JPH095501A - Reflection preventive plastic lens - Google Patents

Abstract

PURPOSE: To make thin and light in weight and to attain excellent transparency, resistance to scuffing and wear, adhesion property and reflection preventive property by applying an organic silicon based coating on an urethane vinyl based plastic and an anti-reflection coating consisting of the oxides of titanium and silicon thereon. CONSTITUTION: This reflection preventive plastic lens is constituted of a plastic lens, which is made of a radical polymer of an aromatic compound expressed by formula I and an isocyanate compound, an organic silicon based coating film, which is provided on the surface of the plastic lens and is composed of a hardened film formed out of an organic silicon compound expressed by formula 11 or the hydrolyzed product and a colloidally dispersed antimony pentoxide sol, antimony trioxide sol or the like, and a multilayered anti-reflection layer, which is provided on the coating film and contains the oxides of titanium and/or silicon. In formula I, X expressed-H or the like. In formula II, R<1> expresses 4-14C organic group, R<2> expresses 1-6C hydrocarbon group or the like, R<3> expresses 1-4C alkyl group or the 72-005501 like and each of (a) and (b) expresses 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antireflection plastic lens. More specifically, the present invention is thin, lightweight and excellent in transparency, scratch resistance, adhesion,
The present invention relates to a new plastic lens having antireflection properties.

[0002]

2. Description of the Related Art In recent years, plastic has come to be used as a lens material instead of conventional glass.
In particular, there is a remarkable tendency as a lens material for spectacles. However, while plastic lens moldings have the advantages of light weight, easy workability, impact resistance, etc., they have insufficient hardness and are easily scratched, easily damaged by solvents, easily charged, and adsorb dust, heat resistance Is insufficient, and there are some drawbacks. Also,
Conventionally, most plastic spectacle lenses are manufactured by casting polymerization of a monomer called allyl diglycol carbonate (hereinafter abbreviated as ADC), and the refractive index of the lens is about 1.50, Since the refractive index is lower than about 1.52 to 1.80, a lens for myopia has a thick edge and a lens for presbyopia has a drawback of thickening the center portion, which is disliked by the wearer. It was the main cause.

Therefore, development of a monomer for a plastic lens having a refractive index higher than that of ADC has been promoted,
For example, JP-A-55-13747 and JP-A-56-16
6214, JP-A-57-23611, JP-A-57-
Various items such as those described in No. 54901 have been proposed. One of them is the composition for a high refractive index lens proposed in JP-A-5-287049. The urethane vinyl lens proposed here has a high refractive index,
It has excellent transparency, dyeability and impact resistance, and has been put to practical use as a plastic lens for spectacles.

However, urethane vinyl lenses have the same problem of scratch resistance as other plastic lenses. On the other hand, efforts have been made to improve the characteristics of plastic lenses. For example, in order to improve scratch resistance, which has been a common problem with conventional plastic lenses such as urethane vinyl lenses, A coating composition containing an organosilicon compound or a hydrolyzate thereof as a main component "(for example, JP-A-52-1).
1261) or the like, or one obtained by adding silica sol dispersed in colloidal form to "organosilicon compound or its hydrolyzate" (for example, JP-A-53-11).
1336), and these proposals have been put to practical use as spectacle lenses.

And, the multi-layer in the plastic lens
As a film anti-reflection coating, SiO ₂And Al₂O_ThreeIn addition to
ZrO₂Or TiO₂Multi-layer coating
Proposal (Japanese Patent Laid-Open No. 52-156643) and Ta₂
O_FiveAnd ZrO₂With a high refractive index component
55-22704), SiO₂Or in addition to SiO
Ta₂O_Five(Japanese Patent Laid-Open No. 60-225101
No.) etc. have been made.

[0006]

Under the circumstances of the prior art as described above, the urethane vinyl lens is
This urethane vinyl-based lens, on the contrary, has a higher refractive index than a conventional ADC resin lens, and therefore, for example, the above-mentioned organosilicon compound or When a coating in which silica sol is added to an organic silicon compound is applied, there is a problem that interference fringes are visible in the coating film and the appearance of the lens is poor.

Further, these coatings also affect the multilayer antireflection coating made of an inorganic oxide formed on the coating film, and the antireflection coating cannot exhibit the performance as designed or causes variations. There was a problem. Due to this problem, it is difficult to apply a high-performance coating having a low reflectance to the antireflection coating.

