JPH11130982A - Coating composition, production thereof, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating compsn. which can form a hard coat film free of cracks by incorporating fine simple or composite particle of a metal oxide selected from among oxides of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti having specified particle sizes, an organosilicon compd., and water into the same. SOLUTION: This compsn. contains 30-80 wt.% (based on the solid content of the compsn.) fine simple or composite particles of a metal oxide selected from among oxides of Si, Al, Sn, Sb, Ta, Ce, La, Fe, Zn, W, Zr, In, and Ti having particle sizes of 1-200 μm, an organosilicon compd. of formula I (e.g. vinyltrichlorosilane), water in an amt. of 10-50 wt.% of the compsn., an organosilicon compd. of formula II, a polyfunctional epoxy compd., and an organosilicon compd. of formula III. In those formulas, R<1> is a 3C or higher org. group having a polymerizable group; R<2> and R<3> are each a 1-6C hydrocarbon group; R<4> and R<5> are a 1-3C hydrocarbon group; X<1> to X<4> are each a hydrolyzable group; Y is an org. group having a carbonate group or the like; and m and n are each 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard coat film provided on the surface of a plastic lens,
Provides a transparent coating with excellent durability, such as abrasion resistance, moisture resistance, and weather resistance, and excellent appearance quality free from defects such as white turbidity and surface cracks. TECHNICAL FIELD The present invention relates to a composition for hard coating capable of providing a protective film (hereinafter referred to as an inorganic vapor-deposited film), a method for producing the same, and a laminate.

[0002]

2. Description of the Related Art In recent years, plastic lenses have been used in various fields.

[0003] In particular, plastic lenses are now the mainstream of spectacle lenses because they are lighter, safer and have more color variations than conventional glass lenses.

In recent years, the refractive index of plastic lens materials has been rapidly increasing. Particularly, plastic lenses made of allyl carbonate resin, acrylate resin, methacrylate resin, and thiourethane resin are difficult to process. It has been widely used because it has excellent heat resistance and impact resistance, and has a thin lens thickness and good appearance.

However, on the other hand, plastic lenses have a drawback that the surface is easily scratched. Therefore, a method of providing a silicone-based hard coat film on the surface of the plastic lens has been adopted. The silicone-based hard coat film contains a colloidal dispersion (sol) of a metal oxide and a silane coupling agent as an organic silicon compound as main components. The metal oxide sol mainly provides abrasion resistance and adhesion to the inorganic vapor-deposited film formed on the hard coat film surface, and the silane coupling agent mainly provides abrasion resistance and metal oxide particles. It provides adhesion to a binding agent and a lens substrate.

Conventionally, a sol of silicon dioxide fine particles has been used exclusively as a metal oxide sol, and the refractive index of the hard coat film was about 1.50. But,
As described above, the refractive index of plastic lenses has been increasing in recent years, and the mainstream is now lens materials having a refractive index of 1.55 or more. When a conventional hard coat film using a sol of silicon dioxide fine particles is applied to such a high refractive index lens material, interference fringes occur due to a difference in refractive index between the lens material and the hard coat film, which is not preferable in appearance. As a technical proposal for solving this problem, JP-A-61-54331 and JP-A-63-37142 disclose a sol of silicon dioxide fine particles in a hard coating composition, Al, Ti, Zr, S
A method has been proposed in which a sol of inorganic oxide fine particles of n and Sb is used. Japanese Patent Application Laid-Open No. Hei 1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide. Further, Japanese Unexamined Patent Application Publication No.
No. 02, a composite inorganic oxide fine particle of Ti and Ce,
JP-A-3-68901 discloses Ti, Ce and Si.
A method is proposed in which fine particles obtained by treating a composite inorganic oxide with an organosilicon compound are used in a coating composition.

[0007]

However, the prior art has the following problems.

As described above, metal oxide fine particles are
It is a very important component in the properties of the hard coat film, such as improving the wear resistance of the hard coat film, imparting adhesion to the inorganic vapor-deposited film, and increasing the refractive index of the hard coat film. In order to sufficiently exhibit such characteristics, it is desirable that the ratio of the metal oxide fine particles in the hard coat film is 30% by weight or more. However, in the conventional technique, there is a problem that cracks occur in the hard coat film when the hard coat is cured by heating.

