JP2002006272A - Plastic photochromic lens for spectacles - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plastic photochromic lens for spectacles which is high in the rates of dyeing and color fading, is constant in color tones of a color fading process and is excellent in appearance performance. SOLUTION: This plastic photochromic lens for spectacles contains (A) photochromic dyes of which the absorption of the main wavelength in color developing in the base material resin of the lens exists at 540 to 640 nm, the half-value width of absorption is >=120 nm, the half-life of color fading at 20 deg.C is within 90 seconds, (B) photochromic dyes of which the absorption at the main wavelength in color developing within the base material resin of the lens exists at 420 to 540 nm and (C) photochromic dyes of which the absorption of the main wavelength in color developing in the base material resin of the lens exists at 540 to 640 nm and the half-life of color fading at 20 deg.C is within a range of 2 to 20 times that of the photochromic dyes having the components (A) within the base material resin of the lens.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic photochromic lens for spectacles, and more particularly, to a plastic photochromic lens for spectacles having a high color developing and fading speed, a constant color tone in a fading process, and excellent appearance performance. .

[0002]

2. Description of the Related Art In recent years, an extremely large variety of organic photochromic dyes have been developed, and the number of dyes available as commercial products has increased. For applications to eyeglass lenses,
The market has become popular with the desire to use plastics, and plastic photochromic lenses using organic photochromic dyes are commercially available for use in eyeglasses.

[0003] These are those which form colors outdoors and have the same anti-glare effect as a high-density color lens, and recover a high transmittance when they are moved indoors. Have been. In particular, the speed at the time of fading requires several tens of minutes to recover the transmittance before color development from a state in which color is sufficiently developed, which is very much compared to the color development process in which a high color density is achieved in about one minute. Late,
Improvement was desired.

The color tone at the time of color development tends to be overwhelmingly preferred to be gray or brown, which requires absorption over the entire visible light range. Is not enough to obtain the desired color tone, and usually, a method of mixing a plurality of types of dyes having different absorption wavelengths to obtain a desired color tone is adopted. However, when a lens containing a plurality of types of dyes at the same time is used, the coloring of each dye,
If the fading speeds are not uniform, there is a problem that the color tone temporarily changes greatly from the originally intended color tone in the middle of the process.

In recent years, a dye having a high reaction rate has been developed and commercially available as a blue dye. However, a yellow dye or a red dye necessary for obtaining gray or brown coloration has an equivalent reaction. There is no dye having a speed, and a lens produced by using these dyes at the same time undergoes a phenomenon in which the color tone changes to a yellowish or reddish color tone larger than the color tone at the time of color fading. Japanese Patent Application Laid-Open No. 7-43525 discloses a method of preliminarily coloring a photochromic molded article as a means for solving this problem. However, in the case of spectacle lenses, coloring before coloring is often not welcomed by users, and is not a preferable method.

As described above, when examining a combination of photochromic dyes, it is customary to select a dye having a uniform reaction rate as much as possible. Therefore, in order to obtain a lens that develops a gray or brown color, a red-yellow dye with the fastest reaction speed is selected, while using a blue dye with a much higher speed is avoided, and a red-yellow dye is used. A method using a combination of dyes having the same speed as the dyes is used,
This also caused the overall reaction rate to be limited.

[0007]

Under such circumstances, the present invention does not have the problem that the color tone during fading temporarily deviates greatly from the originally intended color tone, and furthermore, the reaction speed is reduced. An object of the present invention is to provide a plastic photochromic lens for eyeglasses using a fast blue dye and having a higher reaction speed than that proposed in the prior art.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that two types of photochromic dyes having different coloring and fading characteristics and a photochromic dye having further different coloring characteristics are provided. It has been found that the object can be achieved by combining a dye with a lens base resin, and the present invention has been completed based on this finding.

That is, according to the present invention, (A) the absorption of the main wavelength at the time of color development in the lens base resin is 540 to 640 nm, the half width of absorption is 120 nm or more, and the fading at 20 ° C. is reduced by half. One or more photochromic dyes having a period of 90 seconds or less, (B) one or more photochromic dyes having an absorption of a main wavelength at 420 to 540 nm upon color development in a lens base resin, and (C) a lens. A photochromic dye having an absorption of a main wavelength at 540 to 640 nm at the time of color development in a base resin and a half life of fading at 20 ° C. of 2 to 20 times the photochromic dye of the above-mentioned component (A). The present invention provides a plastic photochromic lens for eyeglasses, characterized in that at least one of the following is contained in a lens base resin.

