JP5855393B2 - Eyeglass lenses - Google Patents

Description

 The present invention relates to a spectacle lens.

 In general, a spectacle lens is processed into an outer shape that matches the shape of a spectacle frame selected by a customer at a retail store, and is fitted into the spectacle frame and delivered to the customer. A processing machine that performs the outer shape processing of such a lens is called a balling processing machine (edger, outer edge processing machine, etc.). In a general lashing machine, an outer shape is processed by grinding an outer edge with a grindstone while holding a spectacle lens with a processing axis.

With reference to FIG. 5, a general lashing method for a spectacle lens will be described.
Here, the case where the lens to be processed (lens for eyeglasses) 110 is processed using the lashing machine 100 will be described.
The lashing machine 100 is schematically configured from a plastic lens lock cap 101, an upper lens processing shaft 102, a lower lens processing shaft 103, and a grindstone 104.

First, the lens to be processed 110 is fixed to the lens lock cap 101 with the double-sided adhesive tape 105.
More specifically, the double-sided adhesive tape 105 is affixed in advance to the adherend surface (surface to which the lens to be processed 110 is bonded and fixed) 101a of the lens lock cap 101. The lens to be processed 110 is fixed to the lens lock cap 101 by affixing the lens to be processed 110 to the surface 105a opposite to the surface of the double-sided adhesive tape 105 that is bonded to the surface to be adhered 101a.
Next, the lens lock cap 101 to which the processing target lens 110 is fixed is fixed to the upper lens processing shaft 102.

Next, the lens to be processed 110 is sandwiched and fixed between the lens lock cap 101 and the lower lens processing shaft 103.
In this state, the grindstone 104 is rotated and moved along the outer periphery of the lens 110 to be processed, and the outer periphery of the lens 110 to be processed is ground by the grindstone 104 so as to have a predetermined outer shape.
Note that such lashing processing may be performed not at a retail store but at a manufacturer's factory.

 In recent years, a spectacle lens in which an oil-repellent coat film is formed on the surface of a lens substrate has been sold. This spectacle lens is popular with spectacle users because its surface is difficult to get dirty. However, since this spectacle lens has a low surface frictional resistance, if the ball processing is performed by the conventional processing method as described above, the processing axis and the center of the lens to be processed are shifted during processing. Produce. There has been a problem in that the outer shape of the spectacle lens cannot be accurately performed due to such an axis deviation.

 As a method for solving such a problem, for example, (1) a fine particle layer in which at least one of metal oxide fine particles and fluoride fine particles is dispersed is formed on the surface of the oil-repellent coat film, and the fine particles are further formed. A method of forming a resin layer made of an organic compound on the layer, or (2) a resin layer made of an organic compound in which at least one of metal oxide fine particles and fluoride fine particles is dispersed on the surface of the oil-repellent coat film. A forming method is known (for example, see Patent Document 1).

International Publication No. 2006/093113

However, the first method described in Patent Document 1, that is, a fine particle layer in which at least one of metal oxide fine particles and fluoride fine particles is dispersed is formed on the surface of the oil-repellent coat film, The method of forming a resin layer made of an organic compound on the fine particle layer has a problem that a two-step process is required for forming the protective film.
Further, the second method described in Patent Document 1, that is, a resin layer made of an organic compound in which at least one of metal oxide fine particles and fluoride fine particles is dispersed is formed on the surface of the oil-repellent coat film. In the method, although the protective film formation process is a single step, there is a problem that the retention of the lens lock cap after the balling process is not sufficient or the stability of the protective film coating liquid is not sufficient.

 The present invention has been made in view of the above circumstances, and provides a spectacle lens that can be glazed by a holding method similar to that of a conventional spectacle lens even when an oil-repellent coat film is provided. The task is to do.

A spectacle lens of the present invention includes a lens base material, an oil repellent coating film formed on at least one surface of the lens base material, and a protective film formed on the oil repellent coating film. The protective film comprises (a) a resin made of an organic compound, (b) inorganic oxide fine particles, and (c) a general formula: R ¹ _a R ² _b Si (OR ³ ) _{4− It} is formed by a coating liquid containing an organosilicon compound represented by _{(a + b)} or a hydrolyzate thereof as an active ingredient, and the composition ratio of the resin composed of the (a) organic compound and the inorganic oxide fine particles (b) Is 85/15 to 40/60 (mass ratio), and (c) an organosilicon compound represented by the general formula: R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} or its hydrolysis The content of the product is the coating liquid Characterized in that it is a 1% to 40% by weight of the total solids contained.
(In the above general formula, R ¹ is a functional group or an organic group having 4 to 14 carbon atoms having an unsaturated double bond, and R ² is a hydrocarbon group or halogenated hydrocarbon having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a and b are each 0 or 1, and a + b is 0, 1 or 2.)

The eyeglass lens of the present invention, the oil-repellent coating film may be formed on the lens substrate at least one surface which is formed on the antireflection film.

 In the eyeglass lens of the present invention, the resin composed of the organic compound includes acrylic resin, urethane resin, urea resin, melamine resin, polyester resin, polyvinyl acetal resin, cellulose polymer, polyalkylene oxide polymer, polyvinyl acetate heavy resin. It is preferable that it consists of 1 type or more of the resin which has a coalescence and a styrene / methacrylic ester copolymer as a main component.

 In the eyeglass lens of the present invention, the resin composed of the organic compound is preferably composed of a resin mainly composed of a polyvinyl acetal resin.