Therefore, the present invention solves the conventional problems in a lens made of a thin and lightweight high refractive index plastic using a urethane vinyl resin, in which interference fringes are not visible in the coating film and a reflection color is generated. It aims to provide a new plastic lens that has a high-performance anti-reflection coating with low reflectance and no unevenness or flapping. Further, the present invention provides a new plastic lens excellent in transparency, scratch resistance, surface hardness, abrasion resistance, flexibility, antistatic property, heat resistance, water resistance, chemical resistance and the like. Is intended.

[0009]

In order to solve the above problems, the present invention provides a plastic lens comprising <A> a radical polymer of an aromatic compound represented by the general formula (I) and an isothiocyanate compound. When,

[0010]

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(In the formula, X is --H, --ROH, or-
R indicates RSH is represented by C _n H _2n, n is 1-4 hydrocarbon group) <B> provided on a surface of the plastic lens, (a) the general formula (II):

[0012]

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(In the formula, R ¹ is a functional group or an organic group having an unsaturated double bond and having 4 to 14 carbon atoms, and R ² is
It is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group, R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, and a and b are 0 or 1 respectively. And a + b is 1 or 2) or a hydrolyzate thereof; (b) colloidally dispersed antimony pentoxide sol, antimony trioxide sol, zirconium oxide sol, titanium oxide sol, Coating tin oxide sol with tin oxide sol, tungsten oxide sol, aluminum oxide sol, composite sol of titanium oxide and cerium oxide, composite sol of titanium oxide and iron, composite sol of tin oxide and tungsten oxide, composite sol of tin oxide and tungsten oxide At least one sol of the prepared sol; and an organosilicon coating characterized by comprising a cured film with the sol. Providing an anti-reflection plastic lens characterized by consisting of: film, <C> the provided coating film, multilayer antireflection film containing an oxide of titanium and / or silicon.

[0014]

The present invention provides a new antireflection plastic lens having the above-mentioned constitution, and its excellent action is the use of the unique elements of <A><B><C> and its It is the first thing to be realized by a close inseparable combination. Therefore, this unique element <A><B
<C> will be described in detail below. <A> Polymer plastic lens In the present invention, as described above, a polymer of an aromatic sulfur-containing compound represented by the formula (I) and an isothiocyanate compound is used. It is used as a plastic lens body, but in this case, as a specific example,

[0015]

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And meta-isomers of these compounds, and mixtures thereof. Of course, it is not limited to these. Further, specific examples of the isothiocyanate compound include xylylenediisothiocyanate, bisisothiocyanatomethylcyclohexane, bisisothiocyanatomethylthiophene, bisisothiocyanatomethyltetrahyphothiophene, bisisothiocyanatocyclohexane, and toluylenediene. Examples thereof include, but are not limited to, isothiocyanate, hexamethylene diisothiocyanate, and their chlorinated and brominated compounds. Preferred of these isothiocyanate compounds are, for example, xylylenediisothiocyanate and bisisothiocyanatomethylthiophene.

The ratio of the aromatic sulfur-containing compound represented by the above formula (I) to the isothiocyanate compound for constituting the plastic lens of the present invention is determined by the OH group or SH group of the aromatic sulfur-containing compound. It is preferable that the ratio of the total number of moles of the above to the total number of moles of the isothiocyanate group is 0.5 or more and 2 or less. More preferably, the ratio of the total number of moles is 0.
It is 7 or more and 1.5 or less. If it is out of this range, the resulting cured product tends to lack heat resistance and strength.

For the production of a radical polymer of an aromatic sulfur-containing compound of formula (I) and an isothiocyanate compound, which constitutes a plastic lens, a radical polymerization initiator, reactivity,
A non-reactive diluent is used. Further, additives such as an antioxidant and an ultraviolet absorber are added to the polymer. The radical polymerization initiator as referred to herein may be any one that generates a radical by heating or ultraviolet rays or electron beams, and various kinds of known initiators such as benzoyl peroxide and azobisisobutyronitrile can be used. Known photopolymerization catalysts such as thermal polymerization catalysts, benzophenone, and benzoyl can be used.

The blending amount of these radical polymerization initiators is
Since it varies depending on the components of the polymerization composition and the curing method, it cannot be determined unconditionally, but it is usually 0.
01 wt% -5.0 wt%, preferably 0.1 wt%-
It is in the range of 2.0 wt%. A known catalyst component may be added to the polymerization composition in a trace amount for the purpose of sufficiently promoting the reaction of the isothiocyanate compound to improve the strength and heat resistance of the cured product. Examples of the catalyst component include tin compounds represented by dibutyltin dilaurate and amine compounds, and the addition amount thereof is usually 0.01 wt% to 5.0 wt%, preferably 0.1 wt% with respect to the total amount of the composition.
% To 2.0 wt%.

