JP5713668B2 - Hard coat layer film forming coating composition - Google Patents

Description

  The present invention relates to a coating composition containing composite oxide fine particles mainly composed of silicon and aluminum in a predetermined range.

In recent years, plastic substrates have been mainly used as substrates for optical lenses, particularly spectacle lenses. However, the plastic substrate has a drawback that it is easily damaged compared to an inorganic glass substrate.
For this reason, it is common practice to provide a hard coat film layer such as silicon on the surface of the substrate. Further, as described in, for example, Patent Document 1, it is known that if silica-based fine particles are blended in a hard coat layer forming coating material, the scratch resistance of these hard coat film layers is improved.

  In addition, when adding a hard coat layer to a spectacle lens substrate, it is necessary to similarly adjust the refractive index of the lens and the hard coat layer in order to suppress the occurrence of interference fringes. Since the refractive index of the resin lens used for the material is increasing, it is a common practice to mix titanium or zirconia oxide fine particles having a high refractive index in the hard coat layer forming coating material. For example, Patent Document 2 describes a hard coat layer containing such oxide fine particles, and has the effect of improving the scratch resistance of the hard coat film by adding such oxide fine particles. Is also described.

JP 2009-197078 A JP 05-264806 A

When silica-based fine particles as described in Patent Document 1 or Patent Document 2 or oxide fine particles containing titanium or zirconium are blended in the paint, the scratch resistance of the hard coat layer film formed from the paint can be improved. However, there has been a demand for development of a hard coat film that further improves the scratch resistance of such a hard coat layer film and that has a higher film hardness.
As a result of diligent research to solve such problems, the present inventors have formulated this coating composition by blending composite oxide fine particles mainly composed of silicon and aluminum into a coating composition within a predetermined range. From the product, it was found that a coating film having excellent hardness and scratch resistance could be formed, and the present invention was completed.

The present invention is a coating composition containing composite oxide fine particles containing silicon and aluminum as main components, and the content of the composite oxide fine particles is based on 100 parts by weight of components other than the composite oxide fine particles. It exists in the range of 0.1-5 weight part, It is characterized by the above-mentioned.
When silicon and aluminum contained in the composite oxide fine particles are combined with each other in terms of SiO ₂ and Al ₂ O ₃ , 70 to 100% by weight based on the total weight of the composite oxide fine particles It is preferable that it exists in the range.

It is preferable that the molar ratio of silicon and aluminum contained in the composite oxide fine particles is in the range of 0.0005 to 0.05 on the basis of Al ₂ O ₃ / SiO ₂ conversion.
The content of the composite oxide fine particles is preferably in the range of 0.1 to 3.0 parts by weight with respect to 100 parts by weight of components other than the composite oxide fine particles.
The surface negative charge density of the composite oxide fine particles is preferably in the range of 0.5 to 1.1 μeq / m ² when the pH of the dispersion sol containing the composite oxide fine particles is 5.0.

The coating composition of the present invention further includes a filler in addition to the composite oxide fine particles.
The filler is preferably inorganic oxide fine particles containing one or more selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium.
The filler is a core-shell type inorganic oxide fine particle, and the core of the inorganic oxide fine particle is a composite oxide fine particle containing one or more selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium. The shell is preferably an oxide or composite oxide containing silicon.
The coating composition of the present invention is preferably a hard coating layer film forming coating composition.

  The coating composition according to the present invention contains the composite oxide fine particles mainly composed of silicon and aluminum in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the components other than the composite oxide fine particles. Furthermore, the film hardness and scratch resistance of the coating film formed from this coating composition can be improved.

  Hereinafter, the coating composition according to the present invention will be specifically described.

Coating composition The coating composition according to the present invention is a coating composition containing composite oxide fine particles mainly composed of silicon and aluminum, and the content of the composite oxide fine particles It is characterized by being in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of other components.
When the coating composition according to the present invention contains the composite oxide fine particles mainly composed of silicon and aluminum in the above range, the scratch resistance and film of the coating film formed using the coating composition Hardness can be improved.
The reason for this is not clear, but it is thought that by adding the composite oxide fine particles to the coating composition in the above range, the hardness of the coating film surface and the interface with the base material is improved. It is done.

In the coating composition, the content of the composite oxide fine particles is 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of components other than the composite oxide fine particles. More preferably, it is in the range of 0.1 to 2.5 parts by weight.
When the content of the composite oxide fine particles is less than 0.1 parts by weight with respect to 100 parts by weight of the components other than the composite oxide fine particles, the effect of improving the scratch resistance and film hardness of the coating film is sufficiently obtained. Since it is not possible, it is not preferable.
When the content of the composite oxide fine particles exceeds 5 parts by weight with respect to 100 parts by weight of the components other than the composite oxide fine particles, the scratch resistance and film hardness of the coating film may be deteriorated.

Composite Oxide Fine Particles The composite oxide fine particles according to the present invention are characterized by containing silicon and aluminum as main components.
When the composite oxide fine particles do not contain silicon and aluminum as main components, the effect of the present invention that improves the film hardness and scratch resistance of the coating film is hardly or cannot be obtained.
However, here, “the composite oxide fine particles contain silicon and aluminum as main components” means that silicon and aluminum contained in the composite oxide fine particles are as SiO ₂ and Al ₂ O ₃ conversion standards. When the respective contents are added together, the combined amount is in the range of 70% by weight to 100% by weight with respect to the total weight of the composite oxide fine particles.
The total amount of silicon and aluminum contained in the composite oxide fine particles is preferably 80-100% by weight, more preferably 90-100% by weight, based on the SiO ₂ and Al ₂ O ₃ conversion standards. It is preferable to be in the range.
That is, the composite oxide fine particles may be composite oxide fine particles containing only silicon, aluminum, and oxygen.

