WO2005068571A1

WO2005068571A1 - Coating agent applied onto eye lens surface

Info

Publication number: WO2005068571A1
Application number: PCT/JP2004/000245
Authority: WO
Inventors: Eri Ito; Takatoshi Kinoshita
Original assignee: Menicon Co., Ltd.
Priority date: 2004-01-15
Filing date: 2004-01-15
Publication date: 2005-07-28

Abstract

A coating agent that enables providing on a lens surface a coating of high stability free from layer peeling which might be caused by daily care. In particular, a coating agent applied onto an eye lens surface, which comprises a block copolymer comprising a hydrophobic block main chain having a hydrophilic block bonded to at least one end thereof, and wherein the hydrophobic block at its side chains has at least one functional group capable of bonding with functional groups being present on the eye lens surface.

Description

Akira Itoda Coating agent for ophthalmic lens surface Technical field

The present invention relates to an ophthalmic lens, particularly to a coating agent for a contact lens surface and a contact lens having a coating layer formed from the coating agent. Background art

Ophthalmic lenses have recently used monomers containing silicon and fluorine with the aim of improving their oxygen permeability, and these components make it possible to achieve unprecedented oxygen permeability. It became. However, these components have low biocompatibility, especially in materials that use a gay-containing component as the main component, and have low hydrophilicity and, due to their unique tackiness, adsorb to the corneal surface Poor biocompatibility, such as causing phenomena, has become a problem, and various surface treatments have been studied.

The adsorption phenomenon is thought to be caused by the interaction between the lens and the corneal surface, where the hydrogel layer becomes semi-dry while the lens loses moisture. The interaction between the lens and the corneal surface means that once tears under the lens are released out of the system, the supply path of tears to the lens cannot be secured, and during that time the lens and the corneal surface Have a positive interaction.

For surface coating of ophthalmic lens materials, in addition to forming a hydrogen layer on the lens surface, alkali treatment, plasma treatment in an atmosphere such as oxygen or nitrogen, plasma graft treatment of a compound containing a hydrophilic group, and polymer Hydrophilicity has been imparted to the surface by performing grafting and the like. In the alkali treatment, the (meth) acrylic acid ester portion, which is a lens component, is hydrolyzed, and the hydrophilic group formed thereby covers the lens surface, improving the hydrophilicity (= water wettability). However, when the lens dries, the effect is not recognized.

In plasma treatment, the coating effect is high for oxygen-permeable hard lenses (RGP lenses), but not so for soft contact lenses (SCL). The reason for this is that in SCL, the polymer chain of the main chain is flexible, and it is considered that the functional group is embedded in the polymer chain of the main chain for stabilization. The group may be localized. Even if the plasma treatment is repeatedly performed, the effect cannot be expected so much.

In plasma grafting, polymerization is carried out at the same time as the treatment, so the possibility that functional groups are buried by forming a polymer layer on the surface is low.However, since the degree of polymerization during polymerization cannot be controlled, the entire surface is Difficult to coat evenly. The inability to uniformly coat the entire surface caused problems such as a decrease in oxygen permeability in areas with a high degree of polymerization and adsorption to the corneal surface in areas with a low degree of polymerization.

In polymer grafting, the entire surface can be uniformly coated by coating with a polymer whose degree of polymerization is controlled, but the reactivity of grafting polymers that have only functional groups at the ends is extremely low. However, since most of them are present on the surface by physical adsorption, low stability of the coating layer such as peeling of the surface treatment layer has become a problem due to daily lens care. Compositions for coating biological and non-biological surfaces include polyethylene glycol (PEG) polylysine (PLL) block or comb copolymers with high molecular weight polylysine, A PEGZPLL copolymer, which is a dendrimer in which PPL is bonded to one end of PEG, and a multilayer composition containing alternating layers of polycationic and polyanionic substances are known (see Japanese Patent Application Publication No. 2002-515932). Since PEG binds to the PLL side chain and binds to the surface at the end of PLL, the bond to the material surface is weak, and the bonding frequency is low, so the surface is efficient There were problems such as a coat not being achieved.

Furthermore, as a method for covering a biomedical material or an ophthalmic device having excellent adhesiveness and durability, a polymer base skeleton such as a polypeptide or the like is suspended and bonded to the material surface. A method is known in which one or more different comb-like polymers containing side chains are coated, and the polymer is fixed to the material surface using heat or irradiation with UV or visible light (Japanese Patent Application Laid-Open No. 2002-348393). See). However, as described above, the comb-like polymer used in this method has a weak bond with the material surface because the hydrophilic block is bonded to the side chain of the polymer basic skeleton, and has a low bond frequency. There were problems such as not being able to achieve efficient surface coating. Disclosure of the invention

The present invention has been made to solve the above-mentioned conventional problems, and provides a coating agent having high stability on a lens surface and capable of coating without peeling of a coating layer by daily care. The purpose is to do.

That is, the present invention provides a coating agent for an ophthalmic lens surface containing a block copolymer having a hydrophilic block bonded to at least one end of a main chain of the hydrophobic block, wherein the side chain of the hydrophobic block has The present invention relates to a coating agent having at least one functional group capable of binding to a functional group present on the surface of an ophthalmic lens. The hydrophobic block is preferably a polypeptide containing an amino acid having at least one functional group in a side chain, and the polypeptide is arginine, asparagine, aspartic acid, cystine, glutamine, glutamic acid, histidine, More preferably, it is selected from the group consisting of lysine, proline, serine, threonine, tritophan and tyrosine.

More preferably, the polypeptide further contains a hydrophobic amino acid, and the hydrophobic amino acid is selected from the group consisting of alanine, isoleucine, leucine, methionine, fenylalanine, proline, cysteine, tryptophan, tyrosine and valine. More preferably, it is selected.

The polypeptide preferably has a residue ratio of amino acid having at least one functional group in a side chain to a hydrophobic amino acid of 20:80 to 100: 0: 0, and the polypeptide is lysine. And more preferably leucine.

More preferably, the polypeptide consists of 15 to 100 residues of amino acids.

It is preferable that the hydrophilic block is composed of a homopolymer of a monomer selected from the group consisting of ethylene glycol, N-vinylpyrrolidone, dimethylacrylamide, methacrylic acid and sugar, or a copolymer thereof. More preferably, the degree of polymerization of the hydrophilic block is from 10 to 500.

The present invention relates to an ophthalmic lens having an ophthalmic lens body and a coating layer formed of the coating agent.

The ophthalmic lens body is preferably a contact lens body. It is preferable that the contact lens body is made of a copolymer containing a gay element and a Z or fluorine element. BEST MODE FOR CARRYING OUT THE INVENTION

The present invention provides a coating agent for an ophthalmic lens surface containing a block copolymer having a hydrophilic block bonded to at least one end of a main chain of the hydrophobic block, wherein the side chain of the hydrophobic block is The present invention also relates to a coating agent having at least one functional group capable of binding to a functional group present on the surface of an ophthalmic lens.

