JPH0372302A - Composition for coating - Google Patents

Abstract

PURPOSE:To improve refractive index, surface hardness and durability by using the colloidal dispersing element of the fine particle of tungsten trioxide, the colloidal dispersing element of the fine particles of the metal oxide of >=1 kinds selected from Al, Ti, Zr, Si, etc., and a specific org. silicon compd. or the hydrolyzate thereof as essential components. CONSTITUTION:This compsn. consists essentially of the colloidal dispersing element of the fine particle of the tungsten trioxide, the colloidal dispersing element of the fine particle of the metal oxide of >=1 kinds selected from the Al, Ti, Zr, Sn, Sb, Ta, Ce, La, In, and Si, and the org. silicon compd. expressed by formula I or the hydrolyzate thereof. In the formula I, R1 denotes 1 to 6C hydrocarbon group, vinyl group, methacryloxy group, mercapto group, amino group or org. group having an epoxy group; R<2> denotes 1 to 4C hydrocarbon group; R<3> denotes 1 to 5C hydrocarbon group, alkoxyalkyl group or hydrogen; (a) denotes 0 or 1. The high refractive index, the high surface hardness and the durability are obtd.

Description

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

More specifically, the present invention relates to a coating composition in which a transparent coating layer is selected that absorbs ultraviolet rays, thereby preventing damage or deterioration of plastic substrates and the like due to ultraviolet rays.

[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, and in recent years, anti-reflection technology, hard coat technology, etc. - With the development of decoat + anti-reflection 11" technology,
It is rapidly becoming popular.

However, since the refractive index of diethylene glycol bis(allyl carbonate) resin is 1.50, which is smaller than that of a glass lens, it has the disadvantage that the outer periphery is thicker than that of a glass lens. For this reason, the use of plastic eyeglass lenses has increased the demand for thin plastic lenses made of high refractive index resin materials. As a technical proposal for this purpose, Japanese Patent Application Laid-Open Nos. 59-133211 and 60-199016
High refractive index resin materials having a refractive index of around 1.60 have been proposed, such as those disclosed in Japanese Patent Application Publication No.

On the other hand, in order to solve the drawback of plastic eyeglass lenses, which is that they are easily scratched, a method of coating the surfaces of plastic lenses with a silicone-based Bartco-1 film is generally practiced.

However, if the same method is applied to a high refractive index resin lens with a refractive index of around 1.60, interference fringes will occur due to the difference in refractive index between the resin lens and the coating film, resulting in poor appearance. As a technical proposal to solve this problem, Japanese Patent Publication No. 61-54 '331, Japanese Patent Publication No. 63-3
A colloidal dispersion of fine particles of silicon dioxide used in silicon-based coating compositions as disclosed in Japanese Patent No. 7142 is replaced with a colloidal dispersion of fine particles of metal oxides of Aj7STi, Zr, So, and sb having a high refractive index. High refractive index coating compositions have been proposed that replace the above.

In addition, when applying the coating film, the resin lens base material is pretreated, and common methods include chemical treatment methods such as alkali treatment and acid treatment, ultraviolet irradiation treatment, plasma treatment, etc. There are physical treatment methods, as well as additive treatment methods such as addition of surface-active substances.

[Problem to be solved by the invention]

However, among the above-mentioned conventional technologies,
The coating compositions disclosed in Japanese Patent Publication No. 63-37142 had the following problems. for example,
When a colloidal dispersion of metal oxide fine particles of AI, ZrsSnNSb is used as a coating composition for a high refractive index resin of around 1.60, the coating composition is lower than that of a silicone-based coating composition. Although it is possible to suppress the occurrence of interference fringes during curing, there is a limit to the refractive index of the coating film. Although it has a relatively high refractive index as a metal oxide fine particle +11° body, when used as a coating material, a silicon-based coupling agent, etc. is generally mixed, so the refractive index of the coating material is The limit was about 1.57, and there was naturally a limit to the improvement of interference fringes. Furthermore, when a colloidal dispersion of Ti metal oxide fine particles is used as a coating composition, the coating formed on TiCh[;1 has a higher refractive index than the metal oxide, and This has the advantage that it not only provides a high refractive index layer, but also allows a wider range of choices for the refractive index of the coating. However, since TiO2 has extremely poor weather resistance, in the case of a film formed from a TiO2 silicon-based coupling agent, it may deteriorate before the organic components of the silicon-based coupling agent or on the surface of the wood 1 and substrate.
There was an issue with its durability.

