JP4676768B2 - Non-hydrous soft ophthalmic lens material and non-hydrous soft ophthalmic lens using the same - Google Patents

Description

  The present invention relates to a non-hydrous soft ophthalmic lens material such as a non-hydrous soft contact lens and an intraocular lens, and a non-hydrous soft ophthalmic lens using the same. More specifically, the present invention relates to a lens material that can be satisfactorily surface-treated due to extremely low adhesiveness, and a non-hydrous soft ophthalmic lens obtained by subjecting the lens material to a surface treatment.

  Conventionally, acrylic acid ester-based materials have been mainstream as non-hydrous soft ophthalmic lens materials.

  This material is characterized by a small number of propagating bacteria that cause serious problems on the ocular tissue and an appropriate shape recovery property (see Patent Document 1). However, it has been pointed out that the acrylic material is sticky on the surface, and as a problem in handling, the material itself has insufficient water wettability, and dirt easily adheres to the lens surface.

  As means for solving such a problem, a method of imparting hydrophilicity to a material surface by subjecting an acrylic ester material to saponification treatment with an alkali or an acid is disclosed (see Patent Document 2). In addition, there is a method for reducing stickiness by plasma treatment with an inert gas or the like for stickiness of the material surface (see Patent Document 3). However, since the acrylate ester has adhesiveness to the material itself, dirt and the like are deposited in a preparatory work process for performing a surface treatment such as a plasma treatment, so that the working environment conditions are complicated and not efficient.

  On the other hand, the non-hydrous soft material includes a silicone rubber material. This material has a feature of high oxygen permeability, but has a fatal defect as an ophthalmic lens material because of high water repellency on the surface of the material.

  Recently, however, it is composed of a soft ophthalmic material using a polysiloxane macromonomer having a urethane bond (see Patent Document 4) and a siloxane-containing polymer containing siloxane macromonomer having a urethane bond and a lower fatty acid vinyl ester as essential components. An ophthalmic lens material (see Patent Document 5) is disclosed. Since the urethane bond in these ophthalmic lens material structures imparts suitable mechanical strength and water wettability, it is considered as a material that has improved the drawbacks of conventional silicone rubber materials.

  However, the urethane bond that imparts water wettability may cause hydrolysis in the material structure over time due to its hygroscopicity, resulting in decreased function as an ophthalmic lens, such as the occurrence of white turbidity and material deterioration. Is also expected. Furthermore, since the preparation of the synthesis of the siloxane macromonomer, which is the main component, is complicated and complicated, the production process and cost of the polymer are problematic.

In the case of non-hydrous soft ophthalmic lenses, in order to solve the problem of stickiness of the material surface and to give good flexibility and water wettability, it is most preferable to perform surface treatment after improving the material itself. it is conceivable that.
Japanese Patent Laid-Open No. 62-127823 JP-A-5-297330 Japanese National Patent Publication No. 7-507356 Japanese Patent Laid-Open No. 3-43711 WO00 / 70388

  An object of the present invention is a non-hydrous soft material that suppresses stickiness of the material itself, is excellent in flexibility, stretchability, oxygen permeability, transparency, and shape recovery properties suitable as an ophthalmic lens material, and is obtained by a simple method. An object of the present invention is to provide an ophthalmic lens material and a non-hydrous soft ophthalmic lens using the ophthalmic lens material.

  The present invention is a non-hydrous soft ophthalmic lens material comprising a copolymer of vinyl polydimethylsiloxane at both ends represented by the following general formula (1), vinyl carboxylate and triallyl isocyanurate. .

(In the formula, n is an integer of 200 to 1,000.)

  Further, the present invention provides a plasma on a copolymer obtained by polymerizing vinyl polydimethylsiloxane at both ends represented by the general formula (1), vinyl carboxylate and triallyl isocyanurate using an organic peroxide polymerization initiator. It is a non-hydrous soft ophthalmic lens obtained by performing irradiation treatment.

  The present invention also provides a non-hydrous soft ophthalmic lens, wherein the organic peroxide polymerization initiator is a tertiary peroxyester.

  According to the present invention, since the stickiness of the material itself is reduced, it is possible to avoid contamination of the lens surface when surface treatment is performed as an ophthalmic lens.

