JPH08334732A - Soft contact lens - Google Patents

Abstract

(57) [Summary] [Structure] The soft contact lens according to the present invention comprises a hydrophilic monomer, a silicon-containing (meth) acrylate, a fluoroalkyl (meth) acrylate or a specific fluorine-containing compound, a (meth) acrylic polymer or a vinyl compound. It is a composition obtained by dispersing and dissolving a base polymer and polymerizing it. [Effects] The poor shape retention characteristic of soft contact lenses with high water content is improved, the oxygen permeability is excellent, and the mechanical strength is excellent without being easily damaged during lens handling such as cleaning. Has durability. In addition, since it is less likely to be contaminated by a tear fluid component or the like during wearing and bacterial growth is suppressed, it is possible to provide a safe contact lens with less influence on the cornea.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention improves the poor shape retention characteristic of a soft contact lens having a high water content, has excellent oxygen permeability, and has sufficient mechanical strength to handle the lens. The present invention relates to a soft contact lens and a composition thereof with less damage. Furthermore, since it contains a fluoroalkyl (meth) acrylate (hereinafter, acrylate and methacrylate together (abbreviated as (meth) acrylate, acrylic acid and methacrylic acid together (abbreviated as (meth) acrylic acid)) or a specific fluorine-containing compound, The present invention relates to a soft contact lens which is less likely to be contaminated by tear components during wearing and has excellent durability.

[0002]

2. Description of the Related Art Soft contact lenses have been widely used by people who have not been able to wear conventional hard contact lenses because they are soft and have a good feeling of wearing. However, its share was lower than that of hard contact lenses because it was easily damaged and had a short product life, but in recent years, due to the commercialization of cleaners using proteolytic enzymes and the advancement of sterilization systems represented by cold sterilization. The number of soft contact lens wearers is increasing, and the market share of hard contact lenses is getting closer to the market. Furthermore, the spread of disposable soft contact lenses is also helping to expand the share of soft contact lenses.
As the material of the soft contact lens which is now widely used, the one having 2-hydroxyethyl methacrylate as a main component occupies the overwhelming majority, and as other materials,
Generally, N-vinyl-2-pyrrolidone, N, N-dimethylacrylamide and the like which are applied to high water content soft contact lens materials are used.

It has been generally pointed out that the problems of the soft contact lens are that the lens care is complicated and that the lens is easily damaged when handling the lens. Further, the soft contact lens is flexible and has a good feeling to wear, but since it is flexible, it has a problem that the shape is likely to change on the cornea during wearing, and the expected optical performance cannot be obtained. Furthermore, since oxygen permeability depends on the water content, it is necessary to increase the water content in order to increase the oxygen permeability, but when the water content of the lens becomes high, the shape retention and mechanical strength decrease. Harm appears.

As means for solving the problems of these soft contact lenses, various techniques have been disclosed by patents and the like. For example, regarding improvement of shape retention and mechanical strength (1) Japanese Patent Publication No. 62-32456,
Soft contact lenses containing 2,3-dihydroxypropylmethacrylate and methylmethacrylate as the main components, which have a relatively high rigidity, are also available in (2) JP-B-54.
Japanese Patent Publication No. 39741 discloses a highly hydrous soft contact lens obtained by copolymerizing a specific crosslinking component with N-vinyllactam and alkyl methacrylate.

On the other hand, several proposals have been made for improving the stain resistance. For example, in (3) Japanese Patent Publication No. 62-62323, a softener containing a monomethacrylate of alkylene glycol and a specific fluorine-containing methacrylate as main components. Contact lenses are also (4) JP-A-63-29
Japanese Patent No. 3520 discloses a soft contact lens containing N, N-dimethylacrylamide and fluoroalkyl (meth) acrylate as main components, which is excellent in stain resistance and mechanical strength and has improved oxygen permeability.

Further, as a soft contact lens having N, N-dialkylacrylamide as one of the constituents and having sufficient mechanical strength despite having a high water content, for example, (5) Japanese Patent Laid-Open No. 2-176624 discloses. , N, N
-Dialkyl (meth) acrylamide and N-vinyl-2
A soft contact lens containing pyrrolidone as a main component, and (6) JP-A-2-70713 discloses N,
Disclosed is a hydrogel obtained by copolymerizing N-dimethylacrylamide, a specific fluoroalkyl (meth) acrylate, a copolymerizable vinyl monomer and a crosslinking component.

[0007]

The problems of the soft contact lens are that the strength is weak and the lens is easily damaged in handling, the handling is complicated, and the shape is likely to change on the cornea during wearing, which is expected. The optical performance cannot be obtained, the oxygen permeability is insufficient, the cornea is burdened, and stains are easily attached and bacteria and fungi are easily proliferated. Due to these problems, soft contact lenses are not widely used as compared with hard contact lenses in spite of a good wearing feeling, and this is also the reason why some questions about safety are proposed.

