HK1203990B - Stable polymerizable uv-absorbing colorant for intraocular lens - Google Patents

Description

Stable polymerizable ultraviolet absorbing pigment for intraocular lens

Technical Field

The present invention relates to a dye for coloring an intraocular lens (intraocular lens), and more particularly to a polymerizable dye having ultraviolet and blue-region light-absorbing abilities.

Background

Cataract is a disease in which clouding occurs in the lens and pigment is formed and deposited to form a state like mist covering the entire visual field. As a method of treatment, a procedure is generally performed in which an opacified Lens is removed, and an Intraocular Lens (IOL) is implanted and placed in the Lens capsule. Most of the materials for intraocular lenses used for therapy are acrylic or silicon polymers, and polymethyl methacrylate (PMMA) and the like have been used in particular.

However, the natural lens has a property of not transmitting ultraviolet rays, and since the conventional polymer for an intraocular lens transmits ultraviolet rays, there is a risk of damaging the retina.

In addition, the natural lens has a slight yellow color, and has a property of suppressing transmission of a part of light in a blue region. However, since the conventional transparent polymer for an intraocular lens transmits light in the blue region almost completely, there are many cases where patients complain about dazzling after implantation of an intraocular lens. Further, when light in a blue region having a short wavelength and high energy reaches the eye, there is a risk of causing a disease derived from the retina such as macular degeneration.

Therefore, materials for intraocular lenses are required to have ultraviolet absorption ability and to be colored with a yellow-based coloring matter, and in recent years, from the viewpoint of safety, most polymers for intraocular lenses are copolymerized with an ultraviolet absorber monomer and a yellow-based coloring matter monomer. Such monomer compounds have been variously developed (patent documents 1 to 4), and monomer compounds having a chromophore such as an azo group and an ultraviolet absorbing moiety such as a benzophenone skeleton in one molecule and copolymerizable with other monomers for intraocular lens materials have been developed (patent documents 5 and 6).

Documents of the prior art

Patent document

Patent document 1 Japanese patent No. 2685980

Patent document 2 Japanese patent application laid-open No. H10-251537

Patent document 3 Japanese examined patent publication No. 7-28911

Patent document 4 Japanese patent No. 2604799

Patent document 5 Japanese patent application laid-open No. 2-232056

Patent document 6 Japanese patent laid-open No. 2006-291006

Disclosure of Invention

Problems to be solved by the invention

The polymerizable ultraviolet-absorbing dye monomers described in patent documents 5 and 6 have a problem that they are poor in stability against pH change, particularly in stability under alkaline conditions, and the dye site (chromophore and ultraviolet-absorbing moiety) is easily detached from the polymer. In particular, in the case of an intraocular lens material having a long intraocular implantation period, the risk of detachment of the pigmented portion is further increased.

Accordingly, an object of the present invention is to obtain a polymerizable ultraviolet-absorbing dye monomer that is stable even under alkaline conditions.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the problem of stability against pH change is caused by the presence of an ester bond between a dye site and a polymerizable group in a monomer. Further, it has been found that the above problems can be solved by a polymerizable ultraviolet-absorbing dye monomer compound represented by the following general formula (1).

That is, the present invention is as follows.

One embodiment of the present invention is a compound represented by the following general formula (1) (hereinafter also referred to as a dye compound of the present invention).

[ solution 1]

In the general formula (1), R¹Is hydrogen atom, hydroxyl group, carboxyl group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, sulfonic group or benzyloxy group, preferably hydrogen atom, methyl group or ethyl group. R²Is hydrogen atom, hydroxyl group, or carbon number 1 toThe alkoxy group of 4 is preferably a hydrogen atom, a hydroxyl group, a methoxy group, or an ethoxy group. R³Represented by the following formula (2).

[ solution 2]

In the general formula (2), R⁴Is a hydrogen atom or a methyl group. In addition, R⁵Is a single bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 4 carbon atoms which does not have a substituent.

In another embodiment of the present invention, the pigment compound of the present invention is copolymerized with one or two or more other polymerizable monomers (hereinafter also referred to as the polymer of the present invention).

Another embodiment of the present invention is an intraocular lens formed by molding the polymer of the present invention (hereinafter also referred to as an intraocular lens of the present invention).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a polymerizable ultraviolet-absorbing dye monomer that is stable even under alkaline conditions can be provided. The compound represented by the general formula (1) has a benzophenone skeleton having ultraviolet absorption ability, an azobenzene skeleton having light absorption ability in a blue region, and a polymerizable group in its molecule, and therefore can be copolymerized with another polymerizable monomer to obtain a polymer, and the polymer is useful as a material for an artificial crystal.

Drawings

FIG. 1 is a graph showing the UV-VIS absorption spectrum of the polymer sheet obtained in example 13.

FIG. 2 is a graph showing the UV-VIS absorption spectrum of the polymer sheet obtained in example 14.

FIG. 3 is a graph showing an ultraviolet-visible absorption spectrum of a filtrate obtained by subjecting a polymer to an alkali treatment.

Detailed Description

The present invention will be described in detail below.

< 1 > the pigment compound of the present invention

The dye compound of the present invention is represented by the following general formula (1).

[ solution 3]

In the general formula (1), R¹Is hydrogen atom, hydroxyl group, carboxyl group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, sulfonic group or benzyloxy group. Among them, from the viewpoint of reaction efficiency in production, a hydrogen atom, a methyl group, or an ethyl group is preferable.

In the general formula (1), R²Is a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms. Among them, a hydrogen atom, a hydroxyl group, a methoxy group, or an ethoxy group is preferable from the viewpoint of reaction efficiency in production, and a hydroxyl group is particularly preferable from the viewpoint of light absorption characteristics.

As shown in the general formula (1), the pigment compound of the present invention has a benzophenone skeleton and an azobenzene skeleton, which are pigment sites.

In the general formula (1), R³Represented by the following formula (2).

[ solution 4]

In the general formula (2), R⁴Is a hydrogen atom or a methyl group.

In the general formula (2), R⁵Is a single bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent, preferably an alkylene group having 1 to 4 carbon atoms which does not have a substituent. The alkylene group having 1 to 4 carbon atoms is specifically a methylene group, an ethylene group, a propylene group or a butylene group. The alkylene group may have a substituent or no substituent, and when having a substituent, there may be mentioned a mode in which a substituent such as an alkyl group having 1 to 2 carbon atoms, a halogen group, a carboxyl group, an alkyl group having 1 to 2 carbon atoms in the carboxyl group, a hydroxyl group, a hydroxyalkyl group having 1 to 2 carbon atoms, an amino group, an aminoalkyl group having 1 to 2 carbon atoms, or the like is bonded to a carbon of the alkylene group.

As mentioned above, the substituent R³The (meth) acryloylamino group as the polymerizable group is bonded with a spacer, and is a site participating in copolymerization in the dye compound of the present invention. By adopting the structure represented by the general formula (2), the dye compound of the present invention has a property of high reaction efficiency with other polymerizable monomers.

Further, the term (meth) acryloyl means acryloyl or methacryloyl.

In addition, the substituent R in the general formula (1)³Preferably to the 3-or 4-position of the azophenyl group.

The dye compound of the present invention represented by the general formula (1) is not particularly limited, but preferable examples thereof include compounds having the following structures.

[ solution 5]

[ solution 6]

[ solution 7]

[ solution 8]

[ solution 9]

[ solution 10]

[ solution 11]

[ solution 12]

[ solution 13]

[ solution 14]

[ solution 15]

[ solution 16]

[ solution 17]

[ solution 18]

[ solution 19]

[ solution 20]

The dye compound of the present invention has a benzophenone skeleton (ultraviolet absorbing portion) having ultraviolet absorbing ability and an azobenzene skeleton (chromophore) having light absorbing ability in a blue region in one molecule. The dye compound of the present invention has a property (light absorption property) of suppressing the transmission of ultraviolet light (wavelength of 380nm or less) and blue light (wavelength of 380 to 500nm) due to the presence of these dye sites. The dye compound of the present invention has more excellent light absorption characteristics than conventional dye compounds (for example, 2, 4 dihydroxy-5- (4- (2- (N-2-methacryloyloxyethyl) carbamoyloxy) ethylphenylazo) Benzophenone (BMAC) described in patent document 6). Specifically, when the ultraviolet-visible absorption spectrum is measured, the curve rises sharply in the vicinity of 420 to 500nm, and the light transmission suppression capability in the ultraviolet and blue regions is excellent.

In addition, since the dye compound of the present invention has an ultraviolet absorbing portion and a chromophore (also referred to as a dye site) in one molecule, the chromophore is less likely to be damaged by ultraviolet light and the dye is less likely to discolor with time.

In the dye compound of the present invention, the polymerizable group and the dye site are linked by an amide bond. Since this bond is stable even under alkaline conditions, the pigment site is not separated from the polymer of the present invention described later. As a result, stability under alkaline conditions which have been insufficient for conventional dye compounds having an ester bond or copolymers using the dye compounds can be achieved.

The method for producing the dye compound of the present invention is not particularly limited, but it can be produced, for example, by the following synthesis methods 1 to 3.

(Synthesis method 1)

The method comprises the following steps: a diazotization step of diazotizing an aminoaryl compound to obtain a diazonium salt; a diazo coupling step of coupling the obtained diazonium salt with a benzophenone compound to obtain a diazonium compound; and an amidation step of introducing a polymerizable group by reacting an acrylic compound, a methacrylic compound, or the like with the obtained diazo compound by an amidation reaction.

