JP4707656B2 - Optical member having antireflection film - Google Patents

Description

  The present invention relates to an optical member having improved scratch resistance.

Conventionally, as a method of imparting scratch resistance to a plastic molded product, it is known to apply a cured film to the surface of a plastic substrate. Such a cured film has been proposed to improve the aesthetics by combining the refractive index with a plastic substrate having a high refractive index, and to improve various physical properties such as weather resistance and moisture resistance. As an example of such a proposal, Patent Document 1 discloses an optical member having a plastic substrate, a cured film, and a multilayer antireflection film formed by vacuum deposition. The raw material of such a cured film coating composition is (A) colloidal particles of stannic oxide obtained by reaction of metallic tin, hydrochloric acid (inorganic acid) and hydrogen peroxide, and colloidal particles of zirconium oxide. Based on the weight of these oxides, a stannic oxide-zirconium oxide composite colloidal particle having a structure in which ZrO ₂ / SnO ₂ is bonded at a ratio of 0.02 to 1.0 and a particle diameter of 4 to 50 nm is cored The surface of the wafer has a WO ₃ / SnO ₂ weight ratio of 0.1 to 100, a SiO ₂ / SnO ₂ weight ratio of 0.1 to 100, and a tungsten oxide-stannic oxide having a particle diameter of ₂ to 7 nm. A modified stannic oxide-zirconium oxide composite colloidal particle having a particle diameter of 4.5 to 60 nm formed by coating with colloidal particles of a silicon dioxide composite, and an organosilicon compound Contains. The antireflection film is formed by laminating a mixed layer of a silicon dioxide layer, tantalum oxide, zirconium oxide, and yttrium oxide by a vacuum deposition method.

  Incidentally, a steel wool test has been used as a method of evaluating the scratch resistance of a film. However, since the steel wool test is not evaluated numerically, in recent years, the Bayer test has begun to be adopted as a method for evaluating the scratch resistance. The optical member disclosed in Patent Document 1 is also desired to be further improved in scratch resistance when evaluated by a Bayer test.

JP 2000-284101A

  The present invention has been made to solve such problems, and an object of the present invention is to provide an optical member that satisfies various physical properties such as aesthetics and adhesion and has improved scratch resistance.

This problem has been solved by the following means. The means is an optical member having, in this order, a plastic substrate, a cured film, a multilayer antireflection film formed by vacuum deposition, and a water-repellent film applied on the antireflection film. A) Oxidation obtained by the reaction of metallic tin , oxalic acid or an organic acid containing at least 80% by weight of oxalic acid in the total organic acid, with formic acid and / or acetic acid as the balance , and hydrogen peroxide. A structure in which colloidal particles of tin and colloidal particles of zirconium oxide are combined in a ratio of 0.02 to 1.0 as ZrO ₂ / SnO ₂ based on the weight of these oxides and a particle size of 4 to 50 nm The core is a stannic oxide-zirconium oxide composite colloidal particle having a surface, and its surface has a WO ₃ / SnO ₂ weight ratio of 0.1 to 100, a SiO ₂ / SnO ₂ weight ratio of 0.1 to 100, and 2 Have a particle size of ~ 7nm Modified stannic oxide-zirconium oxide composite colloidal particles having a particle diameter of 4.5 to 60 nm produced by coating with colloidal particles of tungsten oxide-stannic oxide-silicon dioxide composite (B) ) Using a coating composition containing an organosilicon compound as a raw material, the multilayer antireflection film is sequentially from the substrate side to the outside air side,
First layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic material containing silicon dioxide as a deposition material.
Second layer: a layer containing at least 50% by weight of tantalum oxide based on the second layer
Third layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure and an inorganic material containing silicon dioxide as a deposition material.
Fourth layer: a layer containing at least 50% by weight of tantalum oxide based on the fourth layer
Fifth layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic material containing silicon dioxide as a deposition material.
Sixth layer: a layer containing at least 50% by weight of tantalum oxide based on the sixth layer
Seventh layer: a hybrid layer formed using an organic silicon compound that is liquid at room temperature and pressure and / or a silicon-free organic compound that is liquid at room temperature and pressure and an inorganic material containing silicon dioxide as a deposition material
The water repellent film is an optical member composed of layers formed using a fluorine-substituted alkyl group-containing organosilicon compound as a raw material.

  ADVANTAGE OF THE INVENTION According to this invention, the optical member which scratch resistance improves notably without impairing physical properties, such as adhesiveness and transparency, can be provided.

It is the schematic which shows the film-forming apparatus in this invention.

Explanation of sign

1: Optical film thickness monitor 2: Substrate 3: Dome for holding substrate 4: Organic substance introduction port A
5: Organic substance introduction port B
6: Evaporation source 7: RF ion gun 8: Ionized gas inlet 9: Connection to exhaust system 10: Connection to external monomer heating (vaporization) device

Hereinafter, the present invention will be described in detail.
1. Regarding the plastic substrate The plastic substrate that can be used in the present invention is not particularly limited. Examples of the plastic base material include methyl methacrylate homopolymer, copolymer having methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bisallyl carbonate and one kind. Examples include copolymers containing other monomers as monomer components, sulfur-containing copolymers, halogen-containing copolymers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, polythiourethane, etc. be able to.
Among these, from the viewpoints of the refractive index and aesthetics of the cured film obtained (characteristics in which interference fringes are not observed with respect to optical members) and the like, a polythiourethane resin using a polyisocyanate compound and a polythiol compound as raw materials Preferably, a plastic substrate having a refractive index of about 1.58 to 1.62 can be obtained by using these materials.

2. Coated composition for forming a cured film (1) Modified stannic oxide-zirconium oxide composite colloidal particles The composition of the modified stannic oxide-zirconium oxide composite colloidal particles is the above-mentioned patent. Known from document 1. In the present invention, the modified stannic oxide-zirconium oxide composite colloidal particles disclosed in Patent Document 1 are those using composite colloidal particles prepared by using a different production method, and oxidation as a nucleus. In the stannic-zirconium oxide composite colloidal particles, the stannic oxide colloidal particles obtained by the reaction of tin metal, organic acid and hydrogen peroxide are used, and the composition is further combined with other coating composition components. An optical member capable of achieving the object of the present invention is obtained by obtaining a cured film from the material as a raw material and applying a specific antireflection film and a water-repellent film thereto.

Examples of the method for producing modified stannic oxide-zirconium oxide composite colloidal particles include the following steps (a), (b), (c), (d), (e) and (f). A production method comprising steps is preferred.
Step (a): In an organic acid aqueous solution, hydrogen peroxide solution and metal tin are reacted so that the H ₂ O ₂ / Sn molar ratio is in the range of 2 to 4 and the tin oxide concentration is 40% by weight or less. A step of producing colloidal particles of stannic oxide having a particle diameter of 4 to 50 nm,
(B) Step: stannic oxide containing colloidal particles of stannic oxide having a particle diameter of 4 to 50 nm obtained in step (a) as its oxide SnO _{2 at} a concentration of 0.5 to 50% by weight. Mixing an aqueous sol and an aqueous solution of an oxyzirconium salt having a concentration of 0.5 to 50% by weight as ZrO _{2 in} a weight ratio of 0.02 to 1.0 as ZrO ₂ / SnO ₂ based thereon,
(C) Step: The stannic oxide-zirconium oxide composite having a particle size of 4 to 50 nm is obtained by heat-treating the mixed liquid obtained in the step (b) at 60 to 200 ° C. for 0.1 to 50 hours. Producing an aqueous sol,
Step (d): An aqueous solution containing tungstate, stannate, and silicate in a ratio of 0.1 to 100 as a WO ₃ / SnO ₂ weight ratio and 0.1 to 100 as a SiO ₂ / SnO ₂ weight ratio. Preparing and producing a tungsten oxide-stannic oxide-silicon dioxide composite sol obtained by removing cations present in the aqueous solution;
Step (e): The stannic oxide-zirconium oxide composite aqueous sol obtained in step (c) was obtained in step (d) with 100 parts by weight as the total of ZrO ₂ and SnO ₂ contained therein. A tungsten oxide-stannic oxide-silicon dioxide composite sol having a particle size of _{2 to 7} nm, a WO ₃ / SnO ₂ weight ratio of 0.1 to 100 and a SiO ₂ / SnO ₂ weight ratio of 0.1 to 100 Then, a modified stannic oxide-zirconium oxide composite aqueous sol is produced by mixing at a ratio of 2 to 100 parts by weight as a total of WO ₃ , SnO ₂ and SiO ₂ contained therein at 0 to 100 ° C. Step (f) and Step (f): By contacting the modified stannic oxide-zirconium oxide composite aqueous sol obtained in Step (e) with an anion exchanger, anions present in the sol are removed. Remove Process.

The sol of stannic oxide-zirconium oxide composite colloidal particles as the core particles used in the production of the sol used in the coating composition for forming the cured film of the present invention is the above-mentioned steps (a) and (b). And it can manufacture by the method which consists of (c) process.
The colloidal particles of stannic oxide used in the step (a) are a solution of hydrogen peroxide and metal tin in an organic acid aqueous solution with a H ₂ O ₂ / Sn molar ratio in the range of 2 to 4, and a tin oxide concentration of By making it react and produce | generate so that it may become 40 weight% or less, it can obtain from the colloidal particle of a stannic oxide with a particle diameter of 4-50 nm.
At this time, hydrogen peroxide solution and metallic tin are added to the organic acid aqueous solution while keeping the H ₂ O ₂ / Sn molar ratio in the range of 2 to 4. The total amount of hydrogen peroxide solution and tin metal can be added to the organic acid aqueous solution at once, but a method of adding them alternately in several times is preferable. Although the order of addition of the hydrogen peroxide solution and metal tin is not limited, it is important that the H ₂ O ₂ / Sn molar ratio is kept in the range of 2 to 4. Usually, hydrogen peroxide solution and metal tin are added, and after the reaction is completed, the next hydrogen peroxide solution and metal tin are added. Although the reaction time for one time depends on the amount added, it is usually about 5 to 10 minutes, and the next hydrogen peroxide solution and metal tin are added.

(A) The weight ratio of the organic acid, hydrogen peroxide, and metal tin used in the step is usually organic acid: hydrogen peroxide: metal tin = 0.21 to 0.53: 0.57 to 1.15: 1. 0.
The organic acid aqueous solution is preferably an oxalic acid aqueous solution or an organic acid aqueous solution containing oxalic acid as a main component, but can be particularly preferably produced by using only an oxalic acid aqueous solution. The organic acid aqueous solution containing oxalic acid as a main component is an aqueous solution of an organic acid containing 80% by weight or more of oxalic acid in the total organic acid, and the balance can contain organic acids such as formic acid and acetic acid. These organic acid aqueous solutions can be used in a concentration of preferably 1 to 30% by weight, more preferably 4 to 10% by weight.

