JP2020204736A - Spectacle lens fabrication method, spectacle lens, and water-repellent material composition - Google Patents

Abstract

To provide a method of fabricating a spectacle lens having a water-repellent layer which exhibits superior water repellency and exhibits superior wiping resistance, and to provide such a spectacle lens and a water-repellent material composition used for the manufacturing method.SOLUTION: A method of fabricating a spectacle lens comprises a water-repellent layer forming step for forming water-repellent layers 41f, 41b on an optical member 11 using a water-repellent material composition containing a fluorine-containing silane compound (1) having a group represented by a formula *-Si(OR)3 ...(1a) at one end, and a fluorine-containing silane compound (2) having a group represented by a formula *-Si(OH)(OR)2 ...(2a) at one end, where a mole ratio (fluorine-containing silane compound (2)/fluorine-containing silane compound (1)) of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) is in a range of 65/35 to 90/10.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a method for manufacturing an spectacle lens for forming a water-repellent layer on an optical member and a water-repellent material composition.

When wearing spectacles, stains such as sweat and fingerprints tend to adhere to the surface of the spectacle lens. A water-repellent layer is provided on the surface of the spectacle lens in order to prevent the adhesion of these stains or facilitate wiping (for example, Patent Document 1).

JP-A-2018-4921

By using a fluorine-containing silane compound having a reactive silyl group at one end as the water-repellent material composition for forming the water-repellent layer, a water-repellent layer showing high water repellency is formed. However, by repeating the operation of wiping the surface of the spectacle lens with a cloth or the like, the water repellency of the water repellent layer may decrease, and it is required to improve the wiping resistance of the water repellent layer.
That is, the embodiment according to the present disclosure relates to a method for producing a spectacle lens having a water-repellent layer exhibiting excellent wiping resistance while exhibiting excellent water repellency, the spectacle lens, and a water-repellent material composition used in the production method. ..

The molar ratio of the fluorine-containing silane compound (1) having a group represented by the formula (1a) described later at one end and the fluorine-containing silane compound (2) having a group represented by the formula (2a) at one end. It has been found that by using a water-repellent material composition within a specific range, a water-repellent layer showing excellent water repellency and excellent wiping resistance is formed.

That is, the embodiments according to the present disclosure are as follows.
The method for manufacturing an spectacle lens according to an embodiment according to the present disclosure is as follows.
Including a water-repellent layer forming step of forming a water-repellent layer on an optical member using a water-repellent material composition.
The water-repellent material composition
Formula (1a): * -Si (OR) ₃ ... (1a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site). A fluorine-containing silane compound (1) having a group at one end and
Formula (2a): * -Si (OH) (OR) ₂ ... (2a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site.) A fluorine-containing silane compound (2) having a group represented by (2) at one end,
Contains,
The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65/35 to 90/10. ..

The water-repellent material composition according to the embodiment according to the present disclosure is
Formula (1a): * -Si (OR) ₃ ... (1a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site). A fluorine-containing silane compound (1) having a group at one end and
Formula (2a): * -Si (OH) (OR) ₂ ... (2a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site.) A fluorine-containing silane compound (2) having a group represented by (2) at one end,
Contains,
The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65/35 to 90/10. ..

In the above-described embodiment, the following embodiments are preferable.

The total content of the fluorine-containing silane compound (1) and the fluorine-containing silane compound (2) is preferably 50 to 100% by mass with respect to the total solid content of the water-repellent material composition.

The fluorine-containing silane compound (1) is preferably the formula (1):
(In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, Rf is a linear or branched alkyl fluorinated group having 1 to 16 carbon atoms, and L is 1 carbon number. ~ 6 are alkylene groups, a is 0-10, p is 1-4, b is 0-10, m is 2-4, n is 1-3, (m). −N) is 1 or more, x is 10 to 60, y is 10 to 60, and z is 0 to 10. When a is 2 or more, a plurality of m and a plurality of n are Each of them may be the same or different, and when b is 2 or more, a plurality of bs may be the same or different, and the arrangement order of various structural units is not limited.) ,
The fluorine-containing silane compound (2) is preferably the formula (2):
(In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, Rf is a linear or branched alkyl fluorinated group having 1 to 16 carbon atoms, and L is 1 carbon number. ~ 6 are alkylene groups, a is 0-10, p is 1-4, b is 0-10, m is 2-4, n is 1-3, (m). −N) is 1 or more, x is 10 to 60, y is 10 to 60, and z is 0 to 10. When a is 2 or more, a plurality of m and a plurality of n are Each of them may be the same or different, and when b is 2 or more, a plurality of bs may be the same or different, and the arrangement order of various structural units is not limited.).