  In addition, according to the present invention, a non-hydrous soft ophthalmic lens having extremely small surface stickiness and excellent in flexibility, stretchability, oxygen permeability, transparency, water wettability, and shape recoverability can be obtained.

  The both-end vinyl polydimethylsiloxane used in the present invention is represented by the following general formula (1).

  This compound has a simple chemical structure and can be obtained relatively easily commercially. However, since it has two vinyl groups at both ends, it is highly reactive and difficult to handle. In particular, when n is less than 200, the flexibility, stretchability and oxygen permeability of the polymer obtained are significantly reduced, and when it is more than 1000, the shape stability is lowered, making it difficult to use as an ophthalmic lens. . Therefore, in the present invention, n = 200 to 1000 is used.

(In the formula, n is an integer of 200 to 1,000.)

  The content of vinyl polydimethylsiloxane at both ends is preferably 50 to 90 parts by weight, particularly preferably 60 to 80 parts by weight. If the content is less than 50 parts by weight, the oxygen permeation amount of the resulting polymer tends to decrease, and if the content exceeds 90 parts by weight, it tends to be difficult to stabilize the shape of the resulting polymer. It is not preferable.

  Examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl (meth) acrylate, vinyl crotonate, vinyl benzoate, and vinyl cinnamate. In the present invention, saturated carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, and vinyl stearate are preferably used.

  The content of the carboxylic acid vinyl ester is preferably 10 to 50 parts by weight, particularly preferably 20 to 40 parts by weight. If the content is less than 10 parts by weight, it tends to be difficult to maintain the shape of the lens. If the content exceeds 50 parts by weight, the resulting polymer tends to be clouded, which is not preferable as a lens material. .

  Usually, in order to improve heat resistance and mechanical properties, a polyfunctional crosslinking component is copolymerized. For example, as a multifunctional crosslinking component, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trierythylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) (Meth) acrylate crosslinkers such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl methacrylate, diallyl male Ate, diallyl fumarate, diallyl succinate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, diethylene glycol bisua Le carbonate, triallyl phosphate, triallyl trimellitate, diallyl ether, N, N-diallyl melamine, vinyl crosslinking agent such as divinylbenzene.

  In the case of this invention, a vinyl type crosslinking agent is preferable from the reactivity with the compound which has vinyl groups, such as vinyl polydimethylsiloxane of both ends, and carboxylic acid vinyl ester. Among these, a trifunctional component that can form a good three-dimensional structure between components and exhibit excellent mechanical strength is particularly preferable. Specific examples include triallyl isocyanurate which has three vinyl groups and can be expected to exhibit good heat resistance.

  As a compounding quantity, 0.5-5 weight part is preferable. When the content is less than 0.5 part by weight, the stickiness of the polymer surface increases, the crosslinking effect cannot be exhibited, and the lens shape tends to be difficult to maintain, which is not preferable. Moreover, when content exceeds 5 weight part, since a crosslinking density becomes high and a softness | flexibility falls, it is unpreferable.

  In general, when performing thermal polymerization or photopolymerization, a radical polymerization initiator or a photosensitizer is added. As radical polymerization initiators, 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisbutyrate, 2,2′-azobis Azo polymerization initiators such as (2,4,4-trimethylpentane), diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, distearoyl peroxide, di- n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-tertiarybutylcyclohexyl) -Oxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (3-methoxybutyl) peroxydicarbonate, cumylperoxyneodecanoate, 1, 1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, tertiary hexylperoxyneodecanoate, tertiary butylperoxyneodecanoate , Tertiary hexyl peroxypivalate, tertiary butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di ( 2-Hexanoyl) peroxyhexane, tertiary Sylperoxy-2-ethylhexanoate, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxyisobutyrate, tertiary hexyl peroxyisopropyl carbonate, tertiary butyl peroxymaleic acid, tertiary Butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, tertiary butyl peroxyisopropyl Carbonate, tertiary butyl peroxy-2-ethylhexyl carbonate, tertiary hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tertiary butyl peroxy There are organic peroxide polymerization initiators such as acetic acid and tertiary butyl peroxybenzoate.

  In the case of the composition of the present invention, a peroxyester system that can start the polymerization reaction at a relatively low temperature, specifically about 30 to 60 ° C., is preferably used. By starting at a relatively low temperature, the reaction between the components proceeds uniformly, and the excellent features of the present invention can be exhibited.