Focusing on these problems, the soft contact lens (1) has a high rigidity because it is obtained by copolymerization of 2,3-dihydroxypropyl methacrylate and methyl methacrylate which is generally used as a hard contact lens material. Since the change of the optical surface is small, it has excellent optical performance, and correction of corneal astigmatism by a soft contact lens is possible to some extent. However, it can be said that this contact lens is excellent in mechanical strength in a sense due to its high rigidity, but on the other hand, it has a characteristic that it is difficult to stretch due to the toughness of the material and brittleness, and it is damaged during handling of the lens. There is a problem that it is easy to do. Further, there is a problem that oxygen permeability is insufficient, and when worn for a long time, oxygen required for the cornea is deficient, resulting in hyperemia or corneal metabolic dysfunction. The soft contact lens of (2) above is N- which is a highly hydrophilic monomer.
Vinyl lactam and alkyl methacrylate, which is generally used as a hard contact lens material as above,
Furthermore, since it is obtained by copolymerization of a specific crosslinking component,
The high water content improves the oxygen permeability and the shape retention is relatively good. However, the mechanical strength is still insufficient, and there is a problem that dirt easily adheres.

Next, regarding the improvement of the stain resistance, the above-mentioned technique has been disclosed as a material which hardly stains, but it is still not sufficient. Since the soft contact lens of the above (3) contains a specific fluorinated methacrylate as a main component as a component that makes it difficult for dirt to adhere to the monomethacrylate of alkylene glycol, when the blending ratio of the fluorinated methacrylate increases to some extent, the stain resistance However, there is a problem in that the mechanical strength is lowered and it is easily damaged. Furthermore, since the elasticity is small, the shape retention is poor and the oxygen permeability is not sufficient. In addition, the soft contact lens of (4) above,
Fluoroalkyl (meth) as a component that makes it difficult for dirt to adhere to N, N-dimethylacrylamide and the same as above.
Since the main component is acrylate, there are problems that the shape retention is poor and the mechanical strength is insufficient.

Further, as a soft contact lens material containing N, N-dialkylacrylamide as one of the constituents, the soft contact lens of the above (5) is N, N
-Dialkyl (meth) acrylamide and N-vinyl-2
-Because it contains pyrrolidone as the main component, it has sufficient mechanical strength despite its high water content, but it cannot be said that its optical performance is never sufficient, and the easiness of stains is improved due to its high water content. It can not be said. The hydrogel as the soft contact lens material of the above (6) is N, N-dimethylacrylamide, a specific fluoroalkyl (meth) acrylate that is a component that enhances oxygen permeability and prevents dirt from adhering, similarly to the above. Since it is obtained by copolymerizing it with a copolymerizable vinyl monomer and a crosslinking component, it has both excellent mechanical strength and high oxygen permeability.
There is a problem that the shape retention is poor and the optical performance is insufficient. Further, in the production of this hydrogel, phase separation due to poor copolymerizability of each component is likely to occur, and therefore it is necessary to strictly control the polymerization conditions in order to prevent this.

The advantages and problems of the current soft contact lens have been described above, but the present invention improves the poor shape retention characteristic of a soft contact lens having a high water content and has excellent optical performance. With a focus on obtaining contact lenses, it is an object to produce a water-containing soft contact lens having sufficient oxygen permeability, mechanical strength and stain resistance. That is, in wearing a soft contact lens, it is possible to obtain a safe contact lens composition that provides sufficient visual acuity correction, has little effect on the cornea, and is not easily damaged during lens handling such as cleaning. It is intended.

[0012]

[Means for Solving the Problems] That is, the soft contact lens of the present invention comprises a polymerizable monomer containing the following A, B and C as essential components: A: hydrophilic monomer B: silicon-containing (meth) acrylate C: fluoro Alkyl (meth) acrylate Disperse one or more polymers selected from (meth) acrylic polymers or vinyl polymers,
It is characterized by being dissolved and polymerized, and a polymerizable monomer containing the following A, B and D as essential components: A: hydrophilic monomer B: silicon-containing (meth) acrylate D: Fluorine-containing compound represented by the following general formula (1)

[0013]

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(In the formula, R ¹ and R ² are the same or different groups, and at least one group of R ¹ and R ² is -C.
_i H _j F _{2i + 1-j represents a} linear or branched fluorine-containing group, i is an integer of 1 to 18, j is an integer of 1 to 2i, and only one is -C _i. In the case of H _j F _{2i + 1-j} , the other represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms) (meth) acrylic polymer or Dispersing one or more polymers selected from vinyl-based polymers,
It is characterized by being dissolved and polymerized.

Further, the hydrophilic monomer which is the above-mentioned component A is N, N-dimethylacrylamide.

Further details will be described. The components constituting the soft contact lens of the present invention are roughly classified,
A, B, C and D polymerizable monomer components, and (meth)
It can be classified as a polymer component of an acrylic polymer or a vinyl polymer. Here, each component will be described.

The hydrophilic monomer as the component A will be described. This component is a basic skeleton for making the soft contact lens hydrophilic, and is an essential component for imparting water hydration to the soft contact lens and exhibiting flexibility of the lens. Since this soft contact lens is a copolymer with a highly hydrophobic component such as silicon-containing (meth) acrylate or fluoroalkyl (meth) acrylate, a monomer having relatively high hydrophilicity is suitable.
Specifically, N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, N-methyl-3-methylene-2
-Pyrrolidone, N- (2-methacryloyloxyethyl) pyrrolidone, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate and the like are preferable, and particularly N, N-dimethylacrylamide is generally used as a soft contact lens material. It is more hydrophilic than 2-hydroxyethyl methacrylate, and is suitable because it can obtain the required water content by adding a relatively small amount. Further, the N, N-dimethylacrylamide copolymer is flexible and has high toughness, and the inclusion of this copolymer increases the elongation of the lens and makes it less likely to break.