In the water-repellent layer forming step, it is preferable to form the water-repellent layer by depositing the water-repellent material composition. Then, the vapor deposition is preferably performed at 400 to 1000 ° C.

According to the embodiment according to the present disclosure, a method for producing an spectacle lens having a water-repellent layer exhibiting excellent wiping resistance while exhibiting excellent water repellency, the spectacle lens and the water-repellent material composition used in the production method Provided.

It is a schematic cross-sectional view which shows the main part of the spectacle lens 1 manufactured by the manufacturing method of this embodiment.

Hereinafter, embodiments of the present disclosure (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary, but the present invention is not limited thereto, and a gist thereof. Various deformations are possible within the range that does not deviate from. In the drawings, the same elements are designated by the same reference numerals, and duplicate description will be omitted. Further, unless otherwise specified, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings. Furthermore, the dimensional ratios in the drawings are not limited to the ratios shown.

The method for manufacturing an spectacle lens of the present embodiment includes a water-repellent layer forming step of forming a water-repellent layer on an optical member using a water-repellent material composition.
The water-repellent material composition is
Formula (1a): * -Si (OR) ₃ ... (1a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site). A fluorine-containing silane compound (1) having a group at one end (hereinafter, also simply referred to as “fluorine-containing silane compound (1)”).
Formula (2a): * -Si (OH) (OR) ₂ ... (2a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site.) A fluorine-containing silane compound (2) having a group represented by (1) at one end (hereinafter, also simply referred to as "fluorine-containing silane compound (2)").
Contains,
The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65/35 to 90/10. ..
With the above configuration, according to the method for manufacturing a spectacle lens of the present embodiment, a spectacle lens having a water-repellent layer exhibiting excellent wiping resistance while exhibiting excellent water repellency can be obtained.

The definitions of various terms in the present specification are as follows.
By "one end" is meant one end of a chain molecule.
The "total solid content" in the water-repellent material composition means a component other than the solvent of the water-repellent material composition.

[Glasses lens]
FIG. 1 is a schematic cross-sectional view of the spectacle lens 1 manufactured by the manufacturing method of the present embodiment. The spectacle lens 1 of the present embodiment includes a spectacle lens base material 11, a hard coat layer 21f provided on the object side surface 11a side of the base material 11, and an object side surface 21fa side of the hard coat layer 21f. The functional layer 31f provided in the above, and a water-repellent layer 41f provided on the surface 31fa side of the functional layer 31f on the object side are provided.

When the spectacle lens base material 11 is a finish lens, the spectacle lens 1 of the present embodiment has a hard coat layer 21b provided on the eyeball side surface 11b side of the base material 11 and the hard coat layer 21b. A functional layer 31b provided on the eyeball side surface 21bb side and a water repellent layer 41b provided on the eyeball side surface 31bb side of the functional layer 31b are further provided.

Although not shown, a base layer may be provided between the base material 11 and the hard coat layer 21f, or between the base material 11 and the hard coat layer 21b.

<Base material for spectacle lenses>
The material of the base material for spectacle lenses (hereinafter, also simply referred to as “base material”) may be plastic or inorganic glass. Examples of the material of the base material include polyurethane-based materials such as polythiourethane resin and polyurethane resin; epithio-based materials such as polysulfide resin; and polycarbonate-based materials such as diethylene glycol bisallyl carbonate.
The material of the base material is preferably at least one selected from the polythiourethane resin, the polysulfide resin, and the polyurethane resin, and more preferably at least one selected from the group consisting of the polythiourethane resin and the polysulfide resin. Is.

The base material may be either a finish lens or a semi-finish lens.
The surface shape of the base material is not particularly limited, and may be a flat surface, a convex surface, a concave surface, or the like.
The spectacle lens of the present disclosure may be any of a single focus lens, a multifocal lens, a progressive power lens and the like. For example, as an example, for a progressive power lens, the near portion region (near portion) and the progressive portion region (intermediate region) are usually included in the above-mentioned lower region, and the distance portion region (distance portion). Is included in the upper region.
As the base material, a colorless one is usually used, but a colored one can also be used as long as the transparency is not impaired.

The thickness and diameter of the base material are not particularly limited, but the thickness is usually about 1 to 30 mm, and the diameter is usually about 50 to 100 mm.
The refractive index ne of the base material is preferably 1.53 or more, more preferably 1.55 or more, more preferably 1.58 or more, still more preferably 1.60 or more. The upper limit of the refractive index ne of the base material is not particularly limited, but is preferably 1.80 or less.

<Hard coat layer>
The hard coat layer is, for example, a cured film made of a curable composition containing an inorganic oxide and a silicon compound. The curable composition preferably further comprises a polyfunctional epoxy compound.