  The medium of the stannic oxide sol may be either water or a hydrophilic organic solvent, but an aqueous sol in which the medium is water is preferable. Further, the pH of the sol is good for stabilizing the sol, and is usually about 0.2 to 11. As long as the object of the present invention is achieved, the stannic oxide sol may contain an optional component, for example, an alkaline substance, an acidic substance, an oxycarboxylic acid and the like for stabilizing the sol. The concentration of the stannic oxide sol used is about 0.5 to 50% by weight as stannic oxide, but this concentration should be low, and preferably 1 to 30% by weight.

In the stannic oxide-zirconium oxide composite sol, an oxyzirconium salt is added to the stannic oxide sol so that the ZrO ₂ / SnO ₂ weight ratio is 0.02 to 1.0. It can be obtained by (b) step of mixing for 5 to 3 hours, and then (c) step of heat-treating this at 60 to 200 ° C. for 0.1 to 50 hours.
Examples of the oxyzirconium salt used include zirconium oxychloride, zirconium oxynitrate, zirconium oxysulfate, zirconium oxyacetate, zirconium oxyorganic acid, zirconium oxycarbonate, and the like. These oxyzirconium salts can be used as a solid or an aqueous solution, but are preferably used as an aqueous solution of about 0.5 to 50% by weight as ZrO ₂ . It can be used when the stannic oxide that also mixes a salt insoluble in water, such as zirconyl oxycarbonate, is an acidic sol.
The stannic oxide sol is preferably an alkaline sol stabilized with an organic base such as an amine, and the mixing with the oxyzirconium salt is usually 0 to 100 ° C., preferably about room temperature to 60 ° C. In this mixing, the oxyzirconium salt may be added to the stannic oxide sol under stirring, or the stannic oxide sol may be added to the aqueous oxyzirconium salt solution, but the latter is preferred. This mixing needs to be performed sufficiently, and is preferably about 0.5 to 3 hours.

In the present invention, the WO ₃ , SnO ₂ and SiO ₂ composite colloidal particles used as the coating sol and contained in the tungsten oxide-stannic oxide-silicon dioxide composite sol obtained in the step (d) are analyzed by an electron microscope. The particle diameter can be observed, and the particle diameter is 2 to 7 nm, preferably 2 to 5 nm. As a dispersion medium for the colloidal particles of the sol, any of water, a hydrophilic organic solvent, and a mixture thereof can be used. This sol contains WO ₃ , SnO ₂ and SiO ₂ in a ratio of 0.1 to 100 as a WO ₃ / SnO ₂ weight ratio and 0.1 to 100 as a SiO ₂ / SnO ₂ weight ratio. The total concentration of WO ₃ , SnO ₂ and SiO ₂ contained in this sol is usually 40% by weight or less, preferably 2% by weight or more, and preferably 5 to 30% by weight in practice. This sol is a liquid having a pH of 1 to 9 and having a colorless and transparent or slightly colloidal color. It is stable for 3 months or more at room temperature, and stable for 1 month or more at 60 ° C., and no precipitate is generated in the sol, and the sol does not thicken or cause gelation. .

(D) Stable tungsten oxide-stannic oxide-silicon dioxide composite containing composite colloidal particles of tungsten oxide (WO ₃ ), stannic oxide (SnO ₂ ) and silicon dioxide (SiO ₂ ) obtained in the step (d) The method for producing body sol is, for example,
(D-1) Step: Tungstate, stannate and silicate were contained in a ratio of 0.1 to 100 as a WO ₃ / SnO ₂ weight ratio and 0.1 to 100 as a SiO ₂ / SnO ₂ weight ratio. It can manufacture by performing the process of preparing aqueous solution, and the process of removing the cation which exists in the aqueous solution obtained by the process (d-2) process (d-2).

Examples of tungstates, stannates and silicates used in step (d-1) include tungstates such as alkali metals, ammonium and amine, stannates and silicates. Preferable examples of these alkali metals, ammonium and amine include Li, Na, K, Rb, Cs, NH ₄ ⁺ , or ethylamine, triethylamine, isopropylamine, n-propylamine, isobutylamine, diisobutylamine, di (2- Examples thereof include alkylamines such as ethylhexyl) amine; aralkylamines such as benzylamine; alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine. In particular, sodium tungstate (Na ₂ WO ₄ .2H ₂ O), sodium stannate (Na ₂ SnO ₃ .3H ₂ O) and sodium silicate (water glass) are preferable. Moreover, what melt | dissolved tungsten oxide, tungstic acid, stannic acid, silicic acid, etc. in the aqueous solution of alkali metal hydroxide can be used. Moreover, amine silicates and quaternary ammonium silicates obtained by adding alkylamines such as ethylamine, triethylamine, isopropylamine, n-propylamine, isobutylamine, diisobutylamine, di (2-ethylhexyl) amine to active silicic acid as silicates. Can also be used.

(D-1) As the preparation method of the aqueous solution in the step, a method of preparing an aqueous solution by dissolving each powder of tungstate, stannate, and silicate in water, an aqueous solution of tungstate, an aqueous solution of stannate, and Examples thereof include a method of preparing an aqueous solution by mixing a silicate aqueous solution, a method of preparing an aqueous solution by adding a tungstate and stannate powder, and an aqueous solution of silicate to water.
The aqueous solution of tungstate used for the production of the sol in step (d) preferably has a concentration of 0.1 to 15% by weight as WO ₃ but can be used at a concentration higher than this.
As the aqueous solution of stannate used for the production of the sol in the step (d), a SnO ₂ concentration of about 0.1 to 30% by weight is preferable, but a concentration higher than this can also be used.
Further, the silicate aqueous solution used for the production of the sol in the step (d) preferably has a SiO ₂ concentration of about 0.1 to 30% by weight, but it can also be used at a higher concentration.
The aqueous solution in the step (d-1) is preferably prepared at room temperature to about 100 ° C., preferably at room temperature to about 60 ° C. with stirring. The aqueous solution to be mixed is preferably used such that the WO ₃ / SnO ₂ weight ratio is 0.1 to 100 and the SiO ₂ / SnO ₂ weight ratio is 0.1 to 100.

  Step (d-2) is a step of removing cations present in the aqueous solution obtained in step (d-1). As a method of decation treatment, a method of contacting with a hydrogen ion exchanger or salting out can be performed. The hydrogen-type cation exchanger used here is usually used. For example, a commercially available hydrogen-type cation exchange resin can be used.

When the concentration of the aqueous sol obtained through the steps (d-1) and (d-2) is low, the aqueous sol is subjected to an ordinary concentration method, for example, an evaporation method, an ultrafiltration method, or the like, if desired. The sol concentration can be increased. In particular, the ultrafiltration method is preferable. Also in this concentration, the temperature of the sol is preferably kept at about 100 ° C. or less, particularly 60 ° C. or less.
By replacing the water in the aqueous sol in step (d) with a hydrophilic organic solvent, a hydrophilic organic solvent sol called an organosol is obtained.

The tungsten oxide-stannic oxide-silicon dioxide composite sol obtained in the step (d) is an oxidation obtained by uniformly combining (solid solution) stannic oxide, tungsten oxide and silicon dioxide at the atomic level. It contains composite particles composed of tungsten-stannic oxide-silicon dioxide. Therefore, it cannot be obtained by simply mixing three kinds of sols of tungsten oxide sol, stannic oxide sol and silicon dioxide sol.
The composite sol of tungsten oxide-stannic oxide-silicon dioxide has a solid solution formed by the composite particles of tungsten oxide-stannic oxide-silicon dioxide. There is no decomposition into stannic particles and silicon dioxide particles.
Compared to the composite sol of tungsten oxide-stannic oxide-silicon dioxide, the composite sol of tungsten oxide-stannic oxide-silicon dioxide has water resistance, moisture resistance, and weather resistance when coated on a substrate to form a film. Improves.

As described above, the weight ratio of WO ₃ / SnO ₂ in the sol obtained in the step (d) is preferably 0.1 to 100. If the weight ratio is less than 0.1, the composition may be unstable. If the weight ratio exceeds 100, the sol may not exhibit stability. The oxycarboxylic acid added when making the organosol from the aqueous sol having a high pH also contributes to the stabilization of the sol, but the amount added is 30% by weight with respect to the total of WO ₃ , SnO ₂ and SiO _{2 in} the sol. If it is more than the above, the water resistance of the dried coating film obtained using such a sol will be reduced. Examples of the oxycarboxylic acid used include lactic acid, tartaric acid, citric acid, gluconic acid, malic acid, glycol and the like. Alkali components include alkali metal hydroxides such as Li, Na, K, Rb, and Cs, NH ₄ ⁺ , alkylamines such as ethylamine, triethylamine, isopropylamine, and n-propylamine; aralkyls such as benzylamine Examples include amines; alicyclic amines such as piperidine; alkanolamines such as monoethanolamine and triethanolamine. These can contain 2 or more types in mixture. Moreover, it can also use together with said acidic component. The pH of the sol changes according to the amount of alkali metal, ammonium, amine, oxycarboxylic acid, etc. in the sol. When the pH of the sol is less than 1, the sol is unstable. When the pH exceeds 9, the composite colloidal particles of tungsten oxide, stannic oxide and silicon dioxide are easily dissolved in the liquid. When the total concentration of WO ₃ , SnO ₂ and SiO _{2 in} the sol exceeds 40% by weight, the sol is still poor in stability. If this concentration is too thin, it is impractical and the preferred concentration for industrial products is 5 to 30% by weight.
When the ultrafiltration method is used as the concentration method, polyanions coexisting in the sol, ultrafine particles, etc. pass through the ultrafiltration membrane together with water, so these polyanions that cause destabilization of the sol, Very fine particles and the like can be removed from the sol.

The step (e) is obtained in the step (d) with 100 parts by weight of the stannic oxide-zirconium oxide composite aqueous sol obtained in the step (c) as the total of ZrO ₂ and SnO ₂ contained therein. Tungsten oxide-stannic oxide-silicon dioxide composite sol having a particle size of 2-7 nm, a WO ₃ / SnO ₂ weight ratio of 0.1-100 and a SiO ₂ / SnO ₂ weight ratio of 0.1-100 Is a step of mixing at 0 to 100 ° C. in a ratio of 2 to 100 parts by weight as the total of WO ₃ , SnO ₂ and SiO ₂ contained therein.
In step (e), the tungsten oxide-stannic oxide-silicon dioxide composite sol colloid particles are bonded to the colloidal particle surface of the stannic oxide-zirconium oxide composite sol, and the surface is bonded to the tungsten oxide-oxide. By coating with colloidal particles of stannic-silicon dioxide composite, the surface is modified so that the surface has the properties of tungsten oxide-stannic oxide-silicon dioxide composite with the colloidal particles as nuclei. Tin-zirconium oxide composite colloidal particles can be produced, and the modified stannic oxide-zirconium oxide composite colloidal particles can be obtained as a sol stably dispersed in a liquid medium.

