. I found out what I can do.

That is, styrene represented by the following formula (II) is a polymerizable compound that has a vinyl group and undergoes radical polymerization by heat or light. The specific gravity of styrene is approximately 0.9. Styrene is an optical material compound with a relatively light specific gravity.

On the other hand, the sulfur-containing compound represented by the above formula (I) is an optical material compound that can realize a cured product with a high refractive index. A cured product obtained by polymerizing a curable composition containing these compounds can have both a high refractive index of 1.60 or more and a low specific gravity of 1.13 or less, for example. When the cured product of the curable composition according to the embodiment is used, it is possible to realize a lens that is thin and lightweight, and is therefore particularly suitable for plastic lenses for eyeglasses.

(Sulfur-containing compounds)
The sulfur-containing compound is represented by the following formula (I).

In formula (I), R ¹ is a chain thioalkylene group containing one or more sulfur atoms. The number of carbon atoms in the chain thioalkylene group is, for example, 1 or more and 20 or less. The number of carbon atoms in the chain thioalkylene group is preferably 2 or more and 10 or less, more preferably 3 or more and 6 or less. The number of sulfur atoms contained in the chain thioalkylene group is, for example, 1 or more and 10 or less, preferably 1 or more and 3 or less, and more preferably 1 or 2.

Specific examples of R ¹ include 3-thia-1,5-pentamethylene group, 3-thia-1,5-dimethyl-1,5-pentamethylene group, 4-thia-1,7-heptamethylene group, 3-thia-1,9-nonamethylene group, 3,5-dithia-1,6-hexamethylene group, 3,5-dithia-1,7-heptamethylene group, 3,6-dithia-1,8-octa Included are methylene group, 3,6-dithia-1,8-dimethyl-1,8-octamethylene group, and 3,6,9-trithia-1,11-undecamethylene group. Preferably, R ¹ is a 3-thia-1,5-pentamethylene group.

R ² and R ³ are each independently a hydrogen atom, a methyl group, or an ethyl group. R ² and R ³ may be different groups or may be the same group. R ² and R ³ are preferably hydrogen atoms from the viewpoint of improving the storage stability of the polymerizable composition. R ² and R ³ are preferably methyl groups from the viewpoint of increasing the safety and production efficiency of the polymerizable composition.

In the curable composition, the proportion of the sulfur-containing compound is preferably 10% by mass or more, more preferably 14% by mass or more, and 19% by mass from the viewpoint of increasing the refractive index of the cured product. It is more preferable that it is above. From the viewpoint of lowering the specific gravity of the cured product, the proportion occupied by the sulfur-containing compound is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. .

In the curable composition, the proportion occupied by the sulfur-containing compound can be calculated by, for example, isolating the sulfur-containing compound from the curable composition by silica gel chromatography or the like, and measuring the weight of the obtained sulfur-containing compound.

The sulfur-containing compound represented by formula (I) can be produced, for example, by a known method.

(Styrene compound)
The styrene compound includes at least one selected from the group consisting of styrene and styrene derivatives.

The styrene derivative is a compound having a styrene skeleton represented by the above formula (II). Specific examples of styrene derivatives include 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, α-methylstyrene dimer, 2,4,6-trimethylstyrene, 4-tert-butylstyrene, Vinylphenol, vinylthiophenol, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 3-chloromethylstyrene, 4-chloromethylstyrene, 2-bromostyrene, 3-bromostyrene, 4-bromostyrene, 3 - Bromomethylstyrene, 4-bromomethylstyrene, 4-aminostyrene, 3-cyanomethylstyrene, 4-cyanomethylstyrene, divinylbenzene, trivinylbenzene, 4-vinylbiphenyl, 2,2'-divinylbiphenyl, 4, Included are 4'-divinylbiphenyl, 2,2-bis(4-vinylphenyl)propane, bis(4-vinylphenyl)ether, vinylnaphthalene, and divinylnaphthalene.

The styrene derivative preferably contains at least one of α-methylstyrene and α-methylstyrene dimer. α-methylstyrene and α-methylstyrene dimer can function as chain transfer agents.

The styrene compound preferably contains styrene, and more preferably contains both styrene and styrene derivatives. More preferably, the styrene compound includes styrene, α-methylstyrene, and α-methylstyrene dimer.

In the curable composition, the ratio M1/M2 of the mass M1 of the sulfur-containing compound to the mass M2 of the styrene compound is preferably 0.10 or more, and 0.10 or more, from the viewpoint of increasing the refractive index of the cured product. It is more preferably 15 or more, and even more preferably 0.25 or more. From the viewpoint of lowering the specific gravity of the cured product, the ratio M1/M2 is preferably 0.40 or less, more preferably 0.35 or less, and even more preferably 0.30 or less.

