JP2002308651A - Method for imparting anti-fogging performance and optical article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart an anti-fogging effect excellent in durability to optical articles, such as spectacle lenses and window panes, without impairing their optical characteristics, such as reflection prevention. SOLUTION: The anti-fogging performance excellent in the durability is imparted to the optical articles by successively or simultaneously treating oxide surfaces with organosilanes and surfactants.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to lenses such as glasses and cameras having anti-fog performance, or optical articles such as window glasses, car windshields, helmet shields, underwater glasses, and mirrors used in bathrooms. Etc. relating to the oxide surface.

[0002]

2. Description of the Related Art The phenomenon that the surface of an article is fogged occurs because minute water droplets adhere to the surface and form dew, and the minute water droplets irregularly reflect light. This fogging causes a remarkable decrease in the performance of optical components such as spectacle lenses and optical lenses, and is a major problem in terms of safety as window glass for vehicles such as automobiles.

[0003] In order to impart antifogging performance to an article, 1) the base material is made to absorb water, 2) the base material surface is made hydrophilic,
3) The surface of the base material is made hydrophobic. 4) The surface temperature of the optical article is increased so that moisture in the air does not condense on the surface.
The above four methods have been proposed in the past, and various attempts have been made.

Regarding the method of 1) for imparting water absorbency to a substrate, a water absorbent material is mixed with a coating composition or a synthetic resin substrate itself, or a hydrophilic and water absorbent monomer is copolymerized. There is a method of imparting water absorbency by using water. This is described in JP-A-10-311902 and JP-A-05-156.
202 and the like. As a method of imparting water absorbency to an inorganic substance such as glass having poor water absorbency, a method of imparting water absorbency by making the inorganic substance porous is disclosed in
114543.

[0005] As the method 2) for making the surface of the substrate hydrophilic, the simplest method is to apply a surfactant to the surface to make the surface of the substrate hydrophilic and prevent fogging. Also, in order to expect continuous effects, as described above, a surfactant is mixed with the synthetic resin base material itself, or a hydrophilic, water-absorbing monomer is copolymerized to form the synthetic resin base material. There is a method of imparting anti-fogging performance by using. For this,
JP-A-10-114035, JP-A-10-13051
1, JP-A-10-158453, JP-A-10-1829
12, and JP-A-10-202798. A method of applying a coating having anti-fog performance to the surface of an optical resin article is also well known.
6, JP-A-8-27291, JP-A-9-136374,
It is disclosed in JP-A-9-151368 and JP-A-9-155282.

A method for forming a photocatalytic metal oxide film and exhibiting superhydrophilicity is disclosed in JP-A-2000-3090.
68, JP-A-2000-86933, JP-A-9-7753
5, JP-A-10-68091, JP-A-10-8510
0, JP-A-10-167727, JP-A-10-2979
40 and the like.

[0007] Graft polymerization as a method of surface modification is
This is a method in which a hydrophilic group is monomolecularly introduced into the substrate surface, and is a very effective means on an oxide film having antireflection properties. JP-A-5-202216, JP-A-5-29513
9, JP-A-8-176328, JP-A-9-30174
2. It is disclosed in JP-A-10-90503 and the like. Other surface modification methods include JP-A-10-114543 and JP-A-10-167768.

Further, Japanese Patent Application Laid-Open Nos. 9-202651 and 9-29583 disclose a patent in which pores / concavities and convexities of an inorganic substance are combined with a hydrophilic substance and a patent utilizing surface irregularities.
5, JP-A-11-77876.

Method 3) is a method in which the contact angle on the surface of the base material is increased so that water drops fall off by its own weight. This is disclosed in JP-A-2000-103007, JP-A-10-26703,
It is disclosed in JP-A-10-45429 and JP-A-11-320743.

4) The surface temperature of the optical article is increased so that moisture in the air does not condense on the surface. For information on how,
It is disclosed in JP-A-7-241932 and JP-A-2000-86299.

[0011]

However, the conventional methods have various disadvantages. In particular, in the case of an optical article having antireflection characteristics, it is difficult to provide the outermost surface with antifogging characteristics without changing the antireflection characteristics.

In the method of (1) for imparting water absorbency to the base material, sufficient performance is obtained as anti-fog performance, but when water is absorbed, it becomes very soft and easily scratched. . In addition, if the number of cross-linking points is increased to improve this, it is said that the water absorption decreases. In addition, there is a disadvantage that when the water absorption exceeds the saturated water absorption, clouding occurs. Further, there is a drawback that dirt in the air, for example, cigarette smoke is easily adsorbed, and the optical article is colored. Further, in the case of such a water-absorbing film, it is necessary to have a certain thickness, and it is impossible to formulate the film on a substrate having antireflection properties.