  In particular, it is important when dealing with carboxylic acid vinyl esters that are generally highly volatile and have a low boiling point. Specifically, tertiary peroxy esters such as tertiary hexyl peroxyneodecanoate, tertiary butyl peroxyneodecanoate, tertiary hexyl peroxypivalate, and tertiary butyl peroxypivalate are particularly preferably used. It is done.

  The amount of the polymerization initiator is preferably 0.001 to 1.0 part by weight, more preferably 0.5 to 1.0 part by weight with respect to 100 parts by weight of the copolymer component.

  As a method for producing the ophthalmic lens material of the present invention, a known method such as a method of polymerizing using a lens-shaped mold or a method of polymerizing in a tube-shaped container and then cutting and polishing into a lens shape can be employed. . In addition, when the material of the present invention is used as an intraocular lens, it is possible to attach a lens support part to the lens part after forming the lens, or it is possible to integrally form the lens part and the support part. is there.

  When the material of the present invention is used as an ophthalmic lens, particularly as a non-hydrous soft contact lens, it is preferable to improve the wettability by applying a hydrophilic surface treatment. Hydrophilic surface treatment methods include low-temperature plasma treatment using an inert gas, surface treatment using ultraviolet rays, electron beams, heat, etc., immersion in a hydrophilic monomer solution after low-temperature plasma treatment, and grafting by ultraviolet irradiation or heat treatment. A known method such as polymerization can be employed.

  In the present invention, the hydrophilic treatment of the lens surface with low temperature plasma is preferred. Examples of the active gas or inert gas used for the low temperature plasma treatment include oxygen, nitrogen, air, hydrogen, helium, neon and argon, but oxygen or argon plasma is generally preferably used. As processing conditions, the output is 5 to 800 W, preferably 30 to 700 W, the degree of vacuum is 0.05 to 20 torr, preferably 0.2 to 4 torr, and the processing time is about 30 seconds to 30 minutes, preferably 60 seconds to Set to about 5 minutes.

  It is also possible to introduce an ultraviolet absorber into the material of the present invention. Specific examples of the ultraviolet absorber include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- (meth) acryloyloxy-5-t-butylbenzophenone, 2- (2′-hydroxy-5). '-(Meth) acryloyloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5'-(meth) acryloyloxyethylphenyl) -5-chloro-2H-benzotriazole, 2-hydroxy-4 -Phenyl methacryloyloxymethyl benzoate etc. are mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited only to this Example.

(Evaluation methods)
The following tests and evaluation criteria were adopted as evaluation methods for contact lenses in Examples and Comparative Examples.

[Oxygen permeability coefficient]
Oxygen transmission coefficient (Dk value) based on the "Dk value measurement work procedure by the improved electrode method" described in the contact lens manufacturing / import approval application manual (Japan Contact Lens Association) Was measured.

[Elasticity and strength]
As an evaluation of flexibility, the elongation at break and the strength at break were measured using as a sample a specimen prepared based on the “Plastic Tensile Test Method (JIS K 7113)”.

[Lens shape recovery and lens surface adhesion]
A contact lens molded body is folded in four, a 500 g weight is put on it and held for 1 minute, and then the weight is removed, and the following evaluation criteria are determined according to the behavior of the lens molded body at that time.

<Evaluation criteria>
A: There is no adhesion between lenses, and the original shape is restored within 1 minute.

        ○: There is no adhesion between the lenses, and the original shape is restored within 10 minutes.

        Δ: The lenses do not adhere to each other, but do not return to the original shape even after 30 minutes.

        ▲: Although the lenses adhere to each other, they can be easily peeled off and return to the original shape within 30 minutes.

        X: The lenses are completely adhered to each other and cannot be peeled off.

[Lens shape retention and transparency]
The shape retention property and transparency of the contact lens molded body were visually evaluated.

<Lens shape evaluation criteria>
When the lens front side of the contact lens molding is faced down and placed on a finger and confirmed from the side, ○: The bowl shape is maintained.

        Δ: The bowl shape is slightly open.

        X: The bowl shape cannot be maintained.

<Lens transparency evaluation criteria>
○: Completely transparent △: Some cloudiness (milky white) is present ×: 50% or more cloudiness

[Water wettability]
After the contact lens molded body subjected to the hydrophilization treatment was immersed in pure water for 1 hour, the surface moisture was wiped off, and the contact angle was measured by the droplet method (contact angle meter / CONACT-ANGLE METER manufactured by Kyowa Interface Chemical).

