JPWO2010092686A1 - Ophthalmic lens having hydrophilic surface and method for producing ophthalmic lens - Google Patents

Abstract

A hydrophilization treatment method that enables favorable hydrophilization in a short treatment time under atmospheric pressure or reduced pressure without requiring heating or ultraviolet irradiation, and an ophthalmic lens having sustained hydrophilicity and a method for producing the same Is to provide. The surface is represented by a compound represented by the following general formula (1) (wherein R1 is H or CH3, X is -O- or -NH-, n1 is an integer of 1 to 10, and Y is a zwitterionic group). Hydrophilic ophthalmic lens, method for producing the same, and surface treatment method for an ophthalmic lens.

Description

  The present invention relates to an ophthalmic lens having a hydrophilic surface and a method for producing the same. More specifically, the present invention relates to an ophthalmic lens excellent in water wettability, surface lubricity, water retention and stain resistance, and a method for producing the same. Of the ophthalmic lenses, especially contact lenses, a silicone component is often included in order to impart oxygen permeability to the base material. Recently, hybrid hydrogels with silicone added to soft lenses are becoming mainstream. The problems of surface water repellency and lipid contamination are becoming apparent. Therefore, there has been a demand for a durable treatment method and an ophthalmic lens that can solve such disadvantages and can provide the above-described effects. Moreover, in terms of manufacturing, a method that can be processed more simply and in a short time has been desired.

Various methods for hydrophilizing the surface of the ophthalmic lens as described above have been studied as shown in Patent Documents 1 to 3 below. However, in any of the methods described in the patent documents, the substrate surface is activated with plasma or the like and then immersed in a desired hydrophilic component, but is irradiated with ultraviolet rays, heated, or started as a polymerization aid. A process such as adding an agent is incorporated, which is very complicated. Furthermore, the processing time is long.
JP 2001-337298 (Menicon): relating to surface treatment. However, ultraviolet rays are irradiated when the ionic monomer is immersed. Japanese Patent No. 3324156 (Seiko Epson): relates to surface treatment. Graft polymerization of phosphorylcholine monomer. JP-A-7-72430 (Japanese fats and oils, MPC): relates to surface treatment. A vinyl monomer having a phospholipid-like structure is graft-polymerized.

  Therefore, as a result of intensive studies, the present inventors have obtained the following general formula (1):

（式中、Ｒ¹はＨまたはＣＨ₃、Ｘは−Ｏ−または−ＮＨ−、ｎ₁は１〜１０の整数、Ｙは双性イオン基）で表わされる（メタ）アクリル系の双性イオンモノマーを用いた場合に、その水溶液に浸漬するだけで、何ら加熱や紫外線照射などを必要とせず、しかも極わずかな反応時間でレンズ基材にグラフト重合せしめることを見出したのである。さらには、双性イオンモノマー水溶液に浸漬する前の基材表面を活性化させる手段において、大気圧下または減圧下において、わずかな処理時間で、良好な親水化を可能とするとともに、その耐久性も非常に良好であることを見出したのである。

(Wherein R ¹ is H or CH ₃ , X is —O— or —NH—, n ₁ is an integer of ₁ to 10, and Y is a zwitterionic group). It has been found that when a monomer is used, it can be immersed in the aqueous solution and graft polymerization can be carried out on the lens substrate in a very short reaction time without requiring any heating or ultraviolet irradiation. Furthermore, as a means for activating the substrate surface before being immersed in the aqueous solution of the zwitterionic monomer, it is possible to achieve good hydrophilicity in a short treatment time under atmospheric pressure or reduced pressure, and its durability. Was also found to be very good.

  Therefore, the object of the present invention is to provide a hydrophilic treatment method that does not require heating, ultraviolet irradiation, or the like and enables good hydrophilic treatment in a short treatment time under atmospheric pressure or reduced pressure, as well as sustained hydrophilicity. To provide an ophthalmic lens and a manufacturing method thereof.

  The present invention provides the following.

[1]
An ophthalmic lens having a surface hydrophilized using the compound represented by the general formula (1).

[2]
The hydrophilization treatment includes a step of irradiating the ophthalmic lens with plasma and a step of immersing the ophthalmic lens irradiated with plasma in an aqueous solution of the compound represented by the general formula (1). The ophthalmic lens described.

[3]
The hydrophilization treatment includes a step of irradiating the ophthalmic lens with plasma and a step of immersing the ophthalmic lens irradiated with plasma in a 0.1 to 50% by weight aqueous solution of the compound represented by the general formula (1). [1] The ophthalmic lens according to [1].

[4]
The compound represented by the general formula (1) is represented by the following general formulas (I), (II), (III) and (IV):

（式（I）および（II）中、R₁はHまたはCH₃、ｎは1〜10）

(In the formulas (I) and (II), R ₁ is H or CH ₃ , and n is 1 to 10)

（式（III）および（IV）中、R₁はHまたはCH₃、ｎは1〜5）
で表される化合物からなる群から選ばれる少なくとも１種である、［１］〜［３］のいずれかに記載の眼用レンズ。

(In the formulas (III) and (IV), R ₁ is H or CH ₃ , and n is 1 to 5)
The ophthalmic lens according to any one of [1] to [3], which is at least one selected from the group consisting of compounds represented by:

[5]
The ophthalmic lens according to any one of [1] to [4], wherein the ophthalmic lens is an oxygen-permeable hard contact lens.

