JP2003177204A - Method for dyeing plastic lens and dyed lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for easily dyeing a plastic lens material which is conventionally not easily dyed while avoiding decrease in the light resistance of the dyed lens or aggregation of the dye in a dye liquid and to provide a dyed plastic lens. <P>SOLUTION: The method for dyeing a sulfur-containing urethane plastic lens features that the sulfur-containing urethane plastic lens is dyed in a water bath containing one or more kinds of dispersion dyes, one or more kinds of surfactants, and one or more kinds of benzophenone compounds expressed by general formula (1) and having ≤90°C melting point as a dyeing accelerator. The plastic lens is dyed by the above method. In formula (1), each of R<SB>1</SB>to R<SB>4</SB>independently represents an OH group, 1-10C alkoxy group, 1-5C alkyl group, halogen atom or hydrogen atom and at least one in R<SB>1</SB>to R<SB>4</SB>is an OH group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of dyeing a plastic lens and a dyed plastic lens.

[0002]

2. Description of the Related Art Plastic lenses typified by diethylene glycol bisallyl carbonate have the advantage of being easy to dye, and are widely used in the field of spectacle lenses where fashionability is required due to this advantage.

However, in recent years, in addition to the plastic lens made of diethylene glycol bisallyl carbonate, various plastic lens materials such as various high refractive index plastic lens materials and low specific gravity plastic lens materials have been developed. Some of these plastic lens materials have good dyeability, similar to diethylene glycol bisallyl carbonate. But,
A considerable number of them are difficult to dye and difficult to apply to the field of spectacle lenses where fashionability is required.

Therefore, it has been proposed to use a water-soluble organic solvent such as benzyl alcohol as a dyeing accelerator for the purpose of accelerating the dyeing of such a difficult-to-dye plastic lens (JP-A-4-146278). ). However, when benzyl alcohol is used as a dyeing accelerator, dyeing of a plastic lens is promoted, but the light resistance of the dyed lens is lowered, and aggregation of the dye is observed in the dyeing solution. Therefore, it was not practical to use benzyl alcohol as a dyeing accelerator.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a plastic lens material, particularly a conventional dye, without reducing the light resistance of the dyed lens or causing the dye to aggregate in a dyeing solution. It is an object of the present invention to provide a method for easily dyeing a plastic lens material that could not be easily done.

A further object of the present invention is to provide a dyed plastic lens for a plastic lens material which has not been dyed conventionally.

[0007]

Means for Solving the Problems That is, the present invention is a method of dyeing a sulfur-containing urethane plastic lens with a disperse dye, which comprises one or more surfactants and one or more dyeing accelerators. The present invention relates to a method comprising using two or more kinds of benzophenone compounds represented by the following general formula (1) and having a melting point of 90 ° C. or lower, and a plastic lens dyed by the method.

[0008]

[Chemical 3]

(In the formula, R _{1 to} R ₄ are, independently of each other,
An OH group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₅ alkyl group, a halogen atom or a hydrogen atom, and R ₁
At least one of R ₄ is an OH group. )

The plastic lens targeted by the present invention is a sulfur-containing urethane type plastic lens, and more specifically, it contains a polyiso (thio) ianate having two or more functional groups and a polythiol, polyol or hydroxy group having two or more functional groups. It is a sulfur-containing urethane-based plastic lens obtained by reacting with a polythiol contained therein.

Specific examples of the bifunctional or higher functional polyiso (thio) cyanate compound include isophorone diisocyanate, 1,3-bisisocyanate methylcyclohexane, xylylene diisocyanate, tolylene diisocyanate, 1,3-diisothiocyanate benzene, 1,
3-bisisothiocyanate methylcyclohexane etc. are mentioned.

Specific examples of the bifunctional or higher polyiso (thio) cyanate compound include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), trimethylolpropane tris (3-mercaptopropionate). Nate), trimethylolpropane tris (thioglycolate), 2,5-dimercaptomethyl-1,4-dithiane and the like.