In the curable composition, the ratio M1/M3 of the mass M1 of the sulfur-containing compound to the mass M3 of styrene is preferably 0.15 or more, and 0.20 from the viewpoint of increasing the refractive index of the cured product. It is more preferably 0.30 or more, and even more preferably 0.30 or more. From the viewpoint of lowering the specific gravity of the cured product, the ratio M1/M3 is preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.35 or less.

In the curable composition, the proportion of the styrene compound is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more from the viewpoint of lowering the specific gravity of the cured product. It is even more preferable that there be. From the viewpoint of increasing the refractive index of the cured product, the proportion occupied by the styrene compound is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less. .

In the curable composition, the proportion of styrene is preferably 40% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 75% by mass or less. The proportion occupied by styrene may be 40% by mass or more and 60% by mass or less.

In the curable composition, the proportion of the styrene derivative is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less.

In the curable composition, the proportion of α-methylstyrene is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 5% by mass or less.

In the curable composition, the proportion of α-methylstyrene dimer is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 15% by mass or less.

When the styrene compound contains a mixture of styrene and its derivatives, the proportion of styrene in the mixture is preferably 50% by mass or more and 95% by mass or less, and more preferably 80% by mass or more and 90% by mass or less.

In the curable composition, the proportion of the styrene compound, styrene, styrene derivative, etc. can be calculated, for example, by silica gel chromatography of the curable composition, similarly to the above-mentioned sulfur-containing compound.

((meth)acrylate)
The curable composition according to the embodiment may contain (meth)acrylate in addition to the sulfur-containing compound and styrene compound. (Meth)acrylate is a monomer having at least one of an acryloyl group and a methacryloyl group. (Meth)acrylates include monofunctional (meth)acrylates having one (meth)acryloyl group, di(meth)acrylates having two (meth)acryloyl groups, and polyfunctional (meth)acrylates having three or more (meth)acryloyl groups. Contains meth)acrylates. The (meth)acrylate preferably contains di(meth)acrylate in terms of increasing the static pressure resistance and improving the flexibility of the cured product.

Specific examples of (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and ethylene glycol bisglycidyl (meth)acrylate. acrylate, bisphenol A di(meth)acrylate, hydroxyethyl methacrylate, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, and 2,2-bis(3,5-dibromo-4-(meth) ) acryloyl, oxyethoxyphenyl) propane.

In the curable composition, the ratio M1/M4 between the mass M1 of the sulfur-containing compound and the mass M4 of the (meth)acrylate is preferably 0.1 or more and 4 or less, and preferably 0.5 or more and 3 or less. More preferably, it is 0.5 or more and 2 or less.

In the curable composition, the ratio M3/M4 of the mass M3 of styrene to the mass M4 of (meth)acrylate is preferably 1 or more and 20 or less, more preferably 2 or more and 10 or less.

In the curable composition, the proportion occupied by (meth)acrylate is preferably 5% by mass or more, more preferably 9% by mass or more, from the viewpoint of increasing the static pressure resistance of the cured product, and 14% by mass or more. More preferably, it is at least % by mass. The proportion occupied by (meth)acrylate is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of lowering the specific gravity of the cured product.

The (meth)acrylate preferably includes bisphenol A di(meth)acrylate. When the curable composition contains bisphenol A di(meth)acrylate, a tough cured product with excellent static pressure resistance can be realized.

Bisphenol A di(meth)acrylate contains at least one compound selected from the group consisting of alkoxylated bisphenol A acrylate and alkoxylated bisphenol A methacrylate. The alkoxylated bisphenol A acrylate contains at least one compound selected from the group consisting of ethoxylated bisphenol A acrylate and propoxylated bisphenol A acrylate. The alkoxylated bisphenol A methacrylate contains at least one compound selected from the group consisting of ethoxylated bisphenol A methacrylate and propoxylated bisphenol A methacrylate.

It is preferable that bisphenol A di(meth)acrylate contains a compound shown in the following formula (1).

In the above formula (1), R ⁴ and R ⁵ are each a hydrogen atom or a methyl group. a is an integer of 1 or more and 10 or less. b is an integer of 1 or more and 10 or less. a+b is an integer of 2 or more and 20 or less, and a+b is preferably an integer of 2 or more and 5 or less.

In the curable composition, the ratio M1/M6 of the mass M1 of the sulfur-containing compound to the mass M6 of bisphenol A di(meth)acrylate is preferably 0.1 or more and 4 or less, and 0.5 or more and 3 or less. More preferably, it is 0.5 or more and 2 or less.

In the curable composition, the ratio M3/M6 of the mass M3 of styrene to the mass M6 of bisphenol A di(meth)acrylate is preferably 1 or more and 20 or less, more preferably 2 or more and 10 or less.

