JP2017111413A - Optical element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical element including a water-repellent antifouling film capable of improving further repellency, an antifouling property, and excoriation resistance without damaging processability for setting in a frame.SOLUTION: An optical element whose base-material surface to be treated is a silica-base surface includes a water-repellent antifouling film that is formed by a fluorine-containing organic group introduction silane having a fluorine-modified organic group and a reactive silyl group and indicates a characteristic of a contact angle (for a pure water surface) of 100° or more. Friction properties of the water-repellent antifouling film satisfy μ≥0.100 (to a SUS sphere) and μ<0.095 (to a SUS sphere).SELECTED DRAWING: None

Description

The present invention relates to an optical element provided with a water-repellent antifouling film formed of a fluorine organic group-introduced silane having a silyl group reactive with a fluorine-modified organic group. Examples of optical elements to which the present invention can be applied include glasses, photographic lenses, filters, display covers, and various films.
In the specification and claims of the present application, unless otherwise specified, each numerical value of “friction coefficient” is measured with a friction wear analyzer (Kyogaku Co., Ltd., TSf-300) under the conditions described below. To do.
Moreover, each abbreviation means the following.
“Vs. SUS ball μ _k ”: Dynamic friction coefficient when measured with a contact SUS sphere,
“Vs. SUS sphere μ _s ” ... static friction coefficient,
“Aluminum sphere μ _k ” ・ ・ ・ Dynamic friction coefficient when measured with a contact alumina sphere,
“Alumina sphere μ _s ”: Static friction coefficient.

In the case of glasses, photographic lenses, etc., if water drops or dirt / scratches are attached, the image will be distorted, making it difficult to see, making it difficult for water drops to adhere, dirt or easy to wipe off, scratches, It is desirable that the coefficient of surface friction is low in order to facilitate wiping off dirt.
The cause of water droplet adhesion is the hydrophilic metal oxide / halide layer (hereinafter referred to as “metal oxide layer”) for reducing or increasing the reflectance on the surface of a hydrophilic inorganic glass substrate or organic glass substrate. In addition, dirt such as bruises and dust adheres, and fine scratches occur, resulting in a non-uniform hydrophilic surface.

The metal oxide layer is usually formed by a PVD (Physical Vapor Deposition) method typified by vacuum deposition, sputtering, ion plating and the like. The surface of the metal oxide layer has fine irregularities. For this reason, there are problems that dirt or the like is more likely to adhere, it is difficult to remove after the attachment, fine scratches are easily generated, and the tendency of water droplets to adhere increases.
In order to solve such problems, it may be considered to form a water-repellent antifouling film on the outermost surface of the metal oxide layer. It becomes difficult to stick.

  As in the present invention, Patent Documents 1 to 5 and the like can be cited as prior art documents relating to a water-repellent antifouling film with a fluorine-based silane compound (silicone).

  In Patent Documents 1 and 2, “a silazane compound such as fluoroalkylsilazane is impregnated into a porous material (sintered filter, steel wool, etc.), and a water-repellent antifouling film is formed on the inorganic coating film by vacuum and heating evaporation. It is described.

  Patent Document 3 states that “an organic substance-containing cured substance layer made of an organic polysiloxane polymer or a polymer obtained by polymerizing a perfluoroalkyl group-containing compound is immersed and cured (reacted) to form a water repellent-proof layer on the inorganic coating film. “It forms a fouling film”.

  When the water-repellent antifouling film is formed on the substrate surface as described in Patent Documents 1 to 3, the antifouling property, water repellency and slipperiness are certainly improved as compared with the case where no water-repellent antifouling film is present. In terms of practical use (scratch resistance, etc.), it was still insufficient. Therefore, eyeglass lenses in which a water-repellent antifouling film is formed with a fluorine-containing silane compound (perfluoropolyether polysiloxane copolymer) are on the market. However, these eyeglass lenses are slippery when they are cut to match the shape of the frame at a retail store, making it difficult to hold the lens and making it impossible to frame the frame as usual. The workability was not good (see Patent Document 4, paragraphs 0008 and 0009).

