KR100693656B1 - Stain-proofing spectacle lens and manufacturing method thereof - Google Patents

Abstract

In the spectacle lens in which an antifouling layer is formed on the surface of two or more silane compounds, at least one or more of which is a fluorine-containing silane compound, the dynamic friction of the lens surface formed by using each of the two or more silane compounds as a single component. The spectacle lens capable of reducing the slipperiness of the lens surface to such an extent that the coefficient can be jade-shaped without degrading the antifouling performance of the antifouling layer by making the maximum dynamic friction coefficient value be 1.4 times or more the minimum dynamic friction coefficient value, and It provides a manufacturing method.

Description

Anti-fouling spectacle lens and its manufacturing method {STAIN-PROOFING SPECTACLE LENS AND MANUFACTURING METHOD THEREOF}             

The present invention relates to an antifouling spectacle lens and a manufacturing method thereof, which can prevent the antifouling spectacle lens from slipping at the time of jade processing without increasing its antifouling performance and thereby increase processing accuracy.

The spectacle lens is usually formed with an anti-reflection film on its surface in order to suppress reflection of light and increase light transmittance. However, when used, contamination by fingerprints, sweat, cosmetics, etc. is easily noticeable. There is a problem that the contamination is not easily removed. Therefore, in order to wipe off dirt easily or to wipe off dirt easily, providing an antifouling layer on the surface of an anti-reflection film is performed. Regarding the surface treatment agent for providing the antifouling layer on the spectacle lens, there is a prior art document of Japanese Patent Laid-Open No. 1997-258003 as a method of forming the antifouling layer by surface treatment with a fluorine-containing silane compound.

However, the spectacle lens surface-treated with the fluorine-containing silane compound in Japanese Unexamined Patent Publication No. 1997-258003 has a significantly smaller coefficient of friction and a surface that slides too well compared to conventional surface treatment agents. Therefore, the following problem arises. In other words, so-called jade processing is performed in which a circular spectacle lens is ground and processed into a frame of a spectacle frame at a retail store. This jade processing grinds the spectacle lens rim into a grindstone while holding the spectacle lens with a frictional force such as a method of adsorbing and holding the optical center of the spectacle lens to the chuck of the jade processing machine or by inserting by pressing on both sides. The spectacle lens surface-treated with the fluorine-containing silane compound in Japanese Unexamined Patent Publication No. 1997-258003 at the time of the jade processing has good sliding of the surface of the lens held by the chuck. As a result, an axis shift occurs in which the lens center is shifted from the center of the chuck, and there is a problem in that the correct jade processing cannot be performed.

Therefore, the spectacle lens subjected to the antifouling processing with the fluorine-containing silane compound excellent in the antifouling effect is subjected to the jade processing while devising that no axial shift occurs in the production plant. However, in order to secure the retention of the spectacle lens, the spectacle lens that needs to be jade-processed at the retail store must be provided with a lower surface slippery due to the poor antifouling performance to ensure the retention of the spectacle lens. It is the present situation.

This invention is made | formed in view of the said situation, and an object of this invention is to provide the spectacle lens which can reduce the slipperiness | lubricacy of a lens surface to such an extent that a jade process can be carried out, without reducing the outstanding antifouling effect of an antifouling layer.

Summary of the Invention

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, by forming an antifouling layer by the 2 or more types of silane compound which at least 1 or more types were selected so that the dynamic friction coefficient of the lens surface after a process may differ, It has been found that the slidability of the lens surface can be reduced to the extent that the fluorine-containing silane compound can be subjected to jade processing without reducing the original antifouling effect.

In addition, since the antireflection film provided on the spectacle lens surface has a problem that the contamination is easy to be noticeable and the contamination does not easily fall out, the formation of an antifouling layer is effective.

Therefore, 1st invention provides the spectacle lens which forms an antifouling layer by the 2 or more types of silane compound which is at least 1 type or more is a fluorine-containing silane compound as described in Claim 1, The said 2 or more types of silane compound The kinetic coefficient of friction of the lens surface formed of each of the components as a single component provides an antifouling spectacle lens, characterized in that the maximum kinetic coefficient value is 1.4 times or more of the minimum kinetic coefficient value.

2nd invention is the antifouling spectacle lens of Claim 1 WHEREIN: The content rate of the silane compound from which the surface with the lowest dynamic friction coefficient is obtained among 2 or more types of said silane compounds is 30 to 99 weight% of the total amount of a silane compound, It is characterized by the above-mentioned. An antifouling spectacle lens is provided.

In the antifouling spectacle lens according to claim 1, in the two or more kinds of the above silane compounds, the coefficient of kinetic friction of the lens surface formed by using a silane compound as a single component, the surface having the lowest kinetic coefficient of friction, is 0.2 or less. An antifouling spectacle lens is provided.

The fourth invention provides an antifouling spectacle lens according to the first aspect of the invention, wherein at least one of the two or more silane compounds is represented by the following formula (1).

Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms; X is iodine or hydrogen; Y is hydrogen or lower alkyl group; Z is fluorine or trifluoromethyl group; R ¹ is hydrolyzed Possible groups; R ² is hydrogen or an inert monovalent organic group; a, b, c, d is an integer from 0 to 200; e is 0 or 1; m and n are integers from 0 to 2; p is from 1 to 10 Represents an integer.)