In the method of making an inorganic substance porous so as to have water absorption, the water absorption is small because the film thickness is limited.
By making it porous, the surface becomes brittle, and there is a problem in scratch resistance.

In the method of 2) for making the substrate surface hydrophilic, most kinds of surfactants flow down due to adhesion of water and the like, and a continuous effect cannot be expected. It takes time and effort. However, it is a very effective means for imparting anti-fogging property to a film having anti-reflection properties in that the anti-reflection properties are not hindered.

With respect to the method of forming a photocatalytic metal oxide film and exhibiting superhydrophilicity, it is difficult to develop superhydrophilicity unless it is exposed to ultraviolet rays because of its mechanism. In the case of extremely small water droplets like the above, since they do not have a sufficient size for the crystal structure of the photocatalytic substance,
Spread of water droplets is not enough, and cloudiness is recognized. In addition, in the case of an optical material having an antireflection property, in particular, the presence of a photocatalytic substance having a high refractive index on the outermost surface results in an increase in reflection.

[0016] Various methods have been proposed for graft polymerization, in which a hydrophilic and hydrophobic thin film is formed on the outermost surface. According to the prior art, the reaction is complicated, and the antifogging component does not react densely on the surface of the substrate, so that sufficient antifogging property cannot be obtained.

In the method of 3) in which the contact angle of the surface of the base material is increased and the water droplets fall off by their own weight, the water droplets fall only after the water droplets have a certain size. Therefore, in the case of extremely minute water droplets such as cloudy, the water droplets do not fall naturally because of their insufficient weight.

In the method 4), the heater section and the energy source are indispensable, and the apparatus becomes too complicated.

Accordingly, the present invention has been made to solve the above-mentioned problems and to obtain an optical article having excellent antifogging performance on an oxide surface without deteriorating the optical properties of the optical article. Aim.

[0020]

According to the present invention, there is provided an optical article having an anti-fogging property, wherein an optical article mainly containing an oxide on the surface has a surface where the uncoupling site contains at least one or more sulfur. The organosilane or / and hydrolyzate thereof, which is a chain saturated hydrocarbon, and the surfactant are treated sequentially or simultaneously. Thereby, a chain hydrocarbon chain on the base material side, an intermolecular interaction acts on the chain hydrocarbon chain of the surfactant, and when the surfactant is anionic, it contains sulfur on the base material side Interaction between the functional group and the molecule works. Due to these interactions, the surfactant is strongly bonded to the base material, so that the surface of the oxide film can be given a long-lasting anti-fog performance.

In the case of an optical article made of glass containing silicon oxide as a main component, there is no major problem in the scratch resistance, but the optical article made of a synthetic resin is easily scratched, and the scratch resistance must be improved. In order to improve the scratch resistance of the synthetic resin, a hard coat treatment is often performed. In particular, a hard coat containing colloidal silica is effective and widely used. In the case of a spectacle lens or the like, an antireflection film made of an inorganic substance is formed on the surface to improve the optical characteristics. A low refractive index layer is formed as the uppermost layer of the antireflection film, but silicon dioxide is widely used in terms of durability and ease of handling.

As described above, silicon dioxide is often used for the improvement of scratch resistance and the antireflection film, and silicon dioxide is present on the surface of not only inorganic glass but also optical articles made of synthetic resin. Often. Even when a film made of an organic material is used as the antireflection film, if the uppermost layer contains colloidal silica, silicon dioxide will be present on the surface.

The present invention provides an optical article made of glass containing silicon dioxide and a metal oxide as main components, an optical article made of a synthetic resin having a hard coat containing colloidal silica and a metal oxide applied on the surface, and a silicon dioxide and The present invention can be applied to an optical article having an antireflection film using a metal oxide, and in any case, an article having silicon dioxide and a metal oxide on the surface.

The organosilane and / or the hydrolyzate thereof used in the present invention contains a chain saturated hydrocarbon having at least one functional group containing sulfur at a non-coupling site. The chain saturated hydrocarbon preferably has 3 to 20 carbon atoms. One of the sulfur-containing functional groups is located at the end of the hydrocarbon chain, and the positions of the other sulfur-containing functional groups are not limited. The reaction with silicon dioxide and metal oxide present in the outermost layer is performed by using a silane coupling agent having a group that reacts with silanol on the substrate side, such as chlorosilane, alkoxysilane, or silazane. A reaction with silanol of the metal oxide can be realized. This is a commonly used method.