The coating agent of the present invention is a block copolymer composed of a hydrophobic block and a hydrophilic block.

The hydrophobic block binds to the functional groups on the ophthalmic lens surface and forms a barrier layer, so a material that has at least one functional group in the side chain that can bind to the functional groups present on the ophthalmic lens surface is used Is done. Examples of the material that can be used for the hydrophobic block include a polypeptide, a fluoropolymer composed of a fluorinated alkyl monomer copolymerized with a monomer having a hydroxyl group or an amino group, and the like. Among them, polypeptides are particularly preferred because they have high biocompatibility and do not inhibit oxygen permeability.

The hydrophobic block polypeptide has an α_helical structure, so that the side chains of the polypeptide are oriented outward, and the side chains facing outward are bonded to the functional groups present on the lens surface. The number of binding sites is larger than that of a polypeptide having a functional group only at the main chain terminal, and the stability is enhanced.

In addition, since the functional groups present on the polypeptide side chains and the functional groups on the ophthalmic lens surface are chemically bonded, the resulting coating layer on the ophthalmic lens surface has high stability and low releasability. An ophthalmic lens having a layer can be obtained. Furthermore, since the polypeptide exhibits a rigid α-helical structure and its molecular gap is small, it does not allow proteins and lipids to pass therethrough, thereby preventing dirt from attaching to the ophthalmic lens. Since it is difficult for the hydrophilic block attached to the terminal of the polypeptide main chain to penetrate into the helical structure of α-helix, the hydrophilic block can always be arranged in the outermost layer.

The amino acids constituting the polypeptide chain can be selected according to the functional groups on the surface of the ophthalmic lens to be coated. Here, an amino acid means that one central carbon atom (C) has an amino group (-ボ₂ ), a carboxyl group (1-COOH), a hydrogen atom (1-Η), and a side chain (-R). It is a combination. The side chain is a different atomic group for each amino acid and determines the properties of each amino acid. Amino acids having at least one functional group in the side chain that binds to a functional group present on the surface of the ophthalmic lens (hereinafter referred to as “functional group-containing amino acids”) include arginine, asparagine, aspartic acid, cystine, glutamine, and the like. Examples include glutamic acid, histidine, lysine, proline, serine, threonine, tributofan, and tyrosine. Among them, lysine is preferred because it has an amino group that can be subjected to a highly reactive condensation reaction when forming a chemical bond with an ophthalmic lens. These amino acids may be used alone or in combination of one or more.

Preferably, the barrier layer of the polypeptide further contains a hydrophobic amino acid to prevent the lens from adsorbing to the corneal surface. Here, the hydrophobic amino acid is a generic term for amino acids having a hydrophobic group in a side chain, for example, alanine, isoleucine, leucine, methionine, fenylalanine, proline, cystine, tributofan, tyrosine, Norin. Of these, leucine is preferred because it has high hydrophobicity and low biodegradability, and further enhances the stability of the polypeptide. In addition, these amino acids may be used alone or in combination of one or more.

Proline, cysteine, tributofan and hydrophobic amino acids that are functional group-containing amino acids that bind to the functional groups present on the ophthalmic lens surface As for tyrosine, a hydrophobic block may be formed alone.

If there is no functional group on the surface of the ophthalmic lens, a pretreatment for introducing a hydroxyl group, a carboxyl group, an amino group, an imidazole group, etc. by hydrolysis to the ophthalmic lens surface is performed, and the functional group is added. By applying, the coating according to the present invention becomes possible.

When the amino acid constituting the polypeptide is a polypeptide comprising a functional group-containing amino acid and a hydrophobic amino acid, the residue ratio between the functional group-containing amino acid and the hydrophobic amino acid is 20:80 to: 10: 0: 0, preferably 30:70 to 80:20. When the residue ratio of the functional group-containing amino acid is less than 20 and the residue ratio of the hydrophobic amino acid is more than 80, the number of reaction points (functional groups) with the ophthalmic lens surface is small, and coating is not performed. Tends to be sufficient.

The polypeptide consists of 15 to 100 residues of amino acids, preferably 22 to 80 residues of amino acids. When the number of amino acids is less than 15 residues, the characteristic α-helix structure of the polypeptide cannot be formed, so that regular bonding to the ophthalmic lens surface tends to be insufficient. . On the other hand, if it exceeds 100 residues, industrial productivity tends to be poor.

The hydrophilic block can be used as long as it is a linear polymer and does not self-crosslink. Examples of the hydrophilic block material that can be used in the present invention include single-weight polymers such as ethylene glycol, vinylpyrrolidone, dimethylacrylamide, methacrylic acid, and sugar (for example, polysaccharide, hyaluronic acid, chondroitin sulfate, dermatan sulfate, etc.). And a copolymer thereof. Among them, homopolymers of ethylene glycol, vinylpyrrolidone, dimethylacrylamide, and methacrylic acid, and copolymers thereof are particularly preferable because of their high biocompatibility.

The degree of polymerization of the hydrophilic block is preferably from 10 to 500, more preferably from 15 to 100, and still more preferably from 20 to 500. Hydrophilic When the degree of polymerization of the block is less than 10, the effect as a hydrophilic portion tends to be insufficient. On the other hand, if it exceeds 500, it tends to be difficult to form a block structure with a hydrophobic polymer.

The block copolymer used in the coating agent of the present invention is composed of a hydrophobic block and a hydrophilic block, and is disposed on at least one end of the main chain of the hydrophobic block in the hydrophilic block. Any material may be used, but among them, a diblock copolymer is preferred from the viewpoint of productivity (simplicity of synthesis).

The ratio of the hydrophilic block to the hydrophobic block of the block copolymer is preferably from 1: 10000 to 1100: 1 by weight of hydrophilic block: hydrophobic block, and more preferably. 1: 500 to 500: 1. When the ratio of hydrophilic block: hydrophobic block is less than 1: 10000 by weight, the hydrophilicity of the surface tends to be insufficient. When the weight ratio of the hydrophilic block: hydrophobic block is more than 1: 100, the chemical reaction with the ophthalmic lens surface tends to be inhibited.