When the amount of this component used is relatively large,
The water content of the obtained copolymer is increased and the oxygen permeability is improved, but the mechanical strength and stain resistance are deteriorated, and further, the optical performance may be deteriorated. On the other hand, when the amount used is small, the elongation is small and the feeling of wearing is poor, which is not preferable. The specific amount used is preferably 20 to 80 parts by weight, more preferably 40 to 70 parts by weight.

Next, the silicon-containing (meth) acrylate as the component B will be described. This component is one of the important components for expressing the high oxygen permeability which is one of the objects of the present invention. For example, a compound represented by the following general formula (2) can be given.

[0020]

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(In the formula, R ³ is a hydrogen atom or a methyl group, X and Y are organic groups selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a phenyl group and a Z group,
a is an integer of 1 to 3. Where Z is the following general formula (3)
The group represented by )

[0022]

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(Wherein B represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, and b represents an integer of 0 to 5). Also, a compound having a hydroxyl group in the alkyl group or both ends of the siloxanyl group Compounds containing a (meth) acrylic group are also useful.

Examples of the silicon-containing (meth) acrylate represented by the above general formula include trimethylsilylmethyl (meth) acrylate, pentamethyldisiloxanylmethyl (meth) acrylate, methylbis (trimethylsiloxy) silylmethyl (meth) acrylate and tris. (Trimethylsiloxy) silylmethyl (meth) acrylate, bis (trimethylsiloxy) (pentamethyldisiloxanyloxy) silylmethyl (meth) acrylate, trimethylsiloxybis (pentamethyldisiloxanyloxy) silylmethyl (meth) acrylate, tris ( Pentamethyldisiloxanyloxy) silylmethyl (meth) acrylate, trimethylsilylethyl (meth) acrylate, pentamethyldisiloxanylethyl (meth) acrylate Methyl bis (trimethylsiloxy) silylethyl (meth) acrylate, tris (trimethylsiloxy) silylethyl (meth) acrylate,
Bis (trimethylsiloxy) (pentamethyldisiloxanyloxy) silylethyl (meth) acrylate, trimethylsiloxybis (pentamethyldisiloxanyloxy) silylethyl (meth) acrylate, tris (pentamethyldisiloxanyloxy) silylethyl ( Meta)
Acrylate, trimethylsilylpropyl (meth) acrylate, pentamethyldisiloxanylpropyl (meth) acrylate, methylbis (trimethylsiloxy)
Silylpropyl (meth) acrylate, tris (trimethylsiloxy) silylpropyl (meth) acrylate,
Bis (trimethylsiloxy) (pentamethyldisiloxanyloxy) silylpropyl (meth) acrylate, trimethylsiloxybis (pentamethyldisiloxanyloxy) silylpropyl (meth) acrylate, tris (pentamethyldisiloxanyloxy) Silylpropyl (meth) acrylate, 1,3-bis (meth) acryloyloxyethyl-1,1,3,3-tetramethyldisiloxane, 1,3-bis (meth) acryloyloxypropyl-1,1,3, There are 3-tetramethyldisiloxane and the like. Among these, one kind or two or more kinds can be selected and used.

When the amount of this component used is relatively large,
Since the obtained copolymer has increased flexibility and reduced strength, it is easily broken. On the other hand, when the amount used is small, sufficient oxygen permeability cannot be obtained, which is not preferable. The specific amount used is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

Next, the C component fluoroalkyl (meth) acrylate will be described. This component is one of the important components for developing the high oxygen permeability and the stain resistance for the purpose of the present invention. For example, a compound represented by the following general formula (4) can be given.

[0027]

[Chemical 4]

(In the formula, R ⁴ is a hydrogen atom or a methyl group,
—C _i H _j F _{2i + 1-j} represents a linear or branched fluorine-containing group, i is an integer of 1 to 18 and j is an integer of 1 to 2i) Here, the value of i is large. As the number of branches increases, the stain resistance becomes more excellent and the oxygen permeability becomes higher. On the contrary, when i becomes large, the shape stability decreases and the production becomes difficult, which is not preferable. Further, when j is large, that is, when the number of fluorine atoms is small, the oxygen permeability is lowered, and conversely, when j is 0, the chemical stability of the monomer is deteriorated, so that j is 1 to 2i.
It is preferred that

Examples of the fluoroalkyl (meth) acrylate represented by the above general formula include 2,2,2-trifluoroethyl (meth) acrylate and 2,2,2-
Trifluoro-1-trifluoromethylethyl (meth)
Acrylate, 3,3,4,4,5,5,5-heptafluoropentyl (meth) acrylate, 3,3,4
4,5,5,6,6,6-nonafluorohexyl (meth) acrylate, 3,3,4,4,5,5,6,6
7,7,8,8,8-Tridecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,6
7,7,8,8,9,9,10,10,10-heptadecafluorodecyl (meth) acrylate, 1,1,2,
2-tetrahydroperfluorooctadecyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,3,4,4,5
5,6,6,7,7,8,8,9,9-hexadecafluorononyl (meth) acrylate, 2,2,3,3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
There are 0,10,11,11-eicosafluoroundecyl (meth) acrylate and the like, and one or more of these can be selected and used.

