JP2014199329A - Dyed plastic lens and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a dyed plastic lens which can obtain a dyed plastic lens by selectively dyeing a coating film on a plastic lens base material.SOLUTION: A method of producing a dyed plastic lens includes the steps of: applying, onto a plastic lens base material, a curable composition comprising an acrylic silane compound and subjecting the composition to curing treatment, to form a cured coating film, and to obtain a laminate having the cured coating film on the plastic lens base material; and bringing the formed cured coating film into contact with a dispersion-type cationic dye for dyeing treatment.

Description

The present invention relates to a method for producing a dyed plastic lens, and more particularly to a method for producing a dyed plastic lens capable of providing a dyed plastic lens in which a cured film on a plastic lens substrate is selectively dyed. .
Furthermore, this invention relates also to the dyeing | staining plastic lens obtained by the said manufacturing method.

  In recent years, most of spectacle lenses distributed on the market are dyed lenses that are dyed for the purpose of imparting fashionability, light-shielding properties, and the like.

A dye lens is manufactured mainly by dyeing a plastic lens substrate. As a method for dyeing a plastic lens substrate, an immersion method in which a substrate is immersed in a dyeing solution as described in Patent Document 1 is widely used.
On the other hand, Patent Document 2 proposes a method for manufacturing a dyed lens by dyeing a hard coat film provided on a lens substrate.

Japanese Patent No. 3448616 JP-A 64-78202

However, in the method of obtaining a dyed lens by dyeing a plastic lens substrate as described in Patent Document 1, there are cases where variations occur between the production lots of the substrate and the color tone does not match at the time of dyeing. In addition, when there is any defect in the functional film formed on the plastic lens substrate, the functional film is peeled off with an alkaline aqueous solution to form a new functional film. As a result, color fading may occur, and color unevenness may occur in the plastic lens substrate.
Thus, in the method for producing a dyed lens by dyeing a plastic lens substrate, there is a problem in that variations in color tone tend to occur between the lenses.

  Therefore, as described in Patent Document 2, it is conceivable to employ a method of obtaining a dyed lens by dyeing a film formed on a lens substrate. However, if the lens base material located in the lower layer of the coating is also dyed at the time of coating dyeing, the same problem as in the case of dyeing the plastic lens substrate occurs. In the method described in Patent Document 2, since a glass lens base material that is difficult to dye is used, the lens base material is not dyed at the time of dyeing the hard coat layer (or the degree of dyeing is low). Since materials are generally easily dyed, it has heretofore been difficult to prevent dyeing of a lens substrate during film dyeing.

  Accordingly, an object of the present invention is to provide a method for producing a dyed plastic lens capable of obtaining a dyed plastic lens by selectively dyeing a coating provided on a plastic lens substrate.

As a result of intensive studies to achieve the above object, the present inventor, among various dyes, the dispersive cationic dye has good dyeability of a cured film formed from a curable composition containing an acrylic silane compound. In addition, new findings have been obtained that it is difficult to dye plastic lens substrates.
The present invention has been completed based on the above findings.

That is, the above object has been achieved by the following means.
[1] A laminate having a cured film formed on a plastic lens substrate by applying a curable composition containing an acrylic silane compound on the plastic lens substrate and subjecting the composition to a curing treatment. Obtaining and
The formed cured film is brought into contact with a dispersive cationic dye and subjected to a dyeing treatment,
For producing a dyed plastic lens.
[2] The method for producing a dyed plastic lens according to [1], wherein the dyeing treatment is performed by immersing the entire laminate in a dyeing bath containing the dispersed cationic dye.
[3] The method for producing a dyed plastic lens according to [1] or [2], wherein the curable composition further includes metal oxide particles.
[4] The plastic lens substrate is selected from the group consisting of a diethylene glycol bisallyl carbonate plastic lens substrate, a polythiourethane plastic lens substrate, and a polysulfide plastic lens substrate. ] The manufacturing method of the dyeing plastic lens in any one of.
[5] A stained plastic lens obtained by the production method according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the dyeing | staining plastic lens in which the film provided on the plastic lens base material was dye | stained selectively.

In the present invention, a curable composition containing an acrylic silane compound is applied onto a plastic lens substrate, and a cured film is formed by subjecting the composition to a curing treatment, and the laminate having the cured film on the plastic lens substrate. The present invention relates to a method for producing a dyed plastic lens, comprising: obtaining a body; and contacting the formed cured film with a dispersion-type cationic dye and performing a dyeing treatment.
Furthermore, according to this invention, the dyeing | staining plastic lens obtained by the said manufacturing method is also provided.
Hereinafter, the dyed plastic lens of the present invention and the manufacturing method thereof will be described in more detail.