The block copolymer is obtained by reacting a sharp block material with a hydrophilic block material. Here, when the hydrophobic block is a polypeptide comprising amino acids, a high molecular weight polypeptide (hydrophobic block) can be easily obtained by using N-carboxy amino acid anhydride (NCA). The method of synthesizing NCA can be according to the method described in the fourth edition of Experimental Chemistry Course 28 Polymer Synthesis (edited by The Chemical Society of Japan), pages 288-291. Here, when a functional group-containing amino acid such as lysine is used in synthesizing NCA, it is necessary to protect the functional group. For example, a protecting group for an amino group such as a benzyloxycarbonyl group, a protecting group for a hydroxyl group such as a benzyl group and an acetyl group, and a protecting group for a mercapto group and a carboxyl group such as a benzyl group. Examples of the dino-protecting group include a P-toluenesulfonyl group. Solvents capable of synthesizing block polymers by a polymerization reaction starting from a terminal functional group of a hydrophilic polymer include dimethylformamide, chloroform, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, and the like. In consideration of the solubility of the hydrophilic polymer and the N-carboxylic acid anhydride (NCA) polymer, dimethylformamide is preferred.

After the reaction between the hydrophilic block material and the hydrophobic block material, a hydrophobic block having a functional group on the side chain can be obtained by deprotection of the functional group of the amino acid side chain. Examples of the deprotection method include a method of reacting with hydrogen bromide when a benzyloxycarbonyl group is used as a protecting group for an amino group.

As the material of the lens body of the ophthalmic lens used in the present invention, for example, a siloxane macromonomer (A) having two or more active unsaturated groups and having a number average molecular weight of 2000 to 1000 And siloxane-containing polymers obtained by polymerizing a polymerization component containing a lower fatty acid vinyl ester (B).

The active unsaturated group of the siloxane macromonomer (A) is an active unsaturated group that can be subjected to radical polymerization, and includes, for example, a (meth) a acryloyl group, a vinyl group, an aryl group, and a (meth) group. Examples include an acryloyloxy group and a vinyl carbamate group.

The number average molecular weight of the siloxane macromonomer (A) is preferably at least 200, more preferably at least 250, from the viewpoint of the flexibility of the lens material, and is preferably at least 250, in view of the flexibility of the lens material. It is desirably 0000 or less, preferably 50,000 or less.

The siloxane macromonomer usually has poor water wettability, and often has a relatively low mechanical strength by itself. Therefore, when used in the present invention The siloxane macromonomer (A) used in the macromonomer structure has the formula:

-N-C-0-

Those having a urethane group represented by I II H 2 O are preferable, and the number thereof is preferably 2 or more on average, preferably 4 or more on average, and 20 or less on average, and preferably 14 or less on average.

In the present invention, the siloxane macromonomer (A) is preferably represented by the general formula (I-11):

A ¹ — (— U ¹ -S ¹ ―) _n -U ² -S ² — U ³ -A ² (1— 1) wherein A ¹ and A ² are each independently an active unsaturated group, carbon An active unsaturated group having an alkylene group of 1 to 20 or an alkylene glycol group having 1 to 20 carbon atoms,

U ¹ is a diurethane group which forms a urethane bond with both adjacent A ¹ and S ¹ or with S ¹ and S ¹

U ² is a diurethane group that forms a urethane bond with both adjacent A ¹ and S ² or with S ¹ and S ² ,

U ³ is a diurethane group forming a urethane bond with both adjacent S ² and A ^2, and S ¹ and S ² are each independently a formula:

― R ¹ — 0- -R one R ² — O— R ^1-

(Wherein, R and R ² are each independently an alkylene group having 1 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently fluorine May also be straight chain substituted with atom, an alkyl group, or a group of the formula of branched or cyclic carbon number ^{^{1~ 20: A 3 - U 4}} - R 1 -OR 2 i (wherein, A ³ is an active unsaturated A saturated group, an active unsaturated group having an alkylene group having 1 to 20 carbon atoms, or an active unsaturated group having an alkylenedalycol group having 1 to 20 carbon atoms, U ⁴ is a urethane bond with adjacent A ³ and R ¹ Wherein R ¹ and R ² are the same as described above), X is an integer of 1 to 1500, y is 0 or 1 to: I is an integer of 499, x + y is 1 ~: Indicate an integer of 1500)

n represents 0 or an integer from 1 to 10]

Macro-monomers represented by

General formula (I—2):

B '-S ³ — B ¹ (1 -2)

[Wherein, B ¹ is an active unsaturated group having a urethane bond,

S ³ is the formula:

(In the formula, R ¹ and R ² are each independently an alkylene group having 1 to 20 carbon atoms, and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently substituted with a fluorine atom. A linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or a formula: A ³ -U ⁴ — R ¹ -OR ^2- (where A ³ is an active unsaturated group, An active unsaturated group having an alkylene group having 1 to 20 carbon atoms or an active unsaturated group having an alkylene dalicol group having 1 to 20 carbon atoms; U ⁴ is a diurethane which forms a urethane bond with adjacent A ³ and R ¹ And R ¹ and R ² are the same as defined above), and X is 1-1500 Represents an integer of 0, y represents an integer of 0 or 1 to 1499, and x + y represents an integer of 1 to 1500).

The macromonomer represented by is preferably used.

In the general formula (1-1), as the active unsaturated groups represented by A ¹ and A ² , as described above, for example, a (meth) acryloyl group, a vinyl group, an aryl group, a (meth) α group Examples include a cryloyloxy group and a vinyl carbamate group. Among these, an acryloyloxy group and a bier group are preferred because they can impart more excellent flexibility to the lens material and are excellent in copolymerizability with other polymerization components, and particularly preferred are acryloyloxy groups. Groups are preferred.

Further, when the active unsaturated group has an alkylene group or an alkylene glycol group, the alkylene group or the alkylene glycol group preferably has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

In general formula (I- 1) in the formula represented by S ¹ and S ^2:

One R ¹ — O— R — R ² — O— R ¹ —

(Wherein, RR ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , x and y are the same as defined above), wherein R ¹ and R ² are preferably 1 carbon atoms An alkylene group of 5 to 5, R ^{3 to} R ⁸ are preferably an alkyl group of 1 to 5 carbon atoms, and a formula showing such R ^{3 to} R ⁸ : A ³ -U ⁴ —R ¹ -0-R ² And A ³ in the formula represents an active unsaturated group similar to the above examples. When the active unsaturated group has an alkylene group or an alkylene glycol group, the alkylene group or the alkylene glycol group has 1 to 20 carbon atoms. Preferably, it is more preferably 1 to 10. X is an integer from 1 to 500, y is 0 or Is preferably an integer of 1499, and x + y is preferably an integer of 1500. Further, in the general formula (1-1), n is preferably an integer of 0 or 15.

On the other hand, in the general formula (1 _2), examples of the active unsaturated group having a urethane bond represented by B ¹ include a (meth) acryloyl isocyanate group and a (meth) acryloyl oxy isocyanate group. And a benzyl group, an aryl isocyanate group, and a vinylbenzyl isocyanate group. Further, the group represented by S ³ in the general formula (I-12) is the same as the group represented by S ¹ and S ² in the general formula (1-1).