In the antifouling spectacle lens according to any one of the first to fourth inventions, the fifth aspect of the invention provides an antifouling spectacle lens having an antireflection film under the antifouling layer of the antifouling spectacle lens.

The sixth invention comprises the steps of forming an anti-reflection film on the surface of the lens substrate on which the hard coating film may be formed, and forming an antifouling layer by at least one silane compound on the anti-reflection film, wherein at least one or more fluorine-containing silane compounds are formed. Wherein the coefficient of kinetic friction of the surface of the lens formed by using each of the two or more silane compounds as a single component, wherein the highest coefficient of kinetic friction is 1.4 times or more of the lowest coefficient of kinetic friction, It provides a manufacturing method.

7th invention is a manufacturing method of the antifouling spectacle lens of 6th invention WHEREIN: The step of forming an antifouling layer by the 2 or more types of silane compound which is at least 1 or more types is a fluorine-containing silane compound on an anti-reflective film, The 2 or more types of said silane Provided is a method for producing an antifouling spectacle lens, which is coated with a compound on a surface of a lens.

In the eighth invention, in the method of manufacturing the antifouling spectacle lens of the sixth invention, the step of forming an antifouling layer by at least one silane compound of at least one or more fluorine-containing silane compounds is performed on the antireflection film. Provided is a method for producing an antifouling spectacle lens, characterized in that the compound is evaporated in a vacuum chamber to adhere to the lens surface.

1 is a manufacturing process chart of an antifouling spectacle lens.

2 is a side view showing an example of a chuck holding a lens of an jade processing machine.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of the antifouling spectacle lens of this invention and its manufacturing method is described, this invention is not limited to the following embodiment. The antifouling spectacle lens of the present invention is obtained by forming an antifouling layer with at least one silane compound of at least one or more fluorine-containing silane compounds, selected as described above, so that the coefficient of kinetic friction of the lens surface after treatment is different.

As the base material of the spectacle lens, either inorganic glass or plastic does not interfere. Examples of the plastic include diethylene glycol bisallylcarbonate (CR-39) resin, polyurethane resin, thiourethane resin, polycarbonate resin, acrylic resin and the like.

The antifouling layer may be provided directly on the glass lens in the case of a glass lens, but in general, an antireflection film is provided in the case of a glass lens, and a hard coating film and an antireflection film in the case of a plastic lens, and then an antifouling layer is provided. It is desirable to.

The hard coating film provides scratch resistance to the plastic lens, and in general, the adhesion of the anti-reflection film to the plastic lens is not good. Therefore, the hard coating film is interposed between the plastic lens and the anti-reflection film to improve the adhesion of the anti-reflection film to prevent peeling. Has

As a formation method of a hard coat film, the method of apply | coating the curable composition which can form a hard coat film to the surface of a plastic lens, and hardening a coating film is common. When a plastic lens is a thermoplastic resin, what hardens | cures with electromagnetic waves, such as an ultraviolet-ray, and ionizing radiation, such as an electron beam, is used rather than a thermosetting type. For example, the photocurable silicone composition which consists mainly of the organopolysiloxane which has a silicone compound which produces | generates a silanol group by ultraviolet irradiation, and a halogen atom or an amino group condensation-reacts with a silanol group, and the UK- of Mitsubishi Rayon Co., Ltd. product. the acrylic ultraviolet curable monomer composition, such as 6074, SiO _2, TiO _2, such as the inorganic fine particles having a particle diameter of 1 to 100nm, having a vinyl group, allyl group, acrylic group or methacrylic group, such as a polymerizable group and a hydrolyzable group such as a methoxy group in the The inorganic fine particle containing thermosetting composition etc. which were disperse | distributed in a silane compound and a silane coupling agent are illustrated.

As the coating method, a dipping method, a spin coating method, a spray method, a flow method, a doctor blading method, or the like can be adopted.

Moreover, in order to improve adhesiveness before forming a coating film, it is preferable to surface-treat a plastic lens surface by high voltage discharge, such as a corona discharge and a microwave.

The formed coating film can be cured with heat, ultraviolet rays, electron beams, or the like to obtain a hard coating film.

As a film thickness of a hard coat film, the range of about 0.05-30 micrometers is good. When too thin, basic performance may not be expressed, while when too thin, optical deformation may occur.

The antireflection film is composed of a single layer or a multilayer of an inorganic film and an organic film. Examples of the material of the inorganic coating include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , CeO ₂ , MgO, Y ₂ O ₃ , SnO _2, MgF _2, there may be mentioned an inorganic material such as WO _3, may be used in combinations of them alone or in combinations of two or more. In the case of plastic lenses, SiO ₂ , ZrO ₂ , TiO ₂ , Ta ₂ O ₅ , which can be vacuum deposited at low temperatures, are preferable. In addition, in the case where the multi-film configuration, the outermost layer is preferably in the range of SiO _2.

As the multilayer film of the inorganic film, the total optical film thickness of the ZrO ₂ layer and the SiO ₂ layer is λ / 4 from the lens side, the optical film thickness of the ZrO ₂ layer is λ / 4, and the optical film thickness of the SiO ₂ layer of the uppermost layer is The four layer structure which is (lambda) / 4 can be illustrated. Is the design wavelength, and usually 520 nm is used.

As the film forming method of the inorganic film, for example, a vacuum vapor deposition method, an ion plating method, a sputtering method, a CVD method, a method of precipitation by chemical reaction in a saturated solution, or the like can be adopted.

