JPH067201B2 - Anti-fog lens made of synthetic resin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a synthetic resin lens having a cloud-resistant coating having excellent wear resistance, hot water resistance, weather resistance, and dyeability on the surface of a synthetic resin lens.

[Prior art]

Conventionally, the drawback of synthetic resin lenses is that if the surface temperature is below the dew point of the environment, water vapor in the air will condense on the surface of the lens, causing cloudiness and loss of transparency itself, which is very inconvenient. That is. A number of methods have been proposed and attempts have been made to improve this drawback.However, it has not been possible to obtain one having both cloud resistance and abrasion resistance, and good adhesion. The current situation.

For example, in Japanese Patent Laid-Open No. 58-32664, polyvinyl alcohol is used as a main component to impart cloudiness, but although it is somewhat satisfactory in terms of cloudiness, it has poor wear resistance and weather resistance and has problems in practical use.

In addition, JP-A-58-101164 and JP-A-58-12292.
8 and 58-195127 show anti-cloud coatings using ammonium perchlorate as a curing catalyst, but these cured coatings have difficulty in temperature control during curing. That is, if the temperature during curing is low, a coating having the required wear resistance cannot be obtained. Conversely, if the temperature is high, the lens will turn yellow, which is not desirable in appearance. Another problem is that the pot life of the paint is short.

〔Purpose〕

The present invention has been made for the purpose of solving the above problems. That is, the present invention, by applying a cloud-resistant coating having excellent wear resistance, hot water resistance, weather resistance and dyeability on the surface of a synthetic resin lens, even when the surface temperature of the lens is below the dew point of the environment. Water vapor in the air does not condense on the lens surface, transparency is not lost,
And wear resistance that can be used without any practical problems,
The object is to obtain a synthetic resin lens having hot water resistance, weather resistance, and dyeability.

〔Overview〕

That is, the present invention, on the synthetic resin lens surface, the following (A),
An anti-fog lens made of a synthetic resin, which is provided with an anti-fog coating mainly composed of (B), (C) and (D).

(A) General formula (In the formula, R ¹ is an organic group having a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group or an epoxy group, R ²
Is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or a hydrogen atom, and 0 is
Or represents 1. ) One or more kinds of organosilicon compounds represented by (B) colloidal silica having a particle size of 1 to 100 millimicrons (C) polyhydric alcohol and one or more polyhydric alcohol having an ethylene oxide chain (D) excess Magnesium chlorate Hereinafter, the present invention will be described in detail.

Examples of the component (A) used in the present invention include methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane,
Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltriacetoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-bis (β-hydroxyethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyl (methyl) dimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. These may be used alone or in combination of two or more. Further, the component (A) is preferably used by hydrolyzing in an organic solvent such as alcohol in the presence of an acid, and even if it is mixed with the colloidal silica of the component (B) after hydrolysis alone, the component (B )
It may be either hydrolyzed after mixing with.

The colloidal silica having a particle diameter of 1 to 100 millimicrons as the component (B) is a colloidal solution in which high molecular weight inorganic silica fine particles are dispersed in a water or alcohol dispersion medium, and is commercially available.

As the polyhydric alcohol of the component (C), there are difunctional alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol and alkanediol, or trifunctional alcohols such as glycerin and trimethylolpropane. There are functional alcohols. Polyhydric alcohols having an ethylene oxide chain are also useful. Polyhydric alcohol with ethylene oxide chain is a chain in the molecule It is a polyhydric alcohol having at least one.

When the molecular weight of the polyhydric alcohol having an ethylene oxide chain is too large, the reactivity of the hydroxyl group decreases and curing becomes difficult and sufficient film formability cannot be obtained, and when the molecular weight is too small, that is, the ethylene oxide chain is If the amount is small, sufficient anti-fog property cannot be obtained.
The molecular weight of the polyhydric alcohol having an ethylene oxide chain is preferably in the range of 100 to 3000, particularly preferably 200 to 2000. The polyhydric alcohol having an ethylene oxide chain is typically diethylene glycol, triethylene glycol, having a molecular weight of 100 to 3000, preferably a molecular weight of 200 to 2000.
Polyethylene glycol of the general formula HOC _n H _2n OH (n = 3
1-10 at the both ends of the diol of 10-10, preferably 1-7
One with ethylene oxide added, and one with an ethylene oxide chain added to at least one hydroxyl group in polyhydric alcohols such as glycerin, trimethylolpropane, diglycerin, pentaerythritol, adonitol, sorbitol, and inositol are used. .

Especially the general formula (In the formula, n _{1 to} nm are each independently an integer of 0 to 7,
And at least two of them are integers of 1 or more, and m
Represents an integer of 3 to 9. And a polyhydric alcohol having an ethylene oxide chain represented by the formula ( ₁ ), particularly a compound in which n _{1 to} nm are 1 to 5 in the above formula.

