JPH03154022A - Contact lens - Google Patents

Abstract

PURPOSE:To obtain the lens having high oxygen permeability and excellent contamination resistance and durability by incorporating a specific 1-pentene-2, 3, 4-tricarbonic triester copolymer into the contact lens. CONSTITUTION:The copolymer formed by copolymerizing 2 to 95wt.% 1 or >=2 kinds of the 1-pentene-2, 3, 4-tricarbonic triester monomers expressed by general formula I (where R1, R2, R3 are the same or different groups and denote a hydrogen atom, 1 to 12C alkyl group, 1 to 12C alkenyl group, 3 to 12C cyclic alkyl group or formula II; X, Y, Z are the same or different groups and denote a methyl group, formula III to formula VII; (m), (n) and (l) denote 0 or 1; (p), (q) and (r) denote 0 to 3 integer; (k) denotes 2 to 4 integer) as essential raw material monomers is incorporated into the contact lens.

Description

[Detailed Description of the Invention] <Industrial Field of Application> The present invention relates to contact lenses, and more particularly to contact lenses with excellent oxygen permeability. Known contact lenses include oxygen permeable (hereinafter abbreviated as GP) hard contact lenses and water-containing soft contact lenses. Although the water-containing soft contact lens has 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 the 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 mucous membranes. There is. On the other hand, GP hard contact lenses are highly evaluated for their high oxygen permeability, astigmatism correction 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 have problems in shape stability and stain resistance. On the other hand, JP-A-62-
The dialkyl fumarates used in JP-A No. 99720 and JP-A-62-2''12618 have poor copolymerizability, and even if they can be copolymerized, they are very brittle and easily break, which is dangerous. , Japanese Patent Publication 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 object of the present invention is to provide a device that has an excellent vision correction effect, has oxygen permeability that allows continuous wear for a long period of time, and has shape stability.

Our objective is to provide contact lenses with excellent stain resistance and durability.

<Means for Solving the Problems> According to the present invention, the following general formula (I) (wherein R1, R, and R3 are the same or different groups, a hydrogen atom, a carbon number of 1 to 12 Alkyl group, carbon number 1
~12 alkenyl group, having 3 to 12 carbon atoms X, Y and Z are the same or different groups.

Indicates a methyl group. Also, m, n and Q are O or 1, P+q and r
represents an integer of 0 to 3, and represents an integer of 2 to 4) One or more 1-pentene-2,3,4-tricarboxylic acid triester monomers 2 to 95% by weight % as essential raw material monomers is provided.

The present invention will be explained in more detail below.

The contact lens of the present invention has a specific 1-pentene-2
, 3,4-1-, and a ricarboxylic acid triester monomer as a starting material.

1-pentene-2,3,4-1- used in the present invention.

The recarboxylic acid triester monomer has the following general formula (r
), where R□, R2 and R3 are the same or different groups, including a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and
12 alkenyl groups, having 3 to 12 carbon atoms; X, Y and Z are the same or different groups, and are methyl groups.

