JPS60221702A - Molding having transparent coating layer - Google Patents

Abstract

PURPOSE:To obtain an excellent antireflecting effect and to increase surface hardness by incorporating inorg. pulverous particles consisting of a specific metallic oxide into a transparent coating layer. CONSTITUTION:The pulverous particulate inorg. material consisting of the metallic oxide such as Al, Ti, Zr, Sn or Sb having 1-300mmu average particle size is incorporated at about 5-80wt% into the transparent coating layer provided to the surface layer part of a transparent molding. The molding having <=80% haze [transmittance of diffused rays/total ray transmittance X 100(%)] is used for such molding in which a transparent glass, a transparent plastic are useable as the base body. An org. silicon polymer is further incorporated into the transparent coating layer and the org. high polymer compd. having a crosslinked structure is incorporated therein. Such coating layer is formed by coating a mixture obtd. by mixing the pulverous particulate inorg. material and the above-mentioned vehicle component into, for example, a volatile dispersant on a substrate, evaporating the dispersant and curing the coating by heating. The resulted coating layer has high hardness and good transparency, has no disadvantage such as the interference fringe of the coating layer, is highly effective in preventing reflection and obviates the eyes' fatigue and provides excellent wearing feel when applied for a lens, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a molded article having a transparent coating layer suitable for producing a transparent coating layer with low light reflectance and high light transmittance and high surface hardness. . In other words, it relates to a molded product made of glass, plastics, etc., which has a suitable transparent coating layer on its surface layer.

[Conventional technology]

Reducing the light reflectance of various transparent materials, and ultimately improving the light transmittance, is an extremely important issue, such as effective use of light and eliminating blurring of images due to reflected images, and many methods have been proposed to date. .

The idea is to reduce the light reflectance and improve the light transmittance by forming an optical thin layer, mainly made of inorganic material, 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 make the effect more human-like, it is possible to perform multi-layer coating of thin layers with different refractive indexes, control the thickness of each thin layer according to the wavelength level of the corresponding light beam, or continuously coat the refractive index. Formation of so-called heterogeneous films with different properties has been carried out.

Taking the case of forming a single-layer anti-reflection thin film on one surface of these substrates, the anti-reflection thin film provided on the surface of the base material should be made of an inorganic component with a low refractive index (for example, magnesium fluoride, etc.). ), and it is said to be desirable to adjust the optical thickness of the antifouling 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 layer formation has been most widely applied to transparent materials, mainly glass substrates. The technique of coating a thin inorganic layer on the surface of the substrate, which is often used in this case, has extremely limited application to other techniques.

Examples of the above-mentioned techniques include vacuum evaporation, sputtering, and ion beam methods to improve adhesion. However, these techniques are difficult to apply to plastic materials, which have recently become popular in the field of spectacle lenses among transparent materials, or to plastic films and plastic sheets for which it is advantageous to form an antireflection layer. In particular, there are many problems when applied to plastic materials with high hardness coating materials to improve their abrasion resistance.

That is, plastic materials generally have insufficient heat resistance and cannot withstand the above coating process, and in some cases, the plastic material (substrate) may undergo decomposition, melting, thermal deformation, 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 drop in capacity during heating or humidification is extremely severe, the inorganic material layer may crack. , crank, 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 with such an inorganic layer. This is thought to be mainly due to the notch effect caused by cracks in the inorganic material on the surface layer.

In other words, this indicates that the superiority of plastic materials over glass materials is lost, and is an important problem.

[Problem that the invention aims to solve]

The present inventors have conducted intensive studies to solve these problems and develop a molded product having a transparent coating layer with high surface hardness, which is suitable for manufacturing transparent materials with excellent antireflection effects.As a result, the present invention has been developed. Reached.

That is, the present invention is applicable to any type of base material, such as glass or plastic, and has high surface hardness and low light reflectance and high light transmittance. It is an object of the present invention to provide a molded article having a transparent coating layer suitable for a transparent coating layer.

[Means for solving problems]

In order to achieve the above object, the present invention consists of the following configuration.

"In the molded product having a transparent coating layer, the transparent layer contains 11. Ti, Zr, 3n, with an average particle diameter of 1 to 300 mμ,
1. A molded article having a transparent coating layer, characterized in that it contains 5 to 80% by weight of a particulate inorganic substance made of one or more metal oxides selected from the group consisting of 3b and 3b. ” The particulate inorganic substance used in the present invention has an average particle diameter of about 1 to 300 mμ, preferably about 5 to 200 mμ.

