JP2022071514A - Ophthalmologic material having contrast improving function - Google Patents

Abstract

To provide a polymer suitable for intraocular lenses, which can improve antiglare and contrast properties.SOLUTION: A polymer is prepared by the copolymerization of an organic dye having a yellow region light absorbing ability and one or more polymerizable monomers. The polymerizable monomers include one or more acrylic acid monomers. The polymerizable monomers preferably include one or more acrylic acid monomers having aromatic groups.SELECTED DRAWING: None

Description

The present invention relates to polymers suitable for intraocular lenses that can improve the contrast of visible objects.

Cataract is a disease in which the crystalline lens becomes cloudy and foggy due to the formation and deposition of pigments. It is generally known that the possibility of developing the disease increases with aging.
As a treatment method, an operation is generally performed in which a cloudy crystalline lens is removed and an intraocular lens (IOL) is inserted and placed in the capsular bag.

The sensitivity of the human eye is said to be highest with light at 555 nm. With aging, the crystalline lens turns yellow and the blue light is blocked, so the yellow color is emphasized. The amount of yellow light (around 585 nm) that reaches the retina relatively increases, making it easier to feel glare.
Therefore, it has been proposed to suppress glare by blocking yellow light. Specifically, it has been proposed to include an organic dye having a light-absorbing ability in the yellow region in a plastic composition to use it as a material for an ophthalmic lens (Patent Documents 1, 2, etc.). When yellow light is blocked by such a dye, glare is reduced and red and green are relatively easy to see. In addition, the yellowing of the crystal body greatly affects the S-weight body and the perception of blue light becomes dull, but the perception of blue light is relatively improved by blocking the yellow light, so the contrast sensitivity of the visually recognized object is improved. do.

Patent No. 5778109 Japanese Unexamined Patent Publication No. 2019-66501

As described above, since yellowing of the crystalline lens accompanies aging, there is a demand for improving antiglare and contrast even in an intraocular lens that is expected to be applied to elderly people.
However, the material for an intraocular lens is required to have a softness suitable for insertion during surgery and a high refractive index that can withstand the thinning of the lens, but the conventional material having a yellow light blocking ability is insufficient. ..
In such a situation, it is an object of the present invention to provide a polymer suitable for an intraocular lens material, which can improve antiglare property and contrast property.

As a result of diligent studies, the present inventors have found a polymer obtained by copolymerizing an organic dye having a light absorbing ability in the yellow region with an acrylic acid-based monomer, particularly a polymerizable monomer containing an acrylic acid-based monomer having an aromatic group. The present invention has been completed by finding that it is suitable as a material for an intraocular lens that can solve the above problems.

That is, the present invention is as follows.
[1] A polymer obtained by copolymerizing an organic dye having a light-absorbing ability in the yellow region with one or more polymerizable monomers.
A polymer in which the polymerizable monomer contains one or more acrylic acid-based monomers.
[2] The polymer according to [1], wherein the organic dye has a main absorption peak (P) between 565 nm and 605 nm in a visible light absorption spectroscopic spectrum measured with a chloroform or toluene solution.
[3] The polymer according to [2], wherein the organic dye is a tetraazaporphyrin compound represented by the following general formula (1).

［一般式（１）中、Ａ^１～Ａ^８は各々独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、アミノ基、カルボキシル基、スルホン酸基、炭素数１～２０の直鎖、分岐又は環状のアルキル基、炭素数１～２０のアルコキシ基、炭素数６～２０のアリールオキシ基、炭素数１～２０のモノアルキルアミノ基、炭素数２～２０のジアルキルアミノ基、炭素数７～２０のジアルキルアミノ基、炭素数７～２０のアラルキル基、炭素数６～２０のアリール基、ヘテロアリール基、炭素数６～２０のアルキルチオ基、炭素数６～２０のアリールチオ基を表し、連結基を介して芳香族環を除く環を形成しても良く、Ｍは２個の水素原子、２価の金属原子、２価の１置換金属原子、４価の２置換金属原子、又はオキシ金属原子を表す。］

[In the general formula (1), A ¹ to A ⁸ are independently hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, and directly having 1 to 20 carbon atoms. Chain, branched or cyclic alkyl group, alkoxy group with 1 to 20 carbon atoms, aryloxy group with 6 to 20 carbon atoms, monoalkylamino group with 1 to 20 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, carbon Represents a dialkylamino group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms. , A ring other than the aromatic ring may be formed via a linking group, and M is a two hydrogen atom, a divalent metal atom, a divalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or Represents an oxymetal atom. ]

[4] The polymer according to [3], wherein the tetraazaporphyrin compound is a divalent copper atom in the general formula (1).
[5] The polymer according to [3] or [4], wherein the tetraazaporphyrin compound is a compound represented by the following chemical formula (2).

［式（２）中、Ｃｕは２価の銅原子を、ｔＢｕはターシャリーブチル基を表し、その４個のターシャリーブチル基は式（２）におけるポルフィリン骨格中に存在する４個のピロール環の１個の炭素原子にそれぞれ１個ずつ結合していることを表す。］

[In the formula (2), Cu represents a divalent copper atom, tBu represents a tertiary butyl group, and the four tert-butyl groups are four pyrrole rings present in the porphyrin skeleton in the formula (2). It means that one carbon atom is bonded to each carbon atom. ]

[6] The polymer according to any one of [1] to [5], wherein the acrylic acid-based monomer is 30 parts by weight or more when the entire polymerizable monomer is 100 parts by weight.
[7] The polymer according to any one of [1] to [6], wherein the polymerizable monomer contains one or more acrylic acid-based monomers having an aromatic group.
[8] The polymer according to [7], wherein the acrylic acid-based monomer having an aromatic group is 30 parts by weight or more when the entire polymerizable monomer is 100 parts by weight.
[9] An intraocular lens obtained by molding the polymer according to any one of [1] to [8].

