JPH02293818A - Contact lens - Google Patents

Abstract

PURPOSE:To obtain the contact lens which has an excellent visual correcting effect, oxygen permeability to allow long-period continuous wearing and excellent shape stability, staining resistance and durability by incorporating a copolymer contg. a specific 1-butene-2, 4-dicarboxylate monomer as an essential raw material monomer into the contact lens. CONSTITUTION:The copolymer contg. 2 to 95wt.% 1-butene-2, 4-dicarboxylate monomer expressed by formula I as the essentially raw material monomer is incorporated into the contact lens. In the formula I, R1 and R2 are groups, at least one of which is a group contg. a fluorine atom, and are hydrogen atom, 1 to 12C alkyl group, 1 to 12C alkenyl group, 3 to 12C cyclic alkyl group or aryl group; n and m respectively denote 0 to 4 integer. The oxygen permeability is enhanced in this way and the deposition of protein, lipid and inorg. materials, etc., on the surface is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a contact lens, and more particularly to a contact lens with excellent oxygen permeability and the like.

BACKGROUND ART Currently, oxygen permeable (hereinafter abbreviated as GP) hard contact lenses and water-containing soft contact lenses are known as contact lenses commonly used. Although the water-containing soft contact lenses have excellent wearing comfort, the oxygen permeability of the material is insufficient. Therefore, it is possible to increase the moisture content of the material in order to increase its oxygen permeability, but clinical results have shown that it is more likely to be contaminated with bacteria and cause serious complications for the cornea and conjunctiva. There is. On the other hand, OP hard contact lenses are highly evaluated for their high oxygen permeability, astigmatism correcting effect, durability, and safety, and are becoming the mainstream contact lens. Along with this, research on GP hard contact lenses is also being actively conducted, but the reality is that each of the above GP contact lenses pursues only oxygen permeability, and does not have sufficient other properties required for contact lenses. .

For example, JP-A-62-8769, JP-A-62-6
The contact lenses described in Japanese Patent Publication No. 1928 and Japanese Patent Publication No. 63-36646 have good oxygen permeability, but
There are problems with shape stability and stain resistance. On the other hand, JP-A-62
The dialkyl fumarate used in JP-A-99720 and JP-A-62-212618 has poor copolymerizability, and even if it can be copolymerized, it is very brittle and is dangerous because it is easily broken. Also, JP-A No. 61-176909
The contact lens disclosed in the publication has low oxygen permeability and is unsuitable for continuous wear, which has attracted particular attention in recent years.

Problems to be Solved by the Invention The purpose of the present invention is to provide a contact lens that has an excellent vision correction effect, has oxygen permeability that can be worn continuously for a long period of time, and has excellent shape stability, stain resistance, and durability. It is about providing.

<Means for Solving the Problems> According to the present invention, the following general formula (I) (wherein R and R2 are the same or different groups, and at least one group is a group containing a fluorine atom) , hydrogen atom, alkyl group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms
1-butene-2,4-dicarboxylic acid diester monomer represented by alkenyl group, cyclic alkyl group or aryl group having 3 to 12 carbon atoms, and n and m each represent an integer of 0 to 4) A contact lens is provided that includes a copolymer containing from 2 to 95% by weight of heptamers as essential raw material heptanomers.

The present invention will be explained in more detail below.

The contact lens of the present invention has a specific 1-butene-2,
It is characterized by containing a copolymer containing a 4-dicarboxylic acid ester monomer as a raw material monomer.

