JPH11129337A - Manufacturing method of plastic photochromic lens and plastic photochromic lens - Google Patents

Abstract

[PROBLEMS] To produce a plastic photochromic lens which uniformly develops a color without deforming the lens due to a high temperature or damaging the lens surface due to a solvent. A plastic photochromic lens is manufactured by dispersing a photochromic substance into a disperse dye, dispersing it in an aqueous solution, and immersing a plastic lens in the aqueous solution to impregnate the photochromic substance from the lens surface.

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 photochromic lens used for a correction lens, a fashion lens, and the like.

[0002]

2. Description of the Related Art Photochromism is a reversible effect in which when a certain substance is irradiated with light such as sunlight containing ultraviolet rays, the color of the substance changes rapidly, and when the light is stopped and left in a dark place, the color returns to its original color. That is. Various manufacturing methods have been proposed for manufacturing a plastic photochromic lens having this property.

[0003] As a method generally called a kneading method, for example, a method of mixing a photochromic substance with a polymerizable monomer, injecting it into a molding die, and heating and polymerizing to obtain a photochromic lens. Kaisho 62-
187784. As another method, a solvent dyeing method has been proposed. For example, Japanese Patent Application Laid-Open No. 55-36284 discloses a dyeing method in which an organic light modulating substance such as spirooxazine is dissolved in an alcohol solvent such as diethylene glycol and heated to 120 ° C., and the plastic lens is immersed. ing. Since such a solvent dyeing method can impart photochromic performance to the lens substrate by post-processing,
This is a preferable manufacturing method for eyeglass lenses and the like that require small-scale production.

[0004]

However, when the photochromic performance is provided by the kneading and mixing method, when the difference in thickness between the central portion and the outer peripheral portion of the lens is large, the difference in color density between the central portion and the outer peripheral portion is reduced. There are drawbacks that appear. In other words, when the center thickness is small with a minus lens having a strong strength, the color development at the center becomes lighter, and conversely, the color development at the outer periphery becomes darker.

[0005] In the case of imparting photochromic performance by a solvent dyeing method, depending on the combination of the lens substrate and the solvent, the surface of the lens substrate is damaged, causing surface irregularities (a state in which the lens surface becomes uneven). The appearance of the lens may be poor. In addition, as described above,
When the liquid temperature of the solvent is increased to 120 ° C. as disclosed in Japanese Patent Application Laid-Open No. 5-36284, a lens having low heat resistance has disadvantages such as deformation of the lens due to high temperature.

Therefore, it is more preferable that 1
It is desirable to provide photochromic performance at a temperature of 00 ° C. or lower. Specifically, when dyeing a plastic lens, a photochromic substance is dispersed in an aqueous solution of 100 ° C. or lower, and the plastic lens is immersed in the aqueous solution and dyed from the surface of the lens in the same manner as dyeing with a disperse dye. It is desirable to impregnate a photochromic substance to impart photochromic performance to the lens.

However, general photochromic substances have poor dispersibility in water, and it is very difficult to obtain uniform dispersibility as it is even if a surfactant and other dispersing aids are simultaneously added to water. is there.

According to the present invention, there is provided a method for imparting photochromic performance to a lens without causing shading of the coloring density due to the difference in the thickness of the lens and without causing damage to the lens surface by a solvent or deformation by a high temperature. The purpose is to provide.

[0009]

Means for Solving the Problems In order to achieve the above object, the present inventors have made intensive studies and found that a photochromic substance was converted into a disperse dye and then dispersed in an aqueous solution. It has been found that the above object can be achieved by immersion, and the present invention has been completed.

In the present invention, the method of disperse dyeing is not particularly limited, but it is preferable to perform a treatment of mixing a surfactant and a photochromic substance.

The surfactant used at this time is as follows:
Particularly preferred are anionic surfactants.

Further, as the photochromic substance to be converted into a disperse dye in the present invention, spirooxazine type,
It is preferable to consist of one or more selected from fulgimide, fulgide-based, and chromene-based photochromic substances.

According to the method of manufacturing a plastic photochromic lens according to the present invention, a plastic photochromic lens used for a correction lens, a fashion lens, and the like can be manufactured.

