JP2001075058A - Production of plastic lens and plastic lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make a produced plastic lens colorless and transparent in a process for producing the plastic lens which allows easy yellowing. SOLUTION: After an oil-soluble dye of 0.1 to 10 ppm is mixed with a raw material monomer for the plastic lens, the monomer is polymerized and cured, by which the plastic lens is produced. This effect is great when the plastic lens provided with a UV absorption function is produced by adding 0.1 to 5% UV absorbent to the plastic lens raw material monomer or when 'the plastic lens is produced by polymerizing and curing a compound having a thioepoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a plastic lens used for a correction lens, a sunglass lens, a fashion lens, a photochromic lens, a camera lens, a lens for an optical device, and the like.

[0002]

2. Description of the Related Art Conventionally, various plastic lenses have been studied as alternatives to inorganic glass lenses used for optical applications. 2. Description of the Related Art Plastic lenses have been widely used in recent years as eyeglass lenses because of their light weight, excellent impact resistance, and excellent dyeability. In general, diethylene glycol bisallyl carbonate (CR-39) is widely used for spectacle lenses and the like. However, in making the lens thinner and lighter, the low refractive index of CR-39 is a problem. For this reason, various materials and manufacturing methods have been proposed for producing lenses having a high refractive index for optical applications such as spectacle lenses.

[0003] Japanese Patent Publication No. 4-58489, Japanese Unexamined Patent Publication No.
148340 proposes a thermosetting plastic lens having a thiourethane structure by a reaction between a polythiol compound and a polyisocyanate compound.
Also, JP-A-9-71580, JP-A-9-110
No. 979 and JP-A No. 9-255781 are produced by polymerizing and curing a compound having a thioepoxy group.
A thioepoxy plastic lens has been proposed.

[0004]

However, in general, as the refractive index of plastic lenses increases, the number of materials that can be easily colored yellow increases, and it has been desired to make these high refractive index plastic lenses colorless and transparent. Also recently, U
There is a growing demand in the market for spectacle lenses that have been subjected to V-cut processing, and it is becoming mainstream that plastic lenses have an ultraviolet absorbing function by various methods.
One method for imparting an ultraviolet absorbing function to a plastic lens is to add a large amount of an ultraviolet absorber to a plastic lens material to make the light transmittance at 380 to 400 nm almost 0%. When trying to have an ultraviolet absorption function, it was inevitable to color it pale yellow.

As a method for making a plastic lens colorless and transparent, JP-A-61-83212 discloses a method in which an inorganic pigment or the like is added to a monomer for a plastic lens together with a radical polymerization initiator and then polymerized. A method of dyeing the obtained plastic lens with a disperse dye to improve color tone is disclosed.

[0006] Also, Japanese Patent No. 2856236 discloses that
A method is disclosed in which a coating composition containing an oil-soluble dye is applied to the surface of a plastic lens to reduce the yellowness of the lens.

[0007] However, the former method has a problem in dispersibility of the inorganic pigment in the monomer. When a monomer for a plastic lens mixed with an inorganic pigment is filtered through a filter, the difference in the pore size of the filter and the change in the event of the filter. However, there is a disadvantage that the color tone of the plastic lens changes. In addition, the latter method has a disadvantage that the same coating composition cannot be used for plastic lenses having different yellowness. The use of a common coating composition for many types of plastic lenses is excellent in terms of manufacturing cost and streamlining. .

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, after mixing an oil-soluble dye with a monomer for a plastic lens, polymerizing and curing the mixture. The present inventors have found that by producing a plastic lens, it is possible to achieve a colorless and transparent color of the plastic lens which is easily yellowed, and have completed the present invention.

The present invention is particularly effective in producing a high-refractive index plastic lens which is easy to yellow among general plastic lens production. In particular, a plastic lens material monomer containing a compound having a thioepoxy group is polymerized and cured. The obtained thioepoxy-based plastic lens is highly effective. Further, the effects of the present invention are further enhanced in the production of a plastic lens in which a large amount of an ultraviolet absorber is added to the lens to make the light transmittance at 380 to 400 nm almost 0%.

The oil-soluble dye used in the present invention is preferably an anthraquinone violet or anthraquinone blue oil-soluble dye. In particular, C.I. I. It is preferable to use an oil-soluble dye equivalent to Solvent Violet 14.

Alternatively, an anthraquinone violet or anthraquinone blue oil-soluble dye may be used in combination with another red or orange oil-soluble dye to finely adjust the color tone.

