JPH036276A - Coating composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a transparent plate 1N! having a high refractive index. The present invention relates to a coating composition for forming a layer.

[Conventional technology]

Synthetic resin lenses, especially diethylene glycol bis(allyl carbonate) resin lenses, are superior to glass lenses in terms of safety, ease of processing, and fashionability. With the development of anti-reflection technology, it is rapidly gaining popularity.

However, since the refractive index of diethylene glycol bis(7lyl carbonate) resin is 1.50, which is smaller than that of glass, it has the disadvantage that the outer periphery is thicker than that of a glass lens. For this reason, the use of plastic for eyeglass lenses is
Demand for thin plastic lenses made from high refractive index resin materials is increasing.

As a technical proposal for this purpose, 1.60
High refractive index materials have been proposed that have refractive indexes of about 100%.

On the other hand, in order to improve the problem of easy scratching, which is a drawback of plastic eyeglass lenses, a method of coating the lens surface with a silicone-based hard coat material is generally practiced. In addition, in the case of high refractive index resin lenses with a refractive index close to 1.60, in order to suppress appearance defects caused by interference fringes due to the difference in refractive index between the base material and the coating material,
Special Publication No. 61-54331, Special Publication No. 63-3714
As in Publication No. 2, a colloidal dispersion of metal oxide fine particles of AI, Ti, Zr, 3n, and Sb, which has a higher refractive index than the silicon dioxide fine particles used in silicon-based hard coat materials, is used as a hard coat material. A method has been proposed.

[Problem to be solved by the invention]

However, the coating compositions disclosed in Japanese Patent Publication No. 61-54331 and Japanese Patent Publication No. 63-37142 had the following problems.
A colloidal dispersion of metal oxide fine particles of n, Sb is 1.6
When used as a coating material for a resin with a high refractive index of about 0, interference fringes during application and curing can be suppressed compared to silicon-based coating materials, but there is a limit to the refractive index as a coating film. Although metal oxide fine particles alone have a relatively high refractive index, when used as a conniting material, silicon-based coupling materials are mixed, so the refractive index of the film itself is The limit is about 1.57, and there is naturally a limit to the improvement of interference fringes. In addition, when a colloidal dispersion of Ti metal oxide fine particles is used as a coating material, TiO2 itself has a considerably higher refractive index than the gold 7M oxide, and when used as a hard coat material, the coating Although it has the advantage that the film has a high refractive index and a wide range of refractive index options, TiO2 has extremely poor weather resistance and may cause decomposition of the organic components of the silicon-based coupling agent or This led to decomposition of the resin lens surface, which caused problems with its durability.

Therefore, the present invention is intended to solve these problems, and its purpose is to provide a coating composition for high refractive index resin lenses that has a high refractive index, high surface hardness, and durability.

[Means to solve the problem]

The coating composition of the present invention is characterized by containing the following A and B as main components.

A, colloidally dispersed tungsten oxide sol.

B. An organosilicon compound or a hydrolyzate thereof having the general formula R15i(OR3):<-a.
(Here, R' is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, or an organic group having an epoxy group, R2 is a hydrocarbon group having 1 to 4 carbon atoms, R is
A hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group,
or hydrogen, a represents 0 or 1) The tungsten oxide sol which is the A component of the present invention is an oxide of tetravalent or hexavalent tungsten, and the average particle size of the fine particles of the metal oxide is about 1. ~300μm, preferably about 1~
It is 200 μm.

This is because it is difficult to create particles whose diameter is too small.
It is expensive and impractical, and if it is too large, the transparency generally decreases, so it is preferable to use a tungsten oxide sol within the above range. Also, as a dispersion medium for tungsten oxide sol, water, hydrocarbons, esters, and ketones can be used. Examples include alcohols, organic carboxylic acids, and the like. Moreover, these dispersion media can also be used as a mixture of two or more types. The tungsten oxide sol can be used not only alone, but also in combination with colloidal dispersions of other metal oxide fine particles, such as colloidal silica and antimony pentoxide sol. In addition, tungsten oxide itself can take on a five-piece structure when exposed to ultraviolet rays, and can be expected to be used as a light control material.

