JPH06172742A - Ultraviolet absorber and ultraviolet-absorbing composition containing the same - Google Patents

Abstract

PURPOSE:To obtain an adsorber compsn. which is excellent in ultraviolet absorptivity in a wavelength region of 300-400nm and hardly allows the phase separation of an ultraviolet absorber by compounding a specific benzotriazole compd. as the absorber into the compsn. CONSTITUTION:This absorber compsn. contains, as the ultraviolet absorber, a compd. of formula I (wherein R<1> is 2-3C alkyl; and R<2> is H or CH3), preferably 2-[2'-hydroxy-5'-(beta-methacryloyloxy)-3'-t-butylphenyl]-5-butyl-2H-b enzotriazole of formula II. A pref. useful compsn. contains a copolymer of the absorber with another copolymrizable unsatd. monomer, such as styrene, a compd. having a silicon atom and a double bond, or a (meth)acrylic ester. This compsn. is useful for optical materials, esp. for an intraocular lens, a contact lens, and an ophthalmic lens.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ultraviolet absorber, an ultraviolet absorber composition containing the same, and an optical material using the composition, particularly an intraocular lens, a contact lens and a spectacle lens.

[0002]

2. Description of the Related Art Conventionally, salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based compounds, etc. have been known as ultraviolet absorbers for resins, and various compounds are selected and used according to the use and purpose. ing.

Conventionally, when an ultraviolet absorber is used by adding it to a polymerized composition, performance deterioration due to bleed-out from the polymerized composition and toxicity to ecology become problems in the processing scene or use scene. Therefore, in order to improve such a problem, a method of using an ultraviolet absorber having a polymerizable skeleton and homopolymerizing it or copolymerizing it with a polymerizable monomer is used. For example, a method of copolymerizing an ester of 2,4-dihydroxybenzophenone and acrylic acid (Japanese Patent Publication No. 36-6771) with a polymerizable monomer has been reported. However, the maximum absorption wavelength of acrylates of benzophenone derivatives is relatively short, and the wavelength range (320-4
Was insufficient to absorb (00 nm). Therefore, a benzotriazole-based UV absorber having a high UV absorption effect in the long wavelength region and having a longer maximum absorption wavelength, which is free from elution and bleed-out from the polymerization composition, has been desired.

Also in these methods, when the compatibility with the polymer is poor, the unreacted ultraviolet absorber bleeds out during the polymerization or during use, resulting in deterioration or deterioration of the performance. was there. Further, when the UV absorber has poor compatibility in the polymerization composition, the UV absorber causes phase separation in the polymer, resulting in a decrease in transparency,
In some cases, the physical properties of the polymerization composition itself may be reduced, such as the reduction of mechanical strength.

On the other hand, it is well known that sunlight causes damage to the human eye, especially with regard to the formation of cataracts. The part of the sun that is most involved in this is the near-ultraviolet region of 300-400 nm. This ultraviolet (UV) band is known to cause eye damage by causing chemical changes in the lens and retina. The problem of eye damage caused by this near-ultraviolet light is especially great in aphakic patients. This is because the crystalline lens, which originally plays a role as a UV absorption filter, is extracted, so that it is susceptible to photochemical damage that can be caused by myopia. In order to avoid such problems and protect the human eye, as described in US Pat. No. 3,141,869, a UV absorber is used in a spectacle lens to prevent UV rays from reaching the eye. It was supposed to be mixed. For this purpose, a benzotriazole-based UV absorber is most suitable because a UV absorber having excellent UV absorbing ability in the wavelength range of 300 to 400 nm is desired.

