JPS6337142B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a molded article having a transparent coating layer with a high refractive index. Furthermore, the present invention relates to a molded article having a transparent coating layer suitable for producing a molded article having low light reflectance, high light transmittance, and high surface hardness. That is, the present invention relates to a molded product made of glass, plastic, etc., which has a suitable transparent coating layer on its surface layer. [Prior Art] Reducing the light reflectance of various transparent materials and improving the light transmittance is an extremely important problem, such as effective use of light and eliminating blurring of images caused by reflected images, and many methods have been used to date. is proposed. The idea is to reduce the light reflectance and improve the light transmittance by forming an optical thin layer mainly made of an inorganic substance on the surface of the base material, which has a refractive index different from that of the base material. At this time, in order to maximize the effect, multi-layer coating of thin layers with different refractive indexes is performed, and the thickness of each thin layer is adjusted to
Control is being carried out to match the wavelength level of the corresponding light beam, and so-called inhomogeneous films having continuously different refractive indexes are formed. Taking the case of forming a single-layer anti-reflection thin film on the surface of a substrate as an example, the anti-reflection thin film provided on the surface of the substrate is made of an inorganic component with a refractive index as low as possible (for example, magnesium fluoride, etc.). , and it is said to be desirable to adjust the optical thickness of the antireflection thin film to 1/4 of the wavelength of the target light beam. Such optical thin films are subject to limitations regarding the substrates to which they can be applied, depending on the formation process. To date, antireflection thin film formation has been most widely applied to transparent materials, mainly glass substrates. The technique of coating the surface of the substrate with a thin inorganic layer, which is often used in this case, has extremely limited application to other techniques. Examples of the above techniques include vacuum evaporation, sputtering to improve adhesion,
Ion beam method etc. are used. However, these techniques are difficult to apply to plastic materials, which have recently become popular among transparent materials, especially in the field of eyeglass lenses, or to plastic films and plastic sheets, for which it is advantageous to form an antireflection layer. A number of problems exist especially when applying plastic materials with high hardness coatings to improve their scratch resistance. In other words, plastic materials generally do not have sufficient heat resistance to withstand the above coating process, and in some cases, the plastic material (base material) may decompose, melt, thermally deform, optical distortion, etc. . Adhesion is also generally poor.
This is mainly due to the difference in expansion coefficient between the plastic material (base material) and the inorganic material coated on its surface, and if the adhesion decreases significantly during heating or humidification, the inorganic material layer may crack or crack. etc. may occur. A further serious problem is the significant reduction in impact resistance and flexibility of the plastic material (substrate) that occurs due to the coating of such mineral layers. This is thought to be mainly due to the notch effect caused by the generation of cracks in the inorganic matter on the surface. In other words, this shows that the superiority of plastic materials over glass materials is lost, and is an important problem. Furthermore, conventional corrective lenses and the like having a high refractive index have had the problem of poor appearance due to interference fringes. JP-A-54-87735, JP-A-54-87736, and JP-A-53-130732 disclose techniques for forming a coating layer made of silica colloid, but regarding the refractive index, It wasn't listed. Further, US Pat. No. 2,601,123 also describes a technique for coating only inorganic particles, but there is no mention of refractive index. [Problems to be Solved by the Invention] The present inventors have conducted intensive studies to solve these problems and develop a molded article having a transparent coating layer having a high refractive index and high surface hardness, and as a result, the present invention has been developed. reached. That is, an object of the present invention is to provide a molded article having a transparent coating layer with a high refractive index and free from problems such as poor appearance due to interference fringes. [Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration. "In a molded product having a transparent coating layer, the transparent layer contains Al, Ti, Zr, and
A molded article having a transparent coating layer containing 5 to 80% by weight of a particulate inorganic material made of one or more metal oxides selected from Sn and Sb. "The fine particulate inorganic material used in the present invention has an average particle diameter of about 1 to 300 mμ, preferably about 5 to 200 mμ.