Therefore, in Patent Document 4 relating to the applicant of the present application, an optical element having a configuration in which a water-repellent antifouling film (surface protective film) is “formed with a fluorine-modified organic machine and a reactive silyl group-introduced silane compound” is proposed ( Claim 1 etc.).
In the case of a spectacle lens (optical element) provided with this water-repellent antifouling film, water repellency, antifouling properties and scratch resistance could be secured to some extent while maintaining frameability.
However, further water repellency / antifouling properties and scratch resistance have been required for water-repellent antifouling membranes.

In Patent Document 5, various specific silane compounds (such as amino-modified polysiloxane and epoxy group-containing silane) are added to a fluorine-containing compound (perfluoropolyetherpolysiloxane copolymer-modified silane) to improve durability. A spectacle lens with a water repellent / antifouling film has been proposed.
The spectacle lens (optical element) provided with this water-repellent antifouling film has a dynamic friction coefficient of 0.040 to 0.045, which is estimated to be smaller than that in the present invention, and has sufficient water repellency / antifouling properties and scratch resistance. Is estimated to be obtained. However, the frame workability is considered to be too slippery and the frame workability is not good. This is because in Comparative Example 2 in which a water-repellent antifouling film (“surface protective film 4” in paragraph 0105) was formed with the same fluorine-containing compound (perfluoropolyetherpolysiloxane copolymer-modified silane) in Patent Document 4.・ 4, 6 and 8 are all supported by “×” in the frame workability (Table 2 in paragraph 0138).

  JP-A-5-215905   JP-A-6-340966   Japanese Patent Publication No. 6-5324   JP 2004-61879 A   JP 2009-173787 A

  In view of the above, the present invention provides an optical element provided with a water-repellent antifouling film capable of improving further water repellency and antifouling properties and scratch resistance without impairing frame workability. Objective.

  As a result of diligent development efforts to solve the above problems, the present inventors have come up with an optical element having the following configuration.

The surface to be treated is a silica-based surface and is formed of a fluorine organic group-introduced silane having a fluorine-modified organic group and a reactive silyl group, and has a contact angle (vs pure water) of 100 ° or more. In an optical element with a film,
The friction property of the water-repellent antifouling film satisfies SUS sphere μ _k <vs SUS sphere μ _s , and satisfies SUS sphere μ _s ≧ 0.10 and SUS sphere μ _k <0.095. To do.

That is, since the water-repellent antifouling film is formed of a fluorinated organic group-introduced silane having a silyl group reactive with a fluorine-modified organic group, the surface to be treated of the substrate is a silica-based surface. Similar to the described invention, chemical bonding is made to the surface to be treated of the substrate, and a large number of fluorine atoms are present on the surface side, so that water repellency / antifouling properties and scratch resistance can be ensured. The friction property of the water-repellent antifouling film is such that the SUS ball μ _s is a predetermined value (0.095, preferably 0.100 or more and the SUS sphere μ _k is a predetermined value (0.100, preferably 0.00). It has been found that if the requirement of less than 095 is satisfied, the water repellency / antifouling property and scratch resistance can be improved without impairing the frame forming workability.

In this case, it is desirable that the friction characteristic of the water-repellent antifouling film further satisfies the predetermined value (0.95, desirably 0.90) or less for the SUS sphere μ _k / the SUS sphere μ _s . It becomes easier to improve the water repellency / antifouling property and scratch resistance without deteriorating the frame workability.

The friction characteristics of the water-repellent antifouling film are such that the alumina sphere μ _k is less than a predetermined value (0.08, desirably 0.06), and the alumina sphere μ _k / the alumina sphere μ _s is a predetermined value (0 .80, preferably 0.70) or less. Since the alumina contact μ _k and the alumina contact μ _k / the alumina contact μ _k / the alumina contact μ _s in the alumina contactor which is about three times as hard as SUS are small, the frame workability is hardly impaired and the high hardness scratch The sliding with respect to the material is remarkably improved and the scratch resistance can be improved.
In addition, examples of the water repellent capable of forming a water-repellent antifouling film having friction characteristics as described above include a fluorine organic group-introduced silane compound “X-71-195” manufactured by Shin-Etsu Chemical Co., Ltd. Yes, but not limited to this.

The water-repellent antifouling film, when the substrate treated surface is formed of an optical inorganic thin film which is the outermost layer SiO ₂ layer, attaches the water-repellent antifouling agent to the fibrous conductive material mass, It is desirable to form it by a so-called dry processing method (dry coating method) in which it is heated under a vacuum of 1 to 0.0001 Pa.