When the amount of this component used is relatively large,
The resulting copolymer may become cloudy and is easily damaged. On the other hand, when the amount used is small, sufficient oxygen permeability cannot be obtained and the stain resistance is also reduced, which is not preferable. The specific amount used is preferably 5 to 50 parts by weight, more preferably 15 to 40 parts by weight.

Next, the fluorine-containing compound as the component D will be described. This component is one of the important components for developing the high oxygen permeability and the stain resistance for the purpose of the present invention. The copolymer using this component is generally superior in wettability and oxygen permeability to the copolymer using fluoroalkyl (meth) acrylate and further improved in mechanical strength.

In the general formula (1), the larger the value of i and the more branches, the higher the oxygen permeability, but conversely, the larger i, the lower the shape stability and the i of 19 or more. If so, it is difficult to manufacture and cannot be used. Further, when j is large, that is, when the number of fluorine atoms is small, the oxygen permeability is lowered, and when j is 0, the chemical stability of the monomer is deteriorated. Therefore, j is preferably 1 to 2i. Further, only one of the case of _{-C i H j F 2i + 1} -j, can not be used because the other alkyl group, carbon number of the alkenyl group or a cycloalkyl group production becomes difficult when it is 13 or more. Examples of the fluorine-containing compound represented by the general formula (1) include:
Methyl-2,2,2-trifluoroethyl fumarate,
Methyl-2,2,2-trifluoro-1-trifluoromethylethyl fumarate, methyl-3,3,4,4,4
5,5,6,6,6-nonafluorohexyl fumarate, allyl-2,2,2-trifluoroethyl fumarate, allyl-2,2,2-trifluoro-1-trifluoromethylethyl fumarate, Allyl-3,3,4
4,5,5,6,6,6-nonafluorohexyl fumarate, isopropyl-2,2,2-trifluoroethyl fumarate, isopropyl-2,2,2-trifluoro-1-trifluoromethylethyl fumarate Rate, isopropyl-3,3,4,4,4-pentafluorobutyl fumarate, isopropyl-3,3,4,4,5,5,6
6,6-nonafluorohexyl fumarate, isopropyl-3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctyl fumarate, isopropyl-3,3,4,4,5,5,6,6,7,7,
8,8,9,9,10,10,10-heptadecafluorodecyl fumarate, isopropyl-2,2,3,3-
Tetrafluoropropyl fumarate, isopropyl-
2,2,3,3,4,4,5,5-octafluoropentyl fumarate, t-butyl-2,2,2-trifluoroethyl fumarate, t-butyl-2,2,2-trifluoro -1-trifluoromethylethyl fumarate, t
-Butyl-3,3,4,4,4-pentafluorobutyl fumarate, t-butyl-3,3,4,4,5,5,5
6,6,6-nonafluorohexyl fumarate, t-butyl-3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctyl fumarate, t-butyl-3,3,4,4,5,5,6,6,7,7,8,
8,9,9,10,10,10-heptadecafluorodecyl fumarate, t-butyl-2,2,3,3-tetrafluoropropyl fumarate, t-butyl-2,2
3,3,4,4,5,5-octafluoropentyl fumarate, 2-ethylhexyl-2 ', 2', 2'-trifluoroethyl fumarate, 2-ethylhexyl-
2 ', 2', 2'-trifluoro-1'-trifluoromethylethyl fumarate, 2-ethylhexyl-3 ',
3 ', 4', 4 ', 4'-pentafluorobutyl fumarate, 2-ethylhexyl-3', 3 ', 4', 4 ',
5 ', 5', 6 ', 6', 6'-nonafluorohexyl fumarate, 2-ethylhexyl-3 ', 3', 4 ',
4 ', 5', 5 ', 6', 6 ', 7', 7 ', 8',
8 ', 8'-tridecafluorooctyl fumarate, 2
-Ethylhexyl-3 ', 3', 4 ', 4', 5 ',
5 ', 6', 6 ', 7', 7 ', 8', 8 ', 9',
9 ', 10', 10 ', 10'-heptadecafluorodecyl fumarate, 2-ethylhexyl-2', 2 ',
3 ', 3'-tetrafluoropropyl fumarate, 2-
Ethylhexyl-2 ', 2', 3 ', 3', 4 ',
4 ', 5', 5'-octafluoropentyl fumarate, cyclohexyl-2,2,2-trifluoroethyl fumarate, cyclohexyl-2,2,2-trifluoro-1-trifluoromethylethyl fumarate, cyclohexyl -3,3,4,4,4-pentafluorobutyl fumarate, cyclohexyl-3,3,4,4,5
5,6,6,6-nonafluorohexyl fumarate, cyclohexyl-3,3,4,4,5,5,6,6,7,
7,8,8,8-Tridecafluorooctyl fumarate, cyclohexyl-3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl fumarate, cyclohexyl-
2,2,3,3-tetrafluoropropyl fumarate,
Cyclohexyl-2,2,3,3,4,4,5,5-octafluoropentyl fumarate, bis (2,2,2-
Trifluoroethyl) fumarate, bis (2,2,2-
Trifluoro-1-trifluoroethyl) fumarate,
Bis (3,3,4,4,4-pentafluorobutyl) fumarate, bis (3,3,4,4,5,5,6,6,6)
-Nonafluorohexyl) fumarate, bis (3,3,3
4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) fumarate, bis (3,3,4,4)
4,5,5,6,6,7,7,8,8,9,9,10,
10,10-heptadecafluorodecyl) fumarate,
Examples include fumarates such as bis (2,2,3,3-tetrafluoropropyl) fumarate and bis (2,2,3,3,4,4,5,5-octafluoropentyl) fumarate, and corresponding malates. When used, they can be used alone or as a mixture. At this time, the fluorine-containing compound may be in a cis form or a trans form, but in consideration of homopolymerizability and copolymerizability, fumarate which is a trans form is preferable.

