JPH0688065A - Ultraviolet absorber and ultraviolet-absorbing composition containing the same - Google Patents

Abstract

PURPOSE:To provide an ultraviolet absorber which is excellent in ultraviolet adsorption capacity in a wavelength region of 300-400nm, free from dissolution and bleeding, and compatible with a polymer, and to provide a compsn. contg. a copolymer of the absorber. CONSTITUTION:An ultraviolet absorber has a polymerizable double bond linked through an alkylene chain and a urethane bond to the backbone of a benzotriazole ultraviolet absorber. An ultraviolet-absorbing compsn. contains a copolymer obtd. by copolymerizing the absorber with a monomer having a polymerizable double bond.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel ultraviolet absorbers and ultraviolet absorbing compositions, and optical materials produced from the compositions, particularly intraocular lenses, contact lenses and spectacle lenses.

[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 bleeding out from the polymerized composition and toxicity to the living body become a problem in the processing scene or use scene. Therefore, in order to improve such problems, 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, 2,4-
A method of copolymerizing an ester of 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 in the ultraviolet region of the sun's rays on the ground, a wavelength region (320) having a large integrated energy is obtained.
Was insufficient to absorb (.about.400 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. Further, even in these methods, when the compatibility with the polymer is poor, the unreacted ultraviolet absorber may bleed out during polymerization or during use, resulting in deterioration or deterioration of performance. . Further, when the UV absorber has poor compatibility in the polymerization composition, the UV absorber causes phase separation in the polymer, and the physical properties of the polymerization composition itself are deteriorated such as a decrease in transparency and a decrease in mechanical strength. There was a case to do.

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 the case of such optical materials, particularly medical optical materials in the ophthalmological field, deterioration of physical properties due to the bleed-out and elution of the ultraviolet absorber and poor compatibility with the polymer as described above. 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 typified by PMMA, problems such as elution of an ultraviolet absorbent from a lens substrate, bleed-out, and deterioration of ultraviolet absorption characteristics are remarkable. That is, as can be seen from the fact that the glass transition point of silicone is lower than room temperature and that it is a rubber-like polymer at room temperature, the molecular motion of the siloxane region is large in the polymer of the siloxane compound, and the ultraviolet absorber existing in this part is large. Tended to bleed out and 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 lenses, since the material consists of a hydrophobic component such as silicone and a hydrophilic component that enhances biocompatibility, the added UV absorber is easy to phase separate, There was also a problem of deteriorating the physical properties.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is 300 to 400.
It is an object of the present invention to provide an ultraviolet absorber having excellent ultraviolet absorbing ability in the wavelength region of nm, free from elution and bleed-out, and having good compatibility with a polymer, and a polymerized composition thereof.

[0008]

The present invention is characterized in that a polymerizable unsaturated double bond is bonded to the skeleton of a benzotriazole type ultraviolet absorber by a urethane bond through an alkylene chain. Provide the agent. Also,
The present invention provides an ultraviolet absorbing composition containing a polymer obtained by copolymerizing the above-mentioned ultraviolet absorber of the present invention with a monomer having a polymerizable unsaturated double bond in the molecule. Furthermore, the present invention 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 composition of the present invention.

Since the ultraviolet absorbent of the present invention has a urethane bond and an alkylene chain bonded to it in the molecule, the compatibility with many polymers can be enhanced, and the ultraviolet absorber is incorporated into the polymer through a covalent bond, Ultraviolet absorption ability can be imparted to a polymer containing the same. The urethane bond itself is a polar group, and since the alkylene chain bonded to this urethane bond has low polarity and is hydrophobic, the polarity of the entire ultraviolet absorber molecule can be controlled by adjusting the length of this alkylene chain. By doing so, optimum compatibility with many polymers can be obtained. As a result, the UV absorber reacts more completely with the polymer monomers, which can reduce the amount of unreacted monomer that can be extracted.

The ultraviolet absorber of the present invention is particularly preferably 300 to 4
It has a skeleton of a benzotriazole-based ultraviolet absorber excellent in ultraviolet absorbing ability in the wavelength region of about 00 nm in the molecule.
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. Then, the polymerizable unsaturated double bond is bonded to the skeleton of the benzotriazole-based ultraviolet absorber by a urethane bond via an alkylene chain. As long as these requirements are satisfied, the position of the bond, the presence or absence of other substituents, their types, etc. are not limited, and any one can be used.