The half life of the fading of each dye is 2.0 mm in thickness, in which 0.05% by weight of a photochromic dye alone is uniformly contained in the same base resin as the plastic photochromic lens for eyeglasses of the present invention. Is defined as the time required for the absorption intensity of the main wavelength in the bleaching process to be reduced to half in a dark place after color development of the flat lens by a xenon lamp (1.2 mW / cm ² · UV365) for 5 minutes.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The components (A), (B) and (C) used in the plastic photochromic lens for spectacles of the present invention (hereinafter sometimes simply referred to as "lens for spectacles of the present invention"). There is no particular restriction on the molecular structure of the photochromic dye as a component, and examples thereof include spirooxazine, spiropyran, chromene, fulgide, and fulgimide compounds. It is also possible to use a commercially available dye whose molecular structure is not disclosed.

Photochromic dyes are generally known to be affected by many physical properties, such as absorption wavelength, absorption intensity, light resistance, and reaction rate of color fading, depending on the base resin. Therefore, as the base resin in the present invention, in addition to good dye adaptability to efficiently exhibit these photochromic properties possessed by the dye, high transparency and sufficient heat resistance, rigidity, and cutting and polishing as a spectacle lens are provided. Workability is required.

(A) Used in the eyeglass lens of the present invention
The photochromic dye of the component has an absorption of the main wavelength at the time of color development of 540 to 640 nm in such a lens base resin.
And the half width of absorption is 120 nm or more, and
It is a dye having the property of having a half life of fading at 90 ° C. of 90 seconds or less. That is, the blue dye is characterized by a high reaction rate and a large absorption width. The use of such a dye for gray or brown coloring can increase the overall reaction speed. If the half width of absorption is not 120 nm or more, the effect of the photochromic dyes of the components (B) and (C) having a lower reaction rate becomes stronger, and the effect of improving the reaction rate as a whole becomes insufficient. Examples of such a photochromic dye of the component (A) include “CNN-7” (manufactured by Tokuyama Corporation), which is a commercially available product. In the present invention, as the photochromic dye of the component (A), one type may be used alone, and
A combination of more than one species may be used.

Further, the photochromic dye of the component (B) has an absorption of the main wavelength at the time of coloring in the lens base resin of 4%.
A dye having a wavelength of 20 to 540 nm, which is a yellow or red dye used together with the photochromic dye of the component (A) in order to obtain a gray or brown color. In order to increase the overall reaction rate, a dye having a high reaction rate equivalent to that of a blue dye is preferable, but a dye having both practical durability and such a high reaction rate has not been found. However, even among these, choosing the one with the fastest reaction speed as possible, in order to increase the overall reaction speed,
Needless to say, it is also advantageous in suppressing color tone fluctuation during fading. As such a photochromic dye of the component (B), for example, a commercially available product “CNN-
4 "(manufactured by Tokuyama Corporation)," corn yellow "," ruby "," berry red "(above, manufactured by James Robinson)," Yellow L "(manufactured by Great Lakes) and the like. In the present invention, as the photochromic dye of the component (B), one type may be used alone, or two or more types may be used in combination.

On the other hand, the photochromic dye of the component (C) has an absorption of the main wavelength of 5% at the time of coloring in the lens base resin.
A dye having a wavelength of 40 to 640 nm and a half life of fading at 20 ° C. in the range of 2 to 20 times the photochromic dye of the component (A). That is, it is a blue dye having a slow reaction rate. The component (A) and the component (B)
By adding a small amount to the component photochromic dye, the phenomenon in which the color tone during the fading changes to reddish yellow can be suppressed. This means that even if a red-yellow dye having a low reaction rate is combined with a blue dye having a high reaction rate which satisfies the requirements of the present invention, color tone fluctuation during color fading can be prevented by the effect of the photochromic dye of the component (C), and color formation can be prevented. This indicates that the color can be faded while maintaining the color tone at the time. 20 ° C
If the half-life of the discoloration in (1) is less than twice that of the photochromic dye of the component (A), the effect of preventing color tone fluctuation during discoloration becomes insufficient, and if it exceeds 20 times, the color tone during discoloration tends to be bluish or develops color. It takes a long time to recover the previous transmittance, which is not preferable.

It is essential that the preferable amount of the photochromic dye (C) be selected within a range that does not impair the rapid reaction rate of the photochromic dye (A). The amount is selected in the range of 1/50 to 1/2, preferably 1/40 to 1/4 of the amount of the component photochromic dye added. As such a photochromic dye of the component (C), for example, commercially available products “CNN-3”, “FG-3”, “FG-
7 "[More, manufactured by Tokuyama Corporation]," Oxfort Blue "(manufactured by James Robinson)," Blue A "
(Manufactured by Great Lakes). In the present invention, the photochromic dye of the component (C) is
One type may be used alone, or two or more types may be used in combination.

In the present invention, the component (A)
There is no particular limitation on the total amount of the photochromic dyes of the component (B) and the component (C), but in consideration of the high transmittance at the time of fading and the appropriate light-shielding property at the time of coloring required for the eyeglass lens, 0.00 parts by weight of resin
Advantageously, it is selected in the range from 1 to 0.1 parts by weight.