When the amount of this component used is relatively large,
The resulting copolymer may become cloudy and is easily damaged. On the other hand, when the amount used is small, sufficient oxygen permeability cannot be obtained and the stain resistance is also reduced, which is not preferable. The specific amount used is preferably 5 to 50 parts by weight, more preferably 15 to 40 parts by weight.

Next, methacrylic acid and 2-hydroxyethyl methacrylate which can be added to the polymerizable monomers A, B, C and D will be described. The main components of the present soft contact lens are the above-mentioned A: hydrophilic monomer, B: silicon-containing (meth) acrylate, and C:
Fluoroalkyl (meth) acrylate, D: a specific fluorine-containing compound, but when these components are copolymerized, phase separation occurs due to the difference in the polymerizability of each component, that is, the difference in the reactivity ratio, and the copolymer You can see the phenomenon that it becomes cloudy. This phenomenon is particularly remarkable when a cross-linking component is added to the polymerizable monomer composed of the above-mentioned components, and this is a serious problem in the soft contact lens as an optical material. Methacrylic acid and 2-hydroxyethyl methacrylate have been conventionally known as one of hydrophilic soft contact lens materials, but the copolymerizability is improved by adding this component to the polymerizable monomer composed of the above components. It was found that a soft contact lens composition which is uniform and has sufficient transparency as an optical material can be obtained.

It has been found that a relatively small amount of this component is sufficiently effective, but when the amount of this component is relatively large, the water content of the copolymer obtained is increased and the oxygen content increases. Although the transparency is improved, mechanical strength and stain resistance are deteriorated, and further optical performance may be deteriorated. In particular, when the amount of methacrylic acid used is large, the water content increases remarkably and the shape stability is lost, which is not preferable. on the other hand,
When the amount used is small, the above-mentioned effects are reduced, which is not preferable. The specific amount used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight.

Although the basic components as the polymerizable monomer are as described above, the shape retention as a contact lens and the
It is desirable to use various crosslinking agents in the range of 0.1 to 5 weight percent in order to improve the strength. The purpose of the cross-linking agent is
To improve the thermal properties of the copolymer to improve the shape stability,
The purpose is to provide appropriate hardness and elasticity and to obtain good visual acuity as a contact lens.

Examples of the cross-linking agent include di- or tri (meth) acrylates of polyfunctional alcohols and (meth) acrylates containing a vinyl group. Specific examples include ethylene glycol di (meth) acrylate and diethylene glycol. Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, etc. (Meth) acrylates, polyhydric esters of polyhydric alcohols such as trimethylolpropane and pentaerythritol and (meth) acrylic acid, vinyl (meth) acrylate, allyl (meth) acrylate and the like can be mentioned. More preferably, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinyl methacrylate and N, N'-methylenebisacrylamide are suitable as the crosslinking component used in the present soft contact lens. ing. The amount of the cross-linking agent used is appropriately 0.1 to 5% by weight in the polymerizable monomer.
If it is less than 0.1% by weight, it becomes difficult to control the water content, which is not preferable. On the other hand, if it exceeds 5% by weight, the oxygen permeability decreases with the decrease in water content, and the flexibility as a soft contact lens decreases, which is not preferable.

By copolymerizing each component of the polymerizable monomer described above in an appropriate composition ratio, a transparent hydrogel that can be used as a water-containing soft contact lens material can be obtained. The soft contact lens produced from this hydrogel is excellent in oxygen permeability and stain resistance, and has sufficient mechanical strength, which is a significant improvement over the drawbacks of conventional soft contact lenses. However,
It cannot be said that this soft contact lens is flexible and has a good shape-retaining property, so that there is a drawback that the expected optical performance cannot be obtained. In the situation where the share of soft contact lenses is rapidly expanding, even soft contact lenses are required to have optical performance capable of correcting corneal astigmatism to some extent, so for future development of soft contact lens materials, It seems that optical performance will become more important. Therefore, in order to improve the optical performance and, in turn, the poor shape retention,
It has been found that the addition of a (meth) acrylic polymer or a vinyl polymer is very effective.

Next, the polymer components of the (meth) acrylic polymer and the vinyl polymer will be described. As described above, this component is an additive component for improving the shape retention of the present soft contact lens, and the addition of this component can impart extremely excellent optical performance to other soft contact lens materials. it can.

