JP4832910B2 - Ophthalmic lens surface coating agent and ophthalmic lens obtained thereby - Google Patents

Description

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

  The ophthalmic lens uses a monomer containing silicon and fluorine for the purpose of improving the oxygen permeability, and it is possible to realize a remarkable oxygen permeability by these components. However, these components are low in biocompatibility, especially in materials using silicon-containing components as the main component, have low hydrophilicity, and further cause an adsorption phenomenon on the corneal surface due to their unique adhesion. Low biocompatibility is a problem, and various surface treatments are being studied to solve this problem.

  For example, Patent Document 1 discusses the introduction of a coating layer by graft polymerization by providing an inorganic or organic bulk material having a radical polymerization initiator moiety covalently bonded to the surface of a lens substrate containing fluorine and silicone. ing. However, the surface coating by graft polymerization has a problem that it is difficult to control the coating layer and the target coating layer cannot be formed. Moreover, the polymer to be immobilized was composed of only a hydrophilic polymer, and the biocompatibility was not sufficiently improved.

  Further, Patent Document 2 discloses a contact lens that is excellent in hydrophilicity and antifouling property, and can easily remove the dirt even if the surface is soiled. The hydrophilic polymer having a cross-linked structure is obtained by applying a hydrophilic coating liquid composition containing a hydrophilic graft polymer obtained by introducing a hydrophilic polymer side chain to a trunk polymer having a functional group to be obtained and a crosslinking agent, followed by heating and drying. It is disclosed to obtain a contact lens in which a conductive layer is formed. Further, as a second method, a polymer having a functional group whose hydrophilicity / hydrophobicity is changed by heat, acid or radiation on the surface of the base material, and having a structure that can be directly bonded to the base material surface by a chemical bond. A polymer compound-containing layer in which a compound is present and a predetermined hydrophilic / hydrophobic region is formed by changing the hydrophilicity / hydrophobicity of the surface by heating, supplying acid or irradiating radiation to the predetermined region of the surface. The contact lens provided with is examined. However, the purpose is to cross-link the polymer three-dimensionally on the substrate surface, and there is no intention to control the directionality of the polymer to be introduced.

  Patent Document 3 also shares on the surface a receptor carbohydrate to which one or more additional carbohydrates selected from the group consisting of a specific carbohydrate and an oligosaccharide containing one or more of the carbohydrates are enzymatically bound. Ophthalmic moldings, such as contact lenses or all types of eye prostheses, that include organic bulk materials that are bonded together are being considered. However, a coating layer composed only of a hydrophilic component typified by a sugar chain is insufficient in function as a barrier layer, such as antifouling property and prevention of interaction with living tissue such as cornea. In addition, the effect of the hydrophilic component cannot be sufficiently exhibited, and thus the coating layer on the ophthalmic lens substrate is insufficient.

  In addition, US Pat. No. 6,057,031 discloses an ophthalmic device comprising a bulk material and a hydrophilic coating having one or more wettable surfaces capable of holding a continuous layer of aqueous fluid thereon. Although sugar is coated as a protective coating, the surface improving property is not improved only by the hydrophilic component as in Patent Document 3.

  In order to solve these problems, Patent Document 5 is obtained by coating the surface of an article with a polymerizable composition comprising a hydrophilic monomer and a hydrophobic monomer, and then copolymerizing the composition by irradiation. A coating is disclosed. However, since the polymerization reaction is performed by graft polymerization, the reproducibility of the structural design is not good, and the surface improvement property is not sufficient.

  Patent Document 6 discloses a coating applied to the surface of an ophthalmic lens having a structure in which a block having a hydrophobic block and a hydrophilic block and a reactive group capable of binding to a functional group on the ophthalmic lens surface is bonded. Agents are disclosed. However, in Patent Document 1, the coating agent and the ophthalmic lens surface are fixed by covalently bonding (peptide bond) an amino group in the coating agent and a carboxyl group on the ophthalmic lens surface using a catalyst. There was a point to be improved, such as the need to remove the used catalyst after immobilization.

JP-T-2004-536633 JP 2003-177360 A Special table 2003-503160 gazette JP 7-501256 A JP-A-7-179811 International Publication No. 2005/68571

  An object of the present invention is to provide a biocompatible ophthalmic lens surface coating agent having both hydrophilic and hydrophobic properties that provide lubricity in both dry and wet states. It is another object of the present invention to provide an ophthalmic lens that is excellent in fixing an ophthalmic lens body and a coating layer having a coating layer formed of the coating agent and that has excellent surface modification characteristics.

That is, according to the present invention, the hydrophilic block B is bonded to one end of the main chain of the hydrophobic block A, and the functional group present on the surface of the ophthalmic lens can be bonded to the other end of the hydrophobic block A. The present invention relates to an ophthalmic lens surface coating agent containing a block copolymer represented by the following formula, to which a block C having at least one reactive group X having an alkoxysilane or halogenated silane skeleton is bonded.
B-A-C

  It is preferable that the hydrophobic block A has a fluorine atom-containing substituent.

  The fluorine atom-containing substituent is preferably a C 1-20 alkyl group containing fluorine.

  The hydrophilic block B preferably contains a homopolymer of (meth) acrylate monomers containing at least one sugar chain or a copolymer thereof.

  The hydrophilic block B preferably further contains a homopolymer of a monomer selected from the group consisting of polyethylene glycol, N-vinylpyrrolidone, dimethylacrylamide, and methacrylic acid, or a copolymer thereof.

  The degree of polymerization of the hydrophilic block B is preferably 5 to 5000.

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

  The ophthalmic lens is preferably a contact lens.

  The contact lens body is preferably made of a copolymer containing silicon element and / or fluorine element.