The polymerization composition may be diluted with a radical-reactive compound such as styrene, chlorostyrene, divinylbenzenebenzyl acrylate, hydroxyethyl methacrylate and the like. Further known additives such as antioxidants and ultraviolet absorbers are added to the polymerization composition,
It is possible to further improve the practicality of the obtained resin. It is also possible to add a known release agent to improve the releasability of the resulting resin.

In the present invention, a lens is usually manufactured by polymerizing and curing as follows. That is, the polymerization composition is poured into a mold made of glass or metal, the polymerization and curing reaction is advanced by heating and / or irradiation with ultraviolet rays or electron beams, and then the mold is removed from the mold. Curing time is 0.1 to 100 hours, usually 12 to
48 hours, curing temperature is 10 ~ 140 ℃, usually 20
~ 120 ° C.

The lens thus obtained is well known in the art.
Higher refractive index than lens
It has no shape distortion. <B> Organosilicon coating film A compound of the general formula (II) used as the component (a)
For things, the R ¹Are various functional groups or unsaturated 2
Although it is an organic group having 4 to 14 carbon atoms with a heavy bond,
Typical examples include epoxy group, hydroxy group
Group, ether group, alkoxy group, vinyl group, allyl
Group, carbonyl group, carboxyl group, azyl group, acyl
Oxy group, ester group, cyano group, amino group, halogen
Group, mercapto group, thioether group, glare group, carba
Examples thereof include a mate group and an amide group.

When R ¹ is a functional epoxy group, for example, the following are used. General formula (III):

[0024]

[Chemical 6]

(In the formula, R ⁴ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, and R ⁵ is
A hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon,
R ⁶ is hydrogen or a methyl group, m is 2 or 3, p is 1
-6 and q are 0-2. ) The compound represented by. General formula (IV)

[0026]

[Chemical 7]

(R ⁷ is an alkyl group or alkoxyalkyl group having 1 to 4 carbon atoms or an acyl group, R ⁸ is a hydrocarbon group having 1 to 4 carbon atoms or a halogenated hydrocarbon group,
s is 2 or 3, and r is 1-4. ) The compound represented by. The compounds represented by the general formulas (III) and (IV) each have an epoxy group, and are therefore referred to as epoxysilane.

Specific examples of these epoxysilanes include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
Examples include (3,4-epoxycyclohexyl) ethyltriethoxysilane.

Further, R of the compound of the general formula (II)
Other than those in which ¹ has an epoxy group as a functional group (a = 0
Examples of (including those in) include, for example, the following compounds. Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, aminomethyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane Various trialkoxysilanes, triacyloxysilanes or trialkoxyalkoxysilane compounds.

Exemplary compounds of the general formula (II) listed above
Is an OR that is bonded to the Si atom ^ThreeThere are 3 groups
(A + b = 1) This is an example of trifunctional, but OR^ThreeThere are 2 groups
(A + b = 2) difunctional corresponding compound is also used.
Can be used. As an example of a difunctional equivalent compound
For dimethyldimethoxysilane, diphenyldimethoxide
Sisilane, methylphenyldimethoxysilane, methylbi
Nyldimethoxysilane, dimethyldiethoxysilane, etc.
There is.

The compound of the general formula (II) may be used alone or in combination of two or more depending on the purpose. In particular, when a bifunctional compound is used, it is preferable to use it in combination with a trifunctional compound. When they are used together, 2> a + b> 1 on average. Furthermore, a
It is also possible to use a compound corresponding to a tetrafunctional group of + b = 0. Examples of tetrafunctional corresponding compounds include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, t-butyl silicate, sec-butyl silicate and the like.