The synthesis method 1 is schematically shown in the following reaction scheme. Wherein R represents a protecting group, R' represents a hydroxyl group or a halogen atom, R¹～R⁵The same substituents as those described above are shown.

[ solution 21]

(Synthesis method 2)

The method comprises the following steps: an amidation step of introducing a polymerizable group by reacting an amino aryl compound with an acrylic compound, a methacrylic compound or the like by an amidation reaction; a diazotization step of diazotizing the obtained polymerizable aminoaryl compound to obtain a diazonium salt; and a diazo coupling step of diazocoupling the obtained diazonium salt with a benzophenone compound to obtain the pigment compound of the present invention.

The outline of the synthesis method 2 is shown in the following reaction formula. Wherein R represents a protecting group, R' represents a hydroxyl group or a halogen atom, R¹～R⁵The same substituents as those described above are shown.

In addition, in the amidation step of introducing a polymerizable group into an aminoaryl compound, it is preferable to use a compound in which an amino group bonded to an aromatic group is protected with a protecting group or a protecting group is introduced in advance, and remove the protecting group by acid treatment or the like before the diazotization step.

[ solution 22]

(Synthesis method 3)

The method comprises the following steps: an amidation step of using a nitroaryl compound as a starting material in place of the aminoaryl compound, and introducing a polymerizable group by reacting an acrylic compound, a methacrylic compound, or the like with the nitroaryl compound through an amidation reaction; a reduction step of reducing the nitro group of the obtained polymerizable nitroaryl compound to an amino group; a diazotization step of diazotizing the obtained polymerizable aminoaryl compound to obtain a diazonium salt; and a diazo coupling step of diazocoupling the obtained diazonium salt with a benzophenone compound to obtain the pigment compound of the present invention.

The schematic of synthesis method 3 is shown in the following reaction scheme. Wherein R' represents a hydroxyl group or a halogen atom, R¹～R⁵The same substituents as those described above are shown.

[ solution 23]

The dye compound of the present invention can also be produced by a synthesis method or the like including: a protection step of introducing a protecting group into an aliphatic amine of an aminoaryl compound; a diazotization step of diazotizing an aminoaryl compound in which an aliphatic amine is protected to obtain a diazonium salt; a diazo coupling step of coupling the obtained diazonium salt with a benzophenone compound to obtain a diazonium compound; a deprotection step of removing the protecting group of the aliphatic amine by acid treatment or the like; and an amidation step of introducing a polymerizable group by reacting an acrylic compound, a methacrylic compound, or the like with the obtained diazo compound by an amidation reaction.

The diazotization step in each of the above-mentioned synthetic methods may be carried out by a known method.

As the diazotizing agent, sodium nitrite or an aqueous solution of sodium nitrite, potassium nitrite or an aqueous solution of potassium nitrite, isoamyl nitrite, nitroso sulfuric acid (sulfuric acid solution), and/or the like can be used. The amount of the diazotizing agent used is not particularly limited, but is preferably 1.00 to 1.20 moles, and more preferably 1.02 to 1.10 moles per 1 mole of the aminoaryl compound having a polymerizable group. The reaction temperature in the diazotization step is in the range of-78 to 50 ℃, preferably in the range of-20 to 20 ℃, and more preferably in the range of-20 to 10 ℃. The diazotization step is preferably performed under neutral to acidic conditions, and an acid such as hydrochloric acid may be appropriately added to the reaction solvent.

In the diazo coupling step in the above-mentioned synthesis methods 2 and 3, it is preferable to use a weak base as a catalyst and to carry out the diazo coupling under weak base conditions. This is because, in general, in a strong base such as sodium hydroxide or potassium hydroxide used in the diazo coupling reaction, the amide structure contained in the diazonium salt of the polymerizable aminoaryl compound is decomposed or eliminated to decrease the yield of the objective product, but when a weak base is used, the decomposition can be significantly suppressed and sufficient reactivity can be secured, and as a result, the reaction yield can be greatly increased. It is also known that the vinyl group contained in the diazonium salt is also polymerized in the presence of a strong base as described above, which causes a significant decrease in yield, and that this phenomenon can be suppressed by using a weak base instead of a strong base.

The weak base used herein is not particularly limited as long as it is a salt composed of a strong base and a weak acid, and an aqueous solution thereof does not hydrolyze an amide bond at 1atm and 0 to 25 ℃ and does not cause a polymerization reaction of a vinyl group, and for example, a weak base such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium acetate, or potassium acetate is preferably used. The amount of the weak base to be used is preferably 4.0 to 10.0 moles, more preferably 6.0 to 8.0 moles, in terms of sodium equivalent per 1 mole of the diazonium salt. The reaction temperature in the diazo coupling step is in the range of-10 to 10 ℃ and more preferably in the range of-5 to 5 ℃.

As the reaction solvent in the diazo coupling step, an organic solvent (an alcohol-based solvent such as methanol, ethanol or isopropanol, an amide-based solvent such as N, N-dimethylacetamide, N-dimethylformamide or 1-methyl-2-pyrrolidone, a sulfone-based solvent such as sulfolane, a sulfoxide-based solvent such as dimethylsulfoxide, a ureide-based solvent such as tetramethylurea, a halogen-based solvent such as dichloromethane, chloroform or 1, 2-dichloroethane, an ester-based solvent such as ethyl acetate or butyl acetate, an ether-based solvent such as diethyl ether or tetrahydrofuran, or a pyridine-based solvent such as pyridine, α -picoline or 2, 6-lutine) may be used alone or in a mixture system of a plurality of types, or a mixture system of an organic solvent and water and a water-alone system may be used, and among these, an alcohol-based solvent is preferable, and water is also preferably mixed with them. In addition, an amide solvent, an ester solvent, and an ether solvent may be added in addition to the alcohol solvent and water according to the reaction.

The aminoaryl compound referred to herein is a compound represented by (i) or (v) in the above reaction formula, and the nitroaryl compound is a compound represented by the same formula (ix). The polymerizable aminoaryl compound is a compound represented by (vi) or (vii) in the above reaction formula, and the polymerizable nitroaryl compound is a compound represented by the same formula (x).

The polymerizable aminoaryl compound or the polymerizable nitroaryl compound can be obtained by amidation reaction of an amino-substituted aromatic amine or a nitro-substituted aromatic amine with (meth) acrylic acid, amidation reaction of an amino-substituted aromatic alkylamine or a nitro-substituted aromatic alkylamine with (meth) acrylic acid, amidation reaction of an amino-substituted aromatic amine or a nitro-substituted aromatic amine with (meth) acrylic acid chloride, amidation reaction of an amino-substituted aromatic alkylamine or a nitro-substituted aromatic alkylamine with (meth) acrylic acid chloride, or the like.

As the amino-substituted aromatic compound, a compound in which the amino group is substituted with a protecting group such as tert-butoxycarbonyl, benzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, 2, 2, 2-trichloroethoxycarbonyl, allyloxycarbonyl, p-toluenesulfonyl or 2-nitrobenzenesulfonyl can be used.

Examples of the polymerizable aminoaryl compound include N- (4-aminophenyl) (meth) acrylamide, N- [ (4-aminophenyl) methyl ] (meth) acrylamide, N- [ 2- (4-aminophenyl) ethyl ] (meth) acrylamide, N- [ 3- (4-aminophenyl) propyl ] (meth) acrylamide, N- [ 4- (4-aminophenyl) butyl ] (meth) acrylamide, N- [ (3-aminophenyl) methyl ] (meth) acrylamide, N- [ 2- (3-aminophenyl) ethyl ] (meth) acrylamide, N- [ 3- (3-aminophenyl) propyl ] (meth) acrylamide, N- [ 4- (3-aminophenyl) butyl ] (meth) acrylamide and the like.

Further, examples of the polymerizable nitroaryl compound include N- (4-nitrophenyl) (meth) acrylamide, N- [ (4-nitrophenyl) methyl ] (meth) acrylamide, N- [ 2- (4-nitrophenyl) ethyl ] (meth) acrylamide, N- [ 3- (4-nitrophenyl) propyl ] (meth) acrylamide, N- [ 4- (4-nitrophenyl) butyl ] (meth) acrylamide, N- [ (3-nitrophenyl) methyl ] (meth) acrylamide, N- [ 2- (3-nitrophenyl) ethyl ] (meth) acrylamide, N- [ 3- (3-nitrophenyl) propyl ] (meth) acrylamide, N- [ 4- (3-nitrophenyl) butyl ] (meth) acrylamide and the like.

As the method for producing the dye compound of the present invention, a synthesis method in which an amidation step is performed before the diazo coupling step as in the above-mentioned synthesis method 2 or synthesis method 3 is preferable. This is because, although there is a possibility that a highly reactive by-product is generated by diazotization of an aliphatic amine in the diazotization step of the above-mentioned synthesis method 1, when the above-mentioned synthesis method 2 or synthesis method 3 is used, the generation of such a by-product can be avoided because the diazotization step is performed after the introduction of a polymerizable group by amidation reaction or the like in advance. As a result, according to synthetic method 2 or synthetic method 3, the dye compound of the present invention can be obtained in high yield with excellent reaction efficiency.

