JPWO2009044853A1 - Colorant for ophthalmic lens, ophthalmic lens material, method for producing ophthalmic lens, and ophthalmic lens - Google Patents

Abstract

The present invention is an ophthalmic lens colorant comprising an azo dye having a polymerizable functional group represented by the general formulas (1), (2) and (3). According to the present invention, it is excellent in elution resistance, is difficult to induce modification such as hydrolysis, is stable, and even when a predetermined polymerizable group is introduced, the color tone of the raw material dye changes. There can be provided an ophthalmic lens colorant having a novel structure of red to purple to blue, an ophthalmic lens material, a method for producing an ophthalmic lens, and an ophthalmic lens.

Description

  The present invention relates to an ophthalmic lens colorant, an ophthalmic lens material, a method for producing an ophthalmic lens, and an ophthalmic lens that are suitably used for coloring ophthalmic lenses such as contact lenses, intraocular lenses, and artificial corneas. About.

  Conventionally, various polymerizable dyes have been studied in order to color various articles at the material stage. In particular, in an ophthalmic lens such as a contact lens or an intraocular lens, a predetermined ophthalmic lens material is copolymerized with a polymerizable dye or a polymer dye is uniformly mixed with a predetermined ophthalmic lens material at the material stage. If the target ophthalmic lens is manufactured using the colored ophthalmic lens material, the ophthalmic lens will not be decolorized or discolored due to elution of the pigment. A uniformly colored lens having excellent durability and fastness to light and chemical agents can be obtained.

  For example, in Patent Document 1, an azo dye having a structure in which any hydrogen atom of a naphthyl group bonded to an azo group is substituted with a polymerizable group as a polymerizable dye for coloring an ophthalmic lens. It has been proposed to produce a desired colored ophthalmic lens from a colored vinyl polymer obtained by copolymerizing such an azo polymerizable dye with a vinyl monomer.

  In Patent Document 2, a polymerizable azo compound having a structure in which an unsaturated organic group having an ester structure or an amide structure is introduced to a phenyl group bonded to an azo group via nitrogen or alkyl. Yellow dyes have been proposed, and it has also been proposed to produce colored ophthalmic lens materials by copolymerizing such polymerizable yellow dyes with lens-forming monomers such as acrylate and methacrylate monomers. Yes.

  By the way, in these conventional polymerizable dyes, there is a case where a polymerizable unsaturated group is introduced through an oxygen atom to an aromatic ring in a phenyl group or a naphthyl group bonded to an azo group. In general, a predetermined unsaturated group is introduced through an ester bond, but in a polymerizable dye having an ester bond directly attached to such an aromatic ring, hydrolysis of the ester bond is difficult. Therefore, problems such as inconvenience in handling due to instability of the above-mentioned dyes are inherent. In addition, there is another problem that the color tone of the raw material dye changes due to the introduction of the polymerizable unsaturated group, making it difficult to predict the color tone of the finally obtained dye. Further, in the method described in Patent Document 2, the hue of the obtained pigment is limited to yellow, and the required red to purple-blue hue cannot be expressed.

  On the other hand, in order to color various articles at the material stage, (non) polymerizable polymer dyes containing various azo dyes have been studied. For example, Patent Document 3 and Patent Document 4 disclose polydimethylsiloxane that contains a yellow dye portion and can contain a polymerizable group as a polymer dye for coloring an ophthalmic lens yellow. Yes.

  By the way, in these conventional polymer dyes, as in the case of the polymerizable dyes described above, polymerizable unsaturated groups are bonded via an oxygen atom to an aromatic ring in a phenyl group or a naphthyl group bonded to an azo group. In the case of introducing a group, generally, a predetermined unsaturated group is introduced through an ester bond. However, such a polymer dye having an ester bond directly attached to such an aromatic ring is suitable. Therefore, hydrolysis of the ester bond is likely to be caused, and therefore, there are problems such as instability in handling because the above-mentioned dye is unstable. Moreover, in patent documents 3 and 4, only a yellow pigment | dye can be prepared and the application is limited.

  Furthermore, the yellow azo dyes described in Patent Documents 3 and 4 (particularly Patent Document 4) have a relatively simple structure, have a low molecular weight, and have no polar amide group, which may result in poor solvent resistance. As a result, it is conceivable that when the copolymerization is performed, a non-copolymerized dye remains, so that the remaining dye is easily eluted from the lens later.

  In addition, when the reactivity of the polymerizable dye differs greatly from the reactivity with other monomers to be copolymerized, it is difficult to obtain a dye having the target composition, or the dye that remains unreacted in the lens is eluted from the lens. The drawback is that it is easy to do.

  Patent Document 5 proposes a polymer colorant obtained by reacting a colorant with a polymer compound prepared in advance by polymerization. However, since it is prepared here by reacting a reactive colorant such as chlorotriazine with a hydroxyl group contained in the polymer compound, the compound for that purpose must be polymerized in advance, so it is selected as a polymer compound. Compounds are limited. In addition, it is difficult to control the content necessary as a colorant and the characteristics as a polymer compound because of its low reactivity, and it can be said that there is a problem in the color fastness.

JP-A-1-280464 Japanese National Patent Publication No. 8-503997 Special table 2007-505171 Japanese Patent Laid-Open No. 2003-084242 JP-A-9-020873

  Therefore, the object of the present invention is that it is excellent in elution resistance, is difficult to induce modification such as hydrolysis, is stable, and changes the color tone of the raw material dye even when a predetermined polymerizable group is introduced. An object of the present invention is to provide a colorant for an ophthalmic lens having a novel structure of red to purple to blue, an ophthalmic lens material, a method for producing an ophthalmic lens, and an ophthalmic lens. In addition, for the purpose of improving solubility with other components constituting the ophthalmic lens material, a polymer dye type coloring agent for ophthalmic lenses designed in consideration of solubility with other components in advance, ophthalmic A lens material, a method for manufacturing an ophthalmic lens, and an ophthalmic lens can be provided in the same manner.

  The above object is achieved by the present invention described below. That is, the present invention comprises an azo dye having a polymerizable functional group represented by the following general formula (1) or the following general formula (2) (hereinafter sometimes referred to as “azo dye of the present invention”). A colorant for ophthalmic lenses is provided.

(Where X is a group of atoms necessary for condensing with a benzene ring to form a substituted / unsubstituted naphthalene ring or benzocarbazole ring, Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. And an atomic group selected from an alkoxy group having 1 to 5 carbon atoms, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and an acyl group having 1 to 5 carbon atoms, Z is any of the following: A polymerizable group selected from: B is a polymerizable group selected from any of the following: A is a substituted or unsubstituted aromatic residue bonded to an azo group, n is 1, Indicates 2 or 3.)