This is because the hard coat film cannot withstand the volume shrinkage accompanying the curing / condensation reaction of the hydrolyzable group of the silane coupling agent, which is another main component of the hard coat. Such cracks tend to be remarkable because the toughness of the hard coat film decreases as the ratio of the metal oxide fine particles in the hard coat film increases.
In particular, Al, Sn, Sb, Ta, Ce, La, Fe, Z
Hard coat using single fine particles of an oxide selected from n, W, Zr, In, Ti and / or one or a mixture of two or more selected from composite fine particles of these (referred to as high refractive index metal oxides) In the case of increasing the refractive index of the film, the higher the target refractive index, the larger the amount of these oxides to be added, and therefore the higher the rate of occurrence of cracks in the hard coat film. For example, even when a Ti-based oxide which is one of the oxides having the highest refractive index among the high-refractive-index metal oxides is used, when the refractive index of the hard coat is set to 1.65, the addition rate is increased. Reaches 55 to 65% by weight.
In addition, these high refractive index metal oxides are generally weather resistant,
The abrasion resistance is low, and when silicon dioxide or the like is added to improve the abrasion resistance, it is necessary to further increase the addition rate, and the occurrence rate of cracks in the hard coat film increases.

In order to improve the production efficiency, a method of increasing the heating temperature of the hard coat and shortening the curing time is generally used. In this case, the condensation reaction of the silane coupling agent as described above is more difficult. Since it occurs rapidly, the rate of occurrence of cracks also increases dramatically.

As a method for preventing the occurrence of such a hard coat film crack, there is a method in which the heating temperature of the hard coat is first lowered and the silane coupling agent is slowly condensed. This is not only practical, but also has an effect of only lowering the rate of occurrence of cracks in the hard coat film to some extent, which is not practical.

Further, by replacing a part of the silane coupling agent with a silane coupling agent in which the number of hydrolyzable groups is reduced from three to one or two, the degree of crosslinking is reduced,
There is a method of preventing cracks by reducing the volume shrinkage during the condensation reaction. However, such a method undesirably deteriorates the wear resistance of the hard coat film extremely.

Further, there is a method of adding a polyfunctional hydrocarbon compound having a long molecular chain without a hydrolyzable group to increase the toughness of the hard coat film and prevent cracks.
However, even if this method is used, an extreme decrease in wear resistance of the hard coat film is unavoidable.

The present invention solves the above-mentioned problems of the prior art, realizes sufficient durability such as abrasion resistance, adhesion to an inorganic vapor-deposited film, a high refractive index, and hard coat processing. It is an object of the present invention to provide a coating composition capable of achieving high appearance quality and high productivity while eliminating the occurrence of film cracks in the process, and a method for producing the same. In particular, it is an object of the present invention to provide a coating composition and a method for producing the same, which have a high refractive index, a high content of metal oxide fine particles, and are free from cracks in hard coat processing in which film cracks are easily generated in the processing step. It is an object.

[0015]

In order to achieve the above object, the coating composition of the present invention is characterized by containing at least the following components (A), (B) and (C).

(A) Si, Al having a particle size of 1 to 200 mμ,
Sn, Sb, Ta, Ce, La, Fe, Zn, W, Z
Single fine particles of an oxide of a metal selected from the group consisting of r, In, and Ti, and a mixture of one or more selected from composite fine particles of these metals.

(B) General formula

[0018]

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An organosilicon compound represented by the formula (wherein R ¹
Is an organic group having a polymerizable reactive group and having 3 or more carbon atoms, and X ¹ is a hydrolyzable group. (C) 10 to 50 with respect to the total weight of the coating composition.
Parts by weight water.

Component (A) used in the present invention has a particle size of 1-2.
00mμ Si, Al, Sn, Sb, Ta, Ce, L
Specific examples of a single particle of an oxide of a metal selected from a, Fe, Zn, W, Zr, In and Ti and one or a mixture of two or more selected from composite fine particles of these metals include SiO. ₂ , Al ₂ O ₃ , SnO ₂ , Sb ₂
O ₅ , Ta ₂ O ₅ , CeO ₂ , La ₂ O ₃ , Fe
₂ O ₃ , ZnO, WO ₃ , ZrO ₂ , In ₂ O ₃ , Ti
Of O ₂ inorganic oxide fine particles, dispersing water, for example water, it is obtained by colloidally dispersed in an alcohol or other organic solvents. Alternatively, composite fine particles composed of two or more of these inorganic oxides are colloidally dispersed in water, alcohol, or another organic solvent.

Further, in order to enhance the dispersion stability in the coating solution, it is possible to use those obtained by treating the surfaces of these fine particles with an organosilicon compound or an amine compound. As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane and tetrafunctional silane. The treatment may be performed without treating the hydrolyzable functional group or may be performed by hydrolysis.
After the treatment, the state in which the hydrolyzable group has reacted with the -OH group of the fine particles is preferable, but there is no problem in the stability even when a part remains. Examples of the amine compound include alkylamines such as ammonium, ethylamine, triethylamine, isopropylamine, and n-propylamine; aralkylamines such as benzylamine; alicyclic amines such as pyridine; monoethanol; There are alkanolamines such as ethanol.
It is necessary to add these organosilicon compounds or amine compounds within a range of about 1 to 15% based on the weight of the fine particles.