It is μ's. If the particle size is too small, it is difficult to produce, expensive and impractical, and if the particle size is too large, the transparency generally decreases, so particles within the above range are mainly used. As these particulate inorganic substances, one or more selected from particulates of aluminum oxide, titanium oxide, zirconium oxide, tin oxide, and antimony oxide are used. It is particularly preferred because it has excellent transparency and surface hardness, and also provides a high refractive index. That is, if the refractive index is high, a corrective lens or the like having a high refractive index will not cause poor appearance due to interference fringes in the coating layer. Moreover, these particulate inorganic substances can be used not only alone but also in combination of two or more types. Furthermore, the above-mentioned oxide may be a mixed oxide containing silicon or the like. It is necessary that the particulate inorganic substance be contained in at least the surface layer of the transparent substrate.
This is because the premise is to impart hardness to the surface layer of the base material to improve wear resistance and scratch resistance. As a means of containing inorganic substances in the surface layer,
There are methods in which inorganic substances are uniformly dispersed in the transparent material serving as the base material during the molding process, or inorganic substances are dispersed only in the surface layer. Yet another method is to disperse the inorganic material in a transparent coating material and apply it to the surface of the transparent material. Various known methods can be used to disperse the above-mentioned particulate inorganic material, such as (a) mixing the particulate inorganic material and another base material (transparent material) by heating or at room temperature in the presence or absence of a solvent or other components; how to. (b) Dispersion (particulate inorganic material) in a volatile dispersion medium
and a substance that becomes a substrate (hereinafter referred to as vehicle component)
and then evaporating the volatile dispersion medium. (c) A method is used in which fine particulate inorganic substances are dispersed in a monomer component and then polymerized. Among the above methods, when the present invention is applied to coating materials, the method in section (b) is preferred. In this case, the coating film formed by evaporation of the volatile dispersion medium may be cured. Examples of volatile dispersion media that can be used include water, hydrocarbons, chlorinated hydrocarbons, esters, ketones, alcohols, and organic carboxylic acids. Moreover, these can be used not only alone but also as a mixture of two or more. The amount of the particulate inorganic substance of the present invention contained in the transparent material is 5 to
80% by weight, preferably 10-70% by weight. 5%
If the amount is less than 80%, the effect of addition will be small, and if the amount exceeds 80%, defects such as cracks and decreased transparency will occur. As a method of dispersing inorganic substances into transparent materials,
A method of directly dispersing it in a base material (transparent material) as described above, or a method of dispersing it in a coating material and applying it to a transparent material (hereinafter referred to as coating method)
Although it is not particularly important which method is used, the coating method has the following advantages. In other words, if the fine particulate inorganic substance cannot be easily dispersed in the base material, or if it can be dispersed but causes a significant change in the properties of the base material, the coating method may cause a significant change in the properties of the base material. will not occur. When dispersing the above-mentioned fine particulate inorganic material, it is possible to use a fine powder form before dispersion, but in order to achieve the purpose of the present invention, it is necessary to disperse the fine particulate inorganic material in a colloidal form in a liquid dispersion medium. The ones listed above are particularly effective. The substrate or vehicle component in which the particulate inorganic material of the present invention is dispersed is not particularly limited;
By further treating the surface of the transparent coating layer containing the obtained particulate inorganic substance with an activated gas,
In consideration of providing an antireflection thin film, it is preferable that the surface of the inorganic material is formed by partially or completely volatilizing or disappearing by activated gas treatment, thereby forming a microporous-containing surface of the inorganic material.