The ratio of the content of silicon and aluminum contained in the composite oxide fine particles is in the range of Al ₂ O ₃ / SiO ₂ = 0.0005 to 0.05 in terms of the molar ratio of the silicon and aluminum oxide conversion standard. Preferably there is.
The molar ratio is preferably in the range of Al ₂ O ₃ / SiO ₂ = 0.0005 to 0.05, more preferably 0.005 to 0.05.
The composite oxide fine particles having the Al ₂ O ₃ / SiO ₂ molar ratio in the range of 0.0005 to 0.05 are excellent in stability and can form a uniform and stable coating film. And scratch resistance is improved, which is preferable.
When the molar ratio is less than 0.0005, the composite oxide fine particles may aggregate in the paint, which is not preferable.
When the molar ratio exceeds 0.05, the paint may be thickened, which is not preferable.

The average particle size of the composite oxide fine particles is not particularly limited, but is preferably 5 to 200 nm, more preferably 10 to 100 nm.
When the average particle diameter is less than 5 nm, the composite oxide fine particles may aggregate and thicken, and when the average particle diameter exceeds 200 nm, the transparency and scratch resistance of the coating film may decrease. Therefore, it may not be preferable.

  The shape of the composite oxide fine particles according to the present invention is not particularly limited, and any shape can be used. Specifically, shapes such as a spherical shape, a chain shape, and a confetti shape are exemplified. Further, any other known shape can be used. It is preferable to use chain-like composite oxide fine particles because the hardness and scratch resistance of the coating film are further improved. It is preferable to use gold-peeled complex oxide fine particles because adhesion of the coating film is improved.

  The composite oxide fine particles according to the present invention may be in the form of a powder, in the form of a dispersion such as a colloid or sol, or in the form of a gel. Dispersed liquid composite oxide fine particles are more preferable because they have high dispersibility and stability in the coating film, high effects of improving the hardness and scratch resistance of the coating film, and high transparency of the coating film.

The composite oxide fine particles contain silicon and aluminum as main components, and further include other elements or organic groups such as rare earth elements, alkaline earth metal elements, transition metal elements, amino groups and carboxyl groups. It may contain an organic group.
The composite oxide fine particles preferably include at least a Si—O—Al bond.

The composite oxide fine particles may be silica alumina fine particles, composite oxide fine particles containing silicon and aluminum, or may be a composite fine particle of silica fine particles and alumina fine particles.
The composite oxide fine particles may be core-shell fine particles or hollow fine particles.
Further, the composite oxide fine particles containing silicon and aluminum as main components may be further processed with a known surface treatment agent or surface modifier such as an organic amine or an organic silicon compound.

  Specific examples of the composite oxide fine particles include, for example, Catalloy SN (particle diameter 12 nm, water dispersion sol), Cataloid SN-30 (particle diameter 17 nm, water dispersion sol), OSCAL1132, manufactured by JGC Catalysts & Chemicals. Commercial products such as (particle diameter 12 nm, methanol-dispersed sol) and OSCAL1421 (particle diameter 7 nm, isopropanol-dispersed sol) can be mentioned.

The composite oxide fine particles according to the present invention can be produced by a known method.
Specific examples thereof include, for example, a method of mixing and drying a silica source such as silica gel, silica sol, and silicic acid solution and an alumina source such as alumina gel, sodium aluminate, and aluminum salt, or an aluminum compound solution in silica sol. Examples thereof include a method of adding and surface modifying or reacting, an alkoxide method, or a method of adding an aluminum compound solution to a step of hydrolyzing and / or polycondensing water glass or silicic acid solution.
Moreover, it can manufacture using the manufacturing method of acidic silica sol described in Unexamined-Japanese-Patent No. 63-123807, and the manufacturing method of acidic silica sol described in Unexamined-Japanese-Patent No. 06-199515.

Further, among the composite oxide fine particles according to the present invention, as one of the most preferred embodiments, the surface negative charge density of the composite oxide fine particles is when the pH of the dispersion sol containing the composite oxide fine particles is 5.0. In the range of 0.5 to 1.1 μeq / m ² .
The surface negative charge density is preferably in the range of 0.5 to 1.1 μeq / m ² , more preferably 0.6 to 0.9 μeq / m ² .
When composite oxide fine particles having a surface negative charge density in the range of 0.5 to 1.1 μeq / m ² are used, the effect of improving the hardness and scratch resistance of the coating film is very high, and the transparency of the coating film is also high. Is also preferable.

An example of the composite oxide fine particles having a surface negative charge density in the above range is silica-based fine particles whose surface is modified with aluminum, and the amount of modification of aluminum contained in the silica-based fine particles is Examples thereof include composite oxide fine particles in the range of 0.05 × 10 ^{−6 to} 6.0 × 10 ⁻⁶ mol / m ² in terms of Al ₂ O ₃ when expressed per unit surface area of the system fine particles.
Moreover, as an example of a method for producing such composite oxide fine particles, a production method including the following steps (1) to (3) can be mentioned.

Method for producing silica-based fine particles surface-modified with aluminum
Process (1)
An alkaline silica sol containing silica fine particles having an average particle diameter of 5 to 50 nm and having a pH in the range of 9.0 to 11.5, an aqueous solution of aluminate, and a silicon component contained in the silica sol as SiO ₂ . In addition, when the aluminum contained in the aluminate is represented by Al ₂ O ₃ , the molar ratio (Al ₂ O ₃ / SiO ₂ ) is mixed at a ratio of 0.005 to 0.050. Process,

Step (2)
Heating the mixture obtained in the above step to a temperature of 60 to 200 ° C. and stirring for 0.5 to 20 hours;

Step (3)
The mixed solution obtained in the step (2) is brought into contact with a cation exchange resin to remove the alkali metal ions contained in the mixed solution by ion exchange, and the pH of the mixed solution is adjusted to 3.0 to 6. A step of obtaining an aqueous dispersion containing silica-based fine particles whose surface is modified with aluminum by adjusting to the range of 0.