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.

These particulate inorganic substances include aluminum oxide,
One or more types selected from fine particles of titanium oxide, zirconium oxide, tin oxide, and antimony oxide are used. This is because it has excellent transparency and surface hardness. Among these, aluminum oxide, titanium fluoride, zirconium oxide, and antimony oxide are particularly preferred since they provide 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 fine particulate undefeated substance be contained in at least the surface layer of the transparent substrate.

This is because the premise is to give hardness to the surface layer of the base to improve wear resistance and uneven abrasion resistance.

As a means for containing an inorganic substance in the surface layer portion, there are a method in which the inorganic substance is uniformly dispersed in the transparent material serving as the base A during the molding process, or a method in which the inorganic substance is dispersed only in the surface layer portion. 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) A method in which a dispersion (fine particulate inorganic substance) and a substance serving as a substrate (hereinafter referred to as a vehicle component) are mixed in a volatile dispersion medium, and then the volatile dispersion medium is evaporated.

(C) For fine particulate matter, a method is used in which the material is dispersed in a 7-mer component and then polymerized.

When the present invention is applied to the NvJ charge among the above methods, the method in item (b) is preferable. In this case, the coating film formed by evaporation of the volatile dispersion medium may also harden.

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
The amount is 5 to 80% by weight, preferably 10 to 70% by weight, in the surface layer portion of at least 1 μm or less.

If the amount is less than 5%, the effect of addition will be small, and if the amount exceeds 80%, defects such as cracking and decreased transparency will occur.

Methods for dispersing inorganic substances in transparent materials include a method in which they are directly dispersed in a base material (transparent vJFl) as described above, or a method in which they are dispersed in a coating material and coated on a transparent material (hereinafter referred to as coating method). ) is not particularly important, but 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, that is, the vehicle component in which the particulate inorganic material of the present invention is dispersed, is one that forms a microporous-containing surface of the inorganic material by being partially or completely diffused or eliminated by activated gas treatment. Although there are no particular limitations, compounds containing various elements having organic groups such as organic compounds and/or organosilicon compounds can usually be used, and these high molecular compounds are particularly useful. Examples of these are epoxy resins, acrylic esters and/or methacrylic esters, copolymers of acid esters (including copolymers with other vinyl monomers), polyamides, polyesters (so-called alkyd resins, unsaturated polyesters). resins), various amine resins (including melamine resins, urea resins, etc.), urethane resins, polycarbonates, polyvinyl acetate, polyvinyl alcohol, styrene resins, transparent vinyl chloride resins, silicone resins, cellulose resins, and diethylene glycol resins. Allyl carbonate polymer (CR-39) can be mentioned.

Furthermore, these resins can be used in combination, and cured products obtained by using a suitable curing agent in combination can also be used.

In addition to plasticizers, various curing agents, curing catalysts, etc., the vehicle component may further contain various additives such 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, will increase the surface hardness. It can be effectively used to improve the

Further, the molded article having a transparent coating layer of the present invention may be colorless or colored with dyes and pigments.

Various proposed methods are particularly effective for providing the silicon-based polymer coating layer.

That is, an alkyl, aryl, halogenated alkyl, halogenated aryl, alkenyl, or an organic group having an epoxy group, (meth)acryloxy group, mercapto group, or cyano group of the general formula C1 to CIO, and a 5i-C bond forms a silicon and R3 is an alkyl group, alkoxyalkyl group or acyl group of 01 to C6,
a and bl, to, 1, or 2, a plus 1
Or 2.

Examples of these compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ■
Tyltrimethoxysilane, ethyltriethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxy-1-xysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloro9propyltrimethoxysilane, γ-chloro Propyltriethoxysilane, γ-chloropropyltripropoxysilane, 3゜3.3-trifluoropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, r-(β -glycidoxyethoxy)propyltrimethoxysilane, β-(3,4-epoxycyclosisilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- Trialkoxy or triazyloxysilanes such as mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β(aminoethyl)-γ-aminopropyltrimethoxysilane, β-cyanoethyl 1-liethoxysilane, dimethyldimethoxysilane, phenyl Methyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycid Xypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, T-chloropropylmethyljethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ- Dialkoxysilane or diacyloxysilane such as mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyljethoxysilane, methylvinyldimethoxysilane, methylvinyldimethoxysilane, etc. An example is

These organosilicon compounds can be used alone or in combination of two or more.

Further, although not used alone, there are various tetraalkoxysilanes or their hydrolysates that can be used in combination with the above-mentioned silane compounds.

