JPH0649776A - Optical material - Google Patents

Abstract

PURPOSE:To provide an excellent optical material consisting mainly of a silicon atom-contg. polymer, causing little fading, leaching and bleedout of the colorant contained therein. CONSTITUTION:The objective optical material consisting mainly of a silicon atom-contg. polymer is characterized by containing a metal complex dye. This optical material, which causes little fading and leaching of the colorant contained therein, can be applied as a medical material to come into contact with or to be implanted into the living body, such as contact lens or intraocular implants.

Description

Detailed Description of the Invention

[0001]

The present invention contains a silicon atom,
And colored optical materials.

[0002]

2. Description of the Related Art In recent years, oxygen-permeable contact lenses have been developed as contact lenses that reduce the physiological burden on the cornea and can be worn for a long time. For example, JP-A-58-194014
Such contact lenses are described in Japanese Patent Laid-Open No. 59-28127, Japanese Patent Laid-Open No. 60-146219, Japanese Patent Laid-Open No. 2-198415, Japanese Patent Laid-Open No. 2-147613, and the like. Siloxane compounds are well known as oxygen-permeable substances, and these conventional contact lenses are also composed of a polymer or copolymer of a compound containing a silicon atom.

On the other hand, since conventional contact lenses are almost colorless and transparent, they are often hard to find and lost when dropped on the floor or sink. For this reason, most contact lenses of recent years have been devised so that they can be easily found by wearing them without changing the color of the iris and coloring the eye to the extent that they do not impair vision. As a coloring method, a method of previously adding a colorant at the time of polymerization, a method of coloring a transparent lens later, or the like is adopted.
As the colorant, organic dyes such as monoazo, bisazo, anthraquinone, quinonaphthalone, xanthene, pyrazole, triphenylmethane, indigoid, fluorane and quinoline are used.

Oxygen permeable contact lenses are also colorless and transparent, and are difficult to find and easily lost. Therefore, in order to improve this drawback, the lens is colored with the above coloring agent to improve the visibility. However, since the oxygen permeable contact lens is made of a polymer containing a silicon atom, especially a siloxane-containing polymer, the above organic dyes have problems such as elution of a coloring agent and fading of the lens, unlike conventional contact lenses. That is, as can be seen from the fact that the glass transition point of silicone is lower than room temperature and that it is a rubbery polymer at room temperature, the molecular motion of the siloxane region is large in the polymer of siloxane compound, and the colorant present in this part is Bleed out and elution tended to occur. Further, since the colorant present in the siloxane region is present in a medium having a large molecular motion, the colorant molecules tend to be decomposed and fading easily. For this reason, there is a problem in safety due to discoloration due to long-term use and elution of the coloring agent.
As the content of the siloxane compound is increased in order to improve the oxygen permeability, the above-mentioned problems of safety and discoloration become more remarkable.

On the other hand, when the crystalline lens is removed by cataract surgery or the like, the user feels glare, and the achromatic eye and the phakic eye have different color sensations, which may cause discomfort. This is because the human crystalline lens is colored with aging, so the color vision through such a colored crystalline lens and the ophthalmic lens made of a transparent polymer material applied to an aphakic eye are used. It is caused by the difference in color vision. In order to solve this problem, the intraocular lens is colored to adjust the light transmittance and the spectrum of the light transmitted through the lens, and an organic dye similar to that used for contact lenses is used for coloring. Such an example is disclosed in Japanese Patent Laid-Open No. 3-118029.

In addition, modern surgery requires only a 2-3 mm incision to remove the cataractous lens. However, in polymethylmethacrylate intraocular lenses used today, the incision must be enlarged to allow insertion of the lens. Irregular sutures and incomplete adhesions increase with large incisions, increasing the likelihood of astigmatism progression or endoscopic aberrations. To solve this problem, a flexible intraocular lens has been developed that can be inserted into the eye by a small incision in a compressed state and then returns to the original state after being fixed in the eye. Since silicone-containing polymers represented by silicone have the flexibility required for this purpose, many flexible intraocular lenses consist of polymers containing silicon atoms. . However, in the case of coloring such an intraocular lens, as in the case of contact lenses, there are problems such as discoloration of the coloring agent and safety due to elution.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems. By coloring an optical material, the visibility is improved and the visible light transmission amount is reduced. Another object of the present invention is to provide an optical material that is free from discoloration due to long-term use and safety due to elution from the material.