The kind and amount of application to the coating composition of the present invention may be determined according to the desired film performance, but the amount to be used is preferably 30 to 80% by weight of the solid content. That is, if the content is less than 30% by weight, the adhesion to the inorganic vapor-deposited film becomes insufficient, or the wear resistance of the film becomes insufficient. In particular, the refractive index of the hard coat film is set to 1.60.
In the case where the above is set, 40% by weight or more is required. On the other hand, if the content exceeds 80% by weight, cracks tend to occur in the coating film or the coating film becomes cloudy.

This component (A) is used for the purpose of adjusting the refractive index, further improving the durability of the coating, and improving the appearance.
You may mix and use more than one kind.

Next, in the component (B), R ¹ is an organic group having a polymerizable reactive group and having 1 to 6 carbon atoms, such as vinyl, allyl, acryl, methacryl, 1-methylvinyl. Group, epoxy group, mercapto group, cyano group,
It is a silane compound having a polymerizable reactive group such as an isocyano group and an amino group. X ¹ is a hydrolyzable functional group, and specific examples thereof include a methoxy group, an ethoxy group, an alkoxy group such as a methoxyethoxy group, or
Examples thereof include a halogen group such as a chloro group and a bromo group, and an acyloxy group. The number of the hydrolyzable groups is 3, and it is necessary to be able to form a three-dimensional crosslinked structure. When the number of hydrolyzable groups is 2 or less, the abrasion resistance of the coating film becomes insufficient.

Specific examples of the silane compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane and the like.

The component (B) may be used as a mixture of two or more kinds.

It is more effective to use the component (B) after hydrolysis.

Subsequently, the water of the component (C) accelerates the hydrolysis and condensation of the hydrolyzable group. That is, in the heating / curing step after coating liquid application, when sufficient water molecules are present in the coating liquid, the reaction of the hydrolyzable group is gradually increased from the low temperature region together with the concentration of the solid component by evaporation of the diluting solvent. proceed. As a result, the volume shrinkage accompanying the gradual progress also progresses, so that cracks hardly occur in the coating film. On the other hand, if there are not enough water molecules in the coating liquid, the reaction of the hydrolyzable group mostly depends only on the heat energy supplied by heating, so that the reaction proceeds rapidly from a point in time when a certain energy value is reached. . As a result, the accompanying volume shrinkage also occurs rapidly, so that the coating film is liable to crack.

The amount added to the coating composition may be determined according to the type of the compound having a hydrolyzable group and the amount added, but is preferably 10 to 50% by weight.

When the content is less than 10% by weight, the above-described effect of preventing cracks is not sufficient, and when the content is more than 50% by weight, high surface tension of water causes appearance defects such as stains and cissing, which is desirable. Absent. More preferably, 2
By setting the amount to 0 to 40% by weight, a more remarkable effect can be obtained.

When a compound having a hydrolyzable group is hydrolyzed in advance and used, usually, water molecules corresponding to the number of molecules of 0.6 to 1.5 times the number of hydrolyzable groups are used.
Add as 5 to 1.00 N dilute acid and hydrolyze.
In this case, the addition of water not only accelerates the hydrolysis reaction, but at this point already some of the molecules begin to condense. As a result, a more remarkable effect on crack prevention can be obtained.

The water in the present invention can be added as a diluting acid for hydrolysis without any problem, and the same effect can be obtained.

The present invention is characterized by containing the following components (D) and (E).

(D) General formula

[0035]

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An organosilicon compound represented by the formula (wherein R ²
And R ³ are a hydrocarbon group having 1 to 6 carbon atoms, X ² and X ³ are hydrolyzable groups, Y is an organic group containing a carbonate group or an epoxy group, and m is 0 or 1. is there. (E) Polyfunctional epoxy compounds These compounds not only have an effect of preventing cracks due to their long molecular chains, but also have good dyeing properties on coating films without deteriorating abrasion resistance and adhesion to inorganic vapor-deposited films. Can also be given.

In the general formula of the component (D), R ² and R
³ is a hydrocarbon group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. X ² and X ³ are hydrolyzable groups, and specific examples thereof include an alkoxy group such as a methoxy group, an ethoxy group, and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group. Is raised. Y is an organic group having a carbonate group or an epoxy group, and specific examples thereof include:

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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And the like.

These disilane compounds can be synthesized by various conventionally known methods.

For example, it can be obtained by performing an addition reaction between diallyl carbonate and trichlorosilane or the like, followed by alkoxylation. Further, a compound having an addable substituent at both ends and further containing an epoxy group or an epoxidizable functional group therein is subjected to an addition reaction with trichlorosilane or the like, followed by alkoxylation.

It is more effective to use either component (D) after hydrolysis, or to apply an acid treatment to the cured film.