However, even in such an optical material, particularly in the medical optical material in the ophthalmological region, the bleed-out and elution of the ultraviolet absorbent and the deterioration of the physical properties due to the poor compatibility with the polymer as described above are caused. Was a problem.
In particular, in the case of imparting ultraviolet absorbing ability to the oxygen permeable contact lens or the soft intraocular lens in order to protect the eye function and the eye tissue, since these are composed of a polymer containing a silicon atom, particularly a siloxane-containing polymer, Unlike conventional medical optical materials represented by polymethylmethacrylate, problems such as elution of an ultraviolet absorber from a lens substrate, bleed-out, and deterioration of ultraviolet absorption characteristics are remarkable. In other words, as can be seen from the fact that the glass transition point of silicone is lower than room temperature and it is a rubber-like polymer at room temperature,
In the polymer of the siloxane compound, the molecular motion in the siloxane region is large, and the ultraviolet absorber existing in this part tends to bleed out or elute. For this reason, there is a safety problem due to the ultraviolet absorbing property disappearing after long-term use or the ultraviolet absorbent elutes. Further, as the content of the siloxane compound is increased in order to enhance the oxygen permeability and the flexibility, the problems of the above-mentioned safety and deterioration of the ultraviolet absorbing ability become more remarkable.

Also, particularly oxygen permeable contact lenses,
In medical materials such as soft intraocular men's materials, since the material consists of a hydrophobic component such as silicone and a hydrophilic component that enhances biocompatibility, the added UV absorber is prone to phase separation and There was also a problem of deteriorating the physical properties.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and particularly 300 to 4
It is an object of the present invention to provide an ultraviolet absorber excellent in ultraviolet absorbing ability in the wavelength region of 00 nm, free from elution and bleed-out, and having good compatibility with polymers, and a composition containing the same.

[0009]

The present invention provides the following formula [I]:

[Chemical 2] (In the formula, R ¹ is an alkyl group having 2 to 3 carbon atoms, and R ² is H or CH ₃ ) and an ultraviolet absorber and a composition containing the same are provided. The present invention also provides an optically transparent optical material comprising the composition of the present invention. The present invention also provides a hydrogel comprising the above composition of the present invention. Furthermore, the present invention provides a plastic film comprising the composition of the present invention. Furthermore, the present invention provides a coating material comprising the above composition of the present invention.

Since the ultraviolet absorbing composition of the present invention contains an ultraviolet absorber having a benzotriazole skeleton, it has excellent ultraviolet absorbing ability especially in the wavelength region of about 300 to 400 nm. Here, the skeleton of the benzotriazole-based ultraviolet absorber means that the phenol ring is bonded to the 2-position nitrogen atom of the benzotriazole ring. And it is possible to extract it because it uses an ultraviolet absorber having a polymerizable unsaturated double bond in the molecule, which enables copolymerization with other polymerizable monomers or homopolymerization by itself. The amount of unreacted monomer can be reduced.

In the ultraviolet absorbing composition of the present invention, a benzotriazole compound represented by the above formula [I] is used as an ultraviolet absorber.

A particularly preferred compound is 2- {2'-hydroxy-5 '-(β-methacryloyloxyethoxyethoxy} -3'-t-butylphenyl) -5-t-butyl represented by the formula [II]. -2H-benzotriazole.

[0013]

[Chemical 3] The ultraviolet absorbent of the present invention can be copolymerized with many unsaturated monomers to give a composition having desired ultraviolet absorbing properties. The ultraviolet absorbing composition of the present invention may be composed of only the homopolymer or copolymer of the ultraviolet absorber, or may further contain other polymer and / or various additives and colorants. That is, the homopolymer or copolymer of the ultraviolet absorber can be used as an additive to a wide range of polymers for imparting ultraviolet absorbing characteristics. Suitable representative polymers and copolymers used in the ultraviolet absorbing composition of the present invention and representative polymers and copolymers suitable for blending with the ultraviolet absorbing polymer include the following. is there.

(1) Polymer derived from mono- or diolefin: For example, polyethylene, polypropylene, polyisoprene, polyisobutylene, polymethylbutene-1, polymethylpentene-which may be optionally crosslinked.
1, polyisobutylene, polybutadiene, poly-4-methylpentene.