In the curable composition, the proportion of bisphenol A di(meth)acrylate is preferably 5% by mass or more, more preferably 9% by mass or more, from the viewpoint of increasing the static pressure resistance of the cured product. The content is preferably 14% by mass or more, and more preferably 14% by mass or more. The proportion occupied by bisphenol A di(meth)acrylate is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of lowering the specific gravity of the cured product.

The (meth)acrylate preferably includes a compound containing a (meth)acryloyloxy group. When a compound containing a (meth)acryloyloxy group is included, the adhesiveness between the cured product and a laminated layer such as a hard coat layer tends to increase. The compound containing a (meth)acryloyloxy group is preferably a monofunctional (meth)acrylate.

Examples of the compound containing one (meth)acryloyloxy group include a compound represented by the following formula (2).

In the formula, g is a number from 1 to 20 on average. A is a linear or branched alkylene group having 2 to 5 carbon atoms. R ¹¹ is a hydrogen atom or a methyl group. R ¹² is a hydrogen atom or a methyl group.

Specific examples of compounds having one (meth)acryloyloxy group include 2-(hydroxyethyl)(meth)acrylate, hydroxypropyl(meth)acrylate, 4-(hydroxybutyl)(meth)acrylate, 2-(methoxy) ethyl)(meth)acrylate, 3-(methoxypropyl)(meth)acrylate, 2-(2-(2-methoxyethoxy)ethoxy)ethyl(meth)acrylate, polyethylene glycol monomethyl ether(meth)acrylate, polyethylene glycol mono( meth)acrylate and m-phenoxybenzyl acrylate.

In the curable composition, the ratio M1/M5 between the mass M1 of the sulfur-containing compound and the mass M5 of the compound containing one (meth)acryloyloxy group is preferably 5 or more and 50 or less, and 10 or more and 30 or less. It is more preferable that there be.

In the curable composition, the ratio M3/M5 of the mass M3 of styrene to the mass M5 of the compound containing a (meth)acryloyloxy group is preferably 20 or more and 80 or less, more preferably 30 or more and 70 or less. preferable.

In the curable composition, the proportion of the compound containing one (meth)acryloyloxy group is preferably 0.1% by mass or more from the viewpoint of increasing the adhesion between the cured product and the hard coat layer. , more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The proportion of the compound containing one (meth)acryloyloxy group is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of lowering the specific gravity of the cured product.

In the curable composition, the proportion of the compound containing a (meth)acrylate or (meth)acryloyloxy group can be calculated, for example, by silica gel chromatography of the curable composition, similarly to the above-mentioned sulfur-containing compound.

(Polymerization initiator)
A polymerization initiator is mainly used for curing a curable composition containing at least one of a cationically polymerizable monomer and a radically polymerizable monomer. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator may be used.

As the radical thermal polymerization initiator, at least one selected from the group consisting of dialkyl peroxides, peroxy esters, percarbonates, and azo compounds can be used.

As the radical photopolymerization initiator, at least one selected from the group consisting of benzophenone, acetophenone compounds, α-dicarbonyl compounds, and acylphosphine oxide compounds can be used. Acylphosphine oxide compounds include 2,6-dimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4, 4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine acid methyl ester, 2,6-dichlorobenzoyldiphenylphosphine oxide, and Contains 2,6-dimethoxybenzoyldiphenylphosphine oxide.

The amount of the polymerization initiator in the curable composition is, for example, from 0.01% by mass to 5% by mass, preferably from 0.1% by mass to 2% by mass.

(Ultraviolet absorber)
Preferably, the curable composition contains an ultraviolet absorber. The ultraviolet absorber has a peak in the wavelength region of 400 nm or less in its absorption spectrum. By including the ultraviolet absorber, discoloration of the cured product can be suppressed. That is, sulfur-containing compounds and styrene compounds may be decomposed by ultraviolet light. When these compounds are decomposed, radicals can be generated. Radicals promote oxidative deterioration of the cured product, and can, for example, discolor a colorless and transparent cured product to yellow.

The ultraviolet absorber preferably has a peak in at least one of a wavelength region of 280 nm or more and less than 320 nm and a wavelength region of 320 nm or more and 360 nm or less in its absorption spectrum. It is more preferable that the ultraviolet absorber has a peak in both a wavelength region of 280 nm or more and less than 320 nm and a wavelength region of 320 nm or more and 360 nm or less. The ultraviolet absorber more preferably has a peak in at least one of a wavelength region of 290 nm or more and less than 310 nm, or a wavelength region of 330 nm or more and 350 nm or less, and even more preferably a peak in both of these wavelength regions.