The amount of component (D) used is preferably 3 to 30% by weight. If the amount is less than 3% by weight, the dyeability, the adhesion to the inorganic vapor-deposited film, and various durability cannot be satisfied. On the other hand, if the content exceeds 30% by weight, not only does the water resistance of the coating film tend to decrease, but also the coating film tends to become cloudy, which is not desirable.

Subsequently, the polyfunctional epoxy compound of the component (E) is widely used for paints, adhesives and the like. For example, polyolefin-based epoxy resins synthesized by a peroxide method, alicyclic epoxy resins such as cyclopentadiene oxide and cyclohexene oxide, and polyglycidyl esters obtained from hexahydrophthalic acid and epichlorohydrin, and bisphenol A, catechol, and redosinol. Phenol or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane,
Polyglycidyl ether obtained from polyhydric alcohols such as pentaerythritol, diglycerol and sorbitol and epithrolhydrin, epoxidized vegetable oil, epoxy novolak obtained from novolak-type phenolic resin and epichlorohydrin, epoxy resin obtained from phenolphthalein and epichlorohydrin And a copolymer of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene, and an epoxy acrylate obtained by a glycidyl group ring-opening reaction between the epoxy compound and a monocarboxylic acid-containing (meth) acrylic acid.

Specific examples of the polyfunctional epoxy compound include:
1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene Glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhivalic acid ester, trimethylolpropane diglycidyl ether,
Trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol Aliphatic epoxy compounds such as tetraglycidyl ether, sorbitol tetraglycidyl ether, triglycidyl ether of tris (2-hydroxyethyl) isocyanate, isophoronediol diglycidyl ether, bis-
Alicyclic epoxy compounds such as 2,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ether, phenol novolak Aromatic epoxy compounds such as polyglycidyl ether and cresol novolak polyglycidyl ether are exemplified.

In the present invention, the component (E) is a component (D)
When used alone, it is a component for improving the dyeability when the dyeability is insufficient, and is used for the purpose of improving water resistance and warm water resistance. Therefore, among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, tris (2-hydroxyethyl) isocyanate Aliphatic epoxy compounds such as glycidyl ether are particularly desirable.

The amount of component (E) used is 5% of the total solids composition.
-30% by weight is desirable. That is, if it is less than 5% by weight, the dyeability and water resistance of the coating film are insufficient, and if it exceeds 30% by weight, the abrasion resistance of the coating film becomes insufficient, which is not desirable.

Further, the present invention is characterized by containing the following component (F).

(F) General formula

[0059]

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An organosilicon compound represented by the formula (wherein R ⁴
And R ⁵ is a hydrocarbon group having 1 to 3 carbon atoms, X ⁴ is a hydrolyzable group, and n is 0 or 1. In the component (F), R ⁴ and R ⁵ are a hydrocarbon group having 1 to 3 carbon atoms, and specific examples thereof include a vinyl group, an allyl group,
Examples include an acrylic group, a methacryl group, a 1-methylvinyl group, an epoxy group, a mercapto group, a cyano group, an isocyano group, an amino group, a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. X ⁴ is a hydrolyzable functional group, and specific examples thereof include an alkoxy group such as a methoxy group, an ethoxy group, and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group. And the like.

Specific examples of the silane compound include vinyl trialkoxy silane, vinyl trichlorosilane, vinyl tri (β-methoxyethoxy) silane, allyl trialkoxy silane, methyl trialkoxy silane, methyl dialkoxy silane, methyl vinyl dialkoxy silane , Dimethyldialkoxysilane, 3-chloropropyl trialkoxysilane, 3-chloropropylmethyldialkoxysilane, and the like.

This component (F) is used to further improve the durability of the coating,
In particular, it is effective in improving abrasion resistance, shortening curing time, and improving appearance.

The amount of component (F) used is 2% of the total solids composition.
-30% by weight is desirable. That is, if the amount is less than 2% by weight, the effect of the addition is not obtained.

These compounds may be used alone or as a mixture of two or more.

It is more effective to use this component (F) after hydrolysis.

Further, the present invention is characterized in that at least one of the components (B), (D) and (F) is hydrolyzed in the absence of a solvent and used as a hydrolyzate / partial condensate.

Thus, the silane compound having a hydrolyzable group undergoes a partial condensation reaction immediately after the hydrolysis. In this case, the rate of the condensation reaction is higher than when the hydrolysis is performed in a solvent. The hydrolyzable group that has not been condensed at this time forms a tight three-dimensional crosslinked structure upon heating and curing due to the effect of the subsequent addition of water.

That is, by hydrolyzing in the absence of a solvent and using it as a hydrolyzate / partial condensate, the condensation reaction sufficiently proceeds, so that not only cracks can be prevented more effectively but also the coating film can be effectively prevented. Durability, particularly abrasion resistance, can be improved.