(2) Mixtures of the homopolymers mentioned in (1): polypropylene and polyethylene, polypropylene and polyisobutene, polypropylene and polybutene-1.

(3) Copolymer of monomers based on the polymers listed in (1): for example, ethylene-chloropyrene copolymer,
Propylene-butene-1 copolymer, propylene-isobutylene copolymer, ethylene-butene-1 copolymer, and diene of ethylene and propylene, for example, hexadiene, dicyclopentadiene, terpolymer of ethylidene norbornene, And alpha-olefins such as copolymers of ethylene and (meth) acrylic acid.

(4) Copolymer of styrene or α-methylstyrene: For example, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile- (meth) acrylic acid ester copolymer, imparting impact strength Styrene-acrylonitrile copolymers and block copolymers modified with acrylic acid ester polymers for this purpose, for example styrene-butadiene-styrene block copolymers.

(5) Graft copolymers of styrene: For example, graft copolymers of styrene onto polybutadiene, generally acrytonitrile-butadiene-styrene or AB.
Graft copolymer of styrene and acrylonitrile onto a mixture of polybutadiene called S resin and the copolymer listed in (4) and polybutadiene.

(6) Silicone polymers such as polyorganosiloxane.

(7) Halogen-containing vinyl polymer: For example,
Polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polychloroprene, rubber chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride-vinyl acetate copolymer.

(8) α, β-unsaturated organic acids and their derivatives: esters of polyacrylic acid and polymethacrylic acid, hydroxyethyl polymethacrylate, polyacrylamide and polyacrylonitrile.

(9) Polymers derived from unsaturated alcohols and amines, and acyl polymers thereof, such as polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, vinyl polybenzoate, vinyl polymaleate, polyvinyl butyral, polyphthalate. Copolymers with allyl acid, polyallyl melamine and other vinyl compounds. For example, ethylene-vinyl acetate copolymer.

(10) Homopolymers and copolymers derived from epoxides: for example, polymers derived from polyethylene oxide or bisglycidyl ether.

(11) Polyacetal: For example, polyoxymethylene, and polyoxymethylene containing ethylene oxide as a copolymer.

(12) Polyalkylene oxide: for example, polyoxyethylene, polypropylene oxide or polybutylene oxide.

(13) Polyphenylene oxide (14) Polyurethane and polyurea (15) Polycarbonate (16) Polysulfone (17) Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams: eg , Polyamide 6, polyamide 6
/ 6, polyamide 6/10, polyamide 11, polyamide 12, m-vinyl lactam and poly-m-phenylene-isophthalamide.

(18) Polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxysulfonic acids or the corresponding lactones: eg polyethylene glycol terephthalate, poly-1,4-dimethylcyclohexane terephthalate.

(19) Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand: phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde.

(20) Alkyd resins: for example glycerin-phthalic acid resins and their mixtures with melamine-formaldehyde resins.

(21) Unsaturated polyesters derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and also from vinyl compounds as crosslinking agents and also halogen-containing flame-retardant modifications thereof.

(22) Natural polymer: For example, cellulose and rubber.

(23) A chemically modified homologous derivative of (22):
For example, cellulose acetate, cellulose propionate, and cellulose acetate and cellulose ethers such as methyl cellulose.

Particularly useful compositions are the UV absorbers according to the invention and, for example, styrene, methylstyrene, compounds containing silicon atoms and unsaturated double bonds, acrylates,
Methacrylic acid ester, acrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride,
It includes a copolymer with another monomer having a copolymerizable unsaturated double bond such as vinylidene chloride, vinylidene fluoride, vinyl fluoride, vinyl lactam, ethylene, propylene and a mixture thereof.