Among the macromonomers, from the viewpoint that the effect of imparting flexibility and mechanical strength typified by shape recovery properties is great, the following formula:

A ¹ -U ² -S ² -U ³ -A ²

(Wherein A ¹ A ² U ² U ³ and S ² are the same as above) and a macromonomer represented by the formula:

A ¹ -(-U ¹ -S ^1- ) _n '— U ² — S ² -U ³ -A ² (where A ¹ A ² U ¹ U ² U ³ S ¹ and S ² are the same as above, n 'is an integer of 14), and is preferably a macromonomer represented by the formula:

A-CH ₂ CH ₂ OCH ₂ CH ₂ CH ₂ -S iO- S iO S i— CH ₂ CH ₂ CH ₂ 〇CH ₂ CH ₂ — A

I

(Where A is the formula:

A represents an integer of 20 to 50)

Are preferred.

Representative examples of the lower fatty acid vinyl ester (B) include, for example, those represented by the general formula (II):

H

I

H ₂ C = C— 0 _ C _ R (II)

II

0

(Wherein R represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a hydrogen atom or a halogen atom). Specific examples of such a compound include, for example, vinyl formate, biel acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, mono-acetate biel, monofluoro vinyl acetate, Examples include trichloro-mouth bier acetate and vinyl trifluoroacetate, and these can be used alone or in combination of two or more. Among the lower fatty acid vinyl esters (B), vinyl acetate, vinyl propionate, and vinyl pivalate are preferable, and biel acetate is particularly preferable, from the viewpoint that the effects of imparting shape recovery and imparting hydrophilicity are large. For example, a siloxane-containing polymer which is a lens material used in the present invention is obtained by polymerizing a polymerization component containing the siloxane macromonomer (A) and a lower fatty acid vinyl ester (B). In addition, for example, a monomer containing silicon (C) may be contained. Representative examples of the silicon-containing monomer (C) include, for example, pentamethyldisiloxanylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, Tris (trimethylsiloxy B) Silylpropyl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl (methyl) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, trimethylsilylmethyl (Methyl) acrylate, trimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylethyl tetramethyldisiloxanylmethyl (meth) acrylate, tetramethyltriisopropyl cyclotetrasiloxanyl propyl (meth) acrylate, Tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate, trimethylsiloxydimethyl Lucylyl propyl

Silicon-containing (meth) acrylates such as (meth) acrylate; for example, tris (trimethylsiloxy) silylstyrene, methylbis (trimethylsiloxy) silylstyrene, dimethylsilylstyrene, trimethylsilylstyrene, tris (trimethylsiloxy) siloxanyldimethylsilylstyrene , [Methylbis (trimethylsiloxy) siloxanyl] dimethylsilyl styrene, pentamethyldisiloxanyl styrene, heptane methyltrisiloxanyl styrene, nonamethyltetrasiloxanyl styrene, pentayl decamethyl heptasixanil styrene, heneicosamethyl Desiloxanyl styrene, heptacosamethyl tridecasiloxanyl styrene, hentriacontamethyl pen decasiloxanyl styrene, Methylsiloxy xypenyl methyl disiloxymethylsilyl styrene, tris (penyl methyl disiloxy) silyl styrene, [tris (trimethylsiloxy) siloxanyl] bis (trimethylsiloxy) silyl styrene, methyl bis (heppu methyl methyl trisyloxy) silyl styrene, tris [ Methylbis (trimethylsiloxy) siloxy] silylstyrene, trimethylsiloxybis [tris

(Trimethylsiloxy) siloxy] silylstyrene, Trisiloxanyl styrene, tris [tris (trimethylsiloxy) siloxy] silyl styrene, [tris (trimethylsiloxy) hexamethyltetracyloxy] [tris (trimethylsiloxy) siloxy] trimethylsiloxysilyl styrene , Nonakis (trimethylsiloxy) tetrasiloxanylstyrene, methylbis (tridecamethylhexyl styrene) silylstyrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetra General formulas such as methylcyclotetrasiloxanylstyrene:

CH

(Where p represents an integer of 1 to 15, q represents 0 or 1, and r represents an integer of 1 to 15), and the like. Two or more kinds can be used as a mixture.

Among the above-mentioned silicon-containing monomers (C), silicon-containing (meth) acrylates are preferred from the viewpoint that the effect of simultaneously imparting high oxygen permeability and flexibility to the lens material, particularly shape recovery, is greater. Tris (trimethylsiloxy) silylpropyl acrylate is particularly preferred.

Further, the polymerization component may contain, for example, a fluorine-containing monomer (D) in addition to the siloxane macromonomer (A), the lower fatty acid vinyl ester (B), and the gayne-containing monomer (C).

Typical examples of the fluorine-containing monomer (D) include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3— Tetrafluoro t —Pentyl (meth) acrylate, 2,2,3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,4,4,4_hexafluorot-hexyl (meth) acrylate , 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4,4-hexafluoro Butyl (meth) acrylate, 2,2,2,2 ', 2', 2'_Hexafluoroisopropyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (Meth) acrylate, 2, 2, 3, 3, 4, 4, 5, 5 — Kuta fluoropentyl (Meth) acrylate and other general formulas:

R ₂

H ₂ C = CC-0-CH ₂ -CH-CH.-R ₁

II I O OH

(Wherein represents a fluoroalkyl group having 3 to 15 carbon atoms, and R ₂ represents a hydrogen atom or a methyl group). For example, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-hydroxyhexyl 2-hydroxypropyl (meth) acrylate, 3-fluorooctyl-1-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) 1-2-hydroxypropyl (3-hydroxypropyl (meth) acrylate (Meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-fluoropropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -fluoroalkyl such as 2-hydroxypropyl (meth) acrylate

(Meta) acrylate.

Among these, fluoroalkyl acrylate is preferred because of its great effect of imparting flexibility to the lens material among oxygen permeability, flexibility and resistance to lipid contamination. Furthermore, although fluorine compounds can generally impart oxygen permeability and lipid contamination resistance, they often have poor water wettability. On the other hand, from the viewpoint that the lens material can be provided with flexibility and water wettability without impairing oxygen permeability and lipid contamination resistance, a general formula:

H

I

H ₂ C = CC-0-CH ₂ -CH-CH ₂ -R ' ₁

II I O OH

(Wherein, R ′ i represents a perfluoroalkyl group having 3 to 15, preferably 3 to 8, and more preferably 4 to 6 carbon atoms) a fluoroalkyl acrylate having a hydroxyl group represented by the formula: preferable.

The siloxane macromonomer (A) and the lower fatty acid vinyl ester

The amount of (B) and, if necessary, the silicon-containing monomer (C) should be adjusted so that the lens material has sufficient flexibility and mechanical strength and oxygen permeability. When (C) is not used, it is desirable that (A) Z (B) is 30Z70 or more, preferably 50Z50 or more, and that the lens material is given sufficient shape recovery and hydrophilicity. The ratio is preferably 90 to 10 or less, more preferably 80 to 20 or less.

