JPH06148404A - Colored plastic lens - Google Patents

Abstract

PURPOSE:To stably obtain the colored lens which is uniformly colored in a large quantity by providing a hardened film contg. an org. silicon compd. formed on a plastic substrate and a colored film contg. the org. silicon compd. and oil-soluble dyes formed on the surface of the hardened film. CONSTITUTION:The hardened film is formed of a coating compsn. contg. the org. silicon compd. The colored film is formed of a coating compsn. contg. the org. silicon compd. and the oil-soluble dyes. Particulate org. matter consisting of the oxides of metals, such as Al and Ti may be added to the compsns. forming the hardened film and the colored film in order to lessen the generation of interference fringes by the hardened film or the colored film or in order to improve the scratching resistance thereof or an epoxy compd., such as polyglycerol polyglycidyl ether, may be added thereto in order to improve the adhesion to inorg. antireflection films provided on the colored films at need.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored plastic lens, and is particularly preferably used for eyeglass plastic lenses.

[0002]

2. Description of the Related Art In recent years, a variety of coloring colors have been used for plastic lenses, especially in spectacles. Under such influence, the spectacle maker needs to color a large amount of plastic lenses with a uniform color. By the way, as a conventional method for coloring a plastic lens, Japanese Patent Laid-Open No. 58-5716 (hereinafter simply referred to as "publication 1")
For example, a method of immersing a plastic lens substrate in a dyeing solution having a predetermined temperature and a predetermined concentration using a disperse dye or a basic dye is disclosed in JP-A-53-11136 (hereinafter, referred to simply as "Patent Document 2"). Is known in the art), a method for coloring a coating composition for coating a plastic lens substrate by adding a dye or pigment thereto.

[0003]

DISCLOSURE OF THE INVENTION Problem to be Solved by the Invention
The coloring method disclosed in 1) is easy to change the color tone due to the concentration of dye in the dyeing solution, the amount of auxiliary agent, the temperature of the dyeing solution and the degree of aging, and the dyeability of the plastic lens substrate. In addition, it is difficult to color the plastic lens, and in addition, the plastic lens colored by this method requires a color correction in order to obtain a uniform color, which causes a great obstacle to work efficiency. As a method for solving this problem, for example, it is possible to control the factors to be constant, but it is substantially difficult to control these factors, and it has not been possible to color the plastic lens uniformly in a large amount and stably.

Further, in the coloring method disclosed in Publication 2, the plastic substrate is also colored when the coating composition is applied and cured. For this reason, the plastic lens in which the film is peeled off and the coating composition is applied again due to a processing error has a problem that the color tone is obviously different from that of the plastic lens produced without peeling the film. The present invention has been made to solve the above problems, and an object of the present invention is to provide a uniform and colored colored plastic lens in a large amount and stably.

[0005]

The above-mentioned objects have been achieved by the following inventions. The invention provides a colored plastic provided with a cured film containing an organosilicon compound formed on a plastic substrate, and a colored film containing an organosilicon compound and an oil-soluble dye formed on the surface of the cured film. It is a lens. Hereinafter, the present invention will be described in detail.

In the present invention, as the plastic substrate on which the cured film and the colored film are provided, a homopolymer of methyl methacrylate, a copolymer containing one or more other monomers of methyl methacrylate as a monomer and a component, diethylene glycol bisallyl carbonate alone. Polymer, copolymer containing diethylene glycol bisallyl carbonate and at least one other monomer as a monomer component, sulfur-containing copolymer, halogen-containing copolymer, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene Examples include terephthalate and polyurethane.

The cured film in the present invention is formed by a coating composition containing an organic silicon compound, and the colored film is formed by a coating composition containing an organic silicon compound and an oil-soluble dye. Examples of these organic silicon compounds include, for example, JP-A-53-111336 and JP-A-6-6.
Those disclosed in 0-213902, JP-A-57-177052, JP-A-56-88464 and the like can be mentioned.

