JPS63197635A - Plastic optical product having reflection preventing effect - Google Patents

Abstract

PURPOSE:To enhance performances such as hardness, close adhesiveness or the like, by providing a film based on organopolysiloxane and fine particulate inorg. oxide and a film composed of inorg. oxide being silicon dioxide to the surface of a substrate in this order and further providing a multilayer film on said films. CONSTITUTION:gamma-Glycidoxypropyltrimethoxysilane and gamma- glycidopropylmethyldiethoxysilane are charged in a reactor and hydrolyzed under stirring by an aqueous hydrochloric acid solution to obtain a co-hydrolysate. Methanol acetylacetone and a silicone surfactant are added to and mixed with the co-hydrolysate, and methanol dispersed colloidal silica and aluminum acetylacetonate are further added thereto and sufficient stirring is performed to obtain a coating composition. As a plastic substrate, a molded product composed of diethylene glycol bisallylcarbonate is used and the coating composition is applied thereto by immersion coating and cured under heating to obtain a hard coated plastic substrate. Next, SiO2, ZrO2, Ta2O5 and SiO2 being inorg. oxide substances are applied to the obtained hard coated plastic substrate in this order by a vacuum vapor deposition method to form many layers each having an optical film thickness.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a plastic optical article having an antireflection effect suitable for optical applications such as eyeglass lenses, camera lenses, CRT filters, and optical recording substrates. .

[Prior Art] Plastic molded products, especially molded bodies represented by plastic lenses, have extremely high impact resistance and transparency, are lightweight, and can be easily dyed, so demand has increased significantly in recent years. is increasing.

Conventionally, in order to prevent reflection, a method has been used in which a film of a material having a refractive index different from that of the substrate is formed on the substrate by vacuum evaporation or the like.

JP-A-52-165862 proposes providing an organopolysiloxane resin layer on a plastic molded article, and providing a metal and/or inorganic ceramic layer thereon.

In addition, Japanese Patent Application Laid-open No. 113101/1983 discloses that Si 0 of about 1 micron is coated on a plastic substrate for the purpose of improving both the surface hardness and antireflection properties of plastic.
A method is disclosed in which a multilayer antireflection film is coated on the film by vacuum evaporation.

Furthermore, JP-A-59-78301 discloses that an organopolysiloxane hard coat film containing an organosilicon compound as a main component or an epoxy resin cured film is applied to the surface of a plastic substrate, and then an anti-reflection film made of an inorganic material is applied. A method of coating a membrane is disclosed.

[Problems to be Solved by the Invention] The technique disclosed in JP-A-52-165862 does not provide a sufficiently strong adhesion, resulting in peeling of the coating, decrease in surface hardness, and roughness. There are many drawbacks such as the scratches that occur are thick and deep, and the practical durability is poor.

Furthermore, although the technology disclosed in JP-A-56-11310 has high hardness and anti-reflection properties, it reduces adhesion, impact resistance, weather resistance, and hot water resistance, and furthermore,
There is a big problem with heat resistance.

In addition, although the technology disclosed in JP-A-59-78301 has antireflection properties, it has poor adhesion to the substrate, and is easily immersed in water, alcohol, etc., and does not adhere well after hot water treatment. There are major problems with durability, weather resistance, etc.

The present invention has characteristics such as abrasion resistance, adhesion, abrasion resistance, impact resistance,
Chemical resistance, flexibility, heat resistance, weather resistance, light resistance, dyeability,
The object of the present invention is to provide a plastic optical article having excellent resistance to solvent penetration, etc., and a good antireflection effect.

[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.

That is, the present invention provides a plastic optical article having an antireflection effect, which is characterized in that the following a and openings are provided on the surface of a plastic substrate in this order, and a multilayer coating of two or more layers is further provided on the coating.

B. A coating mainly composed of organopolysiloxane and a particulate inorganic oxide, and a coating consisting of an inorganic oxide in which at least 10% by weight is silicon dioxide.

Examples of the plastic substrate in the present invention include acrylic resins, polycarbonates, diethylene glycol bisallyl carbonate polymers, di(meth)acrylate polymers of (halogenated) bisphenol A and copolymers thereof, and urethane-modified (halogenated) bisphenol A. Examples include molded products such as di(meth)acrylate polymers and copolymers thereof, such as lenses, sheets, films, and compact discs.