In this case, the amount of the diluting acid added during the hydrolysis is desirably an amount corresponding to the number of molecules of 0.5 to 5 times the number of hydrolyzable groups. Sufficient hydrolysis does not proceed, and if the amount exceeds 5 times, a condensation reaction does not occur so as to obtain a remarkable effect.

The coating composition of the present invention may contain, if necessary, a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, an oil-soluble dye, and a fluorescent dye in addition to the above components. In addition, a pigment, a photochromic compound, a light- and heat-resistant stabilizer such as a hindered amine / hindered phenol compound, etc. may be added to improve the coating properties of the coating solution and the film performance after curing.

In applying the coating composition of the present invention, the surface of the base material is previously treated with an alkali, acid, surfactant, inorganic or organic fine particles in order to improve the adhesion between the base lens and the coating. It is effective to perform a peeling / polishing treatment, a primer treatment, or a plasma treatment.

The coating solution may be applied and cured by dipping, spin coating, spray coating, roll coating, or flow coating, and then coating at a temperature of 40 to 200 ° C. The coating can be formed by heating and drying for a period of time.

The thickness of the cured film is desirably 0.05 to 30 μm. That is, if the thickness is less than 0.05 μm, the basic performance cannot be realized, and if it exceeds 30 μm, the smoothness of the surface is impaired and optical distortion occurs, which is not desirable.

As a method of forming an antireflection film made of an inorganic substance on the surface of the coat film thus obtained, a vacuum deposition method, an ion plating method, a sputtering method and the like can be mentioned. In the vacuum evaporation method, an ion beam assist method in which an ion beam is simultaneously irradiated during the evaporation may be used. As the film configuration, either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic substance used at that time include SiO ₂ , SiO, TiO ₂ , TiO, Ti
₂ O ₃ , ZrO ₂ , Al ₂ O ₃ , Ta ₂ O ₅ , Ce
O ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃
And the like. These inorganic substances are used alone or in combination of two or more.

When forming the antireflection film, it is desirable to perform a surface treatment on the hard coat film. Specific examples of the surface treatment include an acid treatment, an alkali treatment, an ultraviolet irradiation treatment, a plasma treatment by a high frequency discharge in an inert gas such as argon or an oxygen atmosphere, and an ion beam irradiation with an inert gas such as argon or oxygen. Processing and the like.

Hereinafter, the present invention will be described in more detail with reference to examples.

[0078]

Now, the present invention will be described in further detail with reference to Examples, but it should be understood that the present invention is by no means restricted thereby.

Example 1 (1) Preparation of Coating Solution Isopropyl alcohol 11 was placed in a reaction vessel equipped with a stirrer.
8.8 g, 300.0 g of distilled water, 139.4 g of γ-glycidoxypropyltrimethoxysilane, and 38.2 g of a 0.05 N hydrochloric acid aqueous solution were added, and the mixture was stirred for 60 minutes. next,
403.3 g of a composite sol of titanium oxide / zirconium oxide / silicon oxide (manufactured by Catalyst Kasei Kogyo Co., Ltd.) and a silicone surfactant (trade name "L-7" manufactured by Nippon Unicar Co., Ltd.)
604 "), and after sufficiently stirring, a hard coat solution was obtained.

(2) Coating and Curing of Coating Solution The hard coat solution obtained in the above operation (1) was applied to a plastic spectacle lens (manufactured by Seiko Epson Corporation, lens fabric for Seiko Super Sovereign, refractive index 1.66). ) Was applied by spin coating and heated and cured at 135 ° C. for 0.5 hour. Thereafter, the same operation was performed on the concave surface, and then the mixture was heated and cured at 135 ° C. for 2.5 hours to obtain a lens with a hard coat.

(3) Formation of Antireflection Film The surface of the hard-coated lens obtained by the operation (1) was subjected to plasma treatment (400 W × Argon plasma).
60 seconds), and an anti-reflection film made of inorganic materials such as silicon oxide and zirconium oxide is multi-layer coated by a vacuum deposition method (BMC-1000, manufactured by Vacuum Instruments Co., Ltd.), and a hard coat and a plastic with anti-reflection are applied. I got a lens.

(4) Evaluation The obtained hard coat and antireflection lens were evaluated by the following methods.

The results are shown in Table 1.

Abrasion Resistance A 1 kg weight was applied with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), and the surface was rubbed for 10 reciprocations. The degree of scratching was visually evaluated in the following stages.

A: No scratches were observed in the rubbed area B: 1 to 10 scratches in the above range C: 10 to 20 scratches in the above range D: Innumerable Scratched, but smooth surface remains E: Innumerable scratches, no smooth surface remaining Humidity Resistance 60 ° C., constant temperature and humidity chamber set at 100 RH% (manufactured by Tabai Espec Corporation) After standing for 7 days in PR-1G), those having no change in the surface state were evaluated as good.