The sols of these stannic oxide-zirconium oxide composite colloidal particles modified with colloidal particles of tungsten oxide-stannic oxide-silicon dioxide composite are used as the stannic oxide-zirconium oxide composite sol. 100 parts by weight as an oxide (ZrO ₂ + SnO ₂ ) and a ratio of 2 to 100 parts by weight of the above-mentioned tungsten oxide-stannic oxide-silicon dioxide composite sol as a total of WO ₃ , SnO ₂ and SiO ₂ In addition, it is preferably obtained by the step (e) of mixing under strong stirring, and then the step (f) of removing the anions in the sol from the mixed sol.

The modified stannic oxide-zirconium oxide composite colloidal particles in the sol obtained by mixing in the step (e) can be observed with an electron microscope and have a particle diameter of approximately 4.5 to 60 nm. . The sol obtained by the above mixing has a pH of approximately 1 to 9, but contains a large amount of anions such as Cl ⁻ , NO ₂ ⁻ and CH ₃ COO ⁻ derived from the oxyzirconium salt used for the modification. Due to the inclusion, the colloidal particles are microaggregated, and the transparency of the sol is low.
By removing the anion in step (f) from the anion in the sol obtained by the above mixing, a sol of modified stannic oxide-zirconium oxide composite colloidal particles having good transparency is obtained. Can do.

The anion removal in the step (f) is obtained by treating the sol obtained by the above mixing with a hydroxyl group anion exchange resin, usually at a temperature of 100 ° C. or lower, preferably room temperature to about 60 ° C. A commercially available product can be used as the hydroxyl type anion exchange resin, but a strong base type such as Amberlite IRA-410 is preferred.
The treatment with the hydroxyl group anion exchange resin in the step (f) is particularly preferably carried out at a metal oxide concentration of 1 to 10% by weight of the sol obtained by mixing in the step (e).

When it is desired to further increase the concentration of the modified stannic oxide-zirconium oxide composite sol obtained by the steps (a) to (f), a conventional method such as an evaporation method or an ultrafiltration method is used up to about 50% by weight. It can be concentrated by, for example. Further, when it is desired to adjust the pH of the sol, it can be performed by adding the alkali metal, ammonium hydroxide or the like, the amine, oxycarboxylic acid or the like to the sol after concentration. In particular, a sol having a total concentration of the metal oxide (ZrO ₂ + SnO ₂ ) and (WO ₃ + SnO ₂ + SiO ₂ ) of 10 to 50% by weight is practically preferable.
The colloidal particles in the modified stannic oxide-zirconium oxide composite sol obtained in the step (f) are silane compounds such as ethyl silicate, methyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or the like The surface can be partially or fully coated with the hydrolyzate.

When the modified stannic oxide-zirconium oxide composite sol obtained by the above mixing is an aqueous sol, an organosol can be obtained by replacing the aqueous medium of the aqueous sol with a hydrophilic organic solvent. This substitution can be performed by a usual method such as a distillation method or an ultrafiltration method. Examples of the hydrophilic organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; linear amides such as dimethylformamide and N, N′-dimethylacetamide; cyclic amides such as N-methyl-2-pyrrolidone And glycols such as ethyl cellosolve, propylene glycol monomethyl ether and ethylene glycol.
The replacement of the water with the hydrophilic organic solvent can be easily performed by a usual method such as a distillation replacement method or an ultrafiltration method.

  The surface is coated with the colloidal particles of the tungsten oxide-stannic oxide-silicon dioxide composite used in the present invention, and the modified stannic oxide-zirconium oxide composite colloidal particles are negatively charged in the sol. The colloidal particles of the stannic oxide-zirconium oxide composite are positively charged, and the colloidal particles of the tungsten oxide-stannic oxide-silicon dioxide composite are negatively charged. Therefore, the tungsten oxide-stannic oxide-silicon dioxide composite charged negatively around the positively charged stannic oxide-zirconium oxide composite colloidal particles by mixing in the step (e). The colloidal particles are electrically attracted, and the tungsten oxide-stannic oxide complex colloidal particles are bonded to the surface of the positively charged colloidal particles by chemical bonds. It is considered that the modified stannic oxide-zirconium oxide composite colloidal particles were formed by covering the colloidal particles of the stannic oxide-silicon dioxide composite.

However, when the stannic oxide-zirconium oxide composite colloidal particles having a particle diameter of 4 to 50 nm as the core sol and the tungsten oxide-stannic oxide-silicon dioxide composite colloidal particles as the coating sol are mixed, If the total amount of metal oxides (WO ₃ + SnO ₂ + SiO ₂ ) in the coating sol is less than 2 parts by weight with respect to 100 parts by weight of the metal oxides (ZrO ₂ and SnO ₂ ) in the sol, it is difficult to obtain a stable sol. . This means that when the amount of colloidal particles of tungsten oxide-stannic oxide-silicon dioxide composite is insufficient, the surface of the composite with colloidal particles of stannic oxide-zirconium oxide as the core It is considered that the resulting coating is insufficient, the resulting colloidal particles tend to aggregate and the resulting sol becomes unstable. Therefore, the amount of the tungsten oxide-stannic oxide-silicon dioxide composite colloidal particles to be mixed may be less than the amount covering the entire surface of the stannic oxide-zirconium oxide composite colloidal particles, but stable modified. The amount of stannic oxide-zirconium oxide composite colloidal particles is not less than the minimum amount necessary to form a sol. When an amount of tungsten oxide-stannic oxide-silicon dioxide composite colloidal particles exceeding the amount used for the surface coating is used for the above mixing, the resulting sol is tungsten oxide-stannic oxide-silicon dioxide. It is only a stable mixed sol of the composite colloidal particle sol and the resulting modified stannic oxide-zirconium oxide composite colloidal particle sol.
Preferably, to modify the stannic oxide-zirconium oxide composite colloidal particle by its surface coating, the amount of colloidal particles of tungsten oxide-stannic oxide-silicon dioxide composite used is the metal oxide of the core sol The total amount of metal oxides (WO ₃ + SnO ₂ + SiO ₂ ) in the coating sol is preferably 100 parts by weight or less with respect to 100 parts by weight of (ZrO ₂ + SnO ₂ ).

The preferred aqueous sol of the modified stannic oxide-zirconium oxide complex used in the present invention preferably has a pH of about 3-11. When the pH is lower than 3, such a sol tends to be unstable, and when this pH exceeds 11, the tungsten oxide-secondary oxide covering the modified stannic oxide-zirconium oxide composite colloidal particles. The tin-silicon dioxide composite is easily dissolved in the liquid. Further, when the total concentration of the metal oxide (ZrO ₂ + SnO ₂ ) and (WO ₃ + SnO ₂ + SiO ₂ ) in the sol of the modified stannic oxide-zirconium oxide composite colloidal particles exceeds 60% by weight. Such a sol tends to be unstable. A preferable concentration for industrial products is about 10 to 50% by weight.
Since the tungsten oxide-stannic oxide-silicon dioxide composite colloidal particles are susceptible to hydrolysis at high temperatures, mixing in (e) step, (f) anion exchange in step, and (f) concentration after step, pH In the case of adjustment, solvent substitution, etc., 100 ° C. or lower is preferable.

（式中、Ｒ¹³およびＲ¹⁴は、それぞれ同一または異なる炭素数１〜４のアルキル基または炭素数２〜４のアシル基、Ｒ¹⁵およびＲ¹⁶は、それぞれ同一または異なる一価の炭素数１〜５の官能基を有する若しくは有しない炭化水素基、Ｙは炭素数２〜２０の二価の炭化水素基、ａおよびｂは、それぞれ０または１を示し、複数のＲ¹³Ｏは、たがいに同一でも異なっていてもよいし、複数のＯＲ¹⁴はたがいに同一でも異なっていてもよい。）で表される化合物およびそれらの加水分解物の中から選ばれる少なくとも１種が挙げられる。(2) About organosilicon compound In the coating composition for obtaining the cured film concerning this invention, an organosilicon compound is used as (B) component. As this organosilicon compound, for example, the general formula (I)
R ¹¹ _k Si (OR ¹² ) _4-k (I)
(In the formula, R ¹¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may or may not have a functional group, R ¹² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the number of carbon atoms. 7-10 aralkyl or an acyl group having 2 to 10 carbon atoms, k represents 0, 1 or 2, when there are a plurality of R ¹¹ s, the R ¹¹ s may be the same with or different from each other, a plurality of OR ¹² may be the same or different.), the compound represented by the general formula (II)

Wherein R ¹³ and R ¹⁴ are the same or different alkyl groups having 1 to 4 carbon atoms or acyl groups having 2 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ are each the same or different monovalent carbon number 1 A hydrocarbon group having or not having a functional group of ˜5, Y is a divalent hydrocarbon group having 2 to 20 carbon atoms, a and b are each 0 or 1, and a plurality of R ¹³ O are Or a plurality of OR ¹⁴ may be the same or different.) And at least one selected from hydrolysates thereof.

In the general formula (I), the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, 2 to 2 carbon atoms. Examples thereof include 20 straight-chain, branched, and cyclic alkenyl groups, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. Here, as a C1-C20 alkyl group, a C1-C10 thing is preferable, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. Group, tert-butyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group and the like. Moreover, as a C2-C20 alkenyl group, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a butenyl group, a hexenyl group, an octenyl group etc. are mentioned. As a C6-C20 aryl group, a C6-C10 thing is preferable, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned. As a C7-20 aralkyl group, a C7-10 thing is preferable, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group etc. are mentioned.

  A functional group may be introduced into these hydrocarbon groups, and examples of the functional group include a halogen atom, a glycidoxy group, an epoxy group, an amino group, a mercapto group, a cyano group, and a (meth) acryloyloxy group. Can be mentioned. The hydrocarbon group having these functional groups is preferably an alkyl group having 1 to 10 carbon atoms having the functional group. For example, γ-chloropropyl group, 3,3,3-trichloropropyl group, chloromethyl group, Sidoxymethyl group, α-glycidoxyethyl group, β-glycidoxyethyl group, α-glycidoxypropyl group, β-glycidoxypropyl group, γ-glycidoxypropyl group, α-glycidoxy Butyl group, β-glycidoxybutyl group, γ-glycidoxybutyl group, δ-glycidoxybutyl group, (3,4-epoxycyclohexyl) methyl group, β- (3,4-epoxycyclohexyl) ethyl group , Γ- (3,4-epoxycyclohexyl) propyl group, δ- (3,4-epoxycyclohexyl) butyl group, N- (β-aminoethyl) -γ-aminopropyl group, γ Aminopropyl group, .gamma.-mercaptopropyl group, beta-cyanoethyl group, .gamma.-methacryloyloxy propyl, .gamma. acrylate such as acryloyloxy propyl group.

On the other hand, the alkyl group having 1 to 8 carbon atoms in R ¹² may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like. As the aryl group, for example, phenyl group, tolyl group and the like can be mentioned. Examples of the aralkyl group include a benzyl group and a phenethyl group. Moreover, as an acyl group, an acetyl group etc. are mentioned, for example.
n is 0, 1 or 2, when there are a plurality of R ¹¹ s, the R ¹¹ s may be mutually identical or different, also, a plurality of OR ¹² each other was the same It may be different or different.