Silica fine particles whose surface is modified with aluminum by the method including the steps (1) to (3), and the amount of modification of aluminum contained in the silica-based fine particles per unit surface area of the silica-based fine particles When expressed, composite oxide fine particles having a range of 0.05 × 10 ^{−6 to} 6.0 × 10 ⁻⁶ mol / m ² in terms of Al ₂ O ₃ can be produced.

Filler The coating composition according to the present invention preferably further contains a filler in addition to the composite oxide fine particles.
When the coating composition contains the filler, the film hardness and scratch resistance of the coating film obtained from the coating composition according to the present invention can be improved.
In the present invention, the filler means particles different from the composite oxide fine particles, that is, the composite oxide fine particles containing silicon and aluminum as main components.
When the filler and the composite oxide fine particles are the same particle, the content of the composite oxide fine particles contained in the coating composition according to the present invention is excessively increased, and the film hardness may be reduced. It is not preferable.
Examples of such a filler include composite oxide fine particles and inorganic oxide fine particles that do not contain silicon and aluminum as main components, organic resin fine particles, or organic-inorganic composite fine particles.
For example, silica fine particles and alumina fine particles are also included.

By blending such a filler, it is possible to adjust the desired performance such as the refractive index, conductivity, smoothness and hardness of the coating film.
The property of the filler is not particularly limited, and may be, for example, a powder, a dispersed liquid such as a colloid or sol, or a gel.
The filler may be core-shell type particles or hollow particles.
Further, the shape of the filler is not particularly limited, and may be any shape including a spherical shape, a rod shape, a chain shape, a confetti shape, and the like.

The filler is preferably inorganic oxide fine particles containing at least one selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium.
If such inorganic oxide fine particles are used as fillers, the refractive index of the coating film, the ultraviolet shielding effect, or the ultraviolet absorption effect can be adjusted in various ways, so that it is particularly suitable for forming a coating film on an optical substrate. Coating compositions can be obtained.
Further, by using such inorganic oxide fine particles as a filler, the effect of improving the film hardness and scratch resistance of the coating film can be enhanced.
The inorganic oxide fine particles may be modified with a known surface treating agent such as an organosilicon compound or an amine.

The method for producing such inorganic oxide fine particles is not particularly limited, and can be produced by a known method.
As an example, a neutralization hydrolysis method using a metal salt or metal alkoxide as a raw material, a hydrolysis method, a neutralization coprecipitation method for peptizing a metal hydroxide obtained by adding an alkali to an aqueous metal salt solution, Hydrothermal synthesis method, alkoxide method, sol-gel method, deflagration method in which metal powder is put into combustion in an oxidization flame, etc., flame melting in which metal oxide powder is put into flame and melted, and then cooled and solidified And evaporation to dryness.

The filler is preferably core-shell type inorganic oxide fine particles.
The core of the inorganic oxide fine particles is preferably composite oxide fine particles containing at least one selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium. Moreover, it is preferable that the shell of the inorganic oxide fine particles is an oxide or composite oxide containing silicon.

The core-shell type inorganic oxide fine particles are inorganic oxide fine particles in which the core is covered with the shell. When such particles are used as fillers, the weather resistance, light resistance, stability, and discoloration resistance of the coating film In addition to improving the properties and acid resistance, it is preferable because the scratch resistance and film hardness of the coating film are improved.
A coating composition containing such a filler is particularly preferable as a coating composition for forming a hard coat layer film, particularly as a coating composition for forming a hard coat layer film for an optical substrate such as an eyeglass lens.
However, such a coating composition can also be used as a coating composition for forming a primer layer film or a coating composition for forming an antireflection layer film.

The shell is preferably a composite oxide containing silicon and zirconium and / or aluminum.
When the inorganic oxide fine particles having such a shell are used as a filler, the weather resistance, light resistance, stability, discoloration resistance, and acid resistance of the coating film are greatly improved, and the scratch resistance and film of the coating film are improved. Hardness is greatly improved, which is more preferable.
More specific examples of the inorganic oxide fine particles having such a shell include composite oxide fine particles described in JP-A-08-048940, metal oxide fine particles described in JP-A 2010-168266, Examples thereof include titanium oxide-based composite particles described in Japanese Unexamined Patent Application Publication No. 2010-042947, inorganic oxide fine particles having a core-shell structure described in Japanese Patent Application Laid-Open No. 2009-15596, and the like. Moreover, as an example of the manufacturing method of such inorganic oxide microparticles | fine-particles, the method described in the cited reference mentioned above and the method according to them can be used.

  In addition, as an example of the filler according to the present invention, 1130Z (S-7 · A8) (particle size 8 nm, anatase-type titanium oxide fine particles, methanol dispersion sol) manufactured by JGC Catalysts & Chemicals Co., Ltd., 2130Z (S-7 · A8) ) (Particle diameter 8 nm, anatase type titanium oxide fine particles, propylene glycol monomethyl ether dispersion sol), 1130Z (8RS-25 · A17) (particle diameter 15 nm, rutile type titanium oxide fine particles, methanol dispersion sol) May be used.

The average particle diameter of the filler is not particularly limited, but is desirably in the range of 5 to 50 nm.
It is more preferable that the average particle diameter of the filler is in the above range because the transparency of the coating film is improved and the hardness of the coating film is improved because the dispersibility and stability of the filler are high.
The shape of the filler is not particularly limited, and any shape such as a spherical shape, a chain shape, and a confetti shape can be used. Use of a chain filler is preferable because the hardness and scratch resistance of the coating film are further improved.