As a preferable example of the ultraviolet absorber of the present invention, 2- {2'-hydroxy-indicated by the following formula [I]:
5 ′-{β- [N- (β- (meth) acryloyloxyalkyl) carbamoyloxy]} phenyl} -2H-
Mention may be made of benzotriazole.

[0012]

[Chemical 2] (However, in the formula, R ¹ is H, halogen, or 1 to 1 carbon atoms.
A C 10 alkoxy group or a C 1-10 alkyl group, R ² is selected from the group consisting of H, CH ₃ and a C 1-10 alkyl group, and X is —O—CO—NH— R ³ —O—CO—C (R ⁴ ) ═CH ₂ (wherein R ³ may be linear or branched C
_{2 to} C ₂₀ alkylene group, and R ⁴ is H or CH
₃ )) Particularly preferred substances of the above structure are those in which R ¹ is an alkyl group, in particular CH ₃ , chlorine, CH ₃ O, R ² is t-butyl, X is R ³
There -C ₂ H ₄ - is of the case where - or -C ₃ H _6. Among them, a particularly preferable compound is 2- {2'-hydroxy-5 '-[N- (β-methacryloyloxyethyl) carbamoyloxy] -3'- represented by the following formula [II].
t-butylphenyl} -5-methyl-2H-benzotriazole.

[0013]

[Chemical 3] The ultraviolet absorber represented by the above formula [I] is obtained by reacting a hydroquinone having a desired R ² with a nitroaniline having a desired R ¹ to give a nitrophenylazohydroquinone derivative, which is alkali-treated to give the desired R 2 ¹ and R
A dihydroxyphenyl-2H-triazole derivative having ² and then O having the desired R ³ and R ⁴
The ^{CN-R 3 -O-CO-} C (R 4) = isocyanate derivative represented by CH ₂ can be prepared by reacting. These individual steps can be carried out on the basis of known organic chemistry reactions, and the preferred specific conditions are described in detail in the examples below.

The UV absorber of the present invention can be copolymerized with many unsaturated monomers to provide a composition having desired UV absorbing properties. The ultraviolet absorbing composition of the present invention may be composed only of the homopolymer or copolymer of the ultraviolet absorbent of the present invention, and may further contain other polymer and / or various additives and colorants. . That is, since the homopolymer or copolymer of the ultraviolet absorbent of the present invention imparts ultraviolet absorption characteristics, it can be used as an additive for a wide range of polymers. Representative polymers and copolymers suitable for containing the ultraviolet absorber of the present invention as a copolymerization component, and representative polymers and copolymers suitable for blending with the ultraviolet absorbing polymer include There are the following.

(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 homopolymers mentioned in (1): polypropylene and polyethylene, polypropylene and polyisobutene, polypropylene and polybutene-1.

(3) Copolymers of monomers based on the polymers listed in (1): for example, ethylene-propylene copolymer, propylene-butene-1 copolymer, propylene-isobutylene copolymer, ethylene A butene-1 copolymer, and ethylene, propylene and a diene, such as hexadiene,
Terpolymers with dicyclopentadiene, ethylidene norbornene, as well as copolymers of alpha-olefins such as ethylene with (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, impact strength Styrene-acrylonitrile copolymers and block copolymers modified with acrylic acid ester polymers for application, such as styrene-butadiene-styrene block copolymers.

(5) Graft copolymers of styrene: For example, graft copolymers of styrene on 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. The UV absorbers according to the invention can advantageously be used in thermosetting acrylic resin lacquers and copolymers of (meth) acrylic acid and one or more derivatives thereof and melamine-formaldehyde resins.

(9) Polymers derived from unsaturated alcohols and amines, and their acyl polymers such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, 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) Polyurethanes and polyureas (15) Polycarbonates (16) Polysulfones (17) Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams: for example , 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 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: for example phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde.

