JPH05215996A - Non-moisture type soft contact lens - Google Patents

Abstract

PURPOSE:To provide the non-moisture type soft contact lens which has sufficient oxygen penetrability and is excellent in a mechanical characteristic, as well. CONSTITUTION:The non-moisture type soft contact lens is formed from (a) an organosiloxane monomer, (b) an acrylic acie ester monomer, (c) a methacrylic acid ester monomer, and (d) an unsatureted carboxylic acid, which are specific, respectively, ester of unsaturated carboxylic acid anhydride or unsaturated carboxilyic acid and a branch-type or ring type hydroxyl group containing compound (fluoroalcohol is contained) and (f) a copolymer mainly composed of a cross-linking monomer. This is non-moisture type soft contact lens is manufactured by allowing a lens base body to be subjected to ester exchange processing and/or esterification processing by linear alcohol of 4-10C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-hydrated soft contact lens and a method for producing the same, and more particularly to a non-hydrated soft contact lens having high oxygen permeability and excellent mechanical strength.

[0002]

2. Description of the Related Art Conventional soft contact lenses include water-containing soft contact lenses made of a water-containing polymer such as poly (2-hydroxyethyl methacrylate) and non-water-containing soft contact lenses made of a silicone polymer. Are known. However, water-containing soft contact lenses generally have insufficient oxygen permeability and are liable to impair the metabolic function of corneal tissues, and must be boiled and sterilized frequently to prevent the growth of bacteria and the like. It's not easy. On the other hand, non-hydrous soft contact lenses made of silicone polymer have excellent oxygen permeability, but they tend to get soiled by tear fluid components, so if they are worn continuously for a long time, the lenses will fog and this fog will be washed. There was a problem that the agent could not be removed even if it was used.

Further, it is desired that the soft contact lens has good compatibility with the eye so that the soft contact lens does not feel a foreign substance when worn. Therefore, in Japanese Patent Publication No. 59-33887,
There has been proposed a non-water-containing soft contact lens having good contact with the eye, which is obtained by subjecting a contact lens-shaped substrate mainly composed of a polyacrylic acid ester or a polymethacrylic acid ester to an esterification treatment and / or a transesterification treatment. However, since this soft contact lens has insufficient oxygen permeability, it cannot be worn continuously for a long time and has a drawback that mechanical strength is low.

Therefore, it has been desired to develop a soft contact lens that does not require disinfection by boiling and does not cause metabolic damage to the corneal tissue even when continuously worn for a long time. As such a soft contact lens, for example, U.S. Pat. No. 3,808,179 discloses a soft contact lens formed of a copolymer of a fluoroalkyl ester of acrylic acid or methacrylic acid and an alkyl ester of acrylic acid or methacrylic acid. Contact lenses are also special Japanese Shosho 5
JP-A 1-46614 proposes soft contact lenses formed from a copolymer of methacrylic acid fluoroalkyl ester and methacrylic acid methyl ester, respectively. However, US Pat. No. 3,808,
The soft contact lens described in Japanese Patent No. 179 has a problem that mechanical strength is not sufficient and it is easily damaged during handling, and the soft contact lens described in Japanese Patent Publication No. 51-46614 uses methyl methacrylate. Therefore, there is a problem that the oxygen permeability is low.

On the other hand, the present inventors have already (i) a fluoroalkyl group having a straight chain structure and having a carbon number of 4 to 10 acrylic acid fluoroalkyl ester, or an alkyl group having a straight chain structure having 4 to 4 carbon atoms. 10 acrylic acid alkyl ester, (ii) fluoroalkyl group is linear and has 8 carbon atoms
-10 fluoroalkyl esters of methacrylic acid and
(iii) It has been proposed to form a non-water-containing soft contact lens from a copolymer mainly composed of a crosslinkable monomer (JP-A-62-229113). However,
This soft contact lens has no deformation because the raw material copolymer can be obtained in a state where the internal stress is small, but it is desired to further improve the oxygen permeability.

[0006]

The problem to be solved by the present invention is that boiling sterilization is not necessary, it has sufficient oxygen permeability, it is resistant to stains by tear components, and An object of the present invention is to provide a new non-water-containing soft contact lens having excellent overall properties such as excellent mechanical properties.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have formed a soft contact lens by forming a soft contact lens from a copolymer of a monomer mixture having a specific composition. They have found that a soft contact lens can be obtained, and completed the present invention. That is, the invention of claim 1 is (a) the following general formula:
5 to 60 mol% of at least one organosiloxane monomer represented by (I), (b) 10 to 80 at least one acrylic ester monomer represented by the following general formula (II)
Mol%, (c) 5 to 60 mol% of at least one methacrylic acid ester monomer represented by the following general formula (III),
(d) unsaturated carboxylic acid, unsaturated carboxylic anhydride, ester of unsaturated carboxylic acid with a branched or cyclic hydroxyl group-containing compound and fluoroalkyl group is selected from branched or cyclic unsaturated carboxylic acid fluoroalkyl ester 1 to 20 mol% of at least one type of monomer, (e)
At least one member selected from an acrylic acid lower alkyl ester having a linear alkyl group having 1 to 3 carbon atoms and an acrylic acid lower fluoroalkyl ester having a linear alkyl group having 1 to 3 carbon atoms and a fluoroalkyl group having 1 to 3 carbon atoms; Monomer 0
To 20 mol% and (f) 0.1 to 10 mol% of at least one crosslinkable monomer, and the total amount of the monomers (a) to (f) is 100 mol%. A non-hydrated soft contact lens (hereinafter, referred to as "soft contact lens of the present invention"), characterized by being formed from a united body, and having a general formula (I)