Specific examples of styrene, aromatic ring-containing acrylates, alicyclic acrylates, aromatic ring-containing methacrylates and alicyclic methacrylates include styrene, chlorostyrene, α-methylstyrene, bromostyrene, divinylbenzene, phenyl acrylate, Benzyl acrylate, bisphenol A diacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,
2-bis (3,5-dibromo-4-acryloxyethoxyphenyl) propane, cyclohexyl acrylate,
Adamantyl acrylate phenyl methacrylate, benzyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4)
-Methacryloxyethoxyphenyl) propane, cyclohexyl methacrylate, adamantyl methacrylate and the like.

As the disperse dye used in the present invention, anthraquinone type or azo type disperse dyes are used. Specifically, C.I. I Disperse Yellow 3, 4, 5, 7,
33, 42, etc., C.I. I Disperse Orange 1, 3, 1
1st, C.I. I Disperse Red 1, 4, 5, 11, 1
7, 58, C.I. I Disperse Blue 1, 3, 7, 4
3 and the like. These dyes are used alone or in combination of two or more so that the plastic lens can be dyed in a desired color. The dye concentration in the dye bath is usually about 1.
Used in the range of up to 20 g / liter.

The surfactant used in the present invention includes:
Examples thereof include anionic surfactants such as alkylbenzene sulfonate, alkylsulfosuccinate, and lauryl sulfate, and nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester. These may be used alone or in combination of two or more. The amount of these surfactants used varies depending on the type of plastic lens to be dyed and cannot be determined uniquely, but in consideration of the dyeing speed and color unevenness, it is usually used in the range of about 1 to 500 ml / liter. It

In the present invention, a benzophenone compound represented by the general formula (1) is used as a dyeing accelerator. In the present invention, a benzophenone compound in which at least one of R _{1 to} R _{4 in} the general formula (1) is an OH group is used as a dyeing accelerator. Preferred is a benzophenone compound in which at least two of R _{1 to} R _{4 in} the general formula (1) are OH groups, for example, 2,2′-dihydroxy-4.
-Methoxybenzophenone (melting point: about 71 ° C), 2,2'-dihydroxybenzophenone (melting point: about 63 ° C) and the like. The benzophenone-based compound usually has almost no solubility in water, becomes an oil at a temperature of the melting point or higher and is slightly soluble in water, and in the present invention, a water-based dye bath is used, Since it is preferable that the compound becomes oily at the temperature of 1 from the viewpoint of solubility, a benzophenone compound having a melting point of about 90 ° C. or less is used.

The dyeing method of the present invention can be carried out, for example, as follows. A dyebath containing a predetermined amount of a disperse dye and a surfactant is prepared and maintained at a dyeing temperature, and then a predetermined amount of a benzophenone compound previously dissolved in water at the same temperature as the dyeing temperature is added as a dyeing accelerator to the dyebath. Adjust. The benzophenone-based compound has a very low solubility in water as described above. Therefore, before use, a certain amount of a liquid prepared by previously dissolving a benzophenone compound in water at the same temperature as the dye bath temperature is added to the dye bath. Alternatively, a fixed amount of a benzophenone compound dissolved in a small amount of an organic solvent can be added to the dye bath.

The amount of the benzophenone compound used can be appropriately determined depending on the benzophenone compound used and the like. For example, it is preferable to make 10 to 300 ml of a saturated aqueous solution of the benzophenone compound per liter of the dyeing bath at the dyeing temperature. When the amount of the benzophenone compound used is 10 ml or less per 1 liter of the dye bath, the effect as a dyeing accelerator is usually hardly obtained. On the other hand, the amount of the benzophenone compound used is 30 per 1 liter of the dye bath.
Even when the amount is 0 ml or more, the effect as a dyeing accelerator reaches a ceiling.

Dyeing is performed by immersing the plastic lens in the dye bath for a predetermined time. The temperature and time of dyeing can be appropriately changed depending on the required dyeing concentration, and usually 70 to 95 ° C. and about 1 minute to 1 hour. The method of the present invention is suitably applied to a non-staining plastic lens, and particularly a remarkable effect can be obtained in a sulfur-containing urethane plastic lens.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to examples. All parts in the examples are parts by weight.