In addition, among the pretreatment methods performed prior to the formation of the transparent coating layer, plasma treatment has a +4 wettability and adhesive property in terms of ensuring good adhesion between the substrate and the coating. The improvement effect is excellent. However, when plasma treatment is applied, although sufficient initial adhesion can be ensured, there is a problem in that during weathering tests, the interface between the film and the base material deteriorates due to ultraviolet rays, leading to a rapid decline in adhesion.

The present invention aims to solve these problems, and its purpose is to have a high refractive index, high surface hardness, and durability, and when plasma treatment is performed as a pretreatment before film formation. The object of the present invention is to provide a composition for coating a high refractive index resin lens, which also has an ultraviolet absorption effect that can prevent a decrease in adhesion in a weather test and a change in the cost of a plastic base material.

[71 assignments? Means for determining] The coating composition of the present invention has the following (1) or (
2).

(1) A coating composition comprising the following A, B and C as main components.

A, Colloidal dispersion of fine tungsten trioxide particles.

B, ANSTiSZrSSs, Sb, Ta5Ce.

A colloidal dispersion of fine particles of one or more metal oxides selected from La and In5Si.

An organosilicon compound or a hydrolyzate thereof whose C1 general formula is represented by 2aR'Si(OR')3-m. (Here, R1 is an organic group having a carbon hydrogen group having 1 to 6 carbon atoms, a vinyl group, a methacryloxy group, a mercapto group, an amino group, or an epoxy group; R2 is a hydrocarbon group having 1 to 4 carbon atoms;
R3 represents a hydrocarbon group 1 having 1 to 5 carbon atoms, an alkoxyalkyl group, or hydrogen; a represents 0 or 1).

(2) AI? STi, Zr, 5nSSbSTaSCe,
A colloidal dispersion of fine particles consisting of one or more metal oxides selected from La, In, and St and tungsten trioxide, and a coating containing the organosilicon compound or its hydrolyzate described in C above as a main component. Composition.

The colloidal dispersion of tungsten trioxide fine particles as the component A in claim (1) of the present invention, and further the Al component as the component B.
, Tis Zr, 5nSSb, Ta5Ce, La, In
The colloidal dispersion of 5Si oxide fine particles is one in which the metal oxide fine particles have an average particle size of about 1 to 300 mμ, preferably about 1 to 200 mμ. If the particle size is too small, it is difficult to produce, high cost, and impractical, and if the particle size is too large, the transparency generally decreases, so particles within the above range are preferable. Further, examples of the dispersion medium for these components A and B include water, hydrocarbons, esters, ketones, alcohols, and organic carboxylic acids. In addition, these dispersion media are 2N
It is also possible to use a mixture of the above. As for component B, a colloidal dispersion of two or more kinds of metal oxide fine particles can be used in combination, and the mixture type and mixing ratio are appropriately determined depending on the desired film characteristics.

Moreover, Al, Ti%Zr in claim (2) of the present invention
1Sn, Sb, Ta, Ce, Las In.

A colloidal dispersion of fine particles consisting of one or more metal oxides derived from St and tungsten trioxide is
One fine particle is a mixed particle of tungsten trioxide and the metal oxide, and the average particle diameter and dispersion medium volume of the fine particle satisfy the same conditions as the A component and the B component of the above claim (1). It is.

