JP2003057403A - Antifog optical article and method for manufacturing the article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart an antifog effect with excellent scratching resistance and durability to optical articles such as lenses of spectacles and window glass without decreasing the optical characteristics of the articles such as surface hardness and antireflective performance. SOLUTION: The surface of an optical article containing oxides as the main component is treated with a silane coupling agent having a part which can be sulfonated or oxidized to produce a sulfonic acid. Then the agent is sulfonated or oxidized to impart high hydrophilicity to the surface and to impart the antifog performance with excellent durability to the optical article.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art The phenomenon that the surface of an article becomes cloudy occurs because minute water droplets adhere and condense on the surface and the minute water droplets diffusely reflect light. This fogging causes a significant deterioration 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.

In order to impart antifogging performance to an article, 1) the substrate is made to absorb water, 2) the surface of the substrate is made hydrophilic.
3) To make the surface of the substrate hydrophobic, 4) To raise the surface temperature of the optical article so that moisture in the air does not condense on the surface.
These four methods have been proposed in the past and various attempts have been made.

Regarding the method of imparting water absorbency to the base material of 1), a water absorbent material is mixed with the coating composition or the synthetic resin base material itself, or a hydrophilic or water absorbent monomer is copolymerized. There is a method for imparting water absorption. Regarding this, JP-A-10-311902, JP-A-05-156
202 and the like. Further, as a method for imparting water absorbency to an inorganic substance such as glass having poor water absorbency, a method of making the inorganic substance porous so as to have water absorbency is disclosed in Japanese Patent Laid-Open No. 10-
114543 and others have been tried.

Regarding the method 2) of making the surface of the substrate hydrophilic, the simplest means is to apply a surfactant to the surface to make the surface of the substrate hydrophilic and prevent fogging. Further, in order to expect a continuous effect, a synthetic resin base material is formed by mixing a surfactant into the synthetic resin base material itself or copolymerizing a hydrophilic or water-absorbing monomer, as described above. There is a method of imparting antifogging performance. For this,
JP-A-10-114035, JP-A-10-13051
1, JP-A-10-158453, JP-A-10-1829
12, JP-A-10-202798 and the like. Further, a method of applying a coating having an antifogging property to the surface of an optical resin article is also well known, and is disclosed in JP-A-8-1764.
6, JP-A-8-27291, JP-A-9-136374,
It is disclosed in Japanese Patent Application Laid-Open Nos. 9-151368 and 9-155282.

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

Graft polymerization as a method of surface modification is
A method in which a hydrophilic group is introduced monomolecularly on the surface of a substrate 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, disclosed in JP-A-10-90503. Other surface modification methods include JP-A-10-114543 and JP-A-10-167768.

Further, Japanese Patent Application Laid-Open No. 9-202651 and Japanese Patent Application Laid-Open No. 9-29583 are disclosed as a patent combining the pores and unevenness of an inorganic substance with a hydrophilic substance and a patent utilizing the unevenness of the surface.
5, JP-A No. 11-77876.

Method 3) is a method in which the contact angle on the surface of the base material is increased and the water droplets are shed 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) Raise the surface temperature of the optical article so that moisture in the air will not condense on the surface. For information on how,
It is disclosed in Japanese Patent Application Laid-Open Nos. 7-241932 and 2000-86299.

[0011]

However, the methods hitherto have various drawbacks. In particular, in the case of an optical article having antireflection properties, it is difficult to provide the outermost surface with antifog properties without changing the antireflection properties.

Regarding the method 1) for imparting water absorbency to the substrate, sufficient antifogging performance can be obtained, 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, the water absorption rate will decrease. In addition, when the saturated water absorption amount is exceeded, there is a drawback that it becomes cloudy. In addition, dirt in the air, such as cigarette smoke, is easily adsorbed, which causes a drawback that the optical article is colored. Further, in the case of such a water-absorbing film, it is necessary to have a certain film thickness, and it is impossible to prescribe it on a substrate having an antireflection property.

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

Regarding the method 2) for making the surface of the substrate hydrophilic, almost all kinds of surfactants run off due to the adhesion of water, etc., and continuous effects cannot be expected, so they must be applied each time. It takes time and effort. However, it is a very effective means for imparting antifogging properties on a film having antireflection properties, since it does not hinder the antireflection properties.