The material of the organic film is selected in consideration of the refractive index of the plastic lens or the hard coating film, and can be formed by a coating method having excellent mass productivity such as spin coating and dip coating in addition to vacuum deposition.

In the antifouling spectacle lens of the present invention, an antifouling layer is formed on the top surface of the spectacle lens, that is, on the above-mentioned hard coating film or vapor deposition film, and the antifouling layer is at least one selected such that the coefficient of kinetic friction of the lens surface after treatment is different. The above is obtained by forming with 2 or more types of silane compounds which are fluorine-containing silane compounds.

The antifouling layer formed by treating the spectacle lens surface with a fluorine-containing silane compound contains a fluorine group, exhibits excellent water and oil repelling performance, and also has an antifouling property inherent in the antifouling layer, that is, antifouling property, and its effect. It is continued to have a characteristic of easy decontamination. On the other hand, since the surface slipperiness is very large, when the spectacle lens is subjected to jade processing, when mounted on the chuck of the jade processing machine, the polishing pressure of the grindstone grinding against the friction holding force of the chuck is superior, and the spectacle lens during the jade processing Axial misalignment may occur. The chuck of the jade processing machine includes a method of adsorbing and holding the spectacle lens in a rubber adsorbing portion formed in a trumpet shape, or a method of holding the spectacle lens by pressing it from both sides of the spectacle lens.

In order to eliminate this axial shift, the surface slipperiness should be reduced so that the frictional holding force of the chuck of the jade processing machine can be made larger than the grinding pressure of the grinding wheel without affecting the original antifouling effect of the antifouling layer. A desired antifouling spectacle lens can be obtained by forming an antifouling layer with at least one or more silane compounds which are at least one or more fluorine-containing silane compounds selected as different treatment coefficients of the surface of the lens after treatment as a treatment agent to be used.

The two or more silane compounds which form an antifouling layer, at least 1 or more of which is a fluorine-containing silane compound are selected so that the kinetic friction coefficient of the lens surface formed using each of the said 2 or more types of silane compounds as a single component differs, Among them, it is preferable to use a fluorine-containing silane compound represented by the following formula (1) proposed in Japanese Unexamined Patent Publication No. 1997-258003 as one which can obtain a lens surface having a relatively low dynamic friction coefficient.

Formula 1

R _f in the formula (1) is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms, preferably CF _3- , C ₂ F _5- , and C ₃ F _7- . R ¹ is a hydrolyzable group, for example halogen, -OR ³ , -OCOR ³ , -OC (R ³ ) = C (R ⁴ ) ₂ , -ON = C (R ³ ) ₂ , -ON = CR ⁵ Is preferred. More preferably, it is chlorine, -OCH ₃ , -OC ₂ H ₅ . R ³ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ⁴ is hydrogen or a lower aliphatic hydrocarbon group, and R ⁵ is a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms. R ² is hydrogen or an inert monovalent organic group, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. a, b, c, d is an integer of 0-200, Preferably it is 1-50, e is 0 or 1. m and n are integers of 0-2, Preferably it is 0. p is an integer of 1 or more, Preferably it is an integer of 1-10. Moreover, molecular weight is 5 * 10 <^2> -1 * 10 <^5> , Preferably it is 5 * 10 <^2> -1 * 10 <^4> .

In addition, examples of the preferable structure of the fluorine-containing silane compound represented by the formula (1) include those represented by the following formula (2).

In the above formula, Y is hydrogen or lower alkyl group, R ¹ is a hydrolyzable group, q is an integer of 1 to 50, m is an integer of 0 to 2, r represents an integer of 1 to 10.

Moreover, as a brand name, "OPTOOL DSX" by Daikin Kogyo Co., Ltd. and KY-130 by Shin-Etsu Chemical Co., Ltd. are mentioned, for example.

Subsequently, examples of the silane compound capable of obtaining a lens surface having a relatively high kinematic coefficient of friction include 3,3,3-trifluoropropyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and heptadecafluoro. Rhodecyltrimethoxysilane, n-trifluoro (1,1,2,2-tetrahydro) propyl silazane, n-heptafluoro (1,1,2,2-tetrahydro) pentyl silazane, n Nonafluoro (1,1,2,2-tetrahydro) hexyl silazane, n-tridecafluoro (1,1,2,2-tetrahydro) octyl silazane, n-heptadecafluoro (1 , 1,2,2-tetrahydro) decyl silazane, octadecyltriethoxysilane, octadecyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, heptylmethyldichlorosilane, isobutyl trichloro Silane, octadecylmethyldimethoxysilane, and hexamethyldisilazane.

In addition, as a brand name, for example, Shin-Etsu Chemical Co., Ltd. KP-801, East LS-1090, East LS-4875, East LS-4480, East LS-2750, East LS-1640, East LS-410, East LS- 7150, GE Toshiba Silicone Co., Ltd. TSL-8257, TSL-8233, TSL-8185, TSL-8186, TSL-8183, and XC95-A9715.

Among these silane compounds, the value of the dynamic friction coefficient is preferably selected so as to be 1.4 times or more the value of the minimum dynamic friction coefficient, and more preferably 1.8 times or more. By doing in this way, the slipperiness | lubricacy of a lens surface can be reduced to the extent that jade process can be performed, without reducing the outstanding antifouling performance.