The 1-butene-2,4-dicarboxylic acid ester monomer used in the present invention can be represented by the following general formula (1), in which RL and R2 are the same or different groups, and at least one of is a group containing a fluorine atom, and represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, or an aryl group, and n and m each represents an integer of 0 to 4. When the number of carbon atoms in Ri and/or R2 is 13 or more,
Alternatively, if n and/or m are 5 or more, manufacturing is difficult. Further, it is preferable that the number of fluorine atoms contained in at least one of R and R2 is 3 or more. Examples of the 1-butene-2,4-dicarboxylic acid diester monomer represented by the general formula (1) include 2-(methoxylponylethyl)-2'2'2'
monotrifluoroethyl acrylate, 2-(methoxylponylethyl)-1'1'1'3'
3'3' -hexafluoroisopropylacrylate, 2-(methoxylponylethyl)-1'
,1'2'2'-Tetrahydroperfluoroctyl acrylate, 2-(methoxyluponylethyl)-1'1'2'2'-tetrahydroperfluorodecyl acrylate, 2-(ethoxyluponylethyl)-2' 2 '2'-trifluoroethyl acrylate, 2-(ethoxylponylethyl)-1'1',.1'3',3' ,
3'-hexafluoro-2-isopropylacrylate, 2-(ethoxylponylethyl)-1',1'
2'2'-tetrahydride-perfluoroctyl acrylate, 2-(ethoxylponylethyl)-1'
1'2'2' -Tetrahydride perfluorodecyl acrylate, 2-(isoprobyloxycarponylethyl)-2',2'2'trifluoroethyl acrylate, 2-(isoprobyloxycarponylethyl)-1'1'1'3'3'
3'-hexafluoro-2-isopropylacrylate, 2-(isopropyloxycarponylethyl)
-1',1',5'trihydroperfluoropentyl acrylate, 2-(isoprobyloxycarponylethyl)-1',1',2'2'-tetrahydroperfluoroctyl acrylate, 2-(isoprobyloxycarponylethyl) carponylethyl)-1'1' 2
'2'-tetrahydride perfluorodecyl acrylate, 2-(tert-butyloxylponylethyl)-
2',2',2'-trifluoroethyl acrylate, 2-(tert-butyloxytriponylethyl)-1',1',1'3'3',3'-1-hexafluoro-2-isopropylacrylate , 2-(
tert-butyloxytriponylethyl)-1',
1'2'2'-Tetrahydroperfluoroctyl acrylate, 2-(tertiarybutinoleoxycanolebonylethyl)-1'1'2'
2'-tetrahydrodeperfluorodecyl acrylate, 2-(2'2'2'-trifluoroethyloxycarponylethyl)ethyl acrylate, 2-(2'
2'2'-trifluoroethyloxycarponylethyl) isoprobyl acrylate, 2-(].'1'
1'3'3'3' monohexafluoro-2-isoprobyloxycarponylethyl)
Ethyl acrylate, 2-(1',1',2'2
2-(2',2'
, 2' monotrifluoroethyloxycarponylethyl) tert-butyl acrylate, 2-(1' 1
',2',2'-te1helahydoperfluorooctyloxyproponylethyl)isoprobyl acrylate,2-(2',2'2'-triphnoleoloethynoleoxyproponylethyl)-2",2' 2 '-trifluoroethyl acrylate, 2-(1',1']'
,3'3'3'-hexafluoro-2-isoprobyloxycarponylethyl)-1',1',1"3'
3'3'-hexafluorisopropyl acrylate, 2-(1'1',2',2'tetrafunoleopropyloxypropylethyl)-1' 1
'2'2'-tetrafluoropropyl acrylate, 2-(1', 1'5' monotrihydroperfluoropentyloxypropyl ethyl)-1'
, 1',5'-trihydroperfluoropentyl acrylate, etc., and can be used alone or as a mixture. The content ratio of the 1-butene-2,4-dicarboxylic acid diester monomer, which is the essential raw material component, is as follows with respect to the total raw material monomers:
It ranges from 2 to 95% by weight. The content of 1-butene-2,4-dicarboxylic acid diester monomer is 2% by weight.
If it is less than 95% by weight, the oxygen permeability will be extremely low, and if it exceeds 95% by weight, it will not be able to maintain its strength as a contact lens, and since it contains fluorine atoms, its water repellency will be too high, making it unusable.