[Wherein A is a polymerizable unsaturated group, X is a carbon number of 1 to 1]
10 divalent hydrocarbon groups, R ^{1 to} R ⁶ are independently of each other a hydrogen atom, an alkyl group, a fluoroalkyl group, a phenyl group, a vinyl group or a Z group, and a Z group is represented by the formula

(Where B is a hydrogen atom or A, A and X
Is the same as described above, R ⁷ and R ⁸ are each independently hydrogen, an alkyl group, a fluoroalkyl group, a phenyl group or a vinyl group, k is an integer of 0 to 100), and Y is a carbon number of 1 to 1. 20 fluoroalkyl groups, C1-C20 alkyl groups or Z groups, and j is an integer of 0-100. ],
General formula (II)

[Wherein R ⁹ is of the formula (CH ₂ ) mCnFpHq (where m is 1
Or an integer of 2, n is an integer of 3 to 8, p is an integer of 4 or more, q is an integer of 0 or more, p + q = 2n + 1) a linear fluoroalkyl group or a formula CrH ₂ r + ₁ (here And r is an integer of 4 to 10) linear alkyl group. ], General formula (III)

[Wherein, R ¹⁰ is the formula (CH ₂ ) sCtFuHv (where s is an integer of 1 or 2, t is an integer of 1 to 10, u is an integer of 3 or more, and v is an integer of 0 or more. , U + v = 2t + 1) or a linear fluoroalkyl group of the formula CwH ₂ w + ₁ (where w is 4 to 10).
Is an integer) of a straight-chain alkyl group. ] Further, the invention according to claim 2 of the present application includes: (a) 5 to 60 mol% of at least one organosiloxane monomer represented by the general formula (I); General formula of 1
(II) Acrylic acid ester represented by (II), a straight-chain alkyl group having a carbon number of 1 to 3 and a fluoroalkyl group having a straight-chain structure having a carbon number of 1 to 1
0-80 mol% of at least one monomer selected from acrylic acid lower fluoroalkyl ester of (3)
5-60 mol% of at least one methacrylic acid ester monomer represented by the general formula (III), (d) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, branched or cyclic unsaturated carboxylic acid 10 to 90 mol% of at least one monomer selected from the group consisting of unsaturated carboxylic acid fluoroalkyl esters having a branched or cyclic unsaturated carboxylic acid ester with a hydroxyl group-containing compound, and (e) at least one crosslinkable compound The total amount of all monomers is 100 mol%, and the total amount of acrylic acid ester and acrylic acid in the monomers (b) and (d) is 0.1 to 10 mol%. To form a contact lens-like lens base made of a hard copolymer obtained by polymerizing a monomer mixture in which at least 10 mol% of all the monomers are present. By contacting with 10 linear unsubstituted alcohols, claim 1 of the copolymer
10-80 mol% of at least one acrylate monomer represented by the general formula (II), and at least one methacrylic acid ester monomer represented by the general formula (III) according to claim 1. 5 to 60 mol% of a monomer, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, ester of unsaturated carboxylic acid with a branched or cyclic hydroxyl group-containing compound, and unsaturated carboxylic acid having a branched or cyclic fluoroalkyl group At least 1 selected from acid fluoroalkyl esters
1 to 20 mol% of the monomer of the seed, and a straight chain alkyl group having 1 to 3 carbon atoms and a straight chain fluoroalkyl group having 1 to 3 carbon atoms
3. The transesterification treatment and / or the esterification treatment until at least one monomer selected from the fluoroalkyl ester of acrylic acid of 3 to 3 becomes 0 to 20 mol%. A method of manufacturing a water-containing soft contact lens.

The present invention will be described in detail below. The component (a) constituting the soft contact lens of the present invention is at least one type of organosiloxane monomer represented by the general formula (I). In the general formula (I), the polymerizable unsaturated group represented by A (including A in the Z group) is the monomer (b)
It is a group copolymerizable with (f), and examples thereof include CH ₂ = CH
-Group, CH ₂ = C (R) COO- group (wherein R is hydrogen atom, fluorine atom, methyl group or fluoromethyl group), CH ₂ = CHCONH
- _{group, CH 2 = CHC 6 H 4} - _{group, CH 2 = C (CN)} - _{group, CH 2 = C (CN)} COO-
A group etc. can be mentioned. When two or more unsaturated bonds represented by A are contained in the general formula (I), those unsaturated bonds may be the same or different.

In the general formula (I), X (including X in the Z group)
Is a divalent hydrocarbon group having 1 to 10 carbon atoms, and preferable examples thereof include an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group. When two or more X's are contained in the general formula (I), those X's may be the same or different.

In the general formula (I), R ^{1 to} R ⁶ are hydrogen atoms, alkyl groups, fluoroalkyl groups, phenyl groups, vinyl groups or Z groups. The alkyl group among them is, for example, a linear or branched alkyl group having 1 to 20 carbon atoms, and preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- group. Carbon number of butyl group, t-butyl group, n-pentyl group, i-pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, undecyl group, etc.
~ 12 alkyl groups. The fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 20 carbon atoms, preferably a trifluoromethyl group, a trifluoroethyl group, a trifluoropropyl group, a pentafluorobutyl group, a heptafluoropentyl group, a nonafluorohexyl group. It is a C3-C8 fluoroalkyl group such as a group. R ¹
To R ⁶ may be present independently of one another, may be the same or different from each other.

In the general formula (I), Y is a fluoroalkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or Z.
Examples of the fluoroalkyl group and the alkyl group are the groups described above for R ^{1 to} R ⁶ .