The method for manufacturing a plastic lens according to the present invention can provide photochromic performance by post-processing a molded lens, and is therefore preferable for eyeglass lenses and the like that require other types and small-scale production. Is the way.

In the present invention, a photochromic substance, which is originally poorly dispersible in water, is converted into a disperse dye by pretreatment to impart photochromic properties to the lens by the same method as that for dyeing a general plastic lens. be able to. Since the photochromic substance is uniformly impregnated from the surface of the lens in water, the completed lens is uniformly colored by the entire lens without being affected by a change in thickness. Further, by performing the treatment in water at a temperature of 100 ° C. or less, damage of the solvent to the lens can be avoided, and since the heat of 100 ° C. or more is not applied, the lens does not deform due to high temperature.

[0016] The disperse dyeing used in the present invention is to carry out a pretreatment so that the photochromic substance can be uniformly dispersed in water, and the method is not particularly limited. The following method is adopted. After mixing the photochromic substance with a dispersant such as a surfactant, the mixture is pulverized using a peptizer such as a colloid mill, a sand mill, or a disper to be dispersed into fine particles having an average particle size of about 1 μm or less. Then, it is dried to make powder or granules, or used as liquid. The type of surfactant used at this time is not particularly limited, and nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and the like are used. Specific examples of nonionic surfactants include alkyl allyl ethers such as polyoxyethylene octyl phenyl ether,
Alkyl ether type such as polyoxyethylene 2-ethylhexyl ether, alkyl ester type such as polyoxyethylene oleate, alkylamine type such as polyoxyethylene alkylamine, sorbitan derivative type such as sorbitan oleate, polyoxyethylene polycyclic phenyl And polycyclic phenyl ethers such as ether. Specific examples of the anionic surfactant include a sulfonic acid type such as a sodium salt of dialkyl succinatesulfonic acid and a sodium salt of a naphthalenesulfonic acid formalin condensate, and a sulfate type such as a polyoxyethylene alkyl ether sulfate salt. . Specific examples of the cationic surfactant include a quaternary ammonium salt type and an imidazoline type such as an alkylimidazoline. Specific examples of the zwitterionic surfactant include a betaine type such as an alkyl betaine. For better dispersibility in an aqueous solution, it is preferable to use an anionic surfactant. Of these, sulfonic acid type anionic surfactants such as dialkyl succinate sulfonic acid Na salt and naphthalene sulfonic acid formalin condensate Na salt are preferable.

When the photochromic substance is formed into a disperse dye, a single surfactant may be used. Further, in order to obtain a sufficient dispersibility in an aqueous solution, the photochromic substance may be converted into a disperse dye by using two or more surfactants.

By pretreating the photochromic substance and converting it into a disperse dye in this manner, uniform dispersion in water becomes possible, and a photochromic lens can be manufactured using a general dyeing pot or the like.

At this time, the lens used may be a lens substrate, but even if a surface layer such as a hard coat is present on the lens surface, the inside of the lens is impregnated with a photochromic substance through the hard coat layer. Therefore, it is possible to manufacture a photochromic lens. At this time, the hard coat layer can be a single hard coat layer with respect to the lens substrate, or can be a two or more layer structure combining a hard coat layer and a shock absorbing coat layer. It is. .

The photochromic substance used in the present invention is not particularly limited, but a photochromic substance having a molecular weight of 1,000 or less is preferable for easy impregnation from the lens surface. Examples include organic photochromic substances such as spirooxazine-based photochromic substances, fulgimide or fulgide-based photochromic substances, chromene-based photochromic substances, spiropyran-based photochromic substances, thionin-based photochromic substances, azobenzene-based photochromic substances, and viologen-based photochromic substances.

Among these, in terms of photochromic performance such as color density, color development / fading speed, and durability,
Spirooxazine-based photochromic substances, fulgimide or fulgide-based photochromic substances, chromene-based photochromic substances, and the like are preferable.

In order to produce a gray or brown plastic photochromic lens generally used for spectacle lenses, it is preferable to use a plurality of photochromic substances in combination. Actually, a spirooxazine-based photochromic substance whose color tone is blue to red and one or more photochromic substances selected from fulgimide or fulgimide-based photochromic substance, and a kind selected from chromene-based photochromic substance whose color tone is orange to yellow It is preferable to use a combination of the above photochromic substances.