The preferred polymer contained in the composition of the present invention is one containing a silicon atom. Here, the polymer containing a silicon atom may be a polymer containing a silicon atom in the main chain and / or side chain of the polymer, and is, for example, a polymer containing a siloxane bond or an organic silane group such as a trimethylsilyl group. It is a polymer as a component. From the viewpoint of oxygen permeability and / or flexibility in these polymers containing silicon atoms, long-chain polymers in which silicon atoms are contained in the polymer through a siloxane bond are preferable. Specific examples of such a polymer include tris (trimethylsiloxy) silylpropyl methacrylate, polydimethylsiloxane having a double bond at both ends, a homopolymer using a silicone-containing (meth) acrylate, or a homopolymer of these monomers and other monomers. Examples include copolymers with monomers. Copolymerizable monomers include (meth) acrylic monomers, aromatic vinyl monomers, monofunctional monomers such as heterocyclic vinyl monomers, or di-, tri-, tetra- (meth) acrylic monomers, aromatic divinyl monomers, aromatic diallyl monomers, etc. Examples include polyfunctional monomers. Examples of the (meth) acrylic monomer include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, halogenated alkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoroethyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate,
Examples thereof include cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate. Above all, the use of methyl methacrylate provides good mechanical properties. In addition, fluoroalkyl (meth)
The use of acrylate is preferable because a polymer satisfying both functions of oxygen permeability and mechanical properties can be obtained. Examples of the aromatic vinyl monomer include vinylbenzene, vinylnaphthalene, vinylethylbenzene and the like. Further, examples of the heterocyclic vinyl monomer include vinylcarbazole, maleimide, maleic anhydride and the like. As these copolymerizable monomers, (meth) acrylate monomers are preferable from the viewpoint of copolymerizability and transparency. Among them, methyl (meth) acrylate, trifluoroethyl (meth) acrylate, from the viewpoints of mechanical properties, transparency, and oxygen permeability.
Most preferred is (meth) acrylic acid. The copolymerizable polyfunctional monomer will be described. Examples of di (meth) acrylic monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate and urethane-modified di (meth) acrylate. ) Acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like. Examples of tri (meth) acrylic monomers include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. Examples of the tetra (meth) acrylic monomer include tetramethylolmethane tetra (meth) acrylate. Examples of the aromatic divinyl compound include o-, m-, and p-diallyl phthalates. Examples of other polyfunctional monomers include bismaleimide and allyl (meth) acrylate. Di-, tri-, tetra-, and (meth) acrylate monomers are preferable in terms of copolymerizability and transparency.

From the above, from the viewpoint of transparency, oxygen permeability and mechanical properties, a polymer containing a silicon atom,
Most preferably, it is a copolymer of a siloxane compound having a double bond and a compound having a (meth) acryloyl group.

When a polymer containing a silicon atom and a copolymerizable monomer are copolymerized, the respective compositions are usually 10 to 90 parts by weight of the polymer containing a silicon atom and 10 to 90 parts of the copolymerizable monomer. It is selected in the range of 90 parts by weight, but is not particularly limited. When the amount of the polymer containing a silicon atom is 9 parts by weight or less, the oxygen permeability is insufficient, and when it is 91 parts by weight or more, the strength decreases.
It may not be preferable. Generally, in a copolymer of a polymer containing a silicon atom and another monomer, as the proportion of the polymer containing a silicon atom increases, the oxygen permeability tends to increase and the strength tends to decrease.

The presence of silicon atoms in the polymer may be uniform throughout the polymer or in a heterogeneous system having a so-called microphase-separated structure.

The oxygen permeability coefficient of the above composition containing silicon atoms is 10 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mmHg.
The above is preferable. The oxygen permeability coefficient here is measured by a known method such as an electrode method, a vacuum method, or a pressure method. When the ultraviolet absorbing composition of the present invention is applied to a contact lens, the oxygen transmission coefficient is 10 × 10.
^-11 cm ³ (STP) · cm / cm ² · sec · If it is smaller than mmHg, it is not possible to supply enough oxygen required for the cornea from the surface of the cornea through the lens, and when worn for a long time, the corneal physiology This is not preferable because it increases the physical burden. In addition, continuous wearing causes undesired corneal edema, which may cause visual impairment.