In the present invention, a hard coat layer consisting of a film mainly composed of organopolysiloxane and particulate inorganic oxide is provided on these plastic substrates.
Typical examples of compositions that form organopolysiloxanes include organically substituted silicon compounds. As such a silicon compound, the following general formula (A) or a hydrolyzate thereof can be mentioned.

RaR1bS! x4-a-b (A)(
Here, R is an organic group having 1 to 10 carbon atoms, R1 is a hydrocarbon group having 1 to 6 carbon atoms, or a halogenated hydrocarbon group,
is a hydrolyzable group, and a and b are O or 1. ) Specific representative examples include tetraalkoxysilanes such as methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, 5ec-butyl silicate and t-butyl silicate, and their hydrolysis. Methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane,
Phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-
Chloropropyltriethoxysilane, T-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, β-
Cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane,
α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane,
β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, T-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltrimethoxysilane Butoxysilane, T-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxy Butyltrimethoxysilane, β-
Glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3 , 4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl)
Methyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,
4-Epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl) Ethyltrimethoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-
Trialkoxysilane, triazyloxysilane or triphenoxysilane such as epoxycyclohexyl)propyltriethoxysilane, β-(3,4-epoxycyclohexyl)butyltrimethoxysilane, β-(3,4-epoxycyclohexyl)butyltriethoxysilane Sisilanes or their hydrolysates and dimethyldimethoxysilane, phenylmethyljethoxysilane, dimethyldimethoxysilane, phenylmethyljethoxysilane, γ
-Chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ -Mercaptopropylmethyljethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyljethoxysilane, glycidoxymethylmethyldimethoxysilane,
Glycidoxymethylmethyldimethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyljethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyljethoxysilane Billmethyldimethoxysilane, γ-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldiptoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ -Glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyljethoxysilane, γ-glycidoxypropylvinyldi゛Methoxysilane, γ-glycidoxypropylvinyljethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, dialkoxysilane, diphenoxysilane or diacyloxysilane or An example is its hydrolyzate.

It is also possible to add one type or two or more types of these organosilicon compounds. Particularly for the purpose of imparting dyeability, it is preferable to use organosilicon compounds containing epoxy groups and glycidoxy groups, resulting in high added value.

The above compositions are usually diluted in volatile solvents and applied as liquid compositions. There are no particular restrictions on what can be used as a solvent, but when using it, it is required not to damage the surface properties of the object to be coated, and also take into consideration the stability of the composition, wettability to the substrate, volatility, etc. This is a place that can be determined by Moreover, it is also possible to use not only one type of solvent but also a mixture of two or more types.

Furthermore, in order to improve the hardness and the adhesion with the inorganic oxide layer, it is preferable that the particulate inorganic oxide is contained in a proportion of 5% or more and 80% or less. That is, if it is less than 5% by weight,
Sufficiently strong adhesion strength with the coating on the mouth cannot be obtained, and if it exceeds 80% by weight, problems such as poor adhesion with the plastic substrate, generation of cracks in the coating itself, and reduction in impact resistance occur.

Such fine particulate inorganic oxides are not particularly limited as long as they do not impair transparency in the coating state, but workability,
A particularly preferred example from the viewpoint of imparting transparency is a colloidally dispersed sol. More specific examples include silica sol, titania sol, zirconia sol, antimony oxide sol, and alumina sol.

Furthermore, various surfactants can be used in these coating compositions for the purpose of improving flow during application, especially block or graft copolymers of dimethylpolysiloxane and alkylene oxide. For roughness, fluorine-based surfactants are effective.

Furthermore, it is also possible to add an ultraviolet absorber for the purpose of improving weather resistance, and an antioxidant to improve heat deterioration resistance.

Furthermore, inorganic compounds other than the particulate inorganic oxides can also be added to these coating compositions within a range that does not significantly reduce coating performance, transparency, etc.

By using these additives in combination, various physical properties such as adhesion to the base material, chemical resistance, surface hardness, durability, and dyeability can be improved. Examples of the inorganic materials that can be added include metal alkoxides, chelate compounds, and/or hydrolysates thereof represented by the following general formula [I].