Examples of the inorganic oxides include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, tungsten oxide, zinc oxide, tin oxide, beryllium oxide, antimony oxide, and composite oxides of two or more of these inorganic oxides. Can be mentioned. These may be used individually by 1 type or in combination of 2 or more type. Among these inorganic oxides, silicon oxide is preferable. In addition, colloidal silica may be used as an inorganic oxide.

The content of the inorganic oxide is preferably 20% by mass or more and 80% by mass or less, more preferably 25% by mass or more and 70% by mass or less, still more preferably 25% by mass, based on the solid content of the curable composition. It is 50% by mass or less.

The silicon compound is, for example, a silicon compound having a hydrolyzable group such as an alkoxy group. The silicon compound is preferably a silane coupling agent having an organic group bonded to a silicon atom and a hydrolyzable group. The organic group bonded to the silicon atom is preferably an organic group having a functional group such as an epoxy group such as a glycidoxy group, a vinyl group, a methacrylicoxy group, an acrylicoxy group, a mercapto group, an amino group or a phenyl group. More preferably, it is an organic group having an epoxy group. The silicon compound may have an alkyl group bonded to silicon.

Examples of commercially available products of the above-mentioned silane coupling agent include products manufactured by Shin-Etsu Chemical Co., Ltd., trade names: KBM-303, KBM-402, KBM-403, KBE402, KBE403, KBM-1403, KBM-502, KBM- 503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9655, KBE-585 Examples thereof include KBM-802, KBM-803, KBE-846, KBE-9007 and the like.

The content of the silicon compound is preferably 20% by mass or more and 90% by mass or less, more preferably 30% by mass or more and 75% by mass or less, and further preferably 50% by mass or more in the solid content of the curable composition. It is 75% by mass or less.

The polyfunctional epoxy compound is a polyfunctional epoxy compound containing two or more epoxy groups in one molecule, and more preferably a polyfunctional epoxy compound containing two or three epoxy groups in one molecule. Commercially available products of polyfunctional epoxy compounds include EX-201, EX-211, EX-212, EX-252, EX-313, EX-314, and EX- of the "Denacol" series manufactured by Nagase ChemteX Corporation. Examples thereof include 321 and EX-411, EX-421, EX-512, EX-521, EX-611, EX-612, EX-614, and EX-614B.

The content of the polyfunctional epoxy compound is preferably 0% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and further preferably 15% by mass in the solid content of the curable composition. % Or more and 30% by mass or less.

In addition to the components described above, the above-mentioned curable composition can be prepared by mixing any components such as an organic solvent, a leveling agent, and a curing catalyst, if necessary.
The above-mentioned hard coat layer can be formed by applying a curable composition onto a substrate and subjecting it to a curing treatment (thermosetting, photocuring, etc.). As a means for applying the curable composition, a commonly used method such as a dipping method, a spin coating method, or a spray method can be applied. The curing treatment is usually performed by heating for a curable composition containing a polyfunctional epoxy compound. The heat curing treatment can be performed, for example, by arranging a lens coated with the above-mentioned curable composition in an environment of an atmospheric temperature of 50 to 150 ° C. for about 30 minutes to 3 hours.

<Underground layer>
The above-mentioned base layer can be formed of, for example, an aqueous resin composition containing at least one resin particle selected from the group consisting of polyurethane resin, acrylic resin, epoxy resin and the like.

As the above-mentioned aqueous resin composition, a commercially available aqueous polyurethane can be used as it is or diluted with an aqueous solvent if necessary. Examples of commercially available water-based polyurethanes include the product name "Evafanol" series manufactured by Nikka Kao Corporation, the product name "Superflex" series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the product name "ADEKA" manufactured by ADEKA Corporation. "Bontita" series, Mitsui Chemicals Co., Ltd. product name "Orestar" series, Dainippon Ink and Chemicals Co., Ltd. product name "Bondic" series, product name "Hydran" series, Bayer Co., Ltd. product name " Impranil "series, Nippon Soflan Co., Ltd. brand name" Sofranate "series, Kao Corporation brand name" Poise "series, Sanyo Kasei Kogyo Co., Ltd. brand name" Samplen "series, Hodoya Chemical Industry Co., Ltd. The product name "Aizelux" series manufactured by ADEKA CORPORATION and the product name "Neo Let's" series manufactured by ADEKA CORPORATION can be mentioned.

The base layer can be formed, for example, by coating and drying the above-mentioned aqueous resin composition on the surface of the base material.

<Functional layer>
Examples of the above-mentioned functional layer include an antireflection layer, an ultraviolet absorbing layer, an infrared absorbing layer, a photochromic layer, an antistatic layer, and an antifogging layer. These functional layers may be used alone or in combination of two or more. Known techniques for spectacle lenses can be applied to these functional layers. Among these, it is preferable to have an antireflection layer.