Regarding the method of forming a photocatalytic metal oxide film and expressing superhydrophilicity, due to the mechanism, it is difficult to express superhydrophilicity and it is cloudy. In the case of extremely small water droplets such as, because they do not have a sufficient size for the crystal structure of the photocatalytic substance,
The spread of water droplets is not sufficient, and cloudiness is recognized. Further, particularly in the case of an optical material having antireflection properties, the presence of a photocatalytic substance having a high refractive index on the outermost surface causes the reflection to increase rather.

Various methods have been proposed for the graft polymerization, which is to form a hydrophilic or hydrophobic thin film on the outermost surface. According to the prior art, the reaction is complicated, and the antifogging component does not react intimately on the surface of the substrate, and sufficient antifogging property cannot be obtained.

In the method of 3) in which the contact angle on the surface of the base material is increased and the water droplets are shed by its own weight, the water droplets drop only after the water droplets have a certain size. Therefore, in the case of a very small water drop such as cloudy weather, it does not naturally fall because its own weight is insufficient.

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

Therefore, the present invention solves the above problems and obtains an optical article having an excellent antifogging property on an oxide surface without deteriorating the optical characteristics of the optical article. To aim.

[0020]

The optical article having the antifogging performance of the present invention is an optical article mainly containing an oxide, and the surface of the optical article is sulfonated or oxidized to sulfonic acid. After being treated with a silane coupling agent having a site capable of being treated with silane, it is characterized by imparting hydrophilicity by sulfonation or oxidation thereof.

Also, the sulfonation-possible site is a vinyl group.

The sulfonation-capable site is an epoxy group.

Further, the sulfonation-possible site is a carbonyl group.

Further, the sulfonation-possible site is an aromatic hydrocarbon.

Further, the sulfonation-possible site is halogen.

The site capable of being oxidized to sulfonic acid is a sulfide such as a mercapto group, a sulfide group, a sulfoxide group, a disulfide group or a sulfone group.

Further, the optical article mainly containing the oxide on the surface is a synthetic resin lens having an antireflection inorganic coating film or a synthetic resin lens having a hard coating layer and an antireflection inorganic coating film. To do.

The optical article mainly containing the oxide on the surface is glass.

The antifogging article of the present invention is characterized by being treated by any one of the above methods for producing an antifogging film.

In the case of a glass optical article containing silicon oxide as a main component, there is no serious problem in scratch resistance, but an optical article made of a synthetic resin is easily scratched, and scratch resistance must be improved. In order to improve the scratch resistance of the synthetic resin, 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 material is formed on the surface in order to improve its optical characteristics. A low refractive index layer is formed on the uppermost layer of the antireflection film, but silicon dioxide is widely used in terms of durability and handleability. As described above, silicon oxide is often used for the improvement of scratch resistance and the antireflection film, and silicon oxide is often present on the surface not only of inorganic glass but also of synthetic resin optical articles. . Even when a film made of an organic material is used as the antireflection film, if colloidal silica is contained in the uppermost layer, silicon oxide will be present on the surface.

The present invention relates to an optical article made of glass containing an oxide as a main component, an optical article made of a synthetic resin having a hard coat containing colloidal silica applied on the surface thereof, and an optical article having an antireflection film using an oxide as the uppermost layer. It can be applied to an article, in any case an article having an oxide present on its surface.

In the present invention, the surface of an optical article containing an oxide mainly on the surface is treated with a silane coupling agent having a site capable of being sulfonated or oxidized to a sulfonic acid. By treating the silane coupling agent first, it is possible to make the silane coupling agent densely present on the surface. Further, good hydrophilicity can be obtained by completely sulfonation or oxidation.

The site capable of being sulfonated or oxidized to a sulfonic acid may be present at any position in the organic chain of the silane coupling agent, but it is at the terminal because hydrophilicity is easily exhibited. Is desirable. Examples of the site capable of being sulfonated include a vinyl group, an epoxy group, a carboxy group, an aromatic hydrocarbon, and a halogen. Examples of the site capable of being oxidized to a sulfonic acid include a sulfide such as a mercapto group, a sulfide group, a sulfoxide group, a disulfide group or a sulfone group. The reaction with silicon oxide existing on the outermost layer can be realized by using a silane coupling agent having a group capable of reacting with silanol such as chlorosilane, alkoxysilane, and silazane, with the silanol possessed by silicon oxide on the surface. This is a commonly used method. As the sulfonation method, as generally used, a method of directly sulfonating with sulfuric acid, a method of reacting a sulfite,
Examples include bisulfite and the like. Oxidation of sulfide is carried out by a commonly used oxidation reaction (oxidation with sodium permanganate, hydrogen peroxide solution, hydrochloric acid, hydrogen bromide, etc.).