Weather resistance A sunshine weather meter (WEL-SUN-HC, manufactured by Suga Test Co., Ltd.) using a xenon lamp was 24.
After exposure for a period of time, those having no change in the surface state were evaluated as good.

Adhesion Evaluated by a cross cut tape test according to JISD-0202.

That is, 1 mm
Cuts are made at intervals to form 100 squares. Next, after strongly pressing a cellophane adhesive tape (manufactured by Nichiban Co., Ltd .; trade name "Cellotape") on the surface, and quickly pulling it off in the direction of 90 degrees from the surface, the number of squares where the coat film remains was determined. The sample was evaluated as an adhesiveness evaluation index, and one having no peeling of the coating film was evaluated as good.

Example 2 (1) Preparation of Coating Solution 139.4 g of γ-glycidoxypropyltrimethoxysilane and 38.2 g of 0.05N hydrochloric acid aqueous solution were charged into a reaction vessel equipped with a stirrer, For a minute. Next, 18.8 g of isopropyl alcohol and 400.0 g of distilled water were charged and stirred for 60 minutes, and then a composite sol of titanium oxide, zirconium oxide, and silicon oxide (manufactured by Catalyst Chemical Industry Co., Ltd.) 4
03.3 g and 0.3 g of a silicone-based surfactant (trade name "L-7604" manufactured by Nippon Unicar Co., Ltd.) were added, and the mixture was sufficiently stirred to obtain a hard coat liquid.

(2) Coating and curing of coating liquid The coating liquid was cured in the same manner as in Example 1. However, the plastic lens used was manufactured by the following method.

Preparation of Monomer of Plastic Lens Material / Injection into Lens Mold In a glass container equipped with a stirrer, a tetrathiol compound represented by the following structural formula (mixing ratio of component A, component B, and component C is a molar ratio). , A / B / C = 80/10/10) 100 parts by weight,

[0092]

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103 parts by weight of m-xylylene diisocyanate, 0.02 parts by weight of dibutyltin dilaurate, 0.15 parts by weight of an internal release agent, and 0.09 parts by weight of 2- (5-methyl-2-hydroxyphenyl) benzotriazole After mixing and stirring sufficiently, the mixture was sufficiently defoamed under a vacuum of 5 mmHg.

The obtained mixed solution was poured into a lens mold in which two glass molds were held by a sealing tape.

Lens Polymerization The lens mold containing the lens material obtained above was heated from 35 ° C. to 120 ° C. in 9 hours by a hot air heating furnace, kept at the maximum temperature of 120 ° C. for 0.5 hour, and then 4 hours After cooling to 40 ° C, release from the lens mold,
A plastic lens substrate was obtained.

(3) Formation of antireflection film The same method as in Example 1 was used.

(4) Evaluation The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3) (1) Preparation of coating liquid In preparation of (1) coating liquid of Example 2, 118.8 g of isopropyl alcohol and 300.0 g of distilled water were used.
(1) Preparation of coating solution, (2) application and curing of coating solution, (3) formation of antireflection film, and (4) evaluation, in the same manner as in Example 2. The results are shown in Table 1.

(Example 4) In the preparation of the coating solution (1) of Example 2, isopropyl alcohol 218.
In the same manner as in Example 2 except that 8 g and 200.0 g of distilled water were used, (1) preparation of a coating solution, (2) application and curing of a coating solution, (3) formation of an antireflection film,
(4) Evaluation was performed. The results are shown in Table 1.

(Example 5) In the preparation of the coating liquid (1) of Example 2, isopropyl alcohol 318.
In the same manner as in Example 2, except that 8 g and 100.0 g of distilled water were used, (1) preparation of a coating solution, (2) application and curing of a coating solution, (3) formation of an antireflection film,
(4) Evaluation was performed. The results are shown in Table 1.

(Example 6) (1) Preparation of coating solution 139.4 g of γ-glycidoxypropyltrimethoxysilane and 38.2 g of a 0.05 N hydrochloric acid aqueous solution were charged into a reaction vessel equipped with a stirrer, For a minute. Next, 118.8 g of isopropyl alcohol and 300.0 g of a 0.05 N hydrochloric acid aqueous solution were charged and stirred for 60 minutes, and then 403.3 g of a composite sol of titanium oxide, zirconium oxide, and silicon oxide (manufactured by Catalyst Kasei Kogyo Co., Ltd.) , Silicone-based surfactant (trade name “L-7604” manufactured by Nippon Unicar Co., Ltd.)
After adding 0.3 g and stirring sufficiently, a hard coat solution was obtained.