The compound of the general formula (II) may be used as it is, but it is preferably used as a hydrolyzate for the purpose of increasing the reaction rate and lowering the curing temperature. When two or more compounds having the same functional number are used in combination of two or four functional compounds, or two or more compounds having different functional numbers are used in combination, they may be used together after hydrolysis, Co-hydrolysis may be carried out in combination before. Upon hydrolysis, the alcohol HOR ³ is liberated and the compound of the general formula (II) has the corresponding silanol:

[0033]

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It becomes Silanol rapidly undergoes dehydration condensation to become an oligomer. Therefore, it may be left (cured) for 1 to 24 hours after hydrolysis so that the reaction proceeds sufficiently. As described above, the sol used as the component (b) is a colloidally dispersed antimony pentoxide sol, antimony trioxide sol, zirconium oxide sol, titanium oxide sol, tin oxide sol, tantalum oxide sol, tungsten oxide sol, aluminum oxide sol, It is at least one of a composite sol of titanium oxide and cerium oxide, a composite sol of titanium oxide and iron, a composite sol of tin oxide and tungsten oxide, and a sol obtained by coating a tin oxide sol with a composite sol of tin oxide and tungsten oxide.

The particle size of the sol in this case is 1 to 200 m.
μ, particularly 5 to 100 mμ is preferable. If it is smaller than this, the production is difficult, the stability of the sol itself is poor, and the effect is small. On the other hand, if it is larger than this, the stability of the coating composition, the transparency of the coating film, the smoothness, etc. are deteriorated. These sols are publicly known, and some of them are commercially available.

The sol is a colloidal solution dispersed in water, an organic solvent or a mixed solvent of both, and is stabilized by adding an appropriate alkali, particularly an organic amine, or by using various organic acids, Alternatively, those stabilized with a surfactant can be used. Especially antimony pentoxide sol, antimony trioxide sol, zirconia oxide sol, titanium oxide sol, tin oxide sol, tantalum oxide sol, tungsten oxide sol, composite sol of titanium oxide and cerium oxide, composite sol of titanium oxide and iron, tin oxide and tungsten oxide. The composite sol of, and a sol obtained by coating a tin oxide sol with a composite sol of tin oxide and tungsten oxide have a high refractive index and are preferable. These sols may be used alone or as a mixture of two or more kinds.

An oxidation catalyst for forming a cured film using these sols can be blended, which has a three-dimensional network structure obtained by polymerizing (a) the organosilicon compound or its hydrolyzate. What is used as necessary to shorten the time for forming the coating film of
Those which impair the stability of the coating composition are not preferable), and the following are used, for example. <1>amines; monoethanolamine, diethanolamine, isopropanolamine, ethylenediamine, isopropylamine, diisopropylamine, morpholine, triethanolamine, diaminopropane, aminoethylethanolamine, dicyandiamide, triethylenediamine, 2-ethyl-4-methylimidazole . <2> Various metal complex compounds: General formula: AlX _n Y _3-n (wherein, X is OL (L is a lower alkyl group), Y is a general formula M ¹ COCH ₂ COM ²
(M ¹ and M ² are lower alkyl groups) and M ¹ COCH ² C
Aluminum chelate compound represented by at least one selected from ligands derived from OOM ² and n is 0, 1 or 2.

As a particularly useful chelate compound, from the viewpoint of solubility, stability and catalytic effect, aluminum acetylacetonate, aluminum bisethylacetoacetate, monoacetylacetonate, aluminum-di-
Examples include n-butoxide monoethylacetoacetate and aluminum-di-iso-propoxide-monomethylacetoacetate.

In addition, chromium acetylacetonate, titanyl acetylacetonate, cobalt acetylacetonate, iron (3) acetylacetonate, manganese acetylacetonate, nickel acetylacetonate. Other metal complex compounds include those represented by the general formula: M (CH ₂ N (CH ₂ COO) ₂ ) ₂ Na
An ethylenediaminetetraacetic acid metal salt compound represented by _x (X = 1 to 3).

Particularly useful compounds are calcium ethylenediamine tetraacetate, magnesium ethylenediamine tetraacetate, aluminum ethylenediamine tetraacetate, manganese ethylenediamine tetraacetate, copper ethylenediaminetetraacetate, zinc ethylenediaminetetraacetate, iron ethylenediaminetetraacetate, cobalt ethylenediaminetetraacetate, ethylenediamine. Bismuth tetraacetate. <3> Metal alkoxide: aluminum triethoxide, aluminum tri n-propoxide, aluminum tri n-butoxide, tetraethotitanium, tetra n-
Butoxy titanium, tetra i-propoxy titanium. <4> Organic metal salt: sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate. <5> Perchlorate: Magnesium perchlorate, ammonium perchlorate. <6> Organic acid or its anhydride: malonic acid, succinic acid,
Tartaric acid, adipic acid, azelaic acid, maleic acid, O-
Phthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid, succinic anhydride, maleic anhydride, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, naphthalic anhydride acid. <7> Lewis acid: ferric chloride, aluminum chloride. <8> Metal halide: stannous chloride, stannic chloride, tin bromide, zinc chloride, zinc bromide, titanium tetrachloride, titanium bromide, thallium bromide, germanium chloride, hafnium chloride, lead chloride, odor Lead.