The coating composition for forming the cured film and the colored film described above contains Al, Ti, Zr, Sn and Sb in order to reduce the generation of interference fringes due to the cured film or the colored film or to improve scratch resistance. , A fine particle inorganic substance composed of an oxide of a metal such as Si, or polyglycerol polyglycidyl ether, glycerol polyglycidyl ether, for improving the adhesion with an inorganic antireflection film provided on the coloring film if necessary. Epoxy compounds such as diglycerol polyglycidyl ether can be added. Further, an ultraviolet absorber, an antioxidant, a curing agent, etc. can also be used. Furthermore, various surfactants may be added to the coating composition for forming a cured film and a colored film in the present invention for the purpose of improving the flowability during application and improving the smoothness of the cured film and the colored film.

The coating composition for forming the colored film in the present invention contains an oil-soluble dye. Examples of the oil-soluble dye include C.I. I. Solvent Yellow 2, C.I. 1.
Solvent Yellow 6, C.I. 1. Solvent Blue 2, C.I. I. Solvent Blue 11, C.I. 1. Solvent Blue 12, C.I. 1. Solvent Blue 25,
C. 1. Solvent Blue 35, C.I. 1. Solvent Red 1, C.I. 1. Solvent Red 3, C.I. 1.
Solvent Red 8, C.I. 1. Solvent Red 23
And so on. It is possible to mix two or more of these oil-soluble dyes.

The amount of the oil-soluble dye used is preferably within the range of more than 0.01% by weight based on the total weight of the coating composition forming the colored film. The reason is that if it is less than 0.01% by weight, coloring is insufficient and a colored plastic lens cannot be produced. In addition,
It is not preferable to use a disperse dye, a cationic dye or an acid dye instead of the oil-soluble dye. The reason is that the above-mentioned dyes have poor solubility and do not disperse uniformly, so that coloring unevenness is likely to occur in the colored film. From the viewpoint of productivity, the dipping method is preferably used as the method for forming the cured film, and the spin method is preferably used as the method for forming the colored film in order to prevent uneven density in the colored film. When the spin method is used as a method for forming the colored film, it is preferable to apply the colored film to one surface of the cured film from the viewpoint of productivity.

The colored plastic lens of the present invention is one in which a cured film is first applied to a plastic substrate and then a colored film is applied onto the cured film. The colored film is applied to the plastic lens substrate and the cured film is applied onto the colored film. It does not apply.
The reason why a colored plastic lens having a colored film on a plastic substrate and a cured film on the colored film is not preferable is
When a colored film is applied to the plastic substrate, the plastic substrate is colored, and the color tone when peeling off and reworking is different from that of the non-reworking product. This is because the oil-soluble dye contained in the colored film easily bleeds out into the coating composition and makes it difficult to produce a uniformly colored plastic lens when immersed in the coating composition that forms.

Further, it is preferable that the difference in refractive index between the cured film and the colored film be within 0.1 in order to prevent the occurrence of interference fringes due to the cured film and the colored film. The coating composition for forming the cured film and the colored film is dried by hot air or irradiated with active energy rays, and the curing condition is preferably 70 to 200 ° C. in hot air, particularly preferably 90 to 150 ° C. Is desirable. Far infrared rays and the like are used as the active energy rays, and the damage due to heat can be suppressed to a low level.

When forming the colored film, it is preferable to subject the cured film to plasma treatment or alkali treatment in order to improve the adhesion to the cured film. The thicknesses of the cured film and the colored film in the present invention are not particularly limited, but from the viewpoint of manufacturing, the range of the cured film thickness is 0.1 to 50 μm, and the range of the colored film thickness is 0.01. 10 micron is preferred. The colored plastic lens of the present invention is preferably used as an eyeglass lens, and a multilayer antireflection film made of an inorganic oxide can be applied on the surface of the colored plastic lens.

[0014]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The obtained colored plastic lenses were subjected to the evaluation test described below.