As such an organosilane, 12-
Trichlorosilyldecylsulfonic acid, sodium 12-trichlorosilyldecylsulfonate, 18-methyldichlorosilyloctadecylsulfate, potassium 16-methyldichlorosilylhexadecylsulfate, 3-mercaptopropyltrimethoxysilane 12-methyldichlorosilyldecylsulfate, 6- Methylsulfoxyhexyltrimethoxysilane, 12- (3-mercaptopropylthio) nonyltrimethoxysilane, 8-methyldimethoxysilyloctylsulfonyl chloride, 12-trimethoxysilyldecylsulfonic acid, sodium 12-triethoxysilyldecylsulfonate, 18-methyldimethoxysilyloctadecyl sulfate, potassium 16-ethyldiethoxysilylhexadecyl sulfate, 12-methyldimethoxysilyldecyl sulfate Such as 18-mercaptopurine octadecyl trichlorosilane and the like, but not limited to this.

In order to enhance the reactivity between the organosilane and the oxide, it is effective to apply a plasma treatment or an alkali treatment to silicon dioxide and metal oxides existing on the surface in advance.
The anti-fog effect is also improved.

The surfactants used in the present invention include surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants and double-sided surfactants, and reactive derivatives thereof. It is desirable to include a chain saturated hydrocarbon as the hydrophobic moiety. From the interaction with the sulfur-containing group on the organosilane side, an anionic surfactant is preferable, and an anionic surfactant in which the anionic group is sulfuric acid or sulfate is more preferably used. The number of carbon atoms is preferably 4 to 20, and more preferably 1 to 3 less than the number of carbon atoms of the organosilane containing chain hydrocarbon. As a result, the chain hydrocarbon chain on the substrate side and the chain hydrocarbon chain of the surfactant are caused by intermolecular interaction, and the terminal sulfur on the substrate side and the sulfate group of the surfactant are caused by electrostatic interaction. Connect tightly. The antifogging substance to be used may be one kind of a specific compound or a mixture of two or more kinds.

Specifically, examples of the anionic surfactant include alkyl sulfate esters such as sodium lauryl sulfate, sodium higher alcohol sulfate and triethanolamine lauryl sulfate; alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate; Alkyl naphthalene sulfonates such as sodium naphthalene sulfonate; alkyl sulfosuccinates such as sodium dialkyl sulfosuccinate; alkyl diphenyl ether disulfonates such as alkyl diphenyl ether disulfonate sodium; alkyl phosphates such as potassium alkyl phosphate A sodium polyoxyethylene lauryl ether sulfate, a sodium polyoxyethylene alkyl ether sulfate, and a triethanol alcohol polyoxyethylene alkyl ether sulfate; Polyoxyethylene alkyl (or alkyl allyl) sulfate such as sodium polyoxyethylene alkyl phenyl ether sulfate; special reactive anionic surfactant; special carboxylic acid surfactant; β-naphthalenesulfonic acid formalin condensate Naphthalenesulfonic acid formalin condensates such as sodium salts of sodium and special aromatic sulfonic acid formalin condensates; special polycarboxylic acid type polymer surfactants; and polyoxyethylene alkyl phosphates.

Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene higher alcohol ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene derivatives; sorbitan monolaurate, sorbitan monopalmitate; Sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, sorbitan distearate, and other sorbitan fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, Polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene Ren sorbitan tristearate,
Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan trioleate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbite tetraoleate; glycerol monostearate, glycerol monooleate, self Glycerin fatty acid esters such as emulsified glycerol monostearate; polyoxyethylene fatty acid esters such as polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate and polyethylene glycol monooleate: polyoxyethylene alkylamine; poly Oxyethylene hydrogenated castor oil; alkyl alkanolamides and the like.

Examples of the cationic surfactant and the double-sided surfactant include alkylamine salts such as coconutamine acetate and stearylamine acetate; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and distearyldimethylammonium. Quaternary ammonium salts such as chloride and alkyl benzyldimethyl ammonium chloride: alkyl betaines such as lauryl betaine, stearyl betaine, lauryl carboxymethyl hydroxyethyl imidazolinium betaine; and amine oxides such as lauryl dimethylamine oxide.

