JPS61264319A - Oxygen permeable contact lens - Google Patents

Abstract

PURPOSE:To obtain a contact lens which has excellent transparency and good oxygen permeability and can be industrially advantageously produced by forming the lens of a polymer constituted essentially of specific siloxanyl alkyl (meth) acrylate and (meth)acrylic acid alkyl monoester of 1-10C. CONSTITUTION:This lens consists of the polymer obtd. by polymerizing the monomer compsn. constituted essentially of 20-80pts.wt. siloxanyl alkyl (meth) acrylate expressed by the formula and 80-20pts.wt. at least one kind of (meth) acrylic acid alkyl monoester of 1-10C. In the formula, R1 is a hydrogen atom or methyl group, l is 1 or 2 or 3, m is 1 or 2, n is 3-m. The contact lens which has the excellent oxygen permeability and can be industrially advantageously produced is thus obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an oxygen-permeable contact lens made of a polymer whose main component is siloxanylalkyl (meth)acrylate (meth)acrylic acid alkyl monoester. Regarding.

[Conventional technology]

Conventionally, two types of contact lenses are known: those based on polymethyl methacrylate and those based on poly-2-hydroxyethyl methacrylate, and contact lenses manufactured from these base materials are transparent. It has good properties and is widely put into practical use.

However, contact lenses based on polymethyl methacrylate have poor transparency and dimensional stability. on the other hand,
Contact lenses based on poly-2-hydroxyethyl methacrylate are flexible69, have relatively good oxygen permeability, and are comfortable to wear, but have poor mechanical strength11 and dimensional stability. In addition, lenses made of silicone rubber tS material are known as contact lenses with good oxygen permeability, but these lenses are difficult to machine and are hydrophobic, making them difficult to wet and easily stained. .

In recent years, attempts have been made to use silicone polymers as base materials for contact lenses in order to further improve oxygen permeability. A copolymer of an ester and a (meth)acrylic acid ester is disclosed in JP-A No. 54-24047, a compound having unsaturated groups at both ends of polysilane, and a copolymer of this compound and an alkyl methacrylate are disclosed. , JP-A-55-102613 discloses a copolymer of a siloxanylalkyl (meth)acrylate having a specific structure containing a tris-based trimethylsiloxysiloxanyl group and a polymerizable acrylic material such as an alkyl methacrylate. No. 58-7124 discloses a copolymer consisting of a siloxanyl alkyl ester, a (meth)acrylic acid ester, and an itaconic acid ester with a specific structure,
In addition, JP-A-58-113911 discloses siloxanes having at least two polymerizable groups in one molecule, and future developments in contact lenses made from these silicone polymers are expected. be done.

[Problem that the invention seeks to solve]

However, although the above-mentioned silicone contact lenses are generally satisfactory in terms of transparency, they are not necessarily satisfactory in terms of oxygen permeability. Although there are some products that exhibit a somewhat high value of oxygen permeability, these methods are difficult to implement industrially because the process for obtaining contact lens materials is complicated and requires harsh conditions.

Therefore, the object of the present invention is to provide a contact lens that has excellent transparency, good oxygen permeability, and can be manufactured industrially advantageously.

[Means for solving problems]

The inventors of the present invention have conducted extensive studies to achieve the above object and have arrived at the present invention. That is, the present invention is based on the following general formula (wherein Rz is a hydrogen atom or a methyl group, and t is 1
or 2 or 3, m is 1 or 2, n is 3-m, and 6) siloxanylalkyl (meth)acrylate 20
~80! Quantity and at least IW! This is an oxygen permeable contact lens made of a polymer consisting essentially of 80 to 20 parts by weight of (meth)acrylic acid alkyl ester having 1 to 10 carbon atoms.

The uninvented contact lens contains a siloxanylalkyl (meth)acrylate represented by the above general formula and at least one
It is produced from a polymer whose main component is an alkyl (meth)acrylate monoester having 1 to 10 carbon atoms.
Such siloxanylalkyl (meth)acrylates are specifically represented by the following formulas (1) and (II).

In the formula, R1 is a hydrogen atom or a methyl group, L is 1, 2 or 3, but more preferably R1 is a methyl group, and t is 3, siloxanylalkyl (meth)acrylate. Specific examples of such siloxanylalkyl (meth)acrylates include 3-methacryloxypropyl-[bis-(trimethylsiloxy)methylsiloxytudimethylsilane and 3-methacryloxypropyl-[bis-(trimethylsiloxy)methylsiloxy]. ) Methylsiloxycomethylsilane is mentioned.

The siloxanylalkyl methacrylate used in the present invention is a combination of the corresponding (meth)acryloxyalkylsilyl chloride or (meth)acryloxyalkylsilyl alkoxide, etc., and bis(trimethylsiloxy)methylsilyl chloride or bis(trimethylsiloxyla It can be easily obtained by hydrolysis and condensation with methylsilylalkoxide.