(Anti-reflective layer)
The antireflection layer has, for example, alternately arranged low refractive index layers and high refractive index layers. The number of layers of the antireflection layer is preferably 4 to 11 layers, and more preferably 5 to 8 layers.

The refractive index of the low refractive index layer is preferably 1.35 to 1.80, more preferably 1.45 to 1.50 at a wavelength of 500 to 550 nm. The low index of refraction layer is made of an inorganic oxide, preferably silicon oxide.

The refractive index of the high refractive index layer is preferably 1.90 to 2.60, and more preferably 2.00 to 2.40 at a wavelength of 500 to 550 nm. The high refractive index layer is made of, for example, an inorganic oxide. The inorganic oxide used for the high refractive index layer is preferably at least one selected from the group consisting of zirconium oxide, tantalum oxide, yttrium oxide, titanium oxide, niobium oxide and aluminum oxide, and more preferably zirconium oxide and aluminum oxide. It is at least one selected from the group consisting of tantalum oxide.

The antireflection layer can be formed by alternately laminating low refractive index layers and high refractive index layers by a vacuum vapor deposition method.

<Water repellent layer>
The water-repellent layer is formed by using the water-repellent material composition described later. The water-repellent layer may be formed on the hard coat layer or the functional layer, but it is preferably formed on the antireflection layer. The water-repellent layer is preferably located on the outermost surface. Details of the water-repellent material composition and the like will be described later.

[Manufacturing method of spectacle lenses]
The method for manufacturing an spectacle lens of the present embodiment includes a water-repellent layer forming step of forming a water-repellent layer on an optical member using a water-repellent material composition.

<Water repellent material composition>
(Fluorine-containing silane compound (1) and fluorine-containing silane compound (2))
The water-repellent material composition used in the production method of the present embodiment has a fluorine-containing silane compound (1) having a group represented by the formula (1a) at one end and a group represented by the formula (2a). It contains a fluorine-containing silane compound (2) at the end.
The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) in the water-repellent material composition [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65 /. It is 35 to 90/10.
According to the water-repellent material composition of the present embodiment, by forming a water-repellent layer using the water-repellent material composition, a water-repellent layer exhibiting excellent water repellency and excellent wiping resistance can be obtained. A spectacle lens to have is obtained.

The fluorine-containing silane compound (1) has the formula (1a): * -Si (OR) ₃ ... (1a) (in the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is It has a group represented by (), which is a binding site, at one end. The fluorine-containing silane compound (1) is preferably a linear fluorine-containing silane compound.

Examples of R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Of these, a methyl group is preferred.

The fluorine-containing silane compound (1) is preferably given by the formula (1): from the viewpoint of further improving the water repellency and wiping resistance of the obtained spectacle lens.
(In the formula, R is the same as the definition of the formula (1a), Rf is a linear or branched alkyl fluorinated group having 1 to 16 carbon atoms, and L is 1 to 6 carbon atoms. It is an alkylene group, a is 0 to 10, p is 1 to 4, b is 0 to 10, m is 2 to 4, n is 1 to 3, and (mn). Is 1 or more, x is 10 to 60, y is 10 to 60, and z is 0 to 10. When a is 2 or more, the plurality of m and the plurality of n are the same. It may be present or different, and when b is 2 or more, a plurality of b may be the same or different, and the sequence order of various structural units is not limited.).

The fluorinated alkyl group of Rf is preferably a linear fluorinated alkyl group, more preferably a linear perfluoroalkyl group.
The fluorinated alkyl group of Rf preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms.
Examples of the fluorinated alkyl group of Rf include a perfluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, a perfluoroisopropyl group, a perfluoro-n-butyl group, and a perfluoro-tert-butyl group. Examples thereof include a perfluoro-n-hexyl group, a perfluoro-n-octyl group, a perfluoro-n-decyl group, and a perfluoro-n-dodecyl group. Among these, a perfluoromethyl group, a perfluoroethyl group, or a perfluoro-n-propyl group is preferable, and a perfluoromethyl group is more preferable.

The alkylene group of L may be linear or branched, but linear is preferable.
The alkylene group of L preferably has 1 to 5 carbon atoms, more preferably 2 to 4 carbon atoms.
Examples of the alkylene group of L include a methanediyl group, an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a hexane-1,6-diyl group. .. Among these, a propane-1,3-diyl group is preferable.

a is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3.
p is preferably 2 to 3, and more preferably 3.

b is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 3.
m is preferably 2 to 3, and more preferably 3.
n is preferably 1 to 2, and more preferably 2.

x is preferably 20 to 60, more preferably 25 to 50, and even more preferably 30 to 45.
y is preferably 20 to 60, more preferably 25 to 50, and even more preferably 30 to 45.
z is preferably 0 to 8, more preferably 0 to 5, and even more preferably 0 to 3.