In the present invention, as a method of combining a plurality of photochromic substances, a photochromic substance which has been made into a disperse dye alone may be mixed at the time of being poured into water such as a dyeing pot, or may be mixed at the time of disperse dyeing. so,
A plurality of photochromic substances may be mixed to simultaneously form a disperse dye.

When imparting photochromic performance to a plastic lens by using the disperse dyed photochromic substance of the present invention, a dyeing pot used for dyeing a general lens can be used. In addition, a large amount of lenses may be processed simultaneously using a large water temperature-controlled water tank.

When dispersing the photochromic substance of the present invention into a disperse dye in water such as a dyeing pot, a dispersing agent such as a surfactant may be added to further aid the dispersion of the photochromic substance. In order to increase the speed at which the photochromic substance is impregnated into the lens, a carrier for dyeing may be added. At this time, phenylphenol, benzyl alcohol and the like are often used as a carrier for dyeing.

When the plastic photochromic 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. It is particularly preferable to provide a hard coat layer for improving the adhesion between the lens substrate and the antireflection film and for preventing the surface from being damaged.

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 reactive group.

(B) silicon oxide, antimony oxide, zirconium oxide, titanium oxide, tin oxide, tantalum oxide,
Fine metal particles such as tungsten oxide and aluminum oxide;
Composite metal fine particles using two or more of titanium oxide, cerium oxide, zirconia oxide, silicon oxide, and iron oxide;
At least one selected from composite metal fine particles obtained by coating tin oxide fine particles 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 in combination. 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.

In coating the hard coat layer and the primer layer, it is preferable to dilute the raw material components of each layer in an appropriate solvent system such as an alcohol system or an aqueous system and use a general coating method such as dipping, spinning and spraying. And heat-curing. Curing can be performed by simply heating, but by adding an appropriate curing catalyst, a hard film can be formed in a shorter time. Examples of the curing catalyst include perchlorates such as magnesium perchlorate and ammonium perchlorate, and chelate compounds such as aluminum acetylacetonate.

As the hard coat layer, the above components (a) and (b) alone can obtain sufficient coating performance, but add the appearance, durability and other functions of the hard coat layer. Therefore, it is also possible to add other components. For example, it is effective to add a polyhydric alcohol, a polycarboxylic acid, a polycarboxylic anhydride, or an epoxy compound in order to improve the water resistance of the hard coat layer or to impart dyeability. Examples of the polyhydric alcohol that can be used include bifunctional alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol, and alkanediol, and trifunctional alcohols such as glycerin and trimethylolpropane. Alcohol or polyvinyl alcohol.
Examples of the polycarboxylic acid include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, o-phthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid and the like. Examples of the polycarboxylic anhydride include succinic anhydride, maleic anhydride, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and naphthalic anhydride. Examples of the epoxy compound include diglycidyl ethers of bifunctional alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol, and alkanediol, and triglycols such as glycerin and trimethylolpropane. Examples include di- or triglycidyl ethers of functional alcohols. When these additives are added, a film having a higher hardness can be obtained particularly by adding a curing catalyst.

Further, in order to prevent deterioration of the hard coat layer due to ultraviolet rays, an ultraviolet absorber, an antioxidant, a light stabilizer and the like can be used. As the ultraviolet absorber or the antioxidant / light stabilizer, for example, salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, nickel complex salts, phenol compounds, hindered amine compounds, and the like can be used.

Further, in order to eliminate coating defects such as yuzu skin and cissing at the time of application, a surfactant and a flow control agent can be used. Among them, silicone-based or fluorine-based surfactants are effective.

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.

[0037]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below based on embodiments, but the present invention is not limited to these embodiments. The structure of the photochromic substance appearing in the examples is shown below.