Examples of silane coupling agents having a site capable of being sulfonated or oxidized to sulfonic acid are vinyltrimethoxysilane, vinyltrichlorosilane, methylvinyldichlorosilane, divinyldichlorosilane, allylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, dimethylethoxy-
3-glycidoxypropylsilane, 3-carbonylpropyltriethoxysilane, benzyltriethoxysilane, 1-chloroethyltrichlorosilane, chloromethylmethyldichlorosilane, 3-bromopropyltrichlorosilane, 4-chlorophenyltrichlorosilane, phenyltrichlorosilane , P-tolyltrichlorosilane, 3
-Mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyldimethylmethoxysilane, 2-mercaptopropyltriethoxysilane, 2-mercaptopropyltrimethoxysilane, 2-mercapto Propylmethyldimethoxysilane, 2-mercaptopropyldimethylmethoxysilane,
2-Mercaptoethyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethyldimethylmethoxysilane, 2- (2-chloroethylthioethyl) triethoxysilane and the like can be mentioned.

In order to enhance the reactivity between the silane coupling agent and the oxide surface, it is effective to subject the oxide existing on the surface to plasma treatment or alkali treatment in advance, and the antifogging effect is also improved.

By the above operation, the sulfonic acid group produced by sulfonation or oxidation is present on the outermost surface of the optical article having the oxide on the surface. Therefore, the oxide surface exhibits high hydrophilicity. To obtain anti-fog performance,
The static contact angle with water is preferably 10 ° or less, but 5 ° or less is required to obtain sufficient performance. This can be achieved by increasing the number of active sites on the surface and increasing the reaction rate of the silane coupling agent.

The optical article having anti-fog performance obtained by the present invention is excellent in scratch resistance and optical characteristics such as antireflection, and is used as a spectacle lens, a camera lens, a mirror in a bathroom, a pair of underwater glasses, and a window. It can be applied to glass, microwave oven window, car window glass, telescope lens, ski goggles, lens of optical equipment used in humid places, mirror, etc.

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION [Example 1] 1. Preparation of base material: Sodium hydroxide solution (0.1
N), washed thoroughly with water, and dried to a plastic lens (made by Seiko Epson Corp., lens cloth for Seiko Super Sovereign, refractive index 1.67) with the coating liquid shown below by dipping to a film thickness of 2. It was applied so as to have a thickness of 5 μm and heat-cured at 135 ° C. for 2.5 hours. The surface of the lens thus obtained is subjected to plasma treatment (400 W of argon plasma for 60 seconds), and then an antireflection film made of inorganic materials such as silicon oxide and zirconium oxide is multilayer-coated by a vacuum vapor deposition method to obtain a hard coating. A coat, an antireflection plastic lens, and a base material A were prepared. The static contact angle of the substrate A with water was 20 °.

(Preparation of coating solution) Isopropyl alcohol 118.8 was placed in a reaction vessel equipped with a stirrer.
g, distilled water 300.0 g, γ-glycidoxypropyltriethoxysilane 139.4 g, and 0.05 N hydrochloric acid aqueous solution 38.2 g were added, and the mixture was stirred for 60 minutes. Next, a composite sol of titanium oxide, zirconium oxide, and silicon oxide (“Optlake 1120Z (U25A manufactured by Catalysts & Chemicals Co., Ltd.)
8) ″) 403.3 g Silicone-based surfactant (“L-7604” manufactured by Nippon Unicar Co., Ltd.) 0.3 g was added and sufficiently stirred to obtain a coating liquid.

2. Silane coupling agent treatment: Next, this substrate A was treated with a vinyltrichlorosilane solution (0.5 wt%,
(n-hexane solvent) at room temperature for 3 minutes, 80 ℃
For 120 minutes. Then, it wash | cleaned by acetone.

Before cleaning, a whitening phenomenon was observed on the lens, but after washing with acetone, it returned to transparent, and no significant change was observed in the appearance and antireflection characteristics of the lens. Further, the contact angle with water at this time was 72 °, and it was confirmed that vinyltrichlorosilane was immobilized on the surface.

3. Sulfonation: Next, 220 g of water, 100 g of sodium hydrogensulfate, 10 g of sodium nitrite,
A solution prepared by dissolving 10 g of sodium nitrate was prepared (treatment liquid A). The silane-coupling-treated lens was immersed in this and allowed to react at room temperature for 3 days. The treated lens was washed with pure water. No significant change was observed in the appearance and antireflection characteristics of the lens after cleaning. Further, the static contact angle with water at this time was 8 °, and it was confirmed that the surface was antifogging.