 In the eyeglass lens of the present invention, the inorganic oxide fine particles preferably have an average particle size of 100 nm or less.

 In the spectacle lens of the present invention, the inorganic oxide fine particles may be any one of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, and Nb. Or it is preferable that it is complex oxide comprised from 2 or more types of these oxides.

In the eyeglass lens of the present invention, the inorganic oxide fine particles are preferably SiO ₂ or a complex oxide composed of two or more kinds containing SiO ₂ .

 According to the present invention, the lens for eyeglasses provided with the oil-repellent coating film can be subjected to a lashing process by the same holding method as before.

It is a schematic sectional drawing which shows 1st embodiment of the lens for spectacles which concerns on this invention. It is the schematic which shows the lash processing method in 1st embodiment of the lens for spectacles which concerns on this invention. It is a schematic sectional drawing which shows 2nd embodiment of the lens for spectacles which concerns on this invention. It is the schematic which shows the measuring method of the axial deviation | shift amount of the lens after a lashing process. It is the schematic which shows the glazing processing method of the general spectacles lens.

Hereinafter, embodiments of a spectacle lens according to the present invention will be described with reference to the drawings.
The following embodiments are specifically described for better understanding of the gist of the invention, and do not limit the present invention unless otherwise specified.
In addition, in the drawings used in the following description, in order to make the features of the present invention easier to understand, for the sake of convenience, a part that is a main part may be shown in an enlarged manner. Not always.

(1) First Embodiment FIG. 1 is a schematic cross-sectional view showing a first embodiment of a spectacle lens according to the present invention.
The spectacle lens 10 includes a lens base 11, oil-repellent coat films 12 and 13 formed on both surfaces (one surface 11 a and the other surface 11 b) of the lens base 11, and one oil-repellent coat film 12. The protective film 14 is formed roughly from the protective film 14 formed thereon.
That is, the protective film 14 is provided on the surface 12a of the oil repellent coating film 12 opposite to the surface in contact with the lens substrate 11.

The lens base material 11 has a predetermined refractive index and power adjusted according to the user of the spectacles, and determines the optical characteristics of the spectacle lens 10.
The material constituting the lens substrate 11 is not particularly limited, and examples thereof include known materials used for spectacle lenses.

 The material constituting the oil-repellent coating films 12 and 13 is not particularly limited, and examples thereof include known materials used for spectacle lenses.

The protective film 14 is formed of a coating solution containing the following components (a), (b), and (c) as active components.
(A) Resin comprising an organic compound (b) Inorganic oxide fine particles (c) Organosilicon compound represented by the general formula: R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (hereinafter “organic” Or a hydrolyzate thereof (in the general formula, R ¹ is a functional group or an organic group having 4 to 14 carbon atoms having an unsaturated double bond, and R ² has 1 to 6 carbon atoms). A hydrocarbon group or a halogenated hydrocarbon group, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a and b are each 0 or 1, and a + b is 0, 1 or 2)

The resin composed of the organic compound is not particularly limited as long as the inorganic oxide fine particles can be dispersed and the transparency of the protective film 14 can be adjusted within a predetermined range. A thermoplastic resin or a thermosetting resin is used.
Examples of the resin composed of such an organic compound include acrylic resin, urethane resin, urea resin, melamine resin, polyester resin, polyvinyl acetal resin, cellulose polymer, polyalkylene oxide polymer, polyvinyl acetate polymer, styrene. / What consists of 1 or more types of resin which has a methacrylic acid ester copolymer as a main component is mentioned.

 Among these resins, a thermoplastic resin is used because it is not necessary to react in order to cure the coating solution after applying the coating solution on the lens substrate 11 (oil repellent coating film 12). Is preferred. Further, among thermoplastic resins, resins which are mainly composed of polyvinyl acetal resin, cellulose polymer, polyalkylene oxide polymer, etc., which are inexpensive and soluble in an alcohol solvent having a relatively high drying rate are particularly preferable. . One kind of these resins may be used alone, or two or more kinds of resins may be mixed and used.

As the inorganic oxide fine particles, those having an average particle diameter of 100 nm or less are preferably used.
When the average particle diameter of the inorganic oxide fine particles exceeds 100 nm, the transparency of the protective film 14 is lowered.

As the inorganic oxide fine particles, for example, any one of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, and Nb, or oxidation thereof Examples include composite oxides composed of two or more kinds of products.
Among these inorganic oxide fine particles, inexpensive and, since it is commercially available as an aqueous dispersion sol or various organic solvent dispersion sol, SiO _2, or the composite oxide composed of two or more kinds containing SiO ₂ Things are preferred. One kind of these inorganic oxide fine particles may be used alone, or two or more kinds of inorganic oxide part particles may be mixed and used.

The composition ratio of the resin composed of the organic compound and the inorganic oxide fine particles (resin composed of the organic compound / inorganic oxide fine particles) is 85/15 to 40/60 (mass ratio), and 70/30 to 40/60. (Mass ratio) is preferable.
When the composition ratio (mass ratio) of the inorganic oxide fine particles is less than 15, the amount of misalignment becomes large during the balling process of the spectacle lens 10 using a balling machine, and the oil-repellent coating film 12; When cutting water enters between the protective film 14 and the lens lock cap of the ball grinder is easily removed, it becomes impossible to cope with the case where secondary processing is necessary. On the other hand, when the composition ratio (mass ratio) of the inorganic oxide fine particles exceeds 60, the protective film 14 becomes brittle, and after the protective film 14 is formed on the oil-repellent coating film 12, the protective film 14 may be naturally peeled off. is there.