[6]
The ophthalmic lens according to [5], wherein the oxygen-permeable hard contact lens is made of a copolymer containing a compound represented by the following general formula (3) as a polymerization component.

（式中l は０または1、ｎおよびｍは1〜15の整数）
［７］
上記酸素透過性ハードコンタクトレンズが、一般式（3）で表わされる化合物以外に、フッ素含有（メタ）アクリル系モノマーと架橋モノマーを重合成分として含む共重合体からなる［６］記載の眼用レンズ。

(Where l is 0 or 1, n and m are integers of 1 to 15)
[7]
The ophthalmic lens according to [6], wherein the oxygen-permeable hard contact lens is made of a copolymer containing a fluorine-containing (meth) acrylic monomer and a crosslinking monomer as polymerization components in addition to the compound represented by the general formula (3). .

[8]
The ophthalmic lens according to any one of [1] to [4], wherein the ophthalmic lens is a hydrous soft contact lens containing a hydrogel containing silicone or a non-hydrous soft contact lens.

[9]
The ophthalmic lens according to [8], comprising a copolymer containing a compound represented by the following general formula (4) as a polymerization component.

［１０］
上記一般式（1）で表される化合物を用いて眼用レンズの表面を親水化処理する工程を含む眼用レンズの製造方法。

[10]
The manufacturing method of the ophthalmic lens including the process of hydrophilizing the surface of an ophthalmic lens using the compound represented by the said General formula (1).

[11]
The hydrophilization treatment step includes a step of irradiating the ophthalmic lens with plasma, and a step of immersing the ophthalmic lens irradiated with plasma in an aqueous solution of the compound represented by the general formula (1). [10] A method for producing the ophthalmic lens according to 1.

[12]
The hydrophilization treatment step includes a step of irradiating the ophthalmic lens with plasma, and a step of immersing the ophthalmic lens irradiated with plasma in a 0.1 to 50% by weight aqueous solution of the compound represented by the general formula (1). The method for producing an ophthalmic lens according to [10].

[13]
The compound represented by the above general formula (1) is represented by the above general formula (I), (II), (III) and (IV).
The method for producing an ophthalmic lens according to any one of [10] to [12], which is at least one selected from the group consisting of compounds represented by:

[14]
The method according to any one of [10] to [13], wherein the plasma irradiation is corona discharge under atmospheric pressure, the output is 1000 W or less, and the irradiation time is within 60 seconds.

[15]
The method according to any one of [10] to [13], wherein the plasma irradiation is glow discharge under reduced pressure, the output is 100 W or less, and the irradiation time is within 5 minutes.

[16]
The method according to any one of [10] to [13], wherein the immersion temperature is 5 to 60 ° C. and the immersion time is within 60 minutes in the immersion step.

[17]
The method according to any one of [10] to [13], wherein the time from the end of the plasma irradiation to the start of the immersion step is within 30 minutes.

[18]
An ophthalmic lens surface treatment method comprising a step of irradiating an ophthalmic lens with plasma and a step of immersing the ophthalmic lens irradiated with plasma in an aqueous solution of the compound represented by the general formula (1).

[19]
The surface treatment method for an ophthalmic lens according to [18], wherein the aqueous solution is a 0.1 to 50% by weight aqueous solution of the compound represented by the general formula (1).

  According to the present invention, since the hydrophilic zwitterionic monomer is graft-polymerized on the surface of the ophthalmic lens, not only water wettability of the surface, but also excellent surface lubricity, water retention, stain resistance, It has become possible to provide ophthalmic lenses.

It is a figure which shows the outline | summary of the apparatus for frictional force measurement.

The ophthalmic lens of the present invention is manufactured by a method including a step of hydrophilizing the surface of the ophthalmic lens using the zwitterionic compound represented by the general formula (1). In this method, the hydrophilization treatment step irradiates the ophthalmic lens with plasma, and an aqueous solution of the compound represented by the general formula (1), particularly 0.1-50 of the compound represented by the general formula (1). It is preferable to comprise a step of immersing the ophthalmic lens irradiated with plasma in a weight% aqueous solution. If the concentration of the compound represented by the general formula (1) is too low, the effect of the surface treatment is difficult to obtain. If the concentration of the compound represented by the general formula (1) is too high, the solution viscosity becomes high and solution preparation becomes difficult. In addition, an effect commensurate with the cost cannot be obtained in terms of cost effectiveness.
[Hydrophilic treatment agent]
In the present invention, the surface treatment of the ophthalmic lens is performed using the zwitterionic compound represented by the general formula (1) as a hydrophilic treatment agent. This zwitterionic compound is represented by the above general formulas (I), (II), (III) and (IV) from the viewpoints of antifouling effect, ease of synthesis, cost of raw materials, etc., and safety. It is preferable that it is at least 1 sort (s) chosen from the group which consists of a compound made.

  Specific examples of zwitterionic compounds are illustrated below. However, it is not limited to the following illustrations, and in the present invention, a compound having a similar structure can be used as long as it is represented by the general formula (1).