The above catalysts can be used without being used alone.
You may mix and use more than one kind. In particular, when the organosilicon compound as the component (a) or its hydrolyzate has an epoxy group, a compound that also serves as a ring-opening polymerization catalyst for the epoxy group may be used. In particular, an aluminum chelate compound is one of the preferred catalysts. A solvent may be used in the above composition for forming a cured film, and this is used as necessary in order to make the coating composition liquid or to reduce the viscosity. For example, water, lower alcohol, acetone, ether, ketone, ester and the like are used.

And in the coating composition,
(A) 10 an organosilicon compound or a hydrolyzate thereof
10-40 parts of (b) sol component per 0 parts by weight (solid content)
0 parts by weight (solid content), preferably 50 to 250 parts by weight (solid content), and 0.00001 parts by weight of the catalyst component per 100 parts by weight (solid content) of the components (a) and (b).
It is suitable to use up to 20 parts by weight.

The solvent is used in an appropriate amount depending on the viscosity of the composition. Further, if necessary, various additives are used in combination for the purpose of, for example, improving the adhesiveness with the base material (molded product) on the coated side, improving the weather resistance, or improving the stability of the coating composition. You may. Examples of additives include pH adjusting agents, viscosity adjusting agents, leveling agents,
Matting agents, dyes, pigments, stabilizers, UV absorbers, antioxidants, etc.

In addition, an epoxy resin or other organic polymer may be used in combination for the purpose of improving the flexibility of the coating film.
Epoxy resin, which is widely used for paints and casting, is a polyolefin epoxy, cyclopentadiene oxide, cyclohexene oxide, or cycloaliphatic epoxy resin such as polyglycidyl ester, polyglycidyl ether, epoxidized vegetable oil, novolac type. Epoxy novolac, which is composed of phenol resin and epichlorohydrin, and further, glycidyl methacrylate-methyl methacrylate copolymer and the like are available.

Other organic polymers include, for example,
Examples include polyols, cellulose resins, and melamine resins.
Various surfactants can be used in combination with the coating composition for the purpose of improving the flow at the time of application, improving the smoothness of the coating film and reducing the friction coefficient of the coating film surface, and in particular, dimethyl siloxane A block or graft copolymer of styrene and an alkylene oxide, and a fluorine-based surfactant are effective.

The <B> coating film of the present invention as described above is particularly useful as a scratch-preventing film for spectacle lenses as urethane vinyl lenses. As a coating means, a normal coating method such as brush coating, dipping, roll coating, spray coating, and flow coating can be used. Furthermore, after the composition for coating of the present invention is applied to a mold, a plastic molded article is molded by casting the raw material to be the <A> base material molded article, or the composition of the present invention is molded into a molded article. After coating, make the surface of the coating film that has not yet cured adhere to the mold,
Then, the coating film can be cured.

After the coating composition is applied, it is often cured by heat treatment to obtain a hard coating film. The coating temperature is about 50 to 200 ° C, preferably 80.
A sufficient effect can be obtained at a temperature of 140 ° C. The thickness of the coating film is generally 0.3 to 30 μ after drying, preferably 0.5 to 10 μ.
There is enough.

The coating film is transparent and has excellent hardness, particularly scratch resistance, and does not cause deterioration of the appearance due to scratching, which is a problem of plastic molded articles, and it is possible to provide a molded article of extremely high commercial value. <C> Oxide Multilayer Antireflection Film The antireflection film in the present invention comprises a low refractive index film and a high refractive index film alternately laminated, and titanium oxide (TiO ₂ ) and a low refractive index are used as the high refractive index layer at this time. Silicon dioxide (Si
O ₂ ) is used. The basic film structure is λ
/ 4-λ / 2-λ / 4 and λ / 2-λ / 4 are preferable, and λ
In the case of the / 4, λ / 2-λ / 4 configuration, the first layer film counted from the substrate side may be a three-layer equivalent film using TiO ₂ and SiO ₂ or a two-layer composite film. A mixed substance of zirconium oxide (ZrO ₂ ) and aluminum oxide (Al ₂ O ₃ ) or a mixture of praseodymium oxide (Pr ₆ O ₁₁ ) and Al ₂ O ₃ can be used for the first layer.