  Since the coating agent of the present invention has a functional group X having an alkoxysilane or halogenated silane skeleton that can be bonded to a functional group present on the surface of an ophthalmic lens, it can be bonded to a substrate by silicon-containing group bonding without using a catalyst. Can be firmly fixed. In addition, since the surface treatment is performed with the coating agent of the present invention, an ophthalmic lens and a contact lens that solve various problems that occur between living tissues such as improved adhesion to lipids, improved hydrophilicity, and improved wearing feeling are provided. Can be provided.

The present invention relates to an alkoxysilane in which a hydrophilic block B is bonded to one end of the main chain of the hydrophobic block A, and a functional group present on the surface of the ophthalmic lens can be bonded to the other end of the hydrophobic block A. Alternatively, the present invention relates to a coating agent for an ophthalmic lens surface containing a block copolymer represented by the following formula, to which a block C having at least one reactive group X having a halogenated silane skeleton is bonded.
B-A-C

  The coating agent of the present invention uses a block copolymer synthesized according to the molecular design, and can introduce a coating layer having a target structure with good reproducibility.

  The hydrophobic block A in the present invention preferably has a fluorine atom-containing substituent. By having a fluorine atom-containing substituent, it induces unfavorable interaction with living tissues such as the cornea, such as surface characteristics of lens base materials mainly composed of silicone, stickiness, and movement on the surface of the eye. The properties such as can be further improved.

  Examples of the hydrophobic block A having a fluorine atom-containing substituent include a fluorine polymer comprising a fluorinated alkyl monomer obtained by copolymerization with a monomer containing a hydroxyl group or an amino group. Of these, the fluorine atom-containing substituent is preferably a fluorine-containing alkyl group having 1 to 20 carbon atoms from the viewpoint of forming a regular arrangement required for the surface modifying substance. The carbon number is more preferably 3-18, and still more preferably 5-15.

  The coating agent of the present invention has a structure in which a hydrophilic block B is bonded to one end of any one of the hydrophobic blocks A. By setting the hydrophilic block B as a terminal, the hydrophilic block can be present on the surface side of the ophthalmic lens. As a result, resistance to contamination is imparted, surface wettability is improved, and wearing feeling is improved. There are advantages such as.

  As the hydrophilic block B, any linear polymer that does not self-crosslink can be used. However, a (meth) acrylate monomer containing at least one sugar chain from the viewpoint of lipid resistance and improved hydrophilicity. Homopolymers (for example, polysaccharides, hyaluronic acid, chondroitin sulfate, dermatan sulfate, glucose, etc.) or copolymers thereof are preferred, and glucose is preferably used. In addition, from the viewpoint of moisture retention, safety as a medical device, and biocompatibility, the hydrophilic block B used in the present invention is a homopolymer of a (meth) acrylate monomer containing the at least one sugar chain. Alternatively, the copolymer may be a homopolymer of a monomer selected from the group consisting of ethylene glycol, N-vinylpyrrolidone, dimethylacrylamide, and methacrylic acid, or a hydrophilic block made of these copolymers. More preferred.

  The degree of polymerization of the hydrophilic block is preferably 5 to 5000, more preferably 15 to 1000, and still more preferably 20 to 500. If the degree of polymerization of the hydrophilic block is less than 5, the effect as the hydrophilic portion tends to be insufficient. Moreover, when it exceeds 5000, it tends to be difficult to form a block structure with a hydrophobic polymer.

  The ratio of the hydrophilic block to the hydrophobic block in the block copolymer is preferably 1: 1000 to 1000: 1 by weight ratio of hydrophilic block: hydrophobic block, more preferably 1: 500 to 500: 1. It is. If the hydrophilic block: hydrophobic block has less hydrophilic blocks than 1: 1000 by weight, the surface hydrophilicity tends to be insufficient. In addition, when the hydrophobic block: hydrophobic block is less than 1000: 1 by weight, the hydrophobic block is buried in the hydrophilic block, the function of which is hindered, or the chemistry with the ophthalmic lens surface. The reaction tends to be inhibited.

  By the hydrophobic block A and the hydrophilic block B, it is possible to form two or more multilayer films that form a hydrophilic layer on the hydrophobic layer at least on the surface of the ophthalmic lens substrate.

  The coating agent of the present invention is a block C having at least one reactive group X having an alkoxysilane or halogenated silane skeleton capable of binding to a functional group present on the surface of the ophthalmic lens at the other end of the hydrophobic block A. Has a bonded structure.

  By having the reactive group X that can bond to the functional group present on the surface of the ophthalmic lens, it can be strongly bonded to the ophthalmic lens substrate. Since the reactive group X has an alkoxysilane or halogenated silane skeleton, a reaction without a catalyst becomes possible.

The reactive groups X with an alkoxysilane or halogenated silane skeleton, for _{example, -Si (-O-CH 3)} 3, -Si (-O-CH 2 CH 3) 3, -Si (CH 3) 2 Cl From the viewpoint of reactivity and safety, —Si (—O—CH ₃ ) ₃ is preferably used.

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

  Here, in the present invention, the ophthalmic lens means a contact lens, an intraocular lens, or the like.

  The ophthalmic lens body is preferably made of a copolymer containing silicon element and / or fluorine element. For example, a siloxane macromonomer (A) having two or more active unsaturated groups and a number average molecular weight of 2000 to 100,000, a lower fatty acid vinyl ester (B), a silicon-containing monomer (C), a fluorine-containing monomer (D) and Examples thereof include a siloxane-containing polymer selected from the group consisting of the crosslinkable compound (E) and obtained by polymerizing a polymerization component containing silicon element and / or fluorine element.

  The active unsaturated group of the siloxane macromonomer (A) is an active unsaturated group that can be used for radical polymerization, such as (meth) acryloyl group, vinyl group, allyl group, (meth) acryloyloxy. Group, vinyl carbamate group and the like.

  The number average molecular weight of the siloxane macromonomer (A) is 2000 or more, preferably 2500 or more from the viewpoint of the flexibility of the lens material, and is 100,000 or less, preferably 50000 or less from the viewpoint of the shape recoverability of the lens material. It is desirable to be.