[0008]

The present invention has the following constitution in order to achieve the above object.

"An optical material containing a polymer containing a silicon atom as a main component and containing a metal complex dye." In the present invention, the polymer containing a silicon atom means a polymer. It is a polymer having a main chain and / or a side chain as long as it contains a silicon atom, for example, a polymer containing as a main component a polymer having a siloxane bond or an organic silane group such as a trimethylsilyl group. Of these polymers containing silicon atoms, long-chain polymers in which silicon atoms are contained in the polymer through a siloxane bond are preferable from the viewpoint of oxygen permeability or flexibility. Specific examples of such a polymer include tris (trimethylsiloxy) silylpropyl methacrylate, polydimethylsiloxane having a double bond at both ends, a homopolymer using a silicone-containing (meth) acrylate, or a homopolymer of these monomers and other monomers. Examples include copolymers with monomers.

As the copolymerizable monomer, a monomer having a (meth) acryloyl group, an aromatic vinyl monomer, a monofunctional monomer such as a heterocyclic vinyl monomer, or a difunctional monomer.
Examples thereof include monomers having three or four (meth) acryloyl groups, polyfunctional monomers such as aromatic divinyl monomers and aromatic diallyl monomers. Examples of the monomer having a (meth) acryloyl group include methyl (meth) acrylate,
Alkyl (meth) acrylates such as ethyl (meth) acrylate and butyl (meth) acrylate, (meth)
Acrylic acid, hydroxyethyl (meth) acrylate,
Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, halogenated alkyl (meth) acrylates such as trifluoroethyl (meth) acrylate and tetrafluoroethyl (meth) acrylate, cyclo such as cyclohexyl (meth) acrylate Examples thereof include alkyl (meth) acrylates. Among them, the use of methyl methacrylate can impart heat resistance and strength, and the use of fluoroalkyl (meth) acrylate can provide a polymer satisfying both functions of oxygen permeability and strength. preferable. Examples of the aromatic vinyl monomer include vinylbenzene, vinylnaphthalene, vinylethylbenzene and the like. Further, examples of the heterocyclic vinyl monomer include vinylcarbazole, maleimide, maleic anhydride and the like. As these copolymerizable monomers, (meth) acrylate monomers are preferable from the viewpoint of copolymerizability and transparency. Among them, methyl (meth) acrylate, trifluoroethyl (meth) acrylate and (meth) acrylic acid are most preferable from the viewpoint of strength. Next, the copolymerizable polyfunctional monomer will be described. Examples of monomers having two (meth) acryloyl groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate and urethane-modified di (meth) acrylate thereof, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate And so on. Examples of the monomer having three (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate. Examples of the monomer having four (meth) acryloyl groups include tetramethylolmethanetetra (meth) acrylate. Examples of the aromatic divinyl compound include o-, m-, and p-diallyl phthalates. Examples of other polyfunctional monomers include bismaleimide and allyl (meth) acrylate. Di-, tri-, tetra-, and (meth) acrylate are preferable from the viewpoint of copolymerizability and transparency. Of these, tri (meth) acrylate is most preferable from the viewpoint of strength.

As described above, a copolymer of a siloxane compound having a double bond and a compound having a (meth) acryloyl group is a polymer containing a silicon atom from the viewpoint of transparency, oxygen permeability and mechanical strength. Most preferably.

When the optical material of the present invention is applied to a contact lens, its oxygen permeability coefficient is 10 × 10 ^-11 cm ³ (S
TP) cm / cm ² · sec · mmHg or more is preferable. If it is smaller than this value, it becomes difficult to supply the necessary oxygen to the cornea from the surface of the cornea through the lens,
When worn for a long time, the physiological burden on the cornea tends to increase. The measurement of the oxygen permeability coefficient as referred to in the present invention,
The electrode method, the vacuum method or the vapor phase method is used.

