JPWO2013002409A1 - Plastic lens - Google Patents

Abstract

A plastic lens comprising a compound represented by the following formula (1): [In the above formula (1), R 1, R 2 and R 3 each independently represents a group selected from a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Description

  The present invention relates to a plastic lens. More specifically, the present invention relates to a plastic lens that is almost colorless and suitable for use as a spectacle lens.

Plastic lenses made of optical resins having excellent transparency are used in a wide range of fields in place of inorganic glass lenses due to their advantages such as light weight and excellent workability, and are particularly suitable as spectacle lenses.
The spectacle lens is required to have an ultraviolet absorbing ability in order to protect the eyes from harmful ultraviolet rays, and an ultraviolet absorber may be added when manufacturing a spectacle lens made of a plastic material. . However, there has been a problem that the plastic lens itself is yellowed by adding an ultraviolet absorber. Moreover, yellowing of a plastic lens also occurs through a manufacturing process such as heat treatment, and various studies have been made to eliminate such yellowing of a plastic lens.
For example, it is known to add a bluing agent or a blue dye in the production process, but the bluing agent or the blue dye is not soluble depending on the type of monomer or discolored during polymerization, etc. In some cases, sufficient effects could not be obtained.
Patent Document 1 discloses a method for manufacturing a lens in which an anthraquinone compound having a specific structure as a blue dye is added to a urethane-based resin. However, the method is a method for manufacturing a lens limited to a urethane-based resin. The transparency of the resulting lens was not satisfactory depending on the application.

Japanese Patent No. 4067204

  An object of the present invention is to provide a plastic lens that is almost colorless and transparent without being yellowed even if it is manufactured through a process such as addition of an ultraviolet absorber or heat treatment.

As a result of diligent investigation, the inventor of the present invention contains an anthraquinone compound having a specific structure, and even when manufactured through a process such as addition of an ultraviolet absorber or heat treatment, it is extremely yellow. The present invention has been completed by finding out that it can be a plastic lens that is nearly colorless and transparent.
That is, this invention is a plastic lens characterized by including the compound represented by following formula (1).

[In said formula (1), R < ¹ >, R < ² > and R < ³ > show the group chosen from a hydrogen atom or a C1-C8 alkyl group each independently. ]

  The plastic lens of the present invention containing an anthraquinone compound having a specific structure is a plastic lens that is almost colorless and transparent without being yellowed even if it is manufactured through a process such as addition of an ultraviolet absorber or heat treatment. .

  The plastic lens of the present invention includes an anthraquinone compound represented by the following formula (1).

In the above formula ^{(1), R 1, R} 2 and R ³ each independently represent a hydrogen atom or a group selected from alkyl group having 1 to 8 carbon atoms, the carbon number of the alkyl group is preferably 1 to 3.
The alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group. , Isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, cyclopentyl group, cyclohexyl group, and the like. Among them, a methyl group and an ethyl group are preferable.

  Examples of the compound represented by the above formula (1) that can be preferably used in the present invention include 1,4-bis [(2,6-dimethylphenyl) amino] anthracene-9,10-dione, 1,4. -Bis [(2,6-diethylphenyl) amino] anthracene-9,10-dione, 1,4-bis [(2,6-dipropylphenyl) amino] anthracene-9,10-dione, 1,4- Bis [(2,6-dimethyl-4-methylphenyl) amino] anthracene-9,10-dione, 1,4-bis [(2,6-diethyl-4-methylphenyl) amino] anthracene-9,10- Dione, 1,4-bis [(2,6-dipropyl-4-methylphenyl) amino] anthracene-9,10-dione, 1,4-bis [(2,6-dimethyl-4-ethylphenol) L) amino] anthracene-9,10-dione, 1,4-bis [(2,6-diethyl-4-ethylphenyl) amino] anthracene-9,10-dione, 1,4-bis [(2,6 -Dipropyl-4-ethylphenyl) amino] anthracene-9,10-dione, 1,4-bis [(2,6-dimethyl-4-propylphenyl) amino] anthracene-9,10-dione, 1,4- Bis [(2,6-diethyl-4-propylphenyl) amino] anthracene-9,10-dione, 1,4-bis [(2,6-dipropyl-4-propylphenyl) amino] anthracene-9,10- Dione, 1,4-bis [(2,4,6-trimethylphenyl) amino] anthracene-9,10-dione, 1,4-bis [(2,4,6-triethylphenyl) ami ] Anthracene-9,10-dione, and 1,4-bis [(2,4,6-propylphenyl) amino] anthracene-9,10-dione can be cited.