The general formula of component B of the present invention is R'-3i (OR3)
Examples of the organosilicon compound represented by 3- or its hydrolyzate include methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, and vinyltriethoxysilane. Silane, vinyltris(β-methoxyethoxy)silane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, β-(3,4-epoxycyclohexyl)ethyl Examples include trimethoxysilane. These may be used alone or in combination of two or more, and
Are these organic such as alcohol? It is preferable to use it by hydrolyzing it in the presence of an acid in a preservative, and it can be used alone after hydrolysis and then mixed with the tungsten oxide sol of component A, or after being mixed with component A and then hydrolyzed. .

Although these organosilicon compounds can be cured at 1 iF even in the absence of a catalyst, various curing catalysts can be used to further promote curing. For example, n-
Amines such as butylamine, triethylamine, guanidine, biguanide, amino acids such as glycine, metal acetylacetonates such as aluminum acetylacetonate, chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, sodium acetate, zinc naphthenate, Organic acid metal salts such as cobalt naphthenate, zinc octylate, and tin octylate, perchloric acids or their salts such as perchloric acid, ammonium perchlorate, and magnesium perchlorate, hydrochloric acid, phosphoric acid, nitric acid, para-toluenesulfone acids such as acids, or 5nC12
, AlCl3! F e CI L T l 'C14
Metal chlorides which are Lewis acids such as 1Z n Cl 21 S b Cl 3 can be used.

In addition, the coating composition of the present invention may contain a polyfunctional epoxy compound, a polyhydric alcohol, a polycarboxylic acid, or a polycarboxylic acid for the purpose of improving the dyeability of the formed film or improving various durability. One or more types selected from acid anhydrides can be used. Polyfunctional epoxy compounds include (poly)ethylene glycol, (poly)
Examples include diglycidyl ethers of trifunctional alcohols such as propylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol, and di- or triglycidyl ethers of trifunctional alcohols such as glycerin and trimethylolpropane. Polyhydric alcohols include difunctional alcohols such as (poly)ethylene glycol, (poly)propylene glycol, neopentyl glycol, catechol, resorcinol, and alkanediol, or trifunctional alcohols such as glycerin and trimethylolpropane, or , polyvinyl alcohol, etc. Polyhydric carboxylic acids include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, orthophthalic acid,
Examples include terephthalic acid, fumaric acid, itaconic acid, and oxaloacetic acid. Examples of polycarboxylic anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, 1.2-
Examples include dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and naphthalic anhydride.

In addition, the coating composition of the present invention may contain solvents such as alcohols, ketones, cellosolves, and carboxylic acids alone or in combination, and if necessary,
It is also possible to improve the coating properties of the coating liquid and the performance of the coating film by adding a small amount of a surfactant, anti-reactive agent, or ultraviolet absorber.

Note that the ratio of component A and component B in the coating composition of the present invention can be changed as appropriate depending on the balance with the refractive FT index of the target coating substrate, and It is preferable to mix the A component and the B component so that the refractive index difference of the formed film is within ±0.1. However, from the viewpoint of the durability of the formed film, the ratio of the A component in the film is 10%. If the ratio of the A component is less than 9%, cracks tend to occur in the film and a sufficient refractive index cannot be obtained.
If it exceeds 0% by weight, the adhesion to the base material will decrease, which is not preferable.

In addition, when applying the coating composition of the present invention, the surface of the substrate is subjected to alkali treatment, acid treatment, surfactant treatment, brimer treatment, plasma treatment, etc. in advance in order to improve the adhesion between the substrate and the coating. What you do is effective.

In addition, as a coating/curing method, the coating liquid is uniformly applied by a detting method, a spinner method, a spray method, or a flow method, and then a film is formed by heating and drying at a temperature of 40 to 200'C for several hours. be able to. The appropriate thickness of the film is 1 to 30 μm, and 1 μm
If it is less than 3, the scratch resistance of the obtained film is insufficient.
If it exceeds 0 μm, cracks are likely to occur in the first pattern.

Note that it is also possible to reduce reflection and improve transmittance by providing a single-layer or multi-layer anti-reflection film made of an inorganic substance on the formed film.

As the coating substrate to which the present invention is applied, transparent materials such as glass and plastic can provide good durability.
It is particularly effective in preventing interference fringes for transparent materials around 0.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples.