The concentration of the ultraviolet absorber added is preferably in the range of 0.01 to 10% by weight with respect to the weight of the mixed liquid of the raw material monomers. If the concentration is 0.01% by weight or less, it tends to be impossible to obtain a sufficient ultraviolet absorbing ability. Also,
If the amount added exceeds 10% by weight, the polymerization rate tends to decrease and the mechanical strength tends to decrease. For contact lenses and intraocular lenses, it is desirable that the transmittance at the maximum absorption wavelength in the ultraviolet range of 200 to 400 nm is less than 20%. To obtain this, a proper concentration of the ultraviolet absorber is determined in consideration of the thickness of the lens.

Since the ultraviolet absorbing composition of the present invention does not transmit a short wavelength, it can be widely used as an optical material as a cut filter. When used for optical materials,
The ultraviolet absorber may be used alone, or a coloring agent may be added to adjust the absorption characteristics in the visible light region. As the coloring agent used, direct dyes, oil-soluble dyes, acid dyes, basic dyes, disperse dyes, vat dyes, monoazo-based bisazo-based organic pigments, bisazo-based, anthraquinone-based, quinonaphthalone-based, xanthene-based, pyrazole-based,
Examples thereof include triphenylmethane-based, indigoid-based, fluorane-based, and quinoline-based organic dyes, but are not limited thereto.

When the ultraviolet absorbing composition of the present invention is used as an optical material, in addition to medical optical materials such as spectacle lenses, intraocular lenses and contact lenses, condenser lenses for spectrophotometers,
Optical fibers, solar energy collectors, fluorescent diffusers and the like can be mentioned, but particularly suitable ones are contact lenses,
It is an intraocular lens.

The UV absorbing composition of the present invention can also be in the form of a hydrogel. Where “hydrogel”
Means a crosslinked polymer having an equilibrium water content of about 10-90%. Hydroxyl lower alkyl (C ₁ -C ₉ ) (meth) acrylate is preferably used as a monomer to give this hydrogel, which is cross-linked with a corresponding diester of (meth) acrylate, for example, several% of ethylene glycol dimethacrylate. Become. Examples of other suitable hydrophilic monomers are N-vinyl heterocyclic monomers, examples of which include N-vinyl-2-pyrrolidone, N-vinyl pyridine and N-vinyl caprolactam. . Further examples of other hydrophilic monomers are polymerizable olefinic acids and amides, such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, acrylamido acid, methacrylamide and N- (1,1 -Dimethyl-3-oxobutylacrylamide) is mentioned as a suitable example. Another suitable group of hydrophilic monomers are the lower alkyl vinyl ethers such as methyl and ethyl vinyl ethers. A preferred UV absorbing hydrogel in the present invention is a copolymer with hydroxyethyl methacrylate. In addition,
This hydrogel can be suitably used as a soft contact lens or an intraocular lens.

The UV absorbing composition of the present invention can also be in the form of a plastic film, which is applicable to transparent plastic films, packaging materials, vinyl window coatings, interior covers and the like.

The ultraviolet absorbing tissue composition of the present invention can also be used as a coating material, and can be applied to polymer coating, automobile paint, interior coating, spectacle lens coating and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

[0046]

【Example】

Example 1 In a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet, 53.4 parts by weight of 2,6-diisocyanatocaproic acid-β-isocyanatoethyl ester, 2- 52 parts by weight of hydroxyethyl methacrylate,
0.01 parts by weight of di-n-butyltin dilaurate was charged, and the mixture was stirred at 50 ° C. under a nitrogen atmosphere until the absorption of hydroxyl groups disappeared in the infrared absorption spectrum. Average molecular weight 94
94.6 parts by weight of a polydimethylcycloxane modified with alcohol at both ends represented by the following formula having 6 is added into the four-necked flask at 50 ° C. until the absorption of the isocyanate group in the infrared absorption spectrum disappears. And stirring under a nitrogen atmosphere, and each having two double bonds at both ends, the following formula [II
A reaction product containing a cyclohexane macromer represented by the formula [I] as a main component was obtained.