If the difference between the highest dynamic friction coefficient value and the lowest dynamic friction coefficient value is less than 1.4 times the ratio, excellent antifouling performance will be exhibited. However, since the surface slipperiness of the lens is large, it is not preferable because of the possibility of axial shift. .

Moreover, in order to ensure the outstanding antifouling performance, the content rate of the silane compound from which the surface with the lowest dynamic friction coefficient is obtained is 30-30 of the total amount of a silane compound among 2 or more types of silane compounds which at least 1 type is a fluorine-containing silane compound. It is preferable to set it as 99 weight%, and further more preferably set it as 50 to 98 weight%. If the content ratio of the silane compound in which the surface having the lowest kinetic coefficient is obtained is less than 30% by weight of the total amount of the silane compound, axial shift does not occur, but it is not preferable because the antifouling performance is lowered. On the contrary, if it exceeds 99% by weight of the total amount of the silane compounds, it is not preferable because there is a possibility of causing an axial shift.

It is preferable that it is 0.2 or less, and also it is more preferable that it is 0.15 or less as a dynamic friction coefficient value of the lens surface formed using as a single component the silane compound from which the surface with the lowest dynamic friction coefficient is obtained as a single component. If the coefficient of kinetic friction of the lens surface exceeds 0.2, it is not preferable because the antifouling performance is lowered.

Although it does not specifically limit about the formation method of an antifouling layer, As shown in the manufacturing process diagram of FIG. 1, at least 1 type has a process of forming an antifouling layer by the 2 or more types of silane compound which is a fluorine-containing silane compound.

In order to form an antifouling layer on the spectacle lens by coating using at least two kinds of the above silane compounds, at least one of which is a fluorine-containing silane compound, a method of dissolving in an organic solvent and applying to the spectacle lens surface can be employed. As the coating method, a dipping method, a spin coating method, a spray method, a flow method, a doctor blade method, roll coating coating, gravure coating coating, curtain flow coating and the like are used. As the organic solvent, perfluorohexane, perfluorocyclobutane, perfluorooctane, perfluorodecane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoro 4-methoxy butane, perfluoro-4-ethoxy butane, metaxylene hexafluoride, etc. are mentioned. Perfluoroether oils and chlorotrifluoroethylene oligomer oils can also be used. In addition, chlorofluorocarbon 225 (mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF) can be exemplified. One of these organic solvents may be used alone or in combination of two or more thereof.

The concentration at the time of dilution with an organic solvent has the preferable range of 0.03-1 wt%. If the concentration is too low, it is difficult to form an antifouling layer with a sufficient thickness, and a sufficient antifouling effect may not be obtained. On the other hand, if the concentration is too high, the antifouling layer may become too thick. The burden may increase.

Although the antifouling layer according to the present invention reacts at room temperature and is fixed to the lens surface, it is preferable to carry out a treatment to complete the reaction more completely by maintaining in a high temperature and high humidity environment as necessary.

Moreover, as a coating method of a silane compound, the vacuum vapor deposition method which evaporates the said silane compound in a vacuum chamber and adheres to the spectacle lens surface can also be employ | adopted. When the antireflection film is formed on the surface of the lens by vacuum deposition, it is preferable that the antifouling layer is continuously formed without exposing the lens to the atmosphere once. In the vacuum evaporation method, the raw material compound can be used in high concentration or without dilution solvent.

Although the film thickness of an antifouling layer is not specifically limited, It is 0.001-0.5 micrometer, Preferably it is 0.001-0.03 micrometer. If the thickness of the antifouling layer is too thin, the antifouling effect is insufficient, and if it is too thick, the surface is sticky, which is not preferable. In addition, when the antifouling layer is provided on the antireflection film surface, it is not preferable because the antireflection effect is lowered when the antifouling layer becomes thicker than 0.03 μm.

After forming an antifouling layer, the process which removes an unreacted molecule or the molecule | numerator which has not completed reaction from an antifouling layer may be performed. For example, it is possible by treating with the organic solvent which melt | dissolves the said silane compound, or by treating with alkaline aqueous solution.

As the organic solvent, an organic compound having a perfluoro group excellent in solubility of the silane compound and having 4 or more carbon atoms is preferable, for example, perfluorohexane, perfluorocyclobutane, perfluorooctane, perfluorodecane, Perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, perfluoro-4-methoxybutane, perfluoro-4-ethoxybutane, and metaxylene hexafluoride. . Perfluoroether oils and chlorotrifluoroethylene oligomer oils can also be used. In addition, chlorofluorocarbon 225 (mixture of CF ₃ CF ₂ CHCl ₂ and CClF ₂ CF ₂ CHClF) can be exemplified. One of these organic solvents may be used alone or in combination of two or more thereof.

As alkaline aqueous solution, it is preferable that it is pH 9 or more. Examples of the alkali source include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. In alkaline aqueous solution, surfactant can be added in order to raise a washing effect. There is no restriction | limiting in particular as surfactant added to alkaline solution, In addition to anionic surfactant, cationic surfactant, nonionic surfactant, and amphoteric surfactant, both silicone type surfactant and fluorine type surfactant can be used. In addition, an alkali source may not be used as long as pH becomes 9 or more by addition of only surfactant component, such as using alkaline soap.