  The present invention also relates to a polymerizable compound in which the azo dye of the present invention and at least one polymerizable compound having a polydimethylsiloxane structure are covalently bonded in advance by a chemical reaction (hereinafter referred to as “the dye polymer 1 of the present invention”). The azo dye of the present invention and at least one compound having a polydimethylsiloxane structure are covalently bonded in advance by a chemical reaction. A colorant for an ophthalmic lens comprising a non-polymerizable compound (hereinafter sometimes referred to as “the dye polymer 2 of the present invention”) is provided.

  Further, the present invention is a color for an ophthalmic lens comprising a polymer compound containing an azo dye represented by the following general formula (3) (hereinafter sometimes referred to as “the dye polymer 3 of the present invention”). Provide the agent.

(Where X is a group of atoms necessary for condensing with a benzene ring to form a substituted / unsubstituted naphthalene ring or benzocarbazole ring, Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. And an atomic group selected from an alkoxy group having 1 to 5 carbon atoms, R is a hydrogen atom, an atomic group selected from an alkyl group having 1 to 5 carbon atoms and an acyl group having 1 to 5 carbon atoms, and W is a diazo group. As a starting point, a polymer chain obtained by polymerizing at least one compound having another polymerizable functional group, A is a substituted or unsubstituted aromatic residue bonded to an azo group, n is 1, Indicates 2 or 3.)

  The present invention also comprises a polymer compound obtained by polymerizing the azo dye of the present invention and at least one ophthalmic lens compound in advance (hereinafter sometimes referred to as “the dye polymer 4 of the present invention”). A colorant for ophthalmic lenses is provided.

  The present invention also includes an ophthalmic lens material comprising a polymer obtained by polymerizing a polymerization component containing the azo dye of the present invention and at least one polymerizable compound, and An ophthalmic lens material comprising a polymer obtained by polymerizing a polymer component containing the dye polymer 3 or 4 of the present invention and at least one polymerizable compound is provided. Here, the polymerizable compound is preferably a polymerizable compound having a polydimethylsiloxane structure.

  The present invention further includes an ophthalmic lens material comprising a polymer obtained by polymerizing a polymer component containing the dye polymer 1 of the present invention and at least one polymerizable compound. I will provide a. Here, the polymerizable compound is preferably a polymerizable compound having a polydimethylsiloxane structure.

  The present invention further includes an ophthalmic lens material comprising a polymer obtained by polymerizing a polymer component containing the dye polymer 2 of the present invention and at least one polymerizable compound. I will provide a. Here, the polymerizable compound is preferably a polymerizable compound having a polydimethylsiloxane structure. In the ophthalmic lens material, the polymer may further contain a hydrophilic monomer as a polymerization component.

  In the ophthalmic lens material, it is preferable that at least one polymerizable compound having a polydimethylsiloxane structure has an ethylenically unsaturated group via a urethane bond.

Moreover, this invention provides the manufacturing method of the ophthalmic lens characterized by including the following processes.
A) a step of mixing a polymerization component for an ophthalmic lens containing the azo dye or dye polymer 1 of the present invention,
B) introducing the mixture into a mold,
C) a step of irradiating the mixture in the mold with ultraviolet rays or heating to cure the mixture, and D) a step of demolding the cured product.

Moreover, this invention provides the manufacturing method of the ophthalmic lens characterized by including the following processes.
A) a step of mixing a polymerization component for an ophthalmic lens containing at least one dye polymer 2 to 4 of the present invention,
B) introducing the mixture into a mold,
C) a step of irradiating the mixture in the mold with ultraviolet rays or heating to cure the mixture, and D) a step of demolding the cured product.

  In the above production method, at least one polymerizable compound having a polydimethylsiloxane structure can be further included as a polymerization component for an ophthalmic lens, and a hydrophilic monomer can be further included as a polymerization component. . Moreover, the process of surface-treating the hardened | cured material after demolding can be included.

  The present invention also provides an ophthalmic lens obtained by the above production method.

  The coloring agent for an ophthalmic lens according to the present invention has a predetermined polymerizable group, and such a coloring matter and a lens material are chemically bonded. Even if it is boiled or immersed in water or an organic solvent, the dye does not elute from the lens, and the problem of color loss of the lens is not caused at all. In addition, the colorant for ophthalmic lenses of the present invention introduces a predetermined polymerizable group via a —NHCO— group, so that there is no modification such as hydrolysis and the dye becomes stable, which is convenient for handling. Therefore, it is possible to provide a red-purple-blue ophthalmic lens colorant having no color change.

  On the other hand, in the case of the dye polymers 1 to 4 of the present invention, the dye is covalently bonded to the polymer compound, and since it is a polymer compound, the polymer composed of other components constituting the ophthalmic lens. Even if the resulting lens is boiled or immersed in water or an organic solvent due to the entanglement effect with the chain, the dye does not elute from the lens, causing a problem of color loss of the lens. There is no. In addition, the ophthalmic lens can be uniformly and easily colored by designing a molecule such as incorporating a structure having excellent solubility with the same or different components constituting the ophthalmic lens into the dye polymers 1 to 4 of the present invention. Can be made.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
[Azo dye of the present invention]
The colorant (azo dye) for ophthalmic lenses of the present invention can be synthesized by a known method. For example, first, a naphthol AS derivative having an amino group and (meth) acrylic acid chloride, glycidyl (meth) acrylate or isocyanate ethyl (meth) acrylate are reacted to synthesize a coupler having a polymerizable double bond group. It can be obtained by diazotizing and coupling a conventionally known aromatic amine to the coupler. Alternatively, the azo dye of the present invention can also be obtained by reacting an azo dye having an amino group with (meth) acrylic acid chloride, glycidyl (meth) acrylate or isocyanate ethyl (meth) acrylate.

  It is essential that the coupler used when synthesizing the azo dye of the present invention has a (meth) acrylamide group, a (meth) acrylic acid ester group or an allyl group in the molecule. The structure of the coupler can be selected in consideration of the hue of the dye to be synthesized and the structure of the diazo component to be used. However, the availability of raw materials, the ease of reaction, and the copolymerizability of the synthesized azo dye In view of the above, the use of N- (methacrylamidophenyl) -3-hydroxy-2-naphthoic acid amide or N- (ethyl methacrylate phenyl phenyl) -3-hydroxy-2-naphthoic acid amide is preferred.