In the Z group in the general formula (I), k is 0 to 1
00, preferably an integer of 1-20. When k is 2 or more, a plurality of R ⁷ and R ⁸ may be the same or different. Further, examples of the alkyl group and the fluoroalkyl group of R ⁷ and R ⁸ include:
The groups exemplified for R ^{1 to} R ⁶ can be mentioned, and R ⁷
And R ⁸ may be the same or different from each other. Further, R ^{1 to} R ⁶ in the general formula (I) and R ⁷ and R ⁸ can exist independently of each other, and any one of R ^{1 to} R ⁶ and R ⁷ and / or R ^{8 can be present.}
May be the same or different.

In the general formula (I), j is an integer of 0 to 100, preferably 1 to 20. When j is 2 or more, a plurality of R ³ and R ⁴ may be the same or different.

In the soft contact lens of the present invention, the at least one organosiloxane monomer is
For example, it means that it can be any of the following (i) to (iv). (i) The organosiloxane monomer is A, X, R ¹ ~
^{R 8, Y, Z, B} , j, similarly to consist only monomers all k. (ii) The organosiloxane monomer is A, X, R ¹ ~
At least one of R ⁸ , Y, Z, B, j and k is composed of a mixture of different monomers. (iii) When R ¹ is an alkyl group, the organosiloxane monomer may have only the same alkyl group,
It may also have two or more alkyl groups.
The same applies to R ^{2 to} R ^{8 and} also when R ^{1 to} R ⁸ are fluoroalkyl groups. (iv) When the Z group has an alkyl group, the organosiloxane monomer may have only the same alkyl group, or may have two or more kinds of alkyl groups. This is also the case when the Z group has a fluoroalkyl group.

Specific examples of the component (a) include siloxanyl monomethacrylate, siloxanyl monoacrylate,
Examples thereof include fluorosiloxanyl monomethacrylate, fluorosiloxanyl monoacrylate, siloxanyl dimethacrylate, siloxanyl diacrylate, fluorosiloxanyl dimethacrylate, and fluorosiloxanyl diacrylate. Specifically, pentamethyldisiloxanylmethyl methacrylate, pentamethyldisiloxanylmethyl acrylate, pentamethyldisiloxanylpropyl methacrylate, pentamethyldisiloxanylpropyl acrylate, methylbis (trimethylsiloxy) silylpropyl methacrylate, Methylbis (trimethylsiloxy) silylpropyl acrylate,
Siloxanyl monomethacrylate or siloxanyl monoacrylate such as tris (trimethylsiloxy) silylpropyl methacrylate, tris (trimethylsiloxy) silylpropyl acrylate; (3,3,3-trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl methacrylate , (3,3,3
-Trifluoropropyldimethylsiloxy) bis (trimethylsiloxy) silylmethyl acrylate, (3,
3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilylpropyl methacrylate, (3,3,4,4,5,5,5-heptafluoropentyl Dimethylsiloxy) (methylbis (trimethylsiloxy) siloxy) trimethylsiloxysilylpropyl acrylate, (3,3,4,4,5,5,5-heptafluoropentyldimethylsiloxy) (pentamethyldisiloxanyloxy) trimethylsiloxysilyl Fluorosiloxanyl monomethacrylate such as methacrylate or fluorosiloxanyl monoacrylate;

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8] A siloxanyl dimethacrylate or siloxanyl diacrylate represented by

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12] Examples thereof include fluorosiloxanyl dimethacrylate and fluorosiloxanyl diacrylate. Preferred component (a) is tris (trimethylsiloxy) silylpropyl methacrylate, pentamethyldisiloxanylpropyl methacrylate, dimethylnonafluorohexylsiloxydimethylpropyl methacrylate, bis (methacryloxypropyl) octamethyltetrasiloxane and the like.

The content of the component (a) in the soft contact lens of the present invention is 5 to 60 mol%, preferably 1
It is 0 to 50 mol%. When the content of the component (a) is less than 5 mol%, the oxygen permeability of the soft contact lens decreases, and when it exceeds 60 mol%, the mechanical strength of the soft contact lens decreases.

The component (b) constituting the soft contact lens of the present invention is at least 1 represented by the general formula (II).
It is a type of acrylic acid ester monomer. In the general formula (II),
R ⁹ is a linear fluoroalkyl group having 4 to 10 carbon atoms or a linear alkyl group having 4 to 10 carbon atoms. When the carbon number of the linear fluoroalkyl group and the linear alkyl group is 3 or less, the soft contact lens becomes too hard and the original characteristics of the soft contact lens are impaired, and the oxygen permeability which is a feature of the present invention. Also drops. On the other hand, when the number of carbon atoms is 11 or more, when the soft contact lens of the present invention is manufactured by the method described below, after releasing from the post-polymerization molding die in the contact lens-shaped molding die,
Alternatively, the soft contact lens may be deformed by releasing the internal stress of the hard copolymer after being softened by the transesterification treatment and / or the esterification treatment.

Specific examples of the component (b) are 2, 2, 3,
4,4,4-hexafluorobutyl acrylate, 2,
2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, 2,2,3,3,4,4,4
5,5,5-nonafluoropentyl acrylate, 2,
2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2,2,3,3,4
4,5,5,6,6,7,7,7-tridecafluoroheptyl acrylate, 3,3,4,4,5,5,6
6,7,7,8,8-dodecafluorooctyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,
8,8-Tridecafluorooctyl acrylate, 3,
3,4,4,5,5,6,6,7,7,8,8,9,
9,10,10-hexadecafluorodecyl acrylate, 3,3,4,4,5,5,6,6,7,7,8,
Acrylic acid fluoroalkyl esters such as 8,9,9,10,10,10-heptadecafluorodecyl acrylate; and n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate , Acrylic acid alkyl esters of n-nonyl acrylate or n-decyl acrylate, and the like. Preferred component (b) is 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 3,3,4,4,5,5,5.
6,6,7,7,8,8,8-tridecafluorooctyl acrylate, 3,3,4,4,5,5,6,6
7,7,8,8,9,9,10,10,10-heptadecafluorodecyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate and the like.