In addition, the nitroaryl compounds used as starting materials in synthetic method 3 are less expensive than the aminoaryl compounds. In addition, in the amidation reaction, usually, when a polymerizable group is introduced, a by-product in which two molecules of the polymerizable group are introduced with respect to the amino group is generated, and in the case of amidating a nitroaryl compound, the generated by-product is more easily removed than in the case of, for example, amidating an aminoaryl compound. From this viewpoint, from the viewpoints of such economy and ease of operation, synthesis method 3 using a nitroaryl compound as a starting material is particularly preferred as the method for producing the dye compound of the present invention.

The dye compound of the present invention can be produced industrially by synthesis method 2 or synthesis method 3, and can be used as a useful dye or a polymerizable ultraviolet-absorbing dye monomer.

< 2 > polymers according to the invention

The pigment compound of the present invention may be copolymerized with one or two or more other comonomers to form a polymer.

The coloring compound of the present invention does not inhibit polymerization because the chromophore and the polymerizable group are sterically separated. Therefore, it can be used as a comonomer having good reactivity with other comonomers.

The other comonomer is not particularly limited as long as it is a monomer generally used, but examples thereof include the following monomers.

Linear, branched, and cyclic alkyl (meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, t-pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenoxy (meth) acrylate;

pentamethyldisiloxanylmethyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, methyldi (trimethylsiloxy) silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris (methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, tris (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) silylpropylglyceryl (meth) acrylate, pentamethyldisiloxy (meth) acrylate, pentamethyldisiloxy) silylpropyl (meth) acrylate, and the like, (meth) acrylic acid esters containing silicon such as trimethylsilylethyltrimethylsiloxypropylglyceryl (meth) acrylate, trimethylsilylmethyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, trimethylsilylpropylglyceryl (meth) acrylate, pentamethyldisiloxypropylglyceryl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxane-based methyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxane-propylpropyl (meth) acrylate, and tetramethyltriisopropylcyclotetrasiloxane-bis (trimethylsiloxy) silylpropyl (meth) acrylate;

fluorine-containing (meth) acrylates such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, tetrafluoro-tert-pentyl (meth) acrylate, hexafluorobutyl (meth) acrylate, hexafluoro-tert-hexyl (meth) acrylate, octafluoropentyl (meth) acrylate, 2, 3, 4, 5, 5, 5-hexafluoro-2, 4-bis (trifluoromethyl) pentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, 2-hydroxyoctafluoro-6-trifluoromethylheptyl (meth) acrylate, 2-hydroxydodecafluoro-8-trifluoromethylnonyl (meth) acrylate, and 2-hydroxydecahexafluoro-10-trifluoromethylundecyl (meth) acrylate;

styrene derivatives such as styrene, pentafluorostyrene, methylstyrene, trimethylstyrene, trifluoromethylstyrene, (pentamethyl-3, 3-bis (trimethylsiloxy) trisiloxane) styrene, (hexamethyl-3-trimethylsiloxy trisiloxane) styrene, and dimethylaminostyrene;

hydroxyl group-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, dihydroxypropyl (meth) acrylate, dihydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, and dipropylene glycol mono (meth) acrylate;

(meth) acrylic acid;

vinyl lactams such as N-vinylpyrrolidone, alpha-methylene-N-methylpyrrolidone, N-vinylcaprolactam and N- (meth) acryloyl pyrrolidone;

(meth) acrylamides such as (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, and N-ethyl-N-aminoethyl (meth) acrylamide;

aminoalkyl (meth) acrylates such as aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, and N, N-dimethylaminoethyl (meth) acrylate;

alkoxy group-containing (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, and methoxydiglycol (meth) acrylate;

aromatic ring-containing (meth) acrylates such as benzyl (meth) acrylate;

alkyl esters such as itaconic acid, crotonic acid, maleic acid and fumaric acid which may be substituted with an alkyl group, a fluorine-containing alkyl group and a siloxane-based alkyl group;

glycidyl (meth) acrylate;

tetrahydrofurfuryl (meth) acrylate;

4-vinylpyridine;

heterocyclic N-vinyl monomers such as vinylimidazole, N-vinylpiperidone, N-vinylpiperidine and N-vinylsuccinimide;

n- (meth) acryloylpiperidine;

n- (meth) acryloylmorpholine.

Further, "(meth) acrylate" means "acrylate" or "methacrylate", which is the same for a (meth) acrylic acid derivative.

Alternatively, one or two or more of the above-mentioned comonomers may be selected and polymerized to form a macromonomer, which is used as 1 comonomer for producing a polymer.

The polymer of the present invention can be obtained by blending the pigment compound of the present invention and one or more other comonomers in an arbitrary amount, uniformly mixing them, and copolymerizing them.

In the copolymerization of the polymer of the present invention, the ratio of the pigment compound of the present invention to be blended is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 2 parts by weight, and further preferably 0.01 to 0.06 part by weight, based on 100 parts by weight of the total comonomer mixture, depending on the application of the polymer, for example, the use of the polymer, for example, an artificial crystal, and the thickness thereof. If the amount is less than 0.001 parts by weight, the color development of the polymer may be deteriorated. When the amount is more than 5 parts by weight, the polymer may be colored too densely to reduce transparency, the physical properties (e.g., strength) of the polymer may be reduced, or the dye compound of the present invention may be easily eluted from the polymer.

The polymers of the present invention can be synthesized using methods commonly practiced in the art. For example, the dye compound of the present invention may be uniformly mixed with one or more other comonomers, and if necessary, a polymerization initiator may be added thereto, and the resulting mixture may be heated slowly at a temperature ranging from room temperature to about 130 ℃ or polymerized by irradiation with electromagnetic waves such as microwaves, ultraviolet rays, and radiation (gamma rays). Further, the polymerization may be carried out by various methods widely used by those skilled in the art, such as radical polymerization, bulk polymerization, or solvent polymerization, and in the case of heating polymerization, the temperature may be raised stepwise.

Examples of the polymerization initiator include radical polymerization initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and benzoyl peroxide, and one or more of them may be used. The amount of the comonomer is preferably in the range of about 0.01 to 1 part by weight based on 100 parts by weight of the total comonomer mixture. In addition, when polymerization is performed by light or the like, a photopolymerization initiator or a sensitizer is preferably further added.

When the polymer of the present invention is synthesized, a known polymerizable ultraviolet absorber (a substance that mainly absorbs ultraviolet light), a polymerizable dye (a substance that mainly absorbs light in the blue region without ultraviolet absorption ability), or a polymerizable ultraviolet absorbing dye may be used in combination. By using these polymerizable ultraviolet absorbers, polymerizable coloring matters, and polymerizable ultraviolet absorbing coloring matters in combination, the balance between the ultraviolet absorbing performance and the light absorbing performance in the blue region of the finally obtained polymer can be finely adjusted. In particular, when the polymer of the present invention is used as a material for an intraocular lens as described later, such a combination is useful for adjusting the color tone of the intraocular lens or for sufficiently imparting ultraviolet absorbability.

The amount of the additive is preferably adjusted to 0.01 part by weight or more, more preferably 0.05 part by weight or more, based on 100 parts by weight of the total comonomer mixture, and is preferably adjusted to 5 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight of the total comonomer in order to secure a sufficient polymerization rate and polymerization degree.

Examples of the polymerizable ultraviolet absorber that can be used for the above purpose include a benzophenone-based polymerizable ultraviolet absorber disclosed in Japanese patent laid-open No. 2003-253248 and a benzotriazole-based polymerizable ultraviolet absorber disclosed in Japanese patent laid-open No. 2685980. Specific examples thereof include benzophenone-based polymerizable ultraviolet absorbers such as 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-tert-butylbenzophenone, 2-hydroxy-4- (meth) acryloyloxy-2 ', 4' -dichlorobenzophenone, and 2-hydroxy-4- (2 '-hydroxy-3' - (meth) acryloyloxypropyloxy) benzophenone; benzotriazole-based polymerizable ultraviolet absorbers such as 2- (2 '-hydroxy-5' - (meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2 '-hydroxy-5' - (meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2- (2 '-hydroxy-5' - (meth) acryloyloxypropylphenyl) -2H-benzotriazole, 2- (2 '-hydroxy-5' - (meth) acryloyloxypropyl-3 '-tert-butylphenyl) -5-chloro-2H-benzotriazole, and 2- (2' -hydroxy-5 '- (2 ″ -methacryloyloxyethoxy) -3' -tert-butylphenyl) -5-methyl-2H-benzotriazole; salicylic acid derivative-based polymerizable ultraviolet absorbers such as 2-hydroxy-4-methacryloyloxymethylbenzoate; methyl 2-cyano-3-phenyl-3- (3' - (meth) acryloyloxyphenyl) acrylate, and the like. They may be used singly or in admixture of 2 or more.

As the polymerizable coloring matter which can be used in combination for the above-mentioned purpose, for example, azo-based, anthraquinone-based, nitro-based, or phthalocyanine-based polymerizable coloring matters disclosed in Japanese patent laid-open No. 10-251537 can be used. They may be used singly or in admixture of 2 or more.