In the present invention, the main purpose of using a colloidal dispersion of tungsten trioxide fine particles or a colloidal dispersion of fine particles composed of an external metal oxide and tungsten dioxide is because tungsten dioxide has an ultraviolet absorption effect. This is to utilize the effect to impart ultraviolet absorption ability to the transparent coating layer and prevent photodeterioration at the interface between the plastic base material and the coating and inside the base material. As a result, even when the coating composition is applied and cured by subjecting the plastic substrate to discharge treatment such as plasma treatment, the interface between the substrate and the transparent coating layer is protected from photodeterioration by the ultraviolet absorption ability of the coating film, making it weather resistant. Good adhesion can be ensured even after the test. Furthermore, since tungsten trioxide itself has a relatively high refractive index,
It is also effective in increasing the commercial refractive index of the transparent coating layer. However, since the hardness of the resulting film is inferior when using tungsten trioxide alone, a colloidal dispersion of the above-mentioned high surface refractive index metal oxide or a colloidal dispersion of composite particles of tungsten trioxide and these metal oxides is used. It is necessary to use

The appropriate proportion of metal oxide fine particles in the solid content of the coating composition is 10% to 90% by weight, and if it is less than 10% by weight, the hardness, ultraviolet absorption ability, and refractive index may be insufficient. If the amount is 90% by weight or more, the adhesion between the base material and the coating decreases2), which is not preferable. In addition, the appropriate proportion of tungsten trioxide in the total metal oxide in the solid content is 20% to 90% by weight, and 20% by weight.
Below 90%, the UV absorption ability of the coating is insufficient.
If it exceeds the hardness of the coating,
Undesirable.

2a The general formula of the C component of the present invention is R'-3i(OR')
Examples of the H silicon compound represented by Q-* or its hydrolyzate include methyltrimethoxysilane, ethyltriethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, and vinyltriethoxysilane. Ethoxysilane, vinyltrimethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-glycidoxybrobyltrimethoxysilane, γ-glycidoxybrobylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ-methacryxypropyltrimethoxysilane, Nβ (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, Examples include N-phenyl-γ-aminopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane. These fli may be used alone or in combination of two or more types. In addition, it is preferable to use these by hydrolyzing them in an organic solvent such as alcohol in the presence of an acid. Hydrolysis may be carried out after mixing with the colloidal dispersion. The appropriate proportion of these organosiliconized metals or their hydrolysates in the solid content of the coating composition is 10% to 90% by weight, and 1-0% by weight.
If the F content exceeds % by weight, the adhesion between the base material and the coating decreases, which is not preferable.

Moreover, if it is more than 90% by weight, the refractive index of the coating becomes low and interference fringes occur, which is not preferable.

Further, these organosilicate metals can be cured even in the absence of a catalyst, but 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 acetylacetopho-1-, chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate,
Hydrochloric acid metal salts such as sodium acetate, zinc naphthenate, cobalt naphthate, zinc octylate, tin octylate, perchloric acids or their salts such as perchloric acid, ammonium perchlorate, magnesium perchlorate, hydrochloric acid , phosphoric acid, nitric acid, para-toluenesulfonic acid, or 5n
C12, AN Cll3, FeCg3, Ti(17*,
Metal chlorides that are Lewis acids such as ZnCl3 and SbCg 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. Examples of polyfunctional epoxy compounds include diglycidyl ethers of difunctional alcohols such as (poly)ethylene glycol, (poly)propylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol, or triglycidyl ethers of difunctional alcohols such as glycerin and trimethylolpropane. Examples include di- or triglycidine ethers of functional alcohols. Examples of polyhydric alcohols include difunctional alcohols such as (poly)ethylene glycol, (poly)propylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol; or trifunctional alcohols such as glycerin and trimethylolpropane; , polyvinyl alcohol, etc.

Examples of polyhydric carboxylic acids include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, orthophthalic acid, terephthalic acid, fumaric acid, itaconic acid, and oxaloacetic acid. Examples of the polycarboxylic anhydride include succinic anhydride, maleic anhydride, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, naphthalic anhydride, and the like.

Furthermore, the solid content concentration of the coating composition of the present invention can be adjusted by adding solvents such as alcoholic acids, ketones, cellosolves, and carboxylic acids singly or in combination.

In addition, if necessary, a small amount of surfactant, antistatic agent,
It is also possible to add an ultraviolet absorber to improve the coating properties of the coating solution and the performance of the coating film.

In 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.