To produce the spectacle lens of the present invention, the component (A)
A method in which the photochromic dyes of the component (B) and the component (C) are contained and polymerized is preferably used.
As the monomer, for example, an aliphatic monomer having an ethylenically unsaturated bond or an aromatic vinyl monomer can be used, but high transparency and sufficient heat resistance as a lens for spectacles can be used. In consideration of the rigidity, cutting and polishing workability, etc., it is preferable to mainly use methacrylic acid ester-based monomers, and a monomer copolymerizable therewith can be used insofar as these physical properties are not impaired. .

Examples of the methacrylate monomer include methyl methacrylate, ethyl methacrylate, n
-Monofunctional methacrylates such as butyl methacrylate, ethylhexyl methacrylate, glycidyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tripropylene glycol Dimethacrylate, 1,
4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, glycerin dimethacrylate, 2,2-bis [4- (methacryloxy) phenyl] propane, 2,2
And polyfunctional methacrylates such as -bis [4- (methacryloxyethoxy) phenyl] propane.

Monomers copolymerizable with these compounds include methyl acrylate, ethyl acrylate, n-
Butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, isobornyl acrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate , 2,2-bis [4- (acryloxy) phenyl] propane, 2,2-
Acrylic acid-based monomers such as bis [4- (acryloxyethoxy) phenyl] propane; styrene, methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene, divinylbenzene, etc. Nuclear-substituted styrene, α-methylstyrene, acrylonitrile, methacrylonitrile,
Examples include maleic anhydride, N-substituted maleimide, and allyl compounds such as diethylene glycol bisallyl carbonate and diallyl phthalate.

As the good monomer composition used in the present invention, it is preferable to use a mixture of two or more of these as appropriate. The present applicants have already proposed an example of such a monomer composition in JP-A-8-169923. As a method for producing the lens of the present invention, a method is employed in which the photochromic dyes of the components (A), (B) and (C) are dissolved in a mixture of these monomers, and the resulting mixture is cast-polymerized. . A known thermosetting polymerization method or ultraviolet curing polymerization method can be applied to the casting polymerization.

Hereinafter, a thermosetting polymerization method will be described as an example. In this method, an appropriate amount of a polymerization initiator is added to a monomer mixture in which a photochromic dye is dissolved, and the mixture is injected into a mold and heated and polymerized. As the polymerization initiator at this time,
Azo initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, and t-butylperoxy-2 -A peroxide initiator such as ethylhexanoate is used, but it is important to determine the type and amount of addition so that a good polymerization state can be obtained without reducing or eliminating the effect of the photochromic dye. It is. These initiators are usually preferably used in the range of 0.001 to 5% by weight of the total amount of the monomers. The heating temperature varies greatly depending on the initiator used, but is usually in the range of 20 to 80 ° C.

The base resin in the spectacle lens of the present invention may contain, if necessary, as long as the object of the present invention is not impaired.
Various additives such as a heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent, and a usual dye can be appropriately added.

In the spectacle lens of the present invention, abrasion resistance is generally imparted to the surface of the base resin by means of a polyfunctional acrylate or methacrylate ultraviolet curable coating or a silicone or melamine thermosetting coating. Of these, the most common method is a method in which an organopolysiloxane-based curing liquid is used and thermally cured. Examples of using an organopolysiloxane-based curing liquid as the acrylic resin include the methods described in JP-A-52-112698 and JP-A-61-166824. Further, as an example of adding a metal colloid to an organopolysiloxane-based curing liquid, see JP-A-60-2217.
No. 02 publication.

The method of using an organopolysiloxane-based curing liquid containing a high concentration of a metal colloid is excellent in surface modification because it can form a film that is very hard and durable as compared with those containing no metal colloid. According to this method, when the base material is an acrylic resin, there is a tendency that as the amount of the metal colloid is increased, the adhesion to the base material is significantly reduced. This tendency is also related to the molecular structure of the base material, and becomes more remarkable as the crosslinking density is increased in order to improve the strength, heat resistance, solvent resistance and the like.

As a method for improving the adhesion between the base resin and the cured film, there is known a method in which the base resin surface is previously treated with an alkali agent such as KOH or NaOH.
In many cases, this alone is insufficient to provide a high-quality cured film containing a high concentration of metal colloid to a tough acrylic base resin having a high crosslinking density.

In order to increase the adhesion between the base resin and the cured film in such a combination, (1) the surface is physically rubbed by rubbing a cloth, paper, sponge or the like containing the base resin with an abrasive. (2) plasma treatment of the base resin, (3) treatment of the base resin with ozone water, (4) ultraviolet light of a specific wavelength to the base resin. A method of activating the surface by irradiation, (5) a method of providing a primer layer between the base resin and the cured film, and the like are effective. It is preferable to appropriately select or combine these depending on the composition of the base resin and the cured film.