In the present invention, the 1-butene-2,4-dicarboxylic acid diester represented by the general formula (1) can be prepared by a known method.

Specifically, it can be obtained, for example, by a method in which fluoroalkyl acrylate is dissolved in dioxane as a solvent and reacted at about 90° C. for about 7 hours in the presence of tertiary phosphine as a catalyst and in an inert gas atmosphere.

The contact lens of the present invention can be copolymerized with any other polymer as long as it contains the 1-butene-2,4-dicarboxylic acid diester monomer represented by the general formula (1) as an essential raw material heptamer. Monomers can be copolymerized, but in view of the thermal safety, mechanical strength, processability, etc. of the resulting contact lenses, other copolymerizable monomers, such as radically polymerizable vinyl monomers and silicon-containing vinyl monomers, are recommended. It is preferable to use a monomer selected from the group consisting of fluorine-containing vinyl monomers, crosslinkable polyfunctional vinyl monomers, mixtures thereof, and the like. Examples of the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer include methyl (meth)acrylate, ethyl (meth)acrylate, isoprobyl (meth)acrylate, and tert-butyl (meth)acrylate. ) acrylate, cyclohexyl (meth)acrylate, benzyl (
meth)acrylate, styrene, p-methylstyrene,
p-Chlorstyrene, 0-chlorostyrene, divinylbenzene, vinyl acetate, vinyl propionate, vinyl piperate, vinyl (meth)acrylate, 2,2.2-trifluoroethyl (meth)acrylate, ethyl vinyl ether, n-butyl Vinyl ether, (meth)acrylic acid amide, 2-hydroxyethyl (meth)acrylate, N-vininolepyrrolidone, vinylepyridine. Allyl(meth)acrylate, trimethylsilylmethyl(meth)acrylate, pentamethyldisyxanylmethyl(meth)acrylate, methylbis(trimethylsiloxy)silylmethyl(meth)acrylate, tris(trimethylsiloxy)silylmethyl(meth)acrylate,
Tris(pentamethyldisyxanyloxy)silylmethyl(meth)acrylate, trimethylsilylethyl(
meth)acrylate, pentamethyldisisoxanyl ethyl (meth)acrylate, methylbis(trimethylsiloxy)silylethyl(meth)acrylate, tris(trimethylsiloxy)silylethyl(meth)acrylate, tris(pentamethyldisisoxanyloxy)silylethyl(meth)acrylate, trimethylsilylpyl (meth)acrylate, pentamethyldisiloxanyl (meth)acrylate, methylbis(trimethylsiloxy)silylpyl(meth)acrylate, tris(trimethylsiloxy)silylpyl(meth)acrylate, tris(pentamethyldisiloxanyloxy)silylpyl Mouth pill (meth)acrylate, methylbis(trimethylsiloxy)silylethylglycerol mono(meth)
Acrylate, Tris(trimethylsiloxy)silylethylglycerol Mono(meth)acrylate, Tris(
Pentamethylsiloxysilylglycerol mono(meth)acrylate, methylbis(trimethylsiloxy)silylglycerol mono(meth)acrylate, tris(trimethylsiloxy)silylglycerol mono(meth)acrylate, tris(pentamethylsiloxy)silylglycerol Glycerol mono(meth)acrylate, dimethyl(triphenylsiloxy)silylpyl(meth)acrylate. 2,2.2-trifluoroethyl (meth)acrylate, 2,2.2-trifluoro-1-trifluoromethyl (meth)acrylate, 3,3,4,4,5,5,6
, 6,6-nonafluorohexyl (meth)acrylate, 2,2,3,3,4,4,5.5-octafluoropentyl (meth)acrylate, 1,l,2.2-tetrahydrideperfluoroctyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, diallyl phthalate, diallyl isofumarate, diallyl terephthalate, diethylene glycol Bisalinolecarbonate, triallyl trimellitate, triallyl cyanurate, diisoprobyl itaconate, ditertiarybutyl itaconate,
2.2.2-trifluoroethyl itaconate, ethyl trimethylsilylprobyl itaconate, ditert-butyl fumarate, 2.2.
2-trifluoroethyl fumarate, isoprobil-3
．． 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9,
Examples include 9,10,10.10-heptadelytic fluorodecyl fumarate, tert-butyltritrimethylsilylprobyl fumarate, methacrylic acid, acrylic acid, itaconic acid, etc., which may be used alone or as a mixture. Can be used. When using the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer, it is desirable to use it in a range of 5 to 85% by weight. At this time, if it is less than 5% by weight, sufficient thermal stability, mechanical strength, processability, etc., cannot be obtained by copolymerization.
Moreover, if it exceeds 85% by weight, the oxygen permeability of the contact lens will be significantly reduced, which is not preferable.