The (meth) acrylic polymer and vinyl polymer are obtained by polymerizing or copolymerizing at least one (meth) acrylic group in the molecule, a (meth) acrylic monomer having a vinyl group, and a vinyl monomer. The obtained polymer or copolymer.

Specific examples of the (meth) acrylic monomer or vinyl monomer which is a raw material of the polymer component usable in the present invention include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylate having 1 to 12 carbon atoms such as hexyl (meth) acrylate, lauryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate and 2,3-dihydroxypropyl (meth) acrylate, or mono (meth) acrylic acid esters of glycerin, acrylamide, N,
Acrylamides such as N-dimethyl (meth) acrylamide, N-isopropylacrylamide, styrene, α
-Methylstyrene, methylstyrene, vinyl acetate, N-
Vinyl-2-pyrrolidone and the like can be mentioned. Further, in some cases, a crosslinking component having two or more polymerizable functional groups in the molecule as described above may be used. Depending on the cross-linking agent used, having different types of polymerizable groups can be expected to have an action of promoting copolymerization. However, it should be noted that when the proportion of the cross-linking component increases, the three-dimensional network structure becomes dense and the dispersibility or solubility in the polymerizable monomer decreases. One or more polymerizable monomers are selected from these (meth) acrylic-based monomers and vinyl-based monomers, and homopolymers thereof or copolymers of two or more polymerizable monomers are copolymerized according to a conventional method. To manufacture. Furthermore, this polymer component may contain a polymerizable group capable of copolymerizing with other polymerizable monomers in its molecule. By containing a polymerizable group, when the polymer component has a low molecular weight, it has an effect of suppressing elution.

In selecting the (meth) acrylic monomer and the vinyl monomer constituting the polymer components of the (meth) acrylic polymer and the vinyl polymer and determining the composition ratio thereof, the above-mentioned components A, B, C and D are used. It is desirable to consider the type and composition ratio of the polymerizable monomer that has as an essential component, the solubility with the polymerizable monomer, and the like,
In particular, great care must be taken when selecting a monomer whose polarity is remarkably different from that of the polymerizable monomer component.

The molecular weight (degree of polymerization) of this component largely depends on the type of the polymerizable monomer, and further reaction conditions for carrying out a chain reaction, such as polymerization temperature, polymerization time, pH,
The total average molecular weight is preferably 1,000 to 500,000, although it varies depending on the addition of a polymerization inhibitor and the like. If the average molecular weight is too small, the effect of improving the shape retention cannot be obtained, and the polymer component may be eluted by boiling or the like, and if it is too large, the compatibility with other polymerizable monomers may be decreased or polymerization such as clouding may occur. It is not preferable because it may adversely affect the physical properties of the contact lens later.

One of the major characteristics of this component is that the effect of improving the shape-retaining property can be seen with the addition of a relatively small amount.
In order not to adversely affect the properties of the respective polymerizable monomers that are the main constituents of the soft contact lens or the copolymers composed of them, it is preferable that the amount of this component used be kept to the minimum necessary. The appropriate amount of this component used is 0.01 to 10% by weight in the polymerizable monomer. If it is less than 0.01% by weight, the effect of improving the shape retaining property becomes small, which is not preferable. Again 1
If it exceeds 0% by weight, the dispersibility in the polymerizable monomer, the solubility, the white turbidity due to phase separation, and the flexibility as a soft contact lens are unfavorably reduced.

In addition to the above, additives such as dyeing agents, colorants, and UV inhibitors, and reactive monomers can be added.

Next, polymerization of the present soft contact lens will be described. Polymerization is carried out according to a conventional method in the presence of a usual polymerization initiator by heating or irradiation with active energy rays such as ultraviolet rays. As a specific polymerization initiator, a radical polymerization initiator is desirable, and for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t -Butylperoxydiisobutyrate, t-butylperoxyisopropyl carbonate, lauroyl peroxide, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile) and the like are used. Further, in the case of irradiation with active energy rays, a photopolymerization initiator such as benzoin ether or a sensitizer is used if necessary. The amount of these polymerization initiators used is 0.001 to the monomer used.
2 weight percent is preferred.

The contact lens of the present invention comprises a glass tube, a polypropylene tube or a polytetrafluoroethylene tube made of a polymerizable monomer having these polymer components dispersed and dissolved therein, or a contact lens having a contact lens-shaped space formed therein. It is suitable to inject it into a resin mold for production and heat it for thermal polymerization, or to irradiate it with ultraviolet rays for photopolymerization. Further, after this, when distortion occurs in the polymer due to polymerization shrinkage or polymerization heat, it is desirable to perform heat annealing in order to eliminate this. Further, the contact lens thus produced is appropriately swollen by immersing it in a physiological saline solution or the like.

[0048]

The soft contact lens according to the present invention disperses and dissolves a (meth) acrylic polymer or a vinyl polymer in a hydrophilic monomer, a silicon-containing (meth) acrylate, a fluoroalkyl (meth) acrylate or a specific fluorine-containing compound. However, since it is obtained by polymerizing this, the poor shape retention characteristic of a soft contact lens having a high water content is improved, the oxygen permeability is excellent, and the mechanical strength is sufficient. In addition, by containing a fluoroalkyl (meth) acrylate or a fluorine-containing compound, excellent durability and characteristics that are unlikely to be contaminated by tear fluid components during wearing can be imparted. In the present invention, a composition that exhibits these advantages is found.