shows. Also, m, n and Q are O or 1, p+'! and r represents an integer of 0 to 3, and k represents an integer of 2 to 4. At this time, if at least one of R1, R, and R1 has 13 or more carbon atoms, or if at least one of n, m, Q, and k is outside the above range, it cannot be used because it is difficult to manufacture. 1-pentene- represented by the above general 2N)
Examples of the 2,3,4-tricarboxylic acid triester monomer include 2-(methoxycarbonyl)-3,4-
Di(tert-butyloxycarbonyl)-1-pentene, 2-(tert-butyloxycarbonyl)-3,
4-(isopropyloxycarbonyl)-1-pentene, 2,3.4-tri(isopropyloxycarbonyl)
-1-pentene, 2-(trimethylsilylmethoxycarbonyl)-3゜4-di(methoxycarbonyl)-1-pentene, 2-[methylbis(trimethylsiloxy)silylmethoxycarbonyl]-3,4-di(methoxycarbonyl)- 1-pentene, 2-(trimethylsilylmethoxycarbonyl)-3,4-di(tert-butyloxycarbonyl)-1-pentene, 2-[methylbis(trimethylsiloxy)silylmethoxycarbonyl]-3,4
-di(isopropyloxycarbonyl)-1-pentene, 2-(pentamethyldisiloxanylmethyloxycarbonyl)-3,4-di(methoxycarbonyl)-1-pentene, 2-[tris(trimethylsiloxy)silylpropyl oxycarbonyl] -3,4-(ethoxycarbonyl)-1-pentene, 2-[tris(trimethylsiloxy)silylpropyloxycarbonyl] -3,
4-(methoxycarbonyl/lz)-1-hen, 2
-(pentamethyldisiloxanylmethyloxycarbonyl) -3,4-di(isopropyloxycarbonyl)
-1-pentene, 2-(pentamethyldisiloxanylmethyloxycarbonyl)-3-(ethoxycarbonyl)
-4-(isopropyloxycarbonyl)-1-pentene, 2-(ethoxycarbonyl) -3,4-di(trimethylsilylmethoxycarbonyl)-1-pentene, 2
-(tert-butyl)-3゜4-di(trimethylsilylmethoxycarbonyl)-1-pentene, 2-(pentamethyldisiloxanylmethyloxycarbonyl)-3,
4-di(isopropyloxycarbonyl)-1-pentene, 2.3.4-tri(trimethylsilylmethoxycarbonyl)-1-pentene, 2-(isoprobyloxycarbonyl)-3,4-di[(2'- Hydroxy-3'-
trimethylsilylethoxy)propyloxycarbonyl]-1-pentene, 2-[(2'-hydroxy-3'-
trimethylsilylethoxy)propyloxycarbonyl]-3,4-di(isopropyloxycarbonyl)-1
-Pentene, 2- [(2'-hydroxy-3'-pentamethyldisiloxanylethoxy)propyloxycarbonyl]-3,4-di(methoxycarbonyl)-1-
Pentene, 2,3,4-tri[(2'-hydroxy-3
'-trimethylsilylethoxy)propyloxycarbonyl]-1-pentene and the like can be used alone or as a mixture. 1-pentene-2,3,4, which is the essential raw material component
-The content ratio of tricarboxylic acid triester monomer is
The content ranges from 2 to 95% by weight based on the total weight of the raw materials.

If the content is less than 2% by weight, the oxygen permeability will be extremely reduced, and if it is more than 95% by weight, the strength as a contact lens cannot be maintained, so it cannot be used.

In the present invention, the 1-pentene-2,3,4-tricarboxylic acid triester represented by the general formula (f) can be prepared by a known method. Specifically, for example, a silicon-containing acrylic ester and a silicon-containing mesaconic diester are dissolved in a solvent such as dioxane,
It can be obtained by a method of reacting in the presence of a catalyst and in an inert gas atmosphere.

In the contact lens of the present invention, any copolymer containing the 1-pentene-2,3,4-tricarboxylic acid triester monomer represented by the general formula (1) as an essential raw material monomer component may be used. Any copolymerizable monomer can be copolymerized, but in view of the thermal stability, mechanical strength, processability, etc. of the resulting contact lenses, other copolymerizable monomers, such as radical polymerization. It is preferable to use a monomer selected from the group consisting of polyvinyl monomers, silicon-containing vinyl monomers, fluorine-containing vinyl monomers, crosslinkable polyfunctional vinyl monomers, and mixtures thereof. 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,
Isopropyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, styrene, p
-Methylstyrene, p-chlorostyrene, 0-chlorostyrene, divinylbenzene, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl (meth)acrylate, ethyl vinyl ether, n-butyl vinyl ether, (meth)acrylic acid amide, 2-hydroxy ethyl(
meth)acrylate, N-vinylpyrrolidone.

Vinyl pyridine, allyl (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 bisallyl carbonate, triallyl trimellitate, triallyl cyanurate, diisopropyl itaconate, ditert-butyl itaconate, ditert-butyl fumarate, trimethylsilylmethyl (meth)acrylate, pentamethyldisiloxanylmethyl (meth) ) acrylate, tris(trimethylsiloxy)silylmethyl(meth)acrylate, tris(pentamethyldisiloxanyloxy)silylmethyl(meth)acrylate.

Trimethylsilylethyl (meth)acrylate.

Pentamethyldisiloxanyl ethyl (meth)acrylate, Tris(trimethylsiloxy)silylethyl(meth)acrylate, Tris(pentamethyldisiloxanyloxy)silylethyl(meth)acrylate, Trimethylsilylpropyl(meth)acrylate, Pentamethyldisilox Sanylpropyl (meth)acrylate, tris(trimethylsiloxy)silylpropyl (meth)acrylate.