  In general, siloxane macromonomers are inferior in water wettability, and by themselves, many have relatively insufficient mechanical strength. Therefore, the siloxane macromonomer (A) used in the present invention has the formula:

で表わされるウレタン基を有するものが好ましく、その個数は平均２個以上、好ましくは平均４個以上、また平均２０個以下、好ましくは平均１４個以下であることが望ましい。

Those having a urethane group represented by formula (1) are preferred, and the number thereof is preferably 2 or more on average, preferably 4 or more on average, and 20 or less on average, preferably 14 or less on average.

In the present invention, the siloxane macromonomer (A) is particularly represented by the general formula (I-1):
^{A 1 - (- U 1 -S} 1 -) n -U 2 -S 2 -U 3 -A 2 (I-1)
[Wherein, A ¹ and A ² each independently represents 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 glycol group having 1 to 20 carbon atoms,
U ¹ is a diurethane group that forms a urethane bond with adjacent A ¹ and S ¹ or S ¹ and S ¹ ,
U ² is a diurethane group that forms a urethane bond with adjacent A ¹ and S ² or S ¹ and S ² ,
U ³ is a diurethane group that forms a urethane bond with S ² and A ^{2 on} both sides,
S ¹ and S ² are each independently of the formula:

（式中、Ｒ¹およびＲ²はそれぞれ独立して炭素数１〜２０のアルキレン基、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸はそれぞれ独立してフッ素原子で置換されていてもよい直鎖状、分岐鎖状もしくは環状の炭素数１〜２０のアルキル基または式：Ａ³−Ｕ⁴−Ｒ¹−Ｏ−Ｒ²−（式中、Ａ³は活性不飽和基、炭素数１〜２０のアルキレン基を有する活性不飽和基もしくは炭素数１〜２０のアルキレングリコール基を有する活性不飽和基、Ｕ⁴は隣りあうＡ³およびＲ¹とウレタン結合を形成するジウレタン性基を示し、Ｒ¹およびＲ²は前記と同じ）で表わされる基、ｘは１〜１５００の整数、ｙは０または１〜１４９９の整数、ｘ＋ｙは１〜１５００の整数を示す）で表わされる基、
ｎは０または１〜１０の整数を示す］
で表わされるマクロモノマーや、
一般式（Ｉ−２）：
Ｂ¹−Ｓ³−Ｂ¹ （Ｉ−２）
［式中、Ｂ¹はウレタン結合を有する活性不飽和基、
Ｓ³は式：

Wherein 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. they may be straight chain, branched chain or cyclic alkyl group, or a group of the formula of 1 to 20 carbon ^{atoms: a 3 -U 4 -R 1 -O} -R 2 - ( wherein, 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 glycol group having 1 to 20 carbon atoms, U ⁴ is a diurethane that forms a urethane bond with adjacent A ³ and R ¹ R ¹ and R ² are the same as described above), x is an integer of 1 to 1500, y is 0 or an integer of 1 to 1499, and x + y is an integer of 1 to 1500). Group,
n represents 0 or an integer of 1 to 10]
A macromonomer represented by
Formula (I-2):
B ¹ -S ³ -B ¹ (I-2)
[Wherein B ¹ is an active unsaturated group having a urethane bond,
S ³ is the formula:

（式中、Ｒ¹およびＲ²はそれぞれ独立して炭素数１〜２０のアルキレン基、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷およびＲ⁸はそれぞれ独立してフッ素原子で置換されていてもよい直鎖状、分岐鎖状もしくは環状の炭素数１〜２０のアルキル基または式：Ａ³−Ｕ⁴−Ｒ¹−Ｏ−Ｒ²−（式中、Ａ³は活性不飽和基、炭素数１〜２０のアルキレン基を有する活性不飽和基もしくは炭素数１〜２０のアルキレングリコール基を有する活性不飽和基、Ｕ⁴は隣りあうＡ³およびＲ¹とウレタン結合を形成するジウレタン性基を示し、Ｒ¹およびＲ²は前記と同じ）で表わされる基、ｘは１〜１５００の整数、ｙは０または１〜１４９９の整数、ｘ＋ｙは１〜１５００の整数を示す）で表わされる基を示す］
で表わされるマクロモノマーが好ましく用いられる。

Wherein 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. they may be straight chain, branched chain or cyclic alkyl group, or a group of the formula of 1 to 20 carbon ^{atoms: a 3 -U 4 -R 1 -O} -R 2 - ( wherein, 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 glycol group having 1 to 20 carbon atoms, U ⁴ is a diurethane that forms a urethane bond with adjacent A ³ and R ¹ R ¹ and R ² are the same as described above), x is an integer of 1 to 1500, y is 0 or an integer of 1 to 1499, and x + y is an integer of 1 to 1500). Show group]
Is preferably used.

In the general formula (I-1), examples of the active unsaturated group represented by A ¹ and A ² include a (meth) acryloyl group, a vinyl group, an allyl group, and a (meth) acryloyloxy group as described above. And vinyl carbamate groups. Among these, an acryloyloxy group and a vinyl group are preferable, and an acryloyloxy group is particularly preferable from the viewpoint that the lens material can be provided with better flexibility and is excellent in copolymerizability with other polymerization components.

  Moreover, when the said active unsaturated group has an alkylene group or an alkylene glycol group, carbon number of this alkylene group or alkylene glycol group becomes like this. Preferably it is 1-20, and it is more preferable that it is 1-10.