[0049]

[Examples] The present invention will be described in more detail with reference to the following examples.
The present invention is not limited to these.

(Example 1) 55 parts by weight of N, N-dimethylacrylamide, 15 parts by weight of tris (trimethylsiloxy) silylpropyl methacrylate, 28 parts by weight of 2,2,2-trifluoroethyl methacrylate, 1 part by weight of ethylene glycol dimethacrylate. Polyvinylpyrrolidone (average molecular weight about 1000
0) 0.5 part by weight is dispersed and dissolved, and azobis (2,4-dimethylvaleronitrile) as a polymerization initiator is added.
2 parts by weight were added and mixed well, this mixture was put into a glass polymerization tube, and after deaeration and nitrogen replacement were repeated, the mixture was sealed under vacuum. This polymerization tube was heated at 30 ° C in warm water for 10 hours at 40 ° C.
After heating at 50 ° C. for 5 hours, at 50 ° C. for 5 hours, at 60 ° C. for 3 hours, and at 70 ° C. for 3 hours to polymerize, the bar material was obtained by annealing at 120 ° C. for 2 hours. The obtained bar material was cut by a usual lace cut method to obtain a contact lens in a dry state. The lens was swollen in pure water and washed, and then autoclave treatment was performed in pure water at 120 ° C. for 2 hours to complete extraction of unreacted monomer. Then, the pure water was replaced with physiological saline to obtain a soft contact lens finished product. The contact lens thus obtained has a water content of 51%, is comfortable to wear, has excellent optical performance, and has a breaking strength of 260 g / mm ² , an elongation of 340%, and an excellent mechanical strength. It was a thing. In addition, as a result of evaluation of stain resistance, it was found that the amount of protein attached was extremely small as compared with conventional soft contact lenses. The oxygen permeability is 2
It was 9 × 10 ⁻¹¹ ml · cm / cm ² · sec · mmHg.

The evaluation method was carried out according to the following criteria.

<Evaluation Criteria> (1) Water Content After washing with pure water and substituting with physiological saline, several lenses were prepared, the total weight (w) thereof was measured, and then with pure water again. After substituting and drying in a vacuum dryer for 24 hours, the total weight (d) of the dried lenses was obtained, and the water content was calculated by the following formula.

Moisture content = (wd) ÷ w × 100 (2) Strength From the obtained bar material, a plate-shaped molded product having a thickness of 0.1 mm and a width of 8 mm in a swollen state with physiological saline was prepared. , A test piece. The test piece was stretched in physiological saline at intervals of 10 mm with the upper and lower ends sandwiched therebetween, and the load at break (breaking strength) and the distance (elongation) between the fulcrums at that time were measured. Regarding the breaking strength, the load per cross-sectional area (g / m
expressed in m ^2), for the elongation, expressed in elongation (%) determined from the distance between the fulcrum at break and the distance between the front fulcrum stretching.

(3) Contamination resistance The obtained soft contact lens was placed in a physiological saline solution containing 0.5% by weight of egg white lysozyme, left at 60 ° C. for 2 hours, washed thoroughly with physiological saline, and then 280 nm. The UV absorbance at the wavelength of was measured to determine the amount of egg white lysozyme adhering to the contact lens.

(4) Oxygen Permeability Coefficient (Dk Value) Samples with a thickness of 12.7 mm changed in physiological saline at 35 ° C. using a Scientific Instruments film oxygen permeability meter manufactured by Rika Seiki Co., Ltd. The thickness and current value (i∞) were measured. Taking the obtained thickness on the x-axis, n ・ F ・ A ・ P
Regression line y = a by the method of least squares with i∞ as the y axis
x + b is calculated, and the reciprocal of this gradient (1 / a) is used as [D
k value]. Here, n is the number of electrons involved in the electrode reaction, F is the Faraday constant, A is the area of the platinum electrode, and P is the atmospheric pressure.

(Examples 2 to 10) Examples 2 to 10 are shown in Table 1.
Shown in Polymerization and various evaluation tests were performed in the same manner as in Example 1 with the compositions shown in Table 1.

[0057]

[Table 1]

The abbreviations of the monomers or polymer components in the table are as follows.

DMA: N, N-dimethylacrylamide NVP: N-vinyl-2-pyrrolidone S2MA: pentamethyldisiloxanylmethylmethacrylate S4MA: tris (trimethylsiloxy) silylpropylmethacrylate F3MA: 2,2,2-trifluoro Ethyl methacrylate F6 MA: 2,2,2-trifluoro-1-trifluoromethylethyl methacrylate IPF3-Fu: Isopropyl-2,2,2-trifluoroethyl fumarate MA: Methacrylic acid HEMA: 2-hydroxyethyl methacrylate EGDMA: Ethylene glycol dimethacrylate AMA: allyl methacrylate PBMA: polybutyl methacrylate (average molecular weight about 24
000) PVP: polyvinylpyrrolidone (average molecular weight about 10,000) P (BMA / HEMA = 3/1): copolymer of 3 parts butyl methacrylate and 1 part 2-hydroxyethyl methacrylate (average molecular weight about 15000) P (ST / HEMA = 5/1): Copolymer of 5 parts of styrene and 1 part of 2-hydroxyethyl methacrylate (average molecular weight of about 20000) (Comparative Example 1) In Example 1, tris (trimethylsiloxy) silylpropyl methacrylate was not contained at all. Dry contact lenses were obtained in the same manner as in Example 1 except that 15 parts by weight of methyl methacrylate was used instead. The dry lens obtained in the same manner as in Example 1 was swollen in pure water and washed, and then unreacted monomer was extracted and replaced with physiological saline to obtain a finished soft contact lens. The contact lens thus obtained had a water content of 52%, was excellent in optical performance and mechanical strength, and had a good wearing feeling, but was slightly inferior in elasticity and had an oxygen permeability of 21 × 10 ^-11. ml ・ cm / cm ²・ sec
・ It was an inadequate value of mmHg.