In the soft contact lens of the present invention
The content of the component (b) is 10 to 80 mol%, preferably 20.
˜70 mol%. If the content of the component (b) is less than 10 mol%, the soft contact lens cannot be imparted with the required flexibility, and if it exceeds 80 mol%, the mechanical strength of the soft contact lens decreases.

The component (c) constituting the soft contact lens of the present invention is at least one methacrylic acid ester represented by the general formula (III). In the general formula (III),
R ¹⁰ is a linear fluoroalkyl group having 2 to 12 carbon atoms or a linear alkyl group having 4 or more carbon atoms. Fluoroalkyl group has 1 carbon atom or alkyl group has 3 carbon atoms
In the following cases, the oxygen permeability of the soft contact lens, which is a feature of the present invention, decreases. Further, the fluoroalkyl group has 13 or more carbon atoms or the alkyl group has 11 carbon atoms.
In the above cases, internal stress is likely to occur in the hard copolymer during the polymerization process for producing the soft contact lens.

Specific examples of the component (c) include 2,2,2-
Trifluoroethyl methacrylate, 2,2,3,3-
Tetrafluoropropyl methacrylate, 2, 2, 3,
3,3-pentafluoropropyl methacrylate, 2,
2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,3,4,4,5,5
-Octafluoropentyl methacrylate, 2,2
3,3,4,4,5,5,5-nonafluoropentyl methacrylate, 2,2,3,3,4,4,5,5,6
6,7,7-dodecafluoroheptyl methacrylate,
2,2,3,3,4,4,5,5,6,6,7,7,7
-Tridecafluoroheptyl methacrylate, 2,2
3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluorooctyl methacrylate, 2,2,2
3,3,4,4,5,5,6,6,7,7,8,8,8
-Pentadecafluorooctyl methacrylate, 2,
2,3,3,4,4,5,5,6,6,7,7,8,
8,9,9,10,10-octadecafluorodecyl methacrylate, 2,2,3,3,4,4,5,5,6
6,7,7,8,8,9,9,10,10,10-methacrylic acid fluoroalkyl ester such as nonadecafluorodecyl methacrylate; and n-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n Examples thereof include methacrylic acid alkyl esters such as heptyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, and n-decyl methacrylate. Preferred component (c) is 2,
2,3,4,4,4-hexafluorobutyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,3,4,4,5
5,6,6,7,7,8,8-tetradecafluorooctyl methacrylate, 2,2,3,3,4,4,5
5,6,6,7,7,8,8,8-pentadecafluorooctyl methacrylate, 2,2,3,3,4,4
5,5,6,6,7,7,8,8,9,9,10,1
0,10-nonadecafluorodecyl methacrylate, n
-Butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate and the like.

In the soft contact lens of the present invention
The content of the component (c) is 5 to 60 mol%, preferably 10 to
It is 50 mol%. When the content of the component (c) is less than 5 mol%, the mechanical strength of the soft contact lens decreases, while when it exceeds 60 mol%, the hardness of the soft contact lens increases and delayed elastic recovery is exhibited.

The component (d) constituting the soft contact lens of the present invention is an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, an ester of an unsaturated carboxylic acid and a branched or cyclic hydroxyl group-containing compound, and fluoroalkyl. The group is selected from branched or cyclic unsaturated carboxylic acid fluoroalkyl esters, said (a) ~ (c), (e) and (f)
It is at least one monomer copolymerizable with the components.

Specific examples of the unsaturated carboxylic acid in the component (d) include unsaturated monocarboxylic acids or unsaturated dicarboxylic acids such as acrylic acid, methacrylic acid and itaconic acid. Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid. As the unsaturated carboxylic acid anhydride, anhydrides of unsaturated dicarboxylic acids such as itaconic acid are used.

The branched or cyclic hydroxyl group-containing compound which forms an ester with the unsaturated carboxylic acid in the component (d) can be an aliphatic, alicyclic or aromatic hydroxyl group-containing compound. May be an alcoholic hydroxyl group or a phenolic hydroxyl group. The hydroxyl group-containing compound preferably has 4 to 10 carbon atoms and may have a substituent, but in that case, fluoroalkanol is not included.

Specific examples of the ester of the unsaturated carboxylic acid and the branched or cyclic hydroxyl group-containing compound include t
-Butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenoxy acrylate, phenoxy methacrylate, benzyl acrylate, benzyl methacrylate, terrahydrofurfuryl acrylate, terrahydrofurfuryl methacrylate, isobornyl acrylate, isobornyl methacrylate, etc. Can be mentioned. Preferred compound is cyclohexyl methacrylate,
Examples thereof include benzyl methacrylate and isobornyl methacrylate.