Compounds containing various elements having organic groups such as organic compounds and/or organosilicon compounds can usually be used, and these polymer compounds are particularly useful. Examples of these include epoxy resins, copolymers of acrylic esters and/or methacrylic esters (including copolymers with other vinyl monomers), polyamides,
Polyester (including so-called alkyd resins and unsaturated polyester resins), various amino resins (including melamine resins, urea resins, etc.), urethane resins,
Examples include polycarbonate, polyvinyl acetate, polyvinyl alcohol, styrene resin, transparent vinyl chloride resin, silicon resin, cellulose resin, and diethylene glycol bisallyl carbonate polymer (CR-39). Furthermore, these resins can be used in combination, and cured products obtained by using an appropriate curing agent in combination can also be used. The vehicle component may further contain various additives such as a plasticizer, various curing agents, curing catalysts, and the like, as well as surface conditioners, ultraviolet absorbers, and antioxidants. The molded article having a transparent coating layer of the present invention preferably has a haze value (percentage) of 80% or less as determined by the following formula. Haze value (%) = (diffuse light transmittance / total light transmittance) × 100 In particular, the coexistence with silicon-based polymer compounds or polymer compounds containing them, which are used as coating agents to improve the surface hardness of plastic articles, is , can be effectively used to provide improved surface hardness. Furthermore, the molded article having a transparent coating layer of the present invention may be colorless or colored with dyes and pigments. Various methods have been proposed for providing a silicon-based polymer coating layer, but the method obtained by curing a compound selected from a group consisting of compounds having the following general formula and/or their hydrolysates has been proposed. The method used is particularly effective. That is, it is a compound consisting of the general formula R ¹ aR ² bSi(OR ³ ) _4-(a+b) , where R ¹ and R ² are C ₁ to
_C10 alkyl, aryl, halogenated alkyl,
Halogenated aryl, alkenyl, or epoxy group, (meth)acryloxy group, mercapto group,
Or it is an organic amount having a cyano group and is bonded to silicon through a Si-C bond, and R ³ is
It is a _C1 to _C6 alkyl group, alkoxyalkyl group, or acyl group, a and b are 0, 1, or 2, and a+b is 1 or 2. Examples of these compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloro propyltriethoxysilane,
γ-chloropropyltripropoxysilane, 3,
3,3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-(β-glycidoxyethoxy)propyltrimethoxysilane, β-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, β-
(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyl Trialkoxy or triacyloxysilanes such as triethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, Phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ -Chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ- Examples include dialkoxysilanes or diacyloxysilanes such as mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane. These organosilicon compounds can be used alone or in combination of two or more. Furthermore, there are various tetraalkoxysilanes or their hydrolysates that can be used in combination with the above-mentioned silane compounds, although they cannot be used alone. Examples of tetraalkoxysilanes include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, sec-butyl silicate and t-butyl silicate.
Butyl silicate, etc. Although these organosilicon compounds can be cured even in the absence of a catalyst, various curing catalysts can be used to further accelerate curing. Various acids or bases, including Lewis acids and Lewis bases, such as organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, bromic acid, selenite, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminic acid , metal salts of carbonic acid, especially alkali metal salts or ammonium salts, alkoxides of aluminum, zirconium, titanium, or complex compounds thereof. Naturally, it is possible to use this in combination with other organic substances, and among these, epoxy resins and acrylic copolymers, especially those having hydroxyl groups, such as polyvinyl alcohol, are useful. Furthermore, when used as a coating material, it is possible to use solvents and various additives to facilitate coating work or to maintain good storage conditions. Any base material may be used, but from the viewpoint of transparency, glass and transparent plastic materials give particularly effective results. The above plastic materials include polymethyl methacrylate and its copolymers, polycarbonate, diethylene glycol bisallyl carbonate polymer (CR-39),
Polyesters, particularly polyethylene terephthalate, unsaturated polyesters, epoxy resins, and the like are preferred. The coating method, drying and/or curing method is appropriately selected from those commonly used in the coating field. In the present invention, the surface of the transparent coating layer containing the fine particulate inorganic substance obtained as described above is
further treated with an activated gas as described above;
A thin anti-reflection layer may also be provided. Furthermore, a single-layer or multilayer anti-reflection film made of an inorganic material may be provided on the transparent coating layer containing a particulate inorganic material by vacuum deposition or sputtering. [Example] Examples 1 to 4, Comparative Example 1 (1) Preparation of silane hydrolyzate 212.4 g of γ-glycidoxypropyltrimethoxysilane was charged into a reaction vessel equipped with a rotor, and the liquid temperature was adjusted to 10°C. While stirring with a magnetic stirrer, add 48.6 g of 0.01N hydrochloric acid aqueous solution.