The arrangement order of the structural unit represented by the repetition number a and the structural unit represented by the repetition number b is preferably the arrangement order represented by the formula (1). In this case, the arrangement order of the structural units represented by the repetition numbers x, y, and z is not limited.

Examples of the fluorine-containing silane compound (1) include compounds represented by the following formula (1-1).
(In the formula, x is 35-40, y is 35-40, z is 0 or 1, a is 1, and b is 1.)

The fluorine-containing silane compound (2) has the formula (2a): * -Si (OH) (OR) ₂ ... (2a) (in the formula, R is an alkyl group having 1 to 3 carbon atoms independently. , * Is a binding site.) Has a group represented by) at one end. The R in the formula (2a) may be the same as or different from the R in the formula (1a), but is preferably the same as the R in the formula (1a). The fluorine-containing silane compound (2) is preferably a linear fluorine-containing silane compound.

The fluorine-containing silane compound (2) is preferably the formula (2):
(In the formula, R is the same as the definition of the formula (1a), and Rf, L, x, y, z, a, p, b, m, n, and (mn) are the same as the definition of the formula (1a). It is the same as the definition of.).

R, Rf, L, x, y, z, a, p, b, m, n, and (mn) may be the same as or different from the compound represented by the formula (1). It may be, but it is preferable that they are the same.

Examples of the fluorine-containing silane compound (2) include compounds represented by the following formula (2-1).
(In the formula, x is 35-40, y is 35-40, z is 0 or 1, a is 1, and b is 1.)

The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) in the water-repellent material composition [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65/35 to 35. It is 90/10. When the molar ratio is within a predetermined range, a spectacle lens having a water-repellent layer exhibiting excellent wiping resistance can be obtained.
The molar ratio [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is preferably 68/32 to 85/15, more preferably 70/30 to, from the viewpoint of further improving wiping resistance. It is 83/17, more preferably 75/25 to 80/20.
The above-mentioned molar ratio can be measured from the peak area ratio of the ¹ H-NMR spectrum. More specifically, the method described in Examples is used.

The total content of the fluorine-containing silane compound (1) and the fluorine-containing silane compound (2) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, based on the total solid content of the water-repellent material composition. It is by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass. When the total content is included in the range, water repellency and wiping resistance are further improved.

(Fluorine-containing silane compound (3))
The water-repellent composition may contain a fluorine-containing silane compound (3) having a reactive silyl group at both ends (hereinafter, also simply referred to as “fluorine-containing silane compound (3)”). Examples of the fluorine-containing silane compound (3) include compounds represented by any of the following formulas (3-1) to (3-6).

Each of r, s and t in the formula is an integer of 1 or more independently, preferably an integer of 1 to 50, and more preferably an integer of 10 to 40.

The content of the fluorine-containing silane compound (3) is preferably 0% by mass or more and 50% by mass or less with respect to the total solid content of the water-repellent material composition, and when the fluorine-containing silane compound (3) is contained, It is more preferably 1% by mass or more and 40% by mass or less, further preferably 1% by mass or more and 30% by mass or less, and even more preferably 1% by mass or more and 20% by mass or less.

The water-repellent material composition of the present embodiment may contain a tetraalkyl orthosilicate, a fluororesin, or the like.

Tetraalkyl orthosilicates have an alkyloxy group. The alkyloxy group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyroxy group, and a butoxy group. Of these, a methoxy group or an ethoxy group is preferable. Examples of the tetraalkyl orthosilicate include tetraethyl orthosilicate and tetramethyl orthosilicate. Of these, tetraethyl orthosilicate is preferable.

The content of the tetraalkyl orthosilicate in the water-repellent material composition is preferably 1% by mass or more and 30% by mass or less, and more preferably 2% by mass or more and 20% by mass with respect to the total solid content of the water-repellent material composition. % Or less, more preferably 3% by mass or more and 15% by mass or less.

Examples of the fluororesin include a polymer of a fluorine-containing olefin compound, and a copolymer composed of a fluorine-containing olefin compound and a monomer copolymerizable therewith. More specifically, examples of the fluororesin include polytetrafluoroethylene, tetraethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetra. Fluoroethylene-hexafluoropropylene copolymer, ethylene-chlorotrifluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinylfluoride Can be mentioned.

The content of the fluororesin in the water-repellent material composition is preferably 1% by mass or more and 30% by mass or less, and more preferably 2% by mass or more and 20% by mass or less, based on the total solid content of the water-repellent material composition. It is more preferably 3% by mass or more and 15% by mass or less.