（上記式中、Ｒ¹はＨまたはＣＨ₃）
［親水化処理方法］
プラズマ照射は、例えば、大気圧下コロナ放電、減圧下グロー放電などにより行うことができる。プラズマ照射が大気圧下コロナ放電である場合、出力が1000W以下で照射時間が60秒以内であることが好ましく、出力が500W以下で照射時間が20秒以内であることがより好ましい。プラズマ照射が減圧下グロー放電である場合、出力が100W以下で照射時間が５分以内であることが好ましく、出力が40W以下で照射時間が1分以内であることがより好ましい。

(In the above formula, R ¹ is H or CH ₃ )
[Hydrophilic treatment method]
Plasma irradiation can be performed, for example, by corona discharge under atmospheric pressure or glow discharge under reduced pressure. When the plasma irradiation is corona discharge under atmospheric pressure, the output is preferably 1000 W or less and the irradiation time is preferably within 60 seconds, more preferably the output is 500 W or less and the irradiation time is within 20 seconds. When the plasma irradiation is glow discharge under reduced pressure, the output is preferably 100 W or less and the irradiation time is preferably within 5 minutes, more preferably the output is 40 W or less and the irradiation time is within 1 minute.

  Since the dipping process can be performed at room temperature, according to the present invention, the manufacturing process can be simplified. Moreover, since the immersion time can be carried out within 60 minutes, preferably within 30 minutes, more preferably within 10 minutes, the production method of the present invention has high production efficiency. The aqueous solution of the compound represented by the general formula (1) can be easily prepared by dissolving a predetermined amount of the compound represented by the general formula (1) in purified water such as deionized water or distilled water. If necessary, additives such as poly-N-vinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid, and other hydrophilic polymers, surfactants, and pH adjusters can be added to the aqueous solution.

[Eye lens material]
Examples of ophthalmic lens materials include silicon-containing monomers such as silicon-containing alkyl (meth) acrylates, silicon-containing styrene derivatives and polysiloxane macromonomers; fluorine-containing monomers such as fluorine-containing alkyl (meth) acrylates; hydroxyl-containing alkyl (meth) Hydrophilic monomers such as acrylate, dialkyl (meth) acrylamide, (meth) acrylic acid, N-vinyl lactam; alkyl (meth) acrylate, styrene, α-methylstyrene, alkyl-α-methyl for adjusting material hardness Use is made of a copolymer obtained by polymerizing a monomer such as styrene; a polymerization component containing a crosslinkable monomer having two or more polymerizable unsaturated double bonds by a normal polymerization method. In particular, in consideration of oxygen permeability and contamination resistance of the material itself, an ophthalmic lens material comprising a copolymer obtained by polymerizing a polymerization component containing a silicon-containing monomer and / or a fluorine-containing monomer is preferably used. It is done.

  When the ophthalmic lens is an oxygen permeable hard contact lens, the oxygen permeable hard contact lens is preferably made of a copolymer containing the general formula (3) as a polymerization component. The oxygen-permeable hard contact lens is more preferably composed of a copolymer containing a fluorine-containing (meth) acrylic monomer and a crosslinking monomer as polymerization components in addition to the compound represented by the general formula (3). When the ophthalmic lens is a hydrous soft contact lens containing a hydrogel containing silicone or a non-hydrous soft contact lens, the ophthalmic lens polymerizes the compound represented by the general formula (4). It preferably comprises a copolymer contained as a component.

  In the compound represented by the general formula (3), when 1 is 0 rather than 1, it is preferable because it is a compound that is easy to synthesize and is stable, and as n and m increase, the compound becomes soft and brittle. With respect to n and m, an ophthalmic lens material having a particularly preferred oxygen permeability, excellent hardness and hardness, and a high refractive index can be obtained when it is about 1 to 5.

  The straight chain and branched chain siloxane bonds can be used for the siloxane bond portion in the compound represented by the general formula (3), but the branched chain is harder than the straight chain. Since it becomes a thing, it is preferable.

  Examples of the compound represented by the general formula (3) include, for example, trimethylsilyl styrene, pentamethyldisiloxanyl styrene, heptamethyltrisiloxanyl styrene, nonamethyltetrasiloxanyl styrene, pentadecamethylheptacyloxa Nyl styrene, heneicosamethyl decasiloxanyl styrene, heptacosamethyl tridecacyloxanyl styrene, hentriacontamethylpentadecasiloxanyl styrene, bis (trimethylsiloxy) methylsilylstyrene, tris (trimethylsiloxy) silylstyrene , Trimethylsiloxy / pentamethyldisiloxy / methylsilylstyrene, tris (pentamethyldisiloxy) silylstyrene, (tris / trimethylsiloxy) siloxanyl / bis (trimethylsiloxy) silylstyrene Bis (heptamethyltrisiloxy) methylsilylstyrene, tris (methylbis-trimethylsiloxy-siloxy) silylstyrene, trimethylsiloxy-bis (tris-trimethylsiloxy-siloxy) silylstyrene, heptakis (trimethylsiloxy) trisiloxanylstyrene, Nonamethyltetrasiloxy / undecylpentasiloxy / methylsilylstyrene, tris (tris / trimethylsiloxy / siloxy) silylstyrene, (tristrimethylsiloxy / hexamethyl) tetrasiloxy / (tris / trimethylsiloxy) siloxy / trimethylsiloxysilylstyrene, nonakis (Trimethylsiloxy) tetrasiloxanylstyrene, bis (tridecamethylhexasiloxy) methylsilylstyrene, and the like. These may be used alone or in combination of two or more.

