JPH02269106A - Contact lens material - Google Patents

Abstract

PURPOSE:To obtain the subject material having sufficiently high transparency and excellent oxygen permeability able to be simply and readily produced, by (co)polymerizing product of addition reaction of (meth)acryl isocyanate and specific compound. CONSTITUTION:(A) (Meth)acryl isocyanate is subjected to addition reaction with (B) silicon compound having both of OH group or amino group and siloxanyl group, then resultant product of said addition reaction is subjected to homopolymerization, or subjected to copolymerization with (C) monomer copolymerizable with the component A to afford the aimed material containing 0-95wt.% component C. Besides, siloxanylamine expressed by the formula, etc., (Z is OH or amino; R is methyl or trimethylsiloxy; m is 1-6; n is 2-20) is preferable as the component B. Furthermore, e.g. methyl (meth)acrylate or styrene is used as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to contact lens materials, particularly contact lens materials having high transparency and good oxygen permeability.

[Conventional technology]

In general, contact lenses have come to be used in addition to spectacle lenses as a means of visual acuity correction.

However, in reality, relatively fewer people wear contact lenses than spectacle lenses. The reason for this is thought to be that there are problems with conventional contact lens materials themselves.

Polymethyl methacrylate can be mentioned as a contact lens material that has been widely used in the past.

Polymethyl methacrylate is a polymer that is easy to machine, has high optical transparency, and has excellent durability; however, contact lenses made from this material are difficult to wear due to their high hardness. It has disadvantages such as being uncomfortable and having a low oxygen permeability, making it impossible to wear it for long periods of time.

On the other hand, in contrast to such hard type contact lens materials, water-containing type so-called soft contact lens materials have been developed. This contact lens material is
Although it has good oxygen permeability and provides a comfortable feeling when worn, it has the disadvantages of low mechanical strength, easy to become a culture medium for fungi, and further disadvantages of being prone to optical inaccuracy. be pointed out.

Therefore, recently, research has been conducted to obtain a hard contact lens material having good oxygen permeability, which combines the advantages of both. As this type of contact lens material, many materials made of bipolymers containing silicon atoms and fluorine atoms, which are known to have good oxygen permeability, have been proposed, for example, in JP-A-57-93315. , JP-A-58-194014, JP-A-58-127914, JP-A-60-146219
No. 60-165617 and other publications.

[Problem that the invention seeks to solve]

As mentioned above, it is known that polymers obtained by polymerizing radically polymerizable monomers containing silicon atoms or fluorine atoms have good oxygen permeability.

However, in order to synthesize radically polymerizable monomers containing silicon atoms and fluorine atoms as described above, it is difficult to set suitable reaction conditions and control reactions such as esterification and amidation reactions. The need to carry out chemical synthesis reactions and purification of the resulting reaction products ultimately makes such contact lens materials fairly expensive.

An object of the present invention is to easily obtain a radically polymerizable monomer containing a silicon atom or a fluorine atom by a simple method, which can be advantageously produced, and which has sufficiently high transparency and good properties. An object of the present invention is to provide a contact lens material having oxygen permeability.

[Means for solving problems]

The contact lens material of the present invention includes an addition reaction between the following component (A) and the following component (B), and a polymerization reaction using the above (A+acid component) or a copolymerization reaction between the above (A) component and the following (C) component. It is characterized by being made of a polymer obtained by carrying out the following steps, in which the proportion of the component (C) is 0 to 95% by weight.

(A) Component Niacrylisocyanate or Methacryl Incyanate (B) Component: A silicon compound having at least one hydroxyl group or amino group and a siloxanyl group, or a silicon compound having at least one hydroxyl group or amino group. Fluorine-containing compound containing a fluorine atom (C) Component: Monomer copolymerizable with the above-mentioned (A) component The present invention will be specifically described below.