The content of the filler in the coating composition according to the present invention is not particularly limited, but preferably 0 of the coating composition forming components other than the composite oxide fine particles containing silicon and aluminum as main components. 0.1 to 40% by weight, more preferably 10 to 30% by weight.
The coating composition having the filler content in the above range has higher film hardness, scratch resistance, transparency, high weather resistance and light resistance, and can improve the refractive index, etc. preferable.

Further, as the filler according to the present invention, as one of the most preferable forms, oxide fine particles or composite oxide containing one or more elements selected from zirconium, tin, titanium, niobium, tungsten, antimony and indium as main components A shell made of a composite oxide having a fine particle as a core particle and a surface containing silicon and aluminum as main components, wherein the content of silicon and aluminum contained in the shell is SiO in terms of a weight ratio on an oxide conversion basis ₂ / Al ₂ O ₃ = core-shell composite oxide fine particles in the range of 2.0 to 30.0.

The core particles include one or more elements selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium in terms of metal oxide (ZrO ₂ , SnO ₂ , TiO ₂ , Nb ₂ O ₅ , WO ₃ , Sb ₂ O ₅ , In ₂ O ₃ ), preferably 70% by weight or more.
Further, the coating amount of the shell with respect to the core particles is in a range in which the solid content of the shell is 5 to 100 parts by weight, more preferably 7 to 80 parts by weight with respect to 100 parts by weight of the solid content of the core particles. It is preferable that it exists in.

The surface of the core-shell type complex oxide fine particles may be surface-treated with a known surface treatment agent such as a silane coupling agent or an organic amine.
Such core-shell composite oxide fine particles have a high surface negative charge amount per unit surface area of the fine particles, high dispersion stability, and are stable in an acidic region, and are excellent as a material for a coating composition. Therefore, the effect of improving the film hardness, scratch resistance and adhesion of the coating film is very high, and the effects of improving light resistance, term resistance and discoloration resistance are also very excellent, which is very preferable.
As an example of a method for producing such core-shell composite oxide fine particles, a method including the following steps (1) to (2) can be mentioned.

Method for producing dispersion of core-shell composite oxide fine particles
Process (1)
A silicon compound solution containing silicon alkoxide and / or silicic acid and an aqueous solution of aluminate are added to an aqueous dispersion of core particles having an average particle size in the range of 5.0 to 50.0 nm. When the silicon component contained is represented by SiO ₂ and the aluminum component contained in the aqueous solution of aluminate is represented by Al ₂ O ₃ , the weight ratio of the oxide conversion standard is SiO ₂ / Al ₂ O ₃ = 2. A step of mixing at a ratio of 0 to 40.0,

Step (2)
A step of obtaining a dispersion of core-shell composite oxide fine particles by heating the mixed liquid obtained in the above step to a temperature of 60 to 200 ° C. and stirring for 0.5 to 20 hours.
The aqueous dispersion of the core particles used in the step (1) is obtained by neutralization hydrolysis using a metal salt or metal alkoxide as a raw material, a hydrolysis method, or by adding an alkali to an aqueous metal salt solution. It can be produced by a known liquid phase method such as a neutralization coprecipitation method for peptizing the obtained metal hydroxide or a hydrothermal synthesis method.

Components other than complex oxide fine particles Next, components other than the complex oxide fine particles containing silicon and aluminum as main components among the components of the coating composition according to the present invention will be described.
One of the components other than the composite oxide fine particles includes a matrix forming component. In addition to the matrix-forming component, the coating composition according to the present invention may be any component that can be blended in the coating, for example, a pH adjuster, a solvent, a catalyst, an acid, an alkali, an ultraviolet absorber, and the like. May be included.
In addition, the component other than the composite oxide fine particles may contain a filler as described in detail in the section “Filler”.
That is, when the coating composition contains the composite oxide fine particles and the filler, when the total weight of the composite oxide fine particles is 100 parts by weight of the filler and the matrix-forming component , 0. It may be in the range of 1 to 5 parts by weight.
When the coating composition contains such a filler, it is particularly preferable because the refractive index and ultraviolet shielding ability of the resulting coating film can be adjusted, and the altitude and scratch resistance of the coating film can be improved.

Examples of the matrix forming component include organosilicon compounds and / or hydrolysates thereof, resins such as thermosetting organic resins, thermoplastic organic resins, and ultraviolet curable organic resins.
Furthermore, as an example of the organosilicon compound, an alkoxysilane compound can be cited as a representative example. Specifically, tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, trimethylchlorosilane. Α-glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , Γ-glycidoxypropylmethyldimethoxysilane, γ-γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -Ethyltri Ethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxy Silane etc. are mentioned. These may be used alone or in combination of two or more.

Furthermore, preferable examples of the thermosetting organic resin include urethane resins, epoxy resins, and melamine resins.
More specifically, examples of the urethane-based resin include a reaction product of a block-type polyisocyanate such as hexamethylene diisocyanate and an active hydrogen-containing compound such as polyester polyol and polyether polyol, and the like. Examples of the epoxy resin include a polyalkylene ether-modified epoxy resin and an epoxy group-containing compound in which a flexible skeleton (soft segment) is introduced into a molecular chain.

  Furthermore, as an example of the said melamine type-resin, the hardened | cured material etc. of etherified methylol melamine, polyester polyol, and polyether polyol are mentioned, for example. Among these, it is preferable to use a urethane-based resin that is a cured product of a block type isocyanate and a polyol. Moreover, these thermosetting organic resins may use not only one type but also two or more types.