Further, in the general formula (I-1), formulas represented by S ¹ and S ² :

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、ｘおよびｙは前記と同じ）で表わされる基において、Ｒ¹およびＲ²は好ましくは炭素数１〜５のアルキレン基、Ｒ³〜Ｒ⁸は好ましくは炭素数１〜５のアルキル基であり、またかかるＲ³〜Ｒ⁸を示す式：Ａ³−Ｕ⁴−Ｒ¹−Ｏ−Ｒ²−中のＡ³は、前記例示と同様の活性不飽和基を示し、かかる活性不飽和基がアルキレン基またはアルキレングリコール基を有する場合、アルキレン基やアルキレングリコール基の炭素数は１〜２０が好ましく、１〜１０であることがより好ましい。またｘは１〜５００の整数、ｙは０または１〜４９９の整数、ｘ＋ｙは１〜５００の整数であることが好ましい。

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , x and y are the same as above), R ¹ and R ² are preferably The alkylene group having 1 to 5 carbon atoms, R ^{3 to} R ⁸ is preferably an alkyl group having 1 to 5 carbon atoms, and also represents such R ^{3 to} R ⁸ : A ³ —U ⁴ —R ¹ —O— A ^{3 in} R ² — represents the same active unsaturated group as in the above examples, and when the active unsaturated group has an alkylene group or an alkylene glycol group, the alkylene group or alkylene glycol group has 1 to 20 carbon atoms. Is preferable, and it is more preferable that it is 1-10. X is preferably an integer of 1 to 500, y is 0 or an integer of 1 to 499, and x + y is preferably an integer of 1 to 500.

  Furthermore, in general formula (I-1), it is preferable that n is 0 or an integer of 1-5.

On the other hand, in the general formula (I-2), examples of the active unsaturated group having a urethane bond represented by B ¹ include (meth) acryloyl isocyanate group, (meth) acryloyloxy isocyanate group, allyl isocyanate group, vinyl And benzyl isocyanate group. In addition, the group represented by S ³ in the general formula (I-2) is the same as the group represented by S ¹ and S ^{2 in the} general formula (I-1).

Among the macromonomers, since the effect of imparting flexibility and mechanical strength represented by shape recoverability is large, the 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
(Wherein A ¹ , A ² , U ¹ , U ² , U ³ , S ¹ and S ² are the same as described above, and n ′ represents an integer of 1 to 4). :

で表わされる基、ａは２０〜５０の整数を示す）
で表わされるマクロモノマーが好ましい。

A represents an integer of 20 to 50)
Is preferred.

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

（式中、Ｒは水素原子またはハロゲン原子で置換されていてもよい炭素数１〜１５のアルキル基を示す）で表わされる化合物が好ましい。かかる化合物の具体例としては、たとえばギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、モノクロロ酢酸ビニル、モノフルオロ酢酸ビニル、トリクロロ酢酸ビニル、トリフルオロ酢酸ビニルなどがあげられ、これらは単独でまたは２種以上を混合して用いることができる。

A compound represented by the formula (wherein R represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a hydrogen atom or a halogen atom) is preferred. Specific examples of such compounds include, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl monochloroacetate, vinyl monofluoroacetate, vinyl trichloroacetate. And vinyl trifluoroacetate. These can be used alone or in admixture of two or more.

  Among the lower fatty acid vinyl esters (B), vinyl acetate, vinyl propionate and vinyl pivalate are preferable, and vinyl acetate is particularly preferable because of the effect of imparting shape recoverability and hydrophilicity.

  Representative examples of the silicon-containing monomer (C) include, for example, pentamethyldisiloxanylmethyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylpropyl (meth) acrylate, tris ( Trimethylsiloxy) silylpropyl (meth) acrylate, mono [methylbis (trimethylsiloxy) siloxy] bis (trimethylsiloxy) silylpropyl (meth) acrylate, tris [methylbis (trimethylsiloxy) siloxy] silylpropyl (meth) acrylate, trimethylsilylmethyl ( (Meth) acrylate, trimethylsilylpropyl (meth) acrylate, methylbis (trimethylsiloxy) silylethyltetramethyldisiloxanylmethyl ( Silicon) such as acrylate, tetramethyltriisopropylcyclotetrasiloxanylpropyl (meth) acrylate, tetramethyltriisopropylcyclotetrasiloxybis (trimethylsiloxy) silylpropyl (meth) acrylate, trimethylsiloxydimethylsilylpropyl (meth) acrylate Containing (meth) acrylates; for example, tris (trimethylsiloxy) silylstyrene, methylbis (trimethylsiloxy) silylstyrene, dimethylsilylstyrene, trimethylsilylstyrene, tris (trimethylsiloxy) siloxanyldimethylsilylstyrene, [methylbis (trimethylsiloxy) siloxanyl] Dimethylsilylstyrene, pentamethyldisiloxanylstyrene, heptamethyltrisiloxanylstyrene , Nonamethyltetrasiloxanyl styrene, pentadecamethyl hepacyloxanyl styrene, heneicosamethyl decacyloxanyl styrene, heptacosamethyl tridecacyloxanyl styrene, hentriacontamethylpentadecylacyloxanyl styrene, trimethyl Siloxypentamethyldisiloxymethylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, [tris (trimethylsiloxy) siloxanyl] bis (trimethylsiloxy) silylstyrene, methylbis (heptamethyltrisiloxy) silylstyrene, tris [methylbis (trimethyl Siloxy) siloxy] silylstyrene, trimethylsiloxybis [tris (trimethylsiloxy) siloxy] silylstyrene, heptakis (trimethylsiloxy) trisiloxa Nylstyrene, tris [tris (trimethylsiloxy) siloxy] silylstyrene, [tris (trimethylsiloxy) hexamethyltetrasiloxy] [tris (trimethylsiloxy) siloxy] trimethylsiloxysilylstyrene, nonakis (trimethylsiloxy) tetrasiloxanylstyrene, methylbis General formulas such as (tridecamethylhexasiloxy) silylstyrene, heptamethylcyclotetrasiloxanylstyrene, heptamethylcyclotetrasiloxybis (trimethylsiloxy) silylstyrene, tripropyltetramethylcyclotetrasiloxanylstyrene:

（式中、ｐは１〜１５の整数、ｑは０または１、ｒは１〜１５の整数を示す）で表わされるケイ素含有スチレン誘導体などがあげられ、これらは単独でまたは２種以上を混合して用いることができる。

(Wherein, p is an integer of 1 to 15, q is 0 or 1, and r is an integer of 1 to 15), and the like. These may be used alone or in combination of two or more. Can be used.