The method for evaluating the antifogging property of the obtained optical article is 1 in accordance with the static contact angle with water and the antifog property in the low temperature part of "JIS-S4030 Test method for antifog agent for eyeglasses".
It was evaluated in grade 4 (grade 1 has the best anti-fog performance and grade 4 is the worst). For scratch resistance, Bonster # 0
000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.)
It was evaluated by the method of scratching when a 1 kg load and 10 reciprocating surfaces were rubbed. (A: No scratches in the range of 1 cm * 3 cm. B: 1 to 10 scratches in the above range. C: 11 to 100 scratches in the above range. D: Within the above range. Countless scratches are attached.) The evaluation results are summarized in Table 1.

[Example 2] 1. Preparation of Substrate: The substrate A prepared in Example-1 was prepared.

2. Silane coupling agent treatment: This substrate A was treated with a 3-glycidoxypropyltrimethoxysilane solution (0.5w%, isopropyl alcohol solvent, 0.5N).
It was immersed in hydrochloric acid (hydrolyzed with hydrochloric acid) for 10 minutes at room temperature and treated at 80 ° C. for 120 minutes. Then, it wash | cleaned by acetone. No significant change was observed in the appearance and reflection characteristics of the lens before and after washing. In addition, the static contact angle with water was 55 °, and it was confirmed that 3-glycidoxypropyltrimethoxysilane was immobilized on the surface.

3. Sulfonation treatment: Next, a solution prepared by dissolving 2.7 g of sodium sulfate in 50 g of water was prepared (treatment liquid B). A lens subjected to silane coupling treatment was dipped in this solution and treated at 50 ° C. for 16 hours. The lens taken out was washed with pure water. No significant change was observed in the appearance and antireflection characteristics of the lens after cleaning. The static contact angle with water at this time was 9 °, and it was confirmed that the surface was antifogging.

Example 3 1. Preparation of substrate: A normal soda glass plate was used as a substrate.

2. Silane coupling agent treatment:
After treatment with Ar plasma having an output of 400 W, 3-carboxypropylmethyldimethoxysilane solution (0.5 w
%, Isopropyl alcohol solvent, hydrolyzed with 0.5N hydrochloric acid) with a spinner (2000 rpm, 5
Second), and dried by heating at 150 ° C. for 1 hour. The same processing was performed on both sides. Then, it wash | cleaned by acetone. No significant change was observed in the appearance and reflection characteristics of the glass before and after washing. Further, the static contact angle with water was 22 °, and it was confirmed that 3-carboxypropylmethyldimethoxysilane was immobilized on the surface.

3. Sulfonation treatment: Treatment liquid A was used in Example 1
The same process was carried out. The glass taken out was washed with pure water. No significant change was observed in the appearance and antireflection characteristics of the glass after washing. Further, the static contact angle with water at this time was 7 °, and it was confirmed that the surface was antifogging.

Example 4 1. Preparation of Substrate: The substrate A prepared in Example-1 was prepared.

2. Silane coupling agent treatment: A phenyltrichlorosilane solution (0.5 w%, n-hexane solvent) was applied with a spinner (2000 rotations, 5 seconds), and 8
It was dried by heating at 0 ° C for 2 hours. The same processing was performed on both sides. Then, it wash | cleaned by acetone. No significant change was observed in the appearance and reflection characteristics of the lens before and after washing. Further, the static contact angle with water was 86 °, and it was confirmed that phenyltrichlorosilane was immobilized on the surface.

3. Sulfonation treatment: Treatment liquid A was used in Example 1
The same process was carried out. The lens taken out was washed with pure water. No significant change was observed in the appearance and antireflection characteristics of the lens after cleaning. Further, the static contact angle with water at this time was 10 °, and it was confirmed that the surface was antifogging.

Example 5 1. Preparation of Substrate: The substrate A prepared in Example-1 was prepared.

2. Treatment with silane coupling agent: Coating with 3-bromopropyltrichlorosilane solution (0.5 w%, n-hexane solvent) by dipping at room temperature, and 8
It was treated at 0 ° C. for 120 minutes. Then, it wash | cleaned by acetone. No significant change was observed in the appearance and reflection characteristics of the lens before and after washing. Further, the static contact angle with water was 65 °, and it was confirmed that 3-bromopropyltrichlorosilane was immobilized on the surface.