Specific examples of the polymerizable azo-based coloring matter include 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-naphthylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (. alpha. -anthrazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- ((4' - (phenylazo) -phenyl) azo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1- (2', 4' -xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, 2- (m- (meth) acryloylamide-anilino) -4, 6-bis (1' - (o-tolylazo) -2 ' -naphthylamino) -1, 3, 5-triazine, 2- (m-vinylanilino) -4- (4' -nitrophenylazo) -anilino) -6-chloro-1, 3, 5-triazine, 2- (1' - (o-tolylazo) -2 ' -naphthyloxy) -4- (m-vinylanilino) -6-chloro-1, 3, 5-triazine, 2- (p-vinylanilino) -4- (1' - (o-tolylazo) -2 ' naphthylamino) -6-chloro-1, 3, 5-triazine, N- (1' - (o-tolylazo) -2 ' -naphthyl) -3-vinylphthalic acid monoamide, N- (1' - (o-tolylazo) -2 ' -naphthyl) -6-vinylphthalic acid monoamide, 3-vinylphthalic acid- (4' - (p-sulfophenylazo) -1 ' -naphthyl) monoester, 6-vinylphthalic acid- (4' - (p-sulfophenylazo) -1 ' -naphthyl) monoester, 3- (meth) acryloylamide-4-phenylazophenol, 3- (meth) acryloylamide-4- (8 '-hydroxy-3', 6 '-disulfo-1' -naphthylazo) -phenol, 3- (meth) acryloylamide-4- (1 '-phenylazo-2' -naphthylazo) -phenol, 3- (meth) acryloylamide-4- (p-tolylazo) phenol, 2-amino-4- (m- (2 '-hydroxy-1' -naphthylazo) anilino) -6-isopropenyl-1, 3, 5-triazine, 2-amino-4- (N-methyl-p- (2 '-hydroxy-1' -naphthylazo) anilino) -6-isopropenyl-1, 3, 5-triazine, 2-amino-4- (m- (4 '-hydroxy-1' -phenylazo) anilino) -6-isopropenyl-1, 3, 5-triazine, 2-amino-4- (N-methyl-p- (4' -hydroxyphenylazo) anilino) -6-isopropenyl-1, 3, 5-triazine, 2-amino-4- (m- (3' -methyl-1 ' -phenyl-5 ' -hydroxy-4 ' -pyrazolylazo) anilino) -6-isopropenyl-1, 3, 5-triazine, 2-amino-4- (N-methyl-p- (3' -methyl-1 ' -phenyl-5 ' -hydroxy-4 ' -pyrazolylazo) anilino) -6-isopropenyl-1, 3, 5-triazine, 2-amino-4- (p-phenylazoanilino) -6-isopropenyl-1, 3, 5-triazine, 4-phenylazo-7- (meth) acryloylamide-1-naphthol, and the like.

Specific examples of the polymerizable anthraquinone-based coloring matter include 1, 5-bis ((meth) acryloylamino) -9, 10-anthraquinone, 1- (4' -vinylbenzamide) -9, 10-anthraquinone, 4-amino-1- (4' -vinylbenzamide) -9, 10-anthraquinone, 5-amino-1- (4' -vinylbenzamide) -9, 10-anthraquinone, 8-amino-1- (4' -vinylbenzamide) -9, 10-anthraquinone, 4-nitro-1- (4' -vinylbenzamide) -9, 10-anthraquinone, 4-hydroxy-1- (4' -vinylbenzamide) -9, 10-anthraquinone, 1- (3' -vinylbenzamide) -9, 10-anthraquinone, 1- (2' -vinylbenzamide) -9, 10-anthraquinone, 1- (4' -isopropenylbenzamide) -9, 10-anthraquinone, 1- (3 '-isopropenylbenzamide) -9, 10-anthraquinone, 1- (2' -isopropenylbenzamide) -9, 10-anthraquinone, 1, 4-bis (4 '-vinylbenzamide) -9, 10-anthraquinone, 1, 4-bis (4' -isopropenylbenzamide) -9, 10-anthraquinone, 1, 5 '-bis (4' -vinylbenzamide) -9, 10-anthraquinone, 1, 5-bis (4 '-isopropenylbenzamide) -9, 10-anthraquinone, 1-methylamino-4- (3' -vinylbenzamide) -9, 10-anthraquinone, 1-methylamino-4- (4 '-vinylbenzoyloxyethylamino) -9, 10-anthraquinone, 1-amino-4- (3' -vinylphenylamino) -9, 10-anthraquinone, 1-amino-2- (4 '-vinylphenylamino) -9, 10-anthraquinone-sulfonic acid, 1-amino-4- (4' -vinylphenylamino) -9, 10-anthraquinone-2-sulfonic acid, 1-amino-4- (2' -vinylbenzylamino) -9, 10-anthraquinone-2-sulfonic acid, 1-amino-4- (3' - (meth) acryloylaminophenylamino) -9, 10-anthraquinone-2-sulfonic acid, 1-amino-4- (3' - (meth) acryloylaminobenzylamino) -9, 10-anthraquinone-2-sulfonic acid, 1- (. beta. -ethoxycarbonylallylamino) -9, 10-anthraquinone, 1- (. beta. -carboxyallylamino) -9, 10-anthraquinone, 1, 5-bis- (. beta. -carboxyallylamino) -9, 10-anthraquinone, 1- (. beta. -isopropoxycarbonylallylamino) -5-benzamide-9, 10-anthraquinone, 2- (3' - (meth) acryloylamide-anilino) -4- (3' -sulfo-4 ' -aminoanthraquinone-1 ' -yl) -amino-anilino) -6-chloro-1, 3, 5-triazine, 2- (3' - (methyl) acryloyl amide-anilino) -4- (3' - (3 "-sulfo-4" -aminoanthraquinone-1 "-yl) -amino-anilino) -6-hydrazino-1, 3, 5-triazine, 2, 4-bis- ((4" -methoxyanthraquinone-1 "-yl) -amino) -6- (3' -vinylanilino) -1, 3, 5-triazine, 2- (2' -vinylphenoxy) -4- (4' - (3" -sulfo-4 "-aminoanthraquinone-1" -yl-amino) -anilino) -6-chloro-1, 3, 5-triazine, and the like.

Specific examples of the polymerizable nitro dye include o-nitroanilinomethyl (meth) acrylate and the like.

Specific examples of the polymerizable phthalocyanine-based coloring matter include (meth) acrylated tetraaminocopper phthalocyanine, (meth) acrylated (dodecylated tetraaminocopper phthalocyanine), and the like.

Specific examples of the polymerizable ultraviolet-absorbing coloring matter which can be used in combination for the above-mentioned purpose include 2, 4-dihydroxy-3 (p-styreneazo) benzophenone, 2, 4-dihydroxy-5- (p-styreneazo) benzophenone, 2, 4-dihydroxy-3- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (meth) acryloyloxymethylphenylazo) benzophenone, 2, 4-dihydroxy-3- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (meth) acryloyloxyethylphenylazo) benzophenone, 2, 4-dihydroxy-3- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (meth) acryloyloxypropylphenylazo) benzophenone, 2, 4-dihydroxy-3- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (meth) acryloyloxymethylphenylazo) benzophenone, 2, 4-dihydroxy-3- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (meth) acryloyloxyethylphenylazo) benzophenone, 2, 4-dihydroxy-3- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (meth) acryloyloxypropylphenylazo) benzophenone, 2, 4-dihydroxy-3- (p- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, and mixtures thereof, 2, 4-dihydroxy-3- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-3- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (N-ethyl-N- (meth) acryloyloxyethylamino) phenylazo) benzophenone, a, Benzophenone-based polymerizable ultraviolet absorbing pigments such as 2, 4-dihydroxy-3- (p- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (p- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2, 4-dihydroxy-3- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, 2, 4-dihydroxy-5- (o- (N-ethyl-N- (meth) acryloylamino) phenylazo) benzophenone, and benzoic acid-based polymerizable ultraviolet absorbing pigments such as 2-hydroxy-4- (p-phenylethanazo) benzoic acid phenyl. They may be used singly or in admixture of 2 or more.

In addition, when a crosslinking agent is added during copolymerization of the polymer of the present invention, or a macromonomer having 2 or more polymerizable groups in the molecule is used as a comonomer, a three-dimensional crosslinked structure can be formed in the resulting polymer. This improves the mechanical strength and hardness of the polymer and suppresses elution of the monomer (including the dye compound of the present invention) from the polymer. In addition, when the polymer of the present invention is used as a material for an intraocular lens as described later, an intraocular lens having excellent optical properties, which is uniform, transparent and free from distortion, can be obtained, or durability (chemical resistance, heat resistance, solvent resistance) can be imparted to the intraocular lens.

When the crosslinking agent and the macromonomer are blended, the blending ratio is preferably within a range of 0.01 to 10 parts by weight per 100 parts by weight of the total comonomer mixture. If the amount is less than 0.01 part by weight, it is difficult to obtain the effect, and if the amount is more than 10 parts by weight, the resulting polymer tends to become brittle.

Examples of the macromonomer include butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, diallyl fumarate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl (meth) acrylate, divinylbenzene, diallyl phthalate, diallyl adipate, triallyl diisocyanate, α -methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, 2-bis ((meth) acryloyloxyphenyl) hexafluoropropane, and mixtures thereof, 2, 2-bis ((meth) acryloyloxyphenyl) propane, 1, 4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1, 3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1, 2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1, 4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1, 3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1, 2-bis (2- (meth) acryloyloxyisopropyl) benzene and the like.