  This dry treatment method makes it easy to obtain a water-repellent antifouling film with good adhesion and excellent leveling (uniformity), and can form a water-repellent antifouling film continuously using the same vacuum chamber. The efficiency is superior to the wet processing method described later.

  The water-repellent antifouling film is applied to the substrate-treated surface of the optical element, and then left for a predetermined time in an atmosphere of humidity (RH) 10 to 90% and temperature 10 to 60 ° C. It may be a so-called wet processing method (wet coating method) to be formed.

  This wet processing method is suitable for forming a water-repellent antifouling film on a large (large area) substrate or a complicated shape in the atmosphere.

  It is a model sectional view showing an example of an optical element to which the present invention is applicable.

  Hereinafter, an embodiment of the present invention will be described taking a spectacle lens as shown in FIG. 1 as an example.

  Here, the optical substrate (lens body) 10 may be an inorganic glass substrate or an organic glass substrate. The optical element includes an optical lens such as a spectacle lens and a camera lens, a front glass or a front filter of various displays, and an optical prism.

As the inorganic glass, those having a refractive index (n _D ) of 1.55 or more are easily obtained, barium crown glass (BaK) 1.54 to 1.60, heavy crown glass (SK)> 1.54, special Heavy crown glass (SSK)> 1.60, light barium flint (BaLF)> 1.55, barium flint (BaF)> 1.56, heavy barium flint (BaSF)> 1.585 and the like are suitable. The numbers after each inorganic glass abbreviation indicates the refractive index of the glass (n _D).

  Examples of the organic glass substrate include those made of polymethyl methacrylate (PMMA) polycarbonate (PC), aliphatic allyl carbonate, aromatic allyl carbonate, polythiourethane and the like.

  The scratch resistance (particularly in the case of an organic glass substrate) is usually formed with a hard coat film 12, and when the hard coat film is further formed, the primer film 14 is formed in order to increase the impact resistance. It is interposed between the lens body 10.

  As the hard coat film, a conventional silicone type or acrylic type is preferable, and as the hard coat film, a primer based on a urethane type (TPU) or ester type (TPEE) thermoplastic elastomer (TPE) is preferably used. Can be used (see Patent Document 4, paragraphs 0028-0056, etc.)

Then, on the hard coat film 14, an optical inorganic thin film (antireflection film or mirror coat) 16 which is the outermost layer SiO ₂ layer is usually formed as in Examples and Comparative Examples described later.

That is, by forming a single layer made of ceramics and metal films such as metal oxides and metal halides or a multilayer thin film made of two or more substances, optically reducing or increasing the reflectance Form.
When the lens body is inorganic glass, the optical inorganic thin film (antireflection film or mirror coat) is directly formed on the inorganic glass.

  Here, the inorganic thin film material is formed by a conventional method in which a conventional material can be used (Patent Document 4, paragraphs 0059 to 0060).

  In the present invention, a water-repellent antifouling film having the following constitution is formed on the inorganic glass substrate or the optical inorganic thin film, that is, on the surface to be treated of the substrate.

  Specifically, the water-repellent antifouling film 18 of the present invention uses a fluorine organic group-introduced silane compound having a silyl group reactive with a fluorine-modified organic group as a film component (main agent), and a contact angle (vs pure water) of 100 °. It is assumed that the above characteristics are exhibited.

  The film thickness of the water-repellent antifouling film (water / oil repellent film) varies slightly depending on the type of water-repellent antifouling agent and the film forming method, but is usually 0.003 to 0.03 μm, preferably 0.005 to 0.025 μm. More preferably, it is 0.005 to 0.02 μm. If the film thickness of the water-repellent antifouling film is less than a predetermined value, water / oil repellency cannot be expected, and problems with the scratch resistance and chemical resistance tend to occur. On the other hand, when the value exceeds the predetermined value, the transmittance tends to decrease due to surface light scattering of the water-repellent antifouling film.

  Specifically, as a surface protective agent (coating agent) containing a fluorinated organic group-introduced silane compound as a film component, a fluorinated organic group-introduced silane compound “X-71-195” manufactured by Shin-Etsu Chemical Co., Ltd. is fluorinated. A solution diluted to an appropriate concentration with a solvent (for example, Novec7200 manufactured by 3M Co., Ltd.) can be used. Although it is the same system as "X-71-130" (this application: Paragraph surface comparative protective film 2) used by patent document 4, it is thought that a molecular weight is a little high.