(Comparative Example 2) In Example 1, 2, 2,
Dry contact lenses were obtained in the same manner as in Example 1, except that 2-trifluoroethylmethacrylate was not contained at all and 28 parts by weight of methylmethacrylate was used instead. The dry lens obtained in the same manner as in Example 1 was swollen in pure water and washed, and then unreacted monomer was extracted and replaced with physiological saline to obtain a finished soft contact lens. The contact lens thus obtained had a water content of 51%, was excellent in optical performance and mechanical strength, and had a good wearing feeling.
The oxygen permeability was also an insufficient value of 21 × 10 ⁻¹¹ ml · cm / cm ² · sec · mmHg, and as a result of the stain resistance evaluation, protein adhesion was observed.

(Comparative Example 3) Polymerization was carried out in the same manner as in Example 1 except that polyvinylpyrrolidone was not added to obtain a dry contact lens. Example 1
The dry lens obtained in the same manner as above was swollen in pure water and washed, and then unreacted monomer was extracted and replaced with physiological saline to obtain a soft contact lens finished product.
The contact lens obtained in this manner had a poor shape-retaining property, so that the optical performance was insufficient, and a phenomenon such that the image did not appear clear in actual wear was observed.

[0062]

According to the inventions of claims 1 and 2, a hydrophilic monomer, a silicon-containing (meth) acrylate, a fluoroalkyl (meth) acrylate or a specific fluorine-containing compound is added to a (meth) acrylic polymer or a vinyl-based polymer. It is obtained by dispersing and dissolving a polymer and polymerizing it, improving the poor shape retention characteristic of soft contact lenses with high water content, excellent oxygen permeability, and easy to handle lenses such as cleaning. It has sufficient mechanical strength to prevent damage and excellent durability. In addition, since it is less likely to be contaminated with tear components during wearing and bacterial growth is suppressed, it can be expected that safety is high.

In particular, according to the invention of claim 2, since it contains a specific fluorine-containing compound, the wettability of the lens is good,
A contact lens with excellent wearing feeling can be obtained.

Claims (8)

[Claims] 1. A polymerizable monomer containing the following A, B and C as essential components: A: hydrophilic monomer B: silicon-containing (meth) acrylate C: fluoroalkyl (meth) acrylate (meth) acrylic polymer or vinyl Dispersing one or more polymers selected from the polymers,
A soft contact lens characterized by being dissolved and polymerized. 2. A polymerizable monomer containing the following A, B and D as essential components: A: hydrophilic monomer B: silicon-containing (meth) acrylate D: fluorine-containing compound represented by the following general formula (1) ] (In the formula, R ¹ and R ² are the same or different groups, and
^At least one group of ¹ and R ^{2 represents} a linear or branched fluorine-containing group represented by —C _i H _j F _{2i + 1-j} , and i
1-18 integers, j represents an integer of 1～2I, and if only one is _{-C i H j F 2i + 1} -j, the other is 1-1 carbon atoms
2 alkyl group, alkenyl group having 2 to 12 carbon atoms or cycloalkyl group having 3 to 12 carbon atoms) 1 or 2 or more polymers selected from (meth) acrylic polymers or vinyl polymers dispersion,
A soft contact lens characterized by being dissolved and polymerized. 3. The (meth) acrylic polymer or the vinyl polymer is a copolymer obtained by copolymerizing two or more kinds of (meth) acrylic monomers or vinyl monomers. Soft contact lens described. 4. The soft contact lens according to claim 1, wherein the (meth) acrylic polymer or the vinyl polymer has at least one polymerizable group in the molecule. . 5. A polymerizable monomer containing methacrylic acid or 2-
The soft contact lens according to any one of claims 1 to 4, wherein hydroxyethyl methacrylate is added in an amount of less than 20 parts by weight based on 100 parts by weight of all the polymerizable monomers. 6. The soft contact lens according to any one of claims 1 to 5, wherein the hydrophilic monomer is N, N-dimethylacrylamide. 7. The soft contact lens according to claim 1, further comprising a cross-linking agent in an amount of less than 5% by weight in addition to the above essential components constituting the polymerizable monomer. 8. The cross-linking agent is one or more cross-linking agents selected from ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinyl methacrylate and N, N′-methylenebisacrylamide. The soft contact lens according to claim 1, wherein the soft contact lens is a hydrophilic monomer.