According to the present invention, a polymer suitable for an intraocular lens material, which can improve antiglare property and contrast property, can be obtained. Since the dye does not easily elute from such a polymer, antiglare and contrast are maintained, and safety is also excellent.

It is a graph which shows the ultraviolet-visible absorption spectrum in each polymer of Examples 1 and 2 and the comparative example 1 after repeating a dissolution test 4 times. It is a graph which shows the ultraviolet-visible absorption spectrum in each polymer of Examples 3-6 after repeating a dissolution test 4 times. It is a graph which shows the ultraviolet-visible absorption spectrum in each polymer of Examples 7-10 after repeating a dissolution test 4 times. It is a graph which shows the relationship between the dye addition amount and the residual amount after elution treatment in Test Example 4. It is a graph which shows the ultraviolet-visible absorption spectrum in each polymer of Examples 11-14 after repeating a dissolution test 4 times.

Next, the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be freely changed within the scope of the present invention.

The polymer of the present invention is a polymer obtained by copolymerizing an organic dye having a light absorbing ability in the yellow region with one or more polymerizable monomers. Here, the polymerizable monomer is characterized by containing one or more acrylic acid-based monomers.
As used herein, the term "acrylic acid-based monomer" refers to a compound having an acryloyl group as a polymerizable group.
As for the content thereof, when the total amount of the polymerizable monomer is 100 parts by weight, the acrylic acid-based monomer is preferably 30 parts by weight or more, more preferably 40 parts by weight or more, and further preferably 50 parts by weight or more. The upper limit of the content of the acrylic acid-based monomer is not particularly limited, and 100 parts by weight may be the acrylic acid-based monomer when the entire polymerizable monomer is 100 parts by weight. As a result, the polymer tends to have a softness (Young's modulus) suitable for an intraocular lens, and an organic dye having a yellow region light absorbing ability is easily retained by the polymer.

The acrylic acid-based monomer is not particularly limited, and examples thereof include:
Acrylic acid;
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tert-butyl acrylate, isobutyl acrylate, pentyl acrylate, tert-pentyl acrylate, hexyl acrylate,
Linear, branched and cyclic alkyl acrylates such as heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate and phenoxy acrylate;

Pentamethyldisiloxanylmethyl acrylate, pentamethyldisyloxylpropylpropyl acrylate, methylbis (trimethylsiloxy) silylpropyl acrylate, tris (trimethylsiloxy) silylpropyl acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) Cyrilpropyl acrylate, Tris (methylbis (trimethylsiloxy) siloxy) Cyrilpropyl acrylate, methylbis (trimethylsiloxy) silylpropylglyceryl acrylate, Tris (trimethylsiloxy) silylpropylglyceryl acrylate, mono (methylbis (trimethylsiloxy) siloxy) bis (trimethylsiloxy) ) Cyrilpropyl glyceryl acrylate, trimethylsilylethyl tetramethyldisyloxylpropylglyceryl acrylate, trimethylsilylmethyl acrylate, trimethylsilylpropyl acrylate, trimethylsilylpropyl glyceryl acrylate, pentamethyldisiroxanylpropylglyceryl acrylate, methylbis (trimethylsiloxy) silylethyltetramethyl Silicon-containing acrylates such as disiroxanylmethyl acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl acrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl acrylate;

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

Hydroxy group-containing acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, dihydroxypropyl acrylate, dihydroxybutyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, dipropylene glycol monoacrylate;
Acrylamides such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N-hydroxyethylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-ethyl-N-aminoethylacrylamide;
Aminoalkyl acrylates such as aminoethyl acrylate, N-methylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate;
Alkoxy group-containing acrylates such as methoxyethyl acrylate, ethoxyethyl acrylate, and methoxydiethylene glycol acrylate;
Benzyl acrylate, 2-phenoxyethyl acrylate, 2-phenylethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxydiethylene glycol acrylate, tribromophenyl acrylate, 2-acryloyloxyethyl-phthalic acid, 2-acryloyloxypropyl Phtalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentyl glycol-acrylic acid-benzoic acid ester, EO-modified phenol acrylate, EO-modified nonylphenol acrylate, EO-modified orthophenylphenol acrylate, EO-modified tribromo Aromatic ring-containing acrylates such as phenyl acrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate;
Glycidyl acrylate;
Tetrahydrofurfuryl acrylate;
N-acryloyl piperidine;
N-Acryloyl morpholine.
Further, one or more of the above-mentioned polymerizable monomers may be selected and polymerized to form a macromonomer, which may be used as one of the polymerizable monomers for polymer production.