Examples of the alkyl (meth)acrylate monoester having 1 to 10 carbon atoms used in the present invention include hydrophobic monoesters such as methyl (meth)acrylate, ethyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Examples include (meth)acrylic acid alkyl monoester. These are 1
Although they may be used in one species or in combination of two or more, methyl methacrylate or those containing methyl methacrylate as the main component are preferred from a practical standpoint.

In the present invention, 20 to 80 parts by weight of siloxanylalkyl (meth)acrylate represented by the above general formula,
The alkyl (meth)acrylate monoester having 1 to 10 carbon atoms is used in an amount of 80 to 20 parts by weight, but from the viewpoint of the sharpness of the appearance of the apex refractive power and the oxygen permeability, siloxanylalkyl (meth)acrylate is used. It is preferable to use 40 to 60ii parts, and 60 to 40x parts of the alkyl (meth)acrylate monoester having 1 to 10 carbon atoms. If the amount of siloxanylalkyl (meth)acrylate is less than 20 parts by weight (if the amount of alkyl (meth)acrylate monoester having 1 to 10 carbon atoms is more than 80 parts by weight), the lens will have low oxygen permeability, and If the amount of sunyl alkyl (meth)acrylate is more than 80 parts by weight (if the alkyl (meth)acrylic acid monoester having 1 to 10 carbon atoms is less than 20 parts by weight), the lens will be too soft. It is difficult to do so.

Furthermore, in the present invention, in order to maintain thermal shape stability, the above-mentioned siloxanylalkyl methacrylate and carbon number 1
It is preferable to add up to 20 parts by weight of a crosslinking agent to a total of 100 parts by weight of the 10 to 10 alkyl monoesters of (meth)acrylate and polymerize to obtain a polymer.

Examples of such crosslinking agents include polyfunctional compounds such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. These may be used as a mixture, but if more than 20 parts by weight is used, it becomes hard and brittle.

In addition, in the present invention, in order to lower the contact angle with water,
A small amount of hydrophilic hydroxy esters such as hydroxyethyl methacrylate may be added as long as the effects of the present invention are not impaired.

The contact lens of the present invention is produced by first polymerizing the siloxanylalkyl (meth)acrylate and alkyl (meth)acrylate monoester to produce a polymer (i.e., contact lens material), and then cutting and polishing the material. Manufactured by The polymerization operation is not particularly limited, and can be carried out by a conventional polymerization operation, for example, by adding a polymerization initiator that generates ordinary free radicals to the above components, such as benzoyl peroxide, lauroyl peroxide, diisopropyl peroxide, etc. After adding about 10.01 to 11 L of honate, azobisisobutyronitrile, etc., and putting it in a suitable container to expel oxygen,
It can be manufactured by sealing and heating polymerization. Further, after expelling oxygen, polymerization may be performed while sealing with nitrogen, or ultraviolet polymerization may be performed.

Contact lenses can be produced from the polymer by a spin casting method, a cast molding method, or a lace cutting method.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

〔Example〕

In the following examples, oxygen permeability was measured using a Seikaken film oxygen permeability meter at a center thickness of approximately 0.2 at 25°C.
Measurements were made using a 1111 lens or disc.

Example 1 3-methacryloxypropyl-[bis-(Trilane synthesis) In a Erlenmeyer flask, 4 f of distilled water, 252 g of concentrated hydrochloric acid, and 2 g of ether were added.
12.7f of 3-ethoxyheptamethyltrisiloxane (bis-(trimethylsiloxy)methylsilyl ethoxide) was added to the dropping funnel.
and 3-methacryloxypropyldimethylchlorosilane 1
After stirring the mixture uniformly, it was added dropwise to the Erlenmeyer flask.

During this reaction operation, the inside of the Erlenmeyer flask was stirred, and a cooling operation was applied from the outside of the Erlenmeyer flask so that the temperature of the contents did not exceed 25°C.

After the dropwise addition was completed, stirring was continued at room temperature for 24 hours.

The reaction mixture was separated, and the ether layer was washed several times with distilled water until the washings became neutral. The ether layer is 1:I-fi
Transfer to IJ-evaporator to remove ether,
Next, low-boiling substances were distilled off at 60°C for one hour, and liquid 3-methacryloxypropyl[bis-(trimethylsilyl)] was distilled off.
) 19.12 of methylsiloxy-dimethylsilane was obtained.

Copolymerization of the liquid with comonomers, o o t and methyl methacrylate (MM
A) Put 4.50F and 0.5 Of of ethylene glycol dimethacrylate (EGDMA) as a crosslinking agent into a polypropylene test tube, add o and is of azobisisobutyronitrile as a catalyst, and close the lid after purging with nitrogen. 5
It was immersed in a constant temperature water bath at 5°C for 24 hours. Then 1 at 70℃
Heat treatment was performed at 130° C. for 2.5 hours to obtain a colorless and transparent polymer.