In the method (1) of rubbing a cloth, paper, sponge, or the like in which an abrasive is contained in a base resin to physically edging the surface, the type and particle size of the abrasive are determined. There is no particular limitation, and known abrasives such as diamond, alumina, iron oxide, chromium oxide, and cerium oxide can be used, and the lens can be uniformly formed to such an extent that sufficient transparency can be maintained as a spectacle lens in a state where a cured film is provided. Polish and edging the surface. A water dispersion, an oil dispersion, or a paste form can be used, but usually, a water dispersion,
A method in which a material having a particle size of about 0.1 to 10 μm is soaked in cloth paper, sponge, or the like, and the surface of the base resin is polished for about 5 to 30 seconds is preferable because it is easy to use.

In the method (2) of subjecting the base resin to plasma treatment, the conditions are somewhat different depending on the size, type and shape of the apparatus used, but usually air, helium, argon, hydrogen, oxygen and the like. This is performed within 600 seconds in an atmosphere of about 1.3 to 1300 Pa of a non-polymerizable gas such as nitrogen. It is preferable that the coating and curing of the coating composition be performed within 24 hours on the lens substrate after the plasma treatment.

Next, in the method (3) in which the base resin is treated with ozone water, the ozone water to be used can be produced, for example, using a commercially available ozone water producing apparatus. The water used as the raw material of this ozone water is ion-exchanged,
Pure water obtained by methods such as distillation and reverse osmosis is used,
Tap water or the like may be mixed as long as a necessary ozone concentration can be obtained.

Further, as long as the ozone concentration in the ozone water does not become unstable, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, alkaline agents such as sodium hydroxide and potassium hydroxide, alcohols and the like. Can be added. The ozone concentration of the ozone water is not particularly limited as long as it has an effect obtained in the present invention.
Considering practicality of at least 5 ppm, 5 ppm or more is particularly preferable.

The treatment temperature of the ozone water is not particularly limited. However, considering that when the temperature of the ozone water is increased, the decomposition of ozone is accelerated and it becomes difficult to maintain the concentration, the temperature is preferably 50 ° C. or less, particularly preferably. 30 ° C. or less. The immersion time of the lens substrate in the ozone water depends on conditions such as the material of the substrate, the material of the cured film, the ozone concentration of the ozone water, and the like, and is not particularly limited.

In the method (4) of irradiating the base resin with ultraviolet rays having a specific wavelength to activate the surface, a low-pressure mercury lamp is preferably used as a light source. This low-pressure mercury lamp contains 185 and 254 nm ultraviolet rays, which generate ozone and active oxygen atoms from the oxygen in the atmosphere to activate the substrate surface, and at the same time, decompose the polymer chains on the substrate surface to activate it. It is said that it will become. Since these ultraviolet rays are absorbed by the atmosphere or generated ozone, irradiation is preferably performed within 20 cm from the lamp, and more preferably within 10 cm. Usually 30
An improvement in adhesion is seen with irradiation for seconds to 600 seconds.

On the other hand, in the method (5) in which a primer layer is provided between the base resin and the cured film, various primer layers can be used, but a polyurethane primer is preferred. As the polyurethane-based primer, any of a thermoplastic type and a thermosetting type can be used. As the thermosetting type polyurethane, for example,
A block obtained by blocking a cyclic trimer of hexamethylene diisocyanate with β-diketone, and addition of several molecules of isophorodiisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate by various methods. Product, isocyanurate, aphanate, buret, carbodiimide obtained by reacting a blocked polyisocyanate such as one blocked with acetoacetic acid, malonic acid, methyl ethyl ketoxime or the like, and a polyol such as a polyester polyol and / or an acrylic polyol. Can be used. These pretreatments can be used in combination of two or more kinds or in combination with an alkali treatment to further enhance the effect.

In the spectacle lens of the present invention, an antireflection film may be applied to the surface of the cured film provided on the base resin in order to improve the antireflection effect of the lens. This anti-reflection film is made of, for example, Si by a vacuum evaporation method, an ion sputtering method, an ion plating method, or the like.
O, SiO ₂ , Si ₃ N ₄ , TiO ₂ , ZrO ₂ , Al
It is formed by laminating a single-layer or multilayer thin film made of a dielectric material such as ₂ O ₃ or MgF ₂ , so that reflection at the interface with the atmosphere can be suppressed low. When the antireflection film is composed of a single layer, its optical film thickness is λ0 / 4.
(Λ0 = 450 to 650 nm). A two-layer film having an optical film thickness of λ0 / 4−λ0 / 4 having a different refractive index, and an optical film thickness of λ0 / 4−λ0 / 2−λ0 / 4 or λ0 / 4−λ0 / 4−λ0 / 4. It is useful to use a multilayer antireflection film composed of a three-layer film having different refractive indices or a multilayer coating antireflection film partially replaced with an equivalent film. Further, antifogging property, antifouling property, antistatic property and the like can be imparted by a known method.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The methods for evaluating physical properties in Examples and Comparative Examples are as follows.