Contact lenses 1 to 1 of the present invention have a DK value of 6 to 1 2 × 1 0 to 10 mQ・
an/al-see-mm! {g is preferable, especially 7 to 11×1 0-”mQ-an/al-sec-mm
Hg is preferred. In this case, 6×10-”mQ-cm
Oxygen permeability is insufficient for long-term continuous wear at less than /a See-mmHg, and l 2 X 10-
If it exceeds ``mQ-cxr/a+f .see .mn+Hg, physical properties such as strength of the contact lens will deteriorate, which is not preferable.

In order to prepare contact lenses in the present invention, known preparation methods can be used. Specifically, for example, the monomer raw materials are copolymerized together with a polymerization initiator in a suitable container such as a test tube to obtain a round piece or a block, and then mechanical processing such as cutting and polishing is performed to form a compound according to the formulation. A method for processing a contact lens, a method in which the monomer is injected together with a polymerization initiator into a single desired mold, and a contact lens is directly molded by mold polymerization, or a copolymer is produced in advance by a radical polymerization method, etc. Afterwards, the copolymer is dissolved in a suitable solvent and the solvent is removed by the Cath method to obtain a contact lens. In the above preparation method, the polymerization initiator used when polymerizing the heptanomer is selected to have a 10-hour half-life temperature of 1.
It can be selected from one or more of the group consisting of organic peroxides of 20'C or less, azo compounds, and the like. Examples of the organic peroxide or azo compound include penzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxydi-2ethylhexanoate, thi-butylperoxypiparate, t-butylperoxydiisobutyrate, lauroyl oxide,
Preferable examples include azobisisobutyroni-1-lyl, azobis(2,4-dimethylvaleroni-1-lyl), sheeptyl peroxyisobutyl carbonate, and the like. The amount of the polymerization initiator used is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of the raw material monomer.

In addition, in the above preparation method, the conditions for copolymerizing each monomer include replacing the polymerization system with an inert gas such as nitrogen, carbon dioxide, helium, etc., or polymerizing under an atmosphere or under deaerated conditions. preferable. The temperature during copolymerization varies depending on the type of polymerization initiator used, but is preferably in the range of 30 to 120°C.

Further, the total time required for polymerization is preferably about 10 to 72 hours.

It is also possible to polymerize the raw heptanomer by adding coloring such as a dye or adding additives such as an ultraviolet absorber.

In the present invention, the surface of the contact lens obtained by the above-mentioned preparation method can be modified by subjecting it to acid or alkali treatment or low-temperature plasma treatment. Furthermore, the wearing comfort can be improved by polymerizing a hydrophilic monomer into Graph 1 by low-temperature plasma treatment.

<Effect of the invention> The contact lens of the present invention has a specific 1-butene-2,
Because it uses a 4-dicarboxylic acid diester monomer, it has higher oxygen permeability than conventional contact lenses, and can prevent the deposition of proteins, lipids, and inorganic substances on the surface. It has excellent performance that improves the shortcomings of

<Examples> The present invention will be explained in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited thereto.