A. Color Tone Test The colored film of the colored film was peeled off from the colored plastic lens (hereinafter, also simply referred to as “colored plastic lens A”) in which the film of the colored film was never removed, and the colored film was formed again. A colored plastic lens (hereinafter may be simply referred to as "colored plastic lens B") and a colored plastic lens in which the colored film of the colored plastic lens B is peeled off to form a colored film again (hereinafter simply referred to as "colored plastic lens B"). C)), and the color difference (ΔE) between the colored plastic lenses B and C based on the colored plastic lens A is measured by a color difference meter (trade name: SM color computer SM- 5, measured by Suga Test Instruments Co., Ltd.

B. Appearance The colored plastic lens A was visually inspected for unevenness in coloring. c. Scratch resistance test Colored plastic lens A with steel wool # 0000
The surface of the film was rubbed and the scratch resistance was visually evaluated.
The judgment criteria were as follows. A: Almost no scratch even if it is rubbed strongly. B: It is considerably scratched if it is rubbed strongly.

D. Adhesion test 100 on the coating of colored plastic lens A at 1 mm intervals
After cross-cutting the eyes, firmly stick the adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) on this cross-cut area, then quickly peel off the adhesive tape, and remove the film after peeling off the adhesive tape. Existence was checked. e. Hot Water Resistance Test The colored plastic lens A was immersed in hot water at 50 ° C. for 5 hours, and it was visually inspected whether cracks were generated in the coating.

Example 1 (Preparation of coating composition for forming cured film)
To 240 parts by weight of colloidal silica having a SiO ₂ concentration of 40%, 2.0 parts by weight of 0.5N hydrochloric acid and 20 parts by weight of acetic acid were added, and the mixture was stirred at 35 ° C. with γ-glycidoxypropyltrimethoxysilane. (Trifunctional organosilicon compound) (95 parts) was added dropwise, and the mixture was stirred at room temperature for 8 hours and stirred at room temperature for 1 hour.
It was left for 6 hours. 80 parts by weight of methyl cellosolve, 120 parts by weight of isopropyl alcohol,
Add 40 parts by weight of butyl alcohol, 16 parts by weight of aluminum acetylacetone, 0.2 parts by weight of silicone surfactant, 0.1 parts by weight of ultraviolet absorber, stir for 8 hours, and then age and cure at room temperature for 24 hours to cure. A coating composition for forming a film was obtained.

(Preparation of coating composition for forming colored film) As an oil-soluble dye, 5.5 parts by weight of Orazol Yellow 2RLN (manufactured by Ciba-Geigy), trade name: Orazol Blue GN (Ciba-Geigy) (Manufactured by the same company), and trade name: Orazol Red B (manufactured by Ciba Geigy Co., Ltd.) of 7.4 parts by weight, except that the same composition and the same composition as the coating composition for forming the cured film described above are added. A coating composition for forming a colored film was obtained by the method.

(Production of Colored Plastic Lens A) Plano lenses of diethylene glycol bisallyl carbonate copolymer (refractive index 1.54) containing diethylene glycol bisallyl carbonate, benzyl methacrylate and diallyl phthalate as main components are treated with an alkali and washed. The coating composition for forming a cured film described above was applied by a dipping method at a pulling rate of 15 cm / min, left at room temperature for 15 minutes, and then heat-cured at 120 ° C. for 2 hours to form a cured film. After forming the cured film, it is dipped in a 2% aqueous solution of sodium hydroxide for 2 minutes, further washed to apply the coating composition film for forming the above-mentioned colored film by a spin method, and left at room temperature for 15 minutes.
A colored film was formed by heat curing at 2 ° C. for 2 hours to prepare a colored plastic lens A. In the spin method, the rotation speed was 850 rpm for 4 seconds at the initial stage, and then the rotation speed was 2,500 rpm.
It was carried out under the conditions of rpm for 10 seconds. The evaluation results of the colored plastic lens A are shown in Table 1. The colored plastic lens had no unevenness in coloring and was excellent in scratch resistance, adhesion, and hot water resistance.