Tris(pentamethyldisiloxanyloxy)silylpropyl(meth)acrylate, ethyl-trimethylsilylethyl itaconate, isopropyl-tris(trimethylsiloxy)silylethylitaconate, isopropyl-tris(pentamethyldisiloxanyloxy)silylmethyl Itaconate, Ethyl-tris(trimethylsiloxy)silylethylitaconate, Isopropyl-tris(pentamethyldisiloxanyloxy)silylethylitaconate, Tert-butyl-trimethylsilylpropylitaconate, Isopropyl-tris(trimethylsiloxy)silylpropyl Itaconate, tert-butylpentamethyldisiloxanylpropyl itaconate, isopropyl-tris(trimethylsiloxy)
Silylpropyl fumarate, tert-butyl-tris(trimethylsiloxy)silylpropyl fumarate, inpropyl-tris(pentamethyldisiloxanyloxy)silylmethyl fumarate, tert-butyl-pentamethyldisiloxanylpropyl fumarate, 2,2.
2-trifluoroethyl (meth)acrylate, 3,3
, 4,4.4-pentafluorobutyl (meth)acrylate, 2゜2.3,3,4,4,5,5-octafluoropentyl (meth)acrylate, 2,2.2-trifluoro-1- Trifluoromethyl (meth)acrylate, l, 1,2,2-tetrahydroperfluorodecyl (
meth)acrylate, ethyl-2゜2.2-trifluoroethyl fumarate, isopropyl-3,3,4,4,
4-pentafluorobutyl (meth)acrylate, isopropyl-2゜2.3,3,4,4,5,5-octafluoropentyl fumarate, isopropyl-2,2,2
-trifluoro-1-trifluoromethyl fumarate,
Isopropyl-1,1,2,2-tetrahydroperfluorodecyl fumarate, cyclohexyl-1,1, 2.
2-tetrahydroperfluorodecyl fumarate, tert-butyl-2,2゜2-trifluoro-1-trifluoromethyl fumarate, bis-2,2.2-trifluoroethyl fumarate, methacrylic acid, acrylic acid, itacon Examples include acids, which can be used alone or as a mixture. When using the radically polymerizable vinyl monomer, silicon-containing vinyl monomer, fluorine-containing vinyl monomer, or crosslinkable polyfunctional vinyl monomer, 5 to 50% of the total raw material monomer components are used.
It is desirable to use it in a range of 85% by weight. In this case, if it is less than 5% by weight, sufficient thermal stability, mechanical strength, processability, etc. can not be obtained by copolymerization, and if it exceeds 85% by weight.

This is not preferred because the oxygen permeability of the contact lens is significantly reduced.

The contact lens of the present invention has a DK value of 6 to 15×1O-100IQ/mouth aJ in order to have excellent oxygen permeability.
・sec ・mmHg is preferable, especially 8 to 14X1
0-10m0-1O/ tyj ・see lmmHg
is desirable ◎ In this case, 6 X 10-”mQ-tyt+
/aJ-see-11 mHg, oxygen permeability is insufficient for long-term continuous wear, and l5XlO
-"mlL am/al.sec.mmHg is not preferable as it deteriorates physical properties such as strength when used as a contact lens.

In order to prepare contact lenses in the present invention, known preparation methods can be used. Specifically, for example, a monomer raw material is polymerized together with a polymerization initiator in a suitable container such as a test tube to obtain a round bar or block, and then cutting,
A method of machining such as polishing, a method of injecting the monomer together with a polymerization initiator into a desired mold and directly forming a contact lens by mold polymerization, or a method of producing a polymer in advance by a radical polymerization method, etc. Examples include a method of obtaining a contact lens by dissolving the polymer in a suitable solvent and removing the solvent by a casting method.

In the above preparation method, the polymerization initiator used when polymerizing the monomer is selected to have a half-life temperature of 120°C for 10 hours.
It can be selected from one or more of the following organic peroxides and azo compounds. Examples of the organic peroxide or azo compound include benzoyl peroxide, diisopropyl peroxydicarbonate,
t-Butylperoxy-2-ethylhexanoate, t
Preferred examples include -butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), and t-butylperoxyisopropyl carbonate. The amount of the polymerization initiator used is based on 100 parts by weight of the raw material monomer.

It is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less.

In addition, in the above preparation method, the conditions for copolymerizing each monomer are such that the polymerization system is inert gas at appropriate times.

For example, it is preferable to carry out the polymerization under an atmosphere of nitrogen, carbon dioxide, helium, etc., or under deaerated conditions.The temperature for copolymerization varies depending on the type of polymerization initiator used, but is 30 to 120°C. A range of is preferred. Further, the total time required for polymerization is preferably about 10 to 72 hours.

It is also possible to polymerize the raw materials by adding coloring agents such as dyes or additives such as ultraviolet absorbers to the raw materials.