  The thermoplastic organic resin used as the matrix-forming component according to the present invention is preferably at least one selected from an acrylic resin, a urethane resin and an ester resin, and more preferably a self-emulsifying aqueous system. More preferably, it is an emulsion resin.

  More specifically, examples of the acrylic resin include, for example, an aqueous emulsion obtained from an (meth) acrylic acid alkyl ester monomer, and a polymer emulsion obtained by copolymerizing the monomer with styrene, acrylonitrile, or the like. Examples of the urethane resin include water-based emulsions obtained by reacting a polyol compound such as polyester polyol, polyether polyol, and polycarbonate polyol with a polyisocyanate, and further examples of the ester resin. For example, a water-dispersed elastomer of a multi-block copolymer using polyester as a hard segment and polyether or polyester as a soft segment can be used. Among these, it is preferable to use water-dispersed urethane resin obtained from polyester polyol or polyether polyol and polyisocyanate. These thermoplastic organic resins may use not only one type but also two or more types.

As the pH adjuster used in the coating composition of the present invention, known ones can be used. Examples thereof include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, tartaric acid, citric acid, Examples thereof include organic acids such as malic acid and acetic acid, and organic amines such as ammonia, isopropylamine, isobibutylamine, diisipropylamine and diisobutylamine.
As the solvent used in the coating composition of the present invention, a known solvent can be used. Examples thereof include alcohols such as methanol, ethanol, butanol, propanol and isopropyl alcohol, ethylene glycol, and the like. Examples thereof include ethers such as monomethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, and ketones such as methyl ethyl ketone and γ-butyrolactone.

Method for producing a coating composition Next, a process for the preparation of the coating composition according to the present invention will be described in detail. These coating compositions are prepared by mixing a dispersion of composite oxide fine particles containing silicon and aluminum as main components and a matrix-forming component. An example is shown below.
However, since the preparation method described here shows the one aspect | mode, the coating composition which concerns on this invention is not limited to what was obtained from these preparation methods.
The pure water used in the present invention refers to ion-exchanged water, and ultrapure water is obtained by further removing impurities contained in pure water, and the content of impurities is 0.01 μg / L or less. Say things.

  An example of a method for producing a coating composition according to the present invention when an organosilicon compound and / or a hydrolyzate thereof is used as a matrix-forming component will be described below.

Manufacturing method of coating composition (1)
When an organosilicon compound and / or a hydrolyzate thereof is used as a matrix-forming component when preparing the coating composition according to the present invention, the organosilicon compound is used in the absence of a solvent or a polar organic solvent such as alcohol. Among them, it is preferable to partially hydrolyze or hydrolyze in the presence of an acid and water, and to mix with the dispersion and filler containing the composite oxide fine particles mainly composed of silicon and aluminum. However, the organosilicon compound may be partially hydrolyzed or hydrolyzed after mixing with the dispersion. The coating composition thus prepared can be suitably used as a coating composition for forming a hard coat layer film.

When the composite oxide fine particles or the filler is in a dispersed liquid, the dispersion medium may be water or an organic solvent.
Preferable examples when the dispersion medium is an organic solvent include alcohols such as methanol and ethanol and ethers such as propylene glycol monomethyl ether. In this case, the dispersion medium of the organosilicon compound can be used without particular limitation as long as it is compatible with the dispersion medium of the organic solvent dispersion sol, but the same kind as the dispersion medium of the composite oxide fine particles and the filler. It is more preferable to use those.
Moreover, about the conditions of the partial hydrolysis of the said organosilicon compound and hydrolysis, it is preferable to carry out for 1 to 48 hours at the temperature of 5-30 degreeC, stirring. Moreover, after hydrolyzing, it may be allowed to stand under a low temperature condition of -10 to 1 ° C for aging.

In addition, the coating composition is added to the above components in order to improve the dyeability of a coating film such as a hard coat layer film and the adhesion to a plastic lens substrate, and to prevent the occurrence of cracks. In addition, an uncrosslinked epoxy compound may be contained.
Examples of the uncrosslinked epoxy compound include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, and the like. Among these, it is preferable to use 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, or the like. These uncrosslinked epoxy compounds may be used not only in one kind but also in two kinds or more.

Further, the coating composition includes components other than those described above, for example, surfactants, leveling agents and / or ultraviolet absorbers, as well as conventionally known documents such as JP-A-11-310755 and International Publication WO2007 / 046357. The described organic compounds and inorganic compounds may be included.
Next, an example of a method for producing a coating composition according to the present invention when a thermosetting organic resin or a thermoplastic organic resin is used as a matrix-forming component will be described below.

Method for producing coating composition (2)
The coating composition according to the present invention is a mixture of the thermosetting organic resin or the thermoplastic organic resin, the composite oxide fine particles containing silicon and aluminum as main components, and, if necessary, other components such as a filler. Prepared. Further, the coating composition is composed of components other than those described above, for example, neutralizers, surfactants or ultraviolet absorbers, and organic compounds and inorganic compounds described in conventionally known documents such as International Publication WO2007 / 026529. Etc. may be included.

In addition, the composite oxide fine particles and other components as necessary may be added to a dispersion obtained by dissolving the thermosetting resin in an organic solvent or a dispersion obtained by dissolving or dispersing the thermoplastic resin in an organic solvent or water. You may mix. In any case, the composite oxide fine particles and the filler may be dispersed or solid, and in the case of the dispersed liquid, the dispersion medium may be water or an organic solvent.
Such a coating composition is particularly preferable as a coating composition for forming a primer layer film.