[0047]

[Chemical 4] Then, 2- {2'-hydroxy-5 '-{β-methacryloyloxyethoxy} -3'-t-butylphenyl} -5-t-butyl-2H-benzotriazole was synthesized as follows.

First, the intermediate 2-t-butyl-4- (2 '
The synthesis of -hydroxyethoxy) phenol is as follows.

In a 500 ml three-necked flask equipped with a mechanical stirrer and Dimroth condenser, t-butyl hydroquinone (42.8 g) was added to 150 g under an argon atmosphere.
Dissolve in ml methanol and add 10.3 g sodium hydroxide, 50 ml water, 20.6 g 2-chloro-1-ethanol and 0.3 g potassium iodide to this solution.
This solution was heated under reflux for 24 hours, and then the reaction solution was allowed to cool to room temperature and diluted with 300 ml of water. The product was extracted from this solution with dichloromethane. After drying with anhydrous sodium sulfate, the solvent was distilled off, and the product was recrystallized from toluene for purification to obtain 15.3 g of the product.

Then, the intermediate 2-t-butyl-4-
The synthesis of (2'-hydroxyethoxy) -6- (4'-t-butyl-2-'nitrophenylazo) -phenol was performed as follows.

500 ml with mechanical stirrer
In a three-necked flask, 12.6 g of 4-t-butyl-2-nitroaniline and 18 ml of concentrated hydrochloric acid were stirred and dissolved at room temperature. The solution was diluted with 50 ml ice water. While this solution was cooled with ice and kept at 4 ° C. or lower, 3.8 g of 97% sodium nitrite dissolved in 15 ml of water was added dropwise. After completion of dropping, the mixture was stirred for 1 hour while continuing to cool. Then, sulfamic acid was added until bubbles were not generated, and excess sodium nitrite was decomposed. This reaction liquid was filtered to obtain a filtrate. 10.7 g of 2-t-butyl-4- (2'-hydroxyethoxy) phenol and 6 g of sodium hydroxide dissolved in 200 ml of water was added to the above filtrate while cooling with ice and keeping the temperature below 4 ° C while stirring. Was dripped. After adding about 1/3 of the diazonium solution, 40 ml of a 10% sodium hydroxide aqueous solution was simultaneously added dropwise. The reaction solution was subsequently stirred at 4 ° C. or lower for 2 hours and then left to stand at room temperature. Hydrochloric acid was added to acidify to obtain crystals of the azo dye,
Separated by filtration.

Then, 2- [2'-hydroxy-5'-
The synthesis of {β-hydroxyethoxy} -3′-t-butylphenyl] -5-t-butyl-2H-benzotriazole was performed as follows.

2-t-butyl-4-obtained as above
(2'-hydroxyethoxy) -6- (4'-t-butyl-2-'nitrophenylazo) -phenol in a 500 ml three-necked flask equipped with a mechanical stirrer, 1
It was dissolved in 50 ml of ethanol. Under argon atmosphere,
A solution prepared by dissolving 18 g of glucose in 150 ml of a 2N aqueous sodium hydroxide solution was added dropwise at room temperature while maintaining the temperature at 30 ° C or lower. To this reaction solution, 12 g of zinc powder was added little by little. The reaction solution was stirred at room temperature for 4 hours and then diluted with 100 ml of water. The generated precipitate was separated by filtration and washed with water. The precipitate was washed with ethanol to dissolve the product and separate it from zinc. Ethanol was distilled off with an evaporator, and the product was dried under vacuum. The product was recrystallized from heptane and purified to give 10 g of product.