〔Example〕

Example 1 In a flask equipped with a stirring device, water-dispersed tungsten oxide sol, manufactured by Nikkei Chemical Industry Co., Ltd., was mixed with wO3? M degree 20% by weight
), 176 g of ethanol, and 45 g of γ-glycidoxypropyltrimethoxysilane were added in this order with stirring, and 12.4 g of 0.05N hydrochloric acid solution was added dropwise over 30 minutes. Subsequently, 0.15 g of a silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "Y-7002") was added, and the mixture was allowed to stand at 0°C for 24 hours to ripen, thereby obtaining a coating liquid.

Next, a high refractive index resin lens fabric (made by Seiko, product name °° Seiko High Road" refractive index 160, diameter 75
mm, -3,0OD lens) with 5 wt% concentration of NaOH
After being immersed in an aqueous solution for 5 minutes, washed and dried, the coating solution was applied by dipping at a pulling rate of 15 cm/min. After coating, it was heated and cured at 80'C for 1 hour and at 100'C for 2 hours.The thickness of the obtained film was 2.6 μm.

The following performance evaluation tests were conducted on the synthetic resin lenses obtained by the above method. The evaluation results are shown in Table 1.

(1) Appearance: To determine the presence or absence of interference fringes, fluorescent lamp light was reflected on the lens surface with a black background, and the occurrence of rainbow patterns due to light interference was observed with the naked eye. Judgment was made as follows. I went.

O; Rainbow pattern not observed.

Δ: A faint rainbow pattern is observed.

X: A rainbow pattern is clearly observed.

(2) FFj11! Scratch Resistance: The state of the film was observed after it was reciprocated 10 times with #OO○○ steel wool at a load of 1 kg/cm 2 .

A: Almost never gets scratched.

B: Slightly damaged (.

C: Many scratches occur.

(3) Adhesion: After soaking in 80@C warm water for 2 hours, use a knife to apply 1 mm increments to the lens surface vertically and horizontally.
Make one parallel line scratch, make 100 squares, adhere cellophane tape, and count the number of squares that remain without the film peeling off after peeling (4) Weather Resistance xenon Long Life Fade Using a meter (manufactured by Suga Test Instruments),
The surface condition after 200 hours of exposure was examined.

Example 2 Into a flask equipped with a stirring device, 90 g of the same water-dispersed tungsten oxide sol used in Example 1, 165 g of ethyl cellosolve, and 38.6 g of γ-glycidoxypropyl methyljethoxysilane were added in order with stirring. ,0,0
6.7 g of 5N hydrochloric acid was added dropwise over 30 minutes. Next, 0.15% of the same silicone surfactant used in Example 1 was added.
After adding g, leave it for 24 hours at O'C to ripen,
A coating liquid was obtained.

Next, the same high refractive index lens fabric used in Example 1 was subjected to the same alkali treatment as in Example 1, and then applied to the coating solution of this example by dipping at a pulling speed of 15 cmZ. It was heated and cured in the same manner as in Example 1. The thickness of the obtained film was 2.5 μm.

The synthetic resin lenses obtained by the above method were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 In a flask equipped with a stirring device, 67.5 g of the same water-dispersed tungsten oxide sol used in Example 1 and isopropyl alcohol-dispersed colloidal silica (manufactured by Catalysts & Chemicals Industry Co., Ltd., trade name: "OS CA L-1432"') , solid content concentration 30% by weight), 154 g of isopropyl alcohol, and 25.7 g of γ-glycidoxypropyl trimethoxysilane were added in order with stirring, and 7.1 g of 0.05N hydrochloric acid was added dropwise over 30 minutes. did. Subsequently, 0.15 g of the same silicone surfactant as used in Example 1 was added, and the mixture was allowed to stand at 0°C for 24 hours to ripen, thereby obtaining a coating liquid.

Using this coating liquid, polycarbonate lenses (
Diameter 75mm, -3,0OD) and pulling speed 14cm/
It was applied using the dipping method under the conditions of 10 minutes. After coating, heating and curing were performed in the same manner as in Example 1. The thickness of the obtained film was 2.7 μm.

The synthetic resin lenses obtained by the above method were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 The water-dispersed tungsten oxide sol in Example 3 was
Tetravalent water-dispersed tungsten oxide sol (WO2, concentration 20
A coating solution was obtained in the same manner as in Example 3, except that the coating solution was changed to (%).

