JPS60131518A - Contact lens material - Google Patents

Abstract

PURPOSE:To obtain a contact lens material having particularly excellent oxygen permeability and wettability with water by using a copolymer of methacryloxyethoxypropyl tris(trimethylsiloxy) silane and (meth)acrylate of mono- or polyhydric alcohol of <=10C. CONSTITUTION:The silane compd. expressed by the formula and the ester of (meth)acrylic acid of mono- or polyhydric alcohol of <=10C are copolymerized. The copolymerization is effected particularly at a monomer ratio of 5-80pts.wt. the silane expressed by the formula and 95-20pts.wt. said ester and 0.01pt.wt. a polymn. initiator such as 2,2'-azobis(2,4-dimethylvaleronitrile) or the like is added thereto. The mixture is cast into a cylindrical mold and the upper space thereof is substd. with gaseous N2. The mixture is polymerized in an oven substd. with gaseous N2. A contact lens is manufactured from the resulted colorless transparent and hard bar-shaped block by an ordinary working method. The hard contact lens which has good wettability with water, has large O2 permeability, permits long-time continuous wearing and strong and tough is thus easily obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a contact lens material, which has particularly excellent oxygen permeability and water swayability, can be worn continuously for a long period of time, and is aesthetically free of water. A rating of 6 relates to contact lenses that are easy to handle.

[Prior art and problems]

BACKGROUND ART Conventionally, for example, □ contact lenses containing polymethyl methacrylate as a main component have been put to practical use. Polymethyl methacrylate, which is the main component of this contact lens, has excellent optical properties and durability, and has the advantage of being thick, but the water wettability of the contact lens surface is not so good. The feeling of wearing it is not very good, and furthermore, the oxygen aptitude is not good, so it has a fatal disadvantage that it cannot be worn continuously for a long time due to the physiology of the cornea. As a solution to the drawbacks of hard type contact lenses, for example, water-containing contact lenses that remove poly 2-hydroxyethyl methacrylate as the main component have been put into practical use. Although the comfort of wearing is satisfactory to some extent, it has drawbacks such as insufficient oxygen permeability, difficulty in continuous wearing for long periods of time, and difficulty in handling due to its water-containing nature.

Contact lenses made of silicone resin have been proposed as a contact lens that exceeds the above-mentioned contact lenses mainly composed of polymethyl methacrylate or poly 2-hydroxyethyl methacrylate, or silicone has the greatest feature of high oxygen permeability. "Contact lenses made of modified silicone resin, which has improved water wettability to some extent by modifying the resin," have been proposed and have been put into practical use in some cases, but they have good water wettability and oxygen permeability, and are comfortable to wear. It is not 100% satisfactory for long-term continuous wear.

[Disclosure of the invention]

The present inventor has discovered that the oxygen permeability of silicone resin contact lenses is greatly affected by the amount of alkylsiloxane bonds contained in the material, and that when the oxygen permeability is increased by increasing the alkylsiloxane bonds, the wettability decreases. Noting that there is a tendency to
A polymer copolymerized using at least 95 to 20 parts by weight of an ester of monohydric or polyhydric alcohol having 10 or less carbon atoms and methacrylic acid or acrylic acid has excellent oxygen permeability and moisture resistance. We discovered that it has excellent hardness, good hardness, and excellent dimensional stability.

Examples of esters of monohydric or polyhydric alcohols having 10 or less carbon atoms and methacrylic acid or acrylic acid include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate), n-propyl methacrylate, n-propyl acrylate, 1so-,2
0 pyl methacrylate, 1so-propyl acrylate, n-butyl methacrylate, n-butyl acrylate, 1so-butyl methacrylate, 1so-butyl acrylate, pentyl methacrylate, pentyl acrylate, □Neopentyl methacrylate, neopentyl acrylate: lyreto, hexyl Methacrylate, hexyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol dimethacrylate Ethylene glycol dimecrylate, tetraethylene glycol dimecrylate,
Tetraethylene glyco, -/l/diacrylate 1.1
．． 3-butanediol dimethacrylate, 1. j-butanediol diacrylate,), 1,4-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, 1
, 6-hexanediol diacrylate, neopentyl glyco, ludimethacrylate, neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate,
Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, ethylene glycol monomethacrylate, ethylene glycol monoacrylate, diethylene glycol monomethacrylate, diethylene glycol diacrylate, triethylene glycol monomethacrylate, triethylene glycol monoacrylate, 2-hydroxypropyl methacrylate, 2- Hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxystyrene methacrylate,
Among these esters, diesters, triesters, and tetraesters of polyhydric alcohols and methacrylic acid or acrylic acid are used as crosslinking components. Among them, esters of monohydric alcohol and methacrylic acid or acrylic acid improve the processability of polymer materials,
Among the above esters, monoesters of polyhydric alcohol and methacrylic acid or acrylic acid are used to improve the hydrophilicity of polymer materials. In addition, instead of monoesters used to improve hydrophilicity, methacrylic acid, acrylic acid, acrylamide,
Methacrylamide, N-methylolmethacrylamide, etc. can also be used.