  The method for forming the water-repellent antifouling film may be the following dry processing method (a) or wet processing method (b).

  (A) Dry treatment method (dry coating method) A coating agent (surface protective agent) in which a fluorine organic group-introduced silane compound is diluted to an appropriate concentration in a fluorine-based solvent is attached to a lump of fibrous conductive material, and under vacuum A water-repellent antifouling film is formed on the optical element by heating (see, for example, Patent Document 2 and Claim 1).

  Here, the vacuum pressure during film formation is 1 to 0.0001 Pa, preferably 0.5 to 0.005 Pa, more preferably 0.1 to 0.001 Pa. When the vacuum pressure is higher than 1 Pa, the average free path of the evaporated molecules is short and an appropriate film forming speed cannot be obtained. When the vacuum pressure is lower than 0.0001 Pa, the film forming speed can be obtained, but it takes time to make the vacuum state. .

  The film forming rate is 0.05 to 5.0 Å / s, preferably 0.1 to 2.0 Å / s. If it is 0.05 kg / s or less, the productivity is inferior and the film forming cost is high, and if it is 5.0 kg / s or more, it is difficult to obtain an appropriate film thickness distribution. The film formation rate can be adjusted by operating the vacuum pressure / heating temperature.

  (B) Wet treatment method (wet coating method) After applying the surface protective agent on the optical element, the humidity (RH) is 10 to 90% (desirably 20 to 80%), and the temperature is 10 to 60 ° C. (20 to 50). The water-repellent antifouling film is formed by being left for a predetermined time in an atmosphere of (° C.). The predetermined time is usually 0.5 to 24 h (desirably 1 to 10 h) although it varies depending on the reaction rate of the surface protective agent and the atmospheric conditions.

  The coating method is arbitrary, such as a dipping method, a spin coating method, a brush coating method, or a spray method.

  In the above, if the atmospheric humidity is too low, it is difficult to obtain sufficient reactivity of the reactive group (by hydrolysis), and conversely if it is too high, poor appearance tends to occur.

  On the other hand, if the ambient temperature is too low, the reaction of the silane compound is slow, whereas if it is too high, appearance defects such as cracks and deformation of the optical element substrate tend to occur in the optical inorganic thin film.

  For example, there is the following method described in the product catalog of “Fluorine antifouling coating agent KY-130 (3)” (Shin-Etsu Chemical Co., Ltd.). Is there a description of what is used in the examples?

  "Dilute to an appropriate concentration with a fluorine-based solvent (Novec 7200 (former name: HPE-7200) [manufactured by 3M Co., Ltd.], etc.) and apply to the surface of the substrate by dipping, brushing, etc. Remove the surface with a dry cloth.

  ・ Room temperature, humidity 40% ... 24 hours or more ・ 60 ℃, humidity 80% ... 2 hours or more (recommended conditions)

  Hereinafter, Examples and Comparative Examples performed for confirming the effects of the present invention will be described in detail.

  (1) The drug and optical substrate are as follows.

<Drug>
TPEE "Pesresin A-160P" (manufactured by Takamatsu Yushi Co., Ltd., polyester-polyether type water-dispersed emulsion (aqueous), solid content concentration 27%)
-Titania-based metal oxide fine particles A "Optlake 1130F-2 (A-8)" (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 30%, dispersion solvent methyl alcohol)
-Titania-based metal oxide fine particle B "Optlake 1120Z (S-7, G)" (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20%, dispersion solvent methyl alcohol)
Colloidal silica “Methanol silica sol” (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30%, dispersion solvent methyl alcohol)
<Optical substrate (lens body)>
Refractive index 1.50: “CR-39” (manufactured by PPG Co)
Refractive index 1.60: “MR-95” (Mitsui Chemicals, Inc.)
Refractive index 1.67: “MR-10” (Mitsui Chemicals, Inc.)
Refractive index 1.74: “MR-174” (Mitsui Chemicals, Inc.)
Each substrate was pre-treated by being immersed in a 10% aqueous sodium hydroxide solution at 40 ° C. for 3 minutes, then washed with water and dried.

  (2) Each primer composition was prepared as follows.