As for the coating and curing method, the coating liquid is uniformly applied by a dipping 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 seconds. I can do it. The appropriate thickness of the film is 1 to 30 μm; if it is less than 1 μm, the scratch resistance of the resulting film is insufficient, and the thickness is less than 30 μm.
If it exceeds m, cracks are likely to occur in the coating. Note that it is also possible to reduce reflection and improve transmission 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, if it is a transparent material, good durability can be obtained for both glass and plastic.
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, 150 g of water-dispersed tungsten trioxide sol (manufactured by Nikrei Kagaku Kogyo Co., Ltd., WO3 concentration 20% by weight) and 5b2o.

Methanol sol (manufactured by Nichirei Kagaku Kogyo Co., Ltd., trade name "Sancolloid AMT-130", 5b20s concentration 30% by weight) toog, 177.2 g of ethanol, 57.1 g of γ-glycidoxypropyltrimethoxysilane were stirred. Then, 15.7 g of 0.05N hydrochloric acid solution was added dropwise over 30 minutes. Subsequently, 0.25 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 (manufactured by IrfIN Seiko Co., Ltd., product name “Seiko High Road °, refraction skewer 1.60
, 75m diameter, -3,0OD) with a concentration of 5% Na
After being immersed in an OH aqueous solution for 5 minutes, washed, and dried, it was coated by a dipping method using the coating wave described above at a pulling speed of 15 cm/min. After coating, heating and curing were performed at 80°C for 1 hour and at 100°C for 2 hours. The thickness of the obtained film was 2.3 μm.

The following performance evaluation tests were conducted on the synthetic resin lenses obtained by the above method, and the 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 formation of rainbow patterns due to light interference was observed with the naked eye. The judgment was made as follows.

○: Rainbow pattern is not observed.

Δ: A faint rainbow pattern is observed.

×: A rainbow pattern is clearly recognized.

(2) Scratch resistance: The state of the coating was observed after it was reciprocated 10 times with #0000 steel wool at a load of 1 kg/cj.

A: It hardly gets scratched.

B: Slight damage.

C: Many scratches occur.

(3) Adhesion: After immersing in warm water at 80℃ for 2 hours, use a knife to make 11 parallel line-shaped scratches on the lens surface at 1-square intervals, creating 100 squares. After gluing cellophane tape and peeling it off, we looked at the number of squares that remained without the film peeling off.

(4) Weather resistance: xenon log life fade meter (
After exposure for 150 hours using Suga Test Instruments Co., Ltd.
The following evaluations were made.

■Appearance: The coloring of the seeds was observed with the naked eye.

(2) Adhesion: After testing, the same cross-cut tape test as in (3) above was performed on the exposed surface of the lens.

Example 2 The same high refractive index lens core as used in Example 1 was treated using a surface treatment plasma device (manufactured by Shinku Kikai Kogyo Co., Ltd.) at an air flow rate of 100 m1/min, an output of 50 W, and a degree of vacuum (1
, 2 torr for 30 seconds, a coating was applied in the same manner using coating i (l) of Example 1.

The film 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 stirrer, 15 g of the same water-dispersed tungsten trioxide sol used in Example 1 and 66.7 g of isopropyl alcohol-dispersed colloidal silica (catalyzed or 66.7 g of γ-glycidoxypropyl methyljethoxy silane (manufactured by Wangye Co., Ltd., product name "05CAL1432", solid content 30% by weight) was added in order with stirring, and (1
, 7.5f of 05N hydrochloric acid solution was added dropwise over 30 minutes.

Next, the same silicone surfactant 0 used in Example 1 was added.
．． After adding 25 g, the mixture was left to stand at 0° C. for 24 hours to age and obtain a coating liquid.

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 cm/min. It was heated and cured in the same manner as in Example 1. The thickness of the obtained film was 2.4 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 same high refractive index lens fabric used in Example 1 was plasma treated in the same manner as in Example 2, and then coated and cured using the coating solution prepared in Example 3. coating,
The curing conditions were the same as in Example 3. (The film thickness of the +-% film was 2.6 μm.

The synthetic resin lens obtained by the above method (Example 1)
The results are shown in Table 1.