The coating composition according to the present invention has high film hardness, scratch resistance and transparency, and can be used for various applications. In particular, it is preferable as a coating composition for forming a hard coat layer film or a coating composition for forming a primer layer.
The substrate on which the coating composition according to the present invention is applied is not particularly limited. For example, as an example of an optical substrate, polystyrene resin, allyl resin (especially aromatic allyl resin), polycarbonate Examples thereof include a plastic lens substrate composed of a resin, a polythiourethane resin, a polythioepoxy resin, or the like. Moreover, as a plastic base material used other than an optical lens, the plastic base material comprised by PMMA resin, ABS resin, an epoxy resin, polysulfone resin, etc. is mentioned. It can also be used for substrates such as glass and metal.

As a method for applying the coating composition on the substrate, it may be applied directly by a known method, or the substrate may be immersed in the coating composition. Examples thereof include spin coating and dip coating. Law.
Thus, if the coating film obtained by apply | coating the said coating composition on a base material is hardened | cured by a conventionally well-known method, a cured coating film will be formed.
Examples of the curing method include thermal curing and ultraviolet curing.
In the case of an optical base material such as an eyeglass lens, the hard coat layer film may be formed directly on the base material or on the primer layer film, and the primer layer film is usually directly on the base material. It is formed.

[Measuring method]
Next, the measurement methods and evaluation test methods used in the examples and others of the present invention will be specifically described as follows.

(1) Measuring method of average particle size
The average particle size of an average particle diameter of the composite oxide fine particles of composite oxide fine particles containing silicon and aluminum as the main component was determined by the following equation from the specific surface area as determined by nitrogen adsorption method (BET method).
Average particle diameter (nm) = 6000 / [specific surface area (m ² / g) × density (ρ)]
Here, as the density (ρ), silica density 2.2 was used.

Average particle diameter of filler (A) Filler having an average particle diameter of less than 200 nm A solid content of 0.15 g prepared by mixing 19.85 g of pure water with 0.15 g of a filler dispersion (solid content of 20% by weight). A 15% sample was placed in a quartz cell having a length of 1 cm, a width of 1 cm, and a height of 5 cm, and an ultrafine particle size analyzer (model ELS-Z2 manufactured by Otsuka Electronics Co., Ltd.) using a dynamic light scattering method was used. The particle size distribution of the particle group is measured. In addition, the average particle diameter as used in the field of this invention shows the value computed by cumulant analysis of this measurement result.

(B) Those having an average particle size of 200 nm or more (such as dry powder)
A slurry liquid (solid content concentration: 1.0% by weight) in which a dry powder or a calcined powder of the particle dispersion is dispersed in a glycerin-containing aqueous solution having a concentration of 40% by weight is prepared. , US-2 type) for 5 minutes after irradiating ultrasonic waves to disperse the particles, this slurry liquid was put into a glass cell (length 10 mm, width 10 mm, height 45 cm), The average particle size was measured over 2 minutes to 2 hours at a rotational speed of 300 to 10000 rpm using a centrifugal sedimentation type particle size distribution analyzer (CAPA-700 manufactured by Horiba, Ltd.).

(2) Method for measuring specific surface area 50 ml of composite oxide fine particles or filler dispersion (dispersion medium may be water or organic solvent) is adjusted to pH 3.5 with HNO ₃ , and 1-propanol 40 ml was added and dried at 110 ° C. for 16 hours. The obtained sample was pulverized in a mortar and then baked at 500 ° C. for 1 hour in a muffle furnace to obtain a measurement sample. About the obtained measurement sample, the nitrogen adsorption amount is measured by a nitrogen adsorption method (BET method) using a specific surface area measuring device (manufactured by Yuasa Ionics, model number Multisorb 12), and the obtained adsorption amount is determined by the BET one-point method. The specific surface area was calculated.

(3) Measuring method of pH Standard solution of pH 4, 7 and 9 in a thermostatic bath maintained at 25 ° C. in a cell containing 50 ml of aqueous dispersion of composite oxide fine particles with solid content concentration of 30% by weight Then, the pH value was measured by inserting a glass electrode of a pH meter (F22, manufactured by Horiba, Ltd.) whose correction was completed.

(4) Method for measuring content of silicon and aluminum contained in composite oxide fine particles (a) Content of silicon Dispersion of composite oxide fine particles containing silicon and aluminum (even if the dispersion medium is water, an organic solvent 2 ml of 50% sulfuric acid aqueous solution is added to 10 g, evaporated to dryness on a platinum dish, the obtained solid is baked at 1000 ° C. for 1 hour, cooled and weighed. Next, dissolve the weighed solid in a small amount of 50% aqueous sulfuric acid, add 20 ml of hydrofluoric acid, evaporate to dryness on a platinum pan, bake at 1000 ° C. for 15 minutes, and cool. Weigh. The weight difference was defined as the silicon content (wt% on the basis of SiO ₂ conversion) contained in the silica sol, the silica-based fine particle water-dispersed sol, or the silica-based fine particle organic solvent-dispersed sol.

(B) Aluminum content 1) 1 g of a dispersion of composite oxide fine particles containing silicon and aluminum (the dispersion medium may be water or an organic solvent) is collected in a platinum dish. Weigh to 1 mg.
2) Add 20 ml of hydrofluoric acid, heat on a sand bath and evaporate to dryness.
3) After cooling the sample obtained in 2) above to room temperature, 5 ml of hydrochloric acid and about 50 ml of water are added and heated on a sand bath to dissolve.
4) After cooling the sample obtained in 3) above to room temperature, it is used in a 200 ml capacity flask and diluted to 200 ml with water to prepare a sample solution.
5) The amount of aluminum contained in the sample solution obtained in 4) above was measured with an inductively coupled plasma emission spectrometer (ICPS-8100, manufactured by Shimadzu Corporation, detection wavelength 396.153 nm), and Al ₂ The weight% based on O ₃ conversion standard was determined.
When the filler is inorganic oxide fine particles, the composition of the metal element contained in the inorganic oxide fine particles is also analyzed by using an ICP device (ICPS-8100, manufactured by Shimadzu Corporation). The content on a conversion basis was measured.