(2) Coating and curing of coating liquid The coating liquid was applied in the same manner as in Example 1.

(3) Formation of anti-reflection film The same method as in Example 1 was used.

(4) Evaluation The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 7 (1) Preparation of Coating Solution In a reaction vessel equipped with a stirrer, 93.0 g of γ-glycidoxypropyltrimethoxysilane, 34.4 g of a disilane compound (DS) having the following structural formula, 0 0.05N hydrochloric acid aqueous solution 3
2.8 g was added and the mixture was stirred for 60 minutes. Next, 100.8 g of 1,4-dioxane and 350.0 g of distilled water were charged,
After stirring for 30 minutes, 36.7 g of isopropyl alcohol-dispersed colloidal silica (trade name “Oscar 1432”, manufactured by Catalyst Chemical Industry Co., Ltd.) was added, and the mixture was stirred for 30 minutes. Thereafter, 330.0 g of a composite sol of titanium oxide / zirconium oxide / silicon oxide (manufactured by Catalyst Chemical Industry Co., Ltd.) was added, and 3
Stirred for 0 minutes. Furthermore, glycerol diglycidyl ether (trade name “Denacol E” manufactured by Nagase Kasei Kogyo Co., Ltd.)
X-313 ") and 0.3 g of a silicone-based surfactant (trade name" L-7604 ", manufactured by Nippon Unicar Co., Ltd.), and after sufficient stirring, a hard coat liquid was obtained.

The structural formula of DS

[0107]

Embedded image

(2) Application and Curing of Coating Solution The plastic lens substrate to which the coating solution is applied is
Example 1 was carried out in the same manner as in Example 1 except that the lens cloth for Seiko Super Lux, manufactured by Seiko Epson Corporation, and the refractive index were changed to 1.60.

(3) Staining Dianix Bl was added to 1 liter of water heated to 90 ° C.
ue AC-E (Mitsubishi Kasei Hoechst) 1.2
g, Miketon Polyester Red4B
F # 300 (manufactured by Mitsui Toatsu Dye Co., Ltd.) 0.05 g, FSP Red Brown S-N (manufactured by Futaba Sangyo Co., Ltd.) 0.6 g, mama lemon (manufactured by Lion Oil & Fat Co., Ltd.) 3 cc as a surfactant, and a carrier agent 30 g of benzyl alcohol was added and stirred to obtain a staining solution.

A lens with a hard coat was immersed in this staining solution for 5 minutes.

(4) Formation of anti-reflection film The same method as in Example 1 was used.

(5) Evaluation The evaluation was performed in the same manner as in Example 1. However, the dyeability was evaluated by the following method.

Dyeability The obtained dyed lens was measured for L * value of CIELAB color system using a spectrophotometer DOT-3 (manufactured by Murakami Color Research Institute).

Those having no uneven dyeing and having an L * value of 85 or less were rated as good.

The results are shown in Table 1.

Example 8 (1) Preparation of Coating Solution 62.0 g of γ-glycidoxypropyltrimethoxysilane was placed in a reaction vessel equipped with a stirrer, and 34.4 g of the same disilane compound (DS) as in Example 7 was used. , 41.5 g of vinyltrimethoxysilane, and 42.3 g of a 0.05 N hydrochloric acid aqueous solution
And stirred for 60 minutes. Next, 94.2 g of 1,4-dioxane and 300.0 g of distilled water were added, and the mixture was stirred for 30 minutes.
2 ") 73.3 g was added and stirred for 30 minutes. Thereafter, 330.0 g of a composite sol of titanium oxide / zirconium oxide / silicon oxide (manufactured by Catalyst Chemical Industry Co., Ltd.) was charged and stirred for 30 minutes. Further, glycerol diglycidyl ether (trade name “Denacol EX-, manufactured by Nagase Kasei Kogyo Co., Ltd.)
313 ") 22.0 g, silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name" L-7604 ") 0.3 g
Was added and stirred sufficiently to obtain a hard coat liquid.

(2) Coating and curing of coating liquid The coating liquid was cured in the same manner as in Example 7.

(3) Staining The staining was carried out in the same manner as in Example 7.

(4) Formation of Antireflection Film The same method as in Example 1 was used.

(5) Evaluation The evaluation was performed in the same manner as in Example 7. The results are shown in Table 1.

Comparative Example 1 (1) Preparation of Coating Solution Methyl cellosolve 418.8 was placed in a reaction vessel equipped with a stirrer.
g, γ-glycidoxypropyltrimethoxysilane 13
9.4 g and 38.2 g of a 0.05 N hydrochloric acid aqueous solution were added, and the mixture was stirred for 60 minutes. Next, a composite sol of titanium oxide, zirconium oxide, and silicon oxide (manufactured by Catalyst Chemical Industry Co., Ltd.)
After adding 403.3 g and 0.3 g of a silicone-based surfactant (trade name "L-7604", manufactured by Nippon Unicar Co., Ltd.), the mixture was sufficiently stirred to obtain a hard coat liquid.