 The organosilicon compound or a hydrolyzate thereof is not necessarily essential in terms of preventing axial misalignment of the eyeglass lens 10 during the balling process, but only a resin composed of an organic compound and inorganic oxide fine particles are combined. In some cases, the stability of the coating liquid for forming the protective film may cause a problem. In particular, when the ratio of the inorganic oxide fine particles is increased, the viscosity of the coating liquid is likely to increase with time, and the usable period is shortened. Therefore, by adding an organosilicon compound, especially its hydrolyzate, to the mixture of the organic compound resin and the inorganic oxide fine particles, the viscosity of the coating liquid is stabilized and the usable period of the coating liquid is extended. be able to.

 Specific examples of organosilicon compounds include alkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane, alkylalkoxysilane compounds such as methyltrimethoxysilane and ethyltrimethoxysilane, and functional groups such as epoxy groups and methacryl groups. Examples thereof include a silane coupling agent having a group. One of these organosilicon compounds may be used alone, or two or more of the organosilicon compounds may be mixed and used.

Content of an organosilicon compound or its hydrolyzate is 1 mass%-40 mass% of the total solid content contained in the coating liquid for protective film formation, and it is preferable that it is 3 mass%-20 mass%.
When the content of the organosilicon compound or the hydrolyzate thereof is less than 1% by mass, the viscosity of the coating liquid is not sufficiently stabilized. On the other hand, when the content of the organosilicon compound or the hydrolyzate thereof exceeds 40% by mass, the content of the resin composed of the organic compound is relatively decreased, the viscosity of the coating liquid is excessively lowered, and the oil-repellent coating film 12 On top, it becomes difficult to apply the coating solution.

As the solvent used for the coating liquid for forming the protective film, a solvent capable of dissolving the resin composed of the organic compound and stably dispersing the inorganic oxide fine particles is used.
Examples of such a solvent include alcohols, ketones, ethers, esters and the like. Among these solvents, lower alcohols such as methanol and ethanol are preferable because they are relatively inexpensive and have a relatively high drying rate after the coating liquid is applied onto the oil-repellent coating film 12.
However, it is more preferable to use a solvent having a high boiling point in combination with only these lower alcohols because the protective film 14 formed of the coating liquid is likely to be clouded due to the influence of humidity. Examples of the high boiling point solvent include alcohols having 3 or more carbon atoms such as propanol and butanol, ethylene glycol monoalkyl ethers (cellosolves), propylene glycol monoalkyl ethers, and the like.

 Moreover, it is preferable that the coating liquid for protective film formation contains a small amount of surfactant. As the surfactant, a commercially available silicon-based surfactant or fluorine-based surfactant is used. When the coating liquid contains a surfactant, the leveling performance of the coating film formed on the oil-repellent coating film 12 is improved by the coating liquid.

 Moreover, it is preferable that the coating liquid for protective film formation contains a small amount of water. By containing water, the viscosity of the coating liquid is lowered, and the leveling effect by the surfactant can be sufficiently exhibited.

Moreover, in order to color the protective film 14, the coating liquid for protective film formation may contain dye and a pigment.
Furthermore, in order to reduce the off-flavor generated during the balling process, the coating liquid for forming the protective film may contain a deodorant, a fragrance, or a microencapsulated product thereof.

The viscosity of the coating liquid for forming the protective film is preferably 40 cps to 200 cps, and more preferably 50 cps to 100 cps. In addition, the viscosity of the coating liquid in this embodiment is a value measured at 25 ° C. using an E-type viscometer.
If the viscosity of the coating liquid is less than 40 cps, the coating liquid is repelled on the surface of the oil-repellent coating film 12 provided on the lens substrate 11 when spin coating is performed, so that a coating film cannot be formed, or the oil-repellent property In order to form a coating film on the surface of the coating film 12, a large amount of coating liquid is required. On the other hand, when the viscosity of the coating liquid exceeds 200 cps, the appearance of the obtained protective film 14 is deteriorated.

As a method for applying the coating liquid for forming the protective film on the oil-repellent coating film 12 provided on the lens substrate 11, a dipping method or a spin coating method is used.
In the spin coating method, the protective film 14 is formed on the oil-repellent coating film 12 provided on the lens substrate 11 using a relatively small apparatus such as a spin coater. In general, the protective film 14 is formed on the convex surface of the lens substrate 11 (the surface on which the lens lock cap is attached).

 In this embodiment, the oil-repellent coat films 12 and 13 are formed on both surfaces (one surface 11 a and the other surface 11 b) of the lens substrate 11, and the protective film 14 is formed on the one oil-repellent coat film 12. Although the spectacle lens 10 formed with is illustrated, the present invention is not limited to this. In the present invention, protective films may be formed on the oil-repellent coat films on both surfaces of the lens substrate.

Next, with reference to FIG. 2, a method of processing the lens for the spectacle lens 10 of the present embodiment will be described.
In the present embodiment, a lashing machine 20 similar to the conventional one is used.
First, the eyeglass lens 10 which is a lens to be processed is fixed to the lens lock cap 21 with the double-sided adhesive tape 25.
More specifically, a double-sided adhesive tape 25 is affixed in advance to the adherend surface (surface to which the spectacle lens 10 is bonded and fixed) 21a of the lens lock cap 21. The spectacle lens 10 is fixed to the lens lock cap 21 by affixing the convex surface of the spectacle lens 10 to the surface 25a opposite to the surface bonded to the adherend surface 21a of the double-sided adhesive tape 25. .
Next, the lens lock cap 21 to which the spectacle lens 10 is fixed is fixed to the upper lens processing shaft 22.