In the present invention, a urethane monomer containing a silicon atom or a fluorine atom is synthesized through an addition reaction between component (A) and component (B), and at the same time, a urethane monomer containing a silicon atom or a fluorine atom is synthesized by using the radical polymerizability of the component (A). Alternatively, a polymerization reaction is carried out with the copolymerizable monomer of component (C), and the resulting polymer provides a contact lens material.

In the present invention, acrylic isocyanate or methacrylic isocyanate (hereinafter referred to as "(meth)acrylic isocyanate") is used as component (A).

The component (B) to be reacted with the component (A) is a compound having at least one hydroxyl group or an amino group, that is, a compound having an active hydrogen-containing group, and is a silicon compound having a siloxanyl group or containing a fluorine atom. A fluorine-containing compound is used.

The silicon compound or fluorine-containing compound used as component (B) in the present invention may be a compound having two or more hydroxyl groups or amino groups. When such a compound having a plurality of active hydrogen-containing groups is used as component (B), the crosslinking density of the polymer will differ depending on the separation state of the plurality of active hydrogen-containing groups within the molecule. Advantageously, contact lens materials can be obtained that have high chemical and heat resistance and good processability without significantly sacrificing oxygen permeability.

The silicon compound used as component (B) in the present invention has the following structural formula (I) or structural formula (n).
Preferred examples include siloxanyl alcohol or siloxanyl amine.

Structural formula (1) %Formula% Structural formula (II) (In each formula, Z represents a hydroxyl group or an amino group, R represents a methyl group or a trimethylsiloxy group, m is an integer of 1 to 6,
n represents an integer of 2 to 20. ) Also, in the present invention (
Specific examples of the fluorine-containing compound used as component B) include 2,2.3.3-tetrafluoro-1-
propatool, 2°2, 3.4.4.4-hexafluorobutanol, 2-(perfluoro-n-hexyl)ethanol, 1.1.1.3°3.3-hexafluoro-
2-propatol, 1.1.2°3.3-pentahydroperfluorononane-1,2-diol, 2.2.3.
3-tetrafluoro-1,4-butanediol, 2.2
．． 3.3.4.4-Hexafluoro-1,5-pentanedionope 2.2.3.3.4.4.5.5-octafluoro-1,6-hexanediol, pentafluorophenol, 3 Examples include 5-bis(trifluoromethyl)phenol, 2,4-difluoroaniline, 4-)lifluoromethylaniline, hydroxyl-terminated perfluoropolyether, and amines having structures similar to these compounds. can.

The compounds listed above are just examples, and the component (B) used in the present invention is not limited to only these compounds. Moreover, not only one type of silicon compound or fluorine-containing compound having this hydroxyl group or amino group can be used, but two or more types can also be used depending on the properties required for the contact lens material finally obtained.

The addition reaction between component (A) and component (B) is a urethanization reaction between the incyanato group of component (A) and the active hydrogen of the hydroxyl group or amino group of component (B). In this addition reaction, the ratio of component (A) to (B) Ift, min is determined by the amount of active hydrogen in the hydroxyl group or amine group in component (B) relative to the molar amount (NCO) of isocyanate groups in component (A). Ratio of molar amount (H) (H)/
[NC0) (hereinafter this ratio is referred to as "active hydrogen equivalent")
It is desirable that the value of is a ratio close to 1. Particularly in the present invention, it is preferable that the value of the active hydrogen equivalent is 0.9 or more and 1.5 or less.

If the value of this active hydrogen equivalent is 1 or more, the component (B) will be in excess, which is preferable in that the obtained contact lens material will have high hydrophilicity, but if it exceeds 1.5, the polymer will This is undesirable because a large amount of low molecular weight alcohols and amines that are not bonded to the polymeric acid remain. On the other hand, if the value of this active hydrogen equivalent is less than 0.9, unreacted incyanato groups will remain in the polymer, and as a result, the resulting contact lens material will deteriorate over time. This is not desirable.