M(OR>IIl [I] (where R
is an alkyl group, an acyl group, or an alkoxyalkyl group, and m is the same value as the number of charges of the metal M. Examples of M include silicon, titanium, zircon, antimony, tantalum, germanium, and aluminum. ) When forming the organopolysiloxane film in the present invention, various curing agents can be used for the purpose of accelerating curing, enabling low-temperature curing, etc. As the curing agent, various epoxy resin curing agents or various organosilicon resin curing agents can be used.

Specific examples of these curing agents include various sigma organic acids and their acid anhydrides, nitrogen-containing organic 41 compounds, various metal complex compounds or metal alkoxides, and organic carboxylates and carbonates of alkali metals. For each loading dock, etc., radical polymerization initiators such as peroxide and ambisisoprodylonitrile are mentioned. It is also possible to use a mixture of two or more of these curing agents. Among these curing agents, the aluminum mura chelate compounds shown below are particularly useful for the purpose of the present invention from the viewpoints of stability of the coating material, prevention of coloring of the coating film after coating, and the like.

The aluminum chelate compound mentioned here has the general formula A
It is an aluminum chelate compound represented by axoY3-n.

(However, in the formula, .M
4 is a lower alkyl group)) At least one ligand derived from the compound shown above is selected, and n is 0, 1 or 2.

・) Among the aluminum chelate compounds represented by AaXnY3-n, solubility in the composition, stability,
From the viewpoint of effectiveness as a curing catalyst, al.
Preferred examples include minilum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum di-10-poxydo monoedylacetoacetate, aluminum di-1SO-propoxide-monomethyl acetoacetate, and the like. These are 2
It is also possible to use a mixture of more than one species.

As the coating method, methods used in ordinary coating operations can be applied, but preferred are, for example, dip coating, flow coating, spin-coating, and the like. The coating composition thus applied is dried or cured by heating.

As a heating method, hot air, infrared rays, etc. can be used. The heating temperature should be determined depending on the substrate to be applied and the coating composition used, but is usually from room temperature to 250°C, more preferably from 35 to 250°C.
00°C is used. If the temperature is lower than this, curing or drying tends to be insufficient, and if the temperature is higher than this, thermal decomposition, cracking, etc. occur, and problems such as yellowing are likely to occur.

When applying the liquid coating composition in the present invention, it is preferable that the surface to be applied is cleaned, and cleaning involves removing stains using a surfactant,
Degreasing with organic solvents and steam cleaning with Freon are applied to the grains.

It is also an effective means to perform various pretreatments for the purpose of improving adhesion and durability. Particularly preferably used methods include activated gas treatment, which will be described later, and chemical treatment with acids, alkalis, etc., depending on the concentration.

The thickness of the coating mainly composed of organopolysiloxane and particulate inorganic oxide in the present invention is not particularly limited. However, from the viewpoint of maintaining adhesion strength and hardness, a thickness of 0.1 to 20 microns is preferably used.

Particularly preferred is 0.4 micron to 10 micron.

In the present invention, a coating made of an inorganic oxide containing at least 10% by weight of silicon dioxide is provided on these hard coat layers. It may be applied. Such activated gas treatment means, under normal pressure or reduced pressure,
They are generated ions, electrons, or excited gases. Methods for generating these activated gases include, for example, corona discharge, direct current under reduced pressure, high voltage discharge using low frequency, high frequency, or microwave. In particular, treatment with low-temperature plasma obtained by high-frequency discharge under reduced pressure is preferably used from the viewpoint of reproducibility, productivity, etc. The gas used here is not particularly limited, but specific examples include oxygen, nitrogen, hydrogen,
carbon dioxide, sulfur dioxide, helium, neon, argon,
Freon, water vapor, ammonia, -carbon oxide, chlorine, -
Examples include nitrogen oxide and nitrogen dioxide. these are,
It is possible to use not only one kind but also a mixture of two or more kinds.

Among the above gases, oxygen is preferred, and gases that exist in nature such as air may also be used. Particularly preferably, pure oxygen gas is effective for improving adhesion.