In the present invention, it is not preferable to add a disperse dye other than the oil-soluble dye, a cationic dye, an acid dye, and the like to the monomer for a plastic lens. This is because these dyes other than oil-soluble dyes have low solubility in monomers for plastic lenses and are not only difficult to disperse uniformly, but also often cause appearance problems such as cloudiness after polymerization and curing. is there.

As described above, the present invention relates to a method for producing a plastic lens, and any method can be used for producing a plastic lens which is easily yellowed. A plastic lens produced by polymerizing and curing a compound having a (meth) acrylic group, or a polythiourethane produced by reacting a compound having an isocyanate group or an isothiocyanate group with a compound having a mercapto group A method for producing a plastic lens such as a thioepoxy plastic lens, which is produced by polymerizing and curing a plastic lens material monomer containing a compound having a thioepoxy group, is used.

Radical polymerizable (meth) containing aromatic ring
The compound having an acryl group is not particularly limited, and a compound having a (meth) acryl group containing a known aromatic ring and capable of radical polymerization can be used without any limitation. As a specific example, 2,2-bis (4- (methacryloxyethoxy)
Phenyl) propane, 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane, 2-acryloyloxyethyl-2-hydroxypropylphthalate, benzyl methacrylate, p-bis (2-methacryloyloxyethylthio) xylylene, p -Screw (2-
Methacryloyloxypropylthio) xylylene, and the like.

As the polyisocyanate which is the main component of the polythiourethane-based plastic lens, a known isocyanate group or a compound having an isothiocyanate group can be used without any limitation. Specific examples of the compound having an isocyanate group include ethylene diisocyanate, trimethylene diisocyanate, 2,4,4-trimethylhexane diisocyanate, hexamethylene diisocyanate, and m-xylylene diisocyanate. Can be

Similarly, the compound having a mercapto group is not particularly limited, and a known compound can be used. For example, 1,2-ethanedithiol, 1,6-
Examples thereof include aliphatic polythiols such as hexanedithiol and 1,1-cyclohexanedithiol, and aromatic polythiols such as 1,2-dimercaptobenzene and 1,2,3-tris (mercaptomethyl) benzene. Further, in order to increase the refractive index of the plastic lens, a polythiol containing a sulfur atom other than a mercapto group is more preferably used, and specific examples thereof include 1,2-bis (mercaptomethylthio) benzene, Examples thereof include 2,3-tris (mercaptoethylthio) benzene and 1,2-bis ((2-mercaptoethyl) thio) -3-mercaptopropane.

Further, as a specific example of the compound having a thioepoxy group used as a raw material monomer of the thioepoxy-based plastic lens, a known compound having a thioepoxy group can be used without any limitation. A thioepoxy compound obtained by replacing part or all of the oxygen of the epoxy group of an existing epoxy compound with sulfur is exemplified. Further, for increasing the refractive index of the plastic lens, a compound containing a sulfur atom in addition to the thioepoxy group is more preferable. Specific examples are 1,2-bis (β-epithiopropylthio) ethane, bis- (β-epithiopropyl) sulfide, 1,4-bis (β-epithiopropylthiomethyl) benzene, 2,5 -Screw (β
-Epithiopropylthiomethyl) -1,4-dithiane and the like.

The polymerization method in the present invention is not particularly limited, and any polymerization method generally used for producing plastic lenses can be used without any limitation. For example, when a vinyl monomer is used, a plastic lens can be manufactured by performing thermosetting using a thermal polymerization initiator such as an organic peroxide. In addition, a plastic lens can be manufactured by irradiating ultraviolet rays with a photopolymerization initiator such as benzophenone to cure the monomer.

In the case of a polythiourethane-based plastic lens produced by reacting a compound having an isocyanate group or an isothiocyanate group with a compound having a mercapto group, a compound having an isocyanate group or an isothiocyanate group is used. And a compound having a mercapto group, and then a curing catalyst for a urethane resin is added, mixed, and then heated and cured. Specific examples of the curing catalyst include ethylamine,
Examples thereof include amine compounds such as ethylenediamine, triethylamine and tributylamine, dibutyltin dichloride, and dimethyltin dichloride.