When a film of TiO _{2 is formed} by a vacuum evaporation method, TiO ₂ itself can be used as an evaporation source, but in general, TiO ₂ emits a large amount of gas and may lack stability during film formation. In this case, a lower oxide of titanium, preferably TiO _x (1 ≦ X <2) is used as a vapor deposition source, and a reactive vapor deposition method in which O ₂ gas is introduced into the vapor deposition tank can be used. According to this method, T is extremely stable.
An iO ₂ film can be formed.

The TiO ₂ film has sufficient durability even when used on a plastic lens substrate.
Since it has a moderately high refractive index, it is advantageous in the design of the antireflection film. That is, it is possible to widen a wavelength range having a low reflectance and an antireflection effect, and it is possible to reduce the number of layers for obtaining the above effects. In forming the above antireflection film, generally, a vacuum vapor deposition method can be used, and also a sputtering method using a sintered body of the above substances, an ion rating method, or the like can be used.

As described above, the urethane vinyl plastic lens is coated with an organosilicon coating, and an antireflection coating composed of an oxide of titanium or silicon is applied, whereby the thin, lightweight and excellent transparency of the present invention is obtained. It is possible to obtain an antireflection plastic lens having scratch resistance, adhesion, and antireflection properties. Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.

[0052]

EXAMPLES Example 1 ( Preparation of urethane vinyl plastic lens) 2-
64 parts by weight of a mixture of (4-vinylbenzylthio) ethanol and 2- (3-vinylbenzylthio) ethanol, m
36 parts by weight of xylene diisothiocyanate, perbutyl ND (t-butyl peroxyneodecanoate) 0.
2 parts by weight, V-40 (1,1-azobis (cyclohexane-1-carbonitrile) 0.2 parts by weight, dibutyltin diralylate 0.2 parts by weight, 2- (2′-hydroxy-5′-t) -Octylphenyl) benzotriazole (0.2 parts by weight) was mixed, and degassing was performed for 30 minutes while cooling under a vacuum of 1 × 10 ^-1 Torr.

Next, a glass lens molding die and a synthetic resin gasket were combined to form a molding die, and the mixture was poured. Polymerization was carried out by continuously raising the temperature linearly from 30 ° C. to 110 ° C. over 15 hours and maintaining it at 110 ° C. for 5 hours. After completion of the polymerization, the gasket was removed and the lens was removed from the lens molding die to obtain a urethane vinyl lens.

The obtained lens is colorless and transparent and has a refractive index of 1.
It was extremely high at 66 and had a low specific gravity of 1.26. It also had good heat resistance and impact resistance, had no distortion, and was excellent in impact resistance, machinability, and polishability. (Preparation of Organosilicon Coating Film) 1) Preparation of Preliminary Composition <M ₁ >: 248 parts by weight of γ-glycidoxypropylmethyldimethoxysilane was charged into a reaction vessel equipped with a rotor, and a magnetic stirrer was used. While stirring vigorously, 0.05N hydrochloric acid aqueous solution 36
Parts by weight were added at once.

Immediately after the addition, it was a heterogeneous solution, but within a few minutes
A uniform, colorless and transparent solution was formed while generating heat. 1 o'clock
Stirring is continued for a while to obtain a hydrolyzate corresponding to the component (a).
Was. The resulting hydrolyzate contains ethanol as a solvent component.
56.6 parts by weight and ethylene glycol 53.4 parts by weight
Aluminum acetyl as a catalyst component after adding
Add 4.7 parts by weight of acetonate, mix well and dissolve
And preliminary composition <M ₁> Was adjusted. 2) Preliminary composition <M₂> Adjustment: reaction volume with rotor
Γ-glycidoxypropylmethoxysilane 21 in a container
2.4 parts by weight were charged and the temperature inside the container was kept at 10 ° C.
While stirring vigorously using a magnetic stirrer,
Gradually add 48.6 parts by weight of 0.01 N hydrochloric acid aqueous solution.
Was. If cooling is stopped immediately after the dropping, uniform and colorless transparent
A hydrolyzate corresponding to clear solution component (a) was obtained.