(A) Color tone at the time of color development Colors were formed on white paper under sunlight under sunny weather satisfying the following conditions, and the color tone after 5 minutes was visually judged. Temperature: 15 ° C or higher, 20 ° C or lower UV intensity: 1.0 mW / cm ² · UV365 or higher,
1.3 mW / cm ² · UV 365 or less,

(B) Discoloration reaction speed A 2.0 mm-thick flat lens was connected to a xenon lamp (1.2
mW / cm ² · UV365) for 5 minutes at 20 ° C., and the time required for the absorption intensity at 550 nm during the fading process to be reduced to half in a dark place was measured as the half life of the lens at the time of fading. And the following criteria. A: Discoloration half-life is less than 60 seconds. B: Discoloration half-life is 60 seconds or more and less than 120 seconds. C: Discoloration half-life of 120 seconds or more.

(C) Color Tone Stability During Fading The lens whose color tone was confirmed during color development was immediately transferred to a room at 23 ° C. where no sunlight was allowed to enter, and the color tone change during the fading process was visually observed under a fluorescent lamp for 10 minutes. Then, the maximum color difference from the color tone at the time of color development was determined based on the following criteria. A: The color fades with the color tone at the time of color development, and almost no difference is visually observed. B: Discoloration is slightly reddish or yellowish compared with the color tone at the time of color development. C: Changes to a strong reddish or yellowish tint that is clearly different from the color tone at the time of color development.

(D) Surface Hardness The surface was rubbed 20 times (reciprocatingly) with steel wool # 0000 and an additional load of 20 N, and the scratch resistance was determined according to the following criteria. A: Almost no damage. B: Very slight damage. C: Slightly scratched. D: Many scratches are made.

(E) Adhesiveness The surface of the cured film is a square pattern (10 × 10) at 1 mm intervals.
Into cellophane adhesive tape (Nichiban N
o. 405) was strongly adhered, and the number of stitches remaining after being peeled off sharply in the direction of 90 degrees was examined.

Reference Example 1 Performance confirmation of photochromic dye in base resin 1 50 parts by weight of 2,2-bis [4- (methacryloxyethoxy) phenyl] propane as a monomer composition and triethylene glycol dimethacrylate 40 Parts by weight, 10 parts by weight of glycidyl methacrylate, 1 part by weight of 2,4-diphenyl-4-methyl-1-pentene as a polymerization rate regulator, and one kind of photochromic dye shown in Table 1 for 0.0
5 parts by weight, 0.50 part by weight of t-butyl peroxyneodecanate as a radical polymerization initiator, and 0.00 as a release agent, "Shin-Etsu Silicone KF353A" manufactured by Shin-Etsu Chemical Co., Ltd.
01 parts by weight were added and mixed and dissolved. This mixture was poured into a mold composed of two glass molds and a plastic gasket, placed in a hot-air circulation heating furnace, heated at 40 ° C. for 12 hours, and then heated to 85 ° C. over 4 hours. The mixture was heated for 2 hours to carry out polymerization. The polymer obtained by removing the mold was a highly transparent resin composition forming a meniscus lens having a diameter of 75 mm, a thickness of 2.0 mm, and a power of 0.00 diopter. This is further heated to 120 ° C.
For 2 hours to perform annealing.

This lens was connected to a xenon lamp (1.2 mW
/ Cm ² · UV 365) and spectroscopic measurement was performed after 5 minutes while developing the color at 20 ° C. The half width of the dye absorption was determined from the absorption curve at this time. Then turn off the lamp,
The time required for the absorption intensity to become half of that at the time of color development was measured and defined as the half-life representing the fading reaction rate. Table 1 shows the performance of each dye in the base resin 1. FIG. 1 is an explanatory diagram for measuring an absorption half width in a photochromic dye.

[0044]

[Table 1]

(Note) CNN-3, CNN-4, CNN-7, FG-3: Co., Ltd.
Tokuyama CY (corn yellow), FL (frame), RU (ruby), BR (berry red), OB (Oxford blue): James Robinson Blue A: Great Lakes

Reference Example 2 Confirmation of Performance of Photochromic Dye in Base Resin 2 In Reference Example 1, the composition of the monomer composition was changed to 50 parts by weight of 2,2-bis [4- (methacryloxyethoxy) phenyl] propane. , Except that 15 parts by weight of triethylene glycol dimethacrylate, 15 parts by weight of trimethylolpropane trimethacrylate, 10 parts by weight of benzyl acrylate, and 10 parts by weight of glycidyl methacrylate,
1. A diameter of 75 mm and a thickness of 2.
A highly transparent resin composition forming a flat lens of 0 mm and a diopter of 0.00 diopter was obtained. Table 2 shows the performance of each dye in the base resin 2.

[0047]

[Table 2] (Note) Each dye is the same as the footnote in Table 1.