<Primer composition 1>
To 100 parts of commercially available TPEE “Pesresin A-160P”, 57 parts of titania-based metal oxide fine particles “Optlake 1120Z (S-7.G)”, 350 parts of methyl alcohol as a diluent, and silicone-based surfactant “L- A primer composition was prepared by mixing 1 part of 7001 "and stirring until uniform.

<Primer composition 2>
It was prepared in the same manner as Primer Coat 1 except that the titania-based metal oxide fine particles “Optlake 1120Z (S-7, G)” were changed to 210 parts.

  The primer composition and the hard coat composition were applied by a dipping method (pickup speed: 105 mm / min).

  (3) Each hard coat composition is prepared as follows.

<Hard coat composition 1>
_To 109 parts of _Y -glycidoxypropyltrimethoxysilane, 40 parts of tetraethoxysilane, and 27 parts of _Y -glycidoxypropylmethyldimethoxysilane, 160 parts of methyl alcohol are added, and 38 parts of 0.01N hydrochloric acid are added dropwise with stirring. Then, hydrolysis was performed all day and night to prepare a hydrolyzate.

  The hydrolyzate is mixed with 390 parts of colloidal silica, 1 part of a silicone surfactant (“SILWET L-7001” manufactured by Nihon Unicar) and 1.5 parts of acetylacetone iron as a catalyst, and stirred for a whole day and hard coat. A composition was prepared.

<Hard coat composition 2>
_To 150 parts of _Y -glycidoxypropyltrimethoxysilane and 25 parts of tetraethoxysilane, 150 parts of methyl alcohol is added, and 40 parts of 0.01N hydrochloric acid are added dropwise with stirring to perform hydrolysis all day and night. Prepared.

  The hydrolyzate was mixed with 170 parts of titania-based metal oxide fine particles “Optlake 1130F-2 (A-8)”, 1 part of a silicone surfactant (L-7001) and 1.0 part of acetylacetone aluminum as a catalyst. The mixture was stirred for a whole day and night to prepare a hard coat composition.

<Hard coat composition 3>
It was prepared in the same manner as the hard coat film 2 except that the titania-based metal oxide fine particles “Optlake 1130F-2 (A-8)” was changed to 350 parts.

  (4) Each optical inorganic thin film (antireflection film or mirror coat) is formed as follows.

<Optical inorganic thin film 1>
While the vacuum chamber was heated to 60 ° C., the pressure was evacuated to 1.33 × 10 ⁻³ Pa and oxygen ion cleaning was performed, and then the first layer SiO ₂ refractive index 1.46 optical film thickness 26 nm from the substrate side.
Second layer ZrO ₂ Refractive index 2.05 Optical film thickness 81 nm
Third layer SiO ₂ refractive index 1.46 Optical film thickness 22 nm
Fourth layer ZrO ₂ refractive index 2.05 Optical film thickness 132 nm
5th layer SiO ₂ refractive index 1.46 Optical film thickness 131 nm
Vacuum deposition is performed in this order to form an antireflection film.

<Optical inorganic thin film 2>
While the vacuum chamber was heated to 60 ° C., the pressure was evacuated to 1.33 × 10 ⁻³ Pa and oxygen ion cleaning was performed, and then the first layer SiO ₂ refractive index 1.46 optical film thickness 26 nm from the substrate side.
Second layer ZrO ₂ Refractive index 2.05 Optical film thickness 93 nm
Third layer SiO ₂ refractive index 1.46 Optical film thickness 18 nm
Fourth layer ZrO ₂ refractive index 2.05 optical film thickness 135 nm
5th layer SiO ₂ refractive index 1.46 Optical film thickness 131 nm
Vacuum deposition is performed in this order to form an antireflection film.

<Optical inorganic thin film 3>
While the vacuum chamber was heated to 60 ° C., the pressure was evacuated to 1.33 × 10 ⁻³ Pa and oxygen ion cleaning was performed, and then the first layer SiO ₂ refractive index 1.46 optical film thickness 26 nm from the substrate side.
Second layer TiO ₂ Refractive index 2.36 Optical film thickness 34 nm
Third layer SiO ₂ refractive index 1.46 Optical film thickness 45 nm
Fourth layer TiO ₂ refractive index 2.36 Optical film thickness 120 nm
Fifth layer SiO ₂ refractive index 1.46 Optical film thickness 18 nm
Sixth layer TiO ₂ Refractive index 2.36 Optical film thickness 94 nm
Seventh layer SiO ₂ refractive index 1.46 Optical film thickness 129 nm
Vacuum deposition is performed in this order to form an antireflection film. The _second , fourth and sixth layers of TiO ₂ were performed by oxygen ion assisted deposition.