In other words, the inventors' research has shown that in sulfur-containing compounds, there is a possibility that the bond between the (meth)acryloyl group and the sulfur adjacent to this (meth)acryloyl group begins to decompose due to ultraviolet light around 340 nm. It was found that there is a possibility that the bond between sulfur and the carbon atom of the thioalkylene group R ¹ adjacent to this sulfur starts to decompose due to ultraviolet rays around 300 nm. In addition, in styrene compounds, the bonds between carbon atoms that are substituents on the benzene ring may begin to decompose due to ultraviolet light around 340 nm, and the bonds between the carbon atoms that are substituents on the benzene ring and the bonds between these carbon atoms. It has been found that there is a possibility that the bond between hydrogen and hydrogen begins to decompose due to ultraviolet light around 300 nm. Therefore, by using an ultraviolet absorber having an absorption peak within the above range in the absorption spectrum, discoloration of the cured product can be more effectively prevented.

In the absorption spectrum of an ultraviolet absorber, the horizontal axis shows wavelength and the vertical axis shows absorbance. Absorption spectra can be measured with a spectrophotometer. As the measurement sample, for example, a chloroform solution in which a 10 μM ultraviolet absorber is dissolved and the temperature is adjusted to 23° C. is used.

An organic compound can be used as the ultraviolet absorber. As the ultraviolet absorber, for example, at least one selected from the group consisting of benzotriazole derivatives, benzophenone derivatives, ethylhexyl methoxycinnamate, and triazine derivatives is used. The ultraviolet absorber preferably contains at least one selected from the group consisting of benzotriazole derivatives, benzophenone derivatives, cyanoacrylate derivatives, and ethylhexyl methoxycinnamate; It is more preferable to contain at least one kind selected from the above, and it is even more preferable to contain a benzotriazole derivative.

It is preferable that the benzotriazole derivative includes a compound represented by the following formula (3).

In formula (3), R ²¹ is an alkyl group having 1 to 10 carbon atoms, or an oxyalkyl group having 1 to 10 carbon atoms. R ²¹ is preferably a methyl group or an oxyoctyl group.

As the benzophenone derivative, octabenzone such as ADEKA Stab 1413 from ADEKA Co., Ltd., SEESORB 107 and SEESORB L58 from Cipro Kasei Co., Ltd., and the like can be used. As the cyanoacrylate derivative, Uvinul (registered trademark) 3039 manufactured by BASF, etc. can be used. As ethylhexyl methoxycinnamate, BASF's Uvinul (registered trademark) MC-80 and the like can be used. As the benzotriazole derivative, ADEKA STAB LA-32 and LA-36 manufactured by ADEKA Co., Ltd., SEESORB 707 manufactured by Cipro Kasei Co., Ltd., etc. can be used. As the triazine derivative, ADEKA STAB LA-46 manufactured by ADEKA Co., Ltd., etc. can be used.

One type of ultraviolet absorber may be used alone, or a plurality of types may be used in combination. For example, a combination of an ultraviolet absorber having a maximum absorption wavelength in a wavelength range of 280 nm or more and less than 320 nm and an ultraviolet absorber having a maximum absorption wavelength in a wavelength range of 320 nm or more and 360 nm or less may be used. Further, a combination of an ultraviolet absorber having a peak in a wavelength region of 280 nm or more and less than 320 nm and a wavelength region of 320 nm or more and 360 nm or less and an ultraviolet absorber having a peak in a wavelength region of 300 nm or more and 320 nm or less is used. Good too.

In the curable composition, the proportion of the ultraviolet absorber contained is, for example, 0.1% by mass or more and 10% by mass or less, preferably 0.5% by mass or more and 5% by mass or less, more preferably 0. .8% by mass or more and 3% by mass or less.

(Photochromic compound)
The curable composition may include a photochromic compound. A photochromic compound is a compound that can reversibly generate two or more isomers having different light absorption spectra by the action of light. When photochromic compounds are blocked from ultraviolet rays, they become isomers that exhibit a colorless state, i.e., colorless substances, and when irradiated with ultraviolet rays, they become isomers that exhibit a colored state, that is, chromic substances. Become. A cured product of a curable composition containing a photochromic compound has a dimming function that changes color depending on the amount of ultraviolet irradiation, that is, photochromic property. Such a cured product is used, for example, in photochromic lenses, accessories, and the like. As the photochromic compound, for example, at least one selected from the group consisting of chromene compounds, fulgide compounds, and spirooxazine compounds is used. As the photochromic compound, it is preferable to use a chromene compound. The chromene compound includes a compound having a 1-benzopyran skeleton, a spiropyran compound having a spiropyran skeleton, and a naphthopyran compound having a naphthopyran skeleton. Naphthopyran compounds include indenonaphthopyran compounds having an indenonaphthopyran skeleton. The chromene compound preferably includes an indenonaphthopyran compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton. A cured product containing a chromene compound having an indeno[2,1-f]naphtho[1,2-b]pyran skeleton tends to have excellent durability.