(20) Alkyd resin: for example, glycerin-
Phthalates 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,
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. In these polymers containing a silicon atom, a long-chain polymer in which a silicon atom is contained in a polymer through a siloxane bond is preferable from the viewpoint of oxygen permeability and / or flexibility. 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. The copolymerizable monomers include (meth) acrylic monomers, aromatic vinyl monomers, monofunctional monomers such as heterocyclic vinyl monomers,
Alternatively, polyfunctional monomers such as di-, tri-, tetra- (meth) acrylic monomers, aromatic divinyl monomers, aromatic diallyl monomers and the like can be mentioned. As the (meth) acrylic monomer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylates such as, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoroethyl ( Examples thereof include halogenated alkyl (meth) acrylates such as (meth) acrylate and cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate. Above all, the use of methyl methacrylate provides good mechanical properties. Further, it is preferable to use a fluoroalkyl (meth) acrylate from the viewpoint that 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) is advantageous in terms of mechanical properties, transparency, and oxygen permeability.
Most preferred are acrylate, trifluoroethyl (meth) acrylate, (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 dimethacrylate propylene thereof. Examples thereof include glycol di (meth) acrylate. 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. As the aromatic divinyl compound, o-, m-,
Examples thereof include p-diallyl phthalate. Examples of other polyfunctional monomers include bismaleimide and allyl (meth) acrylate. From the viewpoint of copolymerizability and transparency, di-, tri-, tetra-,
(Meth) acrylate monomers are preferred. Of these, tri (meth) acrylate is most preferable from the viewpoint of mechanical properties 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 siloxane- (meth) acrylic 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 composition is 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 referred to here is measured by a known method such as an electrode method, a vacuum bubble 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 in the case of long-term wear, 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, sufficient ultraviolet absorption ability cannot be obtained. Further, if the addition amount exceeds 10% by weight, the polymerization rate and the mechanical strength may decrease, which is not preferable. 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 colorant may be added to adjust the absorption characteristics in the visible light region. Examples of the colorant used include direct dyes, oil-soluble dyes, acid dyes, basic dyes, disperse dyes, vat dyes, monoazo-based bisazo-based organic pigments, 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%. Examples of monomers that give this hydrogel include hydroxy lower alkyl (C ₁ -C ₉ ).
(Meth) acrylate, which is the corresponding (meth) acrylate
A hydrogel is cross-linked with a few percent of an acrylate diester, such as ethylene glycol dimethacrylate.
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. . In addition, examples of other hydrophilic monomers are polymerizable olefinic acids and amides,
Suitable examples include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, acrylamide, methacrylamide and N- (1,1-dimethyl-3-oxobutylacrylamide). 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 UV absorbing composition of the present invention can also be used as a coating material, which can be applied to polymer coating, automobile paint, interior coating, spectacle lens coating and the like.

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

Example 1 2- {2'-hydroxy-5 '-{β- [N- (β-methacryloyloxyethyl) carbamoyloxy]}-
Synthesis of 3'-t-butylphenyl} -5-methyl-2H-benzotriazole Intermediate 2-t-butyl-4-hydroxy-6- (4'-
Synthesis of methyl-2-'nitrophenylazo) -phenol In a 500 ml three-necked flask equipped with a mechanical stirrer, 8.2 g of 98% 4-methyl-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. Cool the solution with ice 4
3.8 g of 97% sodium nitrite dissolved in 15 ml of water was added dropwise while keeping the temperature below ℃. After the completion of dropping, the mixture was stirred for 2 hours while continuing cooling. 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. 9.
A solution prepared by dissolving 0 g of t-butylhydroquinone and 6 g of sodium hydroxide in 200 ml of water was cooled with ice and then cooled to 4 ° C.
The above filtrate was added dropwise while maintaining the temperature below. 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 a half, and then left to stand at room temperature. Hydrochloric acid was added to acidify to give crystals of the azo dye, which were separated by filtration.

2- [2 ', 5'-dihydroxy-3'-
Synthesis of t-butylphenyl] -5-methyl-2H-benzotriazole 2-t-butyl-4-hydroxy-6 obtained as above.
-(4'-Methyl-2-'nitrophenylazo) -phenol was dissolved in 150 ml ethanol in a 500 ml three-necked flask equipped with a mechanical stirrer. 2N sodium hydroxide aqueous solution 1 at room temperature under argon atmosphere
A solution prepared by dissolving 12 g of zinc powder in 50 ml was added dropwise while keeping the temperature at 30 ° C or lower. The reaction solution was stirred at room temperature for 40 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 for purification and 10.
2 g of product was obtained.