Polyvinyl alcohol is also useful as the component (C). Polyvinyl alcohol means that obtained by partial or complete hydrolysis of polyvinyl ester such as polyvinyl acetate, and among them, polyvinyl alcohol having an average degree of polymerization of 250 to 3000 and a degree of saponification of 70 mol% or more is preferably used. To be

If the average degree of polymerization is less than 250, the durability, particularly water resistance, is poor, and if it is more than 3000, there is a problem in working such that it is difficult to obtain a smooth coating film because the viscosity becomes large when used as a paint. Further, when the saponification degree is lower than 70 mol%, sufficient performance cannot be expected in terms of antifogging property.

As the polyhydric alcohol as the component (C) of the present invention, one type of the above compounds may be used, or a mixture of two or more types may be used.

Next, the component (D) magnesium perchlorate will be described. Generally, the following curing catalysts are known, but each has the following drawbacks. That is, the hardness of the obtained coating film is insufficient for amines such as n-butylamine, triethylamine, guanidine and biguanide, and amino acids such as glycine. Metal acetylacetonates such as aluminum acetylacetonate, chromium acetylacetonate, titanyl acetylacetonate, and cobalt acetylacetonate are difficult to obtain the hardness of the coating film. Immersion causes a decrease in hardness. In addition, organic metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate, and perchloric acid have short pot lives of coating materials. Ammonium perchlorate has a drawback in that the hardness of the obtained coating film is hard to come out when the temperature at the time of curing is low, and conversely the lens turns yellow when the temperature is high, which makes the temperature control at the time of curing difficult. However, the pot life of the paint is short and not practical. Furthermore, hydrochloric acid, phosphoric acid, nitric acid, paratoluene sulfonic acid, etc. take a long time to cure, and SnCl ₄ , AlCl ₃ , FeCl ₃
Lewis acids such as ₃ , TiCl ₄ , ZnCl ₂ and SbCl ₃ have extremely poor water resistance, so the hardness decreases when immersed in water at room temperature.

From the above results, the present inventors have conducted various studies on various curing catalysts and found that magnesium perchlorate, which is a kind of latent catalyst, is excellent in all properties. That is, by using magnesium perchlorate as a curing catalyst, excellent wear resistance, hot water resistance,
An antifogging coating having weather resistance and dyeability is obtained. In addition, temperature control during curing is practical, and the pot life of the paint is at least one month at room temperature.

In the present invention, the components (A), (B) and (C) are used in a proportion of 5 to 60 parts by weight, 10 to 70 parts by weight, and 10 to 80 parts by weight (100 parts by weight in total). However, more preferably 10 to 40 parts by weight, 20 to 50 parts by weight, and 20 to 20 parts by weight, respectively.
50 parts by weight is recommended. If the amount of component (A) exceeds 60 parts by weight, the antifogging performance is significantly reduced, and if it is less than 5 parts by weight, the abrasion resistance is insufficient.

If the amount of component (B) exceeds 70 parts by weight, the antifogging performance will decrease, and
If it is less than the weight part, abrasion resistance and hot water resistance are insufficient. When the component (C) exceeds 80 parts by weight, the abrasion resistance is not sufficient, but at the same time, the hot water resistance is deteriorated, and the surface is roughened and the hardness is lowered in the long-term use. On the other hand, if it is less than 20 parts by weight, the antifogging performance is deteriorated and the object of the present invention cannot be achieved.

The addition amount of the component (D), magnesium perchlorate, is preferably 0.01 to 5.0% of the total residual solid content.
If the added amount of the component (D) is too large, it causes coloring and is not preferable. On the contrary, if the amount is too small, the hardness of the obtained coating film becomes insufficient.

The coating composition of the present invention is diluted to a suitable concentration for use. Solvents used for dilution include alcohols, ketones, cellosolves, carboxylic acids, esters, ethers, halides and aromatics. However, these may be used alone or as a mixed solvent of two or more kinds.

Further, by adding a small amount of a surfactant, the wettability can be improved and a smooth coating film can be obtained. At this time, a small amount is sufficient, and if used in a large amount, the adhesion of the coating film may deteriorate. Further, if necessary, an antistatic agent or an ultraviolet absorber may be added to improve the performance of the coating film.

As a method for applying the coating material of the present invention to a synthetic resin lens, there are known methods such as a dipping method, a spray method, a spin coating method and a flow coating method. The synthetic resin lens applied in this way becomes a cured film by heating and drying. Conditions such as curing temperature and curing time are determined in consideration of the properties of the anti-fogging film to be obtained, but usually
A temperature of 60-150 ° C is applied.

The thickness of the obtained anti-fog coating is preferably 1 to 20 µ. If it is less than 1 μm, the abrasion resistance is not sufficient and the antifogging performance is deteriorated. In addition, even if the thickness is 20 μm or more, the effect of increasing the film thickness cannot be expected, cracking is likely to occur, and hot water resistance and adhesion are also deteriorated.

For the purpose of improving the adhesion between the synthetic resin lens and the anti-fog coating, it is possible to pre-treat the lens surface with various kinds of primers, or a treatment with an activated gas, a chemical treatment with an acid / alkali, etc. Is useful in the implementation of.