Using this coating liquid, it was applied to the same polycarbonate lens as in Example 3 by dipping at a pulling speed of 15 cm/min, and after coating, it was heated and cured in the same manner as in Example 1. The thickness of the obtained film was 2.2 μm.

The synthetic resin lenses obtained by the above method were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 After exposing the lens obtained in Example 1 to Ar gas plasma with an output of 200 W in a vacuum for 30 seconds, S z 02 was applied from the lens side to the atmosphere side by vacuum evaporation.
．． Z r Oe+ S iOt+ Z r O
a.

A five-layer thin film of 5 iOa was formed. The optical thickness of the formed anti-reflection film is approximately λs/4 for 5iOz, then approximately λs/4 for Z
The total film thickness of rO2 and Sing is about λm/4, the next ZrO
2 is about ^Q/4, and the top layer 5iOa is about λ@/4
It is. Note that the design wavelength λ1 is 510 nm.

The synthetic resin lenses obtained by the above method were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 In a flask equipped with a stirring device, 75 g of the same isopropyl alcohol-dispersed colloidal silica used in Example 3 was added.
1, 185 g of isopropyl alcohol, and 32 g of γ-glycidoxypropyltrimethoxysilane were added in this order with stirring, and 8.8 g of 0.05N hydrochloric acid was added dropwise over 30 minutes.

Subsequently, 0.15 g of the same silicone surfactant as used in Example 1 was added, and the mixture was allowed to stand at 0°C for 24 hours to ripen, thereby obtaining a coating liquid.

Using this coating liquid, it was applied to the same high refractive index lens fabric as in Example 1 by the dipping method at a pulling rate of 15 cm/min, and then heated and heated in the same manner as in Example 1.
Hardened. The thickness of the obtained film was 2.3 μm.

The synthetic resin lenses obtained by the above method were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 The isopropyl alcohol-dispersed colloidal silica in Comparative Example 1 was mixed with water-dispersed antimony pentoxide sol (manufactured by Nikkei Chemical Co., Ltd., trade name: "Sancolloid AMT-13O3")
A coating liquid was obtained in the same manner as in Comparative Example 1, except that the solid content concentration was changed to 30%.

Using this coating liquid, a coating was provided on the same high refractive index lens material as in Example 1 in the same manner as in Comparative Example 1. The film thickness of the film was 2.2 μm.

The synthetic resin lenses obtained by the above method were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 Comparative Example 1 was performed except that the isopropyl alcohol-dispersed colloidal silica in Comparative Example 1 was replaced with water-dispersed titanium dioxide sol (manufactured by Nissan Chemical Industries, Ltd., solid content temperature: 30% by weight).
A coating liquid was obtained in the same manner as above.

Using this coating liquid, a coating was provided on the same high refractive index lens material as in Example 1 in the same manner as in Comparative Example 1. The film J7 of the coating had a thickness of 2.8 μm.

The synthetic resin lenses obtained by the above method were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Table 1 [Effects of the Invention] As described above, by using the coating composition containing A and B as main components of the present invention, a high refractive index resin having a high refractive index and high surface hardness and durability can be obtained. A coating for use can be obtained.

As is clear from the comparative examples in Table 1 above, when silicon dioxide is used, interference fringes occur, and even antimony pentoxide cannot completely suppress interference fringes. Although it is possible to completely suppress the occurrence of interference fringes in such cases, there is a drawback that the durability of the film, particularly its weather resistance, is poor.

As is clear from Examples 1 to 5, the effects of the present invention can completely suppress the occurrence of interference fringes and provide a highly durable coating for high refractive index resin.

The coating composition of the present invention can be applied not only to eyeglass lenses but also to high refractive index resins and glass.

Furthermore, coating compositions made of tungsten oxide can also be expected to be used as coating materials with dimming performance.

that's all

Claims (1)

[Claims] (1) A coating composition characterized by comprising the following A and B as main components. A, colloidally dispersed tungsten oxide sol. B.Organosilicon compounds or their hydrolysates whose general formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼
Here, R^1 is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, or an organic group having an epoxy group, R^2 is a hydrocarbon group having 1 to 4 carbon atoms, and R^3 is a hydrocarbon group having 1 to 4 carbon atoms. , a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or hydrogen a represents 0 or 1. )