Furthermore, it is also possible to raise the temperature of the treated substrate during the above-mentioned use for the same purpose. Among these, pretreatment with activated gas is particularly effective. When applying such an activated gas, the processing conditions should be optimized depending on the composition forming the organopolysiloxane, the type of inorganic oxide fine particles, curing conditions, film thickness, presence or absence of dyeing, etc. Yes, and should be determined experimentally.

In the present invention, when providing a coating made of an inorganic oxide substance containing at least 10% by weight of silicon dioxide,
Liquid coating or dry coating such as vacuum evaporation is effective, but dry coating such as vacuum evaporation is preferably used from the viewpoint of film density and productivity.

Specific examples that can be used in combination with inorganic oxides other than silicon dioxide include titania sol, zirconia sol, and antimony oxide for liquid coating.

Examples include colloidal oxides such as sol and alumina sol, as well as products obtained from metal alkoxides represented by the general formula M(OR)m and/or their hydrolysates. These substances can be used not only alone but also as a mixture of two or more. Inorganic oxides other than silicon dioxide that are preferably used in dry coating include SiQ, ZrO2, A
Q203, Ti01 D102, Ti2O3, Y20
3, Yb203, HgO.

Examples include Ta20s, CeO2, Hf (h, etc.) These substances can be used not only alone, but also in a mixture of two or more. The thickness of such a film is not particularly limited. However, , from the viewpoint of hardness and heat resistance, 0
．． It is preferably used between 0.01 micron and 1 micron. Particularly preferred is 0.02 micron to 0.5 micron p. In particular, a coating made of a mixture of SiO2 and ZrO2 is effective in improving the light fastness of dyed plastic substrates. Further, during co-evaporation, it is effective to add Y2O3 or the like in combination.

In the present invention, a multilayer film of two or more layers is provided on a coating layer made of an inorganic oxide substance containing 10% by weight or more of silicon dioxide. Combinations consisting of oxides are preferably used.

Examples of methods for forming such a layer include vacuum evaporation, ion beam assisted sputtering, and ion blating. The plastic optical article having an antireflection effect obtained by the present invention has higher hardness and higher heat resistance than general plastic antireflection optical articles.
In general, because it is not easily attacked by chemicals, it is used in eyeglass lenses, camera lenses, CRT filters, and more.
In particular, a film containing 1 oam or more of silicon dioxide has gas barrier properties and can therefore be preferably used for optical recording substrates.

[Examples] In order to explain in more detail, examples will be described below, but the present invention is not limited thereto.

Example 1 (1) T-glycidoxypropyltrimethoxysilane,
Preparation of γ-glycidoxypropylmethyljethoxysilane cohydrolyzate In a reactor equipped with a rotor, 35.3 parts of γ-glycidoxypropyltrimethoxysilane and 106 parts of γ-glycidoxypropylmethyljethoxysilane were added. Add 8 parts of ゜ and stir using a magnetic stirrer until the
23.6 parts of a normal aqueous hydrochloric acid solution was added dropwise while maintaining the liquid temperature at 10°C, and stirring was continued for 30 minutes after the dropwise addition was completed to obtain a hydrolyzate.

(2) Preparation of coating composition 185 parts of methanol, 11.1 parts of acetylacetone, and 2.5 parts of a silicone surfactant were added and mixed to the co-hydrolyzate of (1) above, and further methanol-dispersed colloidal silica (average particle size 12±1mμ, solid valve 30%>333.3
After adding 6.0 parts of aluminum acetylacetonate and stirring thoroughly, a coating composition was obtained.

(3) Using Praluns of CR-39 (diethylene glycol bisallyl carbonate polymer) as a plastic substrate, the coating composition prepared in (2) above was applied by dip coating at a pulling speed of 10 cm/min, and then After precuring at 12 minutes at 100° C. and further heating at 100° C. for 4 hours, a hard coat plastic substrate was obtained.

(4) Inorganic oxides such as 5i02 and ZrO are applied on the hard coat plastic substrate obtained in (3) above.
2, D20S and S i 02 were deposited in this order using a vacuum evaporation method to obtain an optical film thickness of λ/2. λ/4. λ/4. λ/4
．． (λ=521 nm) to form a multilayer coating. The reflection interference color of the obtained optical article having an antireflection effect was green, and the total light transmittance was 98.5%.