(Other additives)
The curable composition may also contain other additives. Additives include, for example, mold release agents, blue light absorbers, high-energy visible light absorbers, infrared absorbers, antioxidants, color inhibitors, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, solvents, and leveling agents. and at least one selected from the group consisting of polymerization regulators.

As the blue light absorber, a compound having an absorption peak in the wavelength region higher than 400 nm and lower than 450 nm in the absorption spectrum can be used. Such a compound is, for example, at least one selected from the group consisting of perylene compounds, porphyrin compounds, carotenoid compounds, and cyanine compounds. As the blue light absorber, it is preferable to use a porphyrin compound, and it is more preferable to use a tetraazaporphyrin compound.

The high-energy visible light absorber is a blue light absorber having an absorption peak in a wavelength range of 400 nm or more and 420 nm or less. As the high-energy visible light absorber, those similar to the blue light absorber can be used.

The dye preferably contains a compound having an absorption peak in the wavelength range of 540 nm or more and 650 nm or less, and more preferably contains a compound that has an absorption peak in the wavelength range of 550 nm or more and 600 nm or less in the absorption spectrum. When such a compound is included, the antiglare properties of the cured product can be improved. Examples of such compounds include nitro compounds, azo compounds, anthraquinone compounds, threne compounds, porphyrin compounds, and rare earth metal compounds. As such a compound, it is preferable to use at least one selected from the group consisting of tetraazaporphyrin compounds and neodymium compounds.

[Cured body]
A cured body is obtained by curing the curable composition according to the embodiment.

The cured product of the curable composition according to the embodiment can realize a high refractive index of 1.60 or more. The refractive index of the cured product can be measured using, for example, a commercially available refractometer. Specifically, it can be measured using an Abbe refractometer NAR-3T manufactured by ATAGO.

Further, the cured product of the curable composition according to the embodiment can realize a low specific gravity of 1.13 or less. The specific gravity of the cured product can be measured using, for example, a commercially available hydrometer. Specifically, it can be measured using an automatic hydrometer DSG-1 manufactured by Toyo Seiki Seisakusho.

The shape of the cured product is not particularly limited. The cured product can be used as an optical article. Optical articles include, for example, plastic lenses such as semi-finished lenses and finished lenses, windows for automobiles and buildings, information recording devices, ornaments, and the like. The cured product according to the embodiment is suitably used as a lens base material for a plastic lens.

A cured product of the curable composition can be obtained, for example, by a cast polymerization method. Specifically, it is obtained by filling a mold with a curable composition and thermally polymerizing it. As heating conditions, for example, the temperature is raised from the initial temperature to the curing temperature over 10 hours or more and 60 hours or less. The initial temperature is, for example, at least room temperature and at most 50°C. The curing temperature is, for example, 80°C or higher and 120°C or lower.

[lens]
The lens according to the embodiment includes an optical article including the cured body according to the embodiment. The lens according to the embodiment may be a semi-finished lens or a finished lens.

The lens according to the embodiment may include a lens base material containing the cured product according to the embodiment, and a hard coat layer provided on at least one main surface of the lens base material. The hard coat layer may be provided on both sides of the lens base material. Further, an antireflection film may be present on the surface of the hard coat layer. At least one of a photochromic layer and a polarizing layer may be present between the lens base material and the hard coat layer. The lens according to the embodiment includes, for example, a lens base material, an adhesive layer provided on the surface of the lens base material, a photochromic layer provided on the adhesive layer, and a hard coat layer provided on the photochromic layer. and an antireflection film provided on the hard coat layer.

The lens according to the embodiment may include a lens base material containing a cured product and a photochromic layer provided on at least one main surface of the lens base material.

The hard coat layer contains, for example, a silicon-containing compound such as an organic silane and an inorganic silane, and an inorganic oxide. As the inorganic oxide, a material having a high refractive index such as titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), cerium oxide (CeO ₂ ), etc. is used. These inorganic oxides have ultraviolet absorption ability. Therefore, lenses equipped with a hard coat layer containing these inorganic oxides are less likely to cause discoloration. From the viewpoint of high ultraviolet absorption ability, it is preferable to contain at least one inorganic oxide selected from the group consisting of titanium oxide and cerium oxide.