Among these acrylic acid-based monomers, those having an aromatic group are preferably contained as one or more as a polymerizable monomer. As a result, the polymer tends to have a softness (Young's modulus) suitable for an intraocular lens.
The content thereof is preferably 30 parts by weight or more, more preferably 40 parts by weight or more, and further preferably 50 parts by weight or more when the entire polymerizable monomer is 100 parts by weight. The upper limit of the content of the acrylic acid-based monomer having an aromatic group is not particularly limited, and when the entire polymerizable monomer is 100 parts by weight, it is 96 parts by weight or less, more preferably 90 parts by weight or less, still more preferably 80 parts by weight. It may be less than a part by weight.
Examples of the acrylic acid-based monomer having an aromatic group include benzyl acrylate, 2-phenoxyethyl acrylate, 2-phenylethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxydiethylene glycol acrylate, tribromophenyl acrylate, and 2-acryloy. Loxyethyl-phthalic acid, 2-acryloyloxypropylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentylglycol-acrylic acid-benzoic acid ester, EO-modified phenol acrylate, EO-modified nonylphenol acrylate , EO-modified orthophenylphenol acrylate, EO-modified tribromophenyl acrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate and the like.

The polymerizable monomer in the present invention may contain a monomer other than the acrylic acid-based monomer. The other polymerizable monomer is not particularly limited as long as it is usually used, and examples thereof include the following.
Methacrylic acid:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, tert-pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate. , Dodecyl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, phenoxy methacrylate and other linear, branched and cyclic alkyl methacrylates;

Pentamethyldisyloxanylmethylmethacrylate, pentamethyldisyloxanylpropylmethacrylate, methylbis (trimethylsiloxy) silylpropylmethacrylate, tris (trimethylsiloxy) silylpropylmethacrylate, mono (methylbis (trimethylsiloxy) syroxy) bis (trimethylsiloxy) Cyrilpropyl methacrylate, Tris (methylbis (trimethylsiloxy) siloxy) Cyrilpropylmethacrylate, Methylbis (trimethylsiloxy) Cyrilpropylglyceryl methacrylate, Tris (trimethylsiloxy) Cyrilpropylglyceryl methacrylate, Mono (methylbis (trimethylsiloxy) siloxy) Bis (trimethylsiloxy) ) Cyrilpropyl glyceryl methacrylate, trimethylsilylethyltetramethyldisiloxanylpropylglyceryl methacrylate, trimethylsilylmethylmethacrylate, trimethylsilylpropylmethacrylate, trimethylsilylpropylglycerylmethacrylate, pentamethyldisyloxanylpropylglycerylmethacrylate, methylbis (trimethylsiloxy) silylethyltetramethyl Silicon-containing methacrylates such as disiroxanylmethylmethacrylate, tetramethyltriisopropylcyclotetrasiloxanylpropylmethacrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropylmethacrylate;

Trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, pentafluoropropyl methacrylate, hexafluoroisopropyl methacrylate, tetrafluoro-tert-pentyl methacrylate, hexafluorobutyl methacrylate, hexafluoro-tert-hexyl methacrylate, octafluoropentyl methacrylate, 2,3 4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl methacrylate, dodecafluoroheptyl methacrylate, 2-hydroxyoctafluoro-6-trifluoromethylheptyl methacrylate, 2-hydroxydodecafluoro-8 -Fluorine-containing methacrylates such as trifluoromethylnonyl methacrylate and 2-hydroxyhexadecafluoro-10-trifluoromethylundecyl methacrylate;

Styrene, pentafluorostyrene, methylstyrene, trimethylstyrene, trifluoromethylstyrene, (pentamethyl-3,3-bis (trimethylsiloxy) trisiroxanyl) styrene, (hexamethyl-3-trimethylsiloxytrisiroxanyl) styrene, dimethylaminostyrene Styrene derivatives such as;
Hydroxy group-containing methacrylates such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, dihydroxypropyl methacrylate, dihydroxybutyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, and dipropylene glycol monomethacrylate;
Vinyl lactams such as N-vinylpyrrolidone, α-methylene-N-methylpyrrolidone, N-vinylcaprolactam, N-methacryloylpyrrolidone;
Methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-hydroxyethylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diethylmethacrylamide, N-ethyl-N-aminoethylmethacrylamide, etc. Methacrylamides;

Aminoalkyl methacrylates such as aminoethyl methacrylate, N-methylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate;
Alkoxy group-containing methacrylates such as methoxyethyl methacrylate, ethoxyethyl methacrylate, and methoxydiethylene glycol methacrylate;
Aromatic ring-containing methacrylates such as benzyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, 2-phenylethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate;
Alkyl esters that may be substituted with an alkyl group such as itaconic acid, crotonic acid, maleic acid, fumaric acid, a fluorine-containing alkyl group, or a siroxanyl alkyl group;
Glycidyl methacrylate;
Tetrahydrofurfuryl methacrylate;
4-vinylpyridine;
Heterocyclic N-vinyl monomers such as vinyl imidazole, N-vinyl piperidone, N-vinyl piperidine, N-vinyl succinimide;
N-methacryloyl piperidine;
N-methacryloyl morpholine.
Further, one or more of the above-mentioned polymerizable monomers may be selected and polymerized to form a macromonomer, which may be used as one of the polymerizable monomers for polymer production.

In addition, as other polymerizable monomers, polymerizable ultraviolet absorbers (those that mainly absorb ultraviolet parts), polymerizable dyes (those that do not have ultraviolet absorption performance and mainly absorb light in the blue region), or polymerizable ultraviolet rays. Absorbent dyes can also be used. As a result, when the polymer of the present invention is used as a material for an intraocular lens as described later, it is useful because it can adjust the color tone of the intraocular lens and impart ultraviolet ray absorbing ability and blue region light absorbing ability.