Example 1 Polymerization was conducted by mixing 50 parts by weight of 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 40 parts by weight of triethylene glycol dimethacrylate, and 10 parts by weight of glycidyl methacrylate as a monomer composition. 1 part by weight of 2,4-diphenyl-4-methyl-1-pentene as a speed regulator, 0.040 part by weight of "CNN-7" manufactured by Tokuyama Corporation and 0.020 of "CNN-4" as a photochromic dye Parts by weight, 0.020 parts by weight of "Berry Red" manufactured by James Robinson, "CN" manufactured by Tokuyama Corporation
N-3 "(0.005 parts by weight), t-butyl peroxyneodecanate (0.50 parts by weight) as a radical polymerization initiator, and" Shin-Etsu Silicone K "manufactured by Shin-Etsu Chemical Co., Ltd. as a release agent
F353A "(0.0001 parts by weight) was added and mixed and dissolved.
This mixture was poured into a mold composed of two glass molds and a plastic gasket, placed in a hot-air circulation heating furnace, heated at 40 ° C. for 12 hours, and then heated to 85 ° C. over 4 hours. The mixture was heated for 2 hours to carry out polymerization. The polymer obtained by removing the mold has a diameter of 75 mm,
It was a highly transparent resin composition forming a planar lens having a thickness of 2.0 mm and a diopter of 0.00 diopter. Add one more
Annealing was performed by heating at 20 ° C. for 2 hours.

The evaluation results of this lens are as shown in Table 4. The reaction speed of the color fading is high, and the color tone during the color fading does not differ from the color tone at the time of color development. Therefore, the lens can be suitably used as an eyeglass lens. there were. FIG. 2 is a graph showing the relationship between the wavelength and the light transmittance of the lens at the time of color development and color fading, and FIG. 3 is a graph showing the change of the light transmittance at a wavelength of 550 nm of the lens.

Example 2 A lens was prepared and evaluated in the same manner as in Example 1 except that the composition of the photochromic dye was changed as shown in Table 3. The evaluation results of this lens are as shown in Table 4. The reaction speed of the color fading was high, and the color tone during the color fading did not differ from the color tone at the time of color development, so that the lens could be suitably used as a lens for eyeglasses.

Comparative Example 1 A lens was prepared and evaluated in the same manner as in Example 1 except that the composition of the photochromic dye was changed as shown in Table 3. The results are as shown in Table 4, where the absorption of the main wavelength at the time of color development in the lens base resin which is an essential component of the present invention is 540 to 640 nm, and the half width of absorption is 120 n.
m or more, and the photochromic dye having a half life of fading at 20 ° C. of 90 seconds or less was not included, so that the reaction speed of fading was low, which was not preferable as a lens for spectacles.

Comparative Examples 2 and 3 A lens was prepared and evaluated in the same manner as in Example 1 except that the composition of the photochromic dye was changed as shown in Table 3. The results are as shown in Table 4. The absorption of the main wavelength at the time of color development in the lens base resin, which is an essential component of the present invention, is at 540 to 640 nm, and the half-life of the fading at 20 ° C. is a photochromic dye. Since it does not contain a photochromic dye which is in the range of 2 to 20 times that of (A), the reaction speed of color development and discoloration is fast, but the color tone during color fading largely deviates from the color tone at the time of color development, which is not preferable as a lens for spectacles. Was something.

Example 3 The composition of the monomer composition was changed to 50 parts by weight of 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 15 parts by weight of triethylene glycol dimethacrylate, and 15 parts by weight of trimethylolpropane trimethacrylate. Part, benzyl acrylate 10 parts by weight, and glycidyl methacrylate 10 parts by weight, except that the diameter was 75 mm, the thickness was 2.0 mm, and the frequency was 0.00.
A highly transparent resin composition forming a diopter planar lens was obtained. The evaluation results of this lens are as shown in Table 4. The reaction speed of the color fading was high, and the color tone during the color fading did not differ from the color tone at the time of color development, so that the lens could be suitably used as a lens for eyeglasses.

Example 4 A lens was prepared and evaluated in the same manner as in Example 3 except that the composition of the photochromic dye was changed as shown in Table 3. The evaluation results of this lens are as shown in Table 4. The reaction speed of the color fading was high, and the color tone during the color fading did not differ from the color tone at the time of color development, so that the lens could be suitably used as a lens for eyeglasses.

Comparative Example 4 A lens was prepared and evaluated in the same manner as in Example 3 except that the composition of the photochromic dye was changed as shown in Table 3. The results are as shown in Table 4, where the absorption of the main wavelength at the time of color development in the lens base resin which is an essential component of the present invention is 540 to 640 nm, and the half width of absorption is 120 n.
m or more, and the photochromic dye having a half life of fading at 20 ° C. of 90 seconds or less was not included, so that the reaction speed of fading was low, which was not preferable as a lens for spectacles.