  Examples of the compound represented by the general formula (I) include methyl silicate, ethyl silicate, n-propyl silicate, isopropyl silicate, n-butyl silicate, sec-butyl silicate, tert-butyl silicate, tetraacetoxysilane, methyl Trimethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxy Methyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyl Triethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyl Triethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyl Trimethoxysilane, δ-g Lysidoxybutyltriethoxysilane, (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) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltri Methoxysila , Δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethyl Methyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidyl Sidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, -Glycidoxypropylmethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxy Silane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriacetoxycin 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxy Silane, chloromethyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxy Run, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ -Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane and the like.

On the other hand, in the general formula (II), the alkyl group having 1 to 4 carbon atoms of R ¹³ and R ¹⁴ is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl group, and tert-butyl group. Preferred examples of the acyl group having 2 to 4 carbon atoms include an acetyl group. R ¹³ and R ¹⁴ may be the same or different. The hydrocarbon group of 1 to 5 carbon atoms of the monovalent represented by R ¹⁵ and R ^16, include alkyl and alkenyl groups having 2 to 5 carbon atoms of 1 to 5 carbon atoms. These may be either linear or branched, and examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl. Group, pentyl group, and the like. Examples of the alkenyl group include vinyl group, allyl group, and butenyl group.

A functional group may be introduced into these hydrocarbon groups, and the functional group and the hydrocarbon group having a functional group are the same as those exemplified in the description of R ^{11 in} the general formula (I). Can be mentioned. R ¹⁵ and R ¹⁶ may be the same or different. The divalent hydrocarbon group having 2 to 20 carbon atoms represented by Y is preferably an alkylene group or alkylidene group having 2 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, an ethylidene group, or a propylidene group. Groups and the like.
a and b each represent 0 or 1, and a plurality of R ¹³ Os may be the same or different, and a plurality of OR ¹⁴ may be the same or different.

  Examples of the compound represented by the general formula (II) include methylene bis (methyldimethoxysilane), ethylene bis (ethyldimethoxysilane), propylene bis (ethyldiethoxysilane), butylene bis (methyldiethoxysilane) and the like. It is done.

  In the coating composition for obtaining the cured film according to the present invention, the organosilicon compound as the component (B) is appropriately selected from the compounds represented by the general formulas (I) and (II) and hydrolysates thereof. You may select and use seed | species, You may select 2 or more types and may use them in combination. In addition, the hydrolyzate is added to the organic silicon compound represented by the general formulas (I) and (II) with a basic aqueous solution such as an aqueous solution of sodium hydroxide or ammonia, or an acidic aqueous solution such as an acetic acid aqueous solution or an aqueous citric acid solution. And can be prepared by stirring.

  Regarding the content ratio of the modified stannic oxide-zirconium oxide composite colloidal particles of the component (A) and the organosilicon compound of the component (B) in the coating composition for obtaining a cured film according to the present invention, the refractive index and From the viewpoint of obtaining good transparency, the component (A) is preferably contained in a proportion of 1 to 500 parts by weight as a solid content per 100 parts by weight of the component (B).

(3) Coating Composition Containing Colloidal Particles and Organosilicon Compound The coating composition for obtaining the cured film according to the present invention may contain a curing agent and various base materials to promote the reaction, if desired. In order to match the refractive index of the lens, it is possible to contain fine metal oxides, and various organic solvents and surfactants for the purpose of improving wettability during coating and improving the smoothness of the cured film. . Furthermore, ultraviolet absorbers, antioxidants, light stabilizers and the like can be added as long as they do not affect the physical properties of the cured film.

Examples of the curing agent include amines such as allylamine and ethylamine, and various acids and bases including Lewis acid and Lewis base, such as organic carboxylic acid, chromic acid, hypochlorous acid, boric acid, perchloric acid, bromine Examples include salts or metal salts having acid, selenious acid, thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminate, carbonic acid, metal alkoxides having aluminum, zirconium, titanium, or metal chelate compounds thereof. . A particularly preferred curing agent is an acetylacetonate metal salt from the viewpoint of scratch resistance. As the acetylacetonate metal salt, M ¹ (CH ₃ COCHCOCH ₃ ) n1 (OR ¹⁷ ) n2 (wherein M ¹ is Zn (II), Ti (IV), Co (II), Fe (II), Cr) (III), Mn (II), V (III), V (IV), Ca (II), Co (III), Cu (II), Mg (II), Ni (II), R ¹⁷ has 1 carbon atom 8 hydrocarbon group, n1 + n2 is 2, 3 or 4 with a number corresponding to the valence of M ^1, n2 can be mentioned a metal complex compound represented by 0, 1 or 2.). Examples of R ¹⁷ include those having 1 to 8 carbon atoms among the hydrocarbon groups having 1 to 10 carbon atoms exemplified in the general formula (I).

  Examples of the fine particle metal oxide include conventionally known fine particles such as aluminum oxide, titanium oxide, antimony oxide, zirconium oxide, silicon oxide, cerium oxide, and iron oxide.

  Curing of the coating composition is usually performed by hot air drying or active energy ray irradiation, and the curing condition is preferably 70 to 200 ° C. in hot air, particularly preferably 90 to 150 ° C. Active energy rays include far infrared rays and the like, and damage due to heat can be kept low.

Examples of the method for forming the cured film on the substrate using the coating composition described above include a method of applying the coating composition described above to the substrate. As a coating means, a commonly performed method such as a dipping method, a spin coating method, and a spray method can be applied, but the dipping method and the spin coating method are particularly desirable in terms of surface accuracy.
Furthermore, before applying the coating composition described above to the substrate, the substrate is chemically treated with acid, alkali, various organic solvents, physical treatment with plasma, ultraviolet rays, detergent treatment using various detergents, sandblast treatment, Can improve the adhesion between the base material and the cured film by applying a primer treatment using various resins.

3. Antireflection film The antireflection film used in the present invention is formed by a vacuum deposition method. Moreover, in order to obtain favorable film | membrane intensity | strength and adhesiveness, it is preferable to form by the ion assist method. The film constituent layers other than the hybrid layer of the antireflection film are not particularly limited, but in order to obtain physical properties such as a good antireflection effect, a SiO ₂ layer or a mixture of SiO ₂ and Al ₂ O ₃ as a low refractive index layer It is preferable to have an Nb ₂ O ₅ layer or a TiO ₂ layer as a layer or a high refractive index layer. The inorganic substance used in the hybrid layer in the present invention is at least one selected from silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tantalum oxide, yttrium oxide and niobium oxide, and contains silicon dioxide. Is preferred. These may be used alone or in combination. When a plurality of inorganic substances are used, they may be physically mixed or may be a composite oxide, specifically, SiO ₂ —Al ₂ O ₃ or the like.

In the present invention, the organic material used in the hybrid layer is an organic silicon compound in a liquid state at room temperature and normal pressure and / or liquid at room temperature and normal pressure from the viewpoint of film thickness control and vapor deposition rate control. A silicon-free organic compound is used.
The organosilicon compound preferably has a structure represented by any of the following general formulas (a) to (d), for example.

Formula (a): Silane or siloxane compound

General formula (b): Silazane compound

General formula (c): cyclosiloxane compound

General formula (d): cyclosilazane compound

In the general formulas (a) to (d), m and n in the formula each independently represent an integer of 0 or more. X _{1 to} X ₈ are each independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms (including both saturated and unsaturated), —OR ¹ group, —CH ₂ OR ² group, —COOR ³ group, — OCOR ⁴ group, -SR ⁵ group, -CH ₂ SR ⁶ group, -NR ⁷ ₂ group, or, -CH ₂ NR ⁸ ₂ group (R ¹ to R ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms ( X _{1 to} X ₈ may be any functional group as described above, all may be the same functional group, or part or all may be different from each other. Things are not limited.
Specific examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ^{1 to} R ⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group. Group, vinyl group, allyl group, ethynyl group, phenyl group, cyclohexyl group, propynyl group, isopropenyl group and the like.

  Specific compounds represented by the general formula (a) include trimethylsilanol, diethylsilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxysilane, tetramethoxy Silane, mercaptomethyltrimethylsilane, aminomethyltrimethylsilane, dimethyldimethylaminosilane, ethynyltrimethylsilane, diacetoxymethylsilane, allyldimethylsilane, trimethylvinylsilane, methoxydimethylvinylsilane, acetoxytrimethylsilane, trimethoxyvinylsilane, diethylmethylsilane, ethyltrimethyl Silane, ethoxytrimethylsilane, diethoxymethylsilane, ethyltrimethoxysilane Lan, dimethylaminotrimethylsilane, bis (dimethylamino) methylsilane, phenylsilane, dimethyldivinylsilane, 2-propynyloxytrimethylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, allyltrimethylsilane, allyloxytrimethylsilane, ethoxydimethyl Vinylsilane, isopropenoxytrimethylsilane, allylaminotrimethylsilane, trimethylpropylsilane, trimethylisopropylsilane, triethylsilane, diethyldimethylsilane, butyldimethylsilane, trimethylpropoxysilane, trimethylisopropoxysilane, triethylsilanol, diethoxydimethylsilane, propyl Trimethoxysilane, diethylaminodimethylsilane, bis (ethylamino) dimethyl Silane, bis (dimethylamino) dimethylsilane, tri (dimethylamino) silane, methylphenylsilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, allyloxydimethylvinylsilane, diethylmethylvinylsilane, diethoxymethylvinylsilane, bis (Dimethylamino) methylvinylsilane, butyldimethylhydroxymethylsilane, 1-methylpropoxytrimethylsilane, isobutoxytrimethylsilane, butoxytrimethylsilane, butyltrimethoxysilane, methyltriethoxysilane, isopropylaminomethyltrimethylsilane, diethylaminotrimethylsilane, methyltri (Dimethylamino) silane, dimethylphenylsilane, tetravinylsilane, triacetoxybi Silane, tetraacetoxysilane, ethyltriacetoxysilane, diallyldimethylsilane, 1,1-dimethylpropynyloxytrimethylsilane, diethoxydivinylsilane, butyldimethylvinylsilane, dimethylisobutoxyvinylsilane, acetoxytriethylsilane, triethoxyvinylsilane, tetraethylsilane , Dimethyldipropylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, ethyltriethoxysilane, tetraethoxysilane, methylphenylvinylsilane, phenyltrimethylsilane, dimethylhydroxymethylphenylsilane, phenoxytrimethylsilane, dimethoxymethylphenylsilane, phenyltri Methoxysilane, anilinotrimethylsilane, 1-cyclohexenyloxytrimethylsilane Cyclohexyloxytrimethylsilane, dimethylisopentyloxyvinylsilane, allyltriethoxysilane, tripropylsilane, butyldimethyl-3-hydroxypropylsilane, hexyloxytrimethylsilane, propyltriethoxysilane, hexyltrimethoxysilane, dimethylphenylvinylsilane, trimethylsilylbenzo Nate, dimethylethoxyphenylsilane, methyltriisopropenoxysilane, methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, diacetoxymethylphenylsilane, diethylmethyl Phenylsilane, diethoxymethylphenylsilane, triisopropoxyvinylsilane, 2-ethylhexylo Sitrimethylsilane, Pentillytriethoxysilane, Diphenylsilane, Phenyltrivinylsilane, Triethylphenylsilane, Phenyltriethoxysilane, Tetraallyloxysilane, Phenyltri (dimethylamino) silane, Tetrapropoxysilane, Tetraisopropoxysilane, Diphenylmethylsilane Diallylmethylphenylsilane, dimethyldiphenylsilane, dimethoxydiphenylsilane, diphenylethoxymethylsilane, tripentyloxysilane, diphenyldivinylsilane, diacetoxydiphenylsilane, diethyldiphenylsilane, diethoxydiphenylsilane, bis (dimethylamino) diphenylsilane, Tetrabutylsilane, tetrabutoxysilane, triphenylsilane, diallyldiphenylsilane, Hexylsilane, triphenoxyvinylsilane, 1,1,3,3-tetramethyldisiloxane, pentamethyldisiloxane, hexamethyldisiloxane, 1,3-dimethoxytetramethyldisiloxane, 1,3-diethynyl-1,1, 3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxytetramethyldisiloxane, hexaethyldisiloxane, 1,3-dibutyl- Examples include compounds such as 1,1,3,3-tetramethyldisiloxane.