3. Sulfonation treatment: Treatment liquid A was used in Example 1
The same process was carried out. The lens taken out was washed with pure water. No significant change was observed in the appearance and antireflection characteristics of the lens after cleaning. Further, the static contact angle with water at this time was 12 °, and it was confirmed that the surface was antifogging.

Example 6 1. Preparation of Substrate: The substrate A prepared in Example-1 was prepared.

2. Silane coupling agent treatment: 3-mercaptopropyltrimethoxysilane solution (0.5w%,
It was applied by dipping at room temperature with an isopropanol solvent, hydrolyzed with 0.5N hydrochloric acid) and treated at 80 ° C. for 120 minutes. Then, it wash | cleaned by acetone. No significant change was observed in the appearance and reflection characteristics of the lens before and after washing. Further, the static contact angle with water was 63 °, and it was confirmed that 3-mercaptopropyltrimethoxysilane was immobilized on the surface.

3. Oxidation treatment: The silane-coupling-treated lens was immersed in a 0.02 mol / l manganese peroxide aqueous solution, and was oxidized at room temperature for 1 day. The lens taken out was washed with pure water. The lens after washing was slightly brownish, but no significant change was observed in the antireflection property. Further, the static contact angle with water at this time was 8 °, and it was confirmed that the surface was antifogging.

[Comparative Example 1] Comparative Example 1 was the same as Example 1 except that the silane coupling treatment was not performed.

[Comparative Example 2] Comparative Example 2 was prepared in the same manner as in Example 2 except that n-propyltrimethoxysilane was used instead of 3-glycidoxypropyltrimethoxysilane.

[Comparative Example 3] Instead of the soda glass of Example 3, a plastic lens (manufactured by Seiko Epson Corporation,
Seiko Super Sovereign lens cloth, refractive index 1.6
The same treatment was performed except that 7) was used, and this was used as Comparative Example 3.
And

[0063]

[Table 1]

[0064]

EFFECTS OF THE INVENTION According to the present invention, it is possible to highly antifogging a surface having oxides and having sufficient hardness to have abrasion resistance, and since the antifogging layer is thin, surface hardness, It has become possible to manufacture an optical article having excellent antifogging durability and having an antifogging property that does not optically affect the antireflection film on the surface.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02B 1/11 G02B 1/10 Z 3/00 AF term (reference) 2K009 AA02 AA15 CC03 CC09 CC42 DD03 EE02 4F100 AA17B AA20B AA27B AA33C AG00A AH06C AK01A AK02C AK53C AT00A BA03 BA07 BA10A BA10C CC00C EH46 EH66 JB05C JL07 JN01C JN06C 4G059 AA11 AB09 AC16 AC18 AC21 FA05 FA22

Claims (11)

[Claims] 1. An optical article mainly comprising an oxide, the surface of which is treated with a silane coupling agent having a sulfonation site, and then sulfonated to impart hydrophilicity. A method for producing an antifogging optical article, comprising: 2. The method for producing an anti-fogging optical article according to claim 1, wherein the sulfonationable site is a vinyl group. 3. The method for producing an antifogging optical article according to claim 1, wherein the sulfonation-capable site is an epoxy group. 4. The method for producing an anti-fog optical article according to claim 1, wherein the sulfonation capable site is a carbonyl group. 5. The method for producing an anti-fogging optical article according to claim 1, wherein the sulfonationable site is an aromatic hydrocarbon. 6. The method for producing an anti-fogging optical article according to claim 1, wherein the sulfonationable moiety is halogen. 7. An optical article mainly comprising an oxide, the surface of which is treated with a silane coupling agent having a site capable of being oxidized to a sulfonic acid, and then oxidized. A method for producing an antifogging optical article, which is characterized by imparting hydrophilicity thereby. 8. The protective agent according to claim 7, wherein the site capable of being oxidized to a sulfonic acid is a sulfonate such as a mercapto group, a sulfide group, a sulfoxide group, a disulfide group or a sulfone group. A method for producing a cloudy optical article. 9. The optical article mainly containing the oxide on the surface thereof is a transparent member having an antireflection inorganic coating film, or a transparent member having a hard coat layer and an antireflection inorganic coating film. Item 9. A method for producing an antifogging optical article according to item 1 or 8. 10. The method for producing an antifogging optical article according to claim 1, wherein the optical article mainly containing the oxide on the surface is glass. 11. An antifogging optical article treated by the method for producing an antifogging film according to any one of claims 1 to 10.