Next, the spectacle lens 10 is sandwiched and fixed between the lens lock cap 21 and the lower lens processing shaft 23.
In this state, the grindstone 24 is rotated and moved along the outer circumference of the spectacle lens 10, and the outer circumference of the spectacle lens 10 is ground by the grindstone 24 so as to have a predetermined outer shape.

 According to the eyeglass lens 10, the protective film 14 is almost in close contact with the oil-repellent coating film 12 even after the balling process by the ball driving machine 20, and the holding state of the lens lock cap 21 is also good. In other words, the eyeglass lens 10 can suppress the amount of axial deviation after the stabbing process by the stabbing machine 20 and can accurately perform the outer shape process.

(2) Second Embodiment FIG. 3 is a schematic cross-sectional view showing a second embodiment of the spectacle lens according to the present invention.
The spectacle lens 30 includes a lens base 31, antireflection films 32 and 33 formed on both surfaces (one surface 31 a and the other surface 31 b) of the lens base 31, and the antireflection films 32 and 33. The oil-repellent coat films 34 and 35 formed and a protective film 36 formed on one of the oil-repellent coat films 34 are roughly constituted.
That is, the antireflection film 32 is provided on one surface 31 a of the lens substrate 31, and the antireflection film 33 is provided on the other surface 31 b of the lens substrate 31. The oil repellent coating film 34 is provided on the surface 32 a opposite to the surface of the antireflection film 32 that contacts the lens base material 31, and the oil repellent coating film 35 is provided on the lens base material 31 of the antireflection film 33. Is provided on the surface 33a opposite to the surface in contact with. Further, the protective film 36 is provided on the surface 34 a opposite to the surface of the oil repellent coating film 34 that contacts the antireflection film 32.

As the lens base material 31, the thing similar to the lens base material 11 of the above-mentioned first embodiment is used.
The material constituting the antireflection films 32 and 33 is not particularly limited, and examples thereof include known materials used for spectacle lenses.

As materials constituting the oil-repellent coat films 34 and 35, the same materials as those constituting the oil-repellent coat films 12 and 13 of the first embodiment described above are used.
As a material constituting the protective film 36, the same material as that constituting the protective film 14 of the first embodiment described above is used.

 In the present embodiment, the spectacle lens 30 in which the antireflection films 32 and 33 are formed on both surfaces (the one surface 31a and the other surface 31b) of the lens base material 31 is illustrated. It is not limited. In the present invention, an antireflection film may be formed on one surface of the lens substrate. In the present embodiment, the oil-repellent coating films 34 and 35 are formed on both surfaces (one surface 31 a and the other surface 31 b) of the lens substrate 31, and the protective film is formed on the one oil-repellent coating film 34. Although the spectacle lens 30 formed with 36 is illustrated, the present invention is not limited to this. In the present invention, protective films may be formed on the oil-repellent coat films on both surfaces of the lens substrate.

 The eyeglass lens 30 can be subjected to lashing in the same manner as in the first embodiment described above.

 According to the spectacle lens 30, the protective film 36 is almost in close contact with the oil-repellent coating film 34 even after the balling process by the balling machine, and the holding state of the lens lock cap is also good. That is, the spectacle lens 30 can suppress the amount of axial deviation after the stabbing process by the stabbing machine, and can accurately perform the outer shape process.

 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.

[Preparation of coating liquid A]
To 1.6 parts by mass of methyltrimethoxysilane (trade name: KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), 5.0 parts by mass of a 0.0002N hydrochloric acid aqueous solution was added and stirred for 1 hour for hydrolysis.
Subsequently, 21.3 parts by mass of methanol silica sol (trade name, solid content: 30% by mass, SiO ₂ particle size: 10 nm to 20 nm, manufactured by Nissan Chemical Industries, Ltd.) was added to the hydrolyzate, and the mixture was further stirred for 1 hour.
Next, a polyvinyl butyral resin (trade name: ESREC BM-5, 34.0 parts by mass of methanol, 20.0 parts by mass of 1-butanol, and 10.0 parts by mass of 1-methoxy-2-propanol was added to the mixed solution. 8.0 parts by mass of Sekisui Chemical Co., Ltd.) was dissolved.
Next, the whole solution of hydrolyzed methyltrimethoxysilane and methanol silica sol was added to the mixed solution and stirred. Further, a silicon-based surfactant (trade name: L-7001, manufactured by Toray Dow Corning) The coating liquid A was prepared by adding 0.1 parts by mass and stirring overnight.
The viscosity of the resulting coating liquid A was measured with an E-type viscometer (trade name: VISCONIC ELD viscometer, manufactured by Toki Sangyo Co., Ltd.) and found to be 92 cps (25 ° C.).
Content of the total solid content contained in the coating liquid A excluding the surfactant was 16.0% by mass. The content of the resin comprising the organic compound is 50% by mass of the total solids contained in the coating liquid A, the content of the inorganic oxide fine particles is 40% by mass of the total solids contained in the coating liquid A, and the silane compound. The content of was 10% by mass of the total solid content in the coating liquid A. Furthermore, the composition ratio of the resin composed of the organic compound and the inorganic oxide fine particles (resin composed of the organic compound / inorganic oxide fine particles) was about 56/44.