Comparative Examples 5 and 6 A lens was prepared in the same manner as in Example 3 except that the composition of the photochromic dye was changed as shown in Table 3, and evaluation was performed in the same manner. The results are as shown in Table 4. The absorption of the main wavelength at the time of color development in the lens base resin, which is an essential component of the present invention, is at 540 to 640 nm, and the half-life of the fading at 20 ° C. is a photochromic dye. Since it does not contain a photochromic dye which is in the range of 2 to 20 times that of (A), the reaction speed of color development and discoloration is fast, but the color tone during color fading largely deviates from the color tone at the time of color development, which is not preferable as a lens for spectacles. Was something.

[0057]

[Table 3]

[0058]

[Table 4]

Example 5 The lens obtained in Example 1 was replaced with "PR" manufactured by Yamato Scientific Co., Ltd.
Using "-501A", a plasma treatment was performed in an atmosphere of oxygen 80 Pa for 300 seconds. Subsequently, “KP-64”, an organopolysiloxane-based coating composition containing silica as a metal colloid, manufactured by Shin-Etsu Chemical Co., Ltd. was applied at 10 ° C. by a dipping method (pulling speed: 20 cm / min), and this was applied at 120 ° C. Heat cured for 90 minutes. The evaluation result of the lens with the surface hardened film obtained in this way shows that, like the lens of Example 1, the reaction rate of color development and fading, the color tone during fading is good, and the surface hardness B and adhesion are 100/100. It was suitable for use as a spectacle lens.

Example 6 The lens obtained in Example 3 was replaced with "PR" manufactured by Yamato Scientific Co., Ltd.
-501A ”in an oxygen atmosphere (80 pa).
Plasma treatment was performed for 0 seconds. Subsequently, it was immersed in a 10% by weight aqueous solution of NaOH at 60 ° C. for 360 seconds, washed and dried by heating. After cooling, “KP-64” manufactured by Shin-Etsu Chemical Co., Ltd. was applied as a coating composition at 10 ° C. by a dipping method (pulling speed: 20 cm / min), and then applied at 120 ° C.
For 90 minutes. The evaluation result of the lens with the surface hardened film obtained in this way shows that, like the lens of Example 3, the reaction speed of color development and fading, the color tone during fading is good, and the surface hardness B and adhesion are 100/100. It was suitable for use as a spectacle lens.

On the other hand, the lens obtained in Example 3 was heated at 60 ° C.
Was immersed in a 10% by weight aqueous solution of NaOH for 360 seconds, washed and dried by heating. After cooling, “KP-64” manufactured by Shin-Etsu Chemical Co., Ltd. was applied as a coating composition at 10 ° C. by a dipping method (pulling speed: 20 cm / min), and this was heated and cured at 120 ° C. for 90 minutes. Like the lens of Example 3, the thus-obtained lens with a surface-hardened film has a good reaction rate of color development and fading, a good color tone during fading, and maintains a surface hardness of B. Since the lens was not manufactured by a method including a step of increasing the adhesion to the coating film, the adhesion was 0/100, which was not preferable as an eyeglass lens.

Reference Example 3 Preparation of coating composition (a) Colloidal silica having a SiO ₂ concentration of 40% by weight [“Snowtex-40”, water-dispersed silica, average particle size of 10 to 20]
mμ, manufactured by Nissan Chemical Co., Ltd.]
A solution obtained by adding 2.0 parts by weight of hydrochloric acid and 20 parts by weight of acetic acid was heated to 35 ° C. and stirred while γ-glycidoxypropyltrimethoxysilane (trifunctional organosilicon compound) 95 was added.
A part by weight was added dropwise and the mixture was stirred at room temperature for 8 hours, and then left for 16 hours. To 320 parts by weight of this hydrolysis solution, 80 parts by weight of methyl cellosolve, 120 parts by weight of isopropyl alcohol, 40 parts by weight of butyl alcohol, 16 parts by weight of aluminum acetylacetone, and 0.2 part of a silicone surfactant
After stirring for 8 hours, the mixture was aged at room temperature for 24 hours to obtain a coating composition. This is designated as coating composition (a). The amount of colloidal silica in the coating composition was 80 mol% (in terms of SiO ² solid content) based on the total amount of colloidal silica and γ-glycidoxypropyltrimethoxysilane.

Example 7 The lens obtained in Example 1 was immersed for 30 minutes in a tank of ozone water produced using an ozone water production apparatus “OZ-DW3M” manufactured by Loki Techno Co., Ltd. Since the ozone concentration is lowered by leaving it naturally, a constant concentration of ozone water is always supplied to maintain the concentration in the tank. The water temperature at this time is 24
° C and the ozone concentration were 16 ppm. Subsequently, the coating composition (a) was applied at 10 ° C. by a dipping method (with a pulling rate of 20 cm / min).
Heat cured for minutes. The evaluation result of the lens obtained in this way is similar to the lens of Example 3, and the reaction speed of color development and fading, the color tone during fading is good, and the surface hardness A and adhesion 10
0/100, which was suitable for use as a spectacle lens.