2- {2'-hydroxy-5 '-{β-
Synthesis of [N- (β-methacryloyloxyethyl) carbamoyloxy] -3′-t-butylphenyl} -5-methyl-2H-benzotriazole 2- [2 ′, 5 ′ in a 300 ml three-necked flask equipped with a Dimroth condenser. -Dihydroxy-3'-t-
Butylphenyl] -5-methyl-2H-benzotriazole 2.1 g, tetrahydrofuran 50 ml, di-n-
Butyltin dilaurate 10 μl, hydroquinone 10
mg was taken and stirred at 60 ° C. with a magnetic stirrer. To this, 1.45 g of methacryloyloxyethyl isocyanate was added dropwise. Stirring was continued at 60 ° C. for 6 hours, and after confirming disappearance of methacryloyloxyethyl isocyanate by thin layer chromatography, 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. 120m solids
The product was dissolved in 1 ml of methanol + 60 ml of dichloromethane and purified by recrystallization to obtain 2.9 g of a product.

FIG. 1 shows the UV-visible absorption spectrum of this UV absorber. As shown in the spectrum, a sufficiently large absorption was obtained in the ultraviolet region.

Example 2 53.4 parts of 2,6-diisocyanatocaproic acid-β-isocyanatoethyl ester were placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
52 parts of 2-hydroxyethyl methacrylate, di-n-
Charge 0.01 part of butyltin dilaurate until the absorption of hydroxyl group disappears in the infrared absorption spectrum at 50 ° C.
Stir under a nitrogen atmosphere. 94.6 parts of both-end alcohol-modified polydimethylsiloxane represented by the following formula having an average molecular weight of 946 was added to the four-necked flask, and the mixture was heated at 50 ° C. until the absorption of the isocyanate group in the infrared absorption spectrum disappeared. Then, the mixture was stirred under a nitrogen atmosphere to obtain a reaction product containing a siloxane macromer represented by the following formula [III] as a main component and having two double bonds at each end.

[0052]

[Chemical 4] This reaction product (main component is siloxane macromer) 10
3 parts of trifluoroethyl methacrylate, 0.055 parts of trimethylolpropane trimethacrylate, and azobismethylvaleronitrile of 0.
004 parts were added. UV absorber 2- {2'-hydroxy-5 '-{β- [N-
(Β-methacryloyloxyethyl) carbamoyloxy]}-3′-t-butylphenyl} -5-methyl-2
0.5% by weight of H-benzotriazole 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. 40 ℃ for 40 hours in a constant temperature water bath at 50 ℃, 2
4 hours, 60 ° C, 16 hours, 70 ° C, 4 hours, 90 ° C,
The reaction was allowed to proceed for 2 hours. Further, heating was carried out at 130 ° C. for 3 hours in a circulation dryer to obtain a rod-shaped polymer. 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 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, the decrease in absorbance was 1.1%, which was extremely small.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with a fade meter Even after 200 hours of irradiation, the absorbance is 9 times that before the irradiation.
6.2% was observed, and there was no deterioration in the ultraviolet absorbing ability, and excellent light resistance was exhibited.

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 -3.0
It was possible to process it into a 0D contact lens.

Example 3 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- [N- (β-methacryloyloxyethyl) carbamoyloxy]}-3'-t-butylphenyl}-
0.5% by weight of 5-methyl-2H-benzotriazole
A uniform transparent stock solution was obtained by adding and dissolving. After dissolution, the mixture was sealed in a test tube, heated from 60 ° C. to 110 ° C. over 24 hours, and then held 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, the decrease in absorbance was as small as 0.6%.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with a fade meter Even after 200 hours of irradiation, the absorbance is 9 times that before the irradiation.
7.8% was recognized, and there was no deterioration in the ultraviolet absorbing ability, and excellent light resistance was exhibited.

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 and a base curve of 8.0 m.
m, and a lens power of −3.00D could be processed.

Example 4 Polydimethylsiloxane 45 having double bonds at both ends
Parts by weight, 47.5 parts by weight of trifluoroethyl methacrylate, 3 parts by weight of methacrylic acid, and 4.5 parts by weight of trimethylolpropane trimethacrylate are uniformly mixed, and 0.05 parts by weight of azobisisobutyronitrile, azo 0.15 parts by weight of biscyclohexylcarbonitrile was added. 2- {2'-hydroxy-5 '-{β- [N- (β-methacryloyloxyethyl) carbamoyloxy] -3 as an ultraviolet absorber for this monomer mixture liquid
0.5% by weight of'-t-butylphenyl} -5-methyl-2H-benzotriazole was added and each composition was mixed.
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 heated from 60 ° C. to 110 ° C. over 24 hours and then held at 110 ° C. for 4 hours to obtain a polymer. The obtained polymer had a Shore D hardness of 70 and was hard, and had good machinability,
The polishability was also good.