(solvent)
The water repellent material composition may contain a solvent. By containing the solvent, the viscosity can be lowered, so that the pellets for vapor deposition can be easily impregnated.
As the solvent, a fluorine-modified solvent; a hydrocarbon solvent such as petroleum benzine, mineral spirits, toluene and xylene; a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone; an alcohol solvent such as methanol, ethanol, isopropanol and n-propanol. Can be mentioned. These may be used alone or in combination of two or more. Among these solvents, a fluorine-modified solvent is preferable.

Examples of the fluorine-modified solvent include fluorine-modified aliphatic hydrocarbon solvents such as perfluoroheptane and perfluorooctane; and fluorine-modified aromatic hydrocarbons such as 1,3-di (trifluoromethyl) benzene and trifluoromethylbenzene. Solvents: Fluorine-modified ether solvents such as methyl perfluorobutyl ether and perfluoro (2-butyl tetrahydrofuran); Fluorine-modified alkylamine solvents such as perfluorotributylamine and perfluorotripentylamine can be mentioned. These may be used alone or in combination of two or more. Among these, 1,3-di (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran) or perfluorotributylamine is preferable.

The total amount of solids in the water-repellent material composition is preferably 50% by mass or more and 100% by mass or less, and more preferably 60% by mass or more and 100% by mass or less, based on the total amount of the water-repellent material composition. More preferably, it is 70% by mass or more and 100% by mass or less.

<Water repellent layer forming process>
Examples of the optical member used in the water-repellent layer forming step include the above-mentioned base material, a base material on which a hard coat layer is laminated, and a base material on which a hard coat layer and a functional layer are laminated. Among these, a base material having a hard coat layer and a functional layer laminated is preferable, and a base material having a hard coat layer and an antireflection layer laminated is more preferable.

The method of forming the water-repellent layer on the optical member in the water-repellent layer forming step can be formed by, for example, thin-film deposition or coating, but preferably, the water-repellent layer is formed by depositing the water-repellent material composition. Form.

The vapor deposition is performed, for example, by vacuum vapor deposition. The heating temperature in vacuum vapor deposition is preferably 400 ° C. or higher, more preferably 500 ° C. or higher, still more preferably 550 ° C. or higher, still more preferably 600 ° C. or higher. The heating temperature in vacuum vapor deposition is preferably 1000 ° C. or lower. The heating temperature for vapor deposition means the temperature at which vapor-deposited pellets or the like impregnated with the water-repellent material composition are heated during vapor deposition. The vacuum vapor deposition is preferably performed in a vapor deposition space controlled to a vacuum degree of 3.0 × 10 ⁻² Pa or less.

For heating in the vapor deposition, for example, a halogen heater, resistance heating, an electron gun and the like can be used, and among these, when the film is heated and vapor-deposited using an electron gun, a thin film with high accuracy can be produced. The power of the electron gun varies depending on the substance used, the vapor deposition apparatus, the degree of vacuum, and the irradiation area, but the preferable conditions are an accelerating voltage of 200 to 1000 V and an applied current of about 5 to 400 mA.

The vapor deposition is preferably carried out using vapor deposition pellets impregnated with the water-repellent material composition.
Examples of the pellets for vapor deposition include a metal container, a pellet containing steel wool filled in the metal container, and a pellet made of a porous material.
As the porous material, it is preferable to use a fused silica porous body or a sintered filter obtained by sintering a metal powder having high thermal conductivity such as copper or stainless steel. From the viewpoint of obtaining an appropriate vapor deposition rate, it is appropriate that the mesh of the sintered filter is 40 to 200 microns, preferably 80 to 120 microns.

When the water-repellent layer is formed by coating, a method of applying a water-repellent material composition containing an organic solvent onto the optical member can be adopted. As the coating method, a dipping method, a spin coating method, a spray method, a flow method, a doctor blade method, a roll coating coating, a gravure coating coating, a curtain flow coating and the like are used.

The organic solvent is preferably the above-mentioned fluorine-based solvent. The solid content concentration of the water-repellent material composition when diluted with an organic solvent is preferably 0.03% by mass or more and 1% by mass or less.

The water-repellent layer according to the present embodiment reacts at room temperature and is fixed on the optical member. However, in the method for producing an spectacle lens of the present embodiment, a reaction between a fluorine-containing silane compound and the surface of the optical member is required. May have a heat treatment step of heating the optical member on which the film is formed by the water-repellent material composition.
By the heat treatment step, it is possible to further improve the wiping resistance by suppressing the decrease in water repellency due to physical and chemical loads in daily use such as wiping the surface of the spectacle lens and adhering detergent.
The heating temperature in the heat treatment step is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, and even more preferably 55 to 70 ° C.
The heating time is not particularly limited, but is, for example, 0.5 to 10 hours.