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 also be improved by performing graft polymerization of hydrophilic monomers by low-temperature plasma treatment.

<Effects of the Invention> The contact lens of the present invention has a specific 1-pentene-2
, 3,4-tricarboxylic acid triester polymer, it has higher oxygen permeability than conventional contact lenses and prevents deposition of proteins, lipids, and inorganic substances on the surface. It has excellent performance that improves the shortcomings of contact lenses.

<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.

2-[Tris(trimethylsiloxy)silylpropyloxycarbonyl-3,4-(methoxycarbonyl)-
30 parts of 1-pentene, 10 parts of tris(trimethylsiloxy)silylpropyl(meth)acrylate, 1,1,2
．． Mix 1.5 parts of azobis(2,4-dimethylvaleronitrile) with 30 parts of 2-tetrahydroperfluorodecyl (meth)acrylate, 20 parts of ethyl (meth)acrylate, 5 parts of allyl (meth)acrylate, and 5 parts of methacrylic acid. Then, this mixture was placed in a glass sealed tube, and the inside was repeatedly purged with nitrogen and degassed, and the tube was melt-sealed under vacuum. This sealed tube was left to polymerize for 24 hours in a constant temperature bath at 70°C, and then
Heated at ℃ for 2 hours. After cutting the obtained polymer,
Contact lenses were made by cutting and polishing. Next, various physical properties of the obtained contact lenses were measured by the following methods.

Acid, ゛” DK Direct Xertex Corp.
Product name: [MODEL 211]
0 (Multirange Analyzer for
35°C using
D was measured by laying it on a test contact lens with a diameter of 12.7 mm and a thickness of Q and 2 mm in 0.9% physiological saline.
K value (mQ-cn/al-see ・mmHg)
I asked for

Contamination resistance 12.7 m in diameter in 0.2% egg white lysozyme aqueous solution.
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.

It was measured using a Vickers HV Taiyo Tester Co., Ltd. II Terasawa type MM-2 type ultra-micro hardness meter.

A flat plate sample having a thickness of 2I, a length of 50 m, and a width of 10 nwn, which was separately polymerized with lantern skin in 1, was measured in accordance with the bending test method for hard plastics of JIS K7203. By the same method as in Table 1, raw material monomers having various compositions shown in Table 1 were cured under the radical polymerization initiator 1 polymerization conditions shown in Table 1, contact lenses were prepared, and various physical properties were measured. Table 1 shows the blending ratio of 7-mer, and Table 2 shows the measurement results.

Next, the abbreviations of each component shown in Table 1 will be explained below.

Si40M-A: 2-[tris(trimethylsiloxy)silylpropyloxycarbonyl]-3,4-di(methoxycarbonyl)-1-pentenetBDSi-A: 2-(tert-butoxycarbonyl)-3,4-di( trimethylsilylmethoxycarbonyl)-1-pentene TSi-A: 2,3,4-tristrimethylsilylmethoxycarbonyl)-1-pentene EDtB-A: 2-(ethoxycarbonyl)-3゜4-di(tert-butoxycarbonyl)- 1-Pentene Si-MA Nidris(trimethylsiloxy)silylpropyl methacrylate F3-MA: 2,2,2-trifluoroethyl methacrylate F6-MA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate F17 -MA: 1,1,2,2-tetrahydroperfluorodecyl methacrylate F17-Fu: Isoprobyl-1,1,2,2-tetrahydroperfluorodecyl fumarate MMA: Methyl methacrylate EMA: Ethyl methacrylate A-MA: Allyl Methacrylate V-MA: Vinyl methacrylate MA: Methacrylic acid AA Niacrylic acid ABVN: Azobis(2,4-dimethylvaleronitrile) IPP: Diisopropyl peroxydicarbonate BP○
:Benzoyl peroxide Table 2 Table C* 1) X 10-”mQ-aa/al-see
・mmHg (* 2) kgf/ll1" (* 3) N/++a2 According to the results in Table 2, the contact lens of the present invention.

Compared to the comparative example, it was found that the DK value was higher, the oxygen permeability and stain resistance were better, and moreover, it maintained appropriate physical strength.

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, R_1, R_2 and R_3 are the same or different groups, and each represents a hydrogen atom, a carbon Indicates 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 ▲There are numerical formulas, chemical formulas, tables, etc.▼, and the above X, Y and Z are the same or different. The group includes methyl group, ▲Mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates. Also, m, n and l are 0 or 1, p, q and r
is an integer of 0 to 3, and k is an integer of 2 to 4. % as an essential raw material monomer.