  Among the representative examples, for the purpose of improving oxygen permeability, mechanical strength, workability, and refractive index, for example, the formula:

で示されるトリメチルシリルスチレン、式：

Trimethylsilylstyrene represented by the formula:

で示されるビス（トリメチルシロキシ）メチルシリルスチレン、式：

Bis (trimethylsiloxy) methylsilylstyrene represented by the formula:

で示されるトリス（トリメチルシロキシ）シリルスチレンなどが好ましい。

Tris (trimethylsiloxy) silylstyrene represented by

  Specific examples of other polymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-amyl (meta ) Alkyl esters of methacrylic acid or acrylic acid such as acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate; styrene, p-methylstyrene, m-methylstyrene, p-tert-butyl Styryl compounds such as styrene, m-tert-butylstyrene, p-1,1,3,3-tetramethylbutylstyrene; alkyl esters of itaconic acid or crotonic acid; glycidyl (meth) acrylate; Tetrahydrofurfuryl (meth) acrylate; benzyl (meth) acrylate.

  An alkyl (meth) acrylate having an alkyl group with 1 to 6 carbon atoms and at least one hydrogen atom of the alkyl group substituted with a fluorine atom is resistant to contamination and processing while maintaining oxygen permeability. It is a component for improving the property.

  Specific examples of the alkyl (meth) acrylate include, for example, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3, 3,3-pentafluoropropyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, 2,2,3,3-tetrafluoro-tert-amyl (meth) acrylate, 2,2,3,4,4,4 -Hexafluorobutyl (meth) acrylate, 2,2,3,4,4,4-hexafluoro-tert-hexyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoro Examples thereof include pentyl (meth) acrylate. These may be used alone or in admixture of two or more. Of these, 2,2,2-trifluoroethyl methacrylate, hexafluoroisopropyl methacrylate, 2,2,2 are preferable for improving processability and copolymerization with the silicone-containing monomer represented by the general formula (I). 3,3-tetrafluoropropyl methacrylate and 2,2,3,3,3-pentafluoropropyl methacrylate are preferred.

  Representative examples of hydrophilic monomers include alkyl such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, and N-isopropyl (meth) acrylamide. (Meth) acrylamide; N-vinylformamide; N-vinylacetamide; acryloylmorpholine; N-vinyl-2-pyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylcaprolactam, N- (meth) acryloyloxyethyl N-vinyl lactams such as 2-pyrrolidone; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; Acrylate, polyethylene glycol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylates such as polypropylene glycol mono (meth) acrylate and the like. These may be used alone or in admixture of two or more.

  Specific examples of the crosslinking agent include, for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, diallyl fumarate, allyl (meth) acrylate, vinyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, methacryloyloxyethyl (meth) acrylate, divinylbenzene, diallyl phthalate, adipic acid Diallyl, triallyl diisocyanate, α-methylene-N-vinylpyrrolidone, 4-vinylbenzyl (meth) acrylate, 3-vinylbenzyl (meth) acrylate 2,2-bis ((meth) acryloyloxyphenyl) hexafluoropropane, 2,2-bis ((meth) acryloyloxyphenyl) propane, 1,4-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene 1,3-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyhexafluoroisopropyl) benzene, 1,4-bis (2- (meth)) Examples include acryloyloxyisopropyl) benzene, 1,3-bis (2- (meth) acryloyloxyisopropyl) benzene, 1,2-bis (2- (meth) acryloyloxyisopropyl) benzene. These can be used alone or in admixture of two or more. Among them, ethylene glycol dimethacrylate and 4-vinylbenzyl methacrylate are particularly preferable because they give good mechanical strength and have a great effect of improving workability, hardness, strength, solvent resistance, and copolymerization. preferable.

  When the copolymer is obtained by polymerizing the monomer component and the crosslinking agent, the blending amount of the silicone-containing monomer in the mixture of the monomer component and the crosslinking agent is preferably 45 to 70 parts by weight. If the blending amount is less than 45 parts by weight, the oxygen permeability tends to decrease. On the other hand, when the amount exceeds 70 parts by weight, the oxygen permeability is improved, but the obtained copolymer becomes brittle and the workability is lowered, the solvent resistance is lowered, and the material surface is very easily damaged. There is a problem that the amount of unpolymerized monomer of the silicone-containing monomer is increased, and the shape stability of the ophthalmic lens tends to be affected.

  Moreover, the compounding quantity of the alkyl (meth) acrylate in the mixture of the said monomer component and a crosslinking agent becomes like this. Preferably it is 20-45 weight part. When the blending amount is less than 20 parts by weight, the stain resistance and workability tend to be lowered. On the other hand, if the amount exceeds 45 parts by weight, the relative amount of silicon atoms in the resulting copolymer is reduced, so that the oxygen permeability is lowered, and further, the amount of unpolymerized monomer of alkyl (meth) acrylate is increased. However, it tends to affect the shape stability of the ophthalmic lens.