As the unsaturated carboxylic acid fluoroalkyl ester having a branched or cyclic fluoroalkyl group in the component (d), a branched or cyclic alkyl group having 3 to 10 carbon atoms is preferable. The fluoroalkyl group may have a substituent. Specific examples of the unsaturated carboxylic acid fluoroalkyl ester include 2,2,2-trifluoro-1-trifluoromethylethyl acrylate, 2,2,2-trifluoro-1-trifluoromethylethyl methacrylate and 2,2. , 3,3-Tetrafluoro-t-amyl acrylate, 2,2,3,3-tetrafluoro-t-amyl methacrylate, 2,2,3
4,4,4-hexafluoro-t-hexyl acrylate, 2,2,3,4,4,4-hexafluoro-t-hexyl methacrylate, 2,3,4,5,5,5-hexafluoro-2 , 4-bis (trifluoromethyl) pentyl acrylate, 2,3,4,5,5,5-hexafluoro-2,4-bis (trifluoromethyl) pentyl methacrylate, 2-hydroxy-4,4,5, 5,
6,7,7,7-octafluoro-6-trifluoromethylheptyl acrylate, 2-hydroxy-4,4
5,5,6,7,7,7-octafluoro-6-trifluoromethylheptyl methacrylate, 2-hydroxy-4,4,5,5,6,6,7,7,8,9,9,9 −
Dodecafluoro-8-trifluoromethylnonyl acrylate, 2-hydroxy-4,4,5,5,6,6
7,7,8,9,9,9-dodecafluoro-8-trifluoromethylnonyl methacrylate and the like can be mentioned. Particularly preferred compounds are 2,2,2-trifluoro-1-trifluoromethylethyl acrylate, 2,2
2,2-trifluoro-1-trifluoromethylethyl methacrylate, 2,2,3,4,4,4-hexafluoro-t-hexyl acrylate, 2,2,3,4
4,4-hexafluoro-t-hexyl methacrylate.

In the soft contact lens of the present invention
The content of the component (d) is 1 to 20 mol%, preferably 3 to 1
It is 5 mol%. The component (d) has a function of improving the mechanical strength of the soft contact lens of the present invention, but exhibits a remarkable effect even in a small amount. When the content of the component (d) is less than 1 mol%, the mechanical strength is insufficiently improved, and when it exceeds 20 mol%, the hardness of the soft contact lens is increased and delayed elastic recovery is exhibited.

The component (e) constituting the soft contact lens of the present invention has a straight-chain alkyl group having 1 to 10 carbon atoms.
At least 1 selected from the group consisting of a lower alkyl acrylate of 3 and a fluoroalkyl group having a straight chain and a lower carbon number of 1 to 3
It is the monomer of the species.

Of the component (e), specific examples of the acrylic acid lower alkyl ester having a linear alkyl group and having 1 to 3 carbon atoms are methyl acrylate, ethyl acrylate and n-propyl acrylate.

Of the component (e), specific examples of the acrylic acid lower fluoroalkyl ester having a linear fluoroalkyl group and having 1 to 3 carbon atoms include 2,2,2-trifluoroethyl acrylate and 2 , 2,3,3-tetrafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate and the like.

In the soft contact lens of the present invention
The content of the component (e) is 0 to 20 mol%, preferably 0 to 10 mol%. When the content of the component (e) exceeds 20 mol%, the oxygen permeability of the soft contact lens is lowered.

The component (f) constituting the soft contact lens of the present invention is a crosslinkable monomer and has two or more unsaturated bonds copolymerizable with the above-mentioned (a) to (e). However, the crosslinkable monomer does not include the compound having two or more polymerizable unsaturated bonds in the component (a).

Specific examples of the component (f) include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. Ethylene glycol diacrylate, propylene glycol dimethacrylate, propylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate , Trimethylolpropane triacrylate, etc. it can. Preferred crosslinkable monomers are ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.

In the soft contact lens of the present invention
The content of the component (f) is 0.1 to 10 mol%, preferably 1
~ 5 mol%. When the content of the component (f) is less than 0.1 mol%, the shape stability of the soft contact lens is lowered, and when it exceeds 10 mol%, the soft contact lens becomes brittle.

In the present invention, the monomer (a) used in the production of the soft contact lens is the one shown in the component (a), and the monomer (b) is the component (b) or As shown in component (e), the monomer (C) is as described above.
As shown in the component (c), the monomer (d) is the same as the above (d).
It is the one shown in the component, and the monomer (e) is
It is shown in the component (f). Further, the acrylic acid ester or acrylic acid contained in the monomer (d) forms the component (b) by the transesterification treatment and / or esterification treatment described below, and The methacrylic acid contained in (3) can form the component (c) by its transesterification and / or esterification treatment. Therefore, the acrylic ester component in the monomers (b) and (d) (that is, the acrylic ester represented by the general formula (II), the alkyl group is linear, and the number of carbon atoms is 1 to 3) Acrylic acid lower alkyl ester, fluoroalkyl group is linear and has a carbon number of 1 to 3) and the total amount of acrylic acid component is the total amount of all monomers (a) to (e). At least 10
Must be mol%. Further, the total amount of the acrylic acid ester component and the acrylic acid component is the total monomer (a).
When it exceeds 80 mol% of (e), the conversion rate in the transesterification treatment and / or the esterification treatment is adjusted so that (b), (d) and ( e) The content rate of each component is set to a predetermined value. Furthermore, the number of carbon atoms contained in the monomer (C) is 4
When the methacrylic acid ester with a linear unsubstituted alcohol of 10 to 10 accounts for 60 mol% of all the monomers (a) to (e), the methacrylic acid is contained in the monomer (d). However, in other cases, by adjusting the esterification rate according to the content of the methacrylic acid ester in the monomer (C), the (c) and (d) The content rate of the component is set to a predetermined value. In such a transesterification treatment and / or esterification treatment, an ester component other than a linear alkyl ester of acrylic acid and a linear fluoroalkyl ester and an acid anhydride component which are present in the hard copolymer. Are virtually unaffected.