  Among the silicon-containing monomers (C), a silicon-containing (meth) acrylate is preferable because it has a greater effect of simultaneously imparting high oxygen permeability and flexibility, particularly shape recovery, to the lens material. Siloxy) silylpropyl acrylate is particularly preferred.

  Representative 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-hexafluoro-t- Hexyl (meth) acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl (meth) acrylate, 2,2,3,3,4,4-hexa Fluorobutyl (meth) acrylate, 2,2,2,2 ', 2', 2'-hexafluoroisopropyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobuty (Meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) In addition to such acrylates of the general formula:

（式中、Ｒ₁は炭素数３〜１５のフルオロアルキル基、Ｒ₂は水素原子またはメチル基を示す）で表わされる、たとえば３−パーフルオロブチル−２−ヒドロキシプロピル（メタ）アクリレート、３−パーフルオロヘキシル−２−ヒドロキシプロピル（メタ）アクリレート、３−パーフルオロオクチル−２−ヒドロキシプロピル（メタ）アクリレート、３−（パーフルオロ−３−メチルブチル）−２−ヒドロキシプロピル（メタ）アクリレート、３−（パーフルオロ−５−メチルヘキシル）−２−ヒドロキシプロピル（メタ）アクリレート、３−（パーフルオロ−７−メチルオクチル）−２−ヒドロキシプロピル（メタ）アクリレートなどのフルオロアルキル（メタ）アクリレートがあげられる。

(Wherein R ₁ represents a fluoroalkyl group having 3 to 15 carbon atoms, R ₂ represents a hydrogen atom or a methyl group), for example, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3- Perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- And fluoroalkyl (meth) acrylates such as (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate and 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate. .

  Among these, fluoroalkyl acrylate is preferable because it has a particularly large effect of imparting flexibility to the lens material among oxygen permeability, flexibility, and lipid contamination resistance.

  Furthermore, although fluorine compounds usually can provide oxygen permeability and resistance to lipid contamination, many are poor in water wettability. On the other hand, from the standpoint that flexibility and water wettability can be imparted to the lens material without impairing oxygen permeability and resistance to lipid contamination, the general formula:

（式中、Ｒ′₁は炭素数３〜１５、好ましくは３〜８、さらに好ましくは４〜６のパーフルオロアルキル基を示す）で表わされる水酸基を有するフルオロアルキルアクリレートが好ましい。

(Wherein R ′ ₁ represents a perfluoroalkyl group having 3 to 15 carbon atoms, preferably 3 to 8 carbon atoms, more preferably 4 to 6 carbon atoms).

  When the siloxane macromonomer (A) and the lower fatty acid vinyl ester (B) are used, in order to impart sufficient flexibility and mechanical strength and oxygen permeability to the lens material, (A) / (B ) Is 30/70 or more, preferably 50/50 or more, and in order to impart sufficient shape recovery and hydrophilicity to the lens material, the ratio is 90/10 or less, preferably Is desirably 80/20 or less.

  Further, the ratio ((A) / (C) (weight ratio)) between the siloxane macromonomer (A) and the silicon-containing monomer (C) when the siloxane macromonomer (A) and the silicon-containing monomer (C) are used. In order to impart sufficient mechanical strength to the lens material without deteriorating the shape recoverability, it is desirable that the ratio is 20/80 or more, preferably 25/75 or more. In order to provide oxygen permeability, the ratio is 90/10 or less, preferably 80/20 or less.

  When the siloxane macromonomer (A) and the fluorine-containing monomer (D) are used, the siloxane macromonomer (A) and fluorine are used in order that the effect of the siloxane macromonomer (A) is sufficiently expressed in the lens material. The ratio of the monomer (D) to be contained is preferably 20/80 or more, preferably 40/60 or more, and in order to impart particularly sufficient lipid resistance to the lens material, the ratio is preferably It is 90/10 or less, preferably 85/15 or less.

  Representative examples of the crosslinkable compound (E) include those having two or more polymerizable groups, such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxydiethyl acrylate, divinylbenzene, diallyl phthalate, Adipic acid diallyl, diethylene glycol diallyl ether, triallyl isocyanurate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinyl Benzyl (meth) acrylate, 2,2-bis (p- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis (m- (meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis ( o- (meth) acryloyloxyphenyl) hexafluoropropane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxy) Isopropyl) benzene, 1,2-bis (2- (me And acryloyloxyisopropyl) benzene. These may be used alone or in admixture of two or more.

  Among the crosslinkable compounds (E), ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and adipic acid are effective in imparting optical properties and mechanical strength to the lens material and are easy to handle. Diallyl and diethylene glycol diallyl ether are preferred, and ethylene glycol di (meth) acrylate and diethylene glycol diallyl ether are particularly preferred.

  The content of the crosslinkable compound (E) in the polymerization component is 0.01% by weight or more, preferably 0.05% by weight or more, in order to impart sufficient optical properties and mechanical strength to the lens material. In addition, although mechanical strength is imparted to the lens material, in order to eliminate the possibility that the flexibility is lowered, the amount is desirably 15% by weight or less, preferably 10% by weight or less.

  In the preparation of the lens material, a polymerization reaction is usually performed by first generating radicals in the active unsaturated groups, such as a thermal polymerization method and a photopolymerization method, which will be described later, in a polymerization component whose type 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.