In addition, various functionalities can be imparted to the polymer of the present invention by selecting an appropriate comonomer.

When oxygen permeability is imparted to the polymer of the present invention, a silicon-containing monomer such as a silicon-containing (meth) acrylate or a silicon-containing styrene derivative, or a fluorine-containing alkyl (meth) acrylate may be selected as a comonomer.

When the strength of the polymer is increased or the hardness is adjusted, an alkyl (meth) acrylate, a styrene derivative containing styrene, or (meth) acrylic acid may be selected as the comonomer.

When a fluorine-containing monomer such as a fluorine-containing alkyl (meth) acrylate or a fluorine-containing styrene derivative is selected as a comonomer, a material having a function of preventing lipid contamination can be obtained when the polymer of the present invention is used as a material for an artificial crystal as described later.

When hydrophilicity is imparted to the polymer of the present invention, a monomer having a hydrophilic group such as a hydroxy (meth) acrylate, a (meth) acrylamide, an aminoalkyl (meth) acrylate, a (meth) acrylate, or an N-vinyl lactam may be selected as a comonomer, and when the polymer of the present invention is used as a material for an intraocular lens as described later, a flexible intraocular lens having water-containing properties can be obtained.

When a monomer having an aromatic ring is selected as the comonomer, for example, a styrene-based monomer or an aromatic ring-containing (meth) acrylate, the polymer of the present invention can be used as a material for a lens having a high refractive index.

When comonomers selected to impart various functionalities are blended in the polymer of the present invention as described above, the amount is preferably adjusted to 0.01 parts by weight or more, more preferably 0.05 parts by weight or more, based on 100 parts by weight of the total comonomer mixture, and is preferably adjusted to 5 parts by weight or less, more preferably 3 parts by weight or less, based on 100 parts by weight of the total comonomer mixture.

As described above, since the dye compound of the present invention has light absorption characteristics in an ultraviolet region (wavelength of 380nm or less) and a blue region (wavelength of 380 to 500nm), the polymer of the present invention can block ultraviolet light and reduce the intensity of light in the blue region. Specifically, it is preferable that the light transmittance decreases from around 500nm and reaches 0% at 400nm or less. More preferably, the ultraviolet-visible absorption spectrum is measured so that the profile becomes sharply increased in the vicinity of 420 to 500nm, and the light transmission suppressing ability in the ultraviolet-blue region is more excellent than that of conventional dye compounds (e.g., BMAC). In addition, it is preferable to use another ultraviolet absorber in order not to transmit light having a wavelength of 400nm or less. Therefore, as described later, in the case of the material for an artificial crystal, adverse effects of light on the eyes can be suppressed.

In the polymer of the present invention, the dye compound of the present invention is directly bonded to the polymer chain by copolymerization, and therefore the dye compound of the present invention is not eluted from the polymer of the present invention. This can be confirmed by that the polymer of the present invention does not change in the spectrum of light transmittance before and after being immersed in ethanol at 40 ℃ for 24 hours.

As described above, in the dye compound of the present invention, since the amide bond linking the polymerizable group and the dye site is stable under alkaline conditions (for example, pH12 or more), the dye site is not separated from the polymer of the present invention. As a result, stability under alkaline conditions which is poor in conventional copolymers using a dye compound having an ester bond can be achieved, and high light absorption characteristics can be maintained in the polymer after the alkaline treatment. This can be confirmed by the fact that the light transmittance of the immersion liquid obtained by immersing the polymer of the present invention in a 4N aqueous solution of sodium hydroxide at room temperature for 4 hours is substantially 100%.

< 3 > Artificial Crystal of the present invention

The polymer of the invention can be used as a material for artificial crystals.

Generally, a pigment compound increases its hardness when added to a polymer, but since the pigment compound of the present invention is excellent in flexibility, the intraocular lens of the present invention molded using the polymer of the present invention as a material for an intraocular lens is expected to maintain flexibility, so that handling at the time of surgery becomes easy.

The polymer of the present invention has excellent resistance to light and chemicals, high fastness, and no elution of a dye site from the polymer, and therefore, it is highly safe and can give an excellent artificial lens free from discoloration or discoloration.

In addition, the polymer of the present invention can be used as a material for spectacles, sunglasses, contact lenses, etc., and can be used in a coating material, a building material, etc.

The polymer of the present invention has a chemically stable dye site, and can be used without deterioration even in the open air where a temperature change or a drastic change in pH can be expected or in a severe environment.

When the polymer of the present invention is used as a material for an artificial crystal, it can be molded by a known method. For example, there may be mentioned a method of obtaining a polymer in a rod shape, a block shape or a plate shape by performing a polymerization reaction in an appropriate mold or a container, then processing the polymer into a desired shape by machining such as cutting or polishing, or a method of obtaining a polymer molded product by performing a polymerization reaction in a mold corresponding to a desired shape, and then performing mechanical finishing as needed.

Alternatively, the supporting portion of the intraocular lens may be formed separately from the intraocular lens and then attached, or the supporting portion of the intraocular lens and the intraocular lens may be molded simultaneously (integrally).

In the case of forming the polymer of the present invention into an intraocular lens, surface modification treatment, preferably plasma treatment or treatment with ultraviolet light, more preferably corona discharge treatment, glow discharge treatment or ultraviolet/ozone treatment, may be performed as necessary in order to hydrophilize the surface of the lens. As the processing apparatus and the processing method in this case, conventionally known ordinary apparatuses and methods can be used.

Examples

< Synthesis of polymerizable aminoaryl Compound 1 >

Examples of using an aminoaryl compound as a starting material in the synthesis examples of the polymerizable aminoaryl compound used in the synthesis of the pigment compound of the present invention are given below.

Synthesis example 1 Synthesis of N- [ 2- [ 4- (tert-butoxycarbonylamino) phenyl ] ethyl ] methacrylamide

[ solution 24]

2- [ 4- (tert-butoxycarbonyl) phenyl]Ethylamine (3.54g) and methacrylic acid (1.57g) were dissolved in chloroform (80mL), and water-soluble carbodiimide (2.88g) was added thereto under ice bath. The mixture was stirred at 4 ℃ for 1 hour, then at room temperature overnight, and concentrated under reduced pressure. The residue was washed with 5% potassium hydrogensulfate, saturated sodium bicarbonate and saturated brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the obtained residue was eluted through silica gel column chromatography using hexane-ethyl acetate (volume ratio: 2: 1) and then hexane-ethyl acetate (volume ratio: 1) to obtain the desired product as white needle crystals. The yield was 2.92 g. For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.52(s，9H)，1.91(s，3H)，2.80(t，2H，J＝6.8Hz)，3.54(q，2H，J＝6.8Hz)，5.28(t，1H，J＝1.4Hz)，5.59(s，1H)，5.76(br.s，1H)，6.46(br.s，1H)，7.12(d，2H，J＝8.3Hz)，7.31(d，2H，J＝8.3Hz).

Synthesis example 2 Synthesis of N- [ 2- [ 4- (tert-butoxycarbonylamino) phenyl ] ethyl ] acrylamide

[ solution 25]

Reacting 2- [ 4- (tert-butoxycarbonyl) phenyl]Ethylamine (2.36g) and acrylic acid (0.84g) were reacted in the same manner as in Synthesis example 1 to obtain the desired product as white needle crystals. The yield was 2.02 g. For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.52(s，9H)，2.80(t，2H，J＝6.8Hz)，3.57(q，2H，J＝6.8Hz)，5.51(br.s，1H)，5.62(dd，1H，J＝10.5Hz，0.9Hz)，6.01(dd，1H，J＝17.4Hz，10.5Hz)，6.26(dd，1H，J＝17.4Hz，0.9Hz)，6.45(br.s，1H)，7.12(d，2H，J＝8.2Hz)，7.30(d，2H，J＝8.2Hz).

[ Synthesis example 3] Synthesis of N- [ 4- (tert-butoxycarbonylamino) benzyl ] methacrylamide

[ solution 26]

The desired product was obtained as white needle crystals by reacting 4- (tert-butoxycarbonylamino) benzylamine (5.38g) and methacrylic acid (1.89g) in the same manner as in Synthesis example 1. The yield was 4.15 g. For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.50(s，9H)，1.96(s，3H)，4.43(d，2H，J＝5.4Hz)，5.32(t，1H，J＝0.3Hz)，5.68(s，1H)，5.96(br.s，1H)，6.46(br.s，1H)，7.21(d，2H，J＝8.8Hz)，7.32(d，2H，J＝8.8Hz).

< Synthesis of polymerizable aminoaryl Compound 2 >

Examples of using nitroaryl compounds as starting materials in the synthesis examples of the polymerizable aminoaryl compounds used in the synthesis of the pigment compounds of the present invention are given below.

[ Synthesis example 4] Synthesis of N- [ 2- (4-aminophenyl) ethyl ] methacrylamide

[ solution 27]

2- (4-Nitrophenyl) ethylamine hydrochloride (1.72g) and sodium hydrogencarbonate (5.00g) were dissolved in water (25mL), and ethyl acetate (25mL) was added and stirred in an ice bath. Methacryloyl chloride (1.79g) was added dropwise thereto. After stirring for 10 minutes, the mixture was extracted with ethyl acetate, washed with water and saturated brine, dried over sodium sulfate, and the drying agent was removed by suction filtration. Recrystallization was carried out using a mixed solvent of hexane and ethyl acetate. Obtaining N- [ 2- (4-nitrophenyl) ethyl in the form of yellowish white crystals](ii) methacrylamide. Yield 1.25g (63%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.93(s，3H)，2.99(t，2H，J＝6.8Hz)，3.60(q，2H，J＝6.8Hz)，5.32(t，1H，J＝1.2Hz)，5.61(s，1H)，5.82(br.s，1H)，7.37(d，2H，J＝8.6Hz)，8.17(d，2H，J＝8.6Hz).