As a specific example of anionic surfactant, As cationic surfactant, such as a fatty acid salt, an alkyl sulfate, an alkylbenzene sulfonate, an alkyl phosphate, a polyoxyethylene alkyl sulfate ester, As a nonionic surfactant, such as an alkyl ammonium salt and an alkylamine salt, Polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, oxyethylene-oxypropylene block copolymer, glycerin fatty acid ester, and the like.

In addition to the organic solvent and the aqueous alkali solution, for example, a fluorine-based surfactant having a perfluoro group can be used as a direct treatment agent or as a surfactant added to the organic solvent or the aqueous alkali solution. Examples of the fluorine-based surfactants include perfluoroalkyl (C ₇ to C ₂₀ ) carboxylic acids, perfluoroalkyl (C ₄ to C ₁₂ ) sulfonic acids, and the like.

As a method for treating the antifouling layer using these drugs, a method of cleaning by wiping with a cloth or cloth impregnated with a drug, or by immersing the lens in a container (cleaning bath) in which the drug is put, and applying physical energy such as shaking or ultrasonic wave Conduct.

Examples and comparative examples based on the present invention will be described below.

<Example 1>

When the silane compound (A) having a dynamic friction coefficient of 0.07 on the surface of the lens formed as a single component (trade name "KY-130" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted in a solvent, it was formed as a solid component of 0.186% and a single component. When the silane compound (B) having a dynamic friction coefficient of 0.34 (brand name "KP-801" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted in a solvent, 0.014% of the fluorine-based solvent (brand name "Novec") ) HFE-7200 ", manufactured by Sumitomo 3M Co., Ltd.) to prepare a solution having a solid content concentration of 0.2% to prepare a treatment solution for dipping.

The dynamic friction coefficient ratio ((maximum dynamic friction coefficient value) / (minimum dynamic friction coefficient value)) of the said silane compound (A) and silane compound (B) was 4.9.

As a lens material, a plastic lens for eyeglasses ("Seiko Super Soverein" manufactured by Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer of SiO ₂ film) is prepared, and the plasma is cleaned to clean the surface thereof. Treatment was carried out. The conditions for the plasma treatment were processing pressure: 0.1 Torr, introduction gas: dry air, distance between electrodes: 24 cm, power output: DC 1KV, processing time: 15 seconds.

The anti-fouling layer was formed by immersing the plasma treated lens in the dipping treatment solution and holding it for 1 minute, then taking it out at 40 cm / min, and then putting it in a constant temperature and humidity bath set at 60 ° C and 60% RH for 2 hours. .

<Example 2>

Solid content concentration when dilution of the silane compound (A) (trade name "KY-130" manufactured by Shin-Etsu Chemical Co., Ltd.) having a kinetic friction coefficient of 0.07 on the surface of the lens formed as a single component in a solvent was 0.1% as a single component. When the silane compound (B) having a dynamic friction coefficient of 0.34 (former name "KP-801" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted in a solvent, 0.1% of the fluorine-based solvent (brand name "Novec HFE") was obtained. -7200 "Sumitomo 3M Co., Ltd.) to prepare a solid content concentration 0.2% solution to prepare a treatment solution for dipping.

The dynamic friction coefficient ratio ((maximum dynamic friction coefficient value) / (minimum dynamic friction coefficient value)) of the said silane compound (A) and silane compound (B) was 4.9.

As the lens material, a plastic lens for eyeglasses ("SEIKO SUPER SOVIE" Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer of SiO ₂ film) was prepared, and plasma treatment was performed to clean the surface thereof. As plasma processing conditions, a process pressure: 0.1 Torr, inlet gas: dry air, the distance between electrodes; 24 cm, power output: DC 1KV, treatment time: 15 seconds.

The anti-fouling layer was formed by immersing the plasma treated lens in the dipping treatment solution and holding it for 1 minute, then taking it out at 40 cm / min, and then putting it in a constant temperature and humidity bath set at 60 ° C and 60% RH for 2 hours. .

<Example 3>

Lens formed as a single component as 0.19% of solid content concentration when the silane compound (C) (brand name "Optool DSX" Daikin Kogyo Co., Ltd. product) of the kinetic friction coefficient of the lens surface formed as a single component is diluted in a solvent. Solid content concentration when the silane compound (B) (trade name "KP-801" manufactured by Shin-Etsu Chemical Co., Ltd.) having a surface dynamic coefficient of friction of 0.34 was diluted in a solvent. A% solution was prepared to be a treatment solution for dipping.

The dynamic friction coefficient ratio ((maximum dynamic friction coefficient value) / (minimum dynamic friction coefficient value)) of the said silane compound (C) and silane compound (B) was 3.8.

As the lens material, a plastic lens for eyeglasses (manufactured by Seiko Super Sovereign Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer of SiO ₂ film) was prepared, and a plasma treatment was performed to clean the surface thereof. As conditions for plasma processing, processing pressure: 0.1 Torr, inlet gas: dry air, distance between electrodes; 24 cm, power output: DC 1 KV, processing time: 15 seconds.

The plasma treated lens was immersed in a dipping treatment solution and held for 1 minute, then taken out at 40 cm / min, then placed in a constant temperature and humidity bath set at 60 ° C and 60% RH, and held for 2 hours to form an antifouling layer. It was.