<Optical inorganic thin film 4>
While the vacuum chamber was heated to 60 ° C., the pressure was evacuated to 1.33 × 10 ⁻³ Pa and oxygen ion cleaning was performed, and then the first layer ZrC ₂ refractive index n 2.05 optical film thickness 130 nm from the substrate side.
Second layer SiC ₂ Refractive index n 1.46 Optical film thickness 130 nm
Third layer ZrC ₂ Refractive index n 2.05 Optical film thickness 130 nm
Fourth layer SiC ₂ Refractive index n 1.46 Optical film thickness 130 nm
5th layer ZrC ₂ Refractive index n 2.05 Optical film thickness 130 nm
Sixth layer SiO ₂ refractive index n 1.46 Optical film thickness 130 nm
Vacuum deposition was performed in this order to form a mirror coat.

  In the above, “ion cleaning” and “ion assist method” mean the following methods, respectively.

<1> Ion cleaning When forming an optical inorganic thin film, it is desirable to perform a surface treatment of the hard coat film as a pretreatment in order to increase the adhesion of the optical inorganic thin film. Specific examples include plasma treatment with high-frequency oxygen or argon, chemical treatment with acid or alkali, oxygen ion or argon ion irradiation treatment with an ion gun, and the like.

Of the above, it is desirable to obtain a good surface by irradiating oxygen ions or argon ions with an ion gun. (See JP 10-123301 A, etc.)
<2> Ion assist method:
The deposition of at least the high refractive index layer is performed using the ion beam assist method, and the ion beam assist method may be used for other films, or other physical deposition methods may be used. Also good. (See JP-A-11-174205 etc.)
(5) Each water-repellent antifouling film is formed as follows.

<Water-repellent antifouling film 1>
<1> Chemical preparation Dilute fluorine coating agent ("X-71-195" (20% solid content) manufactured by Shin-Etsu Chemical Co., Ltd.) with fluorine-based solvent (FR thinner manufactured by Shin-Etsu Chemical Co., Ltd.) The product was prepared so as to have a solid content of 3%, and steel copper (manufactured by Nippon Steel Wool Co., Ltd., # 0, wire diameter 0.025 mm) with 0.5 g of opened copper (capacity: inner diameter) After filling a container packed in 16 mm × inner height 6 mm) (chemical filling amount 2.0 g), it was dried at 120 ° C. for 1 hour.

<2> Film formation The above-mentioned container filled with chemicals is set in a vacuum evaporator, and after making a vacuum of 0.01 Pa, it is evaporated at a film formation rate of 0.6 kg / s with a molybdenum resistance heating boat as a heating source. A 0.015 μm water-repellent antifouling film was formed on the surface of each element to be treated.

<Water-repellent antifouling film 2 (corresponding to surface protective film 1 described in Patent Document 4, paragraph 00099)>
<1> Preparation of chemicals Fluorine-based coating agent (“KY-130” manufactured by Shin-Etsu Chemical Co., Ltd. (solid content 3% product)) and steel wool (manufactured by Nippon Steel Wool Co., Ltd., # 0, wire diameter 0. (025 mm) 0.5 g was filled in a container filled with cylindrical copper (capacity: inner diameter 16 mm × inner height 6 mm) open to the top (chemical filling amount 1.0 g), and then dried at 120 ° C. for 1 hour. .

<2> Film formation The above-mentioned container filled with chemicals is set in a vacuum evaporator, and after making a vacuum of 0.01 Pa, it is evaporated at a film formation rate of 0.6 kg / s with a molybdenum resistance heating boat as a heating source. A 0.005 μm water-repellent antifouling film was formed on the surface of each element to be treated.

<Water-repellent antifouling film 3 (corresponding to surface protective film 3 described in Patent Document 4, paragraph 0103)>
<1> Preparation of chemicals 10 parts of dimethylsiloxane having a silanol group at both ends (number average molecular weight: 26000) and 10 parts of a hydrocarbon solvent (“Iper E” manufactured by Exxon Mobil) are added and mixed, and further ethyltriacetoxysilane 1 part and 0.05 part of dibutyltin acetate were added and mixed, and allowed to stand for 24 hours. Thereafter, 540 parts of methyl isobutyl ketone and 540 parts of cyclohexanone were added and mixed.