Example 1 (Preparation of plastic lens) 94 parts of m-xylylene diisocyanate, 122 parts of pentaerythritol tetrakis (mercaptopropionate), 0.5 part of dibutyltin dilaurate as a polymerization catalyst, and dibutylphosphate as an internal mold release agent. 1 part of the fate and 0.1 part of TINUVIN P as an ultraviolet absorber were mixed and stirred to form a uniform solution, which was then poured into a lens molding mold comprising a glass mold and a resin gasket. Then, polymerization was performed under the condition that the temperature was gradually raised from 30 ° C. to 120 ° C. over 24 hours, and then the lens was taken out from the mold. Then, in order to remove the distortion due to the polymerization, heat treatment was carried out at 120 ° C. for 2 hours and then gradually cooled to room temperature to obtain a thiourethane lens.

(Preparation of Dyeing Solution) 5 g of Dyanic Thread ACE (manufactured by Mitsubishi Kasei Co., Ltd.) as a disperse dye and a nonionic Nikkasan Salt 7000 as a surfactant.
3g (Nichika Chemical Co., Ltd.) was added to 1 liter of water,
It was heated to 85 ° C and kept warm. Then, 10 g of 2,2'-dihydroxy-4-methoxybenzophenone and 10 g of Nikkasan Salt 7000 were added in advance to 1 liter of water, and 8
50 ml of the supernatant of the solution kept warm at 5 ° C. was weighed and added to the dye solution to obtain a dye solution.

(Dyeing) The thiourethane lens was immersed in the dyeing solution for 5 minutes to obtain a red plastic lens. The transmittance of this lens at 525 nm was measured to be 40%, which was a good dyed lens with no color unevenness. Also, 200 xenon lamp weather meter
The change in transmittance before and after the time exposure test was 3%, indicating good light resistance.

Example 2 (Preparation of plastic lens) 111 parts of isophorone diisocyanate, 122 parts of pentaerythritol tetrakis (mercaptopropionate), 0.5 part of dibutyltin dilaurate as a polymerization catalyst, and 1 part of dibutyl phosphate as an internal release agent. And Tinuvin P as UV absorber
0.1 part was mixed and stirred to form a uniform solution, and the solution was poured into a lens molding mold including a glass mold and a resin gasket. Then, polymerization was performed under the condition that the temperature was gradually raised from 30 ° C. to 120 ° C. over 24 hours, and then the lens was taken out from the mold. Then, to remove the distortion caused by polymerization, 1
It was heat-treated at 20 ° C. for 2 hours and gradually cooled to room temperature to obtain a thiourethane lens.

(Preparation of Dyeing Solution) 5 g of Dyanics Blue ACE (manufactured by Mitsubishi Kasei Co., Ltd.) as a disperse dye and nonionic Nikkasan Salt 7000 as a surfactant.
(Nichika Chemical Co., Ltd.) 4 g was added to 1 liter of water,
It was heated to 85 ° C and kept warm. Then, 10 g of 2,2'-dihydroxy-4-methoxybenzophenone and 10 g of Nikkasan Salt 7000 were added in advance to 1 liter of water, and 8
50 ml of the supernatant of the solution kept warm at 5 ° C. was weighed and added to the dye solution to obtain a dye solution.

(Dyeing) The thiourethane lens was immersed in the dyeing solution for 5 minutes to obtain a blue plastic lens. The transmittance of this lens at 585 nm was measured and found to be 50%, which was a good dyed lens without color unevenness. Also, 200 xenon lamp weather meter
The change in transmittance before and after the time exposure test was also 4%, indicating good light resistance.

Example 3 The same procedure as in Example 1 was carried out except that predetermined amounts of m-xylylene diisocyanate, 2,5-dimercaptomethyldithiane, and pentaerythritol tetrakis (mercaptopropionate) were used as the monomers. The obtained dyed lens had a transmittance at 525 nm of 48% and was a good dyed lens with no color unevenness. In addition, the change in transmittance before and after the 200-hour exposure test with a xenon lamp weather meter was 3%, indicating good light resistance.

Example 4 (Preparation of plastic lens) 40 parts of 2,2-bis (4-methacryloxyphenyl) propane, 60 parts of styrene, 0.5 part of azobisisobutyronitrile as a polymerization catalyst and an ultraviolet absorber. 0.2 parts of TINUVIN P was mixed and stirred to form a uniform solution, and the solution was poured into a lens molding mold including a glass mold and a resin gasket. Then, 40 ℃
After the polymerization was carried out under the condition that the temperature was gradually raised from 1 to 85 ° C. over 24 hours, the lens was taken out from the mold. afterwards,
Heat treatment was performed at 120 ° C. for 2 hours to remove distortion caused by polymerization, and the plastic lens was slowly cooled to room temperature.