Synthesis of 2- {2'-hydroxy-5 '-(β-methacryloyloxyethoxy) -3'-t-butylphenyl} -5-t-butyl-2H-benzotriazole 300 ml three-neck equipped with a Dimroth condenser. 2- [2'-hydroxy-5 '-{β-hydroxyethoxy} -3'-t-butylphenyl] -5 was added to the flask.
2.4 g of -t-butyl-2H-benzotriazole, 50 ml of tetrahydrofuran, 1 g of triethylamine and 10 mg of hydroquinone were taken and stirred with a magnetic stirrer at room temperature. To this was added dropwise 2 g of methacrylic acid chloride. After continuing stirring for 9 hours, the reaction was terminated and tetrahydrofuran was distilled off. The solid content was dissolved in diethyl ether, washed with water, the ether layer was collected, and the ether was distilled off. The solid content was dissolved in 120 ml of methanol + 60 ml of dichloromethane and purified by recrystallization to obtain 2.6 g of a product.

3 parts by weight of trifluoroethyl methacrylate was added to 10 parts by weight of the reaction product represented by the formula [III] (the main component was a siloxane macromer), and trimethylolpropane trimethacrylate was added. 0.055 parts by weight and 0.004 parts by weight of azobismethylvaleronitrile were added. With respect to this monomer mixed liquid, the ultraviolet absorber 2-
{2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-t-butylphenyl} -5-t-
Butyl-2H-benzotriazole (0.5% by weight) was added, and each composition was mixed and dissolved to obtain a uniform transparent stock solution.
This stock solution was placed in a rod-shaped glass container, degassed, made into a nitrogen atmosphere, and then sealed. This was placed in a constant temperature water bath at 40 ° C, 40 hours, 50 ° C, 24 hours, 60 ° C, 16 hours, 70 ° C, 4
The reaction was carried out at 90 ° C. for 2 hours. Further, heat in a circulation dryer at 130 ° C for 3 hours,
A rod-shaped polymer was obtained. The obtained polymer had a Shore D hardness of 74 and was hard, and had good machinability and polishability and good machinability.

This polymer was made into small pieces with a mixer, and 1 g of this small piece was dipped in 50 g of distilled water and kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. No elution of the ultraviolet absorber was observed spectroscopically in this extract.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm and heat-treated under reduced pressure at 120 ° C. for 16 hours, but no change in color tone or absorbance due to bleed-out was observed.

This polymer was processed into a disk having a diameter of 9 mm and a thickness of 0.2 mm, and then heat-treated at 120 ° C. for 16 hours under reduced pressure in a vacuum. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with fade meter 20
Even after 0 hour irradiation, the absorbance is 98.8 of that before irradiation.
% Was observed, and there was no deterioration in the ultraviolet absorption capacity, indicating excellent light resistance.

The oxygen permeation coefficient of this polymer was 32 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mmHg at 37 ° C., which was determined by a Seikaken film oxygen permeation meter.
Met.

This polymer was cut and polished to give a lens system 9.0.
mm, base curve 8.0 mm, lens power-3.00D
Could be processed into contact lenses.

Example 2 50 parts by weight of tris (trimethylsiloxy) silylpropyl methacrylate, 5 parts of trifluoroethyl methacrylate
0 parts by weight, 0.05 parts by weight of azobisisobutylnitrile and 0.15 parts by weight of azobiscyclohexanecarbonitrile were mixed to prepare a polymerization stock solution. 2- {2'-hydroxy-5 'as an ultraviolet absorber for this monomer mixture
-(Β-methacryloyloxyethoxy) -3'-t-
Butylphenyl} -5-t-butyl-2H-benzotriazole (0.5% by weight) was added and dissolved to obtain a uniform transparent stock solution. After thawing, enclose in a test tube and from 110 ℃ to 110 ℃
The temperature was raised to 0 ° C over 24 hours, and then the temperature was maintained at 110 ° C for 4 hours to obtain a polymer.