S-1:

[0039]

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S-2:

[0041]

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F-1:

[0043]

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F-2:

[0045]

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R-1:

[0047]

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R-2:

[0049]

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(Formation of Disperse Dyeing Photochromic Substance) (Example 1) Photochromic substance A converted into a disperse dye
Preparation of 10 g of S-1 is prepared as a photochromic substance.
10 g of Desroll SH (Nippon Emulsifier Co., Ltd.) is prepared as an anionic surfactant. These are sufficiently ground in a mortar to obtain a fine powder. After adding 20 g of water and stirring sufficiently, water is evaporated by a dryer. The solidified portion is taken out and thoroughly ground in a mortar to obtain a finely divided powder of the photochromic substance A which has been converted into a dye.
And

Example 2 Preparation of Photochromic Substance B Made into Disperse Dye 10 g of F-1 was prepared as a photochromic substance and thoroughly ground in a mortar to obtain a fine powder. 20 g of Escor 30 (Japanese emulsifier) is prepared as a liquid surfactant, into which a fine powdery photochromic substance is charged, and sufficiently stirred. After the stirring, the moisture is evaporated by a dryer, the solidified portion is taken out, and is sufficiently ground again in a mortar to obtain a fine powder of the photochromic substance B which has been converted into a dye.

Example 3 Preparation of Disperse Dyeed Photochromic Material C 10 g of R-1 was prepared as a photochromic material, and thoroughly ground in a mortar to obtain a fine powder. 20 g of Escor 30 (Japanese emulsifier) is prepared as a liquid surfactant, into which a fine powdery photochromic substance is charged, and sufficiently stirred. After the stirring, the water is evaporated by a drier, the solidified portion is taken out, and is sufficiently ground again with a mortar to obtain a fine powder, which is a photochromic substance C that has been converted into a dye.

(Example 4) Preparation of disperse dyeed photochromic substance D 8 g of S-2 and 8 of F-2 were used as photochromic substances.
g and 8 g of R-2 are prepared and ground sufficiently while mixing in a mortar to form a fine powder. 30 g of Escol 30 (Nippon Emulsifier) is prepared as a liquid surfactant, and a finely powdered photochromic substance is charged therein, followed by sufficient stirring. After the stirring, the water is evaporated by a drier, the solidified portion is taken out, and is sufficiently ground again in a mortar to obtain a fine powder, which is a photochromic substance D which has been converted into a dye.

(Production of Plastic Photochromic Lens) The abbreviations, trade names, substance names or production methods of the plastic lenses used in the examples are shown below.

Abbreviation: trade name, substance name or production method CR-NC: polymer of diethylene glycol bisallyl carbonate RX-NC: manufactured by Seiko Epson Corporation Lens cloth for Seiko Plux II Hard RX RX-HC: Seiko Epson Corporation Seiko Plux II Hard RX SL-NC: Seiko Epson Corporation Seiko Super Lucious Lens Fabric (Example 5) A constant temperature water tank whose water temperature was adjusted to 90 ° C was prepared, and a glass speaker containing 1 liter of water was prepared. Submerge in a constant temperature water bath and use as a staining pot. The disperse dyed photochromic material is added to the dyeing pot in the amount shown in Table 1. Surfactant NES-203 as a dispersant
(Nikko Chemicals) 3 cc and 10 cc of benzyl alcohol as a dye carrier were added to the dye pot, and the mixture was stirred with good stirring to use as a dye pot. CR-NC was prepared as a plastic lens, and the lens was completely immersed in the dyeing pot while stirring the dyeing pot. After 30 minutes, the lens was taken out of the dyeing pot to produce a photochromic lens. The evaluation items and the contents of the evaluation experiments are shown below.

Color density: 1 artificial sun illuminator (XC-200, Celic Corporation) was placed in a thermostat set at 25 ° C.
The photochromic lens was irradiated from a distance of 0 cm for 5 minutes. The color density of the lens immediately after the irradiation was evaluated by measuring the visible light transmittance using a BPI photometer.

Color appearance: 1 artificial sun illuminator (XC-200, Celic Corporation) was placed in a thermostat set at 25 ° C.
The photochromic lens was irradiated for 5 minutes from a distance of 0 cm, and the lens immediately after the irradiation was visually evaluated for color tone and whether the color was uniform throughout the lens. Table 2 shows the results.

Lens shape: The curved state of the center of the lens was visually observed and classified into the following ranks. The lens used at this time was a single focus lens having an S power of -5.0 diopters and a C power of 0.0 diopters.