The addition reaction between component (A) and component (B) can also occur simply by heating a mixture of the two, but in order to shorten the reaction time, for example, dibutyltin dilaurate,
1.2.2.6. Preference is given to using initiators commonly used in the production of polyurethanes, such as 6-bentamethyl-4-hydroxypiperidine, stannath octoate, dimethyltin dichloride. The amount of this reaction initiator used is 0.001 to 3
．． It is desirable that the content be within the range of 0% by weight.

In this addition reaction, compounds having multiple hydroxyl groups such as other diols or polyols are added to adjust the mechanical strength, hardness, heat resistance, chemical resistance, processability, etc. of the final polymer. In addition, it is also possible to react together.

In the present invention, the urethane monomer obtained by the addition reaction of the component (A) and the component (B) is purified and separated, and this urethane monomer is used by utilizing the polymerizability of the component (A). A contact lens material can be obtained by a method in which the material is directly polymerized as it is.

In addition, the addition reaction product of component (A) and component (B),
A contact lens material can also be obtained by a method in which a copolymerization reaction is performed with component (C) consisting of a copolymerizable monomer, thereby obtaining a polymer. When this method is used, it is possible to particularly obtain the following effects.

(a) A polymer with higher mechanical strength and hardness can be obtained, and therefore a contact lens material with high mechanical strength can be obtained.

(b) A contact lens material with a higher refractive index can be obtained.

(c) Since a polymer with higher hydrophilicity can be obtained, a contact lens that is compatible with the tear fluid on the cornea can be obtained.

(d) A contact lens material with even better oxygen permeability can be obtained.

In the present invention, a copolymerizable monomer (
Component C) accounts for 95% by weight of all monomers to be subjected to the polymerization reaction.
It can be used in proportions within the following ranges.

Specific examples of copolymerizable monomers used in the present invention include:
Methyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, methacryloxypolyethoxybenzene, 1,6-hexanethiol di(meth)arylate, trimethylolpropane bird
(meth)acrylates such as (meth)acrylate;
Vinyl compounds such as vinylpyrrolidone, styrene, vinyl acetate, allyl compounds such as diallyl phthalate, allyl alcohol, diethylene glycol bisallyl carbonate, di-1so-propyl fumarate, and t-fumarate.
Examples include fumaric acid esters such as ert-butyl and di-2-ethylhexyl fumarate.

Further, when a certain type of water-soluble monomer is used as the comonomer, it is preferable because even higher hydrophilicity can be imparted to the resulting contact lens material. Specific examples of such water-soluble monomers include (meth)acrylic acid, (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2.3 -dihydroxypropyl (meth)acrylate, 2-carboxyethyl (meth)
Examples include acrylate, 2-sulfoethyl (meth)acrylate, and vinylbenzoic acid.

In addition to the above, monomers containing silicon atoms or monomers containing fluorine atoms can also be used as preferred copolymerizable monomers in the present invention.

Examples of monomers containing silicon atoms include tris(trimethylsiloxy)silylpropyl(meth)acrylate, pentamethyldisiloxanylbrobyl(meth)acrylate, and styrene(trimethylsiloxy)silylpropylglycerol(meth)acrylate. ) acrylate,
Examples include tris(pentastyrenesiloxy)silylpropyl(meth)acrylate.

Further, as a monomer containing a fluorine atom, for example, 2
．． 2.2-) Lifluoroethyl (meth)acrylate,
1.1.1.3.3.3-hexafluoroisopropyl (meth)acrylate, 2.2.3.4.4.4-hexafluorobutyl (meth)acrylate, perfluorohexylethyl (meth)acrylate, etc. (Meth)acrylates and fumaric acid esters of fluorine-containing alcohols such as 1.1,2.2-f dorafluoroethyl vinyl ether, 1.1.2.3.3.3-hexafluoropropyl allyl ether, etc. Containing alcohol vinyl ethers and allyl ethers, perfluorohexylethylene, 1-perfluorohexyl-2
Examples include fluorine-containing unsaturated aliphatic compounds such as -methyl-1-propene.