(Examples 1-6)
Both-end vinyl polydimethylsiloxane of general formula (1) (V33 / Gelest / n = 580), vinyl propionate (VPr), vinyl acetate (VAc), vinyl butyrate (VBu) and triallyl isocyanurate (TAIC) Were mixed at the blending amounts shown in Table 1, and then, as a polymerization initiator, tertiary hexyl peroxypivalate (p-HePV) or tertiary butyl peroxyneodecanoate, (p-BuND) was added for each 0.5. Part by weight was added.

  After each component was sufficiently stirred to be uniform, it was poured into a lens-shaped polypropylene mold and heated at 95 ° C. for 5 hours in a nitrogen atmosphere to obtain a lens-shaped polymer.

  The evaluation results of the obtained contact lens molded body are shown in Table 1. Particularly, regarding the stickiness of the surface of the lens molded body, good results could be confirmed by a shape recoverability test.

(Comparative Examples 1-2)
Instead of both-end vinyl polydimethylsiloxane of general formula (1) (V33, n = 580) which is an essential component of the present invention, both-end vinyl polydimethylsiloxane of general formula (1) (V46 / Gelest / n = 1500 or V22 / Gelest / n = 120), a lens was produced and evaluated in the same procedure as in Example 1 with the composition shown in Table 1.

  When V46 having a molecular weight larger than V33 was used, shape recovery and shape retention were poor, and it was unsuitable as an ophthalmic lens. Further, when V22 having a molecular weight smaller than V33 was used, the elongation at break and strength were lowered and the shape recoverability was poor, so that it was insufficient as an ophthalmic lens.

(Comparative Examples 3-4)
In Comparative Example 3, triallyl isocyanurate (TAIC) is not used, and other components are the same as in Example 1. In Comparative Example 4, ethylene glycol dimethacrylate is used instead of triallyl isocyanurate (TAIC). Using (ED), a lens was manufactured and evaluated in the same procedure as in Example 1 with the composition shown in Table 1. In both comparative examples, a polymer having a sufficient cross-linked structure could not be obtained, so the flexibility was poor, the lens shape was not obtained, and it was unsuitable as an ophthalmic lens material.

(Example 7)
The contact lens molded body obtained in Example 1 was subjected to a hydrophilic treatment of the lens surface with low temperature plasma using oxygen gas under the conditions of an output of 50 W, a degree of vacuum of 1.5 torr, and a treatment time of 3 minutes. The contact angle of the lens surface after the surface treatment was 54 degrees, which was about 10 degrees lower than that of a conventional non-hydrous ophthalmic lens.

  Further, as a result of conducting a soil test on the surface-treated contact lens molded body according to a conventional method, the protein adsorption amount per lens (Micro BCA method) was 1.544 μg, and the lipid adsorption amount (vanillin phosphate method) was 1. It was about .562 μg.

  In addition, the abbreviation in Table 1 shows the following compounds. The structures and molecular weights of V33, V46 and V22 are as follows.

VPr: vinyl propionate VAc: vinyl acetate VBu: vinyl butyrate TAIC: triallyl isocyanurate ED: ethylene glycol dimethacrylate p-HePV: tertiary hexyl peroxypivalate (perhexyl PV)
p-BuND: Tertiary butyl peroxyneodecanoate (perbutyl ND)

Dk: × 10 ⁻¹¹ (cm ² · sec) · (mLO ₂ / mL × mmHg)

Claims (3)

A non-hydrous soft ophthalmic lens material comprising a copolymer of vinyl polydimethylsiloxane at both ends represented by the following general formula (1), a carboxylic acid vinyl ester and triallyl isocyanurate.

(In the formula, n is an integer of 200 to 1,000.) Plasma irradiation treatment was performed on a copolymer obtained by polymerizing vinyl polydimethylsiloxane at both ends represented by the following general formula (1), vinyl carboxylate and triallyl isocyanurate using an organic peroxide polymerization initiator. Non-hydrous soft ophthalmic lens obtained.

(In the formula, n is an integer of 200 to 1,000.) The non-hydrous soft ophthalmic lens according to claim 2, wherein the organic peroxide polymerization initiator is a tertiary peroxyester.