A: There is no curvature at all. (The difference between the curvature at the time of design and the curvature at the time of molding is 0 to 1%.) B Slightly curved. (Difference is 1 to 3%) C It is slightly curved. (Difference is 3 to 5%) D Curved. (Difference is 5 to 10%) E It is extremely curved. (Difference is 10 to 20%) F Cannot be used. (The difference is more than 20%)

[0060]

[Table 1]

[0061]

[Table 2]

Examples 6 to 12 Photochromic lenses were prepared under the same conditions as in Example 5 except that the disperse dyed photochromic substances shown in Table 1 and the lenses shown in Table 1 were used. Evaluation was performed in the same manner as in Example 5. Table 2 shows the results.

Example 13 A photochromic lens was produced under the same conditions as in Example 5, except that the disperse dyed photochromic substance shown in Table 1 and the lens shown in Table 1 were used. This lens is immersed in the following coating composition a, pulled up at a speed of 20 cm per minute, coated with the coating composition on the lens surface, and heated at 130 ° C. for 1.5 hours to form a photochromic lens having a hard coat layer. Was prepared and evaluated in the same manner as in Example 5. Table 2 shows the results. Coating composition a: 23 g of γ-glycidoxypropyltrimethoxysilane, 45 g of methanol-dispersed colloidal silica (trade name: OSCAL-1132, manufactured by Catalysis Chemical Co., Ltd.) and 32 g of methyl cellosolve were thoroughly stirred, and the mixture was mixed with 0.05 N 2 g of hydrochloric acid was added and stirred for 30 minutes. Further, a silicone-based surfactant (trade name: L-7604, manufactured by Nippon Unicar Co., Ltd.)
0.03 g was added and stirred to prepare a coating composition.

Comparative Example 1 Example 5 was repeated except that the photochromic substances shown in Table 1 and the lenses shown in Table 1 were used.
A photochromic lens was produced under the same conditions as described above. In this case, instead of using the disperse dyed photochromic substance, the photochromic substance shown in Table 1 was ground in a mortar and used after pulverization. Evaluation was performed in the same manner as in Example 5 using this lens. Table 2 shows the results.

(Comparative Example 2) A constant temperature water tank filled with diethylene glycol instead of water is prepared, and the liquid temperature is adjusted to 120 ° C. A 1 liter glass beaker is filled with diethylene glycol and immersed in a thermostatic water bath, which is used as a dyeing pot. The photochromic substance shown in Table 1 is charged therein, and the mixture is stirred well. While stirring the dyeing pot, the lenses shown in Table 1 were immersed therein, and taken out after 30 minutes to produce a photochromic lens. Using this lens, evaluation was performed in the same manner as in Example 5, and the results are shown in Table 2.

[0066]

According to the method for producing a plastic photochromic lens of the present invention, a plastic photochromic lens in which a photochromic substance is uniformly impregnated in the surface layer portion of a lens substrate can be obtained, without being affected by the difference in the thickness of the lens. Thus, a plastic photochromic lens that develops color uniformly can be obtained. In addition, since the treatment is performed at a temperature of 100 ° C. or less in an aqueous solution, a plastic photochromic lens can be manufactured while avoiding deformation of the lens and damage to the lens surface due to a solvent.

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Claims (5)

[Claims] 1. A method for producing a plastic photochromic lens, wherein a photochromic substance is dispersed and dyed, then dispersed in an aqueous solution, and a plastic lens is immersed in the aqueous solution to impart photochromic performance. 2. The plastic photochromic lens according to claim 1, wherein a surfactant and a photochromic substance are mixed and processed when the photochromic substance is converted into a disperse dye. Manufacturing method. 3. The method for producing a plastic photochromic lens according to claim 2, wherein the surfactant is an anionic surfactant. 4. The method for producing a plastic photochromic lens according to claim 1, wherein the photochromic substance is selected from spirooxazine-based, fulgimide- or fulgide-based, and chromene-based photochromic substances. Alternatively, a method for producing a plastic photochromic lens, comprising two or more types. 5. A plastic photochromic lens manufactured by the method for manufacturing a plastic photochromic lens according to claim 1.