  Preferred diazo components for use in the present invention include 4-benzoylamino-2,5-diethoxyaniline, 4-benzoylamino-2-methoxy-5-methylaniline, 4-benzoylamino-2,5-dimethoxyaniline, 4-aminobenzanilide, 3,3′-dichlorobenzidine, 4,4′-diaminobenzanilide, 2,5-dichloroaniline, 4,4′-diaminodiphenylamine, 4-aminodiphenylamine, 3,3′- Examples of the amine used in known azo pigments and azo dyes such as dimethyl-4,4′-diaminodiphenylmethane can be given, and it is preferable to use the above diazo component properly according to the color tone of the desired dye and the structure of the coupler. .

  Usually, the azo dye is difficult to dissolve in the monomer as described later, but the azo dye for an ophthalmic lens of the present invention has an amide group, an amino group, a urea group, or the like in the molecule. Of course, there are some slightly polar monomers such as methyl methacrylate (MMA) and ethyl methacrylate (EMA) as well as highly polar monomers such as hydroxyethyl methacrylate (HEMA) and N-vinylpyrrolidone (N-VP). Dissolve.

  Since the azo dye of the present invention is chemically bonded to a polymer chain by copolymerization with another monomer, a phenomenon such as elution or color transfer does not occur outside the lens even when used for coloring a lens material. Moreover, since the azo dye of the present invention has a chemical structure similar to that of a general azo pigment, the colored product has excellent light resistance. Furthermore, since the coloring matter is bonded to the polymer chain as a molecule, not as a particle, like a pigment, the colored product is transparent. It is also possible to apply a high molecular weight azo dye obtained by previously mixing and polymerizing the azo dye of the present invention and the monomer A described later, or the monomer A and the monomer B described later, as an ophthalmic lens material component. is there. In this case, the content of the azo dye in the high molecular weight dye is preferably 0.5 to 50% by mass. The solubility of the azo dye in the ophthalmic lens mixture can be increased, and the azo dye of the present invention does not necessarily have a covalent bond with the polymer chain of the ophthalmic lens material. It has been confirmed that the azo dye does not elute or shift to the outside of the lens by binding to each other and appropriately increasing the molecular weight.

Specific examples of the azo dye particularly useful in the present invention represented by the general formula (1) are shown below, but the azo dye of the present invention is not limited thereto. In addition, the manufacturing method of each pigment | dye is based on the synthesis example 1 of a postscript Example.

[Dye polymers 1 and 2 of the present invention]
The dye polymer 1 of the present invention comprises a polymerizable compound in which the azo dye of the present invention and at least one polymerizable compound having a polydimethylsiloxane structure are covalently bonded in advance by a chemical reaction.

  Here, as a method for covalently bonding the azo dye of the present invention to at least one polymerizable compound having the polydimethylsiloxane structure, a general addition reaction such as hydrosilylation can be used. As an example of the above addition reaction, a polymerizable double bond such as a (meth) acryl group or an allyl group in the azo dye of the present invention is added to polydimethylsiloxane having a hydrosilyl group (Si—H) in the structure. A method is mentioned.

  The polydimethylsiloxane here refers to a polysiloxane structure having at least one dimethylsilyl group in its skeleton. Examples of the polydimethylsiloxane having a hydrosilyl group include polydimethylsiloxane-co-hydromethylsiloxane, polydiphenylsiloxane-co-phenylhydrosiloxane, polyhydromethylsiloxane-co-methylphenylsiloxane, and polyhydrophenylsiloxane-co-. Methylphenylsiloxane, polysiloxane-co-hydromethylsiloxane containing fluorine-substituted alkyl group or alkoxy group and methyl group in the side chain, polysiloxane-co-hydromethyl containing polyalkyleneoxyalkyl group and methyl group in the side chain Although siloxane etc. are mentioned, it is not limited to these.

  In addition, in the addition reaction of the azo dye of the present invention to the polydimethylsiloxane, chloroplatinic acid or a platinum / siloxane complex can be used as a catalyst. In the above addition reaction, when a hydrosilyl group or a polymerizable double bond remains in the reaction product, the reaction product further has polymerizability (pigment polymer 1), and the reaction product contains When no hydrosilyl group or polymerizable double bond remains, the reaction product is non-polymerizable (Dye Polymer 2). In such a dye polymer, the content of the azo dye in the dye polymer is preferably 0.5 to 50% by mass. Specific examples of the dye polymers 1 and 2 are shown below.

  Moreover, as a method of covalently bonding the azo dye of the present invention to a polymer compound, a method of copolymerizing in advance with another polymerizable compound constituting the ophthalmic lens material can be mentioned.

[Dye polymer 3 of the present invention]
The dye polymer 3 of the present invention is represented by the general formula (3), and a dye in which W is an amino group in the general formula (3) is prepared, and the amino group is diazotized to form a diazonium salt. When the salt is decomposed in the monomer solution, a free radical is generated at the substitution position of the aromatic ring in which the diazonium group is present, the free radical becomes a polymerization initiator for the monomer, a polymer chain is generated, and the dye polymer 3 is obtained. The content of the azo dye contained in the dye polymer 3 is preferably 0.5 to 50% by mass. The monomer polymerization method using such a dye radical is known, and the dye polymer 3 of the present invention can be obtained according to a known method. The monomer used here is not particularly limited as long as it is a monomer capable of radical polymerization.

[Dye Polymer 4 of the Present Invention]
The dye polymer 4 of the present invention is a polymer compound obtained by previously polymerizing the azo dye of the present invention and at least one ophthalmic lens compound described below. The polymerization method is the same as that for the later-described ophthalmic lens material. The content of the azo dye contained in the dye polymer 4 is preferably 0.5 to 50% by mass.

  As another polymerizable compound constituting the ophthalmic lens material, at least one selected from monomer B (see [0068]) and monomer C (see [0069]), which will be described later, can be selected. In addition, these monomers can be mixed in an appropriate organic solvent and polymerized under the conditions shown in [0076] to [0078] to obtain the dye polymer 3 or 4.

  The appropriate organic solvent is not particularly limited as long as the monomer can be sufficiently dissolved, but the organic solvent used in the present invention is carbon such as methanol, ethanol, 1-propanol, 2-propanol. It is a water-soluble organic solvent selected from alcohols of formula 1 to 3, acetone, methyl ethyl ketone, DMF, DMSO, acetonitrile, N-methylpyrrolidone, N, N-diaminoacetamide. The organic solvent may be appropriately selected from those capable of dissolving the used monomer according to the type of monomer. These organic solvents may be used alone or in combination of two or more. The dye polymers 3 and 4 obtained by polymerization can be washed and purified using the organic solvent.

[Materials for ophthalmic lenses]
The ophthalmic lens material of the present invention is characterized by containing at least one azo dye of the present invention, and may contain a polymerizable compound having a polydimethylsiloxane structure, which will be shown as monomer A below. B and monomer C may be included.