  In the present invention, the content of the anthraquinone compound represented by the above formula (1) contained in the plastic lens depends on the type of monomer used as a raw material for the plastic lens and the type of additive added as necessary. Although it may determine suitably, 0.001-1000 mass ppm is preferable with respect to the whole quantity of a monomer, More preferably, it is 0.01-100 mass ppm, More preferably, it is 0.1-10 mass ppm. If the said content is 0.001 mass ppm or more, the effect which suppresses the yellowness of a plastic lens can be exhibited, and if it is 1000 mass ppm or less, sufficient transparency of a plastic lens can be ensured.

  The plastic lens of the present invention can be produced by mixing and adding an anthraquinone compound represented by the above formula (1) with various raw material monomers, and an anthraquinone compound represented by the above formula (1). The compound can also be produced by adsorbing and penetrating the surface of the plastic lens later.

  The plastic applied to the plastic lens of the present invention is not particularly limited and may be those usually used for resin lenses. For example, urethane resin, thiourethane resin, polycarbonate resin, polystyrene resin, polyacrylate Examples thereof include resins and melamine resins. When a plastic lens is used as a spectacle lens, urethane resins and thiourethane resins, which are excellent in transparency and impact resistance and are suitable for use in spectacle lenses, are preferable.

  In the present invention, when a urethane resin or a thiourethane resin is applied as a plastic, for example, monomers such as a polyisocyanate compound, a polythiol compound, and a polyol compound, and an ultraviolet absorber, a polymerization catalyst, if necessary. Additives such as antioxidants and mold release agents can be used, and the monomers and additives can be used alone or in combination of two or more. Examples of the monomer and additive include the following.

As the polyisocyanate compound, an aromatic polyisocyanate compound, an aliphatic or alicyclic polyisocyanate compound and the like can be used, and among them, an aromatic polyisocyanate compound is preferably used.
Examples of the aromatic polyisocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-xylylene diisocyanate, and m-xylylene diisocyanate. Isocyanate, p-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, isopropylphenylene diisocyanate, diisopropylphenylene Examples include diisocyanate, trimethylbenzene triisocyanate, and benzene triisocyanate. These aromatic polyisocyanate compounds may be used alone or in combination of two or more. Among these, it is preferable to use 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate, which are easily available industrially.

  Examples of the aliphatic polyisocyanate compound include 1,6-hexamethylene diisocyanate, lysine ester triisocyanate, mesitylene triisocyanate, 1,3,6-hexamethylene triisocyanate, and the alicyclic polyisocyanate compound. For example, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, 2,5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) bisi B - [2,2,1] - heptane, 1,3,5-tris (isocyanatomethyl) cyclohexane, bicycloheptane triisocyanate. These aliphatic and alicyclic polyisocyanate compounds may be used alone or in combination of two or more.

  Examples of the polythiol compound include ethylene glycol bis (2-mercaptoacetate), trimethylolpropane bis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptopropio). Nate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptoacetate), dipentaerythritol hexakis (mercaptoacetate), 2,5- Bis (mercaptomethyl) -1,4-dithiane, bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4,7-bis (mercaptomethyl) -3,6,9- Lithiaundecane-1,11-dithiol, 4,8-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol, 5,7-bis (mercaptomethyl) -3,6,9 -Trithiaundecane-1,11-dithiol and the like can be used. These polythiol compounds may be used independently and may use 2 or more types together.

As the polyol compound, an aliphatic or aromatic polyol compound or the like can be used.
Examples of the aliphatic polyol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, butane triol, 1,2-methyl glucoside, penta. Erythritol, dipentaerythritol, tripentaerythritol, triethylene glycol, polyethylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, bicyclo [4.3 .0] -nonanediol, dicyclohexanediol, tricyclo [5.3.1.1] dodecanedi Lumpur, spiro [3.4] octanediol, butyl cyclohexanediol and the like.

Examples of the aromatic polyol compound include dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, and tetrabromobisphenol.
These aliphatic and alicyclic polyol compounds may be used alone or in combination of two or more.

Moreover, as an additive added as needed, a ultraviolet absorber, a polymerization catalyst, antioxidant, a mold release agent, etc. can be used.
In particular, when an ultraviolet absorber is added in the production of the plastic lens of the present invention, the effect of the present invention due to the inclusion of the anthraquinone compound represented by the above formula (1) is exhibited remarkably.
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone. Various benzophenone compounds such as 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone and 2,2′-dihydroxy-4-methoxybenzophenone; 2- (2′-hydroxy-5 '-Methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl) -5'-methylphenyl) -5-chlorobenzotriazole, 2- 2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2 ′ -Hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole and 2- (2-hydroxy-4-octyloxyphenyl) benzotriazole Various benzotriazole compounds; dibenzoylmethane, 4-tert-butyl-4′-methoxybenzoylmethane and the like. These ultraviolet absorbers may be used alone or in combination of two or more.