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

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm, and then heat-treated at 120 ° C. for 16 hours under reduced pressure in a vacuum, 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.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with a fade meter Even after 200 hours of irradiation, the absorbance is 9 times that before the irradiation.
6.6% was observed, and there was no deterioration in the ultraviolet absorbing ability, and excellent light resistance was exhibited.

The oxygen permeability coefficient at 37 ° C. of the oxygen permeability coefficient of this polymer was 130 × 10 ⁻¹¹ cm ³ (STP) · cm / cm ² · sec · mm.
It was Hg.

This polymer was cut and polished to give a lens system 9.0.
mm, base curve 8.0 mm, lens power -3.0
It was possible to process it into a 0D contact lens.

FIG. 2 shows an ultraviolet-visible absorption spectrum (transmittance) of a disk having a thickness of 0.2 mm. As shown in the spectrum, a sufficiently large absorption was obtained in the ultraviolet region.

From the results of Examples 1, 2, 3, and 4, the ultraviolet absorbent obtained by the present invention has excellent ultraviolet absorbing ability in the wavelength region of 300 to 400 nm, is free from elution and bleed-out, and is compatible with the polymer. It is a highly soluble UV absorber,
As a result, the polymerization composition has a stable ultraviolet absorption ability,
It turns out that it can be used for a wide range of purposes.

[0072]

According to the present invention, there is provided an ultraviolet absorber excellent in ultraviolet absorbing ability in the wavelength region of 300 to 400 nm, free from elution and bleed out, and having good compatibility with a polymer, and a polymerized composition thereof. You can

[Brief description of drawings]

FIG. 1 is an ultraviolet-visible absorption spectrum of an ultraviolet absorbent of the present invention obtained in an example.

FIG. 2 is an ultraviolet-visible absorption spectrum (transmittance) of the polymers obtained in Examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08J 5/18 CER 9267-4F C09D 183/08 PMS 8319-4J G02C 7/04

Claims (16)

[Claims] 1. A UV absorber characterized in that a polymerizable unsaturated double bond is bonded to the skeleton of a benzotriazole-based UV absorber by a urethane bond via an alkylene chain. 2. The formula [I]: (However, in the formula, R ¹ is H, halogen, or 1 to 1 carbon atoms.
A C 10 alkoxy group or a C 1-10 alkyl group, R ² is selected from the group consisting of H, CH ₃ and a C 1-10 alkyl group, and X is —O—CO—NH— R ₃ —O—CO—C (R ⁴ ) ═CH ₂ (wherein R ³ may be linear or branched C
₂ -C20 alkylene group, and R ⁴ is H or CH
_{Is 3} . )) The ultraviolet absorber according to claim 1. 3. The ultraviolet absorber according to claim 2, wherein R ¹ is an alkyl group. 4. The ultraviolet absorber according to claim 2, wherein R ¹ is CH ₃ . 5. The ultraviolet absorber according to claim 2, wherein R ² is a t-butyl group. 6. 2- {2'-hydroxy-5 '-[N-
(Β-methacryloyloxyethyl) carbamoyloxy]}-3′-t-butylphenyl} -5-methyl-2
The ultraviolet absorber according to claim 2, which is H-benzotriazole. 7. An ultraviolet absorbing composition containing a polymer obtained by copolymerizing the ultraviolet absorbent according to claim 1 with a monomer having a polymerizable unsaturated double bond in the molecule. 8. The ultraviolet absorbing composition according to claim 7, wherein the polymer is a polymer containing a silicon atom. 9. The oxygen permeability coefficient is 10 × 10.
^{-11 cm 3 (STP) · cm} / cm 2 · sec · ultraviolet absorbent composition according to claim 8, wherein the mmHg or more. 10. The ultraviolet absorbing composition according to claim 7, wherein the ultraviolet absorbing agent is contained in an amount of 0.05 to 10.0% by weight. 11. An optically transparent optical material comprising the composition according to claim 7. 12. The optical material according to claim 11, which is a contact lens, an intraocular lens or a spectacle lens. 13. A hydrogel comprising the composition according to claim 7. 14. The hydrogel-forming monomer is selected from the group consisting of hydroxyalkyl methacrylates, hydroxyalkyl acrylates, N-vinyl heterocyclic monomers, polymerizable olefin acids, polymerizable olefin amides, and lower alkyl vinyl ethers. The hydrogel according to claim 13, wherein 15. A plastic film comprising the composition according to claim 7. 16. A coating material comprising the composition according to claim 7.