As the polymerizable ultraviolet absorber, for example, the benzophenone-based polymerizable ultraviolet absorber disclosed in Japanese Patent Application Laid-Open No. 2003-253248 and the benzotriazole-based polymerizable ultraviolet absorber disclosed in Japanese Patent No. 2685980 can be used. Specific examples include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, and 2-hydroxy-4- (meth) acryloyloxy. Benzophenone-based polymerizable ultraviolet absorbers such as -2', 4'-dichlorobenzophenone, 2-hydroxy-4- (2'-hydroxy-3'-(meth) acryloyloxypropoxy) benzophenone; 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'-t-butylphenyl) -5 -Benzotriazoles such as chloro-2H-benzotriazole, 2- (2'-hydroxy-5'-(2 "-methacryloyloxyethoxy) -3'-t-butylphenyl) -5-methyl-2H-benzotriazole, etc. Polymerizable UV absorber; Salicylic acid derivative-based polymerizable UV absorber such as 2-hydroxy-4-methacryloyloxymethylbenzoate phenyl; 2-cyano-3-phenyl-3- (3'-(meth) acryloyloxyphenyl) Examples thereof include propenyl acid methyl ester. These can be used alone or in combination of two or more.

As the polymerizable dye, for example, an azo-based, anthraquinone-based, nitro-based, or phthalocyanine-based polymerizable dye disclosed in JP-A No. 10-148977 can be used. These can be used alone or in combination of two or more.
Examples of the polymerizable azo dye include 1-phenylazo-4- (meth) acryloyloxynaphthalene, 1-phenylazo-2-hydroxy-3- (meth) acryloyloxynaphthalene, and 1-naphthylazo-2-hydroxy-3-. (Meta) acryloyloxynaphthalene, 1- (α-anthrylazo) -2-hydroxy-3- (meth) acryloyloxynaphthalene, 1-((4'-(phenylazo) -phenyl) azo) -2-hydroxy-3- (Meta) acryloyloxynaphthalene, 1- (2', 4'-xylylazo) -2- (meth) acryloyloxynaphthalene, 1- (o-tolylazo) -2- (meth) acryloyloxynaphthalene, 2- (m-) (Meta) 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- Vinyl phthalic acid- (4'-(p-sulfophenylazo) -1'-naphthyl) monoester, 6-vinylphthalic acid- (4'-(p-sulfophenylazo) -1'-naphthyl) monoester, 3- (Meta) 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-Trillazo) 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'-) Phenolazo) 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 can be mentioned. ..

Specific examples of the polymerizable anthraquinone dye include 1,5-bis ((meth) acryloylamino) -9,10-anthraquinone and 1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 4 -Amino-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 5-amino-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 8-amino-1- (4') -Vinylbenzoylamide) -9,10-anthraquinone, 4-nitro-1- (4'-vinylbenzoylamide) -9,10-anthraquinone, 4-hydroxy-1- (4'-vinylbenzoylamide) -9, 10-anthraquinone, 1- (3'-vinylbenzoylamide) -9,10-anthraquinone, 1- (2'-vinylbenzoylamide) -9,10-anthraquinone, 1- (4'-isopropenylbenzoylamide)- 9,10-anthraquinone, 1- (3'-isopropenylbenzoylamide) -9,10-anthraquinone, 1- (2'-isopropenylbenzoylamide) -9,10-anthraquinone, 1,4-bis (4') -Vinylbenzoylamide) -9,10-anthraquinone, 1,4-bis (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1,5'-bis (4'-vinylbenzoylamide) -9, 10-anthraquinone, 1,5-bis (4'-isopropenylbenzoylamide) -9,10-anthraquinone, 1-methylamino-4- (3'-vinylbenzoylamide) -9,10-anthraquinone, 1-methyl Amino-4- (4'-vinylbenzoyloxyethylamino) -9,10-anthraquinone, 1-amino-4- (3'-vinylphenylamino) -9,10-anthraquinone-2-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- (β-ethoxycarbonylallylamino) -9,10-anthraquinone, 1- (β-carboxyallylamino) -9,10 -Anthraquinone, 1,5-di- (β-carboxyallylamino) -9,10-anthraquinone, 1- (β-isopropoxycarbonylallylamino) -5-benzoylamide-9,10-anthraquinone, 2- (3) '-(Meta) acryloylamide-anilino) -4- (3'-(3 "-sulfo-4" -aminoanthraquinone-1 "-yl) -amino-anilino) -6-chloro-1,3,5- Triazine, 2- (3'-(meth) acryloylamide-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'-Vinyl phenoxy) -4- (4'-(
Examples thereof include 3 "-sulfo-4" -aminoanthraquinone-1 "-yl-amino) -anilino) -6-chloro-1,3,5-triazine.

Specific examples of the polymerizable nitro-based dye include o-nitroanilinomethyl (meth) acrylate and the like.
Specific examples of the polymerizable phthalocyanine dye include (meth) acryloylated tetraamino copper phthalocyanine, (meth) acryloylated (dodecanoylated tetraamino copper phthalocyanine) and the like.