And for the above monomer, dimethyl-2
, 2'-azobisisobutyrate, 2,2-azobis(
4-methoxy-2,4'-dimethylvaleronitrile),
2.2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobisisobutylnitrile, benzoyl peroxide, di-tart-butyl peroxide, methyl ethyl ketone peroxide, inbutyl peroxide, diisopropyl peroxide A free radical polymerization initiator such as carbonate is blended, and polymerization is carried out by an ordinary radical polymerization method.

In addition, in the above monomer formulation, the most desirable ratio is:
The ester of monohydric alcohol and methacrylic acid or acrylic acid is 95 to 80% by weight of methacryloxyethoxypropyltris(trimethylsiloxy)silane.
20% by weight, 15% by weight or less of ester of polyhydric alcohol and methacrylic acid or acrylic acid as a crosslinking agent, and 10% by weight or less of hydrophilic monomer.

[Synthesis method of methacryloxyethoxypropyltris(trimethylsiloxy)silane]

Allyloxyethyl methacrylate ester (boiling point 2, Hg -64~65°C,
n1O=1.4463) with a yield of about 80%.

Then, a reflux condenser, thermometer, dropping funnel, starter
Approximately 1 mol of the above allyloxyethyl methacrylate and 10-s mol of platinum catalyst are added to a three-loaf flask equipped with a methacrylate, and the mixture is heated to about 75°C, and then 1.1 mol of trichlorosilane is added dropwise. Then, the reaction is carried out while stirring while maintaining the temperature at 75 to 80°C, and then unreacted allyloxyethyl methacrylate and trichlorosilane are distilled off under pressure to obtain methacryloxyethoxyprobyltrichlorosilane.

Next, in a three-lobe flask equipped with a stirrer, a thermometer, and a dropping funnel, 3 moles of the above methacryloxyethoxyprobyltrichlorosilane was added at 40oWd! .

was dissolved in dry diethyl ether, and the solution was cooled to -50°C in a dry ice isopropanol cooling bath.
(excess) was added over a period of about 2.5 hours, and 1.2 moles of trimethylsilanol was added via the dropping funnel, and after the addition of trimethylsilanol the temperature was raised to 30° C. and stirred for 30 minutes.

Then, pyridinium hydrochloride is separated by F, the filter cake is washed with diethyl ether, the ether solvent and unreacted substances are distilled off under pressure, the reactant is washed with water, and the upper organic layer is separated. After dehydration with anhydrous sodium sulfate, decolorization by adding an appropriate amount of activated carbon, and passing through a membrane filter (0.2μ), methacryloxyethoxypropyltris(trimethylsiloxy)silane (n, ;o=1.4240) is 80%
obtained with a yield of .

o-5i(c)I3)s The IR and NMR spectra of methacryloxyethoxyzolopyrtris(trimethylsiloxy)silane were measured as shown in FIGS. 1 and 2.

[Examples 1 to 10] Methacryloxyethoxypropyltris(trimethylsiloxy)silane (hereinafter abbreviated as METASI-1) 5 to 8
0 parts by weight, methyl methacrylate (abbreviated as MMA under μ) as an ester of monohydric alcohol and methacrylic acid 7~
82 parts by weight, methacrylic acid (hereinafter M
V-65 (trade name, 2 parts by weight) was added to a mixture of 8 parts by weight of V-65 (trade name, 2 .2'-azobis(2,4-dimethylvaleronitrile)) polymerization initiator 0
．． 01 parts by weight was added, and this was poured into a cylindrical polypropylene 11 polymer fjl- with a diameter of 161 m and a height of 10 m, and after purging the upper space with nitrogen, it was kept at 40 ° C. for 20 hours in an oven purged with nitrogen in advance. , then 70℃
, kept at 90℃ for 10 hours, then 100℃
The polymerization was completed by holding for 10 hours to obtain a colorless, transparent, hard rod-shaped block.