(2) Coating and curing of coating liquid The coating liquid was applied in the same manner as in Example 1.

(3) Formation of anti-reflection film The same method as in Example 1 was used.

(4) Evaluation The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 (1) Preparation of Coating Solution In a reaction vessel equipped with a stirrer, 56.1 g of γ-glycidoxypropyltrimethoxysilane, 78.6 g of γ-glycidoxypropylmethyldimethoxysilane, 0 g 29.1 g of a 0.05N aqueous hydrochloric acid solution was added, and the mixture was stirred for 60 minutes. next,
After adding 420.2 g of methyl cellosolve and stirring for 60 minutes, 416.0 g of a composite sol of titanium oxide / zirconium oxide / silicon oxide (manufactured by Catalyst Kasei Kogyo Co., Ltd.) and a silicone surfactant (manufactured by Nippon Unicar Co., Ltd.) , Product name "L
−7604 ”), and after sufficiently stirring, a hard coat liquid was obtained.

(2) Coating and Curing of Coating Solution The coating was performed in the same manner as in Example 1.

(3) Formation of Antireflection Film The same method as in Example 1 was used.

(4) Evaluation The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 (1) Preparation of Coating Solution A reaction vessel equipped with a stirrer was charged with 46.5 g of γ-glycidoxypropyltrimethoxysilane and 12.7 g of a 0.05 N hydrochloric acid aqueous solution. Stirred for 60 minutes. Next, methyl cellosolve g was added, and the mixture was stirred for 30 minutes. Then, 73.3 g of isopropyl alcohol-dispersed colloidal silica (trade name “Oscar 1432”, manufactured by Catalysis Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. Thereafter, 330.0 g of a composite sol of titanium oxide / zirconium oxide / silicon oxide (manufactured by Catalyst Chemical Industry Co., Ltd.) and glycerol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name "Denacol EX-
313 ") 66.0 g, silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name" L-7604 ") 0.3 g
Was added and stirred sufficiently to obtain a hard coat liquid.

(2) Application and Curing of Coating Solution The coating was performed in the same manner as in Example 1.

(3) Formation of anti-reflection film The same method as in Example 7 was used.

(4) Evaluation The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[0133]

[Table 1]

[0134]

As described above in detail, according to the present invention, sufficient durability such as abrasion resistance, adhesion to an inorganic vapor-deposited film, and high refractive index are realized, and film cracking occurs in a hard coat processing step. In addition, hard coat processing that can achieve high appearance quality and high productivity can be achieved by a simple method. In addition, the present invention is applicable to various materials and plastic lens materials having a refractive index, and its effects are not limited to plastic spectacle lenses, but can be widely applied to consumer or industrial uses such as camera lenses and light beam focusing lenses. The effect is enormous.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 1/10 G02B 1/10 Z 1/11 A

Claims (7)

[Claims] 1. A coating composition comprising at least the following components (A), (B) and (C). (A) Si, Al, Sn, Sb having a particle size of 1 to 200 mμ,
Ta, Ce, La, Fe, Zn, W, Zr, In and T
i or one selected from composite fine particles of a metal oxide selected from the group consisting of
A mixture of more than one species. (B) General formula Wherein R ¹ is an organic group having a polymerizable reactive group and having 3 or more carbon atoms, and X ¹ is a hydrolyzable group. (C) Coating composition 10 to 50 based on the total weight
Parts by weight water. 2. The coating composition according to claim 1, further comprising the following component (D). (D) General formula Wherein R ² and R ³ are a hydrocarbon group having 1 to 6 carbon atoms, X ² and X ³ are hydrolyzable groups, and Y is a carbonate group or an epoxy group. Is an organic group to be contained, and m is 0 or 1.) 3. The coating composition according to claim 1, which further comprises the following component (E). (E) Polyfunctional epoxy compound 4. The coating composition according to claim 1, further comprising the following component (F). (F) General formula Wherein R ⁴ and R ⁵ are a hydrocarbon group having 1 to 3 carbon atoms, X ⁴ is a hydrolyzable group, and n is 0 or 1. 5. A hydrolyzate and / or partial condensation of at least one of the components (B), (D) and (F) according to claim 1 in the absence of a solvent. A method for producing a coating composition, which is used as a body. 6. A laminate comprising an antireflection film made of an inorganic substance provided on the surface of a coat obtained by using the coating composition according to claim 1 as a raw material. 7. After dyeing a coat film obtained using the coating composition according to claim 2 or 3 as a raw material,
A laminate, wherein an antireflection film made of an inorganic substance is provided on the surface of the coat film.