(5) Test Results 1q The performance of the optical article having the antireflection effect was tested according to the following method. The results are shown in Table 1.

(a) Using steel wool with a hardness of #0OOO, rub the painted surface 50 times under a load of 1.5 ka to judge the extent of scratches. The criteria for judgment are: A: No scratches.

B: Many scratches occur.

(b) Adhesion: Insert 100 gongs reaching 1 mm into the substrate on the coating surface using a steel knife, and firmly stick cellophane adhesive tape (trade name: "Cellotape" manufactured by Nichiban Co., Ltd.). It was rapidly peeled off in a 90 degree direction to check for peeling of the coating.

(c) Appearance The obtained optical article having an antireflection effect was observed with the naked eye for its transparency, colorability, and presence or absence of cracks.

(d) Heat resistance The sample was placed in an oven set at 70°C and taken out after 1 hour to observe the presence or absence of cracks.

Example 2 (1) Preparation of transparent substrate to be coated Ethylene oxide 2 of tetrabromobisphenol A
70 parts of heptamer containing a polyfunctional acrylate monomer with 0.9 mole of hexamethylene diisocyanate added to 1 mole of a hydroxyl group-containing compound in which 1 mole of acrylic acid is bonded to the molar adduct by esterification, and 30 parts of styrene.
A substrate obtained by cast polymerization using isopropyl peroxide as a polymerization initiator was subjected to low-temperature plasma treatment to obtain a surface-treated substrate. The refractive index of the obtained resin is 1.6
Met.

(2) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate Charge 95.3 parts of γ-glycidoxypropyltrimethoxysilane into a reactor equipped with a rotor, 0.01 while keeping the liquid temperature at 10℃ and stirring with a magnetic stirrer.
21.8 parts of normal hydrochloric acid aqueous solution is gradually added dropwise. After the dropwise addition was completed, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

(b) Preparation of coating composition The silane hydrolyzate is mixed with 216 parts of methanol, 216 parts of dimethylformamide, 0.5 parts of a fluorine-based surfactant, and a bisphenol A epoxy resin (manufactured by Shell Chemical Co., Ltd.).
Add and mix 67.5 parts of product name Epicoat 827),
In addition, colloidal antimony pentoxide sol, manufactured by Sansan Kagaku Co., Ltd., trade name, antimony sol A-2550, average particle size: 60
mμ) 270 parts, aluminum acetylacetonate 1
After adding 3.5 parts and stirring thoroughly, a coating composition was prepared.

(3) The coating composition prepared in (2) above was immersed into the substrate to be coated obtained in (1) above at a pulling rate of 10 cm/min, and heat curing was performed in the same manner as in Example 1.

(4) Prepare a disperse dye dyeing bath consisting of red, blue, and yellow for the hard coat plastic substrate obtained in (3) above, and dye it for 5 minutes while keeping the liquid temperature at 93°C. The light attenuation rate of the obtained dyed product was 50%.

(5) On the dyed hard coat plastic substrate obtained in (4) above, inorganic oxide ZrO2 and 5
The mixture with i02, ZrO2, and D205.5i02 were vacuum-deposited in this order to give optical film thicknesses of λ/4 and λ, respectively.
/4, λ/4, λ/4 (λ=521 stop), and multilayer coating was performed on both sides. The reflection interference color of the obtained optical article having an antireflection effect was yellow-green.

One half of the dyed antireflection plastic substrate obtained in step (5) above was wrapped in aluminum foil and an accelerated light fastness test was performed using a fade meter (manufactured by Suga Test Instruments Co., Ltd.). There was no fading and it had good light fastness. Other test results are
Shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was repeated except that the hard coat was omitted. The test results are shown in Table 1.

Comparative Example 2 In Example 1, the inorganic oxidizing substance S! All tests were conducted in the same manner except that 02 was omitted. The test results are shown in Table 1.

Comparative Example 3 In Example 2, inorganic oxides ZrO2 and 5i02
Everything was done in the same way except omitting the mixture.