The oxide used in the present invention is not limited to silicon dioxide, but may be any metal oxide film which reacts with organosilane. However, in view of the reactivity of the organosilane, silicon dioxide is preferred. The oxide film used in the present invention may be formed by any method such as evaporation, sputtering, CVD, and dehydration condensation of a condensable organometallic compound.

It is important that the formed processing layer is a thin film that does not adversely affect the reflectivity characteristics of the antireflection layer, and it is preferable that the thickness be 300 ° or less, but the film thickness is determined in consideration of the refractive index of the thin film. It is also possible to incorporate a thin film as antireflection.

By the above operation, the hydrophilic portion of the surfactant is present on the outermost surface of the optical article having the oxide on the surface. In order to obtain anti-fog performance, the static contact angle with water is desirably 10 ° or less, but in order to obtain sufficient performance, 5 ° or less is required.
This can be achieved by increasing the number of active sites on the surface and increasing the amount of surfactant retained. Further, a method of increasing the packing ratio of the hydrophilic group depending on the structure of the surfactant used is also possible.

The optical article having anti-fog performance obtained by the present invention has good durability, excellent scratch resistance, and excellent optical properties such as anti-reflection, and is suitable for spectacle lenses, camera lenses, and mirrors in bathrooms. It can be applied to underwater glasses, window glasses, microwave oven windows, car window glasses, telescope lenses, ski goggles, lenses of optical equipment used in humid places, mirrors, and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION <Preparation of oxide film> In a reaction vessel equipped with a stirrer, isopropyl alcohol was added.
8 g, 300.0 g of distilled water, 139.4 g of γ-glycidoxypropyltriethoxysilane, and 38.2 g of a 0.05 N hydrochloric acid aqueous solution were added, and the mixture was stirred for 60 minutes. Next, a composite sol of titanium oxide / zirconium oxide / silicon oxide ("Optreak 1120Z (U25A
8) ") 3.3 g of silicone-based surfactant (" L-7604 "manufactured by Nippon Unicar Co., Ltd.) was added,
After sufficiently stirring, a coating liquid was obtained.

The above-described coating solution was applied to a plastic lens (lens fabric for Seiko Super Sovereign, refractive index 1.67, manufactured by Seiko Epson KK) which was previously immersed in a sodium hydroxide solution (0.1N), washed well with water, and dried. Was applied by dipping to a thickness of 2.5 μm, and cured by heating at 135 ° C. for 2.5 hours. The surface of the lens thus obtained is subjected to plasma treatment (argon plasma 400 W × 60 seconds), and then an anti-reflection film made of an inorganic substance such as silicon dioxide and zirconium oxide is coated in multiple layers by a vacuum evaporation method. A coat, a plastic lens with antireflection, and a substrate A were prepared. The static contact angle of the substrate A with water was 5 °.

[Example 1] 1. Organosilane treatment 3-A mercaptomethyldichlorosilane (0.5 g) was dissolved in n-hexane (199.5 g), and the above-mentioned base material (A) was dissolved in a liquid.
It was immersed at 5 ° C for 1 hour. Thereafter, the substrate is taken out and n-
Washing was performed with hexane. Thereby, the organosilane was reacted with the oxide surface. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. At this time, the contact angle with water was 34 °, and it was confirmed that the organosilane was immobilized on the surface.

2. Surfactant treatment 0.5 g of sodium lauryl sulfoacetate was added to distilled water 19
The surfactant solution was prepared by dissolving in 9.5 g. 25
The substrate treated with the above-mentioned organosilane was immersed in this liquid kept at 0 ° C. for 1 hour and air-dried. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. At this time, the contact angle with water was 3 °, and it was confirmed that the hydrophilic group was present on the outermost surface.

The method for evaluating the antifogging property of the obtained optical article is "J
The anti-fog properties of low temperature parts of IS-S4030 "Test method for anti-fog agent for spectacles" were evaluated with grades 1 to 4.
(The first grade has the best anti-fog performance, and the fourth grade is the worst.) Here, the second grade or higher was set to a practical level. The abrasion resistance was evaluated by the method of scratching when rubbing the reciprocating surface with a load of 1 kg with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.).
(A: There is no scratch within the range of 1 cm * 3 cm.
B: 1 to 10 scratches are made within the above range. C: 11 to 100 scratches are made in the above range. D: Countless scratches are formed within the above range. Regarding the anti-fogging durability, the produced optical article was immersed in distilled water at 40 ° C. for 10 minutes, air-dried at room temperature for one day, and similarly evaluated for anti-fogging property. The evaluation results are summarized in Table 1.