In addition, when the gayne-containing monomer (C) is used, the ratio ((A) / (C) (weight ratio)) of the siloxane macromonomer (A) and the silicon-containing monomer (C) is determined to improve shape recovery. In order to impart sufficient mechanical strength to the lens material without lowering it, the ratio is preferably at least 20/80, preferably at least 25/75, and the lens material must have sufficient oxygen permeability. In order to be provided, the ratio is preferably 90/10 or less, and more preferably 8020 or less. The siloxane macromonomer (A) and the lower fatty acid vinyl ester

The amounts of (B) and the silicon-containing monomer (C) and the fluorine-containing monomer (D) used as required are determined based on the amount of siloxane macromonomer (A), lower fatty acid vinyl ester (B), monomer

In order for the effect of (C) to be sufficiently exhibited, the total amount of the siloxane macromonomer (A), the lower fatty acid vinyl ester (B), and the monomer containing gayne (C) and the monomer containing fluorine ( D) and percentage ((A),

It is desirable that the total amount Z (D) (weight ratio) of (B) and (C) is not less than 2080, preferably not less than 40/60, and that the lens material has sufficient resistance to lipid contamination. In order to be provided, it is desirable that the ratio is 90/10 or less, preferably 85/15 or less.

The polymer component may further contain a crosslinkable compound (E) having two or more polymerizable groups, if necessary.

Representative examples of the crosslinkable compound (E) include, for example, ethylene glycol di

(Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, aryl (meth) acrylate, vinyl (meth) acrylate , Trimethylolpropane tri (meth) acrylate, methyl acryloyloxyethyl acrylate, divinylbenzene, diaryl phthalate, diaryl adipate, diethylene glycol diaryl ether, triallyl isocyanurate, α-methylene-1-N-vinylpyrroli Don, 4-vinyl benzyl

(Meth) acrylate, 3-vinylbenzyl (meth) acrylate, 2, 2-bis (ρ_ (meth) acryloyloxyphenyl) hexafluorop mouthpan, 2, 2-bis (m_ (meth) acryloyl Oxyphenyl) hexafluoropropane, 2,2-bis (o— (meth) acryloyloxy Phenyl) hexafluoropropane, 1,4-bis (2_ (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2- (meta) acryloyloxyhexaflu 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) Pill) benzene, 1,3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyisopropyl) benzene, etc. These can be used alone or in combination of two or more.

Among the crosslinkable compounds (E), ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, which have a large effect of imparting optical properties and mechanical strength to the lens material and are easy to handle. Preferred are diaryl adipate and diethylene glycol diaryl ether, and particularly preferred are ethylene glycol di (meth) acrylate and dimethylene glycol diaryl ether.

The content of the crosslinkable compound (E) in the polymerization component is at least 0.01% by weight, preferably at least 0.05% by weight, in order to sufficiently impart optical properties and mechanical strength to the lens material. % Or more, and while imparting mechanical strength to the lens material, it is preferably 15% by weight or less, more preferably 10% by weight or less, in order to eliminate the possibility that the flexibility is reduced. desirable.

In the preparation of the lens material, the polymerization reaction is usually carried out by generating radicals on an active unsaturated group, such as a thermal polymerization method or a photopolymerization method, which will be described later, in a polymerization component whose kind and amount are appropriately adjusted. A radical polymerization initiator, a photosensitizer and the like are added according to the radical polymerization method to be used in the above.

Representative examples of the radical polymerization initiator include, for example, azobisbisoptilonitrile, azobisdimethylvaleronitrile, benzoyl peroxyl Thermal polymerization initiators such as peroxides, t-butyl hydride peroxides, and member oxides; methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, Benzoin-based photopolymerization initiators such as benzoin-n-butyl ether; 2-hydr-1-oxy-2-methyl-1-phenylpropane-1-one, p- ^ ヒドロキシ sopropyl α-hydroxyisobutylphenone, p-t -Butyltrichloroacetophenone, 2,2-dimethoxy-l-2-phenylacetophenone, H, dichloro-l-4-phenoxyacetophenone, N, N-N-N-tetraethyl-1,4-diaminobenzophenone, etc. Polymerization initiator; 1-hydroxyc Hexyl phenyl ketone; 1-phenyl-1,2-propanedione 1-2_ (o-ethoxycarbonyl) oxime; thioxanthone-based photopolymerization initiators such as 2_clothoxyxanthone and 2_methylthioxanthone; dibenzosvalon 2-ethylanthraquinone; benzophenone acrylate; benzophenone; benzyl and the like.

The photosensitizer alone is not activated by irradiation with ultraviolet light, but when used together with a photoinitiator, functions as a cocatalyst and exerts an effect superior to that when the photoinitiator is used alone. . Examples of such photosensitizers include amines such as 1,2-benzoanthraquinone キ, n-butylamine, di-n-butylamine, and triethylamine; tri-n-butylphosphine, arylthiourea, and s-benzene. Diisothiuronium_p-toluenesulfuric acid, getylaminoethyl methacrylate, and the like. The radical polymerization initiator, the photosensitizer and the like may be used by appropriately selecting one or more of them. These are used in an amount of about 0.002 to 2 parts, preferably about 0.01 to 1 part, based on 100 parts by weight (hereinafter referred to as "parts") of the total amount of the polymerization components. . In the radical polymerization method, only the polymerization component and the radical polymerization initiator or the photosensitizer may be subjected to polymerization, but for example, a diluent may be used in order to further improve the compatibility between the polymerization components. Good.

Representative examples of diluents include alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol; ketones such as acetone and methylethyl ketone; ethers such as getyl ether and tetrahydrofuran. These can be used alone or as a mixture of two or more.

Among the diluents, alcohols having 1 to 6 carbon atoms are preferable, and n-propanol, n-butanol, and n_pentanol are particularly preferable in terms of excellent solubility of the polymerization component.

The mixing ratio of the polymerization component and the diluent is determined by setting the weight ratio of the polymerization component and the diluent (polymerization component Z diluent) to 910 in order to sufficiently dissolve the polymerization component in the diluent. Below, it is desirable that it is preferably not more than 80 Z 20. Further, in order to eliminate the possibility that the obtained polymer becomes cloudy, the optical properties are reduced, or the mechanical strength is insufficient, the weight ratio is preferably 30/70 or more, preferably 50/50 or more. It is desirable that

The lens material can be manufactured by any known manufacturing method.However, in order to make the best use of the performance of the obtained lens material, the polymer component and, if necessary, The diluent is injected into a mold consisting of a mold corresponding to the shape of the front surface of the soft contact lens and a mold corresponding to the shape of the rear surface of the lens, and then sealed. It is preferable to prepare a polymer by performing the process. (4) After injecting a mixture of a polymerization component and a diluent if necessary, a polymerization reaction is performed to produce a polymer. The method of such a polymerization reaction is not particularly limited, and an ordinary method can be employed. As a method of the polymerization reaction, for example, a mixture of the polymerization component containing the radical polymerization initiator and, if necessary, a diluent is first mixed with, for example, 30 to 60 for several hours to several 10 hours. A method of heating and polymerizing, and then sequentially raising the temperature to about 120 to 140 over several hours to several hours to complete the polymerization (thermal polymerization method); A method of irradiating a light beam having a wavelength corresponding to the absorption band of the activation of the initiator to perform polymerization (photopolymerization method), a method of performing polymerization by combining a thermal polymerization method and a photopolymerization method, and the like can be mentioned. Among these, the photopolymerization method is preferred in that polymerization can be performed in a short time.