  The blending amount of the crosslinking agent in the mixture of the monomer component and the crosslinking agent is preferably 5 to 15 parts by weight. If the blending amount is less than 5 parts by weight, the processability tends to be deteriorated, scratches easily occur, the solvent resistance decreases, and the amount of the unpolymerized monomer of the monomer component increases. On the other hand, if it exceeds 15 parts by weight, the resulting copolymer tends to be brittle.

  In the present invention, as necessary, various additives conventionally used in ophthalmic lens materials, for example, imparting ultraviolet absorbing ability to ophthalmic lens materials or coloring ophthalmic lens materials. For this purpose, a polymerizable or non-polymerizable UV absorber, dye, UV-absorbing dye or the like can be present in the copolymer component and copolymerized, or added after polymerization.

  About polymerization temperature, it is preferable to adjust suitably in the temperature range of 40-120 degreeC, and to heat up in the middle of superposition | polymerization. In a polymerization reaction at a constant temperature in a low temperature range of about 40 to 50 ° C., the polymerization is not completed, or the polymerization time is long, so that a temperature increase is required. For example, when the initial temperature is 40 to 60 ° C., prepolymerization is performed at this temperature for 1 to 4 hours, and then the temperature is raised to 80 to 120 ° C. and heated for 10 to 60 minutes to complete the polymerization reaction. be able to. In addition, when the polymerization reaction is performed at 70 ° C. or higher from the beginning without performing preliminary polymerization, a polymerization time of 3 hours or less is preferable. In the prepolymerization at an initial temperature of 40 ° C. or lower, the progress of the polymerization is slow, and it tends to take time to complete the polymerization reaction. Further, at a polymerization temperature exceeding 120 ° C., the polymerization reaction tends to run away and unpolymerized monomers tend to increase.

  The polymerization time is preferably 30 minutes to 5 hours. If the polymerization time is less than 30 minutes, the polymerization tends to be incomplete (the number of unpolymerized monomers increases). Moreover, when it becomes longer than 5 hours, manufacturing time will become long and there exists a tendency for cost to become high as a result.

  In order to remove distortion of the obtained copolymer, a heat treatment may be further performed for about 1 hour under a temperature condition equal to or higher than the glass transition temperature of the copolymer.

  When copolymerizing the monomer components, conventionally known various radical polymerization initiators, photopolymerization initiators and the like can be appropriately selected and used.

  Examples of the radical polymerization initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, benzoyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and the like. These can be used alone or in admixture of two or more.

  The addition amount is 0.001 to 2 parts by weight, and more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the mixture of the monomer component, the crosslinking agent and other polymerizable monomers.

  Examples of the photopolymerization initiator include benzoin photopolymerization initiators such as methyl orthobenzoyl benzoate, methyl benzoyl formate, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin-n-butyl ether; 2 -Hydroxy-2-methyl-1-phenylpropan-1-one, p-isopropyl-α-hydroxyisobutylphenone, p-tert-butyltrichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, α, α-dichloro Phenone-based photopolymerization initiators such as -4-phenoxyacetophenone and N, N-tetraethyl-4,4-diaminobenzophenone; 1-hydroxycyclohexyl phenyl ketone; 1-phenyl- , 2-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone photopolymerization initiators such as 2-chlorothioxanthone and 2-methylthioxanthone; dibenzosbarone; 2-ethylanthraquinone; benzophenone acrylate; benzophenone; Can be given. These can be used alone or in admixture of two or more.

  As an addition amount, 0 to 2 parts by weight, more preferably 0.001 to 2 parts by weight, and further preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the mixture of the monomer component, the crosslinking agent and other polymerizable monomers. Parts by weight.

  In photopolymerization, when an electron beam is irradiated, the monomer component can be polymerized without adding such a photopolymerization initiator.

  The present invention will be specifically described below based on examples, but the scope of the present invention is not construed as being limited by the following examples.

Preparation of substrate 1 (oxygen permeable hard contact lens)
Mixing 55 parts by weight of tris (trimethylsiloxy) silylstyrene (TMSiSt), 35 parts by weight of 2,2,2-trifluoroethyl methacrylate (3FEMA) and 10 parts by weight of ethylene glycol dimethacrylate (EDMA), and polymerization initiator As a mixture, 0.32 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65) was added, and an additive type UV absorber or dye was added as appropriate to prepare a mixed solution.

  Next, 70 μL of the blended solution was put into a mold made of plastic resin, and heated in a dryer at 90 ° C. for 40 minutes to complete the polymerization.

After removing the lens, the lens surface was irradiated with plasma (according to the substrate activation method-1-), and then subjected to a hydrophilic treatment. For comparison, a plasma irradiation was prepared.