The copolymerizable monomers used in the present invention are not limited to the compounds listed above, and not only one type but two or more types of copolymerizable monomers can be used.

In a typical method for manufacturing the contact lens material according to the present invention, an addition reaction between component (A) and component (B) is first performed. Any suitable solvent can be used for this addition reaction.

By purifying the product of this addition reaction, a urethane monomer containing a silicon atom or a fluorine atom and having radical polymerizability can be separated and obtained.

This urethane monomer is polymerized alone as described above,
Alternatively, it is copolymerized with a copolymerizable monomer as component (C).

When the urethane monomer is copolymerized with component (C), the addition reaction between component (A) and component (B) is performed in the presence of component (C) to be copolymerized,
Furthermore, the produced urethane monomer can be directly subjected to a copolymerization reaction without being purified and separated. According to this method, the process for manufacturing contact lens materials can be greatly simplified, which is very advantageous.

Furthermore, although this method usually results in a urethane monomer, which is a reaction product of components (A) and (B), having a considerably high viscosity, this is not practical in practice. This is an advantageous method because it does not cause any obstacles. That is, even if the urethane monomer produced by the above addition reaction is viscous and difficult to mix or dissolve, according to this method, the reaction product can be formed by the urethane monomer being the component (C). Since the urethane monomer and the component (C) are obtained in a dissolved state, there is virtually no need for a step of mixing and dissolving the urethane monomer and component (C), and therefore the reaction product can be directly subjected to the desired copolymerization reaction.

Moreover, the contact lens of the present invention can also be applied by an embodiment in which the addition reaction and the polymerization reaction are simultaneously performed in parallel, rather than in an embodiment in which the polymerization reaction is performed after the addition reaction between components (A) and (B) is completed. materials can be obtained.

A contact lens made of the contact lens material of the present invention can be produced by injecting the monomer or its composition to be subjected to the above polymerization reaction into a mold having the shape of a contact lens, and performing the polymerization reaction in that state. It can be manufactured directly by The contact lens thus obtained can be further machined or polished using known techniques. Of course, it is also possible to produce a desired contact lens by obtaining the polymer according to the present invention in the form of a block or sheet and subjecting it to cutting, polishing, and the like.

〔Effect of the invention〕

As described above, the contact lens material according to the present invention is
Consisting of a specific radically polymerizable incyanate compound (
Using component A), component (B) consisting of a specific silicon compound or fluorine-containing compound having at least one hydroxyl group or amino group is added to the component (A), and the component (A) is added to the component (A). It consists of a polymer obtained by polymerizing component () alone by utilizing its radical polymerizability or by copolymerizing it together with component (C), which is a copolymerizable monomer. Since the above addition reaction is a normal urethanization reaction, it is easy to set suitable reaction conditions and control the reaction, and the reaction product obtained by this addition reaction can be directly polymerized without purification. It is also possible to subject the contact lens material to a reaction, and therefore a contact lens material made of a polymer containing silicon atoms or fluorine atoms can be obtained by an extremely simple method and at low cost.

In addition, since component (A) of the contact lens material of the present invention is a compound with a simple molecular structure, the polymer contains a relatively high proportion of silicon atoms and fluorine atoms, resulting in a high oxygen permeability. The contact lens thus obtained can be worn for a long period of time without any trouble because sufficient oxygen is supplied to the cornea through the contact lens when the contact lens is worn. In addition, since the polymer contains urethane bonds, it has appropriate flexibility without the use of special additives, and therefore has high mechanical strength (excellent flexibility and flexibility). It is possible to obtain a contact lens that has excellent wearability and is extremely comfortable to wear.