(5) Method for measuring surface negative charge 1.67 g of a dispersion of composite oxide fine particles having a solid content concentration of 30% by weight (the dispersion medium may be water or an organic solvent) is collected, and distilled water is collected. 98.53 g was added to prepare 100.00 g of a mixed solution having a solid content concentration of 0.5% by weight. A hydrochloric acid aqueous solution or an ammonia aqueous solution was added to the obtained mixed solution to prepare a measurement aqueous solution having a pH adjusted to 5.0 at 25 ° C., and 20.00 g was fractionated therefrom to obtain a streaming potential measuring device (MUUTEK). PCD-T3, manufactured by the company, and using a Poly-Dadmac as a cation standard titrant, the flow potential titration value obtained by measuring the cation streaming potential titration value was defined as the surface negative charge amount.
The value obtained by the above measurement is the amount of surface negative charge (μeq / g) per 1 g of composite oxide fine particles. A value obtained by dividing this value by the specific surface area (m ² / g) of the composite oxide fine particles was defined as a negative charge amount existing per unit specific surface area of the composite oxide fine particles.

(6) Appearance of coating film (interference fringes)
A fluorescent lamp “trade name: Mellow 5N” (manufactured by Toshiba Lighting & Technology Co., Ltd., three-wavelength type daylight white fluorescent lamp) was mounted in a box whose inner wall was black, and light of the fluorescent lamp was prepared in Examples and Comparative Examples. Reflection is made on the surface of the antireflection film formed on the plastic lens substrate, and the occurrence of rainbow patterns (interference fringes) due to light interference is visually confirmed, and evaluated according to the following criteria.
S: There is almost no interference fringe. A: The interference fringe is not conspicuous. B: Although the interference fringe is recognized, it is within an allowable range. C: The interference fringe is conspicuous. D: There is a glare interference fringe.

(7) Appearance of the coating (cloudy)
A fluorescent lamp “trade name: Mellow 5N” (manufactured by Toshiba Lighting & Technology Co., Ltd., three-wavelength daylight white fluorescent lamp) is mounted in a box whose inner wall is black, and the plastic lens substrates prepared in the examples and comparative examples are fluorescent. Place them vertically under the lamp, visually check their transparency (degree of cloudiness), and evaluate according to the following criteria.
A: No haze B: Slight haze C: Clear haze D: Significant haze

(8) Test method for film hardness (Bayer test value) A plastic lens substrate prepared in the preparation example of the example using an abrasion tester BTM (manufactured by Colts, USA) and a haze value measuring device (NDH 2000 manufactured by NIPPON DENSGKUKU) Then, the Bayer value is measured by the change in the haze value with respect to the reference lens. The reference lens uses a CR39 base material (diethylene glycol bisallyl carbonate), and first, the respective haze values are measured. The initial haze value of the reference lens is D (std0), and the initial haze value of the lens under test is D (test0). Each lens is placed in an abrasion resistance tester pan, filled with 500 g of abrasive (exclusive sand), and vibrated 600 times to the left and right for testing. Assume that the initial haze value of the reference lens after the test is D (stdf) and the initial haze value of the lens under test is D (testf). The Bayer test value (R) is calculated from the following equation.
R = [D (stdf) -D (std0)] / [D (testf) -D (test0)]

(9) Scratch resistance test of coating film The surface of the plastic lens substrate prepared in Examples and Comparative Examples was manually rubbed with Bonstar Steel Wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.), and the degree of scratches was visually observed. And evaluate according to the following criteria.
A: Almost no flaws B: Some flaws enter C: Some flaws enter D: Most flawed areas are scratched.

(10) Adhesion test of coating film The lens surface of the plastic lens substrate prepared in Examples and Comparative Examples was cut with a knife at intervals of 1 mm to form 100 squares of 1 mm square, and cellophane adhesive tape Is pressed strongly in the direction of 90 degrees with respect to the in-plane direction of the plastic lens substrate, this operation is performed a total of five times, the number of squares that do not peel off is counted, and the following criteria are evaluated.
Good: The number of cells not peeled is 95 or more. Bad: The number of cells not peeled is less than 95.

(11) Weather resistance test of coating film After performing an exposure test on the plastic lens substrates prepared in Examples and Comparative Examples using a xenon weather meter (X-75 type manufactured by Suga Test Instruments Co., Ltd.) A test similar to the adhesion test is performed and evaluated according to the following criteria. The exposure time is 200 hours for a substrate having an antireflection film and 50 hours for a substrate not having an antireflection film.
Good: The number of cells not peeled is 95 or more. Bad: The number of cells not peeled is less than 95.

(12) Light resistance test of coating film Irradiation with ultraviolet rays was performed for 50 hours by a mercury lamp for fading test (H400-E manufactured by Toshiba Corporation), and the color of the plastic lens substrate before and after the test was visually confirmed. evaluate. The irradiation distance between the lamp and the test piece is 70 mm, and the output of the lamp is adjusted so that the surface temperature of the test piece is 45 ± 5 ° C.
○: Not much discoloration is observed Δ: Some discoloration is recognized ×: Clear discoloration is observed

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

[Example 1]
Preparation of aqueous dispersion of composite oxide fine particles containing silicon and aluminum as main components (1)
Process (1)
Commercially available alkaline silica sol in which spherical colloidal silica fine particles are dispersed (trade name Cataloid SI-40, manufactured by JGC Catalysts & Chemicals Co., Ltd., SiO ₂ concentration 40 wt%, Na ₂ O concentration 0.40 wt%, pH 9.5, An average particle diameter of 17 nm, Al ₂ O ₃ / SiO ₂ (molar ratio) = 0.006) 4000 g was supplied to a 13-liter SUS reaction vessel equipped with a stirrer and a heating device, and stirred at a temperature of 25 ° C. However, 2712 g of 0.9 wt% sodium aluminate aqueous solution was added at a constant rate over 1.0 hour based on Al ₂ O ₃ conversion standard to obtain a mixed solution. At this time, Al ₂ O ₃ / SiO ₂ (mixing molar ratio) was 0.009, and the addition rate of the sodium aluminate aqueous solution was 1.5 × 10 ⁻² g / Hr.