  Representative examples of the radical polymerization initiator include thermal polymerization initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, t-butyl hydroperoxide, cumene peroxide; methyl orthobenzoyl benzoate Benzoin-based photopolymerization initiators such as methylbenzoylformate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-n-butyl ether; 2-hydroxy-2-methyl-1-phenylpropane-1 -One, p-isopropyl-α-hydroxyisobutylphenone, pt-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α, α-dichloro- -Phenone photopolymerization initiators such as phenoxyacetophenone and N, N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) ) Oxime; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosubalon; 2-ethylanthraquinone; benzophenone acrylate; benzophenone;

  The photosensitizer is not activated by ultraviolet irradiation alone, but when used together with a photoinitiator, it functions as a co-catalyst and exhibits a better effect than when a photoinitiator is used alone. . Examples of such a photosensitizer include 1,2-benzoanthraquinone, amines such as n-butylamine, di-n-butylamine, and triethylamine; tri-n-butylphosphine, allylthiourea, s-benzylisothiuro. Examples thereof include nium-p-toluenesulfinate and diethylaminoethyl methacrylate.

  A radical polymerization initiator, a photosensitizer, or the like may be appropriately selected from one or more of these. The amount used is desirably about 0.002 to 2 parts, preferably about 0.01 to 1 part, with respect to 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 photosensitizer may be used for polymerization. For example, a diluent may be used in order to further improve the compatibility between the polymerization components. .

  Typical examples of the diluent include alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. A mixture of seeds or more can be used.

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

  The mixing ratio of the polymerization component and the diluent is such that the weight ratio of the polymerization component to the diluent (polymerization component / diluent) is 90/10 or less so that the polymerization component is sufficiently dissolved in the diluent. , Preferably 80/20 or less. Further, the weight ratio is preferably 30/70 or more, preferably 50/50 or more, in order to eliminate the possibility that the obtained polymer becomes cloudy and optical characteristics are deteriorated or mechanical strength is insufficient. .

  The lens material can be manufactured by any known manufacturing method, but in particular, it makes it possible to make the best use of the performance of the obtained lens material. The diluent is poured into a mold consisting of two molds corresponding to the shape of the front surface of the soft contact lens and the shape corresponding to the shape of the rear surface of the lens and sealed, and then a polymerization reaction is carried out to form the polymer. It is preferable to prepare the lens.

  After injecting a mixture of a polymerization component and, if necessary, a diluent into a mold, a polymerization reaction is performed to produce a polymer. The method for the polymerization reaction is not particularly limited, and a usual method can be employed.

  As a polymerization reaction method, for example, a mixture of a polymerization component in which the radical polymerization initiator is blended and a diluent as necessary is first heated at, for example, about 30 to 60 ° C. for several hours to several tens hours. A method of polymerizing and then gradually raising the temperature to about 120 to 140 ° C. for several hours to several tens of hours to complete the polymerization (thermal polymerization method), absorption of activation of radical polymerization initiators such as ultraviolet rays, for example Examples thereof include a method of polymerizing by irradiating light having a wavelength corresponding to the band (photopolymerization method), a method of performing polymerization by combining a thermal polymerization method and a photopolymerization method. Among these, the photopolymerization method is preferable in that the polymerization can be performed in a short time.

  When the thermal polymerization method is used, it may be heated in a thermostatic chamber or a thermostatic chamber, or may be irradiated with electromagnetic waves such as microwaves, and the heating may be performed stepwise. Moreover, when using the said photopolymerization method, you may further add the said photosensitizer.

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

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

  For the purpose of introducing a chemical bond with the coating agent into the lens material, a hydrolysis treatment can be performed.

  The hydrolysis treatment means that a unit derived from a lower fatty acid vinyl ester (B) that can be decomposed by hydrolysis is alkali-treated with an alkaline compound described later or acid-treated with, for example, sulfuric acid to give vinyl alcohol. Alternatively, a compound having an acrylic acid derivative structure can be converted to acrylic acid by hydrolysis. However, the latter hydrolysis treatment by acid treatment has a drawback that the reaction rate is slow, uniform products are difficult to obtain, and side reactions occur, so that the hydrolysis treatment by alkali treatment is desirable. By this hydrolysis treatment, functional groups can be introduced into the lens material without increasing the water content so much.

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

  Examples of the alcohols include methanol, ethanol, propanol, butanol and the like, and examples of the ethers include diethyl ether and tetrahydrofuran.

  Among the alkaline solutions of alkaline compounds used for the hydrolysis treatment, those using alcohols are preferable, and water having a concentration of 0.01 to 1 mol / liter is particularly preferable in order to proceed the hydrolysis treatment more efficiently. A methanol aqueous solution of sodium oxide is preferable, and a methanol aqueous solution having a mixing ratio of methanol and water (methanol / water (volume ratio)) of 10/90 to 90/10 is particularly preferable.

  The hydrolysis treatment is performed by immersing the polymer in the alkali solution or an acidic compound solution.

  The temperature of the hydrolysis treatment is not particularly limited, and is generally set to 0 to 100 ° C, preferably about 10 to 70 ° C.

  The hydrolysis treatment time varies depending on the type of alkaline compound or acidic compound, the concentration of the alkaline compound or acidic compound, the temperature of the hydrolysis treatment, etc., and cannot be determined unconditionally, but the hydrophilicity of the lens material is effective. In order to improve the contact resistance, it is desirable that the time be 0.1 hour or longer, preferably 0.5 hour or longer. Further, the transparency may be lowered due to white turbidity, or the mechanical strength is excessively lowered. In addition to being an inappropriate material for a lens, it is desirable that the time be 30 hours or less, preferably 15 hours or less, in order to eliminate the risk of overworking and a loss of workability.