[Embodiment 2] 1. Treatment with Organosilane and Surfactant 0.8 g of 12-trichlorosilyl decyl sulfonic acid was dissolved in 199.2 g of ethanol, 0.01 g of a 0.5N hydrochloric acid aqueous solution was mixed therein, and the mixture was stirred at 25 ° C. for 2 hours.
Next, 0.5 g of sodium lauryl sulfate was dissolved in this solution to obtain a treatment liquid. Here, the substrate A was immersed at 25 ° C. for 1 hour. Thereafter, the substrate was taken out, washed with ethanol, and air-dried. As a result, the surface of the oxide was reacted with the organosilane to retain the surfactant. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. At this time, the contact angle with water was 5 °, and it was confirmed that the organosilane and the surfactant were immobilized on the surface.

Embodiment 3 Organosilane treatment The substrate A after the vapor deposition was held in a vapor deposition tank, and 1 cc of 12-triethoxysilyldecyl sulfonic acid was injected into the tank and reacted while keeping the degree of vacuum. Thereafter, the substrate was taken out. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. At this time, the contact angle with water was 49 °, and it was confirmed that the organosilane was immobilized on the surface. Also, this lens is 1N NaOH
After being immersed in an aqueous solution for 1 minute, it was washed with distilled water and air-dried to change the sulfonic acid to sodium sulfonate. At this time, the contact angle with water was 10 °.

2. Surfactant treatment Polyoxyethylene octyl phenyl ether 0.5g
Was dissolved in 199.5 g of distilled water to prepare a surfactant solution. The above-mentioned organosilane-treated substrate was immersed in this liquid kept at 25 ° C. for 1 hour and air-dried. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. At this time, the contact angle with water was 3 °, and it was confirmed that the hydrophilic group was present on the outermost surface.

[Embodiment 4] Organosilane and Surfactant Treatment The base material A after the vapor deposition is kept in a vapor deposition vessel, and while keeping the degree of vacuum, 1 cc of 12- (3-mercaptopropylthio) nonyltrimethoxysilane and polyoxyethylene lauryl are placed in the vessel. 1 cc of ether was injected and reacted. Thereafter, the substrate was taken out. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. The contact angle with water at this time was 5 °.

Comparative Example 1 The substrate A itself was used as Comparative Example 1.

Comparative Example 2 A sample was prepared in the same manner as in Example 1 except that magnesium fluoride was vacuum-deposited to a film thickness of 100 nm instead of the antireflection film of the substrate A. Was prepared.

[Comparative Example 3] The result of the organosilane treatment of Example 3 was used as a comparative example.

Comparative Example 4 0.5 g of polyoxyethylene lauryl ether was dissolved to prepare a treatment liquid. Here, the substrate A was immersed at 25 ° C. for 1 hour. Thereafter, the substrate was taken out, washed with ethanol, and air-dried. At this time, no significant change was observed in the appearance and antireflection characteristics of the lens. The contact angle with water at this time was 5 °.

[0049]

[Table 1]

[0050]

According to the present invention, it is possible to hold a surfactant densely on a surface where an oxide is present, and to provide an optical element having an antifogging property which does not have an optical effect such as a decrease in antireflection characteristics. Articles can now be manufactured.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/08 G02B 1/10 Z F-term (Reference) 2D032 GA00 2H042 DA18 DB11 DC02 DE08 2K009 BB02 BB11 CC21 CC42 DD02 DD08 EE02 4G059 AA01 AA11 AC21 FA04 FA05 FA22 FB06 GA01 GA02 GA04 GA11 GA16

Claims (6)

[Claims] 1. An article mainly comprising an oxide on its surface, wherein the surface of the article has an uncoupling site, which is a chain saturated hydrocarbon containing at least one or more sulfur, and / or a hydrolyzate thereof. And a surfactant,
A method for imparting anti-fog performance, wherein the treatment is performed sequentially or simultaneously. 2. The method according to claim 1, wherein the coupling site of the organosilane is alkoxysilane, chlorosilane, or silazane. 3. The method according to claim 1, wherein the surfactant is an ionic surfactant. 4. The method according to claim 3, wherein the ionic surfactant is an anionic surfactant. 5. The method according to claim 3, wherein the ionic surfactant contains a sulfate group or a sulfate. 6. An optical article obtained by the method for imparting anti-fog performance according to any one of claims 1 to 5.