The antifogging film thus obtained is applied to a lens surface made of a transparent resin such as a polycarbonate resin, an acrylic resin, a diethylene glycol bisallyl carbonate resin, or polystyrene, and has transparency, abrasion resistance, hot water resistance, weather resistance, It is possible to provide an anti-fog lens made of synthetic resin having excellent dyeability.

〔Example〕

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

The performance of the coating film was evaluated by the following method.

Appearance: Transparency and presence or absence of coating unevenness were examined by visual observation.

Anti-fogging property: After leaving the lens in a room at 23 ° C. and 50% RH for one day and night, it was examined whether or not clouding occurred when breath was exhaled.

Abrasion resistance: 1 cm ² # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.) with a load of 1 kg, scratches after 10 reciprocating strokes, with 10 grades of A for glass and E'for acrylic resin It was evaluated by.

Hot water resistance: The lens was immersed in boiling pure water for 1 hour, and then tested for abrasion resistance in the same manner as above.

Adhesion: Cross-cut tape test, that is, 11 parallel lines were put on the surface of the coating film at intervals of 1 mm in length and width to cross-cut 100 squares, and then the cellophane adhesive tape was adhered on the cross-cut tape. The number of squares that did not peel off in the 100 squares of the coating film that peeled off was displayed.

Weather resistance: The appearance of the coating film after 500 hours of ultraviolet irradiation with a xenon lamp fade meter and the adhesion as described above were evaluated.

Example 200 parts of ethyl cellosolve were added to the component (A) in the amount shown in Table 1 below, and the component (B) in the amount shown in Table 1 was further added.
Was added to make a uniform solution. 0.05N hydrochloric acid was added to this solution in an amount 1.2 times the amount required for the hydrolysis of the silicate ester, and hydrolysis was carried out at 35 ° C or lower. Further, to this liquid, the amounts of the components (C) and (D) shown in Table 1 and a silicone-based surfactant (“L-7604” manufactured by Nippon Unicar Co., Ltd.) were added and the mixture was added at 0 ° C. to 2
A coating solution was prepared by aging for 4 hours.

The coating solution thus prepared is applied to the surface of a polycarbonate resin lens surface-treated with oxygen plasma or a diethylene glycol bisallyl carbonate resin lens surface-treated with an aqueous sodium hydroxide solution by the dipping method, and is applied at 80 ° C. Minutes, 100 ° C for 2 hours,
It was heated at 130 ° C. for 1 hour to obtain an antifogging film.

PC: Polycarbonate DAC: Diethylene glycol bisallyl carbonate a: γ-glycidoxypropyltrimethoxysilane b: Methyltrimethoxysilane c: Vinyltriethoxysilane d: Snowtex C ((solid content 20%, Nissan Chemical Industries) e: CSCAL -1132 (Solid content 30%, Catalysis Chemical Industry) f: OSCAL-1232 (Solid content 30%, Catalysis Chemical Industry) g: Polyvinyl alcohol (Saponification degree 91.0-94.0 mol%) h: Polyethylene glycol i: Polyoxyethyl Glycerin (molecular weight 420) j: alkanediol k: polyoxyethylated sorbitol (molecular weight 850) *: aluminum acetylacetonate 0.5 part **: ammonium perchlorate 1.0 part [Effect] Prior to the present invention, a polyhydric alcohol was added. Many anti-fog coatings used have been proposed However, even though they have excellent anti-fogging performance, they have poor wear resistance and weather resistance and cannot be used for a long period of time.

Further, a number of improvements in curing catalysts have also been investigated, but they have drawbacks such as difficult temperature control during curing, poor adhesion, poor hot water resistance, and short pot life.

Therefore, in the present invention, by using magnesium perchlorate which is a latent catalyst as a curing catalyst for the antifogging coating, temperature control during curing is facilitated, and abrasion resistance, hot water resistance, and weather resistance are remarkably good. became. In addition, the pot life of the coating solution extended at room temperature for more than 1 month. Exactly the ideal that magnesium perchlorate can improve all the drawbacks so far Curing catalyst.

The use of magnesium perchlorate significantly improved the properties of the anti-fog coating. This effect is tremendous.

Further, the present invention can be applied not only to a lens but also to ski goggles and a watch cover glass, and has a wide range of application.

Claims (1)

[Claims] 1. The following (A), (B), (C) on the surface of a synthetic resin lens:
An anti-fog lens made of a synthetic resin, characterized by being coated with an anti-fog coating mainly composed of (D) and (D). (A) General formula (In the formula, R ¹ is an organic group having a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group or an epoxy group, R ²
Is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or a hydrogen atom, and 0 is
Or represents 1. ) One or more kinds of organosilicon compounds represented by (B) colloidal silica having a particle size of 1 to 100 millimicrons (C) polyhydric alcohol and one or more polyhydric alcohol having an ethylene oxide chain (D) excess Magnesium chlorate