Plastic lens base material The plastic material constituting the plastic lens base material is not particularly limited. For example, methyl methacrylate homopolymer, copolymer of methyl methacrylate and one or more other monomers, diethylene glycol bisallyl carbonate alone Polymer, copolymer of diethylene glycol bisallyl carbonate and one or more other monomers, sulfur-containing copolymer, halogen copolymer, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, poly Thiourethane, polymers made of compounds having epithio groups, homopolymers of monomers having sulfide bonds, copolymers of sulfides with one or more other monomers, polysulfides and one or more other monomers Copolymers of over, and copolymers of poly disulfide and one or more other monomers, and the like. Examples of the plastic lens base material that is preferable from the viewpoint of being hardly dyed include a diethylene glycol bisallyl carbonate plastic lens base material, a polythiourethane plastic lens base material, and a polysulfide plastic lens base material. In the present invention, “system” is used to mean “include”.

  The thickness and diameter of the plastic lens base material are not particularly limited, but usually the thickness is about 1 to 30 mm and the diameter is about 50 to 100 mm.

Cured coating The dyed plastic lens produced by the production method of the present invention has a cured coating on a plastic lens substrate. The cured film may be formed directly on the plastic lens substrate, or may be formed via another functional film such as a primer layer. The primer layer is usually formed from a known resin such as polyurethane that can function as an adhesive layer, and generally has a thickness of about 0.5 to 10 μm. The primer layer is usually formed directly on the plastic lens substrate, but may be formed on the plastic lens substrate via another functional layer.

  The cured film can usually function as a hard coat layer. From the viewpoint of improving durability, the thickness of the hard coat layer is usually about 0.5 to 10 μm, but is not particularly limited.

  In the production method of the present invention, the cured film is formed by applying a curable composition containing an acrylic silane compound on a plastic lens substrate and subjecting the composition to a curing treatment. In the production method of the present invention, dyeing is performed using a dispersive cationic dye (details will be described later), and the dispersive cationic dye has a dyeability of a cured film formed from a curable composition containing an acrylic silane compound. Good and difficult to dye plastic lens substrate. Thereby, according to the manufacturing method of this invention, the dyeing | staining plastic lens by which the cured film was selectively dyed can be provided. This is a finding newly found by the present inventors.

The acrylic silane compound is a silane compound that is contained as an acrylic curable functional group selected from the group consisting of a methacryl group, an acrylic group, a methacryloyloxy group, and an acryloyloxy group. The silane compound is generally called a silane coupling agent, and can be an organosilicon compound represented by the following general formula (I) or a hydrolyzate thereof. The acrylic silane compound includes an acrylic curable functional group in the functional group represented by R ¹ . The acrylic curable functional group may be directly bonded to the silicon atom, or may be indirectly bonded via a linking group such as an alkylene group.
(R ¹ ) _a (R ³ ) _b Si (OR ² ) _{4- (a + b)} (I)

  In general formula (I), a represents 1 and b represents 0 or 1.

R ² can be an alkyl group, an acyl group, or an aryl group.
The alkyl group represented by R ² is, for example, a linear or branched alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
The acyl group represented by R ² is, for example, an acyl group having 1 to 4 carbon atoms, and specific examples thereof include an acetyl group, a propionyl group, an oleyl group, and a benzoyl group.
The aryl group represented by R ² is, for example, an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group, a xylyl group, and a tolyl group.

R ³ can be an alkyl group or an aryl group.
The alkyl group represented by R ³ is, for example, a linear or branched alkyl group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Etc.
The aryl group represented by R ³ is, for example, an aryl group having 6 to 10 carbon atoms, and specific examples thereof include a phenyl group, a xylyl group, and a tolyl group.

  Specific examples of the acrylic silane compound described above include methacryloxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane, and the like. be able to. As these acrylic silane compounds, those commercially available as silane coupling agents can be used. Alternatively, it can be synthesized by a known method.