An antireflection film is a film that prevents reflection of light by interference. The antireflection film has a multilayer structure in which a relatively high refractive index film and a low refractive index film are laminated. The low refractive index film is made of, for example, silicon dioxide (SiO ₂ ) having a refractive index of about 1.43 to 1.47. The high refractive index film is made of a material that has a higher refractive index than the low refractive index layer. Examples of such materials include zirconium oxide (ZrO ₂ ), tin oxide (SnO ₂ ), niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), titanium oxide (TiO ₂ ), and yttrium oxide. (Y ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), a mixture thereof (for example, indium tin oxide (ITO)), etc. are used.

The photochromic layer contains, for example, the photochromic compound and resin described above. The resin is selected from the group consisting of polyester resin, polyamide resin, allyl resin, acrylic resin, methacrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polythiourethane urea resin, polythioepoxy resin, and polycarbonate resin. It may contain at least one kind.

The adhesive layer may contain the resins listed as examples of resins that may be included in the photochromic layer. Providing an adhesive layer tends to increase the impact resistance of the lens. The adhesive layer can be obtained, for example, by applying a primer composition onto a lens base material and drying it. As the primer composition, it is preferable to use a dispersion of a moisture-curable urethane resin or a prepolymer thereof.

The polarizing layer can be formed, for example, by applying a dichroic dye to the surface of the lens base material. Alternatively, a polarizing film may be used as the polarizing layer. As the polarizing film, a film obtained by dyeing a stretched or unstretched polyvinyl alcohol (PVA) film with a dichroic dye can be used.

The lens according to the embodiment may be a laminate of first and second lens base materials containing the cured body according to the embodiment and a binder sheet located between the first and second lens base materials. . One main surface of the binder sheet is covered with the first lens base material, and the other main surface is covered with the second lens base material. The side surfaces of the binder sheet may also be covered with the lens base material. The binder sheet includes, for example, first and second optical sheets and an adhesive layer that is located between the first and second optical sheets and adheres them. The first and second optical sheets are made of polyvinyl alcohol resin, polyethylene terephthalate resin, polycarbonate resin, polyamide resin, polyester resin, cellulose resin, (meth)acrylic resin, polyurethane resin, polyurethane urea resin, polyimide resin, epoxy resin, and polyolefin. Contains at least one selected from the group consisting of resins. When using a polyvinyl alcohol resin film as an optical sheet, it may have a polarizing function. The adhesive layer may contain a functional dye such as a photochromic compound.

FIG. 1 is a cross-sectional view schematically showing an example of a lens according to an embodiment. The lens 10 shown in FIG. Contains a coating layer 3.

FIG. 2 is a cross-sectional view schematically showing an example of eyeglasses according to the embodiment. Eyeglasses 100 shown in FIG. 2 include a lens 101 and a frame 102 that supports this lens 101. Lens 101 includes the optical article according to the embodiment.

<Example 1>
(Preparation of curable composition)
Mix 15 parts by mass of a sulfur-containing compound represented by the following formula (Ia), 77 parts by mass of styrene, 2 parts by mass of α-methylstyrene dimer, 8 parts by mass of α-methylstyrene, and 1 part by mass of perbutyl ND. A curable composition was prepared.

(Preparation of cured body)
The curable composition was thoroughly stirred and mixed and then degassed under vacuum. The degassed curable composition was poured into a mold made of glass plates with a gap of 2 mm, and polymerized by thermal polymerization. The polymerization was carried out over 21 hours while gradually increasing the temperature from 38° C. to 90° C. using an air oven. After the polymerization was completed, the cured product was removed from the mold. The shape of the cured product was a flat plate with a diameter of 80 mm and a thickness of 2 mm.

<Examples 2 to 14>
A cured product was obtained in the same manner as in Example 1, except that the formulation of the curable composition was changed as shown in Table 1 below. The details of the abbreviations in Tables 1 and 2 are as follows.

SA: a sulfur compound represented by the following formula (Ia).

S-MA: a sulfur compound represented by the following formula (Ib).

TAEI: A compound represented by the following formula (4).

MSD: α-methylstyrene dimer.

MS: α-methylstyrene.

BPM: Bisphenol A dimethacrylate represented by the following formula (1a). In formula (1a), a+b is 2.6.

BPA: Bisphenol A diacrylate represented by the following formula (1b). In formula (1b), a+b is 3.

HEMA: Hydroxyethyl methacrylate represented by the following formula (2a).

PI1: Polymerization initiator Perbutyl (registered trademark) ND
PI2: Polymerization initiator Perocta (registered trademark) O
UV1: Ultraviolet absorber represented by the following formula (3a).

UV2: Ultraviolet absorber represented by the following formula (5).

UV3: Ultraviolet absorber represented by the following formula (6).

UV4: Ultraviolet absorber represented by the following formula (7).

UV5: Ultraviolet absorber represented by the following formula (3b).

<Example 15>
(Preparation of cured body)
A cured product was obtained in the same manner as in Example 1, except that the formulation of the curable composition was changed as shown in Table 2 below.