<2> Film Formation The optical element to be treated was immersed in the composition, pulled up at a pulling speed of 100 mm / min, and then dried and cured at room temperature for 24 hours.

  (6) Each Example / Comparative Example was performed as follows.

<Example-1>
A hard coat film 1 was applied to a CR-39 lens (n _{D =} 1.50) and cured under conditions of 110 ° C. × 2 hours to form a hard coat film.

  The lens provided with the hard coat film was set on a rotating lens dome to form an optical inorganic thin film D (mirror coat), and then the surface protective layer 1 was formed on the outermost surface.

<Example-2>
Primer coat 1 is applied to an MR-95 lens (n _{D =} 1.60), cured at 100 ° C. for 20 minutes, then hard coat film 2 is applied, and cured at 110 ° C. for 2 hours. A hard coat film was formed.

  The lens provided with the hard coat film was set on a rotating lens dome to form an optical inorganic thin film A (antireflection film), and then a water repellent antifouling film 1 was formed on the outermost surface.

<Example-3>
The hard coat film 3 was applied to the MR-10 lens and cured under the conditions of 110 ° C. × 2 hours to form a hard coat film.

  The lens provided with the hard coat film was set on a rotating lens dome to form an optical inorganic thin film B (antireflection film), and then a water repellent antifouling film 1 was formed on the outermost surface.

<Example-4>
Primer coat 2 is applied to an MR-174 lens (n _{D =} 1.74), cured at 100 ° C. for 20 minutes, then hard coat film 3 is applied, and cured at 110 ° C. for 2 hours. A coating film layer was formed.

  The lens provided with the hard coat film was set on a rotating lens dome to form an optical inorganic thin film C (antireflection film), and then a water repellent antifouling film 1 was formed on the outermost surface.

<Comparative Example-1>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 1, and then the water-repellent antifouling film 3 was formed on the outermost surface.

<Comparative Example-2>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 1, and then a water-repellent antifouling film 2 was formed on the outermost surface.

<Comparative Example-3>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 2, and then a water-repellent antifouling film 3 was formed on the outermost surface.

<Comparative Example-4>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 2, and then the water-repellent antifouling film 2 was formed on the outermost surface.

<Comparative Example-5>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 3, and then the water-repellent antifouling film 3 was formed on the outermost surface.

<Comparative Example-6>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 3, and then the water-repellent antifouling film 2 was formed on the outermost surface.

<Comparative Example-7>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 4, and then the water-repellent antifouling film 3 was formed on the outermost surface.

<Comparative Example-8>
The process up to the optical inorganic thin film was carried out in the same manner as in Example 4, and then the water-repellent antifouling film 2 was formed on the outermost surface.

  (7) About each Example / comparative example manufactured as mentioned above, the physical property / evaluation test of each following item was done.

<Test items>
<1> Scratch resistance test A load of 1000 g was applied to steel wool (# 0000), and the surface of the antireflection film of each test piece was rubbed at 50 times / 50 seconds to determine the degree of damage of the reflected light from the fluorescent lamp and Judgment was made by visual inspection using transmitted light.

○: Scratched area is within 10% △: Scratched area is over 10% and within 30% ×: Scratched area is over 30% <2> Adhesion test 1 cm per test piece 100 squares were formed at intervals of 1 mm, and the cellophane adhesive tape was strongly pressed, and then peeled off rapidly in the 90 ° direction, and the number of squares not peeled was counted.

<3> Warm water resistance test A test piece was immersed in 80 ° C. hot water for 10 minutes, and an adhesion test (described above) was performed.

<4> Weather resistance test Accelerated weather resistance test: A carbon arc type sunshine super long life weather meter (manufactured by Suga Test Instruments Co., Ltd.) was used for 100 hours to evaluate the scratch resistance and adhesion (described above).

<5> Water repellency test The contact angle with respect to pure water was measured with a contact angle meter (CA-D type manufactured by Kyowa Interface Science Co., Ltd.).