The resulting hydrolyzate contained 77.1 parts by weight of ethanol and 37.
After adding 7 parts by weight, 7.65 parts by weight of aluminum acetylacetonate as a catalyst component was added and sufficiently mixed and dissolved to prepare a preliminary composition <M ₂ >. 3) Preparation of coating composition: In a glass container, weigh 20 parts by weight of the preliminary composition <M ₁ > prepared in 1) and 2) and 80 parts by weight of <M ₂ > (not the solid content ratio). Then, 150 parts by weight of a commercially available antimony pentoxide sol (not a solid content) and 0.45 parts by weight of a silicone-based surfactant are added thereto, and they are sufficiently stirred and mixed to obtain a uniform, colorless and transparent product. A solution-like coating composition was prepared. 4) Application Immersion method (Pulling speed 10
cm / min) and apply the above coating composition to 100
The coating film was cured by heating at 2 ° C. for 2 hours. (Preparation of multilayer antireflection film) A multilayer antireflection coating was formed by a vacuum vapor deposition method using a commercially available vacuum vapor deposition apparatus. SiO ₂ was used as a vapor deposition material for the low refractive index film, and Ti ₉ O ₆ was used as a vapor deposition material for the high refractive index film.

The polyurethane lens coated with the organosilicon coating produced by the above method was placed in a vacuum chamber,
Exhaust while heating to about 80 ° C, 1 × 10 ⁵ Tor
Exhausted to r. The above vapor deposition material was vapor-deposited by an electron beam heating method. 1 × 10 ^-4 Tor during deposition of Ti ₄ O ₅
Oxygen gas was introduced so as to be r, and vapor deposition was performed. Table 1 shows the composition of the antireflection film

[0058]

[Table 1]

(Evaluation) The lens manufactured as described above was subjected to the following test to evaluate the performance. 1. Appearance The following items were evaluated by visual judgment using an illuminating device having an illuminance of 1000 lux with a normal white fluorescent lamp as a light source.

(1) Transparency: No coloring or cloudiness (2) Uniformity within the lens: No nonuniformity of striae inside the lens (3) Uniformity of antireflection film The evaluation that the reflected color is uniform was performed as follows. ○ …… No problem △ …… Some problem × …… Problem 2. Reflection characteristics Spectral reflectance of 350 nm to 800 nm was measured by Hitachi Ltd. model 330 spectrophotometer. 3. Measurement of luminous transmittance The luminous transmittance was measured using a model 304 type luminous transmittance meter manufactured by Asahi Spectroscopy Co., Ltd. 4. Adhesion manufacturing After immersing the created lens in hot water at 90 ° C for 2 hours, make a line of cut lines in the vertical and horizontal directions with a knife every 1 mm on the surface of the coating film to make 100 Gobang eyes, and then stick cellophane. A tape (product name) "Cellotape" manufactured by Nichiban Co., Ltd.) was strongly attached. By holding one end of the tape in a hand and rapidly peeling it in the direction of 90 degrees, it was examined how many gobang eyes of the coating film were peeled off. The number X of the peeled Gobang's eyes is expressed as X / 100 in terms of the numerator. The smaller X is, the better the adhesion is. 5. Scratch resistance test The lens surface was rubbed with steel wool # 0000 to check the scratch resistance. The evaluation was carried out as follows.

⊚ · No scratches even when strongly rubbed. …: Slightly scratched when rubbed quite strongly. △ …… Slight scratches cause scratches. Incidentally, the evaluation of the lens without the coating film was x. The above evaluation results are shown in FIG. 1 and Table 6 below. Example 2 The same urethane vinyl lens as in Example 1 was prepared, and the composite sol of titanium oxide and cerium oxide was used in place of the antimony pentoxide sol of the coating composition of Example 1, and the same method as in Example 1 was used. Then, an organosilicon coating film was applied.

On the organic silicon coating film, a multilayer antireflection film having the constitution shown in Table 2 was prepared by the same vacuum deposition method as in Example 1.

[0063]

[Table 2]

The evaluation results are shown in FIG. 2 and Table 6. Example 3 The same urethane vinyl lens as in Example 1 was prepared, and a composite sol of titanium oxide and iron was used instead of the antimony pentoxide sol of the coating composition of Example 1 in the same manner as in Example 1. An organosilicon coating film was applied.

On the organic silicon coating film, a multilayer antireflection film having the structure shown in Table 3 was prepared by the same vacuum deposition method as in Example 1.