  A preferable monomer A used in the present invention is at least one monomer having an ethylenically unsaturated group and a polydimethylsiloxane structure via a urethane bond, which is described in WO 2004/063795. Specifically, for example, the macromonomer (A1) or the macromonomer (A2) obtained by the production method described in pages 48 to 49 of WO 2004/063795 pamphlet can be used. Hereinafter, the macromonomer (A1) and the macromonomer (A2) will be described.

(Manufacture of macromonomer (A1))
In a 1 L three-necked flask equipped with a Dimroth condenser, a mechanical stirrer, and a thermometer on a side tube previously purged with nitrogen, 75.48 g (0.34 mol) of isophorone diisocyanate (IPDI) and iron acetylacetonate ( FeAcAc) 0.12 g was added. Then, 529.90 g of hydroxyl-terminated dimethylsiloxane (polymerization degree 40, hydroxyl equivalent 1,560 g / mol, Shin-Etsu Chemical Co., Ltd. KF-6002, hereinafter referred to as DHDMSi40) was added and heated to 80 ° C. Stir in for about 4 hours.

Next, 39.47 g (0.34 mol) of 2-hydroxyethyl acrylate (HEA) and 0.20 g of p-methoxyphenol (MEHQ) as a polymerization inhibitor were added to the three-necked flask, and an oil bath at 80 ° C. Stir in. About 3 hours later, the reaction was confirmed from the reaction solution using ¹ H-NMR and FT / IR, and it was confirmed that the predetermined compound was obtained. Furthermore, the crude compound was extracted and washed with n-hexane and acetonitrile, the n-hexane layer was recovered, and the organic solvent and the low molecular compound were distilled off under reduced pressure. 522.33 g (yield 81%) of the purified compound (macromonomer (A1)) was obtained. The analysis results are as follows.

¹ H-NMR (in CDCl ₃ ); δ 0.06 ppm (Si—CH ₃ , m), 0.52 (Si—CH ₂ , 2H, m), 2.91 (NH—CH ₂ , 2H, d), 3.02 (CH ₂ —N═C═O, 2H, s), 3.42 (—O—CH ₂ , 2H, t), 3.61 (—O—CH ₂ , 2H, m), 4. 18-4.34 (- (O) CO- CH 2 -, 6H, m), 4.54 (NH, 1H, s), 4.85 (NH, 1H, s), 5.84 (CH =, 1H, dd), 6.14 (CH =, 1H, dd), 6.43 (CH =, 1H, dd)
FT / IR; 1,262 and 802 cm ⁻¹ (Si—CH ₃ ), 1094 and 1,023 (Si—O—Si), around 1,632 (C═C) 1,728 (C═O, ester and Urethane).

(Production of macromonomer (A2))
Into a 1 L three-necked flask equipped with a Dimroth condenser, mechanical stirrer and thermometer on a side tube previously purged with nitrogen, 44.60 g (0.20 mol) of isophorone diisocyanate (IPDI) and iron acetylacetonate (FeAcAc) ) 0.07 g was added. Next, 90.80 g of both-end hydroxyl group dimethylsiloxane (degree of polymerization 10, hydroxyl group equivalent 1000 g / mol, Shin-Etsu Chemical Co., Ltd. KF-6001, hereinafter referred to as DHDMSi10) was added, and the oil bath was heated to 80 ° C. Stir for about 4 hours.

  Next, a solution prepared by dissolving 0.07 g of iron acetylacetonate (FeAcAc) and 156.80 g of polyethylene glycol (hydroxyl equivalent: 1020 g / mol, manufactured by Aldrich) in 200 mL of chloroform was added and refluxed for about 4 hours. A part of the reaction solution was taken out, the solvent was distilled off under reduced pressure, and then the hydroxyl value of the obtained intermediate was measured (acetylation method, 4210 g / mol).

To a 500 mL three-necked flask in which 106.50 g of the intermediate was separated, 7.90 g (0.05 mol) of 2-isocyanate ethyl acrylate (IEM) was added. As a polymerization inhibitor, 0.05 g of p-methoxyphenol (MEHQ) was added to the three-necked flask and stirred in an oil bath at 80 ° C. After about 3 hours, the reaction was confirmed from the reaction solution using ¹ H-NMR and FT / IR to confirm that a urethane compound was obtained. Further, the crude compound was extracted and washed with n-hexane and methanol, the n-hexane layer was recovered, and the organic solvent and the low molecular compound were distilled off under reduced pressure. 84.56 g (yield 74%) of the purified compound (macromonomer (A2)) was obtained. The analysis results are as follows.

¹ H-NMR (in CDCl ₃ ); δ 0.06 ppm (Si—CH ₃ , m), 0.52 (Si—CH ₂ , 2H, m), 2.91 (NH—CH ₂ , 2H, d), _{3.02 (CH 2 -N = C =} O, 2H, s), around _{3.5 (-O-CH 2, m} ), 4.18-4.34 (- (O) CO-CH 2 -, 6H, m), 4.54 (NH, 1H, s), 4.85 (NH, 1H, s), 5.84 (CH =, 1H, dd), 6.14 (CH =, 1H, dd) , 6.43 (CH =, 1H, dd)
FT / IR; 1,262 and 802 cm ⁻¹ (Si—CH ₃ ), 1,094 and 1,023 (Si—O—Si), around 1,632 (C═C) 1,728 (C═O, Esters and urethanes).

  Specific examples of the monomer B used in the present invention include, for example, hydrophilic monomers exemplified on page 15 of WO 2005/116728 pamphlet, pages 15 and 20 of WO 2004/063795 pamphlet. The pyrrolidone derivatives, N-substituted acrylamides and hydrophilic monomer components exemplified on pages 21 to 23 and 24 to 24 can be used.