[Preparation of coating solution B]
To 1.7 parts by mass of methyltrimethoxysilane (trade name: KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), 5.0 parts by mass of a 0.0002N hydrochloric acid aqueous solution was added and stirred for 1 hour for hydrolysis.
Next, 25.3 parts by mass of methanol silica sol (trade name, solid content 30% by mass, SiO ₂ particle diameter 10 nm to 20 nm, manufactured by Nissan Chemical Industries, Ltd.) was added to the hydrolyzate, and the mixture was further stirred for 1 hour.
Next, to a mixed solution consisting of 30.2 parts by mass of methanol, 20.0 parts by mass of 1-butanol, and 10.0 parts by mass of 1-methoxy-2-propanol, polyvinyl butyral resin (trade name: ESREC BM-5, 7.6 parts by mass of Sekisui Chemical Co., Ltd.) was dissolved.
Next, the whole solution of hydrolyzed methyltrimethoxysilane and methanol silica sol was added to the mixed solution and stirred. Further, a fluorosurfactant (trade name: FC-4432, manufactured by Sumitomo 3M). 2 parts by mass was added and stirred overnight to prepare coating solution B.
The viscosity of the resulting coating liquid B was measured with an E-type viscometer (trade name: VISCONIC ELD viscometer, manufactured by Toki Sangyo Co., Ltd.) and found to be 75 cps (25 ° C.).
The total solid content in the coating liquid B excluding the surfactant was 17.0% by mass. The content of the resin comprising the organic compound is 45% by mass of the total solid contained in the coating liquid B, the content of the inorganic oxide fine particles is 45% by mass of the total solid contained in the coating liquid B, and the silane compound. The content of was 10% by mass of the total solid content in the coating liquid B. Furthermore, the composition ratio of the resin composed of the organic compound and the inorganic oxide fine particles (resin composed of the organic compound / inorganic oxide fine particles) was 50/50.

[Preparation of coating solution C]
To 1.85 parts by mass of methyltrimethoxysilane (trade name: KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.), 5.0 parts by mass of a 0.0002N hydrochloric acid aqueous solution was added and stirred for 1 hour for hydrolysis.
Next, 23.0 parts by mass of MA-ST-L (trade name, manufactured by Nissan Chemical Industries, solid content: 40% by mass, SiO ₂ particle diameter: 40 nm to 50 nm) was added to the hydrolyzate, and the mixture was further stirred for 1 hour. did.
Subsequently, polyvinyl butyral resin (trade name: ESREC BM-5, 13.5 parts by weight of methanol, 19.0 parts by weight of 1-butanol, and 10.0 parts by weight of 1-methoxy-2-propanol was added to a mixed solution. 7.4 parts by mass of Sekisui Chemical Co., Ltd.) was dissolved.
Next, the whole solution of hydrolyzed methyltrimethoxysilane and MA-ST-L was added to the mixed solution and stirred, and further, a silicon surfactant (trade name: L-7001, Toray Dow Corning). 0.2 parts by mass) was added and stirred overnight to prepare coating solution C.
The viscosity of the obtained coating liquid C was 70 cps (25 ° C.) when measured with an E-type viscometer (trade name: VISCONIC ELD viscometer, manufactured by Toki Sangyo Co., Ltd.).
The total solid content in the coating liquid C excluding the surfactant was 18.5% by mass. The content of the resin composed of the organic compound is 40% by mass of the total solids contained in the coating liquid C, the content of the inorganic oxide fine particles is 50% by mass of the total solids contained in the coating liquid C, and the silane compound. The content of was 10% by mass of the total solid content in the coating liquid C. Furthermore, the composition ratio of the resin composed of the organic compound and the inorganic oxide fine particles (resin composed of the organic compound / inorganic oxide fine particles) was about 44/56.

[Preparation of coating solution D]
In a mixed solution composed of 57.4 parts by mass of methanol and 30 parts by mass of 1-butanol, 10 parts by mass of a polyvinyl butyral resin (trade name: ESREC BM-5, manufactured by Sekisui Chemical Co., Ltd.) was dissolved.
Furthermore, 2.5 parts by mass of pure water and 0.1 parts by mass of a silicon-based surfactant (trade name: L-7001, manufactured by Toray Dow Corning) were added to the mixed solution and stirred overnight. A coating solution D was prepared.
It was 185 cps (25 degreeC) when the viscosity of the obtained coating liquid D was measured with the E-type viscosity meter (Brand name: VISCONIC ELD viscometer, the Toki Sangyo company make).
The total solid content in the coating liquid D excluding the surfactant was 10.0% by mass. Further, the total solid content contained in the coating liquid D was a resin composed of an organic compound.

[Preparation of coating solution E]
In a mixed solution composed of 30.1 parts by mass of methanol and 30.0 parts by mass of 1-butanol, 8.0 parts by mass of a polyvinyl butyral resin (trade name: ESREC BM-5, manufactured by Sekisui Chemical Co., Ltd.) was dissolved.
Subsequently, 26.7 parts by mass of methanol silica sol (trade name, solid content: 30% by mass, SiO ₂ particle diameter: 10 nm to 20 nm, manufactured by Nissan Chemical Industries, Ltd.) was added to the mixed solution and stirred.
Furthermore, 5.0 parts by mass of pure water and 0.2 parts by mass of a silicon-based surfactant (trade name: L-7001, manufactured by Toray Dow Corning) were added to the mixed solution and stirred overnight. A coating solution E was prepared.
The viscosity of the resulting coating liquid E was 82 cps (25 ° C.) when measured with an E-type viscometer (trade name: VISCONIC ELD viscometer, manufactured by Toki Sangyo Co., Ltd.).
The total solid content in the coating liquid E excluding the surfactant was 16.0% by mass. The content of the resin composed of the organic compound was 50% by mass of the total solids contained in the coating liquid E, and the content of the inorganic oxide fine particles was 50% by mass of the total solids contained in the coating liquid E. .