(Preparation of Colored Plastic Lens B) To remove the coating of the colored plastic lens A, 10% N
It was immersed in an aOH aqueous solution for 1 hour. Then, again, the colored plastic lens B was manufactured by the same method as the method for forming the cured film and the colored film of the colored plastic lens A described above. The color difference (ΔE) between the colored plastic lens B and the colored plastic lens A was 0, and there was almost no difference in color tone between the colored plastic lens A and the colored plastic lens B.

(Production of Colored Plastic Lens C) To remove the coating of the colored plastic lens B, 10% N
By immersing in an aOH aqueous solution for 1 hour, a colored plastic lens C was manufactured again by the same method as the method for forming the cured film and the colored film of the colored plastic lens A described above. The colored plastic lens C and the colored plastic lens A
The color difference (ΔE) between the colored plastic lens A and the colored plastic lens C was almost zero.

Example 2 In place of the colloidal silica used in Example 1, 240 parts by weight of antimony oxide sol (methanol dispersion, solid content 30%, average particle diameter 20 mm) was used in all Example 1. Colored plastic lenses A, B and C were prepared in the same manner as in. The evaluation results are shown in Table 1. As shown in Table 1, the colored plastic lens A does not have uneven coloring in the same manner as the plastic lens A of Example 1, and has good scratch resistance, adhesion and warm water resistance. Almost no difference in color tone from B and C was observed. Comparative Example 1 The colored plastic lens disclosed in JP-A No. 53-111336 is listed as Comparative Example 1.

(Preparation of coating composition for forming cured film / colored film) Coating composition for forming cured film / colored film was coated with the coating composition for forming the colored film of Example 1 described above. Used as a composition. (Preparation of Colored Plastic Lens A) The plano lens of the diethylene glycol bisallyl carbonate copolymer (refractive index 1.54) used in Example 1 was alkali-treated and washed to pull up the coating composition at a speed of 15
A colored film plastic lens A was prepared by applying the film at a cm / min by a dipping method, leaving it at room temperature for 15 minutes, and then heat-curing at 120 ° C. for 2 hours to form a cured film / colored film. This colored plastic lens A had good scratch resistance, adhesion and warm water resistance, but uneven coloring was observed.

(Preparation of Colored Plastic Lens B) To remove the coating of the colored plastic lens A, 10%
It was immersed in an aqueous solution of NaOH for 1 hour. Then, again, the colored plastic lens B was manufactured by the same method as the method of forming the cured film / colored film of the colored plastic lens described in the comparative example. The color difference (ΔE) between the colored plastic lens B and the colored plastic lens A was 0.7, and the color tones of the colored plastic lens A and the colored plastic lens B were clearly different.

(Production of Colored Plastic Lens C) 10% for peeling off the coating of the colored plastic lens B
It was immersed in an aqueous solution of NaOH for 1 hour. Then, again, the colored plastic lens C was manufactured by the same method as the method for forming the cured film / colored film of the colored plastic lens described in Comparative Example. The color difference (ΔE) between the colored plastic lens C and the colored plastic lens A was 1.0, and the color tones of the colored plastic lens A and the colored plastic lens C were clearly different.

Comparative Example 2 Comparative Example 1 except that 240 parts by weight of antimony oxide sol (methanol dispersion, solid content 30%, average particle size 20 mm) was used in place of the colloidal silica used in Comparative Example 1. Colored plastic lenses A, B and C were prepared in the same manner as in. The evaluation results are shown in Table 1. As shown in Table 1, the colored plastic lens A has the same coloring unevenness as the plastic lens A of Comparative Example 1, and a clear color tone difference is observed between the colored plastic lens A and the colored plastic lenses B and C. It was

[0028]

[Table 1]

[0029]

According to the present invention, it is possible to stably provide a large amount of uniformly colored colored plastic lenses.

Claims (2)

[Claims] 1. A cured film containing an organic silicon compound formed on a plastic lens substrate, and a colored film containing an organic silicon compound and an oil-soluble dye formed on the surface of the cured film. A colored plastic lens characterized in that 2. The colored plastic lens according to claim 1, wherein a difference in refractive index between the cured film and the colored film is within 0.1.