Specific compounds represented by the general formula (b) include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetramethyl. And compounds such as disilazane.
Specific compounds represented by the general formula (c) include hexamethylcyclotrisiloxane, 1,1,3,3,5,5-hexamethylcyclotrisilazane, hexaethylcyclotrisiloxane, 1,3,5 , 7-tetramethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, and the like.
Specific examples of the compound represented by the general formula (d) include compounds such as 1,1,3,3,5,5,7,7-octamethylcyclotetrasilazane.

  The number average molecular weights of these organosilicon compounds are preferably 48 to 600, particularly preferably 140 to 500, from the viewpoint of controlling the organic components in the hybrid film and the strength of the film itself.

  Next, as the silicon-free organic compound constituting the hybrid layer, those containing carbon and hydrogen containing reactive groups at their side chains or terminals as essential components, or those containing a double bond are preferred. Specifically, compounds represented by the general formulas (e) to (g) are preferably used.

General formula (e): silicon-free organic compound containing carbon and hydrogen having an epoxy group at one end as essential components

General formula (f): Silicon-free organic compound containing carbon and hydrogen having epoxy groups at both ends as essential components

General formula (g): a silicon-free organic compound containing carbon and hydrogen as essential components, including a double bond

(In the general formulas (e) and (f), R ⁹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms which may contain oxygen, and R ¹⁰ has 1 to 7 carbon atoms which may contain oxygen. In the general formula (g), X _{9 to} X ₁₂ are each composed of hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or carbon and hydrogen having 1 to 10 carbon atoms as essential components. And an organic group having at least one of oxygen and nitrogen as an essential component)

  Specific examples of the compound of the general formula (e) include methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-sec-butylphenyl glycidyl. Examples include ether, p-tert-butylphenyl glycidyl ether, 2-methyloctyl glycidyl ether, glycidol, and trimethylolpropane polyglycidyl ether.

  Specific examples of the compound of the general formula (f) include neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol. Examples thereof include diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether.

Specific examples of the compound of the general formula (g) include ethylene, propylene, vinyl chloride, vinyl fluoride, acrylamide, vinyl pyrrolidone, vinyl carbazole, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dimethyl. Examples include aminoethyl methacrylate, methacrylic acid, glycidyl methacrylate, vinyl acetate, and styrene.
In addition, the number average molecular weight of the compounds represented by the general formulas (e) to (g) is preferably 28 to 400, particularly preferably, considering the control of organic components in the hybrid film and the film strength of the hybrid. Is 140-360.

As a method for forming an organic silicon compound that is liquid at room temperature and pressure and / or a silicon-free organic compound that is liquid at room temperature and pressure (hereinafter sometimes referred to as “organic material”) in the antireflection film of the present invention. As shown in FIG. 1, when forming a hybrid layer, it is preferable to form a film by simultaneously depositing an inorganic substance and an organic substance in separate vapor deposition sources. Specifically, the inorganic substance is vaporized by heating using an electron gun or the like, the organic substance is stored in an external tank, the organic substance is vaporized in the tank, and the inorganic substance and the organic substance are vapor-deposited simultaneously. The method is preferred.
From the viewpoint of controlling the deposition rate, it is preferable to heat / depressurize the external tank for storing the organic material, supply the organic material into the chamber, and perform ion-assisted film formation using oxygen gas and / or argon gas. . Further, in the present invention, the organic substance is a liquid at normal temperature and normal pressure, and it is not necessary to use a solvent, and it can be directly heated and deposited. Further, as shown in FIG. 1, it is effective to improve the impact resistance and wear resistance of the organic substance introduction port as shown in FIG. The non-containing organic compound is preferably supplied from the top.
The heating temperature of the external tank varies depending on the evaporation temperature of the organic substance, but is preferably 30 to 200 ° C., preferably 50 to 150 ° C. from the viewpoint of obtaining an appropriate deposition rate.
A preferable in-film content of the organic material of the hybrid layer in the present invention is 0.02% by mass to 25% by mass in consideration of a particularly good physical property modification effect.

As a structure of the multilayer antireflection film formed on the plastic substrate in the present invention, a hybrid layer is used as at least one layer of the film structure.
The hybrid layer can be formed in any layer in the multilayer antireflection film. The hybrid layer can be formed into a plurality of layers. As a preferable position of the hybrid layer, in order to obtain particularly excellent impact resistance, it is preferable to apply the hybrid layer at a position closest to the lens base material and / or a position farthest from the lens base material. Further, in order to obtain particularly excellent adhesion, it is preferably formed by an ion assist method.
In the ion assist method, a preferable range for the output is an acceleration voltage of 50 to 700 V and an acceleration current of 30 to 250 mA, particularly from the viewpoint of obtaining a good reaction. It is preferable to use argon (Ar) or a mixed gas of argon and oxygen as the ionization gas used when performing the ion assist method from the viewpoint of reactivity during film formation and oxidation prevention.

The preferred film thickness and refractive index range of the preferred antireflection film in the present invention are as follows. The first layer is the layer closest to the plastic substrate.
1st layer 0.005λ ~ 1.25λ 1.41 ~ 1.50
Second layer 0.005λ to 0.10λ 2.00 to 2.35
3rd layer 0.005λ ~ 1.25λ 1.41 ~ 1.50
4th layer 0.05λ to 0.45λ 2.00 to 2.35
5th layer 0.005λ to 0.15λ 1.41 to 1.50
6th layer 0.05λ to 0.45λ 2.00 to 2.35
7th layer 0.2λ ~ 0.29λ 1.41 ~ 1.50

Further, from the viewpoint of scratch resistance, preferred compositions of the first layer to the seventh layer are as follows.
First layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic material containing silicon dioxide as a deposition material. Second layer: a layer containing a tantalum oxide layer of at least 50% by weight based on the second layer Third layer: an organosilicon compound that is liquid at normal temperature and normal pressure and / or liquid at normal temperature and normal pressure Hybrid layer formed using a silicon-free organic compound and an inorganic substance containing silicon dioxide as a deposition raw material. Fourth layer: a layer in which the tantalum oxide layer contains at least 50% by weight based on the fourth layer Fifth layer: a hybrid formed using an organic silicon compound that is liquid at room temperature and pressure and / or a silicon-free organic compound that is liquid at room temperature and pressure and an inorganic material containing silicon dioxide as a deposition material Layer Sixth layer: Layer containing at least 50% by weight of tantalum oxide layer based on the sixth layer Seventh layer: Organosilicon compound that is liquid at normal temperature and normal pressure and / or Liquid at normal temperature and normal pressure A hybrid layer formed using a silicon-free organic compound and an inorganic substance containing silicon dioxide as vapor deposition materials

4. Water-repellent film The water-repellent film is provided on the outermost layer of the antireflection film, and is formed using a fluorine-substituted alkyl group-containing organosilicon compound as a raw material. The raw material and the forming method are preferably those described in European Patent Publication No. 1351071. As the method, the fluorine-substituted alkyl group-containing organosilicon compound diluted with a solvent is subjected to deposition from the start of heating under reduced pressure within a range not less than the deposition start temperature of the organosilicon compound and not exceeding the decomposition temperature of the organosilicon compound. It is completed within seconds, preferably within 10 seconds. As a method for achieving such a deposition time, a method of irradiating the organic silicon compound with an electron beam is preferably used.

（式中、Rfは炭素数１〜１６の直鎖状のパーフルオロアルキル基、Ｘは水素または炭素数１〜５の低級アルキル基、Ｒ¹⁸は加水分解可能な基、tは１〜５０の整数、ｒは０〜２の整数、ｐは１〜１０の整数）
Ｃ_qＦ_2q+1ＣＨ₂ＣＨ₂Ｓｉ（ＮＨ₂）₃ ・・・（ｉ）
（ただし、ｑは１以上の整数である）
ここで、上記Ｒ¹⁸で示される加水分解可能な基としてはアミノ基、アルコキシ基、特にアルキル部が炭素数１〜２であるアルコキシ基、塩素原子等が挙げられる。
また、上記式（ｉ）で表される化合物の具体例としては、ｎ−CF₃CH₂CH₂Si(NH₂)₃；ｎ−トリフロロ（１，１，２，２−テトラヒドロ）プロピルシラザン、ｎ−C₃F₇CH₂CH₂Si(NH₂)₃；ｎ−ヘプタフロロ（１，１，２，２−テトラヒドロ）ペンチルシラザン、ｎ−C₄F₉CH₂CH₂Si(NH₂)₃；ｎ−ノナフロロ（１，１，２，２−テトラヒドロ）ヘキシルシラザン、ｎ−C₆F₁₃CH₂CH₂Si(NH₂)₃；ｎ−トリデオフロロ（１，１，２，２−テトラヒドロ）オクチルシラザン、ｎ−C₈F₁₇CH₂CH₂Si(NH₂)₃；ｎ−ヘプタデカフロロ（１，１，２，２−テトラヒドロ）デシルシラザン等を例示することができる。As the fluorine-substituted alkyl group-containing organosilicon compound, those represented by the following general formula (h) or those represented by the following unit formula (i) are preferable.