Examples of tetraalkoxysilanes include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, 5ec-
Examples include butyl silicate and t-butyl silicate.

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, Lewis bases, such as organic carboxylic acids, chromic acid, hypochlorous acid, boric acid, bromic acid, selenite, thioWI acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminium. Metal salts of acids and carbonates, particularly alkali metal salts or ammonium salts, as well as alkoxides of aluminum, zirconium, titanium, or complex compounds thereof, can be used. 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 maintain good storage conditions.

Any material may be used as the base material, but from the viewpoint of transparency, glass, transparent plastics (A) give particularly effective results. Examples of the above plastic materials include polymethyl methacrylate and its copolymers, polycarbonate, Preferred are diethylene glycol bisallyl carbonate polymers, polyesters, especially polyethylene terephthalate, unsaturated polyesters, epoxy resins, etc. The coating method, drying and/or curing method is appropriately selected from those normally used in the coating field.

In the present invention, the surface of the transparent coating layer containing the particulate inorganic material obtained as described above may be further treated with an activated gas to provide an antireflection thin layer. Furthermore, a single-layer or multi-layer anti-fouling 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 In a reactor equipped with a rotor, γ-glycidoxypropyl 1
~Prepare rimethoxysilane 212.4CI and set the liquid temperature to 10
'C while stirring with a magnetic stirrer.
48.60 g of 0.01N aqueous hydrochloric acid solution was gradually added dropwise.

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 the silane hydrolyzate 200Q, and 100 g of ethylene chlorohydrin was added as an additive solvent. The amount of the metal oxide added is the weight of the solid content 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) Coating and evaluation A diethylene glyco-rubisallyl carbonate polymer lens (diameter 75 mm, thickness 2) was immersed in a caustic soda aqueous solution using the paint described above and then washed.

1111mSCR-39 Praruns) by a flow coating method. The coated lenses were heated and 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 coated surface with steel wool having a hardness of #0000 and judge the extent of scratches. The criteria for evaluation are: A: No damage at all.

B: There are quite a few scars.

C: Scratches occur on the entire surface to the same extent as ordinary organic plastics.

D: Scratches are more severe than in ordinary organic plastics.

Table 1 The particle diameters of the inorganic fine particles in the coating layer of each of the above Examples were as follows. In addition, the amount of fine particles present in the -tain ink layer was the same as the amount added in Table 1.

Average particle diameter (mμ) Example 1 50 Example 27 Example 3 21 Example 4 10 Actual IM Example 5 The inorganic fine particles in Example 2 were changed to 3b20s sol (addition amount: 100 parts by weight), and methanol was used as the additive solvent. The same procedure was followed except that 10 parts by weight of aluminum acetylacetonate was used as a curing agent.

The obtained lens had a hardness of Δ, a haze value of 0.2%, and a total light transmittance of 89.72%.

The average particle diameter of 5b205 in the coating layer on the surface of the lens thus obtained was 55 mμ.

Example 6 An experiment was conducted in the same manner as in Example 5, except that the amount of 5b205 sol added was changed, the amount of inorganic particles present in the lens coating layer was changed as shown in Table 2, and the lens base material was changed to polycarbonate. . 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. This is what I did.

A: No rainbow pattern was observed.

B: A faint rainbow pattern is observed.

C: A rainbow pattern is clearly recognized.

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.

Note) In experiment number 6 in Table 2, cracks occurred in the coating layer and a favorable result could not be obtained.

[Effects of the Invention] The molded product having the transparent coating layer of the present invention has high hardness and good transparency, and does not have the disadvantage of interference fringes of the coating layer.
An extremely high-quality molded product can be obtained. 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 (5)

[Claims] (1) In a molded article having a transparent coating layer, the transparent layer is made of Am, T having an average particle diameter of 1 to 300 mμ. 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 Zr, 3n, and 3b. (2) The transparency of the molded product is 80% or less in haze value determined by the following formula (
1) A molded article having a transparent coating layer. Haze value (%) - (diffuse light transmittance/total light transmittance) 100 (3) A molded article having a transparent coating layer according to claim (1), characterized in that the layer contains a transparent layer or an organosilicon polymer. (4) A molded article having a transparent coating layer according to claim (1), wherein the transparent layer contains an organic polymer compound having a crosslinked structure. (5) Claim (1) characterized in that the base material of the molded body is transparent glass or transparent plastic.
A molded article having a transparent coating layer as described in 1.