Specific examples of the polymerizable ultraviolet-absorbing dye include, for example, 2,4-dihydroxy-3 (p-styrenoazo) benzophenone, 2,4-dihydroxy-5- (p-styrenoazo) benzophenone, and 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) acryloyl) Oxypropylphenylazo) 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, 2,4-dihydroxy-3- (o- (N, N-di (meth) acryloyloxyethylamino) phenylazo) benzophenone, 2,4-dihydroxy- 5- (o- (N, N-di (meth) acryloylethylamino) 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) acryloyl) Oxyethylamino) phenylazo) benzophenone, 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-based polymerizable ultraviolet-absorbing dyes such as benzophenone, and benzoic acid-based polymerization such as 2-hydroxy-4- (p-styrenoazo) phenyl benzoate. Examples include sexual ultraviolet absorbing dyes. These can be used alone or in combination of two or more.

The organic dye having the ability to absorb light in the yellow region in the present invention is preferably one that exhibits a specific absorption behavior.
Specifically, the organic dye has a main absorption peak (P) between 565 nm and 605 nm in a visible light absorption spectroscopic spectrum measured with a chloroform or toluene solution.
Preferably, the organic dye has an absorption coefficient (ml / g · cm) of ^0.5 × 105 or more at the peak peak (Pmax: a point showing the maximum absorption coefficient in the peak) of the main absorption peak (P). The peak width at the absorbance of 1/4 of the absorbance of (Pmax) of the peak (P) is 50 nm or less, and the peak width at the absorbance of 1/2 of the absorbance of (Pmax) of the peak (P). Is 30 nm or less, and the peak width at the absorbance of 2/3 of the (Pmax) absorbance of the peak (P) is in the range of 20 nm or less.

More preferably, the organic dye has a peak apex (Pmax) of the main absorption peak (P) between 580 nm and 590 nm. Further, the peak width at the absorbance of 1/4 of the absorbance of the peak peak (Pmax) of the main absorption peak (P) is 40 nm or less, and the absorbance of the peak peak (Pmax) of the main absorption peak (P) is 1. The peak width at the absorbance of / 2 may be 25 nm or less, and the peak width at the absorbance at 2/3 of the absorbance at the peak peak (Pmax) of the main absorption peak (P) may be 20 nm or less.

As the organic dye exhibiting such absorption behavior, a tetraazaporphyrin compound represented by the following general formula (1) is preferably mentioned.

In the general formula (1), A ¹ to A ⁸ are independently hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, and linear chain having 1 to 20 carbon atoms. , Branched or cyclic alkyl group, alkoxy group with 1 to 20 carbon atoms, aryloxy group with 6 to 20 carbon atoms, monoalkylamino group with 1 to 20 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, carbon number of carbon atoms. Represents a dialkylamino group of 7 to 20, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms. A ring other than the aromatic ring may be formed via a linking group.
In the general formula (1), M represents two hydrogen atoms, a divalent metal atom, a divalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or an oxymetal atom, and is preferably a divalent metal. It is an atom, more preferably a divalent copper atom.

In the general formula (1), M is a divalent copper atom, and one of A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ is tertiary butyl. It is preferable that the group is a group and the other is a hydrogen atom. That is, as the tetraazaporphyrin compound represented by the general formula (1), a tetra-t-butyl-tetraazaporphyrin-copper complex represented by the following chemical formula (2) is particularly preferable.

In the chemical formula (2), Cu represents a divalent copper atom.
In the chemical formula (2), tBu represents a tertiary butyl group, and the four tertiary butyl groups are one for each carbon atom of the four pyrrole rings present in the porphyrin skeleton in the formula (2). Indicates that they are combined one by one.
The tetra-t-butyl-tetraazaporphyrin-copper complex represented by the chemical formula (2) is available from Mitsui Chemicals, Inc. under the product number "PD-311S".

The polymer of the present invention can be obtained by blending an organic dye having a yellow region light absorbing ability and a polymerizable monomer in an arbitrary amount, mixing them uniformly, and then copolymerizing the polymerizable monomer mixture. Can be done.
The blending amount of the organic dye having a yellow region light absorbing ability is preferably 0.00001 to 0.02 parts by weight, preferably 0.0001 to 0, when the whole polymerizable monomer is 100 parts by weight. It is more preferably 0.01 parts by weight, and even more preferably 0.001 to 0.005 parts by weight. If it is less than 0.00001 parts by weight, sufficient antiglare and contrast may not be obtained. On the other hand, if it exceeds 0.02 parts by weight, the coloring of the polymer becomes too dark and the transparency is lowered, the physical properties of the polymer (for example, strength, etc.) are lowered, and the organic dye is easily eluted from the polymer. There is a risk of doing so.
In the present specification, the blending amount when the components other than the polymerizable monomer used for the copolymerization, that is, the organic dye, the polymerization initiator, the cross-linking agent, the diluent and the like described later are contained in the polymerizable monomer mixture is used. , It is expressed as an amount when the whole polymerizable monomer is 100 parts by weight. Therefore, the total amount of the polymerizable monomer mixture is notated to exceed 100 parts by weight.

The polymers of the present invention can be synthesized by methods commonly used in the art. For example, the organic dye having the ability to absorb light in the yellow region and the polymerizable monomer are uniformly mixed, and if necessary, a polymerization initiator is added, and the mixture is gradually heated in a temperature range of room temperature to about 130 ° C. , Or by irradiating electromagnetic waves such as microwaves, ultraviolet rays, and radiation (gamma rays), the polymerization can be performed. For the polymerization, various methods widely and generally used by those skilled in the art such as radical polymerization, bulk polymerization or solvent polymerization can be adopted, and in the case of thermal polymerization, the temperature is raised stepwise. You may let it.