The obtained dyed antireflection article was subjected to an accelerated light fastness test in the same manner as in Example 2, and the dye fading was severe on the surface irradiated with ultraviolet rays, resulting in poor durability. Other test results are shown in Table 1.

Table 1 [Effects of the Invention] The plastic optical article having an antireflection effect obtained by the present invention has the following effects.

(1) A highly hard coating film that can withstand repeated abrasion with steel wool etc. can be obtained.

(2) Excellent adhesion.

(3) Excellent heat resistance and hot water resistance.

(4) Excellent dyeability.

(5) Excellent gas barrier properties and excellent durability of dyed products.

(6) Excellent solvent resistance.

Patent Applicant Toshi Co., Ltd. Written Amendment to Procedures 1. Description of the case 1986 Patent Application No. 29701 2 Name of the invention Plastic optical article having anti-reflection effect 3 Person making the amendment Relationship to the case Patent applicant address 2-2-1 Nihonbashi Muromachi, Chuo-ku, Tokyo Name (
315) Toshi Co., Ltd. 5. Number of inventions to be increased by amendment None 6. "Claims" of the specification subject to the amendment and "(1) "Claims" in the specification of the invention are amended as shown in the attached sheet. To do.

(2) On page 21, line 11, "legal spatter" is corrected to "legal, spatter."

(3) Page 21, line 16, ``From the beginning, 1, for glasses is corrected to ``From the fact, for glasses.''

(4) On page 21, line 18, "more than weight" is corrected to "more than weight%".

(5) On page 22, line 18, correct "rll, 1 part silicone" to "N1.1 part, silicone."

(6) On page 23, line 15, "film" is corrected to "coating."

(7) On page 24, line 4, correct "painted surface" to "covered surface."

(8) Page 27, line 5, “Mixture, Zr02J [Mixture (ZrO2/S i 02 =50150
(Weight ratio) ), correct with Zr02J.

(9) In the second line from the bottom of page 29, ``Nimokitsu'' has been corrected to ``Nimo-endai''.

Attachment Claims (1) A plastic optical device having an antireflection effect, characterized in that the following a and openings are provided in this order on the surface of a plastic substrate, and a multilayer coating of two or more layers is further provided on the coating. Goods.

(2) A coating consisting of an inorganic oxide whose main components are organopolysiloxane and oxide in the form of fine particles, and at least 10% by weight of which is silicon dioxide.
A plastic optical article having an antireflection effect according to claim (1), which is an organosilicon compound represented by:

RR1S'! X4-a-b (A>b (where R is an organic group having 1 to 10 carbon atoms, R1 is a hydrocarbon group or halogenated hydrocarbon group having 1 to 6 carbon atoms,
is a hydrolyzable group, and a and b are O or 1. ) (3) The organopolysiloxane has the general formula (A
A plastic optical article having an antireflection effect according to claim (1), characterized in that it is a hydrolyzate of an organosilicon compound shown in (1).

(4) Claim No. 1, characterized in that the particulate inorganic oxide is contained in a proportion of 5% by weight or more and 80% by weight or less (
A plastic optical article having the antireflection effect described in item 1).

Claims (4)

[Claims] (1) A plastic optical article having an antireflection effect, characterized in that the following A and B are provided in this order on the surface of a plastic substrate, and a multilayer coating of two or more layers is further provided on the coating. A. A coating mainly composed of organopolysiloxane and a particulate inorganic oxide. B. A coating consisting of an inorganic oxide in which at least 10% by weight is silicon dioxide. (2) A plastic optical article having an antireflection effect according to claim (1), wherein the organopolysiloxane is an organosilicon compound represented by the following general formula (A). R_aR^1_bSiX_4_-_a_-_b(A)(
Here, R is an organic group having 1 to 10 carbon atoms, R^1 is a hydrocarbon group or halogenated hydrocarbon group having 1 to 6 carbon atoms, and X
is a hydrolyzable group, and a and b are 0 or 1. ) (3) A plastic optical article having an antireflection effect according to claim (1), wherein the organopolysiloxane is a hydrolyzate of an organosilicon compound represented by the general formula (A). . (4) Particulate inorganic oxide content is 5% by weight or more and 80% by weight
Claim No. (1) characterized in that it includes the following:
A plastic optical article having an antireflection effect as described in Section 1.