(Preparation of laminate)
After the surface of the obtained cured product was subjected to plasma treatment, it was chemically treated with a 20% by mass sodium hydroxide solution. A thermosetting composition HC1 containing cerium oxide was applied onto the main surface of the cured product after the chemical treatment by dip coating to form a coating film. After sufficiently drying this coating film, the dried coating film was thermally cured. During thermosetting, heating was performed at a temperature of 110° C. for 3 hours. In this way, a laminate in which a hard coat layer was laminated on one main surface of the cured body was obtained. Note that the thickness of the hard coat layer was 2 μm.

Note that the following composition was used as the thermosetting composition HC1. 77% by mass methanol-dispersed titanium oxide sol (solid content concentration 30%), 18% by mass 3-glycidyloxypropyltrimethoxysilane, 1% by mass 3-glycidoxypropyldimethoxymethylsilane, 2% by mass distilled water, A composition containing 1.5% by mass of curing catalyst and 0.5% by mass of leveling agent was used. ).

<Example 16 to Example 22>
A cured product and a laminate were obtained in the same manner as in Example 15, except that the formulation of the curable composition and the photocurable composition for forming a hard coat layer were changed as shown in Tables 2 and 4 below. Ta.

The thermosetting composition HC2 contains 11% by mass of cerium oxide sol, 34% by mass of zirconium oxide sol, 18% by mass of 3-glycidyloxypropyltrimethoxysilane, and 1% by mass of 3-glycidoxypropyldimethoxymethylsilane. , 32% by mass of methanol, 2% by mass of distilled water, 1.5% by mass of curing catalyst, and 0.5% by mass of leveling agent. Note that the concentrations of cerium oxide and zirconium oxide in the cerium oxide sol and zirconium oxide sol were each 15% by mass.

<Evaluation test>
(Refractive index)
The refractive index of the cured products of Examples 1 to 22 was measured using an Abbe refractometer NAR-3T manufactured by ATAGO. The test results are shown in Tables 3 and 4.

(specific gravity)
The specific gravity of the cured bodies of Examples 1 to 22 was measured using an automatic hydrometer DSG-1 manufactured by Toyo Seiki Seisakusho. The test results are shown in Tables 3 and 4.

(static pressure test)
The cured bodies of Examples 1 to 22 were subjected to a static pressure test in accordance with Japanese Industrial Standards JIS T 7331:2006. After the test, the cured product was visually checked to see if any cracks had occurred. The test results are shown in Tables 3 and 4.

<Weather resistance test>
A weather resistance test was conducted on the cured bodies or laminates according to Examples 1 to 22 using a xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd.

Specifically, first, the sample was irradiated with ultraviolet rays for 144 hours using a xenon lamp. The test temperature was 50° C., and the irradiance was 40 W/m ² (300 nm to 400 nm). Next, the ultraviolet irradiation was stopped and the yellowness of the sample was measured to obtain the yellowness YI of the sample after the weather resistance test. A touch panel color computer SM-T manufactured by Suga Test Instruments Co., Ltd. was used to measure the degree of yellowness. The test results are shown in Tables 3 and 4.

<Example 23>
(Production of photochromic optical article)
A photochromic optical article was obtained by using the cured product (without hard coat layer formed) obtained according to the formulation shown in Table 2 and Example 22 as a lens base material, and laminating the photochromic cured product on the surface of the lens base material.

(Preparation of photochromic curable composition)
A photochromic curable composition was prepared by mixing radically polymerizable monomers in the following formulation.

Polyethylene glycol dimethacrylate (average molecular weight 736): 42 parts by mass Polyethylene glycol dimethacrylate (average molecular weight 536): 12 parts by mass Trimethylolpropane trimethacrylate: 38 parts by mass γ-methacryloyloxypropyltrimethoxysilane: 2 parts by mass Glycidyl methacrylate: 1 part by mass.

Note that 0.27 mmol of a photochromic compound represented by the following formula (8) was added to 100 g of the curable composition.

Furthermore, the following additives were added. In addition, the following compounding quantity is a compounding ratio with respect to 100 mass parts of said curable compositions.

Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photopolymerization initiator: Omnirad819): 0.3 parts by mass Ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-) m-tolyl) propionate] (stabilizer, Irganox245): 1 part by mass Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate: 3 parts by mass Leveling agent manufactured by Dow Corning Toray Co., Ltd. L7001): 0.1 part by mass.

(Manufacture of photochromic laminate)
First, a cured product (with no hard coat layer formed) having a center thickness of 2 mm obtained from the prescription shown in Table 2, Example 22 was prepared as a lens base material. Note that this lens base material was previously subjected to alkaline etching at 50° C. for 5 minutes using a 10% aqueous sodium hydroxide solution, and then thoroughly washed with distilled water.