When the polymer of the present invention is produced by copolymerization, the polymerizable monomer mixture may contain a polymerization initiator.
Examples of the polymerization initiator include lauryl peroxide, benzoyl peroxide, isopropylpercarbonate, azobisisobutyronitrile, azobisdimethylvaleronitrile, and 2,2'-azobis (2), which generate free radicals at a slightly high temperature. , 4-Dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and the like. .. Further, photoinitiators such as aromatic α-hydroxyketone, alkoxyoxybenzoin, acetophenone, acylphosphine oxide, bisacylphosphine oxide and tertiary amine + diketone can also be used. Typical examples of photoinitiators are 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, bis (2,6-dimethoxybenzoyl) -2,4- 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzyldiphenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, benzoinmethyl Examples thereof include esters, phenylquinone and ethyl 4- (N, N-dimethylamino) benzoates. As the polymerization initiator, one or more of these can be used.

The amount of the polymerization initiator used is preferably 0.01 to 5.0 parts by weight, more preferably 0.05 to 2.5 parts by weight, and 0.1 to 1 part by weight when the entire polymerizable monomer is 100 parts by weight. The weight part is more preferable.

When the polymer of the present invention is produced by copolymerization, the polymerizable monomer mixture may contain a diluent. The diluent has a role of increasing the reaction rate of the copolymer and also enhancing the releasability of the copolymer polymer.
The diluent is preferably water-soluble, for example, 1-decanol, 1-octanol, 1-pentanol, 1-hexanol, 2-hexanol, 2-octanol, 3-methyl-3-pentanol, 2-pentanol. , Tersary Amyl Alcohol (tAA), Tersary Butyl Alcohol, 2-Butanol, 1-Butanol, 2-Methyl-2-pentanol, 2-Ethyl-1-Butanol, 1-propanol, 2-propanol, Ethanol, Methanol , 3,3-Dimethyl-2-butanol, decanoic acid, octanoic acid, dodecanoic acid, 1-ethoxy-2-propanol, 1-tert-butoxy-2-propanol, EH-5, 2,3,6,7- Tetrahydroxy-2,3,6,7-tetramethyloctane, 9- (1-methylethyl) -2,5,8,10,13,16-hexaoxaheptadecane, 3,5,7,9,11 , 13-Hexamethoxy-1-tetradecanol, tripropylene glycol methyl ether, water and the like are preferable, and these may be used alone or in combination of two or more.

The amount of the diluent used is preferably 0 to 75 parts by weight, more preferably 10 to 70 parts by weight, still more preferably 30 to 65 parts by weight, when the entire polymerizable monomer is 100 parts by weight.

Further, when the polymer of the present invention is produced by copolymerization, a three-dimensional crosslinked structure can be formed in the obtained polymer by adding a crosslinking agent to the polymerizable monomer mixture. This makes it possible to improve the mechanical strength and hardness of the polymer, and to suppress the elution of monomers and dyes (including organic dyes having a light absorbing ability in the yellow region) from the polymer. Further, when the polymer of the present invention is used as a material for an intraocular lens as described later, an intraocular lens that is uniform, transparent, and has no distortion and has excellent optical properties can be obtained, and the intraocular lens is durable (durable). Chemical resistance, heat resistance, solvent resistance) can also be imparted.
When the cross-linking agent is blended, the blending ratio is preferably in the range of 0.01 to 10 parts by weight when the entire polymerizable monomer is 100 parts by weight. If it is less than 0.01 parts by weight, the effect is difficult to obtain, and if it exceeds 10 parts by weight, the obtained polymer tends to be brittle.
Examples of the cross-linking agent as described above include butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 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. , Dialyl adipate, Triallyldiisocyanate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate, 2,2-bis ((meth) acryloyloxyphenyl) hexa Fluoropropane, 2,2-bis ((meth) acryloyloxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxy) Hexafluoroisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2-) Examples thereof include (meth) acryloyloxyisopropyl) benzene and 1,2-bis (2- (meth) acryloyloxyisopropyl) benzene.

Further, as long as the effect of the present invention is not impaired, an appropriate polymerizable monomer can be selected to impart various functions to the polymer of the present invention.
When imparting oxygen permeability to the polymer of the present invention, silicon-containing monomers such as silicon-containing (meth) acrylates and silicon-containing styrene derivatives, fluorine-containing alkyl (meth) acrylates, and the like can be selected as the polymerizable monomer. good.
When increasing the strength or adjusting the hardness of the polymer, alkyl (meth) acrylates, styrene derivatives including styrene, (meth) acrylic acid and the like may be selected as the polymerizable monomer.
If a fluorine-containing monomer such as a fluorine-containing alkyl (meth) acrylate or a fluorine-containing styrene derivative is selected as the polymerizable monomer, it has an anti-lipid contamination function when the polymer of the present invention is used as a material for an intraocular lens as described later. Can be given.
When imparting hydrophilicity to the polymer of the present invention, hydroxy (meth) acrylates, (meth) acrylamides, aminoalkyl (meth) acrylates, (meth) acrylates, N-vinyllactams and the like can be used as polymerizable monomers. A monomer having a hydrophilic group may be selected, and a water-containing flexible intraocular lens can be obtained when the polymer of the present invention is used as a material for an intraocular lens as described later.
If a monomer containing an aromatic ring, for example, a styrene-based monomer, an aromatic ring-containing (meth) acrylate, or the like is selected as the polymerizable monomer, the polymer of the present invention can be used as a material for a lens having a high refractive index. ..
When the polymerizable monomer for imparting various functions to the polymer of the present invention is selected and blended as described above, it is preferably 0.01 weight by weight when all the polymerizable monomers are 100 parts by weight. The amount is appropriately adjusted to be 5 parts by weight or more, more preferably 0.05 parts by weight or more, and preferably 5 parts by weight or less, more preferably 3 parts by weight or less when all the polymerizable monomers are 100 parts by weight or less. ..