[Examples] Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 A mixture of compounds represented by the following structural formula was prepared by subjecting 24 g of methacrylic isocyanate and 100 g of di(hydroxypropyl)polydimethylsiloxane to a urethane reaction in a solvent consisting of isopropyl ether, and then removing the solvent. An oligosiloxane derivative having an average p value of 1001 was obtained. Note that the value of active hydrogen equivalent in this urethanization reaction is 1.0.

6.0g of the above oligosiloxane derivative and 2.2゜3
, 4.4.4-hexafluorobutyl methacrylate 3
．． 0 g of α-methylstyrene, 0.5 g of diethylene glycol, and 0.1 g of tert-butylperoxypipare as a polymerization initiator.
g was added into a test tube, and a polymerization reaction was carried out according to a heating program of 8 hours at 45°C, 4 hours at 60°C, 2 hours at 80°C, and 1 hour at 90°C.

Thereafter, the molded polymer was taken out from the test tube and had a thickness of 5. Slice into Owm discs, polish the surface,
A contact lens material of the present invention made of a flexible, colorless and transparent polymer was obtained.

Regarding this contact lens material, "Haze)-1-
(HAZBMETBR) When the parallel light transmittance was measured using TC-HmJ (manufactured by Tokyo Denshokusha), it was 95% or more.

Regarding this contact lens material, the oxygen permeability of a 200m thick sample was measured using a Seikagakuken oxygen permeability meter, and it was found to be 81 x 10 at a temperature of 35°C.
-"cc-c11+/cmLsec-mml (g).

Example 2 5.0 g of the same oligosiloxane derivative used in Example 1, 3.5 g of tris(trimethylsiloxy)silylpropyl methacrylate), and 2, 2.3.4.
4.4-hexafluorobutyl methacrylate 1.0g
and l,3-butylene glycol dimethacrylate 0.
This mixture was mixed with 0.1 g of tert-butylperoxypivalet and injected into a test tube, and a polymerization reaction was carried out in the same manner as in Example 1, resulting in a colorless and transparent polymer. A contact lens material of the present invention was obtained.

Regarding this contact lens material, parallel light transmittance and oxygen transmittance were measured in the same manner as in Example 1. The results are as follows.

Parallel light transmittance: 95% or more Oxygen transmittance: 85xlO-1lCCjCIIl/Cm3
・SeCjmLIIHg Example 3 2.25 g of methacrylic isocyanate and 2.2.3
゜3,4.4.5.5-year-old tafluorohexane-1,
1.62 g of 6-diol, 2.13 g of siloxanyldiamine in which Z is an amino group, m is 3, and n is 5 in the structural formula (II) described above, and tris (trimethylsiloxy).
Silylpropyl methacrylate) 3.0g and tert-
Put 0.5 g of butyl methacrylate, 0.5 g of neopentyl glycol dimethacrylate, and 0.02 g of dibutyl tin dilaure into a test tube, and heat at 60°C for 1 hour.
A time urethanization reaction was carried out. The value of active hydrogen equivalent in this urethanization reaction is 1.0.

After the reaction is completed, tert-butyl peroxybivalate 0
．． 1 g was added and a polymerization reaction was carried out in a test tube in the same manner as in Example 1 to obtain a contact lens material of the present invention made of a colorless and transparent polymer.

Regarding this contact lens material, parallel light transmittance and oxygen transmittance were measured in the same manner as in Example 1. The results are as follows.

Parallel light transmittance: 95% or more Oxygen transmittance: 1Q2xlQ-"cc-cm/cm'
-sec-mm) Ig Example 4 (methacrylic isocyaner) 2.36 g, and 3.96 g of siloxanyldiamine in which 2 is an amino group, m is 3, and n is 9 in the structural formula (II) described above. , 0.68 g of glycerin, and 2.2.3.4.4.4-hexafluorobutyl methacrylate. 0.5 g of 1.6-hexanethiol dimethacrylate, 0.5 g of tert-butyl methacrylate, and 0.02 g of dibutyl tin dilaure) were placed in a test tube, and a urethane reaction was performed at 60° C. for 1 hour. Ta. The value of active hydrogen equivalent in this urethanization reaction is 1.49.

