JP2003010775A - Method of making non-fogging film and non-fogging article treated by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make a non-fogging film provided with non-fogging property persistence and scratching flaw resistance without the occurrence of the deterioration in non-fogging performance and the degradation in scratching flaw resistance in a base material. SOLUTION: A coating film containing an epoxy compound is formed on a base material and this film is impregnated with a phosphorus non-fogging material having active hydrogen to react an epoxy group and the active hydrogen of the phosphorus compound, by which the compound is uniformly distributed at a high concentration near the extreme surface of the coating film and the non-fogging film having the excellent non-fogging property persistence and scratching flaw resistance is made.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an antifogging film having excellent antifogging performance and excellent surface hardness, and an antifogging article treated by the method.

[0002]

2. Description of the Related Art As a method for imparting antifogging performance to a substrate,
Conventionally, various methods as described below have been adopted.

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 surfactant is kneaded into the synthetic resin base material itself, hydrophilicity,
There is a method in which a water-absorbing monomer is copolymerized to form a synthetic resin substrate to impart antifogging performance. This is disclosed in JP-A-10-114035, JP-A-10-130511, JP-A-10-158453, JP-A-10-182912, and JP-A-10-202798.

A well-known method is to knead an antifogging substance on the surface of a resin material and apply a coating having an antifogging property, as disclosed in JP-A-8-17646 and JP-A-8-2729.
1, JP-A-9-136374, JP-A-9-15136
8 and Japanese Patent Laid-Open No. 9-155282.

The above-described method is intended to impart hydrophilicity and water absorption to the substrate itself or a thick coating film to achieve antifogging performance.

On the other hand, as a method of directly imparting antifogging performance to an inorganic material such as glass having poor water absorption, a method of treating the outermost surface to have hydrophilicity or hydrophobicity, or making the inorganic material porous. There are known a method of imparting water absorption and a method of forming a photocatalytic metal oxide film to express superhydrophilicity.

Graft polymerization as a method of surface modification is
It is disclosed in JP-A-5-202216, JP-A-5-295139, JP-A-8-176328, JP-A-9-301742, and JP-A-10-90503. Other surface modification methods include JP-A-10-114543 and JP-A-10-143543.
For example, 167768 can be mentioned.

Further, Japanese Patent Application Laid-Open No. 9-202651 and Japanese Patent Application Laid-Open No. 9-29583 are patents in which pores and irregularities of an inorganic substance are combined with hydrophilic substances and patents utilizing irregularities on the surface.
5, JP-A No. 11-77876.

Various patents have been filed for the method of expressing the superhydrophilic function using a photocatalytic metal oxide, and JP-A-9-77535, JP-A-10-68091, JP-A-10-85100, and JP-A-10-85100 have been filed. -167727 and JP-A-10-297940.

In order to impart antifogging performance to optical articles, including the above-mentioned methods, 1) the substrate is made to have water absorbency.
2) Make the substrate surface hydrophilic. 3) Make the substrate surface hydrophobic. 4) 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.

[0012]

However, the conventional method has the following problems. As a method of imparting antifogging performance to the surface of a base material, a method of applying a generally used surfactant to the surface has a problem in sustainability because the surfactant is easily dropped by water.

The method of kneading the resin substrate itself or the coating film with the antifogging substance to impart the antifogging property can obtain sufficient performance as the antifogging property. They were likely to exist locally, and because they were organic substances, they were soft and were very easily scratched. Also,
Since the hydrophilic substance is dissolved by water and washed away, there is a problem in anti-fogging sustainability. Furthermore, in order to improve the durability, even when the water absorbent resin is used together, when the water absorbent resin absorbs water, the water absorbent resin becomes very soft and is more likely to be scratched. When these are used in a portion such as a spectacle lens where scratch resistance is required, the optical characteristics are deteriorated due to the scratch, and it is not practical. further,
Dirt in the air, such as cigarette smoke, is easily adsorbed, and the optical article is disadvantageously colored.

In addition, in the case of imparting hydrophobicity, the contact angle of water on the surface is about 160 ° in the conventional technique, but in the case of minute water droplets such as cloudiness, the drop due to its own weight does not occur. Therefore, it cannot be said that sufficient antifogging performance is obtained.

Regarding the method of making the inorganic material porous so as to have water absorbency, the porous material itself makes the surface fragile and easily broken. In addition, in the method of forming a photocatalytic metal oxide film and exhibiting superhydrophilicity, high temperature baking is required in the film forming step, and it cannot be used for a resin substrate. In addition, the photocatalytic metal oxide coating generally has a high refractive index, and must be used on the outermost surface in order to efficiently utilize the superhydrophilic function. as a result,
Since the reflectance is high, it is unsuitable for a substrate having a controlled reflectance such as a lens.

Therefore, it is an object of the present invention to provide a method for producing an antifogging film which solves the above problems and an antifogging article treated by the method.

[0017]

The method for producing an antifogging film according to the present invention comprises forming a coating film containing an epoxy compound on a substrate, and impregnating and retaining a phosphorus antifogging substance having active hydrogen on the coating film. And imparts anti-fogging property.