The monomer (d) contains i) methacrylic acid or ii) a methacrylic acid alkyl ester whose alkyl group is branched or cyclic, and a fluoroalkyl group which is branched or cyclic methacrylic acid fluoroalkyl ester. It is preferable to contain at least one of the above and acrylic acid, and in the case of the above i), it is preferable to further contain acrylic acid. When the monomer (d) contains methacrylic acid, its content is preferably 5 to 40 mol% of the monomer (d), and when the monomer (d) contains acrylic acid. The content is preferably 20 to 75 mol% of the monomer (d). Furthermore, when the monomer (d) contains both methacrylic acid and acrylic acid, the total amount thereof is preferably 30 to 80 mol% of the monomer (d).

In the production of the soft contact lens of the present invention, the contact lens-shaped lens base body made of a hard copolymer is, for example, (1) the above monomers (a) to (e).
A method of directly polymerizing a monomer mixture having a predetermined composition of in a contact lens-shaped mold, (2) polymerizing a monomer mixture having a predetermined composition of the monomers (a) to (e) After obtaining a block-shaped hard copolymer, a method of cutting and polishing the block-shaped hard copolymer into a contact lens shape,
And the like. Of these, the method (1) requires a large number of precise molding dies according to the shape and size of the contact lens, and thus has problems in economic efficiency, workability, etc. The method is preferred.
Hereinafter, the method (2) will be mainly described, but the polymerization behavior here basically also applies to the method (1).

Now, the polymerization in the above method (2) is
Generally, radical polymerization is used. For that purpose, a monomer mixture having a predetermined composition is stepwise heated in the range of 30 to 120 ° C. in the presence of a thermal polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile. Polymerization by heating or irradiation with ultraviolet rays in the presence of a suitable photopolymerization initiator such as benzophenone, Michler's ketone, benzoin methyl ether, benzoin isopropyl ether and the like, and generally polymerization at a temperature of 0 to 120 ° C. Can be adopted. When the polymerization temperature is raised stepwise using a thermal polymerization initiator to perform polymerization, two or more thermal polymerization initiators having different decomposition temperatures can be used in combination. In these polymerizations, the thermal polymerization initiator or the photopolymerization initiator is generally used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of all the monomers. The hard copolymer thus obtained is cut and then polished to obtain a hard lens substrate having the same shape as the intended soft contact lens.

Next, the contact lens-shaped lens substrate made of the hard copolymer obtained as described above is brought into contact with a linear unsubstituted alcohol having 4 to 10 carbon atoms to give the above-mentioned monomer ( (B) and (d), the acrylic ester or the ester bond and / or the carboxyl group derived from acrylic acid are subjected to a transesterification treatment and / or an esterification treatment with the linear unsubstituted alcohol having 4 to 10 carbon atoms, In some cases, the other unsaturated carboxylic acid in the monomer (d) is simultaneously esterified with the straight chain unsubstituted alcohol having 4 to 10 carbon atoms. The transesterification rate of the acrylic acid ester in the monomers (b) and (d) is selected in consideration of the content rate of the acrylic acid ester, the reaction time, etc., but is usually 60% or more, preferably 70 to 90%. The esterification rate of unsaturated carboxylic acids such as acrylic acid and methacrylic acid in the monomer (d) is preferably 70 to 95% as a whole. By the transesterification treatment and / or the esterification treatment, a lens substrate made of the hard copolymer having a glass transition point of about 50 ° C. or higher is generally a glass of about 20 ° C. or lower, preferably 0 ° C. or lower. It changes to a soft copolymer having a transition point, and the desired soft contact lens can be obtained.

The transesterification treatment and / or esterification treatment of the lens substrate in the present invention can be carried out by bringing the lens substrate into contact with alcohol, preferably by immersing the lens substrate in alcohol. Examples of the linear unsubstituted alcohol having 4 to 10 carbon atoms used here include n-butyl alcohol and n.
-Pentyl alcohol, n-hexyl alcohol, n-
Examples thereof include heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, and n-decyl alcohol, and these alcohols may be used alone or in combination of two or more.

In the transesterification treatment and / or the esterification treatment, it is preferable to use an appropriate catalyst such as an esterification catalyst in order to accelerate the reaction. Examples of the catalyst include concentrated sulfuric acid, methanesulfonic acid, toluenesulfonic acid and the like. The concentration of these catalysts in alcohol is preferably 0.2 to 10% by weight, and the treatment time is usually about 1 to 100 at a temperature of about 20 to 200 ° C.
It's time. Appropriate conversion rate of transesterification and / or esterification depending on the specific components in the monomers (b) to (d) and the content of each component is to adjust the treatment temperature, treatment time, etc. The appropriate processing conditions in each case can be found by experiments and the like. Also, the transesterification treatment and / or
Alternatively, during the esterification treatment, the lens substrate is contacted with a hydrocarbon such as toluene in advance, an ether such as ethyl ether, water or the like, or a linear unsubstituted alcohol having 4 to 10 carbon atoms is mixed with a hydrocarbon such as toluene. By doing so, it is possible to prevent the soft contact lens from being damaged during processing. In the lens substrate after the transesterification treatment and / or the esterification treatment in the present invention, unreacted alcohol, alcohol by-produced, catalyst used, solvent, water, etc. are contained.
It is preferable to wash using a Soxhlet extractor or the like. Examples of the washing solvent therefor include hydrocarbons such as toluene, halogenated hydrocarbons such as dichloromethane and chloroform, acetone, methyl ethyl ketone, 2-
Examples include ketones such as pentanone, alcohols such as methyl alcohol, ethyl alcohol, and n-hexyl alcohol, which have a boiling point of 150 ° C. or less. When washing using a Soxhlet extractor, the boiling temperature of the washing solvent is 1 to 100 hours, preferably 2 to 4
Reflux for 8 hours. It is sufficient to dry the washed soft contact lens as it is at 20 to 150 ° C., but in some cases, solvent washing may be followed by water washing.