Wherein Rf is a linear perfluoroalkyl group having 1 to 16 carbon atoms, X is hydrogen or a lower alkyl group having 1 to 5 carbon atoms, R ¹⁸ is a hydrolyzable group, and t is 1 to 50 An integer, r is an integer of 0-2, p is an integer of 1-10)
C _q F _{2q + 1} CH ₂ CH ₂ Si (NH ₂ ) ₃ (i)
(However, q is an integer of 1 or more)
Here, examples of the hydrolyzable group represented by R ¹⁸ include an amino group, an alkoxy group, particularly an alkoxy group having an alkyl part of 1 to 2 carbon atoms, a chlorine atom, and the like.
Specific examples of the compound represented by the formula (i) include n-CF ₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ; n-trifluoro (1,1,2,2-tetrahydro) propylsilazane, _{n-C 3 F 7 CH 2} CH 2 Si (NH 2) 3; n- Heputafuroro (1,1,2,2-tetrahydro) _{Penchirushirazan, n-C 4 F 9 CH} 2 CH 2 Si (NH 2) 3 N-nonafluoro (1,1,2,2-tetrahydro) hexylsilazane, nC ₆ F ₁₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ; n-tridefluoro (1,1,2,2-tetrahydro) octyl _{silazanes, n-C 8 F 17 CH} 2 CH 2 Si (NH 2) 3; n- Heputadekafuroro (1,1,2,2-tetrahydro) Deshirushirazan like can be exemplified.

  Further, as a raw material for the water repellent layer, a raw material mainly composed of two components of a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether can be used, and further, these materials are used. A water repellent layer may be formed by forming a first layer and forming a second layer using a raw material mainly composed of silicon-free perfluoropolyether in contact with the first layer. Is preferred.

The silicon-free perfluoropolyether has the following structural formula (j) that does not contain silicon.
− (R ¹⁹ O) − (j)
(In the formula, R ¹⁹ is a perfluoroalkylene group having 1 to 3 carbon atoms)
Are preferably used, and those having an average molecular weight of 1000 to 10000, particularly 2000 to 10000 are preferred. R is a perfluoroalkylene group having 1 to 3 carbon atoms, and specific examples thereof include CF ₂ , CF ₂ -CF ₂ , CF ₂ CF ₂ CF ₂ , and CF (CF ₃ ) CF ₂ . These perfluoropolyethers are liquid at room temperature and are called so-called fluorine oils.

  In addition, the optical member of the present invention has a catalytic action when forming a hybrid layer, which will be described later, such as nickel (Ni), silver, etc. A layer made of at least one selected from (Ag), platinum (Pt), niobium (Nb), and titanium (Ti) can be applied. A particularly preferable undercoat layer is a metal layer made of niobium in order to give better impact resistance. When a metal layer is used as the underlayer, the reaction of the hybrid layer provided on the underlayer is facilitated, a substance having an intramolecular stitch structure is obtained, and impact resistance is improved.

5. Primer layer In the present invention, it is not denied that a primer layer composed of an organic compound is applied between a plastic substrate and a cured film, as described in JP-A-63-141001, etc. In order to further improve impact resistance, a primer layer made of an organic compound as a raw material may be provided between the plastic substrate and the cured coating.
Examples of the primer layer include those that form a urethane film using polyisocyanate and polyol as raw materials. Examples of polyisocyanates include hexamethylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate combined with various molecules, isocyanurate, allophanate, burette, carbodiimide, acetoacetic acid, Examples of the polyol include those blocked with malonic acid, methyl ethyl ketoxime, and the like. On the other hand, examples of the polyol include polyester, polyether, polycaprolactone, polycarbonate, and polyacrylate having a plurality of hydroxyl groups in one molecule. Moreover, in order to improve the refractive index of the primer layer, metal oxide fine particles such as titanium oxide fine particles can be contained in the primer layer.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
In addition, the physical property evaluation of the optical member obtained in the Example and the comparative example was performed as follows.
(1) Luminous transmittance luminous transmittance Y ₁ of the plastic lens, a plastic lens having an antireflection film on both surfaces as a sample was measured using a Hitachi spectrophotometer U-3410.
The luminous reflectance Y ₂ (2) luminous reflectance plastic lens, a plastic lens having an antireflection film on both surfaces as a sample was measured using a Hitachi spectrophotometer U-3410.
(3) Adhesion Create 100 squares of 1mm x 1mm with a razor on the surface of a plastic lens, apply cellophane tape (manufactured and sold by Nichiban Co., Ltd.) on the squares, remove the tape at once, and evaluate by the number of squares remaining did. In the table, it is described as the number of remaining squares / 100.
(4) Abrasion resistance A 98 kPa (1 kgf / cm ² ) load was applied to the surface of the plastic lens with steel wool (standard # 0000, manufactured by Nippon Steel Wool Co., Ltd.), and the surface was rubbed for 10 strokes. did.
UA: Almost no scratches A: Some thin scratches B: Many thin scratches, some thick scratches C: Many thin scratches, many thick scratches D: Almost film flaking (5) Heat resistance Plastic lens in a dry oven The temperature was raised from 60 ° C. by 5 ° C. and heat-treated for 1 hour, and the cracking temperature was measured.
(6) Alkali resistance Plastic lenses were immersed in a 10% NaOH aqueous solution at 20 ° C. for 1 hour, and evaluated according to the following criteria depending on the surface condition.
UA: Almost no change A: There are several point-shaped film baldness B: There are dot-shaped film baldness on the entire surface C: There are dot-shaped baldness on the entire surface, several sheet-shaped baldness D: Almost all film baldness (7 ) Bayer Value Measurement Using a wear tester BTE ^™ Abrasion Tester (manufactured by COLTS, USA) and a haze value measuring device (Murakami Color Research Laboratory), the Bayer value was measured by the difference in haze value change from the reference lens.
(Number of samples, measuring method)
(A) Three reference lenses (CR39 base material) and three sample lenses were prepared.
(B) The haze value before wear test was measured.
(C) Abrasion test was performed with BTE ^™ Abrasion Tester.
(Surface wear due to sand 600 round trips)
(D) The haze value was measured after the wear test.
(E) The Bayer value was calculated (the average value for three sheets). Here, the Bayer value is expressed by the change in transmittance of the reference lens / change in transmittance of the sample lens.
(8) Mechanical strength test (JIS static pressure test)
A test was conducted by the method described in JIS T 7331: 2000 to determine whether it had the mechanical strength described in the general requirements of JIS (Japanese Industrial Standard) T 7331: 2000.

Production Example 1
(1) Production of modified stannic oxide-zirconium oxide composite colloidal particles (a) step 37.5 kg of oxalic acid ((COOH) ₂ .2H ₂ O) was dissolved in 363 kg of pure water, The container was heated to 70 ° C. with stirring, and 150 kg of 35% hydrogen peroxide water and 75 kg of metal tin (manufactured by Yamaishi Metal Co., Ltd., AT-SN, No200N) were added.
Hydrogen peroxide solution and metallic tin were added alternately. First, 10 kg of 35% hydrogen peroxide solution was added, and then 5 kg of metallic tin. This operation was repeated after the reaction was completed (5 to 10 minutes). The time required for the addition was 2.5 hours. After the addition was completed, 10 kg of 35% aqueous hydrogen peroxide was further added, followed by heat treatment at 90 ° C. for 1 hour to complete the reaction. The molar ratio of aqueous hydrogen peroxide to metallic tin was 2.60 for H ₂ O ₂ / Sn.
The obtained tin oxide sol had very good transparency. The yield of the tin oxide sol was 626 kg, the specific gravity was 1.154, the pH was 1.56, and the SnO ₂ concentration was 14.9%. Moreover, when the obtained sol was observed with an electron microscope, it was 10-15 nm spherical particles with good dispersibility. This sol showed a slight tendency to thicken upon standing, but no gelation was observed and it was stable.
The obtained sol (626 kg) was diluted with pure water to 5 wt% as SnO ₂ , added with 4.66 kg of isopropylamine, and passed through a column packed with an anion exchange resin (Amberlite IRA-410). The solution was aged by heating at 0 ° C. for 1 hr, and further passed through a column packed with an anion exchange resin (Rohm & Haas, trade name: Amberlite IRA-410) to obtain 2535 kg of an alkaline tin oxide sol. Subsequently, the obtained sol was heat-treated at 140 ° C. for 5 hours.

(B) Step 300 kg of pure water and 3.3 kg of 35% hydrochloric acid were added to 78.2 kg (containing 13.8 kg of ZrO ₂ ) of an aqueous zirconium oxychloride solution (ZrO ₂ concentration was 17.68 wt%), and then Under stirring, 2529 kg of the alkaline stannic oxide aqueous sol obtained in the step (a) (91.0 kg as SnO ₂ ) was added at room temperature. The mixed solution was a sol having a colloidal color with a ZrO ₂ / SnO ₂ weight ratio of 0.15 and good transparency.

(C) Process The mixed liquid prepared at the (b) process was heat-processed at 95 degreeC for 5 hours, stirring, and 3471 kg of stannic oxide-zirconium oxide composite sol was obtained. The sol had 2.62% by weight SnO _2, 0.40% by weight as ZrO _2, has a colloidal color at 3.01 wt% as SnO ₂ + ZrO _2, the transparency was good.

Step (d) No. 3 diatomaceous (containing 29.3 wt% as SiO _2.) 49.8kg was dissolved in pure water 898Kg, then sodium tungstate _{Na 2 WO 4 · 2H 2 O} (WO 3 as 69. 10.5 kg (containing 8 wt%) and 13.1 kg sodium stannate NaSnO ₃ .H ₂ O (containing 55.7 wt% as SnO ₂ ) were dissolved. Next, this was passed through a column of hydrogen-type cation exchange resin (Rohm & Haas, trade name: Amberlite IR-120B), whereby an acidic tungsten oxide-stannic oxide-silicon dioxide composite sol (pH 2.0, WO ₃ As 0.6 wt%, SnO ₂ as 0.6 wt%, SiO ₂ as 1.2 wt%, WO ₃ / SnO ₂ weight ratio 1.0, SiO ₂ / SnO ₂ weight ratio 2.0 1179 kg was obtained.

(E) Step (c) The tungsten oxide-stannic oxide-silicon dioxide composite sol prepared in step (1179 kg) (containing 29.2 kg as WO ₃ + SnO ₂ + SiO ₂ ) is stirred at room temperature (c ) 3471 kg of stannic oxide-zirconium oxide composite sol prepared in step (containing 104.8 kg as ZrO ₂ + SnO ₂ ) was added in 60 minutes, and stirring was continued for 10 minutes. The resulting mixed liquid had a ratio of stannic oxide-zirconium oxide composite colloidal particles (ZrO ₂ + SnO ₂ ) to tungsten oxide-stannic oxide-silicon dioxide composite colloidal particles (WO ₃ + SnO ₂ + SiO ₂ ) (WO ₃ + SnO ₂ + SiO ₂ ) / (ZrO ₂ + SnO ₂ ) by weight ratio of 0.25, and the total metal oxide was 2.9% by weight.