Then, the N- [ 2- (4-nitrophenyl) ethyl group is reacted]Methacrylamide (1.20g) was dissolved in ethanol (15mL) and water (5 mL). Ammonium chloride (364mg) and iron powder (933mg) were added to the solution, and the mixture was refluxed at 80 ℃ for 4 hours. The iron powder was filtered off and concentrated using a rotary evaporator. Adding water and ethyl acetate to the mixtureThe extraction was performed by washing with water and saturated brine. After drying over sodium sulfate and filtering out the drying agent, the objective compound was obtained as a pale red oil by concentration. Yield 1.01g (97%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.91(s，3H)，2.74(t，2H，J＝6.8Hz)，3.51(q，2H，J＝6.8Hz)，3.61(br.s，2H)，5.27(t，1H，J＝1.4Hz)，5.59(s，1H)，5.76(br.s，1H)，6.64(d，2H，J＝8.3Hz)，6.98(d，2H，J＝8.3Hz).

[ Synthesis example 5] Synthesis of N- (4-aminobenzyl) methacrylamide

[ solution 28]

4-Nitrobenzylamine hydrochloride (1.51g) and sodium hydrogencarbonate (4.13g) were dissolved in water (25mL), and ethyl acetate (25mL) was added thereto and stirred in an ice bath. Methacryloyl chloride (1.26g) was added dropwise thereto. After stirring for 10 minutes, the mixture was extracted with ethyl acetate, washed with water and saturated brine, dried over sodium sulfate, and the drying agent was removed by suction filtration. Thereafter, recrystallization was carried out using a mixed solvent of hexane and ethyl acetate. The N- (4-nitrobenzyl) methacrylamide was obtained as yellowish white crystals. Yield 1.05g (60%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：2.01(s，3H)，4.61(d，2H，J＝6.0Hz)，5.41(t，1H，J＝1.0Hz)，5.76(t，1H，J＝1.0Hz)，6.29(br.s，1H)，7.45(d，2H，J＝8.8Hz)，8.17(d，2H，J＝8.8Hz).

Then, N- (4-nitrobenzyl) methacrylamide (811mg) was dissolved in ethanol (12mL) and water (4 mL). Ammonium chloride (183mg) and iron powder (573mg) were added to the solution, and the mixture was refluxed at 80 ℃ for 4 hours. The iron powder is filtered out,concentration was performed using a rotary evaporator. Water and ethyl acetate were added to conduct extraction, and the mixture was washed with water and saturated brine. After drying over sodium sulfate and filtering out the drying agent, the objective compound was obtained as a pale red oil by concentration. Yield 580mg (89%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.97(t，3H，J＝1.3Hz)，3.67(br.s，2H)，4.37(d，2H，J＝5.6Hz)，5.31(t，1H，J＝1.4Hz)，5.68(br.t，1H)，5.92(br.s，1H)，6.65(d，2H，J＝8.3Hz)，7.09(d，2H，J＝8.3Hz).

< Synthesis of polymerizable ultraviolet-absorbing coloring matter >

The polymerizable ultraviolet absorbing dye of the present invention is synthesized using the polymerizable aminoaryl compound synthesized as described above. Examples 1 to 12 are given below.

EXAMPLE 1 Synthesis of 2, 4-dihydroxy-5- [ 4- [ 2- (methacrylamide) ethyl ] phenylazo ] benzophenone (hereinafter abbreviated to HBZ-PHM)

[ solution 29]

Reacting N- [ 2- [ 4- (tert-butoxycarbonylamino) phenyl]Ethyl radical]Methacrylamide (609mg) was dissolved in ethyl acetate (2mL), and a 4M solution of hydrogen chloride in ethyl acetate (5mL) was added. The mixture was stirred at room temperature for 40 minutes and then concentrated under reduced pressure. The concentrated residue was dissolved in 1M hydrochloric acid (4mL), and a solution of sodium nitrite (145mg) in water (10mL) was added dropwise while cooling on ice, followed by stirring at 4 ℃ for 40 minutes to prepare a diazonium salt. Then 2, 4-dihydroxybenzophenone (428mg) was dissolved in ethanol (20mL), and a solution of sodium carbonate (423mg) in water (20mL) was added. To this mixture was added dropwise a solution containing the aforementioned diazonium salt under ice bath. The mixture was stirred at 4 ℃ for 1 hour and then at room temperature 4After the completion of the reaction, 4M hydrochloric acid was added dropwise to adjust the pH to 6. To the mixture was added water (40mL), and the precipitate was filtered off and washed with water. The precipitate was dissolved in chloroform without drying, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Methanol was added to the concentrated residue and the mixture was left at 4 ℃ overnight, and then the desired product was precipitated as orange crystals. Yield 326mg (38%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

¹H－NMR(400MHz，CDCl₃)：1.93(t，3H，J＝1.0Hz)，2.94(t，2H，J＝6.8Hz)，3.61(q，2H，J＝6.8Hz)，5.31(t，1H，J＝1.0Hz)，5.61(t，1H，J＝1.0Hz)，5.80(br.t，1H)，6.58(s，1H)，7.33(d，2H，J＝8.8Hz)，7.56(t，2H，J＝7.2Hz)，7.64(tt，1H，J＝7.3Hz，2.4Hz)，7.73－7.76(m，4H)，8.23(s，1H)，12.89(s，1H)，13.94(s，1H).

EXAMPLE 2 Synthesis of 2-hydroxy-5- [ 4- [ 2- (methacrylamide) ethyl ] phenylazo ] benzophenone (hereinafter referred to as NBZ-PHM)

[ solution 30]

N- [ 2- [ 4- (tert-Butoxycarbonylamino) phenyl ] is reacted with the same procedure as in example 1]Ethyl radical]Methacrylamide (609mg) was subjected to acid treatment, diazotization and diazo coupling with 2-hydroxybenzophenone (396mg), whereby the desired compound was obtained as orange crystals. Yield 630mg (76%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

¹H－NMR(400MHz，CDCl₃)：1.92(s，3H)，2.93(t，2H，J＝6.8Hz)，3.61(q，2H，J＝6.8Hz)，5.29(t，1H，J＝1.2Hz)，5.61(s，1H)，5.79(br.t，1H)，7.20(d，1H，J＝8.8Hz)，7.32(d，2H，J＝8.3Hz)，7.57(t，2H，J＝7.3Hz)，7.66(t，1H，J＝7.3Hz)，7.77－7.81(m，4H)，8.15(dd，1H，J＝9.3Hz，2.4Hz)，8.26(d，1H，J＝2.4Hz)，12.44(s，1H).

EXAMPLE 3 Synthesis of 2-hydroxy-5- [ 4- [ 2- (methacrylamide) ethyl ] phenylazo ] -4-methoxybenzophenone (hereinafter referred to as MBZ-PHM)

[ solution 31]

N- [ 2- [ 4- (tert-Butoxycarbonylamino) phenyl ] is reacted with the same procedure as in example 1]Ethyl radical]Methacrylamide (609mg) was subjected to acid treatment, diazotization, and diazo coupling with 2-hydroxy-4-methoxybenzophenone (456mg), whereby the desired compound was obtained as orange crystals. Yield 553mg (62%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

¹H－NMR(400MHz，CDCl₃)：1.92(s，3H)，2.92(t，2H，J＝6.8Hz)，3.60(q，2H，J＝6.8Hz)，4.09(s，3H)，5.29(t，1H，J＝1.4Hz)，5.60(s，1H)，5.76(br.t，1H)，6.71(s，1H)，7.29(d，2H，J＝8.8Hz)，7.53(t，2H，J＝8.8Hz)，7.61(t，1H，J＝7.8Hz)，7.71(d，2H，J＝6.8Hz)，7.76(d，2H，J＝6.8Hz)，8.03(s，1H)，12.91(s，1H).

EXAMPLE 4 Synthesis of 4-ethoxy-2-hydroxy-5- [ 4- [ 2- (methacrylamide) ethyl ] phenylazo ] benzophenone (hereinafter, abbreviated to EBZ-PHM)

[ solution 32]

N- [ 2- [ 4- (tert-Butoxycarbonylamino) phenyl ] is reacted with the same procedure as in example 1]Ethyl radical]Methyl propylThe enamide (609mg) was treated with acid, and then diazotized, and diazotized with 4-ethoxy-2-hydroxybenzophenone (485mg) to give the objective compound as orange crystals. Yield 652mg (71%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

¹H－NMR(400MHz，CDCl₃)：1.59(t，3H，J＝6.8Hz)，1.92(s，3H)，2.92(t，2H，J＝6.8Hz)，3.60(q，2H，J＝6.8Hz)，4.33(q，2H，J＝6.8Hz)，5.29(t，1H，J＝1.2Hz)，5.60(s，1H)，5.77(br.t，1H)，6.68(s，1H)，7.30(d，2H，J＝8.3Hz)，7.53(t，2H，J＝7.3Hz)，7.61(t，1H，J＝7.3Hz)，7.71(d，2H，J＝7.3Hz)，7.78(d，2H，J＝8.4Hz)，8.03(s，1H)，12.90(s，1H).