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

  Examples of the method for 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 or 1,2-dichloromethane in which the block copolymer is soluble, and immerse the ophthalmic lens body in the block copolymer. Coating method.
(2) A method of regularly coating the surface by immersing or pulling out the ophthalmic lens main body in a development layer where a block copolymer and, if necessary, a catalyst are developed.
(3) A method in which a powdery block copolymer and a catalyst are mixed, and the mixture is applied onto an ophthalmic lens body and reacted by heating to coat.

  In (1) and (2), for example, a combination of dipropylcarbodiimide and 1-hydroxy-7-azabenzotriazole or a combination of dicyclohexylcarbodiimide and N-hydroxybenzotriazole is preferably used as the catalyst. Then, it is preferable to use p-toluenesulfonic acid.

  The coating thickness of the block copolymer on the surface of the ophthalmic lens body is 0.1 to 1000 mm, preferably 5 to 500 mm. When the thickness is less than 0.1 mm, there is a tendency that the effect of coating cannot be obtained. On the other hand, when it exceeds 1000%, substrate properties such as oxygen permeability tend to be impaired.

  The ophthalmic lens surface coating agent of the present invention and the ophthalmic lens obtained thereby will now be described in more detail by way of specific examples. The following examples are for illustrative purposes only and are not intended to limit conditions and technical scope.

Production Example 1
0.4 mol D-glucose was dissolved in 40 mL pyridine, and 0.6 mL vinyl methacrylate was added. The reaction was started by adding 2 g of protease enzyme (trade name Proleather-FG, manufactured by Amano Enzyme Co., Ltd.) and allowed to react at 25 ° C. for 40 hours. The enzyme was removed by filtration to complete the reaction, and the filtrate was vacuum dried to obtain a tan oil. The oil was recrystallized in an ethyl acetate / methanol solution to obtain 2.92 g of a white powder. It was identified as 6-0-methacryloylglucose by infrared spectroscopy and NMR.

Example 1
10 mL of dimethylformamide, 10 nmol of 6-O-methacryloylglucose and 50 mg of benzyl peroxide were added to a 100 mL three-necked flask in a nitrogen atmosphere, and the mixture was stirred using a magnetic stirrer. The reaction was carried out at 70 ° C. for 5 hours.

  Next, 10 nmol of 2- (perfluoroheptyl) ethyl acrylate was added to the three-necked flask and the reaction was continued for another 3 hours.

  2 mmol of 3- (trimethoxysilyl) propyl acrylate was added to modify the terminal portion. Chloroform was added to complete the reaction. The product was recovered using ethyl acetate. The yield was 65%. It was identified as amphiphilic block copolymer poly-6-O-methacryloylglucose-2- (perfluoroheptyl) ethyl acrylate (Glu-PF1) by infrared spectroscopy, ultraviolet-visible spectroscopy and NMR.

Example 2
A reaction similar to Example 1 was carried out except that 20 mmol of 6-O-methacryloyl glucose and 30 mg of benzyl peroxide were used, and a reaction product with a yield of 50% was recovered. It was identified as an amphiphilic block copolymer 6-O-methacryloylglucose-2- (perfluoroheptyl) ethyl acrylate (Glu-PF2) by infrared spectroscopy, ultraviolet-visible spectroscopy and NMR.

Example 3
A reaction similar to Example 1 was carried out except that 50 mmol of 6-O-methacryloyl glucose and 20 mg of benzyl hydroxide were used, and a reaction product with a yield of 50% was recovered. It was identified as an amphiphilic block copolymer 6-O-methacryloylglucose-2- (perfluoroheptyl) ethyl acrylate (Glu-PF5) by infrared spectroscopy, ultraviolet-visible spectroscopy and NMR.

Production Example 2
A reaction was carried out in the same manner as in Production Example 1 except that 0.4 mol of chondroitin sulfate and 0.6 mol of vinyl methacrylate were used to obtain 3 g of white powder. It was identified as chondroitin sulfate methacrylate by infrared spectroscopy, ultraviolet-visible spectroscopy and NMR.

Example 4
A reaction was carried out in the same manner as in Example 1 except that 50 mmol of chondroitin sulfate methacrylate and 20 mg of benzyl peroxide were used, and a reaction product having a yield of 54% was recovered. It was identified as amphiphilic block copolymer chondroitin sulfate methacrylate-2- (perfluoroheptyl) ethyl acrylate (Con-PF1) by infrared spectroscopy, ultraviolet-visible spectroscopy and NMR.

Example 5
Preparation of ophthalmic lens material 31 parts by weight of a 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-hydroxypropyl acrylate A monomer mixed solution consisting of 0.8 parts by weight of diethylene glycol diallyl ether and 0.2 parts by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one was filled in a polypropylene mold, and ultraviolet rays (main wavelength: An ophthalmic lens material was obtained by exposure to 360 nm, irradiation intensity: 10 mW / cm ² ) for 10 minutes.

Structural formula of siloxane macromonomer:

  Furthermore, the obtained ophthalmic lens was pretreated by immersing it in a 0.5 mol / L sodium hydroxide methanol / water mixed solution (methanol / water = 1/1) at 35 ° C. for 6 hours.

Example 6
A 5% by weight methylformamide solution of the coating agent Glu-PF1 obtained in Example 1 was prepared. The ophthalmic lens produced in Example 5 was immersed for 12 hours in a nitrogen atmosphere. The ophthalmic lens taken out after completion of the reaction was washed with methanol and water to remove unreacted copolymer from the surface.

Example 7
A 5% by weight methylformamide solution of the coating agent Glu-PF2 obtained in Example 2 was prepared. The lens material manufactured in Example 5 was immersed for 12 hours in a nitrogen atmosphere. The ophthalmic lens taken out after completion of the reaction was washed with methanol and water to remove unreacted copolymer from the surface.

Example 8
A 5 wt% methylformamide solution of the coating agent Glu-PF5 obtained in Example 3 was prepared. The ophthalmic lens produced in Example 5 was immersed for 12 hours in a nitrogen atmosphere. The ophthalmic lens taken out after completion of the reaction was washed with methanol and water to remove unreacted copolymer from the surface.