(Preparation of Dyeing Solution) 5 g of Dyanic Thread ACE (manufactured by Mitsubishi Kasei Co., Ltd.) as a disperse dye and nonionic Nikkasan Salt 7000 as a surfactant.
3g (Nichika Chemical Co., Ltd.) was added to 1 liter of water,
It was heated to 85 ° C and kept warm. Then, 10 g of 2,2'-dihydroxy-4-methoxybenzophenone and 10 g of Nikkasan Salt 7000 were added in advance to 1 liter of water, and 8
50 ml of the supernatant of the solution kept warm at 5 ° C. was weighed and added to the dye solution to obtain a dye solution.

(Dyeing) The plastic lens was immersed in the dyeing solution for 5 minutes to obtain a red plastic lens.
The transmittance of this lens at 525 nm was measured to be 42%, which was a good dyed lens without color unevenness. In addition, the change in transmittance before and after the 200-hour exposure test with a xenon lamp weather meter was 4%, indicating good light resistance.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the supernatant containing 2,2'-dihydroxy-4-methoxybenzophenone was not used. The transmittance of the obtained dyed lens is 78%,
The dyeability was not good. In addition, the change in transmittance before and after the 200-hour exposure test with a xenon lamp weather meter was 9%, which was not good light resistance.

Comparative Example 2 The procedure of Example 1 was repeated except that 20 ml of benzyl alcohol was used as a carrier instead of the supernatant containing 2,2'-dihydroxy-4-methoxybenzophenone. The transmittance of the obtained dyed lens was 45% and the dyeability was good, but color unevenness was observed. or,
The change in transmittance before and after the 200-hour exposure test with a xenon lamp weather meter was 8%, which was not good light resistance. Further, aggregation of the dye was observed in the dyeing solution, which was not practical.

[0033]

According to the dyeing method of the present invention, it is possible to easily dye a difficult-to-dye plastic lens which could hardly be dyed by the usual dyeing method without causing aggregation of the dye. Further, since a benzophenone compound having an ultraviolet absorbing property is used as a dyeing accelerator, the dyed lens obtained by the method of the present invention has excellent light resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Yukawa             2-7-5 Nakaochiai, Shinjuku-ku, Tokyo Ho             Within Ya Co., Ltd. F term (reference) 2K009 BB25 CC21 CC47 EE01                 4H057 AA02 CA03 CB15 CB21 CC02                       DA02

Claims (4)

[Claims] Claims: 1. One or more disperse dyes and one or two
One or more surfactants and one or more benzophenone compounds having the melting point of 90 ° C. or less, represented by the following general formula (1) as a dyeing accelerator, in a water bath containing a sulfur-containing urethane-based compound A method of dyeing a sulfur-containing urethane-based plastic lens, which comprises dyeing a plastic lens. [Chemical 1] (In the formula, R _{1 to} R ₄ are each independently an OH group, C ₁ to
It represents a C ₁₀ alkoxy group, a C _{1 to} C ₅ alkyl group, a halogen atom or a hydrogen atom, and at least one of R _{1 to} R ₄ is an OH group. ) 2. The method according to claim 1, wherein the water bath is prepared by dissolving a surfactant and a benzophenone compound in warm water, and mixing the resulting solution with a solution containing a disperse dye. . 3. A sulfur-containing urethane-based plastic lens dyed by the method according to claim 1. 4. A dyed plastic lens, comprising:
The plastic lens is a sulfur-containing urethane plastic lens, and the dyed portion of the plastic lens is at least one or more disperse dyes, one or more surfactants, and the following general formula (1) ), And one or more benzophenone-based compounds having a melting point of 90 ° C. or less, a plastic lens. [Chemical 2] (In the formula, R _{1 to} R ₄ are each independently an OH group, C ₁ to
It represents a C ₁₀ alkoxy group, a C _{1 to} C ₅ alkyl group, a halogen atom or a hydrogen atom, and at least one of R _{1 to} R ₄ is an OH group. )