[Preparation of coating solution F]
In a mixed solution composed of 27.1 parts by mass of methanol and 15.0 parts by mass of 1-butanol, 6.0 parts by mass of a polyvinyl butyral resin (trade name: ESREC BM-5, manufactured by Sekisui Chemical Co., Ltd.) was dissolved.
Next, 46.7 parts by mass of methanol silica sol (trade name, solid content: 30% by mass, SiO ₂ particle diameter: 10 nm to 20 nm, manufactured by Nissan Chemical Industries, Ltd.) was added to the solution and well stirred.
Next, 5.0 parts by mass of pure water and 0.2 parts by mass of a silicon-based surfactant (trade name: L-7001, manufactured by Toray Dow Corning Co., Ltd.) are added and stirred overnight. Prepared.
The viscosity of the obtained coating liquid F was measured with an E-type viscometer (trade name: VISCONIC ELD viscometer, manufactured by Toki Sangyo Co., Ltd.) and found to be 44 cps (25 ° C.).
Content of the total solid content contained in the coating liquid F excluding the surfactant was 20.0% by mass. Further, the content of the resin composed of the organic compound was 30% by mass of the total solids contained in the coating liquid F, and the content of the inorganic oxide fine particles was 70% by mass of the total solids contained in the coating liquid F. .

[Evaluation of coating solution]
Sample lenses to be described later are prepared using the above coating liquids A to F, and the coating liquids A to F are stored at room temperature for two months, and then again an E type viscometer (trade name: VISCONIC ELD viscometer, Toki The viscosity of the coating liquids A to F was measured by Sangyo Co., Ltd. Increase in viscosity after storing coating liquids A to F for 2 months from viscosity immediately after preparing coating liquids A to F (initial viscosity) and viscosity after storing coating liquids A to F for 2 months The rate was calculated.
Concerning coating liquids A to F, content of total solids, composition ratio of resin and inorganic oxide fine particles composed of organic compounds, content of silane compound in total solids, initial viscosity, increase in viscosity after storage for 2 months The rates are shown in Table 1.

"Example 1"
[Production of sample lens for measuring film thickness and sample lens for measuring luminous transmittance]
A plastic lens for spectacles (with no surface treatment) having a refractive index of 1.60, a power of -2.00 diopter, and an outer diameter of 75 mm was placed on a spin coater with the convex surface facing upward.
Next, while rotating the plastic lens for spectacles at 500 RPM with a spin coater, about 3 mL of coating solution A was applied to the central portion of the convex surface and rotated as it was for 5 seconds.
Next, the plastic lens for spectacles was rotated at 1500 RPM for 10 seconds to form a coating film made of the coating liquid A on the convex surface of the plastic lens for spectacles.
Then, the coating film was dried for 1 day, and the plastic lens for spectacles in which the protective film was formed in the convex surface was obtained.

[Preparation of sample lens for lashing]
Two types of lenses having different refractive indexes were prepared as sample lenses for lashing.
(1) Lens with an oil-repellent coating film having a refractive index of 1.74, S degree -6.00 diopter / C degree -2.00 diopter, and an outer diameter of 80 mm (trade name: VIDA5 AS ECC, Nikon Essilor) (Hereinafter referred to as “sample lens 1”).
(2) Polycarbonate lens having an index of refraction of 1.59, an S degree of −5.50 diopter, an outer diameter of 70 mm, and an antireflection film made of SiO _{2 on} the outermost layer (an untreated oil repellent coating film lens) ) Was prepared. This polycarbonate lens was placed in a fluorinated liquid (trade name: Novec HFE-7200, manufactured by Sumitomo 3M) solution containing 0.1% by mass of an oil repellent (trade name: KY-130, manufactured by Shin-Etsu Chemical Co., Ltd.) for 10 seconds. Soaked. Thereafter, the polycarbonate lens was pulled up from the fluorine-based liquid at a speed of 8 mm / second to obtain a polycarbonate lens on which a coating film was formed. Thereafter, the polycarbonate lens was heated at 50 ° C. for 1 hour to stabilize the coating film to obtain a polycarbonate lens with an oil-repellent coating film (hereinafter referred to as “sample lens 2”).

Each of the two types of lenses (sample lens 1 and sample lens 2) was placed on a spin coater with the convex surface facing upward.
Next, while rotating the lens at 500 RPM with a spin coater, about 3 mL of coating solution A was applied to the central portion of the convex surface and rotated as it was for 5 seconds.
Subsequently, the lens was rotated at 1500 RPM for 10 seconds to form a coating film made of the coating liquid A on the convex surface of the plastic lens for spectacles.
Thereafter, the coating film was dried for 1 day to obtain lenses (sample lens 1, sample lens 2) having a protective film formed on the convex surface.

[Measurement of protective film thickness]
The film thickness of the protective film of the above-mentioned film thickness measurement sample lens was measured with a lens reflection measuring instrument (trade name: USPM-RU, manufactured by Olympus Corporation).