  Examples of these monomers B include (meth) acrylamide; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as hydroxybutyl (meth) acrylate; 2-dimethylaminoethyl (Meth) acrylate, (alkyl) aminoalkyl (meth) acrylate such as 2-butylaminoethyl (meth) acrylate; alkylene glycol mono (meth) acrylate such as ethylene glycol mono (meth) acrylate and propylene glycol mono (meth) acrylate Polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; ethylene Ethyl glycol vinyl ether; (meth) acrylic acid; aminostyrene; hydroxystyrene; vinyl acetate; glycidyl (meth) acrylate; allyl glycidyl ether; vinyl propionate; N, N-dimethylacrylamide, N, N-dimethylmethacrylate Amides, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N- (2-hydroxyethyl) methacrylamide, N-isopropyl (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, acryloylmorpholine, methacryloyl Morpholine; N-vinyl-2-pyrrolidone, N-vinyl-3-methyl-2-pyrrolidone, N-vinyl-4-methyl-2-pyrrolidone, N-vinyl-5-methyl-2-pyrrolidone, -Vinyl-6-methyl-2-pyrrolidone, N-vinyl-3-ethyl-2-pyrrolidone, N-vinyl-4,5-dimethyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone N-vinyl-3,3,5-trimethyl-2-pyrrolidone, N-vinyl-2-piperidone, N-vinyl-3-methyl-2-piperidone, N-vinyl-4-methyl-2-piperidone, N -Vinyl-5-methyl-2-piperidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-3,5-dimethyl-2-piperidone, N -Vinyl-4,4-dimethyl-2-piperidone, N-vinyl-2-caprolactam, N-vinyl-3-methyl-2-caprolactam, N-vinyl-4-methyl-2-caprolactam, N- Vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, N-vinyl-3,5-dimethyl-2-caprolactam, N-vinyl-4,6-dimethyl-2-caprolactam, N-vinyl lactams such as N-vinyl-3,5,7-trimethyl-2-caprolactam; N-vinylformamide, N-vinyl-N-methylformamide, N-vinyl-N-ethylformamide, N-vinylacetamide, N-vinylamides such as N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylphthalimide; 1-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2- Pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolide 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, 1-n-propyl-3-methylene-2-pyrrolidone, 1-n-propyl-5-methylene-2 -Pyrrolidone, 1-i-propyl-3-methylene-2-pyrrolidone, 1-i-propyl-5-methylene-2-pyrrolidone, 1-n-butyl-3-methylene-2-pyrrolidone, 1-t-butyl Examples include pyrrolidone derivatives whose polymerizable group is a methylene group, such as -3-methylene-2-pyrrolidone.

  Examples of other monomers (hereinafter sometimes referred to as “monomer C”) include, for example, alkyl (meth) acrylate, siloxanyl (meth) acrylate, fluoroalkyl (meth) acrylate, phenoxyalkyl (meth) acrylate, and phenylalkyl (meth). Monomers such as (meth) acrylic acid esters such as acrylate, alkoxyalkyl (meth) acrylate, and styrene derivatives can be used.

  In addition, polyfunctional monomers such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate are used as a crosslinking agent as necessary. More specific examples of these monomers, and other different examples. Is disclosed in detail in Japanese Patent Application Laid-Open No. 1-280464 related to the earlier application of the applicant of the present application, and in the present invention, various monomers disclosed therein are also various other known to those skilled in the art. These monomers, for example, polymerizable ultraviolet absorbers, are appropriately selected and used.

  Specific examples of the polymerizable ultraviolet absorber include, for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, 2-hydroxy- Benzophenone-based polymerizable ultraviolet absorbers such as 4- (meth) acryloyloxy-2 ′, 4′-dichlorobenzophenone and 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) act Royloxypropylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5 ′-(meth) acryloyloxypropyl-3′-t-butylphenyl) -5-chloro-2H-benzotriazole, 2- ( Benzotriazole-based polymerizable UV absorbers such as 2′-hydroxy-5 ′-(2 ″ -methacryloyloxyethoxy) -3′-t-butylphenyl) -5-methyl-2H-benzotriazole; 2-hydroxy-4 -Salicylic acid derivative-based polymerizable UV absorbers such as phenyl methacryloyloxymethylbenzoate; 2-cyano-3-phenyl-3- (3 '-(meth) acryloyloxyphenyl) propenyl acid methyl ester, etc. These can be used alone or in admixture of two or more.

  When the desired ophthalmic lens is a non-hydrous ophthalmic lens substantially free of moisture, monomer C can be added to monomer A as a material. The monomer A is preferably 5 to 100% by mass when the total polymerization component is 100% by mass. If the amount of monomer A used is too small, sufficient oxygen permeability necessary for an ophthalmic lens may not be obtained. When adding the monomer C, it is preferable that the monomer C is 0-95 mass% when all the polymerization components are 100 mass%. If the amount of monomer C used is too small, the expected strength or hardness may not be exhibited. On the other hand, if the amount of monomer C used is too large, the ophthalmic lens material may become brittle.

Moreover, the said azo pigment | dye has a preferable ratio of 0.001-0.5 mass part when all the polymerization components are 100 mass parts. When the amount of the azo dye used is less than 0.001 part by mass, the coloring effect cannot be sufficiently exerted, and when it is more than 0.5 part by mass, the color tone becomes too dark and practical. This causes problems such as disappearance and difficulty in transmitting visible light.
Moreover, the said pigment | dye polymer has the preferable ratio of 0.01-5 mass parts, when all the polymerization components are 100 mass parts. When the amount of the dye polymer used is less than 0.01 parts by mass, the coloring effect cannot be sufficiently exhibited, and when it is more than 5 parts by mass, the color tone becomes too dark and impractical. Or it becomes difficult to transmit visible light, or it becomes difficult to dissolve in a polymerization component.

  When the desired ophthalmic lens is a hydrous ophthalmic lens, monomer B (hydrophilic monomer) can be added to monomer A as a material. In this case, the monomer A is preferably 10 to 90% by mass when the total polymerization components (excluding the azo dye, hereinafter the same) are 100% by mass. If the amount of monomer A used is too small, sufficient oxygen permeability necessary for an ophthalmic lens may not be obtained. When the amount of the monomer A used is too large, depending on the molecular structure of the monomer A, the mechanical properties cannot be controlled such that the ophthalmic lens material becomes too soft or conversely becomes too hard.

  On the other hand, the monomer B is preferably 10 to 90% by mass when the total polymerization component is 100% by mass. If the amount of the monomer B used is too small, the expected hydrophilicity may not be expressed. On the other hand, if the amount of the monomer B used is too large, the expected oxygen permeability may not be expressed. In addition, as a polymerization component, when all the polymerization components are 100 mass%, monomers other than the said monomers A and B can contain 1-60 mass%.

  Further, in order to polymerize a mixture of an ophthalmic lens material component such as an azo dye and a monomer as described above in order to obtain a desired colored ophthalmic lens material, a method usually performed in the technical field, It will be adopted as appropriate. For example, if necessary, a radical polymerization initiator is added to such a mixture and gradually heated in a temperature range from room temperature to about 130 ° C., or electromagnetic waves such as microwaves, ultraviolet rays, and radiation (γ rays) are emitted. Polymerization is carried out by irradiation. The polymerization may be a bulk polymerization method or a solution polymerization method using a solvent. In addition, in the case of heat polymerization, the temperature may be raised stepwise, Various known methods can be employed in the same manner as in the past.

  Specific examples of radical polymerization initiators include, for example, azobisisobutylnitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc. Species or two or more are selected and used.