Further, the method for holding the antifogging substance is characterized in that the active hydrogen of the phosphorus compound is chemically reacted with the epoxy group and held.

Further, the method of impregnating with the antifogging substance is characterized in that the coating film provided on the substrate is immersed in the antifogging substance or the solution of the antifogging substance, and swelled, impregnated and held. .

Further, the method of impregnating with the antifogging substance is characterized in that the coating film provided on the substrate is heated and expanded to impregnate and hold the antifogging substance or the solution of the antifogging substance. .

Further, the method of impregnating with the antifogging substance is characterized in that the coating film provided on the substrate is pressurized, impregnated and held in the antifogging substance or the solution of the antifogging substance.

Further, the method of impregnating the antifogging substance is characterized in that the coating film provided on the base material is heated, pressurized, impregnated and held in the antifogging substance or the solution of the antifogging substance. To do.

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

That is, since the anti-fogging film according to the present invention is impregnated with the anti-fogging substance by post-treatment, it is often present on the surface, which is a site necessary for exhibiting the anti-fogging effect. Therefore, the required antifogging performance can be exhibited. Further, since the antifogging substance in the film is uniformly present in the gap of molecular order near the surface of the coating film, there is no problem such as clouding of the film and the original hardness and scratch resistance of the coating film are not impaired. In addition, since they are dispersed in the membrane in a size close to the molecular level and are held by chemical bonds, there is no outflow due to water, and expansion at the time of water absorption can be suppressed by a certain amount. This makes it possible to prevent deterioration of antifogging performance persistence, hardness upon water absorption, and scratch resistance.

The coating film containing the epoxy compound used in the present invention can be applied to all coating films such as thermosetting and photocuring, but the thermosetting coating is preferable from the viewpoint of handling property. Further, the thermosetting coating preferably contains a metal oxide sol, an inorganic alkoxide and a partial hydrolyzate thereof as main components, and an organic component to give a little flexibility. Further, it is necessary to adopt a method in which a large amount of epoxy groups remain in the coating film at the time of treating the antifogging substance.

Next, the antifogging substance used in the present invention is preferably a phosphorus type surfactant having active hydrogen. Specific examples include mono (di) polyoxyethylene alkyl (phenyl) ether phosphoric acid. The number of polyoxyethylene groups is preferably 4 to 16, and the number of carbon atoms of alkyl (phenyl) is preferably 3 to 12. The ratio of mono / di is not particularly specified, but it is desirable to increase the ratio of mono in order to improve the hardness and increase the ratio of di in order to improve the antifogging property. Further, each may be used alone. The antifogging substance used may be a mixture of two or more kinds. Further, it may be used as a solution using a solvent, and in this case, it is necessary to select a solvent having a boiling point higher than the treatment temperature.

Next, the method of impregnating the antifogging substance into the coating film is not particularly specified as long as it has the effect of allowing the antifogging substance to come into contact with the coating film and penetrate into the film. Specifically, general dyeing or a method applying the same is used. For example, a method of dipping, swelling and impregnating a coated substrate in an antifogging substance or solution,
A method of immersing a coated substrate in an antifogging substance or solution and heating it to impregnate it, a method of pressurizing and impregnating the coating film in contact with the antifogging substance or solution, and a method of preventing relatively low molecular weight Examples of the method include a method of vaporizing a cloudy substance and using it like a sublimation dye to infiltrate and impregnate it, and a method of thermally transferring and impregnating an antifogging substance to a coating film.

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, 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.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION [Example 1] 1. In a reaction vessel equipped with a coating liquid adjusting and stirring device, 445.4 g of isopropyl alcohol, 89.9 g of γ-glycidoxypropyltriethoxysilane, and 31.2 g of bis [3- (diethoxymethylsilyl) propyl] carbonate. , 0.05
31.3 g of N hydrochloric acid aqueous solution was added, and the mixture was stirred for 120 minutes.
Next, silicon oxide sol (“Oscal-
1432 ") 330.2 g, glycerol polyglycidyl ether 67.4 g, and a silicone-based surfactant (" L-7604 "manufactured by Nippon Unicar Co., Ltd.) 0.3 g were added and sufficiently stirred to obtain a coating liquid. Coating treatment Pre-soaked in sodium hydroxide solution (0.1N), washed thoroughly with water, and dried plastic lens (Seiko Epson
Co., Ltd., Seiko Super Frontier lens cloth,
Refractive index 1.56) 1. Apply the coating solution prepared in step 1 above by dipping to a film thickness of 2.5 μm.
Heated at 0 ° C. for 30 minutes. 3. The lens base material treated with the antifogging agent is immersed in polyoxyethylene (8) octyl ether phosphoric acid (mono / di = 2/1) which has been heated to 50 ° C. in advance, and the temperature is kept at 120 ° C. for 120 minutes and then 135 ° C. And heated for 120 minutes. Then 1 ° C
The lens was slowly cooled at a heating speed of 1 minute / minute, and the lens returned to room temperature was taken out, washed with pure water, and air-dried. No significant change was observed in the appearance of the lens after washing.