In the present invention, metal complex salt dyes such as direct dyes, oil-soluble dyes, acid dyes, basic dyes, disperse dyes, vat dyes and organic pigments are used as colorants. As Sea. Eye. Solvent Blue 70, C.I. Eye. Solvent blue 2
5, sea. Eye. Solvent Black 42, C.I. Eye. Solvent Black 43, C.I. Eye. Solvent Black 22, C.I. Eye. Solvent Black 27,
C. Eye. Solvent Black 34, C.I. Eye. Solvent Red 118, C.I. Eye. Solvent Red 177, C.I. Eye. Solvent Red 84, C.I. Eye. Solvent Red 122, C.I. Eye. Solvent Red 119, C.I. Eye. Solvent Red 160,
C. Eye. Solvent Orange 45, C.I. Eye. Solvent Orange 71, C.I. Eye. Solvent Orange 40, C.I. Eye. Solvent Orange 37, C.I.
Eye. Solvent Orange 5, Sea. Eye. Solvent Orange 6, C. Eye. Solvent Orange 54, C.I. Eye. Solvent Orange 99, C.I. Eye. Solvent Yellow 25, C.I. Eye. Solvent Yellow 21, C.I. Eye. Solvent Yellow 32, C.I. Eye. Solvent Yellow 82, C.I. Eye. Solvent Brown 37, C.I. Eye. Solvent brown 58,
C. Eye. Solvent Violet 21, C.I. Eye. Solvent violet 2 etc. can be mentioned.

Of these, 1: 2 type metal complex salt dyes are preferable, and specific examples of such dyes include C.I. Eye. Solvent Black 42 ,, C. Eye. Solvent black 4
3, sea. Eye. Solvent Black 22, C.I. Eye. Solvent Red 118, C.I. Eye. Solvent Red 177, C.I. Eye. Solvent Red 84, C.I. Eye. Solvent Orange 45, C.I. Eye. Solvent Orange 71, C.I. Eye. Solvent Orange 40, C.I. Eye. Solvent Orange 37, C.I. Eye. Solvent Yellow 25, C.I. Eye. Solvent Brown 37, C.I. Eye. Solvent violet 21 is mentioned.

Further, among these, particularly excellent coloring agents are coloring agents in which the metal complex salt is a chromium complex or a cobalt complex. Specific examples of such dyes include C.I. Eye. Solvent Black 42, C.I. Eye. Solvent Black 43, C.I. Eye. Solvent Red 118, C.I.
Eye. Solvent Orange 45, C.I. Eye. Solvent Yellow 25 is included. These colorants may be used alone, or a plurality of these colorants may be used in combination in order to produce more various color tones.

As a method of coloring, a method of adding a colorant at the time of polymerization, a method of dyeing at a later time, and the like can be mentioned. Among them, a method of adding a colorant at the time of polymerization is taken into consideration in consideration of coloring durability. desirable.

The concentration of the colorant to be added depends on the use of the optical material of the present invention and is not particularly limited, but 0.0005 relative to the weight of the mixed liquid of the raw material monomers.
The range of 5 wt% is desirable. If the addition amount exceeds 5% by weight, the polymerization rate may be lowered and the mechanical strength may be lowered. Explaining more concretely by the use of the optical material, for example, in the case of a contact lens, a concentration that does not change the color of the iris or the white of the eye where the cornea can be seen, and which enhances the visibility of the lens from the appearance is preferable. That is, in the corneal lens, the transmittance at the maximum absorption wavelength in the visible light region of 400 to 800 nm is 30 to 90%, and in the lens that covers a part of the white eye, the transmittance is about 70 to 98%. Is desirable. For intraocular lenses, 400-8
It is desirable that the transmittance at the maximum absorption wavelength in the visible light region of 00 nm is 10 to 99%.