Finally, it is subjected to normal processing and made into contact lenses.

The characteristics of the contact lenses thus obtained are shown in Table 1.

Table 1 The unit of mi transmission coefficient is 1G-”cc(8TP)c++
+/cj ・sec day H'g [Examples 11 to 24] METASI-14, 5 parts by weight, 42 parts by weight of ester of monohydric alcohol and methacrylic acid or acrylic acid shown in Table 2, as a hydrophilic monomer 8 parts by weight of MA, TG as an ester (crosslinking agent) of polyhydric alcohol and methacrylic acid
D 5 m foot, V- as free radical initiator
601 (illfi product name, dimethyl = 2.2'-
Using 0.03 parts by weight of azobisisobutylene), a colorless and transparent hard rod-shaped block was obtained in the same manner as in Example 1, and this was processed to obtain a contact lens.

The properties of the contact lenses obtained in this manner are as shown in Table 2.

Table 2 The unit of oxygen permeability coefficient is 10-” cc (8TP)a
m/c++f ・5ec-guh Hg [Examples 25 to 42] METASI-130 to 60 parts by weight, ester of monohydric alcohol and methacrylic acid or acrylic acid 22 to 57
Parts by weight, 5 to 10 parts by weight of ester of polyhydric delcol and methacrylic acid or acrylic acid, 5 to 10 parts by weight of hydrophilic monomer
A contact lens is obtained in the same manner as in Example 1 using 0.01 part by weight of the free radical polymerization initiator.

The characteristics of the contact lenses thus obtained are shown in Table 3.

i-BI'V4A: 1so-butyl methacrylate, 2-EHA,: 2-ethylhexyl acrylate,
EMA: Ethyl methacrylate, C-HMA dichlorohexyl methacrylate.

2-EHMA: 2-ethylhexyl methacrylate, 11MA: hexyl methacrylate, i-PMA: 1ao-propyl methacrylate,
n-BMA: n-butyl methacrylate, NPMA:
Neopentyl methacrylate, EMA: ethyl methacrylate, 1.3BDMA: 1,3-butanediol dimethacrylate V
-), EDA: ethylene glycol diacrylate, T
MTMA: ) Limethylolpropane trimethacrylate, PE4MA: Pentaerythritol tetramethacrylate, 2-2-11P: 2-hydroxypropyl methacrylate, EGMA: Ethylene glyconyl monomethacrylate, 2-HBMA: 2-hydroxybutyl methacrylate, The unit of rR elementary permeability coefficient is 10-”cC (8
TP) crIL/crl-sec Association g Il g [Effect] The hydrophilic contact angle is small, so it operates under water drying properties,
Further, a contact lens having a large oxygen permeability coefficient and which can be worn continuously for a long period of time can be obtained.

Furthermore, since a substantially water-free and tough hard contact lens can be obtained, it is easy to handle and is less likely to be damaged.

In addition, since it has appropriate hardness when processed into contact lenses, it is easy to process, and the manufacturing cost of contact lenses is low.

Further, since it has a desirable refractive index of -11, the thickness of the contact lens can be relatively thin, and a contact lens with improved wearability can be obtained.

[Brief explanation of drawings]

FIGS. 1 and 2 are an I-level chart and an NMR chart of METASI-1. , -7I N13-

Claims (1)

[Claims] Methacryloxyethoxypropyltris (
A contact lens material characterized in that it is copolymerized using at least trimethylsiloxy) silane, an ester of a monohydric or polyhydric alcohol having a carbon atom number of 10 or less, and methacrylic acid or acrylic acid. □ ■ The contact lens material according to claim 1, in which the proportion of methacryloxyethoxypropyl tris(trimethylsiloxy)silane is 5 to 80 parts by weight and the proportion of ester is 95 to 20 parts by weight.