Examples of the photopolymerization initiator include phosphine oxide photopolymerization initiation such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Agents: Benzoin-based photopolymerization initiators such as methyl orthobenzoylbenzoate, methylbenzoylformate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin-n-butyl ether; 2-hydroxy-2-methyl- 1-phenylpropan-1-one, p-isopropyl-α-hydroxyisobutylphenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α , Α-dichloro-4-phenoxyacetophenone, N, N-tetraethyl-4,4-diaminobenzophenone and other phenone photopolymerization initiators; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl-1,2-propanedione-2 -(O-ethoxycarbonyl) oxime; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosvalon; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; . These can be used alone or in admixture of two or more.
And the usage-amount is made into the range of about 0.01-5 mass parts generally with respect to 100 mass parts of all the monomer mixtures with which it uses for superposition | polymerization.
Moreover, it can also be used by adding a solvent to the monomer mixture. Examples include water-soluble solvents such as water, methanol, ethanol, 1-propanol, 2-propanol, acetone, acetonitrile, tetrahydrofuran, and N-methyl-2-pyrrolidone, but are not limited thereto.

  The above explanation is the case where the azo dye of the present invention is used as the dye, but the same applies even when at least one of the dye polymers 1 to 4 of the present invention is used instead of the azo dye of the present invention. Results.

[Production method of ophthalmic lens]
The manufacturing method of the ophthalmic lens of this invention is characterized by including the following processes. A) a step of preparing the ophthalmic lens material (mixture) of the present invention,
B) introducing the mixture into a mold,
C) a step of irradiating the mixture in the mold with ultraviolet rays or heating to cure the mixture, and D) a step of demolding the cured product.

  In step A), the azo dye of the present invention and the first compound for one or more ophthalmic lenses can be mixed and polymerized to synthesize a new azo dye-containing polymer colorant. Further, the resulting polymer colorant can be further mixed with one or more second ophthalmic lens compounds. In addition, a novel azo dye-containing polymer colorant of the polymerizable or non-polymerizable compound (the dye of the present invention) is obtained by chemically reacting the azo dye of the present invention with at least one compound having a polydimethylsiloxane structure in advance. Polymers 1 and 2) can be synthesized, and a further second one or more ophthalmic lens compounds can be mixed into the resulting polymer colorant. The first one or more ophthalmic lens compounds and the second one or more ophthalmic lens compounds referred to here are selected from the monomer A, the monomer B, and the other monomer C.

  In the said manufacturing method, hydrophilic property and contamination | pollution resistance can be provided to the lens surface by surface-treating the hardened | cured material after mold removal further. As the surface treatment, for example, plasma treatment using various reaction gases or inert gas, or dry process by corona discharge, excimer VUV irradiation, or the like can be applied. It is also possible to apply a wet process such as graft polymerization by generating radical active species on the surface in advance by a by-layer method) or plasma treatment, and then contacting with a hydrophilic monomer.

  In addition, when polymerizing ophthalmic lenses such as contact lenses and intraocular lenses, a molding method commonly performed by those skilled in the art can be employed. For example, polymerization is performed in a suitable mold or container, After obtaining block-like or plate-like material (polymer), it is processed into a desired shape by mechanical processing such as cutting and polishing, and a die corresponding to the desired shape is prepared. In this, a method is used in which the monomer mixture is polymerized to obtain a molded product and mechanically finished as necessary. Furthermore, in the case of forming an intraocular lens, a method in which the lens support is manufactured separately from the lens and attached to the lens, or is molded simultaneously with the lens (integrally) is adopted. Become.

  Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples. In the text, “parts” and “%” are mass-weighted.

Synthesis example 1
(1) Synthesis of Exemplary Azo Dye 2 <Synthesis of Coupler>
13.92 g of 3-hydroxy-2-naphthoic acid (3′-aminoanilide) is dispersed in THF (tetrahydrofuran), and 6.8 g of methacryloyl chloride is slowly added dropwise while cooling the surroundings. After completion of dropping, the mixture is stirred at room temperature for several hours. Next, a solution obtained by dissolving 4.45 g of potassium carbonate in 30 ml of water is dropped, and after completion of the dropping, the mixture is stirred for several hours at the reflux temperature. After cooling, the mixture is filtered, and the residue is washed with methanol and water in this order. It was dried to obtain 11.3 g of 3-hydroxy-2-naphthoic acid (3′-methacryloylaminoanilide) (yield 65%).

(1) Melting point: 226 ° C
(2) Elemental analysis values: The values in parentheses are theoretical values: C; 72.4% (72.8)%, H; 5.27% (5.24), N; 8.11% (8.09)
(3) The infrared absorption spectrum is shown in FIG.
(4) NMR spectrum (TMS standard, solvent: DMSO-d6)
1.97 ppm (s · 3H), 5.53 (s · 1H), 5.84 (s · 1H), 7.32 to 7.53 (m · 6H), 7.76 to 7.79 (d · 1H), 7.92 to 7.95 (d · 1H), 8.18 (s · 1H), 8.53 (s · 1H), 9.88 (s · 1H), 10.62 (s · 1H) ) 11.41 (s · 1H). The spectrum is shown in FIG.

<Synthesis of azo dyes>
9.54 g of the above coupler is dissolved in 500 ml of N, N-dimethylacetamide and a solution of 13.8 g of sodium acetate trihydrate in 50 ml of water is added. Next, 7.51 g of blue BB base is diazotized by a conventional method, and the obtained diazo liquid is dropped into the above coupler solution for coupling. After stirring for several hours at room temperature, it is filtered and the filtrate is washed thoroughly with 1-butanone and then with water. By drying, 14.8 g of the exemplified azo dye 2 was obtained (yield 90%). The obtained azo dye was bright purple.
(1) Melting point: 254 ° C
(2) Elemental analysis values: The parenthesized values are theoretical values: C; 69.0% (69.4)%, H; 5.39% (5.36), N; 10.68% (10.65)
(3) The infrared absorption spectrum is shown in FIG.

Synthesis Examples 2-6
In the same manner as in Synthesis Example 1, the exemplified azo dyes 1 and 3 to 6 were synthesized. The melting point (decomposition point), maximum absorption wavelength, and hue of the obtained dye are shown in Table 1 below. The infrared absorption spectrum of Example Compound 4 is shown in FIG. 4, and the infrared absorption spectrum of Example Compound 5 is shown in FIG.

Synthesis example 7
Polydimethylsiloxane-co-hydromethylsiloxane (Mn = 7,600, converted to polystyrene, Si-Me: Si-H = 90: 10) capped at both ends with allyl alcohol and then with isocyanate ethyl methacrylate is synthesized. 2.2 g (0.29 mmol) of this siloxane compound and 0.18 g (0.29 mmol) of Exemplified Compound 6 are dissolved in 20 mL of toluene and stirred at room temperature for 30 minutes while bubbling an inert gas (nitrogen). Thereafter, 20 μL of platinum catalyst is added to the solution, and the mixture is reacted at a temperature of 60 ° C. or more for 20 hours or more.