As the method for producing the optical material of the present invention, cast polymerization, injection molding, extrusion molding or the like can be used without particular limitation. Particularly, when the polymer has three-dimensional crosslinking, cast polymerization is preferably used. In order to obtain a predetermined shape, it is possible to form a desired shape simultaneously with molding using an appropriate mold. When it is necessary to create a wide variety of shapes such as contact lenses and intraocular lenses, it is also possible to first create a columnar or flat plate shaped product and then use cutting, polishing, etc. This is a useful method.

The optical material of the present invention is preferably used as a medical device, such as a contact lens or an intraocular lens, which comes into contact with or is embedded in a living body, because the color fading and the elution of the coloring agent are small.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.

[0021]

【Example】

Example 1 53.4 parts of 2,6-diisocyanatocaproic acid-β-isocyanatoethyl ester were added to a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet.
52 parts of 2-hydroxyethyl methacrylate, di-n-
Charge 0.01 part of butyltin dilaurate until the absorption of hydroxyl group disappears in the infrared absorption spectrum at 50 ° C.
Stirred under nitrogen atmosphere. 94.6 parts of both-end alcohol-modified polydimethylsiloxane represented by the following formula having an average molecular weight of 946 was added to the four-necked flask, and the mixture was heated at 50 ° C. until the absorption of the isocyanate group in the infrared absorption spectrum disappeared. Then, the mixture was stirred under a nitrogen atmosphere to obtain a reaction product containing a siloxane macromer as a main component and having two double bonds at each end.

[0022]

[Chemical 1] This reaction product (main component is siloxane macromer) 10
To 3 parts, 3 parts of methyl methacrylate was added, and trimethylolpropane trimethacrylate 0.0
55 parts and 0.004 parts of azobismethylvaleronitrile were added. As a coloring agent for the monomer mixture liquid, Eye. 0.015% by weight of Solvent Red 118
After addition, each composition was mixed and dissolved to obtain a uniform black stock solution. This stock solution was placed in a rod-shaped glass container, degassed, made into a nitrogen atmosphere, and then sealed. 40 at 40 ℃ in a constant temperature water bath
The reaction was carried out under conditions of 50 ° C. for 24 hours, 60 ° C. for 16 hours, 70 ° C. for 4 hours, and 90 ° C. for 2 hours. Further, heating was carried out at 130 ° C. for 3 hours in a circulation dryer to obtain a rod-shaped polymer. The obtained polymer had a Shore D hardness of 80 and was hard, and had good machinability and polishability.

This polymer was made into small pieces with a mixer, and 1 g of this small piece was immersed in 50 g of distilled water, and the mixture was kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. No elution of dye was observed spectroscopically in this extract.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm and heat-treated under reduced pressure in vacuum at 120 ° C. for 16 hours. No change in color tone or absorbance due to bleed-out was observed.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disk was subjected to an irradiation test with a fade meter at room temperature. Irradiation with fade meter 60
No decrease in absorbance was observed even with time, and even after irradiation for 200 hours, the absorbance was 60% of that before irradiation, indicating excellent light resistance.

When the oxygen permeability coefficient of this polymer was determined by a Seikaken film oxygen permeability meter, the oxygen permeability coefficient at 37 ° C. was 20 × 10 ^-11 cm ³ (STP) cm / cm ² · sec.
It was mmHg.

This polymer was cut and polished to give a lens system 9.0.
mm, base curve 8.0 mm, lens power -3.0
It was processed into a 0D contact lens. This lens was light red and was easily identifiable.

Example 2 In the same manner as in Example 1, a reaction product containing a siloxane macromer having two double bonds at both ends as main components was obtained.
This reaction product (main component is siloxane macromer) 10
3 parts of trifluoroethyl methacrylate, 0.055 parts of trimethylolpropane trimethacrylate, and azobismethylvaleronitrile of 0.
004 parts were added. As a coloring agent for the monomer mixed liquid, C.I. Eye. Solvent Orange 45 to 0.0
15 wt% was added, and each composition was mixed and dissolved to obtain a uniform yellow stock solution. This stock solution was polymerized in the same manner as in Example 1 to obtain a rod-shaped polymer. The obtained polymer is
It had a Shore D hardness of 74 and was hard, and had good machinability and polishability.