Apply a moisture-curing primer (product name: TR-SC-P, manufactured by Tokuyama Co., Ltd.) to the surface of the above lens base material using a spin coater (1H-DX2, manufactured by MIKASA) at a rotation speed of 70 rpm for 15 seconds. Subsequently, coating was performed for 10 seconds at 1000 rpm. Thereafter, about 2 g of the photochromic curable composition obtained above was spin-coated at a rotation speed of 60 rpm for 40 seconds, then at 600 rpm for 10 to 20 seconds so that the coating layer had a thickness of 40 μm.
The lens whose surface was coated with the coating agent in this way was irradiated with light for 90 seconds using a metal halide lamp with an output of 200 mW/cm ² in a nitrogen gas atmosphere to cure the coating film. Thereafter, by further heating at 110° C. for 1 hour, a photochromic optical article in which a photochromic cured product was laminated on the surface of the lens base material was obtained.

The obtained photochromic optical article was evaluated by the following method, and the evaluation results are shown in Table 5.

〔Evaluation methods〕
<Photochromic properties>
The following values were measured using a spectrophotometer (instantaneous multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd.

Maximum absorption wavelength (λmax): Maximum absorption wavelength after color development.

Color density: This is the difference between the absorbance (A ₃₀₀ ) after irradiation with light for 300 seconds at 23° C. and the absorbance (A ₀ ) without irradiation at the maximum absorption wavelength.

Half-life of fading [τ _1/2 (sec)]: At 23°C, after light irradiation for 300 seconds, when light irradiation is stopped, the absorbance of the sample at the maximum absorption wavelength is 1 of {A ₃₀₀ - A ₀ } This is the time required to decrease to /2.

<durability>
Remaining rate (%) = [(A ₉₆ )/(A ₀ ) x 100]: The photochromic cured product was accelerated for 96 hours to undergo accelerated deterioration using a xenon weather meter X25 manufactured by Suga Test Instruments. The color density was evaluated before and after the accelerated deterioration test, and the ratio (A ₉₆ /A ₀ ) of the color density of the photochromic cured product before _the test (A ₀ ) and the color density of the photochromic cured product after the test (A 96 ) was determined. This was used as an index of the durability of color development. The higher the residual rate, the higher the durability of color development.

<Example 24>
A photochromic optical article was obtained in the same manner as in Example 23, except that a thiourethane plastic lens having a center thickness of 2 mm and a refractive index of 1.60 was used as the lens base material.
The obtained photochromic optical article was evaluated in the same manner as in Example 23, and the evaluation results are shown in Table 5.

Claims (18)

A curable composition comprising a sulfur-containing compound represented by the following formula (I) and at least one styrene compound selected from the group consisting of styrene and styrene derivatives:
In the formula (I),
R ¹ is a chain thioalkylene group containing one or more sulfur atoms,
R ² and R ³ are each independently a hydrogen atom, a methyl group, or an ethyl group. The curable composition according to claim 1, wherein a ratio M1/M2 of the mass M1 of the sulfur-containing compound and the mass M2 of the styrene compound is 0.10 or more and 0.40 or less. The curable composition according to claim 1 or 2, wherein the proportion of the sulfur-containing compound is 10% by mass or more and 30% by mass or less. The curable composition according to claim 1 or 2, wherein the styrene compound accounts for 40% by mass or more and 80% by mass or less. The curable composition according to claim 1 or 2, further comprising an ultraviolet absorber. The curable composition according to claim 5, wherein the ultraviolet absorber has a peak in at least one of a wavelength region of 280 nm or more and less than 320 nm, and a wavelength region of 320 nm or more and 360 nm or less. The curable composition according to claim 1 or 2, further comprising di(meth)acrylate. The curable composition according to claim 7, wherein the proportion of the di(meth)acrylate is 5% by mass or more and 30% by mass or less. The curable composition according to claim 1 or 2, further comprising a compound having a (meth)acryloyloxy group. The curable composition according to claim 9, wherein the proportion of the compound having the (meth)acryloyloxy group is 0.1% by mass or more and 10% by mass or less. A cured product of the curable composition according to claim 1 or 2. The cured product according to claim 11, which has a refractive index of 1.60 or more. The cured product according to claim 11 or 12, which has a specific gravity of 1.13 or less. An optical article comprising the cured product according to claim 11. A lens comprising the optical article according to claim 14. a lens base material containing the cured body;
The lens according to claim 15, further comprising a hard coat layer provided on at least one main surface of the lens base material. a lens base material containing the cured body;
The lens according to claim 15, further comprising a photochromic layer provided on at least one main surface of the lens base material. Eyeglasses comprising the lens according to claim 15 or 16.