The polymer of the present invention retains an organic dye having a light-absorbing ability in the yellow region inside the polymer. As a result, when used as a material for an intraocular lens, the contrast becomes clear at the time of visual recognition.
In addition, the organic dye having the ability to absorb light in the yellow region is also excellent in antiglare property. Specifically, the polymer of the present invention is excellent in absorption of yellow region light, and specifically, the light transmittance at 590 nm is preferably 90% or less, more preferably 80% or less, still more preferably 70% or less. ..

The polymer of the present invention is also excellent in the retention of the organic dye having the ability to absorb light in the yellow region to be retained inside. Therefore, when used as a material for an intraocular lens, the dye does not elute during use, the antiglare and contrast performances are maintained for a long period of time, and the safety is also excellent.

The polymer of the present invention has a high refractive index. Specifically, it is preferably 1.49 or more, more preferably 1.50 or more, and further preferably 1.51 or more. Due to the high refractive index of the polymer, it is useful in that the thickness of the lens can be reduced and the thickness can be reduced when the polymer is used as a material for an intraocular lens.

The polymer of the present invention is excellent in softness. Specifically, Young's modulus is less than 10 MPa at 25 ° C., more preferably less than 8 MPa, still more preferably less than 6 MPa. Having such softness is useful because it can be smoothly inserted during surgery when used as a material for an intraocular lens.

Further, the polymer of the present invention has a softening point of room temperature environment (25 ° C.) or lower, and is easily in a rubber state and easily deformed. Specifically, it has a softening point of preferably 25 ° C. or lower, more preferably 20 ° C. or lower, still more preferably 15 ° C. or lower. Since the softening point is low, it tends to be in a rubber state and is not easily affected by the temperature environment when the intraocular lens is inserted, which is useful.

The polymer of the present invention is suitable for application when it is used as a material for an intraocular lens because it has transparency.
Here, transparency means that the transmittance of visible light (average transmittance of 400 to 700 nm) is preferably 60% or more, more preferably 70% or more.

The polymer of the present invention is suitable as a material for an intraocular lens.
When used as a material for an intraocular lens, it can be molded by a known method. For example, a polymerization reaction is carried out in an appropriate mold or container to obtain a rod-shaped, block-shaped, or plate-shaped polymer, which is then processed into a desired shape by mechanical processing such as cutting or polishing, or a desired shape. After obtaining a polymer molded product by carrying out a polymerization reaction in a mold corresponding to the above, a method of mechanically finishing it as necessary can be mentioned.
Further, the support portion of the intraocular lens may be manufactured separately from the intraocular lens and attached later, or may be molded at the same time as the intraocular lens (integrally).

When the polymer of the present invention is molded into an intraocular lens, a surface modification treatment may be performed as necessary in order to make the surface of the lens hydrophilic, plasma treatment or treatment with ultraviolet rays is preferable, and corona Discharge treatment, glow discharge treatment or UV / ozone treatment are more preferred. As the processing device and processing method at that time, a conventional device and method known conventionally can be used.

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

<Test Example 1> Comparison of Acrylic Acid-based Monomer and Methacrylic Acid-based Monomer The components shown in Table 1 are uniformly mixed, placed in a polymerization mold (length 30 mm, width 30 mm, thickness 1 mm), and polymerized at 70 ° C. for 90 minutes. , A polymer sheet having a thickness of 1 mm was prepared, and the polymer sheet was released from the mold. Each of the obtained polymer sheets was subjected to the following tests and evaluated.

(1) Dye retention rate The obtained polymer sheet was cut into a size of 10 mm × 10 mm × 1 mm, and the light transmittance was measured (0th time). Then, the polymer sheet was immersed in 10 mL of ethanol at 50 ° C. for 16 hours, and the light transmittance of the eluate was measured. The polymer sheet taken out from the eluate is 50.
After drying at ° C. for 1 hour and then at 60 ° C. for 2 hours, the light transmittance was measured. Elution was performed 4 times per polymer sheet, and the light transmittance of the eluate and the polymer sheet was measured each time. The light transmittance of the polymer sheet is measured in the range of 250 to 800 nm using an integrating sphere ultraviolet-visible absorbance meter (U-4100, Hitachi High-Tech Science) and the eluent using an ultraviolet-visible absorptiometer (UV-2700, Shimadzu Corporation). bottom. The dye retention rate was calculated by the following formula from the measured values of the absorbances at 590 nm of the polymer sheets at the 0th and 4th elutions.
Dye retention rate (%) = {1- (4th absorbance) ÷ (0th absorbance)} x 100

(2) Young's modulus The polymer sheet after the fourth elution and drying was dried at 80 ° C. for 2 hours, and then allowed to stand in a temperature control humidity control device (25 ° C., RH 50%) for 24 hours. After temperature control and humidity control, static Young's modulus measurement was performed using a thermomechanical analyzer (TMA402F1, NETZSCH).

(3) Refractive index The refractive index of the polymer sheet after the fourth elution and drying was measured using an Abbe refractive index meter (DR-M2, Atago) (25 ° C, e-line (546 nm)).