This polymer was made into small pieces with a mixer, and 1 g of this small piece was dipped in 50 g of distilled water and kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. No elution of dye was observed spectroscopically in this extract.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm and heat-treated under reduced pressure in vacuum at 120 ° C. for 16 hours, but no change in color tone or absorbance due to bleed-out was observed.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disc was subjected to an irradiation test with a fade meter at room temperature. Irradiation with a fade meter Even after irradiation for 200 hours, the absorbance is 40% of that before irradiation.
% Was recognized, indicating excellent light resistance.

The oxygen permeability coefficient of this polymer was 32 × 10 ^-11 cm ³ (STP) cm / cm ² · sec · mmHg at 37 ° C., which was determined by a Kaken film oxygen permeability meter. It was

This polymer was cut and polished to give a lens system 9.0.
mm, base curve 8.0 mm, lens power -3.0
It was processed into a 0D contact lens. The lens was pale yellow and was easily identifiable.

Example 3 50 parts by weight of tris (trimethylsiloxy) silylpropyl methacrylate, 50 parts by weight of trifluoroethyl methacrylate, 0.05 part by weight of azobisisobutylnitrile and 0.15 part by weight of azobiscyclohexanecarbonitrile were mixed and polymerized. Stock solution. As a coloring agent for the monomer mixed liquid, C.I. Eye. Solvent Yellow 25
0.015% by weight was added and dissolved to obtain a uniform yellow stock solution. After dissolution, the mixture was sealed in a test tube, heated from 60 ° C. to 110 ° C. over 24 hours, and then held at 110 ° C. for 4 hours to obtain a polymer.

This polymer was made into small pieces with a mixer, and 1 g of this small piece was immersed in 50 g of distilled water and kept at 100 ° C. for 30 minutes.
It was extracted by heating for an hour. No elution of dye was observed spectroscopically in this extract.

This polymer was processed into a disk having a diameter of 17 mm and a thickness of 5 mm and then heat-treated under vacuum reduced pressure at 120 ° C. for 16 hours, but no change in color tone or absorbance due to bleed-out was observed.

The polymer is 9 mm in diameter and 0.2 mm in thickness.
After being processed into a disk of No. 1, the mixture was heat-treated under reduced pressure at 120 ° C. for 16 hours. This disk was subjected to an irradiation test with a fade meter at room temperature. Even after irradiation with a fade meter for 200 hours, the absorbance was 30% of the absorbance before the irradiation, showing excellent light resistance.

From the results of Examples 1, 2, and 3, the optical materials containing a metal complex dye as a colorant in the polymer containing a silicon atom obtained according to the present invention showed that the colorant was fading, eluted from the material, and bleed out. It has been found that it is an excellent optical material with less.

[0039]

INDUSTRIAL APPLICABILITY According to the present invention, a colorant containing a polymer containing a silicon atom as a main component is discolored, eluted from a material,
An excellent optical material with little bleed-out can be obtained. INDUSTRIAL APPLICABILITY The optical material of the present invention can be applied to medical devices such as contact lenses and intraocular lenses that come into contact with or are embedded in a living body, because the color fading and the elution of the coloring agent are small.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 43/04 LKA 7921-4J 83/04 LRV 8319-4J G02B 1/04 7132-2K // G02C 7/04

Claims (6)

[Claims] 1. An optical material containing a polymer containing a silicon atom as a main component, which contains a metal complex salt dye. 2. An oxygen permeability coefficient of 10 × 10 ^-11 cm ³ (STP) c
The optical material according to claim 1, which has a m / cm ² · sec · mmHg or more. 3. The optical material according to claim 1, wherein the polymer containing a silicon atom is a copolymer of a siloxane compound having a double bond and a compound having a (meth) acryloyl group. 4. The optical material according to claim 1, wherein the metal complex salt dye is a 1: 2 type metal complex salt dye. 5. The optical material according to claim 1, wherein the metal complex salt is a chromium complex or a cobalt complex. 6. The optical material according to claim 1, wherein the optical material is a contact lens or an intraocular lens.