EXAMPLE 5 Synthesis of 5- [ 4- [ 2- (acrylamido) ethyl ] phenylazo ] -2, 4-dihydroxybenzophenone (hereinafter, abbreviated as HBZ-PHA)

[ solution 33]

Reacting N- [ 2- [ 4- (tert-butoxycarbonylamino) phenyl]Ethyl radical]Acrylamide (581mg) was treated with acid in the same manner as in example 1, and then diazotized, and diazo-coupled with 2, 4-dihydroxybenzophenone (428mg) to obtain the objective compound. Yield 313mg (38%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：2.94(t，2H，J＝6.8Hz)，3.64(q，2H，J＝6.4Hz)，5.56(br.t，1H)，5.64(dd，1H，J＝10.8Hz，1.5Hz)，6.03(dd，1H，J＝17.1Hz，10.8Hz)，6.28(dd，1H，J＝17.1Hz，1.5Hz)，6.58(s，1H)，7.33(d，2H，J＝8.3Hz)，7.54－7.59(m，2H)，7.65(t，1H，J＝78Hz)，7.73－7.76(m，4H)，8.23(s，1H)，12.90(s，1H)，13.94(s，1H).

EXAMPLE 6 Synthesis of 5- [ 4- [ 2- (acrylamido) ethyl ] phenylazo ] -2-hydroxy-4-methoxybenzophenone (hereinafter referred to as MBZ-PHA)

[ chemical 34]

N- [ 2- [ 4- (tert-Butoxycarbonylamino) phenyl ] is reacted with the same procedure as in example 5]Ethyl radical]Acrylamide (581mg) was subjected to acid treatment, diazotization, and diazo coupling with 2-hydroxy-4-methoxybenzophenone (456mg) to obtain the objective compound. Yield 510mg (59%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：2.92(t，2H，J＝6.8Hz)，3.62(q，2H，J＝6.8Hz)，4.09(s，3H)，5.56(br.t，1H)，5.63(dd，1H，J＝10.2Hz，1.5Hz)，6.02(dd，1H，J＝17.1Hz，10.2Hz)，6.26(dd，1H，J＝17.1Hz，1.5Hz)，6.70(s，1H)，7.29(d，2H，J＝8.3Hz)，7.53(t，2H，J＝7.3Hz)，7.61(t，1H，J＝7.8Hz)，7.70－7.76(m，4H)，8.03(s，1H)，12.92(s，1H).

EXAMPLE 7 Synthesis of 5- [ 4- [ 2- (acrylamido) ethyl ] phenylazo ] -4-ethoxy-2-hydroxybenzophenone (hereinafter referred to as EBZ-PHA)

[ solution 35]

N- [ 2- [ 4- (tert-Butoxycarbonylamino) phenyl ] is reacted with the same procedure as in example 5]Ethyl radical]Acrylamide (581mg) was subjected to acid treatment, diazotization, and diazo coupling with 4-ethoxy-2-hydroxybenzophenone (485mg), to obtain the objective compound. Yield 583mg (66%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.59(t，3H，J＝7.1Hz)，2.93(t，2H，J＝6.9Hz)，3.64(q，2H，J＝6.9Hz)，4.33(q，2H，J＝7.1Hz)，5.52(br.t，1H)，5.63(dd，1H，J＝10.4Hz，1.3Hz)，6.02(dd，1H，J＝16.9Hz，10.4Hz)，6.27(dd，1H，J＝16.9Hz，1.3Hz)，6.68(s，1H)，7.29(d，2H，J＝8.5Hz)，7.50－7.55(m，2H)，7.61(t，1H，J＝7.4Hz)，7.69－7.72(m，2H)，7.96(d，2H，J＝8.3Hz)，8.02(s，1H)，12.89(s，1H).

EXAMPLE 8 Synthesis of 5- [ 4- [ 2- (acrylamido) ethyl ] phenylazo ] -2-hydroxybenzophenone (hereinafter referred to as NBZ-PHA)

[ solution 36]

N- [ 2- [ 4- (tert-Butoxycarbonylamino) phenyl ] is reacted with the same procedure as in example 5]Ethyl radical]Acrylamide (581mg) was subjected to acid treatment, diazotization and diazo coupling with 2-hydroxybenzophenone (396mg) to obtain the objective compound. Yield 525mg (66%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：2.94(t，2H，J＝6.8Hz)，3.64(q，2H，J＝6.8Hz)，5.56(br.t，1H)，5.63(dd，1H，J＝10.3Hz，1.5Hz)，6.02(dd，1H，J＝17.1Hz，10.3Hz)，6.27(dd，1H，J＝17.1Hz，1.5Hz)，7.20(d，1H，J＝9.3Hz)，7.32(d，2H，J＝8.3Hz)，7.57(tt，2H，J＝7.3Hz，1.5Hz)，7.66(t，1H，J＝7.8Hz)，7.77－7.81(m，4H)，8.15(dd，1H，J＝9.3Hz，2.4Hz)，8.26(d，1H，J＝2.4Hz)，12.45(s，1H).

EXAMPLE 9 Synthesis of 2, 4-dihydroxy-5- [ 4- [ 2- (methacrylamide) ethyl ] phenylazo ] benzophenone (HBZ-PHM)

[ solution 37]

HBZ-PHM was synthesized by the following method different from example 1.

To N- [ 2- [ 4-aminophenyl group]Ethyl radical]Methacrylamide (930mg) was added with 1M hydrochloric acid (15mL), and a solution of sodium nitrite (355mg) in water (5mL) was added dropwise in an ice bath, followed by stirring at 4 ℃ for 1 hour to prepare a diazonium salt. Then, 2, 4-dihydroxybenzophenone (975mg) was dissolved in ethanol (40mL), and a solution of sodium carbonate (970mg) in water (40mL) was added. To this mixture was added dropwise a solution containing the aforementioned diazonium salt under ice bath. The mixture was stirred at 4 ℃ for 1 hour, then at room temperature for 2 hours, and 4M hydrochloric acid was added dropwise to adjust the pH to 6. To the mixture was added water (40mL), and the precipitate was filtered off and washed with water. After drying, the mixture was dissolved in chloroform, adsorbed on silica gel, and purified by column chromatography using ethyl acetate to obtain orange crystals. Methanol was added to the crystals to reflux, and the mixture was left at room temperature overnight to obtain the target product as orange crystals. Yield 774mg (40%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.93(t，3H，J＝1.0Hz)，2.94(t，2H，J＝6.8Hz)，3.61(q，2H，J＝6.8Hz)，5.31(t，1H，J＝1.0Hz)，5.61(t，1H，J＝1.0Hz)，5.81(br.t，1H)，6.58(s，1H)，7.33(d，2H，J＝8.5Hz)，7.56(t，2H，J＝7.2Hz)，7.64(tt，1H，J＝7.2Hz，2.4Hz)，7.72－7.76(m，4H)，8.22(s，1H)，12.89(s，1H)，13.93(s，1H).

EXAMPLE 10 Synthesis of 5- [ 4- [ 2- (methacrylamide) methyl ] phenylazo ] -2, 4-dihydroxybenzophenone (hereinafter, abbreviated as HBZ-BZM)

[ solution 38]

Reacting N- [ 4- (tert-butoxycarbonylamino) benzyl]Methacrylamide (581mg) was subjected to the same acid treatment as in example 1, then to diazotization, and subjected to diazo coupling with 2, 4-dihydroxybenzophenone (428mg), whereby the objective compound was obtained. Yield was 470mg (57%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：1.99(s，3H)，4.56(d，2H，J＝5.9Hz)，5.37(s，1H)，5.73(s，1H)，6.13(br.t，1H)，6.57(s，1H)，7.25(s，1H)，7.41(d，2H，J＝8.8Hz)，7.53－7.57(m，2H)，7.63(t，1H，J＝7.3Hz)，7.72－7.76(m，4H)，8.22(s，1H)，12.88(s，1H)，13.89(s，1H).

EXAMPLE 11 Synthesis of 5- [ 4- [ 2- (methacrylamide) methyl ] phenylazo ] -2-hydroxy-4-methoxybenzophenone (hereinafter referred to as MBZ-BZM)

[ solution 39]

N- [ 4- (tert-Butoxycarbonylamino) benzyl group in the same manner as in example 10]Methacrylamide (581mg) was subjected to acid treatment, diazotization and diazo coupling with 2-hydroxy-4-methoxybenzophenone (456mg) to obtain the objective compound. Yield 511mg (59%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：2.00(s，3H)，4.09(s，3H)，4.56(d，2H，J＝5.9Hz)，5.37(s，1H)，5.73(s，1H)，6.10(br.t，1H)，6.70(s，1H)，7.39(d，2H，J＝8.8Hz)，7.51－7.55(m，2H)，7.61(t，1H，J＝7.8Hz)，7.69－7.72(m，2H)，7.78(d，2H，J＝8.3Hz)，8.03(s，1H)，12.92(s，1H).