UV absorber: 2- (5-chloro-2H-benzotriazol-2-yl) -6- (1,1-dimethylethyl) -4-methylphenol Dye: D & C Green No. 6

Preparation of base material 2 (hydrous silicone hydrogel lens)
25 parts by weight of tris (trimethylsiloxy) silylpropyl methacrylate (TMSiMA), the following formula:

で表されるシリコーンウレタンマクロマー（ＭＡＵＳ）３０重量部、Ｎ，Ｎ−ジメチルアクリルアミド（ＤＭＡＡ）１０重量部、Ｎ−ビニル−２−ピロリドン（ＮＶＰ）３５重量部、エチレングリコールジメタクリレート（ＥＤＭＡ）０．４重量部を混合し、重合開始剤として２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（ＨＭＰＯ）０．４重量部を加え、配合液を調合した。

30 parts by weight of silicone urethane macromer (MAUS), 10 parts by weight of N, N-dimethylacrylamide (DMAA), 35 parts by weight of N-vinyl-2-pyrrolidone (NVP), ethylene glycol dimethacrylate (EDMA) 0. 4 parts by weight was mixed, and 0.4 parts by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one (HMPO) was added as a polymerization initiator to prepare a mixed solution.

Next, 100 μL of the compounded solution was placed in a mold made of plastic resin, and polymerization was performed for about 20 minutes at an irradiation intensity of about 10 mW / cm ² using an ultraviolet lamp having a dominant wavelength at 365 nm.

  After demolding the lens, elution treatment with purified water, drying again, plasma irradiation of the lens surface (according to the substrate activation method -1- and -2-), and then to the hydrophilic treatment agent solution Immersion was performed. For comparison, a plasma irradiation was prepared.

Preparation of base material 3 (Non-hydrous silicone soft lens)
40 parts by weight of silicone urethane macromer (MAUS) represented by the above formula, 40 parts by weight of 2-methoxyethyl acrylate (MTA), 20 parts by weight of phenoxyethyl acrylate (POEA), 2-hydroxy-2-methyl- as a polymerization initiator 0.2 parts by weight of 1-phenylpropan-1-one (HMPO) was added to prepare a blended solution.

Next, 100 μL of the compounded solution was placed in a mold made of plastic resin, and polymerization was performed for about 15 minutes at an irradiation intensity of about 10 mW / cm ² using an ultraviolet lamp having a dominant wavelength at 365 nm.

  After demolding the lens, elution treatment of unpolymerized components is performed using 2-fluoroanol, dried again, and the lens surface is irradiated with plasma (according to the substrate activation method-1-), followed by hydrophilization treatment. went. For comparison, a plasma irradiation was prepared.

Substrate activation method -1-
The removed lens was fixed on the pedestal of the corona discharge treatment apparatus, and the treatment was performed under the following conditions in such a manner that the lens was hidden under the discharge wire.

  The removed lens was subjected to corona discharge treatment under the following conditions.

<Corona discharge treatment conditions>
・ Plasma processing equipment: CORONA GENERATOR MODEL CT-0212 manufactured by Kasuga Electric Co., Ltd.
・ Output: 350W
・ Irradiation speed (workpiece movement speed): 1cm / sec
・ Irradiation height: 5mm distance between lens and discharge wire
・ Number of treatment: 2 to 5 times for both FC and BC surfaces (Lens irradiation time is about 5 seconds on one side or less)
Substrate activation method -2-
The removed lens was subjected to glow discharge treatment under the following conditions.

<Glow discharge treatment conditions>
・ Plasma processing equipment: Kyoto Electronics Measurement Co., Ltd. Low-temperature ashing equipment PA-102AT
・ Output: 30W
・ Gas: O2
・ Gas flow rate: 0.8 Torr
・ Processing time: 30 sec

Hydrophilic treatment method For the lens plasma-treated according to the substrate activation method -1- or -2-, 5% to 50% by weight of [3- (acryloylamino) propyldimethylammonio] propionate ( APDAP) was immersed in an aqueous solution at room temperature for 1 to 30 minutes and grafted. Thereafter, the lens was taken out and washed with running water to remove unreacted APDAP. In the case of oxygen permeable hard contact lenses and non-hydrous silicone soft lenses, the water on the lenses was dried with air to complete the treatment. In the case of hydrous silicone high jersey, it was brought into a hydrous state through a predetermined hydration step.

<Treatment concentration>
Oxygen permeable hard contact lenses are 5 wt% aqueous solution Hydrous silicone hydrogel lenses are 10 wt% aqueous solution and 50 wt% aqueous solution Non-hydrous silicone soft lenses are 10 wt% aqueous solution

Various evaluation test items
The following tests were conducted on lenses grafted with APDAP.

1) Water wettability 1. Visual wettability and contact angle over time Water wettability and surface elemental analysis before and after scrubbing cleaning (oxygen-permeable hard contact lenses only)
2) Lipid adhesion test with artificial tears 3) Friction measurement

Various test methods 1) Visual wettability evaluation method Hold the treated lens with a suitable holder, or pinch with tweezers and visually observe the wettability when distilled water is dropped on the lens. Judged as follows. The measurement was performed immediately after the treatment (indicated as “Initial” in the following table) and after 7 days.