<Example 4>

Lens formed as a single component as 0.19% of solid content concentration when the silane compound (C) (brand name "Optool DSX" Daikin Kogyo Co., Ltd. product) of the kinetic friction coefficient of the lens surface formed as a single component is diluted in a solvent. The solid content concentration when the silane compound (D) having a dynamic coefficient of friction of 0.44 (trade name "TSL-8185" manufactured by Toshiba Silicone Co., Ltd.) was diluted in a solvent. HFE-7200 "manufactured by Sumitomo 3M Co., Ltd.) was diluted in the mixed solution so as to have a weight ratio of 1/1, to prepare a solid content concentration 0.2% solution to prepare a treatment solution for dipping.

The dynamic friction coefficient ratio ((maximum dynamic friction coefficient value) / (minimum dynamic friction coefficient value)) of the said silane compound (C) and silane compound (D) was 5.3.

As the lens material, a plastic lens for eyeglasses ("SEIKO SUPER SOVIE" Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer of SiO ₂ film) was prepared, and plasma treatment was performed to clean the surface thereof. As plasma processing conditions, a process pressure: 0.1 Torr, inlet gas: dry air, the distance between electrodes; 24 cm, power output: DC 1 KV, processing time: 15 seconds.

The anti-fouling layer was formed by immersing the plasma treated lens in the dipping treatment solution and holding it for 1 minute, then taking it out at 40 cm / min, and then putting it in a constant temperature and humidity bath set at 60 ° C and 60% RH for 2 hours. .

The lens was taken out of the constant temperature and humidity chamber, cooled, and then attached to a lens fixing jig, immersed in an ultrasonic cleaning tank filled with perfluorohexane, and then subjected to cleaning treatment by applying ultrasonic waves. As ultrasonic cleaning conditions, bath capacity: 2.6 liters, oscillation frequency: 38 kHz, output: 120 W, treatment time: 30 sec.

<Example 5>

Lens formed as a single component as 0.18% of solid content concentration when the silane compound (C) (brand name "Optool DSX" Daikin Kogyo Co., Ltd. product) of the kinetic friction coefficient of the lens surface formed as a single component is diluted in the solvent. Dynamic friction of the lens surface formed as 0.01% as a solid content concentration when the silane compound (B) (brand name "KP-801" Shin-Etsu Chemical Co., Ltd. product) whose surface dynamic coefficient of friction is 0.34 is diluted in the solvent. The solid content concentration when the silane compound (D) having a coefficient of 0.48 (trade name "TSL-8185" manufactured by Toshiba Silicone Co., Ltd.) was diluted in a solvent. Sumitomo 3M Co., Ltd.) was diluted in a mixed solution so as to have a weight ratio of 1/1, to prepare a solution having a solid content concentration of 0.2% to prepare a treatment solution for dipping.

The kinetic friction coefficient ratio ((maximum kinetic coefficient of friction value) / (minimum kinetic coefficient of friction value)) of the said silane compound (A) and silane compound (B) was 5.3.

As the lens material, a plastic lens for eyeglasses ("SEIKO SUPER SOVIE" Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer of SiO ₂ film) was prepared, and plasma treatment was performed to clean the surface thereof. As plasma processing conditions, process pressure: 0.1 Torr, introduction gas: dry air, the distance between electrodes: 24 cm, power output: DC 1KV, processing time: 15 sec.

Remove the lens from the thermo-hygrostat, cool it, and then use wiping paper ("Dusper" Ozu Sangyo Co., Ltd.) that was permeated with perfluorohexane until the unevenness of the application of the breath is not seen. Wipe repeatedly and wash.

<Example 6>

The antifouling layer was formed on the surface of the plastic lens for spectacles ("SEIKO SUPER SOVIE" Seiko Epson Corporation) by the vacuum evaporation method by the following method.

When the silane compound (A) having a dynamic friction coefficient of 0.07 on the surface of the lens formed as a single component (trade name "KY-130" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted in a solvent, it was formed as a solid component concentration of 1.86% and a single component. When the silane compound (B) having a dynamic friction coefficient of 0.34 (brand name "KP-801" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted in a solvent, 0.14% of the fluorine-based solvent (brand name "Novec HFE- 7200 "Sumitomo 3M Co., Ltd.) was prepared to prepare a solid content concentration 2% solution, which was impregnated with 1 g of porous ceramic pellets.

The dynamic friction coefficient ratio ((maximum dynamic friction coefficient value) / (minimum dynamic friction coefficient value)) of the said silane compound (A) and silane compound (B) was 4.9.

After drying, the pellets were set in a vacuum evaporator and evacuated until the attained pressure was 2-3 Pa.

Next, a plastic lens for eyeglasses having a hard coating film and an antireflection film layer ("SEIKO Super Sovereign" Seiko Epson Co., Ltd.) was introduced into the vacuum evaporator, and the pellet was heated to 400 ° C to 500 ° C to evaporate the silane compound to form a film on the lens surface. It was. At this time, the pellets were heated by a halogen lamp, and the deposition time was set to 7 minutes. After the deposition was completed, the inside of the evaporator was gradually returned to atmospheric pressure, the lens was taken out, and the antifouling layer was formed by placing the lens in a constant temperature and humidity chamber set at 60 ° C and 60% RH for 2 hours.