(4) After the polymer sheet having been eluted and dried for the fourth softening point was dried at 80 ° C. for 2 hours, it was allowed to stand in a temperature control humidity control device (25 ° C., RH 50%) for 24 hours. Thermomechanical analyzer (TM) after temperature control and humidity control
Using A), a constant load of 0.2 N was applied in the range of −10 ° C. to 50 ° C., and the softening point at which the glass state changed to the rubber state was measured.

The results are also shown in Table 1.
The elution decreased the absorbance at 590 nm in the polymer, while the absorbance at 590 nm in the eluate increased, so that the dye (tetra-t-butyl-tetraazaporphyrin-copper complex "PD-311S") was eluted from the polymer. It was admitted that he did. In Examples 1 and 2, the degree of dye elution was smaller than that in Comparative Example 1, and no dye elution was observed in the third and subsequent elution tests.
Comparative Example 1 prepared without using an acrylic acid-based monomer has a small dye retention rate, a high Young's modulus and a high softening point, and is not suitable as a material for an intraocular lens.
Further, the ultraviolet-visible absorption spectra of the polymers of Examples 1 and 2 and Comparative Example 1 in the fourth elution are shown in FIG.

<Test Example 2> Examination of the effect of acrylic acid-based monomer having an aromatic group A polymer was prepared in the same manner as in Test Example 1 with the components and formulations shown in Table 2, and Young's modulus, refractive index, softening point, and dye retention. The rate was evaluated.

The results are also shown in Table 2.
The dye retention rate was high in all of Examples 3 to 6. Example 6 prepared without using an acrylic acid monomer having an aromatic group had a higher Young's modulus than Examples 3 to 5.
Further, the ultraviolet-visible absorption spectrum of each of the polymers of Examples 3 to 6 in the fourth elution is shown in FIG.

<Test Example 3> Examination of the effect of acrylic acid-based monomer ratio A polymer was prepared in the same manner as in Test Example 1 with the components and formulations shown in Table 3, and Young's modulus, refractive index, softening point, and dye retention rate were evaluated. bottom.

The results are also shown in Table 3.
Comparing Examples 7 to 10, it was found that the larger the ratio of the acrylic acid-based monomer in the polymerizable monomer used for preparation, the higher the dye retention rate. No dye was dissolved in any of the polymers in the third and subsequent dissolution tests.
In addition, the ultraviolet-visible absorption spectrum of each polymer of Examples 7 to 10 in the fourth elution is shown in FIG.

<Test Example 4>
A polymer was prepared with the components and formulations shown in Table 4 in the same manner as in Test Example 1, and the dye retention rate was evaluated.

The amount of dye remaining in the polymer is calculated from the dye retention rate, and the result of plotting the amount of residual dye with respect to the amount of dye added is shown in FIG. Since the residual amount (retention amount) of the dye is proportional to the amount of the added dye, it was confirmed that the residual rate did not change with the added amount.
Further, the ultraviolet-visible absorption spectrum of each of the polymers of Examples 11 to 14 in the fourth elution is shown in FIG.

Claims (9)

A polymer obtained by copolymerizing an organic dye having a light absorbing ability in the yellow region with one or more polymerizable monomers.
A polymer in which the polymerizable monomer contains one or more acrylic acid-based monomers. The polymer according to claim 1, wherein the organic dye has a main absorption peak (P) between 565 nm and 605 nm in a visible light absorption spectroscopic spectrum measured with a chloroform or toluene solution. The polymer according to claim 2, wherein the organic dye is a tetraazaporphyrin compound represented by the following general formula (1).

[In the general formula (1), A ¹ to A ⁸ are independently hydrogen atom, halogen atom, nitro group, cyano group, hydroxy group, amino group, carboxyl group, sulfonic acid group, and directly having 1 to 20 carbon atoms. Chain, branched or cyclic alkyl group, alkoxy group with 1 to 20 carbon atoms, aryloxy group with 6 to 20 carbon atoms, monoalkylamino group with 1 to 20 carbon atoms, dialkylamino group with 2 to 20 carbon atoms, carbon Represents a dialkylamino group having 7 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group, an alkylthio group having 6 to 20 carbon atoms, and an arylthio group having 6 to 20 carbon atoms. , A ring other than the aromatic ring may be formed via a linking group, and M is a two hydrogen atom, a divalent metal atom, a divalent monosubstituted metal atom, a tetravalent disubstituted metal atom, or Represents an oxymetal atom. ] The polymer according to claim 3, wherein the tetraazaporphyrin compound is a divalent copper atom in the general formula (1). The polymer according to claim 3 or 4, wherein the tetraazaporphyrin compound is a compound represented by the following chemical formula (2).

[In the formula (2), Cu represents a divalent copper atom, tBu represents a tertiary butyl group, and the four tert-butyl groups are four pyrrole rings present in the porphyrin skeleton in the formula (2). It means that one carbon atom is bonded to each carbon atom. ] The polymer according to any one of claims 1 to 5, wherein the acrylic acid-based monomer is 30 parts by weight or more when the whole polymerizable monomer is 100 parts by weight. The polymer according to any one of claims 1 to 6, wherein the polymerizable monomer contains one or more acrylic acid-based monomers having an aromatic group. The polymer according to claim 7, wherein the acrylic acid-based monomer having an aromatic group is 30 parts by weight or more when the total amount of the polymerizable monomer is 100 parts by weight. An intraocular lens obtained by molding the polymer according to any one of claims 1 to 8.

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