Step (f) 2.3 kg of diisobutylamine was added to 4650 kg of the mixed solution obtained in step (e), and the solution was passed through a column packed with a hydroxyl-type anion exchange resin (supra: Amberlite IRA-410) at room temperature. Next, a modified stannic oxide-zirconium oxide composite aqueous sol (dilute liquid) was obtained by heating and aging at 90 ° C. for 1 hour. This sol had a pH of 9.10 and exhibited a colloidal color but had good transparency.

(F) The modified stannic oxide-zirconium oxide composite aqueous sol obtained in the step (dilute liquid) is concentrated at 40 to 50 ° C. with a filtration device of an ultrafiltration membrane having a fractional molecular weight of 100,000, A high concentration modified stannic oxide-zirconium oxide composite aqueous sol (358 kg) was obtained. This sol was stable with 31.9% by weight of all metal oxides (ZrO ₂ + SnO ₂ + WO ₃ + SiO ₂ ).
While stirring the above high-concentration modified stannic oxide-zirconium oxide composite aqueous sol 358 kg at room temperature, 1.1 kg of tartaric acid, 1.7 kg of diisobutylamine, an antifoaming agent (manufactured by San Nopco, trade name: SN Former 483) 1 drop was added and stirred for 1 hour. This sol was distilled in a reaction vessel equipped with a stirrer under normal pressure while adding 5010 liters of methanol to distill water off, so that 220 g of a modified stannic oxide-zirconium oxide complex methanol sol in which the water in the aqueous sol was replaced with methanol. Got. This sol has a specific gravity of 1.280, a pH of 6.59 (equal mixture with water), a viscosity of 2.1 mPa · s, a total metal oxide (ZrO ₂ + SnO ₂ + WO ₃ + SiO ₂ ) of 42.8% by weight, and a water content of 0 The particle diameter was 10 to 15 nm as observed by an electron microscope.
This aqueous sol having a total metal oxide (ZrO ₂ + SnO ₂ + WO ₃ + SiO ₂ ) concentration of 46.8% by weight was placed in a 100 cc graduated cylinder. The viscosity measured at 60 rpm using one rotor was 6.3 mPa · s.
The sol had a colloidal color, high transparency, and was stable at room temperature with no formation of precipitates, white turbidity, thickening, and the like. The refractive index of the dried sol was 1.85.

Comparative production example 1
Production of modified stannic oxide-zirconium oxide composite sol <Preparation of stannic oxide sol> Specific gravity obtained by reaction of tin metal powder, aqueous hydrochloric acid solution and aqueous hydrogen peroxide solution, pH 1.40, immediately after stirring Viscosity of 32 mPa · s, SnO ₂ content 33.0% by weight, HCl content 2.56% by weight, spindle colloidal particle diameter of 10 nm or less by electron microscope, specific surface area of particles by BET method 120 m ² / g, from this specific surface area After a dispersion of 1200 g of a light yellow transparent stannic oxide aqueous sol in a water-dispersible stannic oxide aqueous sol of 7.2 nm, a dynamic light scattering method particle diameter of 107 nm using a N4 apparatus manufactured by Coulter, USA, in 10800 g of water, 8 g was added, and then this liquid was passed through a column filled with a hydroxyl group-type anion exchange resin to obtain an alkaline stannic oxide aqueous sol 1 3440 g was obtained. This sol is stable and has a colloidal color, but is very transparent, specific gravity 1.029, pH 9.80, viscosity 1.4 mPa · s, SnO ₂ content 2.95% by weight, isopropylamine The content was 0.036% by weight.

(A) containing 60.87g zirconium oxychloride step reagent (ZrOCl ₂ · 8H ₂ O) aqueous solution of zirconium oxychloride was prepared by dissolving in water (2.0 wt% as ZrO ₂₎ as 3043g (ZrO _2. ) While stirring, 10791 g of alkaline stannic oxide aqueous sol (409.5 g as SnO ₂ ) prepared above was added at room temperature and stirring was continued for 2 hours. The mixed solution was a sol having a colloidal color with a ZrO ₂ / SnO ₂ weight ratio of 0.15 and a pH of 1.50 and having good transparency.

(B) Step (Preparation of stannic oxide-zirconium oxide composite sol)
The mixed solution prepared in step (a) was heat-treated at 90 ° C. for 5 hours with stirring to obtain 13834 g of a stannic oxide-zirconium oxide composite sol. The sol had 2.96% by weight SnO _2, 0.44% by weight as ZrO _2, SnO ₂ + ZrO ₂ as 3.40 wt%, in PH1.45, particle size 9.0 nm, have a colloidal color, transparent The property was good.

Step (c) (Preparation of tungsten oxide-stannic oxide-silicon dioxide composite sol)
113 g of No. 3 silica (containing 29.0% by weight as SiO ₂ ) was dissolved in 2353.7 g of water, and then sodium tungstate Na ₂ WO ₄ .2H ₂ O (containing 71% by weight as WO ₃ ). 33.3 g and 42.45 g of sodium stannate NaSnO ₃ .H ₂ O (containing 55% by weight as SnO ₂ ) are dissolved. Then, this was passed through a column of a hydrogen-type cation exchange resin, whereby an acidic tungsten oxide-stannic oxide-silicon dioxide composite sol (pH 2.1, 0.75 wt% as WO ₃ , 0.75 as SnO _2). 3% by weight, containing 1.00% by weight as SiO ₂ , WO ₃ / SnO ₂ weight ratio 1.0, SiO ₂ / SnO ₂ weight ratio 1.33, and particle size 2.5 nm.) Got.

Step (d) Step (c) The tungsten oxide-stannic oxide-silicon dioxide composite sol 3150 g (containing 78.83 g as WO ₃ + SnO ₂ + SiO ₂ ) prepared in step (c) is stirred at room temperature (b ) 11592.6 g of stannic oxide-zirconium oxide composite sol prepared in step (containing 394.1 g as ZrO ₂ + SnO ₂ ) was added in 20 minutes, and stirring was continued for 30 minutes. The resulting mixed liquid had a ratio of stannic oxide-zirconium oxide composite colloid (ZrO ₂ + SnO ₂ ) to tungsten oxide-stannic oxide-silicon dioxide composite colloid (WO ₃ + SnO ₂ + SiO ₂ ) (WO ₃ + SnO ₂ + SiO ₂ ) / (ZrO ₂ + SnO ₂ ) Weight ratio was 0.20, pH was 2.26, and the total metal oxide was 3.2% by weight, and showed a tendency to cloudiness due to micro-aggregation of colloidal particles.

Step (e) (Preparation of modified stannic oxide-zirconium oxide composite sol)
(D) 9.5 g of diisobutylamine was added to 14742.6 g of the mixed solution obtained in the step, and then the solution was passed through a column packed with a hydroxyl type anion exchange resin (supra: Amberlite IRA-410) at room temperature, 16288 g of modified stannic oxide-zirconium oxide composite aqueous sol (dilute liquid) was obtained by heating and aging at 80 ° C. for 1 hour. This sol had 2.90% by weight of all metal oxides and a pH of 10.43, had a colloidal color, but had good transparency.

The modified stannic oxide-zirconium oxide composite aqueous sol (dilute liquid) obtained in the step (e) is concentrated at room temperature with a filtration device of an ultrafiltration membrane having a molecular weight cut off of 50,000, and high concentration modified oxidation. 2182 g of a stannic-zirconium oxide composite aqueous sol was obtained. This sol was stable at pH 8.71 and 18.3% by weight of all metal oxides (ZrO ₂ + SnO ₂ + WO ₃ + SiO ₂ ).
With stirring to 2182 g of the above-described high-concentration modified stannic oxide-zirconium oxide composite aqueous sol, at room temperature, 4.0 g of tartaric acid, 6.0 g of diisobutylamine, 1 drop of an antifoaming agent (supra: SN deformer 483) Was added and stirred for 1 hour. By distilling off water while adding 20 liters of methanol little by little under normal pressure in a reaction flask equipped with a stirrer, 1171 g of a modified stannic oxide-zirconium oxide complex methanol sol in which water in the aqueous sol was replaced with methanol was obtained. Obtained. This sol has a specific gravity of 1.124, a pH of 7.45 (equal mixture with water), a viscosity of 2.3 mPa · s, a total metal oxide (ZrO ₂ + SnO ₂ + WO ₃ + SiO ₂ ) of 32.7% by weight, and a water content of 0.7. The particle size was 47 to 15% by electron microscope observation and was 10 to 15 nm. This sol had a colloidal color, high transparency, and was stable with no abnormalities such as precipitate formation, white turbidity, and thickening even after standing at room temperature for 3 months. The refractive index of the dried sol was 1.76.

Example 1
(1) Preparation of coating composition 45 parts by weight of modified stannic oxide-zirconium oxide-tungsten oxide-silicon oxide composite methanol sol as component (A) prepared in Production Example 1 in an atmosphere at 5 ° C. and (B) The component, 15 parts by weight of γ-glycidoxypropyltrimethoxysilane and 3 parts by weight of tetraethoxysilane were mixed and stirred for 1 hour. Thereafter, 4.5 parts by weight of 0.001 mol / L hydrochloric acid was added and stirred for 50 hours. Thereafter, 25 parts by weight of propylene glycol monomethyl ether (PGM) as a solvent, 9 parts by weight of diacetone alcohol (DAA) and 1.8 parts by weight of aluminum trisacetylacetonate (AL-AA) as component (C), perchloric acid 0.05 parts by weight of aluminum was sequentially added and stirred for 150 hours. The obtained solution was filtered through a 0.5 μm filter to obtain a coating composition.

(2) Formation of cured film A lens base material [manufactured by HOYA, trade name: IAS (EYAS, refractive index 1.60) (polythiourethane lens)] in 60 ° C., 10% by weight sodium hydroxide aqueous solution It was immersed for 300 seconds, and then washed with ion-exchanged water for 300 seconds under application of ultrasonic waves of 28 kHz. Finally, a series of steps for drying in a 70 ° C. atmosphere was used as a substrate pretreatment. Thereafter, the plastic lens was immersed in the coating solution, and after the immersion, the plastic lens pulled up at a lifting speed of 20 cm / min was heat-treated at 120 ° C. for 1 to 2 hours to form a cured film (hard coat A layer).