Moreover, the cured film formed using an acrylsilane compound can also contain metal oxide particles. The metal oxide particles can contribute to the adjustment of the refractive index of the cured coating and the improvement of the hardness. Specific examples include tungsten oxide (WO ₃ ), zinc oxide (ZnO), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tin oxide. Examples thereof include particles such as (SnO ₂ ), beryllium oxide (BeO), and antimony oxide (Sb ₂ O ₅ ), and two or more kinds of metal oxide particles can be used in combination. Alternatively, a composite oxide composed of two or more kinds of oxides can also be used. The particle size of the metal oxide particles is preferably in the range of 5 to 30 nm from the viewpoint of achieving both scratch resistance and optical properties. For the same reason, the content of the metal oxide particles in the cured coating can be appropriately set in consideration of the refractive index and the hardness, but usually 5 to 80 per solid content of the curable composition for forming the cured coating. It is about mass%. Moreover, it is preferable that the said metal oxide particle is a colloid particle from the point of the dispersibility in a cured film.

  The cured film is prepared by mixing the above components and, if necessary, optional components such as resin components such as acrylic resin, urethane resin, silicone resin, and epoxy resin, organic solvent, surfactant (leveling agent), and curing catalyst. It can form by apply | coating the made curable composition on a plastic lens base material, and giving the hardening process (thermal curing, photocuring, etc.) according to a curable group. As a means for applying the curable composition, a conventionally performed method such as a dipping method, a spin coating method, or a spray method can be applied.

  After the cured coating is formed on the plastic lens substrate, a dyeing process is performed. It is also possible to form one or more known functional films on the cured film before or after the dyeing process.

The cured coating formed from the curable composition containing the dyed acrylic silane compound is then subjected to a dyeing process. The dyeing process is performed by bringing the formed cured film into contact with a dispersed cationic dye. Here, in the present invention, as described above, a dispersed cationic dye that is a dye capable of selectively dyeing an acrylic silane compound is used. The dispersive cationic dye refers to a cationic dye in which a normal cationic dye is water-soluble, but has poor water solubility (or insolubility) and dispersibility in a solvent (a property of being dispersed in a fine particle form in a solvent). . For example, a dispersive cationic dye is prepared by binding an anionic dispersant to a cationic dye and further dispersing with an excess of an anionic dispersant. In addition, as a dispersion type cationic dye that is made water-dispersible by blocking a basic group, Kayacryl ED (manufactured by Nippon Kayaku Co., Ltd.), KIWA CDP (manufactured by Kiwa Chemical Industry Co., Ltd.), Nichilon CDPN (Nissei Kasei ( And Aizen Cathilon DP (Hodogaya Chemical Co., Ltd.) are commercially available. For the dyeing treatment in the present invention, a commercially available product or a dispersed cationic dye prepared by a known method can be used.

  The eyeglass lens is usually dyed by immersing the entire lens in a dye bath containing the dye. Also in the present invention, the dyeing process can be performed by immersing the cured film and the entire plastic lens substrate in a dyeing bath, as in the case of a normal dyeing process. As the dyeing bath, for example, a commercially available dispersion type cationic dye can be used by diluting with water, alcohol, or a mixed solvent thereof, preferably water. The dye concentration in the dyeing bath is, for example, 0.01 to 10 g / L, and the temperature of the dyeing bath is, for example, in the range of 0 to 100 ° C. Moreover, well-known additives, such as surfactant, can also be added to a dyeing bath as needed. Although the immersion time in a dyeing bath is not specifically limited, For example, it is about 1 minute-1 hour.

  After the dyeing, heat treatment may be performed to fix the dye. The heating temperature in this heat treatment is, for example, 30 ° C. to 120 ° C., and the heat treatment time is, for example, 15 minutes to 2 hours, but is not particularly limited. Moreover, the dyeing | staining plastic lens by which the cured film on the plastic lens base material was dye | stained selectively can be obtained by performing post-processings, such as washing | cleaning and functional film formation, as needed after dyeing. The dyed plastic lens thus obtained is suitable as a spectacle lens because it has fashionability, light-shielding properties and the like by dyeing.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to the aspect shown in an Example.

[Example 1]
(1) Preparation of curable composition In a glass container equipped with a magnetic stirrer, 17 parts by weight of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Silicone Co., Ltd.), 30 parts by weight of methanol, 0.01 0.3 parts by mass of hydrochloric acid and 6 parts by mass of water-dispersed colloidal silica (solid content 40% by mass, average particle size 15 nm) were added and mixed well, followed by stirring at 5 ° C. for 24 hours. Next, 10 parts by mass of propylene glycol monomethyl ether, 0.05 part by mass of a silicone-based surfactant, and 1.5 parts by mass of aluminum acetylacetonate as a curing agent were added and stirred sufficiently, followed by filtration. To prepare a hard coating solution (curable composition).