A cylinder with a height of about 7 mm was cut out from this polymer and a contact lens was made from it by the lace cutting method, and the cutting properties were good. Using this lens, the measured nine oxygen permeability was 1s, 5x11j (1CC (STP)
) ・cyn/crii-sea-wrHf (25
℃) was 6.

Example 2 Synthesis of 3-methacryloxypropyl-bis-[bis-(trimethylsiloxy)methylsiloxycomethylsilane] 351 L of concentrated hydrochloric acid and 351 L of ether were placed in an Erlenmeyer flask and stirred.Meanwhile, 35 L of ether was placed in a dropping funnel. 4
5.9 f of 3-ethoxyheptamethyltrisiloxane and 20 t of 3-methacryloxypropyldimethoxymethylsilane were added, stirred uniformly, and then dropped into the Erlenmeyer flask. Thereafter, in the same manner as in Example 1, liquid 3-methacryloxypropyl-bis-[bis-(trimethylsiloxy)methylsiloxycomethylsilane 57.5%
ft obtained 0 The liquid material 5.0091 MMA4.5 Of and EGDM
Polymerization operations were carried out in exactly the same manner as in Example 1 using Ao, 50F to obtain a colorless and transparent polymer.

When a contact lens was produced from the polymer by cutting out cylinders similar to those in Example 1 by the lace cutting method, the cutting properties were good and the lenses were sold. Also, oxygen permeability is 22.3
10-11CC (STP) ・I:IR/ca ・s
ea -mHf (25°C). Example 3 3-methacryloxypropyl[bis-(trimethylsiloxy)methylsiloxytudimethylsilane obtained in Example 1]3. OO5' and methyl methacrylate 7.0Of
A copolymer was obtained in the same manner as in Example 1 using Contact lenses were produced from the copolymer in the same manner as in Example 1, and the oxygen permeability was measured in the same manner.
゜Ox 10”-11CC (STP) ・art/
crA-sec-mHf (25°C).

Examples 4-5 3-Methacryloxypropyl-[bis-(trimethylsiloxy)methylsiloxy2-dimethylsilanes obtained in Example 1 4.0Of and 5.50f.

Methyl methacrylate s, o o and 4.50f,
1. Ethylene glycol dimethacrylate. Contact lenses were manufactured in exactly the same manner as in Example 1, except that OO was changed to 1.50 r (Examples 4 and 5, respectively).

The oxygen permeability of the contact lenses was measured, and each k16. -6 x 10-11 and rE 18. OXl
0-”CC(STP’>・cm/ctA-see
-tmHt (25°C).

Example 6 3-methacryloxypropyl-[bis-(trimethylsiloxy)methylsiloxytudimethylsilane obtained in Example 1 7.007. Methyl methacrylate 3.0Of and ethylene glycol dimethacrylate (EGDMA)
A copolymer was obtained by adding 1.5Of. Contact lenses were produced from the copolymer in the same manner as in Example 1, and the oxygen permeability was measured in the same manner.
-11CC(STP)・elII/-・lee・mHf
(at 25°C), there was no problem with its performance as a contact lens, but the copolymer was a little soft.
The appearance of the apex refractive power, which had a tendency to be negative, was found in Example 4.
Compared to the contact lenses No. 5, they were a little blurry and rare.

Comparative Examples 1 to 2 Contact lenses were manufactured from the polymer disclosed in Japanese Patent Publication No. 52-33502, and the oxygen permeability was measured in the same manner as in the Examples. Ox 10-”CC(S
TP)-cIR,/cfA・see-wHf (25°C)
Deatsu9 (Comparative Example 1).

In addition, contact lenses were manufactured from the polymer disclosed in JP-A-55-102613, and the oxygen permeability was measured in the same manner as in the examples.
CC(STP) ・cm/ctA-see-mHf
(25℃) c's ivy.

Furthermore, this method requires many synthesis steps to obtain siloxane, and cannot be said to be an industrially advantageous method (Comparative Example 2).

The effects of the present invention are clear from the above Examples and Comparative Examples.

〔effect〕

According to the present invention, the oxygen permeability is superior to the conventional one,
Moreover, it is possible to provide a contact lens that can be manufactured industrially advantageously, and has extremely great industrial utility.

Patent applicant: r:”ishi Co., Ltd. Representative: Patent Attorney Ken Honda

Claims (4)

[Claims] (1) General formula below ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a hydrogen atom or a methyl group, and l is 1
or 2 or 3, m is 1 or 2, n is 3-m) siloxanylalkyl (meth)acrylate 20
A polymer obtained by polymerizing a monomer composition consisting essentially of ~80 parts by weight and 80 to 20 parts by weight of at least one alkyl (meth)acrylate monoester having 1 to 10 carbon atoms. Oxygen permeable contact lens consisting of a combination. (2) Claim No. (1) in which R_1 is a methyl group
Contact lenses as described in section. (3) Claims (1) or (3) where l is 3.
Contact lenses described in section 2). (4) A contact lens according to claim (1), which is obtained by further adding a crosslinking agent to the monomer composition and polymerizing the monomer composition.