When the above-mentioned thermal polymerization method is used, heating may be performed in a thermostatic chamber or a thermostatic chamber, or electromagnetic waves such as microwaves may be irradiated, and the heating may be performed stepwise. When the photopolymerization method is used, the photosensitizer may be further added.

The polymer thus obtained can be desorbed from the mold 铸 to obtain a lens material.

The lens material may be subjected to mechanical processing such as cutting and polishing as necessary.

The lens material may be subjected to a hydrolysis treatment for the purpose of introducing a chemical bond with the coating agent.

The hydrolysis treatment means that a unit derived from a lower fatty acid vinyl ester (B) which can be decomposed by hydrolysis is alkali-treated with an alkaline compound described later or acid-treated with, for example, sulfuric acid to obtain vinyl alcohol. For a compound having an acrylic acid derivative structure, acrylic acid can be obtained by hydrolysis. However, the latter hydrolysis treatment by acid treatment has the disadvantages that the reaction speed is slow, it is difficult to obtain a uniform product, and side reactions occur. Yes. By such a hydrolysis treatment, a functional group can be introduced into the lens material without significantly increasing the water content.

Examples of the alkaline compound used in the alkaline treatment include ammonium, alkali metal hydroxides and alkaline earth metal hydroxides. Specific examples of such an alkaline compound include, for example, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Since these alkaline compounds are mainly solid, they are preferably dissolved in, for example, water, alcohols, ethers, etc., and used as an alkaline solution for the hydrolysis treatment.

Examples of the alcohols include methanol, ethanol, propanol, and butyl alcohol, and examples of the ethers include getyl ether and tetrahydrofuran.

Among the aqueous solutions of the alkaline compounds used in the hydrolysis treatment, those using alcohols are preferable. In order to proceed the hydrolysis treatment more efficiently, the concentration is preferably 0.01%. An aqueous methanol solution of sodium hydroxide of about 1 mol liter is preferable. Particularly, the aqueous methanol solution has a mixing ratio of methanol and water (methanol Z water (volume ratio)) of 10/90 to 90/10. Are preferred.

The hydrolysis treatment is carried out by immersing the polymer in the above solution or a solution of an acidic compound.

There is no particular limitation on the temperature of the hydrolysis treatment, and it is generally desirable to set the temperature at about 0 to 100, preferably at about 10 to 70.

The hydrolysis treatment time cannot be determined unequivocally because it varies depending on the type of alkaline compound or acidic compound, the concentration of alkaline compound or acidic compound, the temperature of the hydrolysis treatment, etc. In order to improve the effectiveness effectively, the time should be at least 0.1 hour, preferably at least 0.5 hour. In addition, there is a possibility that transparency may decrease due to cloudiness or the like, mechanical strength may decrease too much, making it unsuitable as a contact lens, and it may take too much time to deteriorate workability. In order to eliminate it, it is desirable that the time be 30 hours or less, preferably 15 hours or less.

The hydrolyzed lens material may be boiled for several hours, for example, in physiological saline (0.9% aqueous sodium chloride solution).

Examples of the method of coating the surface of the ophthalmic lens body with the coating agent of the present invention include the following three methods, but are not limited thereto.

(1) Dissolve the block copolymer and, if necessary, the catalyst in a solvent such as dimethylformamide, dichloromethane, 1,2-dichloromethane, etc., in which the block copolymer is soluble, and immerse the ophthalmic lens body in the solvent. How to coat by doing.

(2) A method in which the surface of the ophthalmic lens body is regularly coated by immersing or pulling it out into the spreading layer in which the block copolymer and, if necessary, the catalyst are spread.

(3) A method in which a powdery block copolymer is mixed with a catalyst, and this mixture is applied to the ophthalmic lens body and reacted by heating to perform coating.

As the catalyst, in (1) and (2), for example, a combination of dipropyl carbodiimide and 1-hydroxy-7-azabenzotriazole or a mixture of dicyclohexyl carbodiimide and N-hydroxybenzotriazole Preferably, p-toluenesulfonate is used in (3).

The thickness of the coating of the block copolymer on the surface of the ophthalmic lens body is between 0.1 and 100 A, preferably between 5 and 50 OA. If the thickness is less than 0.1 A, the effect of the coating tends not to be obtained. Also, 1 0 If it exceeds 0 OA, there is a tendency that substrate properties such as oxygen permeability are impaired.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples are for illustrative purposes only and are not intended to limit conditions, technical scope, and the like.

Examples 1-4

(N ^E - force Rupobenzokishi -L one lysine N "- carboxy anhydride (Synthesis of N CA))

3. 5 X 1 (J- ² moles of New ^epsilon - a force Rupobenzokishi -L- lysine, and heated to 60, the sufficiently dried in tetrahydrofuran is reacted with 0.33 moles of triphosgene, New ^£ - Power Lupobenzoxy-L-lysine Ν CA was obtained.

(Synthesis of L-leucine N ^a- lipoxylic anhydride (NCA))

1. 3 X 10- ¹ mol of L- leucine, and heated to respectively 6, in sufficiently dried in tetrahydrofuran, is reacted with Torihosuge emissions of 0.33 mol, L - was obtained leucine NCA.

(Synthesis of block copolymer)

The molecular weight of polyethylene glycol (terminal amino group PE G) having an amino group at the terminal (M) and the amount, and N ^E - carbobenzoxy one L - the amount of lysine NC A and L bite leucine NC A, Table 1 Shown in Dimethylformamide solution of polyethylene glycol (terminal amino group PE G) with a terminal amino group, New ^epsilon - carbobenzoxy -L- dimethylformamide mixed solution of lysine NC Alpha and L- leucine NC Alpha dropwise, Thereafter, the mixture was stirred at room temperature for 2 days.