  40 mL of distilled water is added to the resulting solution and heated at 100 ° C. for 2 hours or more. After distilling off the reaction solvent, 200 mL of dichloromethane and 150 mL of 50% brine are added and stirred. The dichloromethane layer separated by the separatory funnel was collected and washed again with 200 mL of 50% brine to remove the catalyst. After the dichloromethane solution is filtered, the dichloromethane is distilled off, and 300 mL of n-hexane is added and redissolved. The n-hexane layer taken out after repeated washing with acetonitrile is filtered, and the n-hexane is distilled off to obtain 0.55 g of an oily polymer colorant (Exemplary Compound 7) (yield 22%).

Synthesis example 8
Polydimethylsiloxane-co-hydromethylsiloxane (Mn = 7,000, polystyrene conversion, Si-Me: Si-H = 90: 10) (also used for the synthesis of Exemplified Compound 7) 2.0 g (0.29 mmol) The procedure is carried out according to the synthesis of Exemplified Compound 7 except that it is used to obtain 0.68 g of oily polymer colorant (Exemplary Compound 8) (yield 31%).

Synthesis Example 9
Dye (E) -N- (3-aminophenyl) -4-((4-benzamido-2,5-dimethoxyphenyl) diazenyl) -3-hydroxy- having an amino group in 600 parts of N, N-diaminoacetamide Dissolve 22.48 parts of 2-naphthamide and cool to 0 ° C. or lower. After adding 14.4 parts of concentrated hydrochloric acid (35% aq.), A solution prepared by dissolving 3.12 parts of sodium nitrite (97%) in 40 parts of water was added dropwise so that the internal temperature did not exceed 10 ° C. Stir for an additional hour. 20.8 parts of 2-hydroxyethyl methacrylate and 67.65 parts of silicone-containing methacrylic acid ester (trade name: Silaplane TM-0701T manufactured by Chisso Corporation) were added to the diazonium salt solution of the obtained pigment at 70 ° C. Stir for 2 hours. After cooling, it is poured into 3,000 parts of water, and the resulting precipitate is filtered. Example compound 9 was obtained by washing in order of methanol and water and drying. Yield 91.7 parts (yield 85%).

Synthesis Example 10
In 1 part of N-methyl-2-pyrrolidone, 28.0 parts of the azo dye shown in Exemplified Compound 4, 20.8 parts of 2-hydroxyethyl methacrylate and a silicone-containing methacrylate (trade name: Sila manufactured by Chisso Corporation) (Plain TM-0701T) (67.65 parts) and azobisisobutyronitrile (2.0 parts) are added, and the mixture is stirred at 78-80 ° C for 2 hours. After cooling, it is poured into 5,000 parts of water, and the resulting precipitate is filtered. Example compound 10 was obtained by washing in order of methanol and water and drying. Yield 98.6 parts (yield 96%).

Examples 1-11
A contact lens mixture containing the azo dye (exemplary compound) 1 to 6, 8, 10, and a macromonomer (A1) was prepared. Details are shown in Table 2. These mixtures are injected into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens having a diameter of about 14 mm and a thickness of 0.1 mm), and then the mold is irradiated with ultraviolet rays for 20 minutes to perform photopolymerization. It was. After polymerization, a contact lens-shaped polymer was obtained from the mold, and surface treatment was performed for 3 minutes under plasma irradiation (output 50 W, pressure 100 Pa) in an oxygen atmosphere. The treated product was immersed in a physiological saline solution to absorb water and subjected to hydration treatment to obtain a contact lens.

Example 12
A mixture for contact lenses comprising the azo dye (exemplary compound) 1 and monomers not containing silicone was prepared (see Table 2). The mixture is poured into a mold having a contact lens shape (made of polypropylene, corresponding to a contact lens having a diameter of about 14 mm and a thickness of 0.1 mm), and the mold is then conditioned for 60 minutes in a dryer adjusted to 90 ° C. Then, thermal polymerization was performed. After polymerization, a contact lens-shaped polymer was obtained from the mold, immersed in a physiological saline solution, absorbed, and hydrated to obtain a contact lens.

Comparative Example 1
Using a colorant having no polymerizable functional group, a contact lens mixture was prepared as described above, and polymerized in the same manner as in Examples 1 to 11 to obtain a contact lens of Comparative Example 1.

The monomer ratio in a table | surface is the quantity (mass part) with respect to 100 parts of polymerizable components whole quantity except a crosslinking agent. The abbreviations in the table are as follows.
TRIS: Tris (trimethylsiloxy) silylpropyl methacrylate Macromonomer (A1): obtained by the production method on pages 48 to 49 in International Publication No. 2004/063795 pamphlet.
2-MTA: 2-methoxyethyl acrylate N-VP: N-vinylpyrrolidone DMAA: N, N-dimethylacrylamide 1,3-MMP: 1-methyl-3-methylene-2-pyrrolidone MMA: methyl Methacrylate, AMA: Allyl methacrylate, EDMA: Ethylene glycol dimethacrylate, HMPPO: 2-hydroxy-2-methyl-1-phenylpropan-1-one, AIBN: 2,2′-azobisisobutyronitrile, G # 6 : 1,4-bis (p-methylphenylamino) anthraquinone

Evaluation Example The appearance, lens standard, absorbance, and extraction rate of the colored contact lenses obtained in Examples 1 to 12 and Comparative Example 1 were evaluated as follows. The results are shown in Table 3.
(1) Appearance Appearance (color, transparency, presence / absence of foreign matter, presence / absence of deformation) of the colored contact lenses obtained in Examples 1 to 12 and Comparative Example 1 was examined.
(2) Lens standard The diameter, vertex refractive index, and radius of curvature of the rear surface of 10 lenses were measured in a flow preservation solution adjusted to 20 ° C.
(3) Absorbance measurement The visible absorption spectrum of the lens was measured using an integrating sphere, and the absorption λmax based on the colorant was measured.

(4) Extraction rate In order to confirm the elution behavior (dye polymerizability) of the dye from the lens, the contact lens is immersed in 2 mL of an eye fat component (wax ester) or 2 mL of acetone and extracted at room temperature for about 24 hours. Absorption due to the dye before and after extraction was measured with an ultraviolet-visible spectrophotometer. In the measurement, the apparatus (3) and the integrating sphere for lens measurement were used. Using the maximum absorbance for the peak derived from each dye, the extraction rate was measured according to the following formula. In each of the extraction tests using wax ester or acetone, five lenses were used, and the extraction rate was determined for each lens using the following formula, and the average value was displayed.
Extraction rate (%) = (absorbance before extraction−absorbance after extraction) / absorbance before extraction × 100
A low extraction rate means that the dye does not elute from the lens.