[0066]

[Table 3]

Here, Z + A represents a mixed substance of zirconium oxide and aluminum oxide. P + A represents a mixed substance of praseodymium oxide and aluminum oxide. The evaluation results are shown in FIG. 3 and Table 6. Example 4 The same urethane vinyl lens as in Example 1 was prepared, and a sol obtained by coating a tin oxide sol with a composite sol of titanium oxide and tungsten oxide in place of the antimony pentoxide sol of the coating composition of Example 1. Was used to apply an organosilicon coating film in the same manner as in Example 1.

On the organic silicon coating film, a multilayer antireflection film having the constitution shown in Table 4 was prepared by the same vacuum deposition method as in Example 1.

[0069]

[Table 4]

The evaluation results are shown in FIG. 4 and Table 6. Comparative Example 1 ( Preparation of plastic lens) The same method as in Example 1 was used. (Preparation of Organosilicon-Based Coating Film) Instead of the antimony pentoxide sol of the coating composition of Example 1, a silicon dioxide sol was used to prepare and apply the coating composition to prepare an organosilicon-based coating film. (Preparation of Multilayer Antireflection Film) A multilayer antireflection film having the structure shown in Table 5 was formed on the organosilicon coating film by a vacuum deposition method.

[0071]

[Table 5]

The evaluation results are shown in FIG. 5 and Table 6. The antireflection property had fine irregularities, and the reflection color was notably uneven. In addition, the transmittance was slightly inferior. Comparative Example 2 Using a polycarbonate molded lens as a plastic lens, the same organosilicon coating film and multilayer antireflection film as in Example 1 were prepared.

The evaluation results were almost the same as in FIG. 1, but as shown in Table 6, the transparency, internal uniformity, adhesion and scratch resistance were poor.

[0074]

[Table 6]

[0075]

As described above, according to the present invention, an antireflection plastic lens having the following features can be obtained. (1) A thin, lightweight antireflection plastic lens having excellent transparency and internal uniformity.

(2) An antireflection plastic lens which has excellent antireflection properties, has less glare on the surface, and has clear neat eyes when used in a spectacle lens. (3) An antireflection plastic lens having a high transmittance and capable of obtaining a neat field of view when used in a spectacle lens. (4) An antireflection plastic lens in which the reflection color of the antireflection film is uniform.

(5) An antireflection plastic lens in which a high-performance antireflection film having a low reflectance can be formed with a small number of layers. (6) An antireflection plastic lens that has excellent scratch resistance, surface hardness, and abrasion resistance, and also has excellent coating film adhesion. (7) An antireflection plastic lens having excellent flexibility, heat resistance, hot water resistance, and chemical resistance.

(8) An antireflection plastic lens having excellent antistatic properties and being relatively free from stains.

[Brief description of drawings]

FIG. 1 is a diagram showing a reflection characteristic of a lens in Example 1 of the present invention.

FIG. 2 is a diagram showing a reflection characteristic of a lens in Example 2 of the present invention.

FIG. 3 is a diagram showing a reflection characteristic of a lens in Example 3 of the present invention.

FIG. 4 is a diagram showing a reflection characteristic of a lens in Example 4 of the present invention.

5 is a diagram showing the reflection characteristics of the lens in Comparative Example 1. FIG.

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Claims (1)

[Claims] <A> A plastic lens comprising a radical polymer of an aromatic compound represented by the following general formula (I) and an isothiocyanate compound: (In the formula, X represents —H, —ROH, or —RSH and R is represented by C _n H _2n , and n is a hydrocarbon group of 1 to 4) <B> On the surface of the plastic lens Provided (a) general formula (II): (In the formula, R ¹ is a functional group or an organic group having an unsaturated double bond and having 4 to 14 carbon atoms, and R ² is a hydrocarbon group having 1 to 6 carbon atoms or a halogenated hydrocarbon group. , R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or an acyl group, a and b are 0 or 1, and a + b is 1 or 2). (B) colloidally dispersed antimony pentoxide sol, antimony trioxide sol, zirconium oxide sol, titanium oxide sol, tin oxide sol, tantalum oxide sol, tungsten oxide sol, aluminum oxide sol, and titanium oxide. Cerium oxide composite sol, titanium oxide and iron composite sol, tin oxide and tungsten oxide composite sol, and tin oxide and tungsten oxide composite sol An organosilicon coating film comprising a cured film of at least one sol of a sol coated with a tin oxide sol; <C> multilayer reflection containing an oxide of titanium and / or silicon provided on the coating film An antireflection plastic lens comprising an antireflection film.