This polymer was made into small pieces with a mixer, and 1 g of this small piece was immersed in 50 g of distilled water and kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. No elution of the ultraviolet absorber was observed spectroscopically in this extract.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm, and then heat-treated under vacuum reduced pressure at 120 ° C. for 16 hours, and the decrease in absorbance due to bleed-out was examined spectroscopically. As a result, changes in color tone and absorbance due to bleed-out were not observed. This polymer was processed into a disk with a diameter of 9 mm and a thickness of 0.2 mm, and then the pressure was reduced to 120
Heat treatment was performed at 16 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Even after 200 hours of irradiation with a fade meter, the absorbance was 98.2% of the absorbance before irradiation, and there was no deterioration in the ultraviolet absorption capacity, indicating excellent light resistance.

The oxygen permeation coefficient of this polymer was 30 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mmHg at 37 ° C., which was determined by a Seikaken film oxygen permeation meter.
Met.

This polymer has good machinability, and was cut and polished to give a lens system of 9.0 mm, a base curve of 8.0 mm,
It was possible to process a contact lens with a lens power of −3.00D.

From the results of Examples 1 and 2, the ultraviolet absorbent obtained by the present invention is excellent in the ultraviolet absorbing ability in the wavelength region of 300 to 400 nm and is free from elution and bleed-out.
It is a UV absorber with good compatibility with the polymer, and as a result,
It can be seen that the polymerized composition has a stable ultraviolet absorbing ability and can be used in a wide variety of applications.

[0067]

EFFECTS OF THE INVENTION According to the present invention, an ultraviolet absorber having excellent ultraviolet absorbing ability particularly in the wavelength region of 300 to 400 nm, having no elution and bleed-out, and having good compatibility with a polymer, and an ultraviolet absorbing composition containing the same Could be provided.

[Brief description of drawings]

1 is an ultraviolet-visible absorption spectrum (transmittance) of a polymer obtained in an example.

Claims (13)

[Claims] 1. The following formula [I]: (However, in the formula, R ¹ is an alkyl group having 2 to 3 carbon atoms, and R ² is H or CH _3. ) 2. An ultraviolet absorbent composition comprising the ultraviolet absorbent according to claim 1. 3. The ultraviolet absorber is 2- {2'-hydroxy-
5 '-(β-methacryloyloxyethoxy) -3'-
The ultraviolet absorbent composition according to claim 2, which is t-butylphenyl} -5-t-butyl-2H-benzotriazole. 4. A polymer obtained by copolymerizing at least one monomer and / or macromer having a polymerizable unsaturated double bond in the molecule with an ultraviolet absorber represented by the formula [I]. An ultraviolet absorber composition comprising: 5. The ultraviolet absorbent composition according to claim 4, wherein the polymer is a polymer containing a silicon atom. 6. An oxygen permeability coefficient of 10 × 10 ^-11 cm ³ (ST
P) · cm / cm ² · sec · mmHg or more, The ultraviolet absorbent composition according to claim 5, which is characterized in that 7. An ultraviolet absorber in an amount of 0.01 to 10.0% by weight.
The ultraviolet-absorbing composition according to claim 2, which further comprises: 8. An optically transparent optical material comprising the composition of claim 4. 9. The optical material according to claim 8, which is a contact lens, an intraocular lens or a spectacle lens. 10. A hydrogel comprising the composition according to claim 4. 11. A hydrogel-forming monomer is hydroxyalkyl methacrylates, hydroxyalkyl acrylates, N-vinyl heterocyclic monomers, polymerizable olefin acids, polymerizable olefin amides and 1 to 1 carbon atoms.
The hydrogel according to claim 10, which is selected from the group consisting of 5 alkyl vinyl ethers. 12. A plastic film comprising the composition according to claim 4. 13. A coating material comprising the composition according to claim 4.