On the other hand, the lens obtained in Example 1 was heated at 60 ° C.
Was immersed in a 10% by weight aqueous solution of NaOH for 360 seconds, washed and dried by heating. Cooling coating composition (a)
At 10 ° C. by a dipping method (with a lifting speed of 20 cm /
Min) and cured by heating at 120 ° C. for 90 minutes. Like the lens of Example 1, the thus-obtained lens with a surface-hardened film has a good reaction rate of discoloration and color tone during discoloration, and maintains a surface hardness of B. Since the lens is not manufactured by a manufacturing method including a step of increasing the adhesion to the coating film, the adhesion is 0/10.
0, which is not preferable as a spectacle lens.

Example 8 The lens obtained in Example 3 was used as a low-pressure mercury lamp irradiator, i.
"2506" for 180 seconds at an irradiation distance of 30 mm. Subsequently, 3% aqueous solution of 10% by weight of NaOH at 60 ° C.
After immersion for 60 seconds, it was washed and dried by heating. After cooling, the coating composition (a) was applied at 10 ° C. by a dipping method (with a pulling rate of 20 cm / min).
It was cured by heating for 0 minutes. The evaluation result of the lens with the surface hardened film obtained in this way is the same as the lens of Example 3, showing that the reaction rate of the color fading and the color tone during the fading are good, and that the surface hardness A and the adhesion are 100/100. It can be suitably used as a lens for use.

Example 9 An alumina abrasive “Hexalite-A9” manufactured by Fujimi Incorporated, which was dispersed in twice the amount of water, was added to a sponge, and the surface of the lens obtained in Example 3 was added to the sponge.
Rubbed uniformly for 0 seconds. 60 ° C after washing off the abrasive
Was immersed in a 10% by weight aqueous solution of NaOH for 360 seconds, washed and dried by heating. Cooling coating composition (a)
At 10 ° C. by a dipping method (with a lifting speed of 20 cm /
Min) and cured by heating at 120 ° C. for 90 minutes. The evaluation result of the lens with the surface hardened film obtained in this way is similar to that of the lens of Example 3 in that the reaction speed of color development and fading, the color tone during fading are good, and the surface hardness A and adhesion 1
00/100, which was suitable for use as a spectacle lens.

[0067]

According to the present invention, the reaction speed of the color fading is fast, and the color tone during the color fading largely deviates from the target gray or brown, and temporarily changes to a strong yellow or reddish color. Thus, a plastic photochromic lens for spectacles in which the problem has been solved can be provided.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram for measuring an absorption half width in a photochromic dye.

FIG. 2 is a graph showing the relationship between the wavelength and light transmittance of the lens obtained in Example 1 during color development and color fading.

FIG. 3 is a graph showing a change in light transmittance at a wavelength of 550 nm of the lens obtained in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 7/04 C08J 7/04 E CEY CEYK C08K 5/00 C08K 5/00 C08L 101/00 C08L 101/00 F term (reference) 2H006 BE02 4F006 AA22 AB39 AB73 AB74 BA01 CA05 DA04 4F073 AA01 BA18 CA01 CA53 DA07 4J002 BG051 BG061 FD096 FD097 FD098 GP01 4J011 PA22 PB25 PB40

Claims (8)

[Claims] (A) Absorption of a main wavelength at the time of color development in a lens base resin is 540 to 640 nm, a half width of absorption is 120 nm or more, and a half-life of fading at 20 ° C. is 9
At least one photochromic dye within 0 seconds;
(B) Absorption of main wavelength at the time of color development in lens base resin is 4
One or more of the photochromic dyes having a wavelength of 20 to 540 nm and (C) the absorption of the main wavelength at the time of color development in the lens substrate resin is 540 to 640 nm, and the half-life of the fading at 20 ° C. A) Photochromic dye 2 of the component
A plastic photochromic lens for eyeglasses, characterized in that one or more photochromic dyes in a range of up to 20 times are contained in a lens base resin. 2. A lens base resin comprising: component (A);
The plastic photochromic lens for eyeglasses according to claim 1, which is obtained by polymerizing a monomer containing a component and a photochromic dye of the component (C). 3. The lens base resin having a cured film on a surface polished by an abrasive.
2. The plastic photochromic lens for eyeglasses according to 1. 4. The plastic photochromic lens for eyeglasses according to claim 1, wherein the lens base resin has a cured film on a surface obtained by plasma treatment in a non-polymerizable gas atmosphere. 5. The plastic photochromic lens for eyeglasses according to claim 1, wherein the lens base resin has a cured film on a surface treated with ozone water. 6. The plastic photochromic lens for eyeglasses according to claim 1, wherein the lens base resin has a cured film on a surface irradiated with a low-pressure mercury lamp. 7. The plastic photochromic lens for eyeglasses according to claim 1, wherein the lens base resin has a cured film on the surface provided with the adhesion layer. 8. A cured film formed by using a cured liquid mainly composed of an organosilicon compound having an alkoxyl group and an epoxy group and a metal colloid.
8. The plastic photochromic lens for eyeglasses according to any one of items 7 to 7.