Comparative Example 1

A silane compound (A) having a coefficient of dynamic friction of 0.07 on the surface of the lens formed as a single component (trade name "KY-130" manufactured by Shin-Etsu Chemical Co., Ltd.) was added to a fluorine-based solvent (trade name "Novek HFE-7200" manufactured by Sumitomo 3M Corporation). The mixture was diluted to prepare a solution having a solid concentration of 0.2% to prepare a treatment solution for dipping. As the lens material, a plastic lens for eyeglasses ("SEIKO SUPER SOVIE" Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer of SiO ₂ film) was prepared, and plasma treatment was performed to clean the surface thereof. As plasma processing conditions, process pressure: 0.1 Torr, introduction gas: dry air, the distance between electrodes: 24 cm, power output: DC 1KV, processing time: 15 sec.

Plasma treated lenses were immersed in the dipping treatment solution, held for 1 minute, taken out at 40 cm / min, then placed in a constant temperature and humidity bath set at 60 ° C. and 60% RH for 2 hours to form an antifouling layer. .

Comparative Example 2

When the silane compound (A) having a coefficient of kinetic friction of 0.07 on the surface of the lens formed as a single component (trade name "KY-130" manufactured by Shin-Etsu Chemical Co., Ltd.) is diluted in a solvent, the solid content is 0.1% and is formed as a single component. Solid content concentration when dilution of the silane compound (C) (trade name "Optool DSX" from Daikin Kogyo Co., Ltd.) having a dynamic friction coefficient of 0.09 on the surface of the lens in a solvent was performed by diluting 0.1% in perfluorohexane to give a solid content of 0.2. A% solution was prepared to be a treatment solution for dipping.

The dynamic friction coefficient ratio ((maximum kinetic coefficient of friction value) / (minimum kinetic coefficient of friction value)) of the said silane compound (A) and silane compound (C) was 1.3.

As a lens material, a plastic lens for eyeglasses ("SEIKO SUPER SOVIE" Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer is a SiO ₂ film) was prepared, and plasma treatment was performed to clean the surface thereof. As plasma processing conditions, process pressure: 0.1 Torr, inlet gas: dry air, distance between electrodes: 24 cm, power supply output: DC 1KV, processing time: 15 seconds.

The anti-fouling layer was formed by immersing the plasma treated lens in the dipping treatment solution and holding it for 1 minute, then taking it out at 40 cm / min, and then putting it in a constant temperature and humidity bath set at 60 ° C and 60% RH for 2 hours. .

Comparative Example 3

When the silane compound (A) having a dynamic friction coefficient of 0.07 on the surface of the lens formed as a single component (trade name "KY-130" manufactured by Shin-Etsu Chemical Co., Ltd.) is diluted in a solvent, it is formed as a solid component of 0.04% and a single component. When the silane compound (B) having a dynamic friction coefficient of 0.34 (brand name "KP-801" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted in a solvent, 0.16% of the fluorine-based solvent (trade name "Novec HFE- 7200 "Sumitomo 3M Co., Ltd.) to prepare a solid content concentration 0.2% solution to prepare a treatment solution for dipping.

The dynamic friction coefficient ratio ((maximum dynamic friction coefficient value) / (minimum dynamic friction coefficient value)) of the said silane compound (A) and silane compound (B) was 4.9.

As the lens material, a plastic lens for eyeglasses ("SEIKO SUPER SOVIE" Seiko Epson Co., Ltd.) having a hard coating film and an antireflection film (outer layer of SiO ₂ film) was prepared, and plasma treatment was performed to clean the surface thereof. As plasma processing conditions, process pressure: 0.1 Torr, inlet gas: dry air, the distance between electrodes: 24 cm, power supply output: DC 1KV, processing time: 15 seconds.

The anti-fouling layer was formed by immersing the plasma treated lens in the dipping treatment solution and holding it for 1 minute, then taking it out at 40 cm / min, and then putting it in a constant temperature and humidity bath set at 60 ° C and 60% RH for 2 hours. .

The following evaluation test was done about the antifouling spectacle lens obtained in this way. The evaluation results are shown in Table 1.

(1) Dynamic friction coefficient measurement

For the measurement of the dynamic friction coefficient, a dynamic friction coefficient between the lens (using a flat lens for measuring the dynamic friction coefficient) and a cotton fabric was measured using a digital friction coefficient measuring tester (manufactured by Sagawa Seisakusho Co., Ltd.). The measurement conditions were as follows.

Vertical load: 600 gf

Traveling speed: 100 mm / min

(2) shaft displacement test

Test method: This evaluation checks for the presence or absence of shaft misalignment caused by slippage between the chuck (the part holding the lens and the axis of the machine) and the lens surface when grinding the lens to a predetermined frame shape using an edge machine. It observed by observing.

First, a test lens was prepared and set in the lens fixing jig. At this time, the astigmatism is fixed so that the astigmatism axis is in the prescribed direction (for example, 180 °), and that the astigmatism is not in the straight line passing through the optical center of the lens, and this is the prescribed direction (for example, 180 °). A crab-shaped frame having a large aspect ratio was prepared to be a reference frame.

As shown in FIG. 2, the lens 1 was fixed to the chucks 2 and 3 of an edge processing machine ("LE-8080" NIDEK Corporation make). The chucks 2 and 3 were pressed to fit the lenses on both sides of the lens optical axis. In addition, the tip of one chuck 2 is pressing the surface of the lens 1 through the lens fixing seal 4.