After completion of the reaction, 0.0% of tert-butylperoxy-2-ethylhexanoate was added. Add Ig and in vitro
8 hours at 0℃, 2 hours at 60℃, 1 hour at 80℃, 10
A polymerization reaction was carried out according to a heating program of 1 hour at 0°C and 0.5 hour at 120°C to obtain a contact lens material of the present invention made of a colorless and transparent polymer.

Regarding this contact lens material, parallel light transmittance and oxygen transmittance were measured in the same manner as in Example 1. The results are as follows.

Parallel light transmittance: 95% or more Oxygen transmittance: 73 x 10-cc-cm/cm”
sec-mmHg Example 5 3.01 g of methacrylic isocyanate and 2.2.3.
3゜4,4.5.5-year-old tafluorohexane-1,6
-2.71 g of diol and 1.2 g of 1.1.2.3.3-pentafluoroperfluorononane-1,2-diol
8g and perfluorohexylethyl methacrylate) 1
．． 5 g of tert-butyl methacrylate, and 0.02 g of dibutyltin dilaurate were placed in a test tube, and a urethane reaction was carried out at 60° C. for 1 hour. The value of active hydrogen equivalent in this urethanization reaction is 1.0.

After completion of the reaction, 0.1 g of tert-butylperoquine-2-ethylhexanoate was added and a polymerization reaction was carried out in a test tube in the same manner as in Example 4 to obtain a contact lens of the present invention made of a colorless and transparent polymer. I got the material.

Regarding this contact lens material, parallel light transmittance and oxygen transmittance were measured in the same manner as in Example 1. The results are as follows.

Parallel light transmission $: 95% or more Oxygen transmission rate: 57 x IQ-” cc-cm /
cm' sec-mmHg Example 6 1.04 g of methacrylic isocyanate, and 3.96 g of siloxanyldiamine in which Z is an amino group, m is 3, and n is 9 in the structural formula (n) described above. 3.0 g of pentamethyldisiloxanylpropyl methacrylate, 0.5 g of neopentyl glycol dimethacrylate, and ter
Put 1.0 g of t-butyl methacrylate and 0.02 g of dibutyl tin dilaure into a test tube and heat at 60°C.
The urethane reaction was carried out for 1 hour. The value of active hydrogen equivalent in this urethanization reaction is 1.0.

After completion of the reaction, 0.1 g of tert-butylperoxy-2-ethylhexanoate was added and a polymerization reaction was carried out in a test tube in the same manner as in Example 4 to obtain a contact lens of the present invention made of a colorless and transparent polymer. I got the material.

Regarding this contact lens material, parallel light transmittance and oxygen transmittance were measured in the same manner as in Example 1. The results are as follows.

Parallel light transmittance = 95% or more Oxygen permeability + 92 x 10

Claims (1)

[Claims] 1) an addition reaction between the following component (A) and the following component (B),
From a polymer in which the proportion of the component (C) is 0 to 95% by weight, which is obtained by carrying out a polymerization reaction using the component (A) or a copolymerization reaction using the component (A) and the component (C) below. A contact lens material characterized by: (A) Component: Acrylic isocyanate or methacrylic isocyanate (B) Component: A silicon compound having at least one hydroxyl or amino group and a siloxanyl group (C) Component: Can be copolymerized with the above (A) component Monomer 2) Addition reaction of the following component (A) and the following component (B),
From a polymer in which the proportion of the component (C) is 0 to 95% by weight, which is obtained by carrying out a polymerization reaction using the component (A) or a copolymerization reaction using the component (A) and the component (C) below. A contact lens material characterized by: (A) Component: Acrylic isocyanate or methacrylic isocyanate (B) Component: Fluorine-containing compound having at least one hydroxyl group or amino group and containing a fluorine atom (C) Component: Same as the above (A) component. Polymerizable monomer