<Criteria>
A: The entire lens is wet
B judgment: Slight repellency is seen at the lens periphery or center
C judgment: Although a puddle is formed in some places, the repelling is quick when the water is drained, and there are many repelling parts.
D judgment: Completely repels water

2) Contact angle measurement method Using a contact angle meter (Drop Master 500, manufactured by Kyowa Interface Science Co., Ltd.), place a 2μL droplet on the lens with a microsyringe, and read the angle between the lens surface and the droplet at that time. It was. The measurement was performed immediately after the treatment (indicated as “Initial” in the following table) and after 7 days. In the case of the oxygen-permeable heart contact lens, it was stored in the atmosphere after the treatment, and the hydrous silicone hydranger and the non-hydrous silicone soft lens were stored and measured in a physiological saline solution.

3) Surface elemental analysis (XPS)
Various surface elemental analyzes were performed using the X-ray photoelectron spectrometer (JPS-9000MX ESCA photoelectrometer manufactured by JEOL Datum Co., Ltd.) under the following analysis conditions.

X-ray Type: MgKa
Setting Voltage: 10 kV
Setting Current: 10 mA

４）人工涙液による脂質付着性試験
人工涙液（スクアレン、コレステロール、ワックス、コレステロールパルミテート）中に実施例（各基材）のコンタクトレンズを浸漬し、37℃にて16時間振とうしたのち、クロロホルム/メタノール（=70/30）溶液にて30分間抽出を行い、抽出液中の脂質成分をガスクロマトグラフィー/マススペクトロメトリー（GC/MS）にて定量した。なお、人工涙液、抽出液、およびGC/MSDによる操作手順・分析条件等の詳細は、下記のとおりである。

4) Lipid adhesion test with artificial tears After immersing the contact lenses of the examples (each substrate) in artificial tears (squalene, cholesterol, wax, cholesterol palmitate) and shaking at 37 ° C for 16 hours Then, extraction with chloroform / methanol (= 70/30) solution was performed for 30 minutes, and lipid components in the extract were quantified by gas chromatography / mass spectrometry (GC / MS). The details of the artificial tears, the extract, and the operation procedures and analysis conditions by GC / MSD are as follows.

  1. Sodium chloride 1.8g, sodium dihydrogen phosphate 0.09g, calcium chloride 0.02g, egg white lysozyme 0.24g, bovine blood albumin 0.76g, γ-globulin 0.32g was dissolved in ultrapure water to make a total volume of 100mL (solution) 1). 1.0 g of squalene, 1.0 g of octyldodecyl oleate, 0.9 g of cholesterol palmitate and 0.1 g of cholesterol were mixed and dissolved by heating (solution 2). After adjusting Solution 1 to pH 7, 20 μL of Solution 2 maintained at 37 ° C. was added to obtain an artificial tear.

  2. 16 mg of cholesteryl acetate (internal standard substance) was weighed into a 200 mL volumetric flask, dissolved in chloroform / methanol = 70/30, and then this chloroform / methanol was added until the total amount became 200 mL (solution 3). 5 mL of Solution 3 was added to a 100 mL volumetric flask and dissolved in chloroform / methanol = 70/30. Then, this chloroform / methanol was added until the total amount reached 100 mL to obtain an extract (extract).

  3. 0.02 g of squalene, 0.02 g of cholesterol, 0.02 g of wax and 0.02 g of cholesterol palmitate were weighed in a vial, and the extract was added to make a total amount of 27 g (solution 4). 0.14 g of Solution 4 was weighed in a vial, and the extract was added to make a total amount of 24 g (standard solution).

  4). A vial bottle to which 2 mL of artificial tears and a sample lightly rinsed with ultrapure water were added one by one was left in a constant temperature shaker set at 37 ° C. with shaking for 16 hours.

  5). The sample removed from the vial and rinsed with ultrapure water was transferred to another vial, and 0.75 mL of the extract was added and left for 10 minutes or longer.

  6). Only the extract or standard solution was transferred to an autosampler vial, and the solvent was removed with a vacuum dryer.

  7). 50 μL of chloroform / methanol = 70/30 was added to the autosampler vial from which the solvent had been removed, and analyzed by GC / MSD.

  8). The measurement conditions are as follows.

GC / MSD Agilent Technologies 5973N MSD System Column UA1 (manufactured by Frontier Laboratories)
100% dimethylpolysiloxane
Inj. Temperature 320 ℃
Oven 200 ℃ (2min)-(15 ℃ / min) -260 ℃-(30 ℃ / min) -360 ℃ (2min)
Carrier gas Helium Flow rate 2.4mL / min (0 ~ 0.5min), 1.2mL / min (0.5min ~)
Detector MSD
Split 15: 1
Injection volume 2μL
9. From the obtained chromatograph, the amount of each lipid component in the extract was calculated from the area ratio with the internal standard substance to obtain the total amount of lipid.

5) Friction force measurement method Friction force measurement device as shown in FIG. 1 was attached to Shimadzu Corporation precision universal testing machine AG-IS MS type, and the friction force was measured by the following procedure.

  1. Fix the lens to the fixture.

  2. A 0.3 mm thick silicon sheet is attached to the glass plate. In this case, the surface of the silicon sheet is washed with running water and pasted to prevent bubbles from entering the glass plate.

  3. Drop a drop of physiological saline between the silicon sheet and the lens, set the lens slowly on the sheet, switch on the tester and start measurement. The load was 6 g.

  4). The measurement speed was a set value of 500 mm / min.