○: Contact angle of 100 ° or more Δ: Contact angle of 80 ° or more ×: Contact angle of less than 80 ° <6> Chemical resistance ・ Acid resistance: After immersing the test piece in a 20 ° C. nitric acid aqueous solution (PH1) for 6 hours and washing with water The contact angle (relative to pure water) was measured (described above).

  Alkali resistance: The test piece was immersed in an aqueous solution of sodium hydroxide (PH11) at 20 ° C. for 6 hours, washed with water, and then contact angle was measured (described above).

<7> Antifouling property 1 (stain removal property)
A 1 cm long line was drawn on the surface of the test piece with a commercially available oil-based magic (Magic Ink No. 500 manufactured by Teranishi Chemical Industry Co., Ltd.), and rubbed 5 times with a handkerchief to determine whether or not it could be wiped off.

○: Completely wiped off △: Slightly left ×: Spread without wiping off

<8> Antifouling property 2 (droplet dropping property)
Tap water was dropped on the lens drop by drop with a dropper on a test piece inclined at 30 ° from the horizontal plane, and the water flow-down was visually evaluated.
○: Water droplets flowed down quickly △: Water droplets stayed on the lens, but gradually dropped ×: Water droplets stayed on the lens and did not flow down <9> Frameworkability Frameworking machine ("SEDEC made by Nidec Co., Ltd.) −9090 ”), it was determined whether or not the frame could be processed according to the specified mold. 20 pieces of each base material was used, and a non-defective product rate survey was conducted.

○: Good product rate of 95% or more ×: Good product rate of less than 95%

<10> Coefficient of Friction Measurement was performed with an automatic friction and wear analyzer TSf-300 manufactured by Kyowa Interface Science Co., Ltd. under the conditions of a load of 100 g, a moving speed of 10 mm / s, and a moving distance of 30 mm. The contacts in contact with the test pieces were SUS spheres and alumina spheres.

<11> Antifouling property 3 (wiping workability)
The test piece was rubbed with a cloth for glasses (Toray Co., Ltd. Toraysee), and the ease of wiping was evaluated.

×: There is surface resistance, and it cannot be wiped unless the test piece is strongly pressed. △: There is a little surface resistance, and it is necessary to lightly press the test piece. ○: There is no surface resistance and the test piece is not pressed. <Effect confirmation>
The test results are shown in Tables 1 and 2.

Each embodiment of the present invention has various practical properties (scratch resistance / sticking property, weather resistance, water repellency, chemical resistance), excellent alkalinity) and antifouling without impairing frame workability. It can be seen that the properties 2 and 3 (water dropability and wiping workability) are even better than before.
This is considered to be based on the friction characteristics of the water-repellent antifouling film being such that the SUS sphere μ _s is not less than the predetermined value and the SUS sphere μ _k is less than the predetermined value.

10 Optical substrate (lens body)
12 Primer coat 14 Hard coat film 16 Optical inorganic thin film (antireflection film or mirror coat)
18 Water repellent antifouling film

Claims (7)

The surface to be treated is a silica-based surface and is formed of a fluorine organic group-introduced silane having a fluorine-modified organic group and a reactive silyl group, and has a contact angle (vs pure water) of 100 ° or more. In an optical element with a film,
Friction characteristics of the repellent flood fouling film, a pair SUS ball mu _s> vs. SUS ball mu _k, and satisfy the pair SUS ball mu _s ≧ 0.100 and pair SUS ball mu _k <0.095 Optical element to do. 2. The optical element according to claim 1, wherein the frictional characteristic further satisfies the ratio SUS sphere μ _k / pair SUS sphere μ _s <0.95. 3. The optical element according to claim 2, wherein the friction characteristic further satisfies the relationship with respect to alumina sphere μ _k <0.08 and satisfies the relationship with respect to alumina sphere μ _k / with respect to alumina sphere μ _s <0.80.   4. The optical element according to claim 1, wherein the water-repellent antifouling film has a thickness of 0.005 to 0.03 [mu] m. 4. The optical element according to claim 1, wherein the surface to be treated is formed of an optical inorganic thin film that is an outermost layer SiO ₂ layer.   The optical element according to claim 1, wherein the optical element is a spectacle lens.   6. The method for producing an optical element according to claim 5, wherein the water repellent antifouling agent is attached to a lump of fibrous conductive material and heated under a vacuum of 1 to 0.0001 Pa. A method for producing an optical element, comprising forming a fouling film.

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