In the case of a thioepoxy-based plastic lens obtained by polymerizing a monomer material for a plastic lens containing a compound having a thioepoxy group, the compound having a thioepoxy group may be used alone or may be copolymerized with a thioepoxy group. After mixing with other possible monomers, it can be produced by adding and mixing a curing catalyst for an epoxy resin, and performing polymerization and curing by heating. The curing catalyst for the epoxy resin is not particularly limited, and specific examples include tertiary amines such as dimethylbenzylamine, dimethylcyclohexylamine, diethylethanolamine, dibutylethanolamine, and tridimethylaminomethylphenol, and ethylmethylimidazole. And imidazoles. Examples of other monomers that can be copolymerized with a compound having a thioepoxy group include a compound having a hydroxyl group, a compound having a mercapto group, a primary or secondary amine, and a compound having a carboxyl group. Specific examples of the compound having a hydroxyl group include alcohols such as isopropyl alcohol and n-hexyl alcohol, and polyhydric alcohols such as ethylene glycol, 1,6-hexanediol, pentaerythritol dimethacrylate, and pentaerythritol diacrylate. . Specific examples of the compound having a mercapto group include thiophenol, ethylthioglycolate, bis (2-mercaptoethyl) sulfide, and 2,5-dimercaptomethyl-1,4-dithiane.

The oil-soluble dye used in the present invention is not particularly limited, but is preferably an anthraquinone violet oil-soluble dye or an anthraquinone blue oil-soluble dye. Specific examples of these oil-soluble dyes include C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Blue 11,
C. I. Solvent Blue 12 and the like are preferred. Among them, C.I. I. Solvent Violet 14 is particularly preferred, since the yellowness of the plastic lens is reduced and the color becomes almost colorless and transparent. At this time, the preferable addition amount of the oil-soluble dye to the plastic lens monomer is such that the addition amount of the oil-soluble dye to the plastic lens monomer is 0.1.
1 ppm to 10 ppm, more preferably 0.3 ppm to
The range is 5 ppm. If the addition amount is less than 0.1 ppm, the effect of reducing the yellowness of the plastic lens is very small, and there is no significant difference from the plastic lens without the oil-soluble dye. Also, if added in excess of 30 ppm, the color tone of the plastic lens becomes too blue or purple, resulting in a color tone more like a dyed color lens than colorless and transparent.

The UV absorber used in the present invention is not particularly limited, and known UV absorbers such as benzotriazole UV absorber and benzophenone UV absorber can be used. Above all, benzotriazole-based ultraviolet absorbers are preferred because of their high ultraviolet absorption ability and low yellowness among the ultraviolet absorbers. The amount of the ultraviolet absorber added in the present invention is preferably in the range of 0.1% to 5%. When the amount of the ultraviolet absorber added is less than 0.1%, the light transmittance at 380 to 400 nm is high, and the advantage is less than that of the material without the ultraviolet absorber. Also,
If the UV absorber is added in excess of 5%, the yellowness becomes too strong, and it becomes impossible to make the color tone close to colorless and transparent even with the addition of an oil-soluble dye.

The color tone of the plastic lens can be finely adjusted by using the red and orange oil-soluble dyes simultaneously with the blue and violet oil-soluble dyes. The red and orange oil-soluble dyes are not particularly limited, but specific examples include C.I. I. Solvent Red 111, C.I. I. Solvent Red 179, C.I. I. Solvent Orange 60 and the like.

In the present invention, a plastic lens is produced by mixing a monomer for a plastic lens before polymerization and curing with a light stabilizer or an antioxidant, if necessary, and then performing polymerization and curing to produce a plastic lens. It is possible to improve the performance. Specific examples of the light stabilizer or the antioxidant include a hindered amine-based light stabilizer, a hindered phenol-based antioxidant, a phosphite-based antioxidant, and a thioether-based antioxidant.

When the high refractive index plastic lens according to the present invention is used as a correcting lens or a fashion lens, it is preferable to apply an antireflection film in order to increase light transmittance and prevent flicker due to surface reflection. Further, it is particularly preferable to provide a hard coat layer for improving the adhesion between the lens substrate and the antireflection film and preventing scratches on the surface.

Preferred examples of the hard coat layer include those obtained by applying and curing a coating composition containing the following (a) and (b) as main components. (A) One or more silane compounds having at least one or more reactive groups. (B) Metal fine particles such as silicon oxide, antimony oxide, zirconium oxide, titanium oxide, tin oxide, tantalum oxide, tungsten oxide, and aluminum oxide; two of titanium oxide, cerium oxide, zirconia, silicon oxide, and iron oxide Composite metal fine particles using the above; one or more selected from composite metal fine particles in which tin oxide fine particles are coated with composite metal fine particles of tin oxide and tungsten oxide.

The component (b) is a component effective for adjusting the refractive index of the hard coat and increasing the hardness, and can be used alone or as a mixture. However, (b)
The film forming property is poor only with the component (a), and a transparent and tough film can be obtained by using the component (a) together. The component (a) can be used as it is, but it is preferable to use it after hydrolysis since the water resistance and hardness of the film can be improved.