Example 5 A colloidal equinox of metal oxide fine particles consisting of tungsten dioxide, antimony pentoxide and silicon dioxide in a weight ratio of 4:3 &=J3 using water as a dispersion medium was prepared in France equipped with a stirring device. While stirring 158.96 g of 1-methyl cellosolve into 250 g of medium (manufactured by 1-sanka Kirigyo Co., Ltd., solid content concentration 20! T! amount %) and γ-glycidoxybrobyltrimethoxysilane 71°43, add, then 0
．． 19.61 sr of 05N hydrochloric acid solution was added dropwise over 30 minutes. Subsequently, 0.25 g of the same silicone surfactant as used in Example 1 was added, and the mixture was aged for 24 hours at 0.degree. C. to obtain a coating liquid.

Next, high refractive semi-resin lens/E: Ground (manufactured by Hanbe Seiko Co., Ltd., product name "Seiko Blacks ■", refraction r+, %1
．． 56, diameter 75 mm, -3,0 OD) was treated with alkali in the same manner as in Example 1, and then treated with the dipping method using the coating liquid obtained in this example at a pulling rate of 17 (7) 7 minutes. Coated. 1 at 80℃ after coating
Heating and hardening was performed at 110° C. for 3 hours. The thickness of the obtained film was 2.7 μm.

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

Example 6 The same high refractive index lens fabric as used in Example 5 was plasma treated in the same manner as in Example 2, and then coated and cured using the Coach 2f liquid prepared in Example 5. The coating and curing conditions were the same as in Example 5. The film thickness of the obtained film was 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.

Example 7 After exposing the lens obtained in Example 1 to Ar gas plasma with an output of 200 W in vacuum for 30 seconds, 5i02, Z was applied from the lens side toward the atmosphere side by vacuum evaporation method.
A five-layer thin film of rO2, 5i02 and ZrO2, 5i02 was formed. The optical thickness of the formed antireflection film is approximately λ for 5tO2. /4, the total film thickness of the next ZrO2 and 5i02 is about λo/4, and the next ZrO2 is about λ. /4, and the top layer 5i02 is about λo/4. Note that the design wavelength λ0 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.

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-glycidoxybrobyltrimethoxysilane 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 left to mature at 0° C. for 24 hours to obtain a coating liquid.

Using this coating liquid, the same high refractive index lens fabric used in Example 1 was plasma treated in the same manner as in Example 2, and then coated by dipping at a pulling speed of 15 cm/min. It was heated and cured in the same manner as in 1. The film thickness of the obtained film was 2.5 ttm.

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 A coating liquid was obtained in the same manner as in Comparative Example 1, except that the isopropyl alcohol-dispersed colloidal silica in Comparative Example 1 was replaced with the 5b205 methanol sol used in Example 1.

Using this coating liquid, the same high refractive index lens fabric used in Example 1 was plasma treated in the same manner as in Example 2, and then a coating was provided in the same manner as in Comparative Example 1. The film thickness of the 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.

〔Effect of the invention〕

As described above, by using the coating composition of the present invention, a high refractive index resin coating for lenses having a high refractive index and high surface hardness and durability can be obtained.

Furthermore, as is clear from the examples, in order to have the ultraviolet absorption effect, the coating obtained by the coating composition of the present invention can be used after a weathering test when plasma treatment is performed as a pretreatment during coating formation. There is no decrease in adhesion and yellowing of the plastic base material can also be prevented.

The coating composition of the present invention can be applied not only to high refractive index resin lenses, but also to other high refractive index resin materials, high refractive index glasses, and the like.

Claims (2)

[Claims] (1) A coating composition characterized by comprising the following A, B and C as main components. A, Colloidal dispersion of fine tungsten trioxide particles. B, Al, Ti, Zr, Sn, Sb, Ta, Ce, La
A colloidal dispersion of one or more metal oxide fine particles selected from , In, and Si. C. An organosilicon compound or its hydrolyzate 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, a mercapto group, an amino group, or an organic group having an epoxy group, and R^2 is a hydrocarbon group having 1 to 4 carbon atoms. The group R^3 represents a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or hydrogen; a represents 0 or 1). (2) Al, Ti, Zr, Sn, Sb, Ta, Ce, L
A colloidal dispersion of fine particles composed of one or more metal oxides selected from a, In, and Si and tungsten trioxide, and an organosilicon compound represented by the general formula of C according to claim 1 or its A coating composition characterized by containing a hydrolyzate as a main component.