  5). 1. Rinse the lens and silicon sheet surface cleanly. ~ 4. The above operation was repeated three times, and the average value of the load applied to the testing machine was defined as the frictional force (N).

上記表２〜４に示された実験結果から、本発明の方法は１〜３０分という短い親水化処理時間で水濡れ性、脂質付着性、表面潤滑性に優れた眼用レンズを与えることがわかる。この水濡れ性は処理後７日間たっても著しく低下することはなかった。

From the experimental results shown in Tables 2 to 4 above, the method of the present invention can provide an ophthalmic lens excellent in water wettability, lipid adhesion, and surface lubricity in a short hydrophilization treatment time of 1 to 30 minutes. Recognize. This water wettability was not significantly reduced even after 7 days from the treatment.

Claims (19)

An ophthalmic lens whose surface is hydrophilized using a compound represented by the following general formula (1).

(Wherein R ¹ is H or CH ₃ , X is —O— or —NH—, n ₁ is an integer of ₁ to 10, and Y is a zwitterionic group)   The hydrophilization treatment includes a step of irradiating the ophthalmic lens with plasma and a step of immersing the ophthalmic lens irradiated with plasma in an aqueous solution of the compound represented by the general formula (1). The ophthalmic lens described.   The hydrophilization treatment includes a step of irradiating the ophthalmic lens with plasma and a step of immersing the ophthalmic lens irradiated with plasma in a 0.1 to 50% by weight aqueous solution of the compound represented by the general formula (1). The ophthalmic lens according to claim 1. The compound represented by the general formula (1) is represented by the following general formulas (I), (II), (III) and (IV):

(In the formulas (I) and (II), R ₁ is H or CH ₃ , and n is 1 to 10)

(In the formulas (III) and (IV), R ₁ is H or CH ₃ , and n is 1 to 5)
The ophthalmic lens according to claim 1, which is at least one selected from the group consisting of compounds represented by:   The ophthalmic lens according to claim 1, wherein the ophthalmic lens is an oxygen-permeable hard contact lens. The ophthalmic lens according to claim 5, wherein the oxygen-permeable hard contact lens is made of a copolymer containing a compound represented by the following general formula (3) as a polymerization component.

(Where l is 0 or 1, n and m are integers of 1 to 15)   The ophthalmic lens according to claim 6, wherein the oxygen-permeable hard contact lens comprises a copolymer containing a fluorine-containing (meth) acrylic monomer and a crosslinking monomer as polymerization components in addition to the compound represented by the general formula (3). .   The ophthalmic lens according to claim 1, wherein the ophthalmic lens is a hydrous soft contact lens containing a hydrogel containing silicone or a non-hydrous soft contact lens. The ophthalmic lens according to claim 8, comprising a copolymer containing a compound represented by the following general formula (4) as a polymerization component.

The following general formula (1):

(Wherein, R ¹ is H or CH ₃ , X is —O— or —NH—, n ₁ is an integer of ₁ to 10, and Y is a zwitterionic group). A method for producing an ophthalmic lens comprising a step of hydrophilizing a surface.   The hydrophilization treatment step includes a step of irradiating the ophthalmic lens with plasma and a step of immersing the ophthalmic lens irradiated with the plasma in an aqueous solution of the compound represented by the general formula (1). A method for producing the ophthalmic lens according to 1.   The hydrophilization treatment step includes a step of irradiating the ophthalmic lens with plasma, and a step of immersing the ophthalmic lens irradiated with plasma in a 0.1 to 50% by weight aqueous solution of the compound represented by the general formula (1). The method for producing an ophthalmic lens according to claim 10. The compound represented by the general formula (1) is represented by the following general formulas (I), (II), (III) and (IV):

(In the formulas (I) and (II), R ₁ is H or CH ₃ , and n is 1 to 10)

(In the formulas (III) and (IV), R ₁ is H or CH ₃ , and n is 1 to 5)
The manufacturing method of the ophthalmic lens in any one of Claims 10-12 which is at least 1 sort (s) chosen from the group which consists of a compound represented by these.   The method according to any one of claims 10 to 13, wherein the plasma irradiation is corona discharge under atmospheric pressure, the output is 1000 W or less, and the irradiation time is within 60 seconds.   The method according to any one of claims 10 to 13, wherein the plasma irradiation is glow discharge under reduced pressure, the output is 100 W or less, and the irradiation time is within 5 minutes.   The method according to any one of claims 10 to 13, wherein an immersion temperature is 5 to 60 ° C and an immersion time is within 60 minutes in the immersion step.   The method according to any one of claims 10 to 13, wherein the time from the end of the plasma irradiation to the start of the immersion step is within 30 minutes. The process of irradiating the ophthalmic lens with plasma and the following general formula (1):

(Wherein R ¹ is H or CH ₃ , X is —O— or —NH—, n ₁ is an integer of ₁ to 10, and Y is a zwitterionic group). A method for surface treatment of an ophthalmic lens, comprising the step of immersing the ophthalmic lens.   The surface treatment method for an ophthalmic lens according to claim 18, wherein the aqueous solution is a 0.1 to 50% by weight aqueous solution of the compound represented by the general formula (1).

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