The polymerization catalyst is preferably used in the case of adjusting the reaction rate of the monomer polymerization. For example, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, Examples thereof include organic tin compounds such as tributyltin chloride, tributyltin fluoride, and dimethyltin dibromide. These polymerization catalysts may be used alone or in combination of two or more.
Examples of the antioxidant include 2,6-di-tert-butyl-p-cresol, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. ], Phenolic antioxidants such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, and the like. The antioxidants may be used alone or in combination of two or more.

  Examples of the release agent include isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, nonyl acid phosphate, decyl acid phosphate, isodecyl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, Phosphoric acid monoester compounds such as propyl phenyl acid phosphate and butyl phenyl acid phosphate; diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, diisodecyl acid phosphate, bis (tridecyl acid phosphate), distearyl Acid phosphate, dipropyl phenyl acid phosphate, dibutyl phenol Such as phosphoric acid diester compounds such as Le acid phosphate and butoxyethyl acid phosphate. These mold release agents may be used independently and may use 2 or more types together.

The present invention also provides a method for producing a plastic lens, wherein in the production of a plastic lens obtained by polymerizing a monomer composition, the compound represented by the above formula (1) is added to the monomer composition for polymerization. .
In the plastic lens of the present invention, the anthraquinone compound represented by the above formula (1) is added to a monomer composition containing the above-mentioned monomers and additives used as necessary, and this is usually cast polymerization. Can be manufactured. The monomer composition preferably contains an aromatic polyisocyanate compound.
There is no restriction | limiting in particular in a mixing order, What is necessary is just to adjust suitably with the kind of monomer or additive.
In the casting polymerization, for example, the mixture is poured into a mold die in which a glass or metal mold and a resin gasket are combined, and the polymerization is performed by heating. The polymerization temperature and polymerization time are generally about 0.5 to 72 hours at 0 to 150 ° C., although depending on the type of raw material used.

The present invention will be described with reference to examples, but the present invention is not limited to these examples.
In Examples and Comparative Examples, the yellowing degree (YI value) of the obtained lens was measured according to the plastic yellowness and yellowing degree test method defined in JIS K7103-1977.

[Example 1]
A 500 ml eggplant type flask was charged with 22.88 g of 4,4′-diphenylmethane diisocyanate and 25.09 g of 1,6-hexamethylene diisocyanate, and JP-506H (trade name, manufactured by Johoku Chemical Co., Ltd.) as a release agent. 0.20 g, 0.06 g of dimethyltin dichloride as a polymerization catalyst, 1.00 g of Seesorb 701 (trade name, manufactured by Cypro Chemical Co., Ltd.) as an ultraviolet absorber, Compound 1, represented by the following formula (1-1) 0.8 mass ppm of 4-bis [(2,6-diethyl-4-methylphenyl) amino] anthracene-9,10-dione was added, and stirring was continued for 30 minutes under a nitrogen purge at 50 ° C. When these were completely dissolved, 52.03 g of pentaerythritol tetrakis (2-mercaptoacetate) was blended and stirred under reduced pressure at 1.3 kPa for 20 minutes to obtain a mixture.
This mixture was cast into a lens mold having a center thickness of 2 mm through a PTFE membrane filter having a thickness of 1.0 μm, and polymerized by a temperature program from an initial temperature of 30 ° C. to a final temperature of 120 ° C. over 24 hours to obtain a lens. .
The obtained lens was almost yellowish and colorless and transparent, and the YI value was 1.40.

[Example 2]
In Example 1, 1,4-bis [(2,6-diethyl-4-methylphenyl) amino] anthracene-9,10-dione was converted to compound 1,4- represented by the following formula (1-2): A lens was obtained by the same procedure except that bis [(2,4,6-trimethylphenyl) amino] anthracene-9,10-dione was used.
The obtained lens was almost yellowish and colorless and transparent, and the YI value was 1.41.

[Comparative Example 1]
A lens was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-1) was replaced with the compound represented by the following formula (2).
The obtained lens was extremely yellowish and had a YI value of 7.81.

[Comparative Example 2]
A lens was obtained in the same manner as in Example 1, except that the compound represented by the formula (1-1) was replaced with the compound represented by the following formula (3).
The obtained lens was extremely yellowish and had a YI value of 8.03.