[Visibility transmittance measurement]
The luminous transmittance of the sample lens for measuring the luminous transmittance was measured with a luminous transmittance meter (trade name: STS-3, manufactured by Fuji Photoelectric Industry Co., Ltd.).

[Evaluation of threading processability]
On the convex surface of the lens (sample lens 1, sample lens 2) on which the protective film was formed, three points on a straight line α including a point passing through the optical center were marked by a lens meter.
Next, a straight line α passing through three points marked on the convex surface when viewed from the concave surface side and a straight line β passing through the optical center and perpendicular to the straight line α were drawn on the concave surfaces of these lenses with a cutter knife.
Next, after the sample lens 1 is placed on a lens blocker (manufactured by NIDEK) and the position of the marking line is adjusted, a double-sided tape (trade name: LEAPIII, Sumitomo) is attached to the optical center of the sample lens 1 on the convex surface side. The lens lock cap (minimum size) of the lashing machine was attached by 3M). Next, after the lens lock cap with the sample lens 1 attached is fitted into one lens processing shaft of the ball grinder, the sample lens 1 is sandwiched and fixed between the lens lock cap and the other processing shaft. Then, after setting the amount of eccentricity on the lashing machine side, lashing was performed.
In addition, after the sample lens 2 is placed on a lens blocker (manufactured by Nidec Co., Ltd.) and the position of the marking line is adjusted, on the convex surface side of the sample lens 2, the center of the frame (position shifted from the optical center by an eccentric amount) Then, a lens lock cap (wide size) of a lashing machine was attached with a double-sided tape (trade name: LEAPIII, manufactured by Sumitomo 3M). Next, after fitting the lens lock cap with the sample lens 2 attached to one lens processing shaft of the ball grinder, the sample lens 2 is sandwiched and fixed between the lens lock cap and the other processing shaft. Then, the lashing process was performed on the lashing machine side with the amount of eccentricity being zero.

In addition, the following was used as the balling machine.
(1) Ball milling machine LE9000 SX (trade name, normal load machine with one grindstone built in) manufactured by NIDEK, chuck pressure value: 60 kg
(2) Ball shape Nikon Kurashio, product number 9018 (octagonal approximate shape of width 48mm, top and bottom 30mm), processing eccentricity: horizontal direction 5mm, vertical direction 2mm
(3) Lens lock cap Nidec's smallest cap, Nidec's wide cap

As shown in FIG. 4, the amount of misalignment after the stabbing process is performed by fitting the lens (sample lens 1, sample lens 2) 40 that has been staked into the template 51, and using a profile projector (manufactured by Nikon Corporation). A straight line drawn on the concave surface of the lens 40 in advance (a straight line passing through three points on a straight line including a point marked on the convex surface of the lens 40 and passing through the optical center 41 as viewed from the concave surface side of the lens 40); Inspected by measuring the amount of deviation from the axis deviation measurement reference line 52 provided on the template 51.
The state of the protective film after crushing was visually evaluated. Further, the lens lock cap retention after the balling process was simply evaluated as to how much force was necessary to peel off the lens lock cap.

As a result of the above evaluation, it was confirmed that the sample lens of Example 1 had no practical problems with respect to the film thickness of the protective film, the luminous transmittance, and the balling processability.
In addition, the amount of misalignment of the sample lens 1 and the sample lens 2 after the balling process was 1 degree or less.
Further, even after the lens lens 1 and the sample lens 2 were balled, the protective film was almost in close contact with the surface of the lens, and the lens lock cap was held well.
Furthermore, the rate of increase in viscosity of the coating liquid A after storage for 2 months was 10% or less, and the stability of the coating liquid A was also good.
Table 2 shows the evaluation results of the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap retention after the tumbling process.

"Example 2"
A sample lens for measuring film thickness, a sample lens for measuring luminous transmittance, and a sample lens for lashing processing were produced in the same manner as in Example 1 except that the coating liquid B was used.
For these sample lenses, in the same manner as in Example 1, the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap after the tumbling process Retention was evaluated.
As a result, it was confirmed that the sample lens of Example 2 had no problem in practical use with respect to the film thickness of the protective film, the visibility transmittance, and the balling processability.
In addition, the amount of misalignment of the sample lens 1 and the sample lens 2 after the balling process was 1 degree or less.
Further, even after the lens lens 1 and the sample lens 2 were balled, the protective film was almost in close contact with the surface of the lens, and the lens lock cap was held well.
Furthermore, the rate of increase in viscosity of the coating liquid B after storage for 2 months was 10% or less, and the stability of the coating liquid B was also good.
Table 2 shows the evaluation results of the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap retention after the tumbling process.

"Example 3"
A sample lens for measuring film thickness, a sample lens for measuring luminous transmittance, and a sample lens for lashing processing were produced in the same manner as in Example 1 except that the coating liquid C was used.
For these sample lenses, in the same manner as in Example 1, the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap after the tumbling process Retention was evaluated.
As a result, it was confirmed that the sample lens of Example 3 had no problem in practical use with respect to the film thickness of the protective film, the visibility transmittance, and the balling processability.
In addition, the amount of misalignment of the sample lens 1 and the sample lens 2 after the balling process was 1 degree or less.
Further, even after the lens lens 1 and the sample lens 2 were balled, the protective film was almost in close contact with the surface of the lens, and the lens lock cap was held well.
Furthermore, the rate of increase in viscosity of the coating liquid C after storage for 2 months was 10% or less, and the stability of the coating liquid C was also good.
Table 2 shows the evaluation results of the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap retention after the tumbling process.