  In the colorant for an ophthalmic lens of the present invention, the dye itself has a predetermined polymerizable group, and such a dye and the lens material are chemically bonded. Even if it is immersed in water or an organic solvent, the dye does not elute from the lens, and the problem of color loss of the lens is not caused at all. Alternatively, by using a polymer dye, the dye does not elute from the lens even when the obtained lens is boiled or immersed in water or an organic solvent. It is not triggered. In addition, the colorant for ophthalmic lenses of the present invention introduces a predetermined polymerizable group into an azo dye via a —NHCO— group, so that there is no modification such as hydrolysis, and the dye becomes stable. Therefore, a red-purple-blue ophthalmic lens colorant having no color change can be provided.

The figure which shows the infrared absorption spectrum of the coupler synthesize | combined in Example 1. FIG. The figure which shows the NMR spectrum of the coupler synthesize | combined in Example 1. FIG. FIG. 3 shows an infrared absorption spectrum of the azo dye synthesized in Example 1. The figure which shows the infrared absorption spectrum of the illustration azo pigment | dye 4. The figure which shows the infrared absorption spectrum of the illustration azo dye 5.

(Wherein X is a group of atoms necessary for condensing with a benzene ring to form a substituted / unsubstituted naphthalene ring , Y is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms and 1 carbon atom) An atomic group selected from ˜5 alkoxy groups, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and an atomic group selected from acyl groups having 1 to 5 carbon atoms, Z is selected from any of the following: B is a polymerizable atomic group selected from any of the following, A is a substituted or unsubstituted aromatic residue bonded to an azo group, n is 1, 2 or 3 ( However, when n is 1, those having atomic group a. Or atomic group b. Are excluded .)

Claims (20)

A colorant for an ophthalmic lens comprising an azo dye having a polymerizable functional group represented by the following general formula (1) or the following general formula (2).

(Where X is a group of atoms necessary for condensing with a benzene ring to form a substituted / unsubstituted naphthalene ring or benzocarbazole ring, Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. And an atomic group selected from an alkoxy group having 1 to 5 carbon atoms, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms and an acyl group having 1 to 5 carbon atoms, Z is any of the following: A polymerizable group selected from: B is a polymerizable group selected from any of the following: A is a substituted or unsubstituted aromatic residue bonded to an azo group, n is 1, Indicates 2 or 3.)

  The at least one azo dye having a polymerizable functional group according to claim 1 and at least one polymerizable compound having a polydimethylsiloxane structure are composed of a polymerizable compound covalently bonded in advance by a chemical reaction. A colorant for ophthalmic lenses characterized by the above.   The non-polymerizable compound in which at least one azo dye having a polymerizable functional group according to claim 1 and at least one compound having a polydimethylsiloxane structure are covalently bonded in advance by a chemical reaction. A colorant for an ophthalmic lens. A colorant for an ophthalmic lens, comprising a polymer compound containing an azo dye represented by the following general formula (3).

(Where X is a group of atoms necessary for condensing with a benzene ring to form a substituted / unsubstituted naphthalene ring or benzocarbazole ring, Y is a hydrogen atom, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. And an atomic group selected from an alkoxy group having 1 to 5 carbon atoms, R is a hydrogen atom, an atomic group selected from an alkyl group having 1 to 5 carbon atoms and an acyl group having 1 to 5 carbon atoms, and W is a diazo group. As a starting point, a polymer chain obtained by polymerizing at least one compound having another polymerizable functional group, A is a substituted or unsubstituted aromatic residue bonded to an azo group, n is 1, Indicates 2 or 3.)   An ophthalmic lens colorant comprising a polymer compound obtained by polymerizing at least one azo dye according to claim 1 and at least one ophthalmic lens compound in advance.   An ophthalmic lens material comprising a polymer obtained by polymerizing a polymerization component containing at least one azo dye according to claim 1 and at least one polymerizable compound.   A polymer obtained by polymerizing a polymer component containing at least one polymer compound containing at least one azo dye according to claim 4 and at least one polymerizable compound, Ophthalmic lens material.   The ophthalmic lens material, wherein the at least one polymerizable compound according to claim 6 or 7 is a polymerizable compound having a polydimethylsiloxane structure.   A polymerization component comprising at least one polymerizable compound having a polydimethylsiloxane structure containing at least one azo dye according to claim 2 and at least one polymerizable compound is polymerized. An ophthalmic lens material comprising a polymer to be obtained.   The ophthalmic lens material, wherein the at least one polymerizable compound according to claim 9 is a polymerizable compound having a polydimethylsiloxane structure.   A polymerization component containing at least one non-polymerizable compound having a polydimethylsiloxane structure containing at least one azo dye according to claim 3 and at least one polymerizable compound is polymerized. An ophthalmic lens material comprising the resulting polymer.   The ophthalmic lens material, wherein the at least one polymerizable compound according to claim 11 is a polymerizable compound having a polydimethylsiloxane structure.   The ophthalmic lens material according to any one of claims 6 to 12, wherein the polymer further contains a hydrophilic monomer as a polymerization component.   The ophthalmic lens material according to any one of claims 6 to 12, wherein at least one polymerizable compound having a polydimethylsiloxane structure has an ethylenically unsaturated group via a urethane bond. The manufacturing method of the ophthalmic lens characterized by including the following processes.
A) a step of mixing an ophthalmic lens polymerization component containing at least one azo dye having a polymerizable functional group according to claim 1 or 2;
B) introducing the mixture into a mold,
C) a step of irradiating the mixture in the mold with ultraviolet rays or heating to cure the mixture, and D) a step of demolding the cured product. The manufacturing method of the ophthalmic lens characterized by including the following processes.
A) A step of mixing a polymerization component for an ophthalmic lens containing a non-polymerizable polymer compound containing at least one azo dye according to any one of claims 3 to 5,
B) introducing the mixture into a mold,
C) a step of irradiating the mixture in the mold with ultraviolet rays or heating to cure the mixture, and D) a step of demolding the cured product.   The method for producing an ophthalmic lens according to claim 15 or 16, further comprising at least one polymerizable compound having a polydimethylsiloxane structure as a polymerization component for an ophthalmic lens.   The method for producing an ophthalmic lens according to claim 15, further comprising a hydrophilic monomer as a polymerization component.   Furthermore, the manufacturing method of the ophthalmic lens of Claim 15 or 16 including the process of surface-treating the hardened | cured material after mold removal.   An ophthalmic lens obtained by the method according to any one of claims 15 to 19.

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