[Comparative Example 3]
A lens was obtained in the same procedure as in Example 1, except that the compound represented by the formula (1-1) was replaced with the compound represented by the following formula (4).
The obtained lens was extremely yellowish and had a YI value of 7.50.

[Comparative Example 4]
A lens was obtained in the same manner as in Example 1 except that the anthraquinone compound represented by the formula (1-1) was not blended.
The obtained lens was slightly yellowish and had a YI value of 2.1.

[Example 3]
A 500 ml eggplant-shaped flask was charged with 22.25 g of 4,4′-diphenylmethane diisocyanate, 15.74 g of 1,6-hexamethylene diisocyanate and 11.44 g of isophorone diisocyanate, and JP-506H (trade name, Johoku) as a release agent. 0.20 g of Chemical Industry Co., Ltd., 0.06 g of dimethyltin dichloride as a polymerization catalyst, 1.00 g of Seasorb 701 (trade name, manufactured by Sipro Kasei Co., Ltd.) as an ultraviolet absorber, and 2,6 as an antioxidant -1.00 g of di-tert-butyl-p-cresol, compound 1,4-bis [(2,6-diethyl-4-methylphenyl) amino] anthracene-9 represented by the formula (1-1) , 10-dione was added at 0.4 mass ppm, and stirring was continued for 30 minutes under a nitrogen purge at 50 ° C. When these were completely dissolved, 50.58 g of pentaerythritol tetrakis (2-mercaptoacetate) was blended and stirred under reduced pressure at 1.3 kPa for 20 minutes to obtain a mixture.
This mixture was cast into a lens mold having a center thickness of 2 mm through a PTFE membrane filter having a thickness of 1.0 μm, and polymerized by a temperature program from an initial temperature of 30 ° C. to a final temperature of 120 ° C. over 24 hours to obtain a lens. .
The obtained lens was almost yellowish and colorless and transparent, and the YI value was 1.92.

[Example 4]
In Example 3, 1,4-bis [(2,6-diethyl-4-methylphenyl) amino] anthracene-9,10-dione was converted to compound 1,4- represented by the above formula (1-2). A lens was obtained by the same procedure except that bis [(2,4,6-trimethylphenyl) amino] anthracene-9,10-dione was used.
The obtained lens was almost yellowish and colorless and transparent, and the YI value was 1.88.

[Comparative Example 5]
A lens was obtained in the same manner as in Example 3, except that the compound represented by formula (1-1) was replaced with the compound represented by formula (2).
The obtained lens was extremely yellowish and had a YI value of 2.69.

[Comparative Example 6]
In Example 3, a lens was obtained in the same procedure except that the compound represented by the formula (1-1) was replaced with the compound represented by the formula (3).
The obtained lens was extremely yellowish and had a YI value of 2.81.

[Comparative Example 7]
In Example 3, a lens was obtained in the same procedure except that the compound represented by the formula (1-1) was replaced with the compound represented by the formula (4).
The obtained lens was extremely yellowish and had a YI value of 2.72.

[Comparative Example 8]
In Example 3, a lens was obtained in the same procedure except that the anthraquinone compound represented by the formula (1-1) was not blended.
The resulting lens was somewhat yellowish and had a YI value of 2.31.

  The plastic lens containing an anthraquinone compound having a specific structure according to the present invention has a characteristic of being almost colorless and transparent without being yellowed even if it is manufactured through a process such as addition of an ultraviolet absorber or heat treatment. Therefore, it is suitable as an application requiring such characteristics, particularly as a spectacle lens.

Claims (6)

A plastic lens comprising a compound represented by the following formula (1):

[In said formula (1), R < ¹ >, R < ² > and R < ³ > show the group chosen from a hydrogen atom or a C1-C8 alkyl group each independently. ]   The plastic lens of Claim 1 which contains 0.001-1000 mass ppm of compounds represented by said Formula (1).   The plastic lens according to claim 1, which is a urethane plastic lens.   The plastics according to claim 1 or 2, which is a thiourethane plastic lens. In the manufacturing method of the plastic lens obtained by superposing | polymerizing a monomer composition, the manufacturing method of the plastic lens which adds and polymerizes the compound represented by following formula (1) to the said monomer composition.

[In said formula (1), R < ¹ >, R < ² > and R < ³ > show the group chosen from a hydrogen atom or a C1-C8 alkyl group each independently. ]   The method for producing a plastic lens according to claim 5, wherein the monomer composition contains an aromatic polyisocyanate compound.