The thickness of the hard coat layer is usually 0.2 μm
About 10 μm, more preferably 1 μm
It is about 3 μm. In the present invention, a hard coat in which a primer layer is provided between the lens material and the hard coat layer can also be used. This primer layer has the effect of further improving the adhesion between the lens material and the hard coat layer, and improving the impact resistance of the lens after the hard coat treatment.

When used as a correcting lens, the optical performance is further improved by applying an antireflection film to the surface of the hard coat layer as described above. The antireflection film is a multilayer film obtained by laminating thin films having different refractive indices, and may be an inorganic material or an organic material as long as the reflectance is reduced. However, in order to emphasize the surface hardness and prevention of interference fringes, it is most preferable to provide a single-layer or multilayer antireflection film made of an inorganic substance. Examples of usable inorganic substances include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, hafnium oxide, and magnesium fluoride, and so-called PVD such as ion plating, vacuum evaporation, and sputtering. It can be applied by law.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The abbreviations of the substances used in the examples and comparative examples are as follows. Abbreviation: substance name A-1: bis- (β-epithiopropyl) sulfide B-1: bis (2-mercaptoethyl) sulfide (oil-soluble dye) V-1: OPLAS VIOLET 732 (Orient Chemical Industry Co., Ltd. V-2: OPLAS VIOLET 730 (equivalent to CI Solvent Violet 13) R-1: OPLAS RED 330 (equivalent to CI Solvent Red 11)
(Equivalent to 1) (Example 1) As a plastic lens raw material, 100 g was prepared in an amount shown in Table 1, and SEESO was used as an ultraviolet absorber.
1.0 g of RB701 (Cipro Kasei Kogyo) and the amounts shown in Table 1 were added as oil-soluble dyes. 0.10 g of diethylethanolamine was added and mixed as a polymerization catalyst, and the mixture was stirred well at room temperature.
Degassed for minutes. This raw material was poured into a mold held by an adhesive tape using two mirror-finished glass plates, and the temperature was raised from 30 ° C. to 100 ° C. over 20 hours to polymerize and cure. After that, the lens is released from the mold,
Annealing was performed by heating at 3 ° C. for 3 hours.

The quality of the plastic lens thus manufactured was evaluated by the following method, and the results are shown in Table 2. Refractive index: 589.3 n at 20 ° C. by Abbe refractometer
The refractive index of the m-line D was measured. YI value: The YI value of the lens was measured as an index of yellowness. Appearance and color tone: The appearance and color tone of the lens were visually observed under a fluorescent lamp. A colorless and transparent substance and a substance very close to colorless and transparent were evaluated as ○, and a substance that was not colorless and transparent was evaluated as ×.

[0032]

[Table 1] (Examples 2 to 6) As plastic lens materials, Table 1
100g was prepared at the ratio shown in Example 1.
In the same manner as in the above, a plastic lens was manufactured and its quality was evaluated. Table 2 shows the results. (Comparative Examples 1 to 3) As plastic lens materials, Table 1
100g was prepared at the ratio shown in Example 1.
The production and quality evaluation of the plastic lens were performed in the same manner as described above. Table 2 shows the results.

[0033]

According to the method for producing a plastic lens of the present invention, a method for producing a plastic lens which is easily yellowed, in particular, a yellow absorber is particularly easily colored by mixing an ultraviolet absorber with a plastic lens material and polymerizing and curing. In the production method of a plastic lens, a production method for making it colorless and transparent has been found.

Claims (7)

[Claims] 1. The method according to claim 1, wherein 1
A method for producing a plastic lens, comprising adding and mixing at least one or more oil-soluble dyes, followed by polymerization and curing. 2. The method according to claim 1, wherein at least one dye selected from anthraquinone violet or anthraquinone blue oil-soluble dyes is used as the oil-soluble dye. 3. The method according to claim 1, wherein the oil-soluble dye is at least C.I. I.
The method for producing a plastic lens according to claim 1, wherein an oil-soluble dye corresponding to Solvent Violet 14 is used. 4. The method according to claim 1, wherein when the total amount of the oil-soluble dye added to the monomer material for the plastic lens is A, A is the addition amount represented by the following formula. A method for producing a plastic lens according to any one of the preceding claims. 0.1 ppm ≤ A ≤ 10 ppm 5. The method according to claim 1, wherein 0.1% to 5% by weight of an ultraviolet absorber is added to the monomer material for the plastic lens in addition to the oil-soluble dye, mixed and then polymerized and cured. 5. The method for producing a plastic lens according to any one of items 4 to 4. 6. A plastic lens raw material monomer comprising a compound having a thioepoxy group.
A method for manufacturing a plastic lens according to claim 1. 7. A plastic lens manufactured by the method for manufacturing a plastic lens according to claim 1.