Example 9
A 5% by weight methylformamide solution of the coating agent Con-PF1 obtained in Example 4 was prepared. The ophthalmic lens produced in Example 5 was immersed for 12 hours in a nitrogen atmosphere. The ophthalmic lens taken out after completion of the reaction was washed with methanol and water to remove unreacted copolymer from the surface.

Comparative Example 1
A block polymer was obtained in the same manner as in Example 1 except that 3- (trimethoxysilyl) propyl acrylate was not used. A 5% by weight methylformamide solution of the obtained block polymer was prepared and reacted with an ophthalmic lens in the same manner as in Example 6. The ophthalmic lens taken out after completion of the reaction was washed with methanol to remove unreacted copolymer from the surface.

  The following evaluation was performed using the ophthalmic lenses having the coating layers obtained in Examples 1 to 9 and Comparative Example 1.

(Surface analysis by total reflection attenuation spectroscopy (ATR method))
The surface analysis of the ophthalmic lenses obtained in Examples 5 to 9 was thoroughly cleaned by the ATR method using a Fourier transform infrared spectrophotometer. When the analysis results were compared, the ophthalmic lens surfaces obtained in Examples 6 to 9 compared to the ophthalmic lens obtained in Example 5 had a decrease in the peak around 1280 cm ⁻¹ attributed to carbonyl, increase in the vicinity of the peak near 1204cm ^-1 and around 1149cm ^-1 fluorine from was observed. Further, the ophthalmic lens surface obtained in Comparative Example 1 was not different from the surface analysis by the ART method in the ophthalmic lens not treated with the coating agent obtained in Example 5.

(Surface analysis by X-ray photoelectron spectrometer (XPS))
Using an X-ray photoelectron spectrometer (JPS-9000MX, manufactured by JEOL Ltd.), irradiating MgKα rays as X-rays at an output of 10 kV and 10 mA, and passing through the analyzer for fluorine, oxygen, nitrogen, carbon and silicon The surface of the ophthalmic lens having the coating layer obtained in Examples 5 to 9 was measured at 10 eV (resolution: 0.9 eV) and compared with the surface of the ophthalmic lens before coating.

  When the ophthalmic lens surface analysis obtained in Examples 5 to 9 was performed using an X-ray photoelectron analyzer, the ophthalmic samples of Examples 6 to 9 were compared to Example 5 in which about 15% of the silicon component was present. The abundance ratio of the silicon component on the lens surface was reduced to about 10%.

(Measurement of oxygen permeability coefficient (Dk))
Using GTG (GAT to GAS) ANALYZER (manufactured by REHDERDEVELOPMENT COMPANY), the measurement time was 2 minutes and the temperature was measured at 35 ° C., and the obtained measurement value was normalized to ISO 9912-2 Menicon EX (Dk Dk value was determined by conversion using = 64 × 10 ⁻¹¹ (cm ² / sec) · (mLO ₂ / (mL · mmHg)).

The oxygen transmission coefficient of the ophthalmic lens produced in Example 5 is 200 × 10 ⁻¹¹ (cm ² / sec) · (mLO ₂ / (mL · mmHg)), and the oxygen transmission coefficient of Example 6 is 185 × 10 ^{−. 11} (cm ² / sec) · (mLO ₂ / (mL · mmHg)), and the change in the oxygen permeability coefficient was slight before and after coating.

(Lipid adhesion)
The ophthalmic lens obtained in Example 5 is immersed in artificial eye oil (squalene, cholesterol, wax, cholesterol palmitate), shaken at 37 ° C. for 16 hours, and extracted with chloroform / methanol solution for 30 minutes. The lipid component in the extract was quantified by gas chromatography / mass spectrometry (GC / MS).

  The ophthalmic lens produced in Example 5 can reduce the lipid component adhering to an average of 15 μg / lens in Example 8 and up to 10 μg / lens compared to an average of 60 μg lipid component adhering. It has become possible.

  Therefore, without damaging the advantages of the ophthalmic lens main body mainly composed of a silicon component called gas permeability, the lipid adhesion, which is the biggest problem in the surface characteristics of the ophthalmic lens main body mainly composed of a silicon component, is achieved. By being able to reduce, it became possible to improve the function as an ophthalmic lens.

  The coating agent of the present invention can be applied to various ophthalmic lenses.

Claims (9)

An alkoxysilane or halogenated silane having a hydrophilic block B bonded to one end of the main chain of the hydrophobic block A and a functional group present on the surface of the ophthalmic lens to the other end of the hydrophobic block A An ophthalmic lens surface coating agent comprising a block copolymer represented by the following formula, to which a block C having at least one reactive group X having a skeleton is bonded.
B-A-C The coating agent according to claim 1, wherein the hydrophobic block A has a fluorine atom-containing substituent. The coating agent according to claim 2, wherein the fluorine atom-containing substituent is a C 1-20 alkyl group containing fluorine. The coating agent according to any one of claims 1 to 3, wherein the hydrophilic block B includes a homopolymer of a (meth) acrylate monomer containing at least one sugar chain or a copolymer thereof. The coating agent according to claim 4, wherein the hydrophilic block B further comprises a homopolymer of a monomer selected from the group consisting of polyethylene glycol, N-vinylpyrrolidone, dimethylacrylamide, and methacrylic acid, or a copolymer thereof. The coating agent according to any one of claims 1 to 5, wherein the degree of polymerization of the hydrophilic block B is 5 to 5000. The ophthalmic lens which has a coating layer formed with the ophthalmic lens main body and the coating agent in any one of Claims 1-6. The contact lens which has a coating layer formed with the contact lens main body and the coating agent in any one of Claims 1-6. The contact lens according to claim 8, wherein the contact lens body is made of a copolymer containing silicon element and / or fluorine element.