[0043]

EXAMPLES The specific modes and effects of the present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Example 1 42 mol% acrylic acid, tris (trimethylsiloxy)
Silyl propyl methacrylate 25 mol%, 3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
30 mol% of 0,10,10-heptadecafluorodecyl methacrylate and 3 mol% of ethylene glycol dimethacrylate were mixed, and benzoin methyl ether was used as a photopolymerization initiator in an amount of 0.1 part by weight based on 100 parts by weight of the monomer mixture. In a polyethylene container, UV light was irradiated at room temperature for polymerization for 16 hours under a nitrogen atmosphere. After the polymerization, the obtained block copolymer was cut and polished to form a contact lens-shaped lens substrate. This lens substrate was immersed in n-butyl alcohol, 0.5% by weight of methanesulfonic acid was added, and the mixture was reacted at reflux temperature for 48 hours to esterify acrylic acid in the copolymer with n-butyl alcohol. .. After esterification, the product was washed with acetone using a Soxhlet extractor and dried to obtain a non-hydrated soft contact lens. The esterification rate of acrylic acid in the copolymer with n-butyl alcohol was determined from the weight change before and after esterification, and it was about 90%. Therefore, the copolymer composition after the esterification treatment is 4.2 mol% acrylic acid, 37.8 mol% acrylic acid ester of n-butyl alcohol, 3,3,4,4,4.
5,5,6,6,7,7,8,8,9,9,10,1
0,10-heptadecafluorodecyl methacrylate 3
It becomes 0 mol% and ethylene glycol dimethacrylate 3 mol%. Then, the following test was performed on the obtained soft contact lens. In addition, in the test of oxygen permeability coefficient, a test piece having a thickness of 0.2 mm and a diameter of 15 mm, and in the test of presence or absence of deformation and mechanical strength, a thickness of 0.5
A test piece having a diameter of 15 mm and a diameter of 15 mm was separately prepared from the copolymer obtained in the same manner as above and used for the test. (1) Oxygen Permeability Coefficient: Measured in a 0.9 wt% physiological saline solution at 35 ° C. using a Seikaken film oxygen permeation meter manufactured by Rika Seiki Co., Ltd. (2) Visible light transmittance: measured with a double beam spectrophotometer 200-20 manufactured by Hitachi, Ltd. before wearing soft contact lenses and after wearing for 1 week. (3) Deformation: NEITZ type radioscope C
Tested with GD type. (4) Mechanical strength: Tensile strength and elongation at break were measured by Autograph IS-2000 manufactured by Shimadzu Corporation. The test results are shown in Table 1.

Examples 2 to 8 Polymerization, processing, transesterification and / or esterification were carried out in the same manner as in Example 1 except that the monomers used and the amounts used were as shown in Table 2, and the softening was performed. I got contact lenses. When the esterification rate and the transesterification rate were determined in the same manner as in Example 1, in each Example,
The esterification rate of acrylic acid was about 90%, the esterification rate of methacrylic acid was about 80%, the transesterification rate of methyl acrylate was about 85%, and the transesterification rate of butyl acrylate was about 80%. Table 3 shows the copolymer composition after the esterification treatment and the transesterification treatment. The obtained non-hydrous soft contact lens was tested in the same manner as in Example 1. The test results are shown in Table 1.

Comparative Example 1 76 mol% of acrylic acid, 3,3,4,4,5,5,6,6
21 mol% of 6,7,7,8,8,8,9,9,10,10,10-heptadecafluorodecyl methacrylate and 3 mol% of ethylene glycol dimethacrylate were mixed, and benzoin methyl ether was used as a photopolymerization initiator. 0.02 parts by weight was added to 100 parts by weight of the monomer mixture, and polymerization was carried out in the same manner as in Example 1. After the polymerization, the obtained block copolymer was cut and polished to form a contact lens-shaped lens substrate. This lens substrate was immersed in n-hexyl alcohol, 4% by weight of methanesulfonic acid was added, and the mixture was reacted at reflux temperature for 48 hours to esterify acrylic acid in the copolymer with n-hexyl alcohol. After esterification, wash with acetone, dry,
I got a soft contact lens. When the esterification rate of acrylic acid in the copolymer was determined in the same manner as in Example 1, it was about 97%. Therefore, the copolymer composition after the esterification treatment was 2.3 mol% of acrylic acid, 73.7 mol% of n-hexyl acrylate, 3,3,4,4.
5,5,6,6,7,7,8,8,9,9,10,1
0,10-heptadecafluorodecyl methacrylate 2
1 mol% and ethylene glycol dimethacrylate 3
It was mol%. The obtained soft contact lens was tested in the same manner as in Example 1. The test results are shown in Table 1.

Comparative Example 2 Tris (trimethylsiloxy) silylpropyl methacrylate 30 mol%, 2,2,3,4,4,4-hexafluorobutyl methacrylate 35 mol%, butyl acrylate 32 mol% and bis (methacryloxypropyl) Mixing 3 mol% of octamethyltetrasiloxane,
After adding 0.3 parts by weight of azobisisobutyronitrile as a thermal polymerization initiator to 100 parts by weight of the monomer mixture, the mixture is poured into a contact lens mold under a nitrogen atmosphere and circulated at 50 ° C. 10 hours in water, 70 °
Polymerization was performed by heating stepwise at C for 2 hours and at 100 ° C. for 4 hours to obtain a soft contact lens. The soft contact lens obtained is dried under reduced pressure at 100 ° C. for 20 hours,
Unreacted monomer was removed. This soft contact lens was tested in the same manner as in Example 1. The test results are shown in Table 1.