(3) Ion gun treatment On the cured film, ion irradiation was performed with an ion gun under the conditions of ion acceleration voltage, irradiation time, and gas atmosphere described in the table.
(4) Formation of an antireflection film having a hybrid film An antireflection film composed of first to seventh layers is formed on the hard coat layer irradiated with ions under the conditions shown in Table 1 to obtain a plastic lens. It was.
Note that conditions were set so that the hybrid layer was deposited almost simultaneously as a binary deposition of an inorganic material and an organic material using the apparatus shown in FIG. During the vapor deposition of the organic substance, the vaporized organic substance was introduced into the vapor deposition apparatus using a gas valve and a mass flow controller. When forming the hybrid layer, an ion assist method was used in an atmosphere of a mixed gas of argon gas and oxygen gas. Moreover, what is described as "-" in a table | surface formed the layer by the normal vacuum evaporation method, without using the ion assist method. In the table, M1 represents an inorganic oxide, CM1 represents an organosilicon compound, and CM2 represents a silicon-free organic compound.
The details of the organic compounds described in the table are as follows.
(a) Epolite 70P (propylene glycol diglycidyl ether, average molecular weight of about 188, manufactured by Kyoeisha Chemical Co., Ltd.)
(b) TM2 (γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM403”)) and γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE903”) )) In a molar ratio of 1: 1, the structure of the mixture is (H ₃ CO) ₃ —Si— (CH ₂ ) ₃ —O—CH ₂ —CH (OH) —CH ₂ —NH— ( CH ₂ ) ₃ —Si— (OC ₂ H ₅ ) ₃ with a molecular weight of about 457.)
(c) Epiol P200 (polypropylene glycol glycidyl ether, average molecular weight of about 304, manufactured by NOF Corporation)
(d) Denacol EX920 (polypropylene glycol diglycidyl ether, average molecular weight 354, manufactured by Nagase Chemtex Co., Ltd.)
KY-130 is a “fluorine-substituted alkyl group-containing organosilicon compound” (manufactured by Shin-Etsu Silicone Co., Ltd.) for forming an antifouling film.

(5) Formation of water-repellent film Stainless steel sintered filter (mesh 80-100 μm, 18φ × 3 mm) impregnated with 0.3 ml of KY-130 (manufactured by Shin-Etsu Silicone) containing a fluorine-substituted alkyl group-containing organosilicon compound ) Was set in a vacuum deposition apparatus, and the entire sintered filter was heated using an electron gun under the following conditions to form a water repellent film.
(A) Degree of vacuum: 2.3 × 10 ^{−6 to} 6.0 × 10 ⁻⁶ Torr
(B) Electron gun conditions: acceleration voltage: 6 KV, applied current: 40 mA, irradiation area: 3.5 × 3.5 cm square, deposition time: 5 seconds The above-described physical property evaluation was performed on the optical material obtained as described above. . The results are shown in Table 2.

Examples 2-12
A lens was manufactured in the same manner as in Example 1 except that an antireflection film was applied under the conditions described in Table 1. However, in Example 5 and later, a primer layer was applied between the base material and the cured film. The method for forming the primer layer is as follows.
(Formation of primer layer)
Polyester type polyol (trade name of Sumitomo Bayer Urethane Co., Ltd., using Desmophen A-670) 6.65 parts by weight, block type polyisocyanate (trade name of Sumitomo Bayer Urethane Co., Ltd., using BL-3175) 6 0.08 part by weight, 0.17 part by weight of dibutyltin dilaurate as a curing catalyst, 0.17 part by weight of a fluorine-based leveling agent (using a trade name of Sumitomo 3M Co., Ltd., Florad FC-430) as a leveling agent, and as a solvent A mixture consisting of 95.71 parts by weight of diacetone alcohol was sufficiently stirred until it became uniform. The liquid primer thus obtained was applied on an alkali-treated base lens as a pretreatment by a dipping method (pickup speed: 24 cm / min), cured by heating at 100 ° C. for 40 minutes, and a thickness of 2 A primer layer of ˜3 μm was formed.
Table 2 shows the physical property evaluation results for the optical members obtained in each example.
In the lenses obtained in Examples 1 to 12, no interference fringes were generated.

Comparative Example 1
Preparation of coating agent In a reactor equipped with a rotor, 15 parts by weight of γ-glycidoxypropyltrimethoxysilane and 49 parts by weight of the modified stannic oxide-zirconium oxide complex methanol sol obtained in Comparative Production Example 1 The mixture was stirred at 4 ° C. for 3 hours, and then 3.5 parts by weight of 0.001 N hydrochloric acid was gradually added dropwise into the reactor, followed by stirring at 4 ° C. for 48 hours. Next, 30 parts by weight of propylene glycol monomethyl ether and 0.04 parts by weight of a silicone-based surfactant were added and mixed with this, followed by stirring at 4 ° C. for 3 hours, and then 0.60 parts by weight of aluminum acetylacetonate and aluminum perchlorate. 0.05 parts by weight (manufactured by Aldrich) was added and mixed. After stirring at 4 ° C. for 3 days, the coating agent was prepared by allowing to stand at 4 ° C. for 2 days. Using the coating agent, a cured film was formed on the lens substrate iris as in Example 1. Further, an antireflection film similar to that of Example 1 was formed and evaluated. The evaluation results are shown in Table 1. The Bayer value was 3.

Comparative Example 2
Comparative Example 1 was the same as Comparative Example 1 except that 15 parts by weight of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was used instead of 15 parts by weight of γ-glycidoxypropyltrimethoxysilane. Carried out. The evaluation results are shown in Table 1. The Bayer value was 3.

According to the present invention, it is possible to obtain an optical member that satisfies various physical properties such as aesthetics and adhesion, and has improved scratch resistance, and can efficiently produce the optical member. The optical member of the present invention is particularly excellent as a spectacle lens.

Claims (10)

An optical member having a plastic substrate, a cured film, a multilayer antireflection film formed by vacuum deposition, and a water-repellent film applied on the antireflection film in this order, and the cured film is described below (A ) Component and the coating composition containing the component (B) as a raw material, the multilayer antireflection film is sequentially from the substrate side to the outside air side,
First layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic material containing silicon dioxide as a deposition material.
Second layer: a layer containing at least 50% by weight of tantalum oxide based on the second layer
Third layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure and an inorganic material containing silicon dioxide as a deposition material.
Fourth layer: a layer containing at least 50% by weight of tantalum oxide based on the fourth layer
Fifth layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic material containing silicon dioxide as a deposition material.
Sixth layer: a layer containing at least 50% by weight of tantalum oxide based on the sixth layer
Seventh layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic material containing silicon dioxide as an evaporation source.
An optical member comprising the seven-layer structure and the water-repellent film formed from a fluorine-substituted alkyl group-containing organosilicon compound as a raw material.
(A) and the metal tin, an organic acid containing formic acid and / or acetic acid as a 80% or more by weight of oxalic acid and the balance in oxalic acid, or total organic acids, oxidation obtained by reaction with hydrogen peroxide Structures in which colloidal particles of stannic and colloidal particles of zirconium oxide are bonded in a ratio of 0.02 to 1.0 as ZrO ₂ / SnO ₂ based on the weight of these oxides and particles of 4 to 50 nm stannic oxide having a diameter - as zirconium oxide composite colloidal particles nuclei, and WO ₃ / SnO ₂ weight ratio of the surface 0.1 to 100, and SiO ₂ / SnO ₂ weight ratio of 0.1 to 100 , tungsten oxide having a particle size of 2 to 7 nm - stannic oxide - stannic oxide which is modified particle diameter 4.5~60nm formed by being coated with colloidal particles of silicon dioxide complex - oxide Rukoniumu composite colloidal particles (B) an organosilicon compound 2. The optical member according to claim 1, wherein the hybrid layer is formed by simultaneously vapor-depositing the inorganic material and an organic silicon compound and / or a silicon-free organic compound as a vapor deposition raw material of the hybrid layer with different vapor deposition sources. . The inorganic substance is vaporized by heating using an electron gun, and an organic silicon compound and / or a silicon-free organic compound as a deposition raw material of the hybrid layer is stored in a tank, and the organosilicon compound is stored in the tank. 3. The optical member according to claim 2 , wherein the inorganic material and the organic silicon compound and / or the silicon-free organic compound are vapor-deposited simultaneously by heating the silicon-free organic compound. The optical member according to any one of claims 1 to 3 , wherein the number average molecular weight of an organosilicon compound that is a raw material for vapor deposition of the hybrid layer is 48 to 600. The optical member according to any one of claims 1 to 4 , wherein the silicon-free organic compound has a number average molecular weight of 28 to 400 . The optical member according to any one of claims 1 to 5 , wherein an organosilicon compound that is a raw material for vapor deposition of the hybrid layer has a structure represented by any one of the following general formulas (a) to (d).
Formula (a): Silane or siloxane compound

General formula (b): Silazane compound

General formula (c): cyclosiloxane compound

General formula (d): cyclosilazane compound

(In the general formulas (a) to (d), m and n in the formula each independently represent an integer of 0 or more. In addition, X _{1 to} X ₈ are each independently hydrogen, C 1-6. Hydrocarbon group (including both saturated and unsaturated), -OR ¹ group, -CH ₂ OR ² group, -COOR ³ group, -OCOR ⁴ group, -SR ⁵ group, -CH ₂ SR ⁶ group, -NR ⁷ ₂ groups or —CH ₂ NR ⁸ ₂ group (R ^{1 to} R ⁸ are hydrogen or hydrocarbon group having 1 to 6 carbon atoms (including both saturated and unsaturated bonds in the bond between carbon atoms)) The silicon-free organic compound of the following general formula (e) ~ optical member according to any one of claims 1 to 6 having a structure represented by any one of (g).
General formula (e): silicon-free organic compound containing carbon and hydrogen having an epoxy group at one end as essential components

General formula (f): silicon-free organic compound containing carbon and hydrogen having epoxy groups at both ends as essential components

General formula (g): silicon-free organic compound containing unsaturated bonds and containing carbon and hydrogen as essential components

(In General Formulas (e) and (f), R ⁹ may be hydrogen or a hydrocarbon group having 1 to 10 carbon atoms which may contain oxygen, and R ¹⁰ may contain oxygen having 1 to 7 carbon atoms. In the general formula (g), X _{9 to} X ₁₂ are each composed of hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or carbon having 1 to 10 carbon atoms and hydrogen as essential components. And an organic group having at least one of oxygen and nitrogen as an essential component) The optical member according to any one of claims 1 to 7 , wherein an in-film content ratio of the organic silicon compound and / or the silicon-free organic compound in the hybrid layer is 0.02% by mass to 25% by mass. The (B) organosilicon compound has the general formula (I)
R ¹¹ _k Si (OR ¹² ) _4-k (I)
(In the formula, R ¹¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may or may not have a functional group, R ¹² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the number of carbon atoms. 7-10 aralkyl or an acyl group having 2 to 10 carbon atoms, k represents 0, 1 or 2, when there are a plurality of R ¹¹ s, the R ¹¹ s may be the same with or different from each other, a plurality OR ^{12 in the above} may be the same or different, and a compound represented by the general formula (II):

Wherein R ¹³ and R ¹⁴ are the same or different alkyl groups having 1 to 4 carbon atoms or acyl groups having 2 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ are each the same or different monovalent carbon number 1 A hydrocarbon group having or not having a functional group of ˜5, Y is a divalent hydrocarbon group having 2 to 20 carbon atoms, a and b are each 0 or 1, and a plurality of R ¹³ O are Or a plurality of OR ¹⁴ may be the same or different from each other.) And a hydrolyzate thereof. The optical member according to any one of 8 . The optical member according to any one of claims 1 to 9 , wherein the plastic substrate is a polythiourethane resin having a refractive index of 1.58 to 1.62.

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