Note that the middle part of the example represents parts by weight.

11U-2-(isopropynoleoxycanolebonylethyl)-1
' , 1'5' - 40 parts of trihydroperfluorobentyl acrylate, 15 parts of tristrimethylsiloxysilylpropyl methacrylate, ■, 1. ,2.2
-tetrahydride perfluorodecyl methacrylate 15
parts, ethyl methacrylate 20 parts, allyl methacrylate
1 to 5 parts of methacrylic acid and 1.0 part of azobis(2,4-dimethylvaleronitrile) were mixed, the mixture was charged into a glass sealed tube, the inside was replaced with nitrogen, degassing was repeated, and the solution was dissolved under vacuum. Sealed. This sealed tube was placed in a thermostatic oven at 70'C for 2 hours.
External polymerization was carried out for 4 hours, and the mixture was further heated at 100° C. for 2 hours.

Next, the obtained polymer was cut, then cut and polished to produce a contact lens. Various physical properties of the obtained contact lenses were measured by the following methods. Table 1 shows the blending ratio of each raw material heptanomer and polymerization initiator, and Table 2 shows the measurement results.

,', DK value Xertex Corporation (XertexCorp
Product name: [MODEL 211]
0] (Multirange Analyzer f
or Dissolved Oxygen)
Test contacts with a diameter of 12.7 Rl and a thickness of 0.2 on in 0.9% saline at ℃! - The lens was measured and the DK value (cc-cM/d-sec/mmHg) was determined.

12.7 volumes in diameter in 0.2% egg white lysozyme aqueous solution by Ai Gojosaku.
Test contact lenses with a thickness of 0.2 mm were heated at 37°C for 2 hours.
The sample was immersed for 4 hours, and the change in absorbance at 280 nm was measured to determine the amount of the egg white lysozyme aqueous solution attached.

Vickers hardness HV Measured using a Terasawa type MM-2 ultra-micro hardness tester manufactured by Taiyo Tester Co., Ltd.

2) Separately polymerized indigo skin, thickness 2m, length 50n+m, width 10nyn
A flat plate sample was measured in accordance with JIS K7203 bending test method for hard plastics. After curing using the radical polymerization initiator shown in Table 1, contact lenses were prepared and various physical properties were measured. Table 1 shows the blending ratio of the raw heptanomer and polymerization initiator, and Table 2 shows the measurement results.

Table 1 Table (units are parts by weight) iPF8-A: 2-(isoprobyloxycarponylethyl)-1',l',5'-trihydro a perfluoro a pentyl acrylate Si-MA: tristrimethylsiloxysilylpropyl methacrylate F6
-MA: 1,1,l,3,3,3-hexafluorisoprovir methacrylate F17~MA: 1,1,
2.2-tetrahydride perfluorodecyl methacrylate MMA: methyl methacrylate, EMA: ethyl methacrylate A-MA: allyl methacrylate, V
-MA: vinyl methacrylate MA: methacrylate,
AA: Acrylic acid ABVN: Azobis(2,4-
dimethylvaleronitrile) P: diisopropyl peroxydicarbonate BPO: benzoyl peroxide ($l) XIO-”mQ-am/a#-sec・m
mHg (*2) kdld ' (Book 3) N/Door ♂ From the results in Table 2, it was found that the contact lens of the present invention has significantly superior oxygen permeability and excellent stain resistance. .

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R_1 and R_2 are the same or different groups,
In addition, at least one of the groups is a group containing a fluorine atom, such as a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a group having 1 to 12 carbon atoms.
12 alkenyl group, cyclic alkyl group or aryl group having 3 to 12 carbon atoms, and n and m each represent an integer of 0 to 4). A contact lens comprising a copolymer containing 2 to 95% by weight of a copolymer as an essential raw material monomer.