The method for manufacturing an spectacle lens of the present embodiment is a step of removing unreacted components of an antifouling agent with a fluorine-based solvent in order to remove unreacted molecules and molecules whose reaction has not been completed from the film after forming the film. May have. By performing this step, the water repellency of the surface of the spectacle lens can be improved. Examples of the fluorine-based solvent are the same as those of the fluorine-based solvent in the above-mentioned water-repellent material composition.
As a method of removing the unreacted component of the antifouling agent using a fluorine-based organic solvent, a method of wiping with a paper or cloth soaked with a chemical or a method of immersing the lens in a container (cleaning tank) containing the chemical It is performed by applying physical energy such as rocking or ultrasonic waves.
According to the above manufacturing method, a spectacle lens having excellent water repellency and easy wiping of sebum can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

Various physical properties were measured by the following methods.

<Mole ratio of fluorine-containing silane compound (2) and fluorine-containing silane compound (1)>
The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) was ¹ H-NMR spectrum obtained by dissolving the sample in hexafluoroisopropanol-d ₂ and using a 600 MHz nuclear magnetic resonance apparatus. .. The molar ratio was calculated from the area ratio of various peaks in the obtained ¹ H-NMR spectrum.

Example 1
A fluorine-containing silane compound (1-1) having a trialkoxysilyl group at one end and a fluorine-containing silane compound (2-1) having a dialkoxysilyl group at one end are mixed to form a water-repellent material composition shown in Table 1. Was prepared.

The water-repellent material composition was impregnated with vapor deposition pellets filled with steel wool in a copper container so that the total solid content was 15 mg. After impregnating the water-repellent material composition, the solvent was evaporated by heating in an oven set at 80 ° C. for 20 minutes.

In a glass container, 90 parts by mass of colloidal silica "Snowtex 40" (product name, Nissan Chemical Industry Co., Ltd.), as other organic silicon compounds, 81.6 parts by mass of methyltrimethoxysilane, γ-glycidoxypropyltri A solution containing 176 parts by mass of methoxysilane, 2.0 parts by mass of 0.5N hydrochloric acid, 20 parts by mass of acetic acid, and 90 parts by mass of water was stirred at room temperature for 8 hours and then left at room temperature for 16 hours to be a hydrolyzed solution. Got To this solution, 120 parts by mass of isopropyl alcohol, 120 parts by mass of n-butyl alcohol, and 16 parts by mass of aluminum acetylacetone were added, stirred at room temperature for 8 hours, and aged at room temperature for 24 hours to obtain a hard coat solution.

The spectacle lens base material "EYAS" (product name, manufactured by HOYA Corporation, thiourethane resin, formulations S0.00, C0.00) pretreated with an alkaline aqueous solution is immersed in the above-mentioned hard coat solution, and the immersion is completed. After that, the spectacle lens pulled up at a pulling speed of 20 cm / min was heated at 120 ° C. for 2 hours to form a cured film and a hard coat layer.

Next, an antireflection layer in which silica and zirconia were alternately laminated was formed on the hard coat layer by a vacuum vapor deposition method. After the antireflection layer was vapor-deposited, an ion gun treatment was performed to activate the surface. The ion gun treatment was performed under the following conditions.
Acceleration voltage: 450V
Acceleration current: 200mA
Introduced gas: Oxygen (20 sccm)
Ion irradiation time: 30 seconds

The spectacle lens was then moved to a chamber where the water repellent material composition was deposited. In the chamber, the pellets for vapor deposition impregnated with the water-repellent material composition prepared in 1 were set on a halogen heater heating table. The water-repellent material composition contained in the pellets for vapor deposition was deposited by heating with a halogen heater. The reached temperature during heating was about 600 ° C. The spectacle lens after the water-repellent layer was taken out, put into an oven set at 60 ° C., and held for 4 hours.

Comparative Example 1
The ratio of the fluorine-containing silane compound (1-1) having a trialkoxysilyl group at one end and the fluorine-containing silane compound (2-1) having a dialkoxysilyl group at one end in the water-repellent material composition is as shown in Table 1. An optic lens having a water-repellent layer formed was obtained by the same method as in Example 1 except that it was prepared.

Various physical properties of the obtained spectacle lenses were evaluated as follows.

[Water repellency (initial contact angle)]
Using a contact angle meter "CA-D type" (product name, Kyowa Interface Science Co., Ltd.), make a water droplet with a diameter of 2 mm on the needle tip at 25 ° C, and touch this to the top of the convex surface of the spectacle lens. I made a droplet. The angle between the droplet and the surface generated at this time was measured and used as the static contact angle. The static contact angle θ is calculated by the following equation, where r is the radius of the water droplet (the radius of the portion where the water droplet is in contact with the surface of the spectacle lens) and h is the height of the water droplet.
θ = 2 × tan- ¹ (h / r)
The contact angle was measured within 10 seconds after the water droplet was brought into contact with the spectacle lens in order to minimize the measurement error due to the evaporation of water.