(2) Formation of laminate (lens with hard coat) Meniscus diethylene glycol bisallyl carbonate lens (trade name HL, center wall thickness 2.0 mm, diameter 75 mm, manufactured by HOYA Co., Ltd.) as a plastic spectacle lens base material After the lens was washed, the hard coating solution prepared in the above (1) was coated on one surface of the lens substrate by a spin coating method. Thereafter, a hard coat layer (cured film) having a thickness of 3 μm was formed by heating and curing at 120 ° C. for 60 minutes.

(3) Dyeing treatment The entire laminate (lens with hard coat) obtained in (2) above was immersed in a dyeing bath for the time shown in Table 1 and dyeing treatment was performed.
As a dyeing bath, a dye dispersion prepared by diluting a dispersion type cationic dye shown in Table 1 (Kayaacryl ED series manufactured by Nippon Kayaku Co., Ltd.) with warm water so as to have a dye concentration of 0.5 / L was used. The temperature of the dyeing bath during dyeing was 80 ° C.

  Through the above process, a dyed plastic spectacle lens was obtained.

[Comparative Example 1]
The silane compound used for the preparation of the curable composition was changed from 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Silicone) to 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone). Except for the points described above, the same steps as in Example 1 were performed to obtain a dyed plastic spectacle lens.

Evaluation of dyed plastic spectacle lenses Confirmation of the presence or absence of dyeing of the plastic lens substrate The color density of the lens substrate used in Example 1 before the formation of the hard coat layer and the dyeing treatment was measured by the following method and found to be 7.8%.
Further, the hard coat layer was peeled off by immersing the dyed plastic spectacle lens obtained in Example 1 in a 5 mass% sodium hydroxide aqueous solution (liquid temperature 50 ° C.) for 5 minutes. When the color density of the plastic lens substrate after peeling off the hard coat layer was measured by the following method, it was about 8%, which was visually confirmed to be transparent.
From the above results, it was confirmed that the surface hard coat layer was selectively dyed.

2. Evaluation of dyeing degree About each lens obtained in Example 1 and Comparative Example 1, for a lens using a yellow dye with a densitometer Color Density Meter DMX-280-1 manufactured by Asahi Spectroscopic Co., Ltd., a measurement wavelength of 435 nm and a blue dye were used. The color density was measured at 585 nm for the lens and 525 nm for the lens using the red dye. The results are shown in Table 1. A larger numerical value (unit:%) means that the color density is dyed darker.

From the results shown in Table 1, in Example 1 where a cured film was formed using an acrylic silane compound, the dyeability of the cured film was much higher than in Comparative Example 1 where a cured film was formed using an epoxysilane compound. Can be confirmed.
Further, as described above, in Example 1, the plastic lens substrate was kept transparent even after the dyeing treatment.
From the above results, it was confirmed that the cured coating formed from the acrylic silane compound on the plastic lens substrate can be selectively and highly dyed with the dispersed cationic dye.

[Example 2]
As a plastic spectacle lens base material, instead of a diethylene glycol bisallyl carbonate type lens (trade name HL made by HOYA), a polythiourethane type lens (EYAS made by HOYA), a polysulfide type plastic lens base material (HOYA) Except for using EYRY (manufactured by Co., Ltd.), the same steps as in Example 1 were performed. As in Example 1, a stained plastic spectacle lens in which the cured coating was selectively dyed at a high concentration was obtained. I was able to.

  The present invention is useful in the field of manufacturing eyeglass lenses.

Claims (5)

A cured film is formed by applying a curable composition containing an acrylic silane compound on a plastic lens substrate and subjecting the composition to a curing treatment to obtain a laminate having the cured film on the plastic lens substrate. ,and,
The formed cured film is brought into contact with a dispersive cationic dye and subjected to a dyeing treatment,
For producing a dyed plastic lens. The method for producing a stained plastic lens according to claim 1, wherein the dyeing treatment is performed by immersing the entire laminate in a dyeing bath containing the dispersed cationic dye. The method for producing a dyed plastic lens according to claim 1, wherein the curable composition further comprises metal oxide particles. The plastic lens substrate is selected from the group consisting of a diethylene glycol bisallyl carbonate plastic lens substrate, a polythiourethane plastic lens substrate, and a polysulfide plastic lens substrate. A method for producing a dyed plastic lens according to Item. The dyed plastic lens obtained by the manufacturing method of any one of Claims 1-4.