EXAMPLE 12 Synthesis of 5- [ 4- [ 2- (methacrylamide) methyl ] phenylazo ] -2-hydroxy-4-methoxybenzophenone (HBZ-BZM)

[ solution 40]

MBZ-BZM was synthesized by the following method different from example 11.

To N- [ 4-aminobenzyl group]Methacrylamide (574mg) was added with 1M hydrochloric acid (9mL), and a solution of sodium nitrite (210mg) in water (3mL) was added dropwise in an ice bath, followed by stirring at 4 ℃ for 1 hour to prepare a diazonium salt. Then 2, 4-dihydroxybenzophenone (637mg) was dissolved in ethanol (25mL), and a solution of sodium carbonate (644mg) in water (25mL) was added. To this mixture was added dropwise a solution containing the aforementioned diazonium salt under ice bath. The mixture was stirred at 4 ℃ for 1 hour, then at room temperature for 2 hours, and 4M hydrochloric acid was added dropwise to adjust the pH to 6. To the mixture was added water (25mL), and the precipitate was filtered off and washed with water. After drying, the extract was dissolved in chloroform, adsorbed on silica gel, and purified by column chromatography using ethyl acetate to obtain orange crystals. Methanol was added to the crystals to reflux, and the mixture was left at room temperature overnight to obtain the target product as orange crystals. Yield was 370mg (29%). For the resulting compounds, give¹H－NMR(400MHz、CDCl₃) The spectral data of (a).

：2.00(t，3H，J＝1.1Hz)，4.57(d，2H，J＝6.0Hz)，5.38(t，1H，J＝1.4Hz)，5.73(br.t，1H)，6.16(br.s，1H)，6.57(s，1H)，7.41(d，2H，J＝8.5Hz)，7.56(t，2H，J＝7.4Hz)，7.63(tt，1H，J＝7.3Hz，2.4Hz)，7.71－7.78(m，4H)，8.22(s，1H)，12.88(s，1H)，13.89(s，1H).

< example of copolymerization of polymerizable ultraviolet-absorbing coloring matter with other polymerizable monomer >

The polymerizable ultraviolet absorbing dye obtained in example was copolymerized with another polymerizable monomer.

[ example 13]

0.03 part by mass of the polymerizable ultraviolet absorbing dye (HBZ-PHM) obtained in example 1, 60 parts by mass of 2-phenoxyethyl acrylate, 40 parts by mass of ethyl acrylate, and 0.5 part by mass of 2, 2' -azobis (2, 4-dimethylvaleronitrile) were uniformly blended and polymerized at 80 ℃ for 40 minutes to prepare a polymer sheet having a thickness of 1 mm. The obtained polymer sheet is used as a sample, and the light transmittance at a wavelength of 220-800 nm is measured. The results are shown in fig. 1.

Then, the sample was immersed in ethanol at 40 ℃ for 24 hours to be subjected to elution treatment, and then the light transmittance was measured again, and as a result, the spectrum did not change before and after the elution treatment. This result shows that the polymerizable ultraviolet-absorbing dye is chemically bonded to the material, and it was confirmed that even when the dye compound of the present invention is used in combination with another ultraviolet absorber in polymer synthesis, the dye compound does not elute after polymerization. In addition, an ultraviolet-visible spectrophotometer (the same applies hereinafter) was used for the measurement of the light transmittance.

< example of copolymerization of polymerizable ultraviolet-absorbing coloring matter with polymerizable ultraviolet absorber and other polymerizable monomer >

The polymerizable ultraviolet-absorbing coloring matter obtained in the examples was copolymerized with another polymerizable monomer together with another polymerizable ultraviolet absorber.

[ example 14]

A polymer sheet was produced in the same manner as in example 13, except that 0.15 parts by mass of 2- [ 2' -hydroxy-5 ' - (2 "-methacryloyloxyethoxy) -3 ' -tert-butylphenyl ] -5-methyl-2H-benzotriazole was further added as an ultraviolet absorber. The transmittance of light having a wavelength of 220 to 800nm was measured in the same manner as in example 13 using the obtained sheet as a sample. The results are shown in fig. 2. It can be confirmed that: the spectrum of the light transmittance before and after the elution treatment does not change, and even when the polymerizable ultraviolet absorbing dye of the present invention is used in combination with another polymerizable ultraviolet absorber, the polymerizable ultraviolet absorbing dye is incorporated into the polymer as a copolymer component and does not elute after the polymerization.

< comparison of stability under alkaline conditions >

The HBZ-PHM (1 part by weight) and methyl methacrylate (26 parts by weight) obtained in example 1 were added to a mixed solvent of dioxane (52 parts by weight), N-dimethylformamide (22 parts by weight) and water (20 parts by weight), and 2.4 parts by weight of 2, 2' -azobis (2, 4-dimethylvaleronitrile) was added, and polymerized at 75 ℃ for 5 hours under an argon atmosphere to obtain an HBZ-PHM copolymer.

As a comparative example, a BMAC copolymer was obtained by carrying out a polymerization reaction in the same manner using 2, 4-dihydroxy-5- (4- (2- (N-2-methacryloyloxyethyl) carbamoyloxy) ethylphenylazo) Benzophenone (BMAC) synthesized according to the procedure disclosed in Synthesis example 1 of patent document 6 (Japanese patent application laid-open No. 2006-291006) in place of HBZ-PHM.

The obtained copolymer powders were subjected to Soxhlet extraction with ethanol for 12 hours, and the resulting powdery polymers (200mg) were suspended in ethanol (5mL), and 4N-NaOH (5mL) was added thereto and the mixture was stirred at room temperature for 4 hours. The pH test paper shows that the test solution has a pH of 12-14. After stirring was complete, the reaction mixture was neutralized with 4N-HCl and ethanol (15mL) was added. After insoluble matter was filtered off, the filtrate was observed, and as a result, the HBZ-PHM copolymer was colorless and transparent. On the other hand, in the case of the BMAC copolymer, the filtrate was colored yellow. FIG. 3 shows the results of measuring the transmittance of each filtrate at a wavelength of 220 to 800 nm. The filtrate after the alkali treatment of the BMAC copolymer showed the same transmittance pattern as the BMAC copolymer. This result strongly suggests that the pigment site of BMAC is detached from the copolymer by the alkali treatment. On the other hand, it was confirmed that: the filtrate of the alkali-treated HBZ-PHM copolymer transmits light of any wavelength, and the dye component is not released from the copolymer even under the condition of pH12 or more by the alkali treatment, i.e., the filtrate is more stable against pH change than the BMAC copolymer, and is not substantially affected by pH change.

Industrial applicability

According to the present invention, a polymerizable ultraviolet-absorbing dye monomer that is stable even under alkaline conditions can be provided. The dye compound of the present invention has a benzophenone skeleton having ultraviolet absorption ability, an azobenzene skeleton having light absorption ability in a blue region, and a polymerizable group in its molecule, and therefore can be copolymerized with another polymerizable monomer to obtain a polymer, and the polymer is useful as a material for an intraocular lens and the like.

Claims (10)

1. A compound represented by the following general formula (1),

[ solution 1]

In the general formula (1), R¹Is hydrogen atom, hydroxyl group, carboxyl group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, sulfonic group or benzyloxy group, R²Is a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, R³Is represented by the following formula (2)Shown in the specification;

[ solution 2]

In the general formula (2), R⁴Is a hydrogen atom or a methyl group; in addition, R⁵Is a single bond or C1-4 alkylene.

2. The compound of claim 1, wherein,

R¹is a hydrogen atom, a methyl group or an ethyl group.

3. The compound of claim 1, wherein,

R²is hydrogen atom, hydroxyl, methoxyl or ethoxyl.

4. A polymer obtained by copolymerizing the compound according to claim 1 with one or more other polymerizable monomers.

5. An intraocular lens formed from the polymer of claim 4.

6. A method for producing the compound according to claim 1,

a compound represented by the following general formula (3) or (4) is used as a starting material or an intermediate,

[ solution 3]

In the general formula (3), R⁵Is a single bond or C1-4 alkylene, R is hydrogen or a protecting group,

[ solution 4]

In the general formula (4), R⁵Is a single bond or C1-4 alkylene.

7. The manufacturing method according to claim 6,

having a step of obtaining a polymerizable aminoaryl compound represented by the following general formula (5),

[ solution 5]

In the general formula (5), R³Represented by the following formula (2),

[ solution 6]

In the general formula (2), R⁴Is a hydrogen atom or a methyl group; in addition, R⁵Is a single bond or C1-4 alkylene.

8. A method for producing the compound according to claim 1,

the method comprises the following steps: a diazotization step of diazotizing a polymerizable aminoaryl compound represented by the following general formula (5) to obtain a diazonium salt; and a diazo coupling step of diazotizing the diazo salt obtained in the diazotization step and a benzophenone compound to obtain the compound of claim 1, wherein the diazo coupling step uses a weak base as a catalyst,

[ solution 7]

In the general formula (5), R³Represented by the following formula (2),

[ solution 8]

In the general formula (2), R⁴Is a hydrogen atom or a methyl group; in addition, R⁵Is a single bond or C1-4 alkylene.

9. The manufacturing method according to claim 8,

the weak base used in the diazo coupling step contains one or more selected from sodium carbonate, sodium bicarbonate, potassium carbonate, sodium acetate, and potassium acetate.

10. The compound of claim 1, wherein,

R¹is a hydrogen atom, R²Is hydroxy, R⁵Is an ethylene group.