Gradually drip. After the dropwise addition was completed, cooling was stopped to obtain a silane hydrolyzate. (2) Preparation of Paint Various metal oxide sols shown in Table 1 were added to 200 g of the silane hydrolyzate, and 100 g of ethylene chlorohydrin was further added as an additive solvent.
Note that the amount of the metal oxide added is the solid content weight relative to 100 parts by weight of the solid content of the silane hydrolyzate. Further, as a comparative example, the same procedure was conducted for a sample to which no metal oxide was added. Only in Example 1, 100 g of dimethylformamide was further added as a solvent to prepare a paint. (3) Application and evaluation A diethylene glycol bisallyl carbonate polymer lens (diameter 75 mm, thickness
2.1mm, CR-39 plano lens) using a flow coating method. The coated lenses were heat cured for 4 hours in a hot air dryer at 120°C. The painted lenses were evaluated by the method described below. (4) Rub the painted surface with #0000 hardness steel wool to determine the extent of scratches. The criteria for evaluation are: A: No scratches. B...Slight scars are observed. C...Abrasion marks are left on the entire surface to the same extent as normal organic plastics. D: Scratches are more severe than in ordinary organic plastics.

[Table] The particle diameters of the inorganic fine particles in the coating layer of each of the above examples were as follows. Further, the amount of inorganic fine particles present in the coating layer was the same as the amount added in Table 1. Average particle diameter (mμ) Example 1 50 Example 2 7 Example 3 21 Example 4 10 Example 5 The inorganic fine particles in Example 2 were changed to Sb ₂ O ₅ sol (addition amount: 100 parts by weight) and used as an additive solvent. The same procedure was followed except that methanol was used and 10 parts by weight of aluminum acetylacetonate was added as a hardening agent. The obtained lens had a hardness of A, a haze value of 0.2%, and a total light transmittance of 89.72%. Moreover, the average particle diameter of Sb ₂ O ₅ in the coating layer on the surface of the obtained lens was 55 mμ. Example 6 The same procedure was carried out as in Example 5 except that the amount of Sb ₂ O ₅ sol added was changed, the amount of inorganic particles present in the coating layer of the lens was changed as shown in Table 2, and the lens base material was changed to polycarbonate. I did an experiment. The results are shown in Table 2. The presence or absence of interference fringes in Table 2 is determined by observing with the naked eye the occurrence of rainbow patterns due to light interference when fluorescent light is reflected on the lens surface with a black background. That's what I did. A: No rainbow pattern was observed. B: A faint rainbow pattern is observed. C: A bright rainbow pattern is observed. In addition, the overall judgment was made as follows from the viewpoint of practical usefulness. A: It has no practical problems and is of high quality. B: Practical level. C: Not practical.

【table】

〔Effect of the invention〕

The molded product having a transparent coating layer of the present invention has high hardness and good transparency, and has no defects such as interference fringes of the coating layer, and can be made into an extremely high-quality molded product. It has an excellent antireflection effect, and when applied to lenses, etc., it can be made to be comfortable to wear without causing eye fatigue.

Claims (1)

[Claims] 1. In a molded article having a transparent coating layer, the transparent layer contains Al, Ti, Zr,
A molded article having a transparent coating layer containing 5 to 80% by weight of a particulate inorganic material made of one or more metal oxides selected from Sn and Sb. 2. A molded article having a transparent coating layer according to claim 1, wherein the transparency of the molded article is 80% or less in haze value determined by the following formula. Haze value (%) = (diffuse light transmittance/total light transmittance) × 100 3 The transparent layer has a transparent coating layer according to claim 1, characterized in that the transparent layer contains an organosilicon polymer. Molded object. 4. Claim 1, wherein the transparent layer contains an organic polymer compound having a crosslinked structure.
A molded article having a transparent coating layer as described in 1. 5. A molded article having a transparent coating layer according to claim 1, wherein the base material of the molded article is transparent glass or transparent plastic.