[Wipe resistance]
Wrap the lens wipe "Dasper" (product name, manufactured by Ozu Corporation) around the eraser cut to 19 mm x 24 mm, and attach it to the reciprocating friction wear tester "Tribo Gear 30S" (product name, manufactured by Yamato Scientific Co., Ltd.). It was. A load of 2 kg was applied to it, and every time the surface of the spectacle lens was rubbed 100 times, the contact angle was confirmed by the method shown in the above-mentioned [Initial contact angle], and the total number of wipes was 4000 times. The wiping resistance was evaluated according to the following criteria.
<Evaluation criteria>
A: Even if the number of wiping times is 4,000 or more, the contact angle lowered from the initial contact angle is less than 5 °.
B: When the number of wiping times is 3,000 or more and less than 4,000, the contact angle lowered from the initial contact angle is 5 ° or less.
C: When the number of wiping times is 2,000 or more and less than 3,000, the contact angle lowered from the initial contact angle is 5 ° or less.
D: When the number of wiping times is less than 2,000, the contact angle lowered from the initial contact angle becomes 5 ° or less.

From the results of Examples and Comparative Examples, the molar ratio [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65/35 to 90/10, which provides excellent wiping resistance. It can be seen that it shows.

1 ... Eyeglass lens, 11 ... Base material for spectacle lens, 11a, 21fa, 31fa ... Object side surface, 11b, 21bb, 31bb ... Eyeball side surface, 21f, 21b ... Hard coat layer, 31f, 31b ... Functional layer, 41f, 41b ... Water repellent layer

Claims (7)

Including a water-repellent layer forming step of forming a water-repellent layer on an optical member using a water-repellent material composition.
The water-repellent material composition
Formula (1a): * -Si (OR) ₃ ... (1a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site). A fluorine-containing silane compound (1) having a group at one end and
Formula (2a): * -Si (OH) (OR) ₂ ... (2a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site.) A fluorine-containing silane compound (2) having a group represented by (2) at one end,
Contains,
The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65/35 to 90/10. , How to manufacture spectacle lenses. The first aspect of claim 1, wherein the total content of the fluorine-containing silane compound (1) and the fluorine-containing silane compound (2) is 50 to 100% by mass with respect to the total solid content of the water-repellent material composition. How to manufacture spectacle lenses. The fluorine-containing silane compound (1) has a formula (1):
(In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, Rf is a linear or branched alkyl fluorinated group having 1 to 16 carbon atoms, and L is 1 carbon number. ~ 6 are alkylene groups, a is 0-10, p is 1-4, b is 0-10, m is 2-4, n is 1-3, (m). −N) is 1 or more, x is 10 to 60, y is 10 to 60, and z is 0 to 10. When a is 2 or more, a plurality of m and a plurality of n are Each of them may be the same or different, and when b is 2 or more, a plurality of bs may be the same or different, and the arrangement order of various structural units is not limited.) ,
The fluorine-containing silane compound (2) has a formula (2):
(In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, Rf is a linear or branched alkyl fluorinated group having 1 to 16 carbon atoms, and L is 1 carbon number. ~ 6 are alkylene groups, a is 0-10, p is 1-4, b is 0-10, m is 2-4, n is 1-3, (m). −N) is 1 or more, x is 10 to 60, y is 10 to 60, and z is 0 to 10. When a is 2 or more, a plurality of m and a plurality of n are Each of them may be the same or different, and when b is 2 or more, a plurality of bs may be the same or different, and the arrangement order of various structural units is not limited.) The method for manufacturing a spectacle lens according to claim 1 or 2. The method for producing an spectacle lens according to any one of claims 1 to 3, wherein the water-repellent layer is formed by depositing the water-repellent material composition in the water-repellent layer forming step. The method for manufacturing an spectacle lens according to claim 4, wherein the vapor deposition is performed at 400 to 1000 ° C. An spectacle lens obtained by the manufacturing method according to any one of claims 1 to 5. Formula (1a): * -Si (OR) ₃ ... (1a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site). A fluorine-containing silane compound (1) having a group at one end and
Formula (2a): * -Si (OH) (OR) ₂ ... (2a) (In the formula, R is an alkyl group having 1 to 3 carbon atoms independently, and * is a binding site.) A fluorine-containing silane compound (2) having a group represented by (2) at one end,
Contains,
The molar ratio of the fluorine-containing silane compound (2) to the fluorine-containing silane compound (1) [fluorine-containing silane compound (2) / fluorine-containing silane compound (1)] is 65/35 to 90/10. , Water repellent material composition.