[0047]

The non-hydrous soft contact lens formed from the hard copolymer of the specific composition of the present invention has a significantly higher oxygen permeability than the conventional hydrous or non-water-containing soft contact lens, and therefore has a long life. Even when worn for a long time, there is no metabolic disorder in the corneal tissue, and the feeling of wearing is good. Further, it is excellent in mechanical strength such as tensile strength and elongation at break, has good elastic recovery, and does not deform.
Moreover, it does not require boiling sterilization and is highly resistant to stains from tear components. Therefore, the soft contact lens of the present invention exhibits excellent overall characteristics.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08J 7/12 7258-4F G02B 1/04 7132-2K

Claims (2)

[Claims] 1. (a) 5 to 60 mol% of at least one organosiloxane monomer represented by the following general formula (I), and (b) at least one type represented by the following general formula (II). Acrylic ester monomer 10 to 80 mol%, (c) 5 to 60 mol% of at least one methacrylic acid ester monomer represented by the following general formula (III), (d) unsaturated carboxylic acid, At least one monomer 1 selected from a saturated carboxylic acid anhydride, an ester of an unsaturated carboxylic acid and a branched or cyclic hydroxyl group-containing compound, and an unsaturated carboxylic acid fluoroalkyl ester having a branched or cyclic fluoroalkyl group 1 ˜20 mol%, (e) Acrylic acid lower alkyl ester having a straight-chain alkyl group having 1 to 3 carbon atoms and a fluoroalkyl group having a straight chain having lower carbon number of 1 to 3 D A monomer (a) to (f) containing 0 to 20 mol% of at least one monomer selected from the ter, and (f) 0.1 to 10 mol% of at least one crosslinkable monomer. ) Total amount is 100 mol%
A non-hydrous soft contact lens characterized by being formed from a copolymer of General formula (I) [In the formula, A is a polymerizable unsaturated group, X is a C 1-10 2
A valent hydrocarbon group, R ^{1 to} R ⁶ are independently of each other a hydrogen atom, an alkyl group, a fluoroalkyl group, a phenyl group, a vinyl group or a Z group, and a Z group is represented by the formula: (Wherein B is a hydrogen atom or A, A and X are the same as above, R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, a fluoroalkyl group, a phenyl group or a vinyl group,
k is an integer of 0 to 100), Y is a carbon number of 1 to
20 fluoroalkyl groups, C1-C20 alkyl groups or Z groups, and j is an integer of 0-100. ], General formula (II) [Wherein R ⁹ is of the formula (CH ₂ ) mCnFpHq (where m is 1 or 2
Is an integer, n is an integer of 3 to 8, p is an integer of 4 or more, and q is 0.
A linear fluoroalkyl group of the above integer, p + q = 2n + 1) or a linear alkyl group of the formula CrH ₂ r + ₁ (where r is an integer of 4 to 10). ], The general formula (III): [Wherein R ¹⁰ is a formula (CH ₂ ) sCtFuHv (where s is an integer of 1 or 2, t is an integer of 1 to 10, u is an integer of 3 or more, v
Is an integer of 0 or more, a linear fluoroalkyl group of u + v = 2t + 1) or a formula CwH ₂ w + ₁ (where w is an integer of 4 to 10)
Is a linear alkyl group. ]. 2. (a) At least one organosiloxane monomer 5-6 represented by the general formula (I) according to claim 1.
0 mol%, (b) The acrylic acid ester represented by the general formula (II) according to claim 1, a straight-chain alkyl group, and a straight-chain acrylic acid lower alkyl ester having 1 to 3 carbon atoms and a fluoroalkyl group. 0 to 80 mol% of at least one monomer selected from acrylic acid lower fluoroalkyl esters having a chain structure and having 1 to 3 carbon atoms, (c) at least represented by the general formula (III) according to claim 1. 5-60 mol% of one methacrylic acid ester monomer, (d) unsaturated carboxylic acid, unsaturated carboxylic acid anhydride,
10 to 90 mol% of at least one monomer selected from an ester of an unsaturated carboxylic acid and a branched or cyclic hydroxyl group-containing compound and a fluoroalkyl group selected from branched or cyclic unsaturated carboxylic acid fluoroalkyl ester,
And (e) 0.1 to 10 mol% of at least one crosslinkable monomer, the total amount of all monomers is 100 mol%, and the amount of the monomers (b) and (d) is The total amount of acrylic acid ester and acrylic acid is at least 1 of all monomers.
A contact lens-shaped lens base made of a hard copolymer obtained by polymerizing 0 mol% of a monomer mixture is formed, and then the lens base is contacted with a linear unsubstituted alcohol having 4 to 10 carbon atoms. At least 1 represented by the general formula (II) according to claim 1 in the copolymer.
10-80 mol% of acrylic acid ester monomer,
5-60 mol% of at least one methacrylic acid ester monomer represented by the general formula (III) according to claim 1, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a branched carboxylic acid of unsaturated carboxylic acid Or 1 to 20 mol% of at least one kind of monomer selected from ester with cyclic hydroxyl group-containing compound and fluoroalkyl group having branched or cyclic unsaturated carboxylic acid, and linear alkyl group And 0 to 20 mol of at least one monomer selected from an acrylic acid alkyl ester having 1 to 3 carbon atoms and a fluoroalkyl group having a linear structure and having a carbon number of 1 to 3 The non-hydrous soft contact lens according to claim 1, characterized in that the transesterification treatment and / or the esterification treatment are carried out until the content becomes%. The method of production.