The resulting polymer hydrobromide (HB r) N ^E by reaction with acetic acid solution - Deprotection of Amino groups carbobenzoxy -L- lysine NC A, to obtain a di-block copolymer. table 1

(Polymerization of ophthalmic lens materials)

31 parts by weight of siloxane macromonomer having the structure shown below, 21 parts by weight of tris (trimethylsiloxy) silylpropyl acrylate, 28 parts by weight of vinyl acetate, 20 parts by weight of 3-perfluoro-2-hydroxypropylacrylate 0.8 part by weight of diethylene glycol diaryl ether, 0.2 part by weight of 2-hydroxy-2-methyl-1-phenylpropane-one-one, and 0.2 part by weight of a monomer mixture liquid are filled in a polypropylene mold, and ultraviolet rays ( Ophthalmic lens material was obtained by exposure to main wavelength: 360 nm, irradiation intensity: 10 mWZcm ² ) for 10 minutes.

Structural formula of siloxane macromonomer:

(Introduction of functional groups on the surface of ophthalmic lens materials)

The ophthalmic lens material was immersed in 4 0.5 mol ZL sodium hydroxide solution (50% methanol + 50% purified water) for 240 minutes to introduce carboxyl groups on the surface of the ophthalmic lens material.

(Coating of ophthalmic lens material)

The block copolymer 0. 10 g, was dissolved in dimethylformamide 3mL, 3. 2 X 10- ⁴ mole of 1, 3-diisopropyl Cal positive imide and 3. 2 X 10- ⁴ mole of 1-hydroxy - 7 § The The pretreated ophthalmic lens material was immersed in a solution mixed with 2 mL of dimethyltriamide solution containing benzotriazole at room temperature for 7 days to obtain a coated ophthalmic lens material. Examples 5 to 7

According to the conditions described in Table 2, the same ophthalmic lens material as that obtained in Example 1 was added in a 0.5 mol / L sodium hydroxide solution (50% methanol + 50% purified water). Then, a coated ophthalmic lens material was obtained in the same manner as in Example 1, except that a functional group was introduced into the surface of the ophthalmic lens material. Table 2

Pretreatment conditions for ophthalmic lens materials

Comparative Example 1

The ophthalmic lens material obtained in Example 1 was immersed in a 3% solution of polyethylene glycol having a terminal amino group and having a molecular weight of 2000 and having a molecular weight of 2000 for 7 days at room temperature. Comparative Example 2

2. 5 X 10- ⁴ mole to n- Kishiruamin dimethylformamide solvent In the liquid, 6. 0 X 10- ³ mole of N ^£ - carbonitrile and benzoxycarbonyl _L- lysine NC A 2. dropwise 6 X 10- 3 mole of L- leucine NCA dimethylformamide mixed solution, then at room temperature Stir for 2 days.

The resulting polymer hydrobromide (HB r) N ^E by reaction with acetic acid solution - carbobenzoxy -L Deprotection of Amino groups one lysine NC A, to obtain a block copolymer. A coating ophthalmic lens material was obtained in the same manner as in Example 1 except that this block copolymer was used.

Comparative Example 3

1. in dimethyl formamide solvent solution of 2 X 10- ⁴ Kishiruamin moles to n-, 1. 4X 10- ³ moles of N ^E - carbonitrile and benzoxycarbonyl -L- lysine NC A 2. 9 X 10- ³ mole Of L-leucine NCA in dimethylformamide was added dropwise, followed by stirring at room temperature for 2 days.

The resulting polymer hydrobromide (HB r) N ^E by reaction with acetic acid solution - carbobenzoxy one L - Deprotection of Amino groups of lysine NC A, to obtain a block copolymer. A coated ophthalmic lens material was obtained in the same manner as in Example 1 except that this block copolymer was used.

Test method

(Residue number and N ^E -L-Lenpobenzoxy-L-Lysine to L-Leucine NCA ratio)

Examples 1-4 and Comparative Example 1 to 3 residues and N hydrophobic block of the resulting block copolymer ^epsilon - carbobenzoxy _ L-lysine and L one leucine ratio of NCA is, NMR measurements (Superconducting FT-NM R, manufactured by Varian, GEMI NI 2000/400 BB). Table 3 shows the results.

The following evaluation was performed for each of the obtained coated ophthalmic lens materials. Table 4 shows the evaluation results. (Surface analysis by infrared spectrophotometer (IR) (Amido / Sio)) The surface analysis of the thoroughly cleaned ophthalmic lens material was performed by infrared spectrophotometer (Perkin E 1mer S pectra One), and measured by attenuated total reflection spectroscopy (ATR method). The coverage was calculated from the ratio of the peak derived from the amide bond at 1650 cm- ¹ and the peak intensity derived from the SiO bond at 1010 cm- ¹ .

Am id oZS i O ratio (%) = 1650 cnT ¹ peak height

Peak height of / 1010 cm- ¹ The progress of the hydrolysis treatment was confirmed for the carbonyl group by an increase in the peak derived from the carbonyl group near 1560 cm- ¹ .

(Surface analysis by X-ray photoelectron spectroscopy (XPS))

Using an X-ray photoelectron spectrometer (JPS-9000MX, manufactured by JEOL Ltd.), irradiate MgKa rays as X-rays at 10 kV and 10 mA output to obtain fluorine, oxygen, nitrogen, carbon and silicon. The coated ophthalmic lens material was measured at an analyzer passing energy of 10 eV (resolution 0.9 eV) and compared with the ophthalmic lens material before coating.

(Measurement of contact angle)

Using a goniometer type contact angle measuring device (G-1 manufactured by Elma Optical Co., Ltd.), the contact angle was measured by a droplet method.

(Measurement of oxygen permeability coefficient (Dk))

Using a GTG (GAT to GAS) ANALYZER (manufactured by REHDERDE VELOPMENT COMPANY), measurement was performed at a measurement time of 2 minutes and at a temperature of 35 X :, and the obtained measurement value was standardized by ISO 9912-2. EX (Dk = 64 × 10 ¹¹ (cm ² sec) · (m LO (mL−mmHg))) was used to calculate the Dk value. Table 3

Table 4

Remarks

* ° Use n-hexylamine which is hydrophobic instead of hydrophilic block

' ²⁾ +: 1650cm- ¹ The peak height derived from the amide bond near ¹ is less than 20% of the peak height derived from the SiO bond near lOlOcnr ^1.

++: The peak height derived from the amide bond around 1650 cm- ¹ is 20% or more and less than 50% of the peak height derived from the SiO bond around 1010 cm- ¹ H +: The peak height derived from the amide bond around 1650 cm- ¹ Peak height is more than 50% of the peak height derived from SiO bond near 1010cm

' ³⁾ +: 1560cm— The peak height from the liponyl group near ¹ slightly increased

++: Moderate increase in peak height due to carbonyl group around 1560cm- ¹

+++: The peak height derived from the carbonyl group around 1560cnfi greatly increases

' ⁴⁾ 1: Significantly lower than before treatment

→: No change before and after processing

' ^{5) No} peak derived from amide bond or coating thickness detected

Test results

(- ratio of carbobenzoxy -L- lysine and L- leucine NC A residues and N ^e)

Residues and New ^epsilon of proc copolymer obtained in Examples 1 to 4 and Comparative Example 1 to 3 - the ratio of the force Rupobenzokishi -L- lysine and L- leucine NC A, shown in Table 3.