The method for evaluating the antifogging property of the obtained antifogging film is as follows:
"JIS-S4030 Anti-fog test method for eyeglasses"
According to the anti-fogging property in the low temperature part, the grades 1 to 4 were evaluated (the grade 1 has the best antifogging performance and the grade 4 is the worst). Also,
As for abrasion resistance, Bonster # 0000 Steel Wool (manufactured by Nippon Steel Wool Co., Ltd.) under a load of 1 kg, 10
How to scratch when rubbing the reciprocating surface (A: 1 cm * 3
There are no scratches in the cm range. B: 1 in the above range
-10 scratches are attached. C: 11 to 100 scratches are attached within the above range. D: Countless scratches are attached within the above range. ). The antifogging performance persistence was evaluated by holding the temperature at 40 ° C. and a relative humidity of 90% for 60 minutes and then performing the above antifogging property evaluation. The evaluation results are summarized in Table 1. [Example 2] A base material coated in the same manner as in Example 1 was preheated to 50 ° C with polyoxyethylene (6) hexylphenyl ether phosphate (mono / di = 1).
/ 1), keep the temperature for 120 minutes, take out the lens, remove the antifogging substance, and then raise the temperature to 135 ° C.
Minute heat treatment was performed. No significant change was seen in the appearance of the lens. [Example 3] A substrate coated in the same manner as in Example 1 was immersed in polyoxyethylene octylphenyl ether preheated to 135 ° C, held for 120 minutes, and then slowly cooled at 1 ° C / minute to room temperature. The lens returned to the above condition was washed with pure water and evaluated. No change was observed in the appearance of the lens. [Example 4] A substrate treated in the same manner as in Example 1 was immersed in polyoxyethylene (10) decyl ether phosphoric acid (mono / di = 3/7) and heated in an autoclave at 120 ° C for 60 minutes. Pressure and heat treatment were performed. The lens returned to room temperature was washed with pure water and evaluated. Also,
No change was observed in the appearance of the lens.

Comparative Example 1 A substrate coated in the same manner as in Example 1 was further kept at 50 ° C. for 120 minutes and then 13
It heated up at 5 degreeC and heated for 120 minutes. Polyoxyethylene (8) octyl ether phosphoric acid (mono / di = 2 /
The 0.5 wt% aqueous solution of 1) was applied by spin coating and dried at 100 ° C. for 10 minutes. No major change was observed in the appearance of the obtained lens. [Comparative Example 2] 7.5 g of polyoxyethylene (6) hexyl phenyl ether phosphoric acid (mono / di = 1/1) was mixed with the coating liquid prepared in Example 1 and the thickness of the lens cloth was measured by a dipping method. Apply so that it becomes 2.5 μm, and
The mixture was heated at 0 ° C. for 30 minutes and further kept at 50 ° C. for 120 minutes, then heated to 135 ° C. and heated for 2 hours. The appearance of the obtained lens was slightly clouded.

[0033]

[Table 1]

[0034]

According to the present invention, a large amount of antifogging agent is present on the outermost surface, and the antifogging substance is optimally distributed in the film.
Since the anti-fogging property is excellent and the coating film component and the anti-fogging substance are chemically bonded, it becomes possible to produce an anti-fogging article having anti-fogging durability and scratch resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 2K009 BB23 CC02 CC47 DD02 EE02                 4D075 AB01 BB22Y BB56Y BB62Y                       BB63Y BB68Y CA02 CA37                       CA39 CB03 CB06 DA06 DA11                       DA23 DB13 DB31 DC02 DC13                       DC24 EA07 EB33 EB43 EB47                       EC07                 4F100 AH10B AH10H AK53B AT00A                       BA02 BA10A BA10B CA10B                       CC00B EH462 EJ172 EJ422                       EJ822 GB90 JK14 JL07B                       JL07H JM02B

Claims (7)

[Claims] 1. An antifogging property, characterized in that a coating film containing an epoxy compound is formed on a substrate, and a phosphorus-based antifogging substance having active hydrogen is impregnated into and held on the substrate to impart antifogging property. Membrane fabrication method. 2. The antifogging film according to claim 1, wherein the method of holding the antifogging substance is a method of holding active hydrogen of a phosphorus compound by chemically reacting with an epoxy group. Manufacturing method. 3. The method of impregnating with the antifogging substance is characterized in that the coating film provided on the substrate is immersed in an antifogging substance or an antifogging substance solution, and swelled, impregnated and retained. The method for producing an antifogging film according to claim 1. 4. The method of impregnating with an antifogging substance is characterized in that a coating film provided on a substrate is heated and expanded to impregnate and hold an antifogging substance or an antifogging substance solution. The method for producing an antifogging film according to claim 1. 5. The method of impregnating with an antifogging substance comprises pressurizing, impregnating and holding a coating film provided on a substrate in an antifogging substance or an antifogging substance solution. Item 3. A method for producing an antifogging film according to Item 1 or 2. 6. The method of impregnating with the antifogging substance comprises heating, pressurizing, impregnating and holding a coating film provided on a substrate in an antifogging substance or an antifogging substance solution. The method for producing an antifogging film according to claim 1 or 2. 7. An antifogging article treated by the method for producing an antifogging film according to any one of claims 1 to 6.