"Comparative Example 1"
Except that the coating liquid D was used, a sample lens for film thickness measurement, a sample lens for measurement of luminous transmittance, and a sample lens for lashing processing were produced in the same manner as in Example 1.
For these sample lenses, in the same manner as in Example 1, the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap after the tumbling process Retention was evaluated.
As a result, it was confirmed that the sample lens of Comparative Example 1 had no problem with respect to the thickness of the protective film and the luminous transmittance.
However, the amount of misalignment after the stabbing of the sample lens 1 was 3.4 degrees, and the amount of misalignment after the stabbing of the sample lens 2 was 17.2 degrees.
In addition, after the sample lens 1 and the sample lens 2 were balled, the protective film was peeled off and the lens lock cap was easily removed.
Table 2 shows the evaluation results of the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap retention after the tumbling process.

"Comparative Example 2"
A sample lens for measuring film thickness, a sample lens for measuring luminous transmittance, and a sample lens for lashing processing were produced in the same manner as in Example 1 except that the coating liquid E was used.
For these sample lenses, in the same manner as in Example 1, the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap after the tumbling process Retention was evaluated.
As a result, it was confirmed that the sample lens of Comparative Example 2 had no problem with respect to the film thickness of the protective film, the visibility transmittance, and the balling processability.
In addition, the amount of misalignment of the sample lens 1 and the sample lens 2 after the balling process was 1 degree or less.
Further, even after the lens lens 1 and the sample lens 2 were balled, the protective film was almost in close contact with the surface of the lens, and the lens lock cap was held well.
However, the rate of increase in viscosity of the coating liquid E after storage for 2 months was 100% or more, and there was a problem with the stability of the coating liquid E.
Table 2 shows the evaluation results of the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap retention after the tumbling process.

“Comparative Example 3”
Except that the coating liquid F was used, a sample lens for measuring film thickness, a sample lens for measuring visibility transmittance, and a sample lens for processing a ball were manufactured in the same manner as in Example 1.
For these sample lenses, in the same manner as in Example 1, the film thickness of the protective film, the visibility transmittance, the tumbling processability, the state of the protective film after the tumbling process, and the lens lock cap after the tumbling process Retention was evaluated.
As a result, it was confirmed that the sample lens of Comparative Example 3 had no problem with respect to the thickness of the protective film and the luminous transmittance.
However, when the coating liquid F was applied to the surfaces of the sample lens 1 and the sample lens 2 in order to produce a sample lens for lashing processing, the coating film began to peel off as the coating film dried, and after a few minutes, the coating film was fully coated. It peeled.
Further, the increase rate of the viscosity of the coating liquid F after 2 months storage was 200% or more, and there was a problem in the stability of the coating liquid F.

DESCRIPTION OF SYMBOLS 10 ... Lens for spectacles, 11 ... Lens base material, 12, 13 ... Oil-repellent coating film, 14 ... Protective film, 30 ... Lens for spectacles, 31 ... Lens base material, 32, 33 ... antireflection film, 34, 35 ... oil-repellent coat film, 36 ... protective film.

Claims (7)

A lens for eyeglasses comprising a lens substrate, an oil-repellent coat film formed on at least one surface side of the lens substrate, and a protective film formed on the oil-repellent coat film,
The protective film is represented by (a) a resin made of an organic compound, (b) inorganic oxide fine particles, and (c) a general formula: R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b).} Formed by a coating liquid containing an organosilicon compound or a hydrolyzate thereof as an active ingredient,
The composition ratio of the resin composed of the (a) organic compound and the inorganic oxide fine particles (b) is 85/15 to 40/60 (mass ratio),
The content of the organosilicon compound represented by (c) general formula: R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} or a hydrolyzate thereof is the total solid content contained in the coating liquid. A lens for spectacles characterized by being 1% by mass to 40% by mass.
(In the above general formula, R ¹ is a functional group or an organic group having 4 to 14 carbon atoms having an unsaturated double bond, and R ² is a hydrocarbon group or halogenated hydrocarbon having 1 to 6 carbon atoms. R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a and b are each 0 or 1, and a + b is 0, 1 or 2.) The oil-repellent coating film, ophthalmic lens according to claim 1, characterized in that it has been formed on the lens substrate at least one surface which is formed on the antireflection film.   Resins composed of the above organic compounds include acrylic resins, urethane resins, urea resins, melamine resins, polyester resins, polyvinyl acetal resins, cellulose polymers, polyalkylene oxide polymers, polyvinyl acetate polymers, and styrene / methacrylate esters. The spectacle lens according to claim 1, comprising at least one resin mainly composed of a polymer.   The spectacle lens according to claim 1, wherein the resin made of the organic compound is made of a resin mainly composed of a polyvinyl acetal resin.   The eyeglass lens according to claim 1, wherein the inorganic oxide fine particles have an average particle diameter of 100 nm or less.   The inorganic oxide fine particles may be any one of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, Ti, and Nb, or of these oxides. The eyeglass lens according to claim 1, wherein the eyeglass lens is a composite oxide composed of two or more kinds. The spectacle lens according to claim 1, wherein the inorganic oxide fine particles are SiO ₂ or a composite oxide composed of two or more kinds containing SiO ₂ .

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