(Surface analysis by infrared spectrophotometer (IR))

In Examples 1 to 4 and Comparative Examples 2 and 3 showed a peak derived from an amide bond near 1650 cm one near and 1530 cm- ¹ with ^1. In Comparative Example 1, no calculation could be performed because no amide bond was observed in the ophthalmic lens material.

(Surface analysis by infrared spectrophotometer (IR))

The coverage was calculated from the intensity ratio of the peak derived from the amide bond at 1650 cm- ¹ and the peak derived from the Sio bond at 1010 cm- ^{1. In} Examples 1-4 and 6 and Comparative Examples 2 and 3, The peak height derived from the amide bond around 1650 cm- ¹ was 20% or more and less than 50% of the peak height derived from the Sio bond around 1010 cm- ¹ .

For the carbonyl group, the progress of the hydrolysis treatment was confirmed by an increase in the peak derived from the carbonyl group near 1560 cm- ¹ .

(Surface analysis by X-ray photoelectron spectroscopy (XPS))

In Examples 1 to 4 and Comparative Examples 2 and 3, 20% of the silicon atoms present on the ophthalmic lens material surface before the treatment were reduced to 5% or less. In Comparative Example 1, the gay atom ratio did not change before and after the coating treatment. (Measurement of contact angle)

In Examples 1 to 4, the contact angle was clearly smaller than in Comparative Example 1 (untreated lens), and the water wettability was improved. Also, instead of hydrophilic blocks, hydrophobic In Comparative Examples 2 and 3 using sex n-hexylamine, no change in the contact angle was observed.

(Measurement of oxygen permeability coefficient (Dk))

The oxygen transmission coefficient before and after coating the ophthalmic lens material described in the examples with the block copolymer obtained in the example 1 was measured. Oxygen permeability coefficient before ^{^{coating, 201 X 10- 11 (cm 2}} sec) · (mL0 2 / (m L · mmHg)), oxygen permeability after coating is 1 90 X 1

(cm ² / sec) · - a _{(mL0 2 / (mL mmH g} )), before and after coatings, changes in the oxygen permeability coefficient was observed.

Therefore, in the surface treatment of the ophthalmic lens material, particularly the surface treatment of the ophthalmic lens material mainly containing silicon and a fluorine-containing component, the coating agent of the present invention makes it possible to reduce the abundance of gayene in the outermost layer by a thin layer. It has become possible to reduce it efficiently. As a result, it became possible to improve only the problematic surface characteristics without deteriorating the lens characteristics caused by the silicon and fluorine components. Industrial applicability

When a polypeptide is used as the hydrophobic block in the coating agent of the present invention, it is difficult for the hydrophilic block bonded to the terminal of the polypeptide main chain to enter the α-helix helical structure. Therefore, it can always be arranged on the outermost layer.

With the coating agent of the present invention, a water-free hydrophobic block is laminated as a barrier layer on the lens surface to prevent adsorption to the corneal surface, and a hydrophilic block is laminated on the barrier layer. By doing so (two layers), a hydrophilic layer can be efficiently and uniformly introduced on the ophthalmic lens surface. Also, if the contact lens surface is coated with two layers, Since the hydrophobic layer remains even during evaporation, the phase between the ophthalmic lens material and the cornea can be suppressed, and adsorption of the contact lens to the cornea can be prevented.

Furthermore, the polypeptide in the hydrophobic block adopts a helix structure, whereby the side chains of the polypeptide are oriented outward, and the outwardly directed side chains are bonded to the functional groups present on the lens surface. However, since the number of binding sites is larger than that at the end of the polypeptide, the stability is increased, and the functional group present on the polypeptide side chain is chemically bonded to the functional group on the ophthalmic lens surface. The stability of the obtained coating layer on the surface of the ophthalmic lens is high, and the ophthalmic lens with low releasability can be obtained. Thereby, peeling of the coating layer due to daily care can be prevented. In addition, since the polypeptide has a rigid α-helix structure and its molecular gap is small, it does not allow proteins and lipids to pass therethrough, thereby preventing contamination of the ophthalmic lens.

Claims

The scope of the claims

1. A coating agent for an ophthalmic lens surface containing a block copolymer having a hydrophilic block bonded to at least one end of a main chain of a hydrophobic block, wherein an ophthalmic lens is provided on a side chain of the hydrophobic block. A coating agent having at least one functional group capable of binding to a functional group present on the surface.

The coating agent according to claim 1, wherein the hydrophobic block is a polypeptide containing an amino acid having at least one functional group in a side chain as a component.

3. The coating according to claim 2, wherein said amino acid is selected from the group consisting of arginine, asparagine, aspartic acid, cystine, glutamine, glutamic acid, histidine, lysine, proline, serine, threonine, tributofan and tyrosine. Agent.

4. The coating agent according to claim 2, wherein the polypeptide further comprises a hydrophobic amino acid.

5. The coating agent according to claim 4, wherein the hydrophobic amino acid is selected from the group consisting of alanine, isoleucine, leucine, methionine, fenilalanine, proline, cystine, tributofan, cinnamate and parin.

6. Claims 2 and 3, wherein the residue ratio of the amino acid having at least one functional group in the side chain to the hydrophobic amino acid in the polypeptide is 20:80 to 100: 0. Item 6. The coating agent according to item 4 or 5.

7. The coating agent according to claim 6, wherein the amino acid having at least one functional group in a side chain is lysine, and the hydrophobic amino acid is leucine.

8. The claim wherein the polypeptide consists of 15 to 100 residues of amino acids. 7. The coating agent according to paragraph 2, 3, 3, 4, 5, 6, or 7.

9. The method according to claim 1, wherein the hydrophilic block comprises a homopolymer of a monomer selected from the group consisting of ethylene glycol, N-vinylpyrrolidone, dimethylacrylamide, methacrylic acid and sugar, or a copolymer thereof. 9. The coating agent according to paragraphs 2, 3, 4, 5, 5, 6, 7, or 8.

10. The degree of polymerization of the hydrophilic block is from 10 to 500, wherein the degree of polymerization of the hydrophilic block is 10 to 500. Item 10. The coating agent according to item 8 or 9.

11. Ophthalmic lens body and claims 1, 2, 3, 4, 5, 6, 7, 7, 8, 9 or 10 An ophthalmic lens having a coating layer formed with the coating agent as described above.

12. The contact lens body and claims 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 Contact lens having a coating layer formed of a coating agent.

13. The contact lens according to claim 12, wherein the contact lens body is made of a copolymer containing a silicon element and Z or fluorine element.