The edge processing was performed using the grindstone 5 based on the previous frame data in the state fixed to the chucks 2 and 3. The lens after the jade processing was inserted into the frame of the reference frame, and the deviation of the astigmatism axis was measured with a lens meter. When a straight line passing through the optical center of the lens was drawn, the deviation angle between the marking line and the horizontal line passing through the optical axis of the reference frame was measured.

20 lenses were edge-processed to calculate the ratio at which the axial deviation exceeded the allowable range. In addition, the permissible range of axial shift was made into +/- 2 degrees or less.

(3) Antifouling performance evaluation (wiping endurance test by cotton fabric)

Test Method: Using a cotton fabric, the convex surface of the lens was reciprocated 5000 times under a load of 200 g. Antifouling performance before and after wiping endurance test was evaluated by contact angle and oil ink wiping property.

Evaluation ①: Contact Angle Measurement

For the measurement of the contact angle, a water contact angle by the droplet method was measured using a contact angle meter ("CA-D type" manufactured by Kyowa Chemical Co., Ltd.).

Evaluation ②: Oily Ink Wiping

On the convex surface of the lens, a straight line of about 4 cm was drawn with a black oil marker ("Hi-Mackee Care" Zebra Co., Ltd.) and left for 5 minutes. After standing, the marking part was wiped with wiping paper ("Kaydry" Cresia Co., Ltd.), and the ease of wiping was determined based on the following criteria.

○: Completely removed with 10 or fewer wipes

(Triangle | delta): It removes completely by 11-20 times of wiping

X: The part which is not removed after 20 wiping remains

From the results in Table 1, spectacle lenses in which an antifouling layer was formed of at least one silane compound of at least one or more fluorine-containing silane compounds selected to have different kinetic coefficients of friction after treatment (Examples 1 to 6) Is a spectacle lens (Comparative Example 1) or the highest copper having a fluorine-containing silane compound having a low coefficient of kinetic friction on the surface of the lens formed as a single component and having a fluorine-containing silane compound as a single component as a single component. Compared with the spectacle lens (Comparative Example 2) in which the friction coefficient value was less than 1.4 times the minimum dynamic friction coefficient value (Comparative Example 2), the antifouling effect and its sustainability were almost the same, and the incidence of axial shift was significantly reduced. .

Moreover, the spectacle lens in which the antifriction coefficient of the lens surface formed as a single component is low, and the content rate of the silane compound with the high slipperiness | lubricacy of a lens surface is less than 30 weight% of the total amount of a silane compound (Comparative Example 3). Although the surface slipperiness | lubricacy fell to the extent which can be processed into an jade form, the original antifouling effect of a fluorine-containing silane compound will fall.

In this regard, the spectacle lens in which an antifouling layer is formed of at least one or more silane compounds of at least one or more fluorine-containing silane compounds selected to have different kinetic friction coefficients on the surface of the lens after treatment is subjected to jade processing without deteriorating the antifouling effect. It is recognized that the slipperiness | lubricacy of a lens surface can be reduced to the extent possible.

The present invention is used for, but is not limited to, antifouling spectacle lenses.

Claims (8)

In the spectacle lens in which an antifouling layer is formed on the surface of two or more silane compounds of at least one or more fluorine-containing silane compounds, a lens formed of each of the two or more silane compounds as a single component. The antifriction spectacle lens, wherein the surface dynamic coefficient of friction is 1.4 times or more the value of the maximum coefficient of dynamic friction. The method of claim 1, The antifouling spectacle lens according to claim 2, wherein the content ratio of the silane compound in which the surface having the lowest kinetic coefficient is obtained is 30 to 99% by weight of the total amount of the silane compound. The method of claim 1, An antifouling spectacle lens comprising, among the two or more kinds of silane compounds, a coefficient of kinetic friction of the lens surface formed by using a silane compound having a surface having the lowest kinetic coefficient as a single component as 0.2 or less. The method of claim 1, Of at least two silane compounds, at least one of the antifouling spectacle lenses is characterized by the following formula (1). Formula 1

(Wherein R _f is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms; X is iodine or hydrogen; Y is hydrogen or lower alkyl group; Z is fluorine or trifluoromethyl group; R ¹ is hydrolysis Possible groups; R ² is hydrogen or an inert monovalent organic group; a, b, c, d is an integer from 0 to 200; e is 0 or 1; m and n are integers from 0 to 2; p is from 1 to 10 Represents an integer.) The method according to any one of claims 1 to 4, An antifouling spectacle lens comprising an antireflection film under the antifouling layer of the antifouling spectacle lens. Forming an anti-reflection film on the surface of the lens substrate on which the hard coating film may be formed; And forming an antifouling layer on the antireflective film by at least one silane compound, at least one of which is a fluorine-containing silane compound, A method of manufacturing an antifouling spectacle lens, wherein the coefficient of kinetic friction of the lens surface formed of each of the two or more silane compounds as a single component is 1.4 times or more the value of the lowest kinetic coefficient of friction. The method of claim 6, In the step of forming an antifouling layer with at least one silane compound which is at least one or more fluorine-containing silane compounds on the antireflection film, an antifouling property characterized by coating a surface of the lens with a treatment agent containing at least two silane compounds. Method of manufacturing spectacle lenses. The method of claim 6, In the step of forming an antifouling layer by at least one silane compound of at least one or more fluorine-containing silane compound on the anti-reflection film, the two or more silane compounds are evaporated in a vacuum chamber to be attached to the lens surface Method for producing antifouling eyeglass lens.

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