Step (1.1)
The resulting mixed solution was heated to 95 ° C. with stirring, and then stirred for 6.0 hours while maintaining the temperature at 95 ° C. The pH of this mixed solution was 10.9, the solid content concentration based on SiO ₂ was 24.2% by weight, and the solid content concentration based on Al ₂ O ₃ was 0.36% by weight.
Step (1.2)
A cation exchange resin (Mitsubishi Chemical Corporation Diaion SK1BH) was added to the mixed solution obtained in the above step to adjust the pH to 9.
Step (2)
After separating and removing the resin from the mixed solution obtained in the above step, heat treatment was performed at 165 ° C. for 1 hour in an autoclave to obtain an aqueous dispersion of alkaline silica-based fine particles.

Step (3)
Next, after cooling the aqueous dispersion of alkaline silica-based fine particles obtained by the above process to room temperature, a cation exchange resin (Mitsubishi Chemical Corporation Diaion SK1BH) was added and adjusted to pH 3.5. The resin was not separated and aged for 7 hours while maintaining at 80 ° C. with stirring.
Thereafter, the cation exchange resin was separated and removed to obtain an aqueous dispersion of composite oxide fine particles having a solid content concentration of 24.2% by weight, a viscosity of 1.99 mPa · s, and a pH of 4.9 on the basis of SiO ₂ conversion.
The aqueous dispersion of composite oxide fine particles obtained above is concentrated using an ultrafiltration membrane, and an aqueous dispersion of composite oxide fine particles containing, as main components, silicon and aluminum having a solid content concentration of 30% by weight ( SW1) 5400 g was obtained. This aqueous dispersion has a SiO ₂ concentration of 29.34% by weight, an Al ₂ O ₃ concentration of 0.42% by weight, a Na ₂ O concentration of 0.24% by weight, and an Al ₂ O ₃ / SiO ₂ molar ratio of 84 ×. 10 ⁻⁴ , pH was 4.8. The composite oxide fine particles contained in the aqueous dispersion of the composite oxide fine particles are spherical, the average particle diameter determined by the BET method is 16.8 nm, the specific surface area is 162 m ² / g, and the unit of the composite oxide fine particles The amount of negative charges existing per specific surface area was 0.9 μeq / m ² .
The modification amount of aluminum contained in the composite oxide fine particles was 0.85 × 10 ⁻⁶ mol / m ² in terms of unit surface area.

Preparation of methanol dispersion of fine composite oxide particles containing silicon and aluminum as main components (1)
5400 g of the aqueous dispersion (SW1) of the composite oxide fine particles obtained in the above step was converted from water to methanol (Jun Hayashi) using an ultrafiltration membrane device (a filtration membrane manufactured by Asahi Kasei Corporation, SIP-1013). The product was replaced by Yakuhin Co., Ltd., methyl alcohol concentration: 99.9% by weight.
The water content of the obtained complex oxide fine particle methanol dispersion (SM1) is about 10% by weight, the solids concentration is 30% by weight, the solids concentration on the basis of SiO ₂ is 29.34% by weight, When diluted 10 times with distilled water, the pH was 5.2 and the viscosity was 1.5 mPa · s. The composite oxide fine particles contained in the methanol dispersion of the composite oxide fine particles have an average particle diameter of 16.8 nm and a specific surface area of 162 m ² / g. The amount of aluminum modified into the composite oxide fine particles is The amount of negative charge existing per unit specific surface area of the composite oxide fine particles was 0.9 μeq / m ² in terms of unit surface area based on Al ₂ O ₃ and 0.85 × 10 ⁻⁶ mol / m ² .

Preparation of coating composition (1)
41.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) 13 A plurality of containers each containing 0.7 g of a mixed solution were prepared, and 36.1 g of a 0.1N hydrochloric acid aqueous solution was dropped into the mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, 16.8 g of a methanol dispersion (SM1) containing composite oxide fine particles containing silicon and aluminum as main components, prepared in the above step, in a container containing these hydrolyzed solutions, and further inorganic oxidation Dispersed methanol-containing sol (Optical 1120Z (8RS-25 / A17) manufactured by JGC Catalysts & Chemicals Co., Ltd., solid content concentration 20% by weight, average particle size 15 nm, TiO ₂ , SnO ₂ , SiO ₂ , K in the core and an inorganic oxide fine particles) 313.2G including the shell comprises ₂ O to SiO _2, ZrO _2, of propylene glycol monomethyl ether (PGM) 6.6 g, tris (2,4-pentanedionato) aluminum III (Tokyo Kasei Kogyo Kogyo Co., Ltd.) 1.4 g and leveling agent silicone surfactant (Toray Dow Corning Co., Ltd., L- 001) 0.2 g was added and stirred overnight at room temperature, paint compositions as a hard coat layer film-forming coating material for optical substrate (1) was prepared. At this time, the content of the composite oxide fine particles was 4.3 parts by weight with respect to 100 parts by weight of components other than the composite oxide.

Creation of plastic lens substrate (1)
(1) Pretreatment of plastic lens substrate 10 weight of commercially available plastic lens substrate “monomer name: MR-7” (manufactured by Mitsui Chemicals, Inc., refractive index of substrate 1.67) maintained at 40 ° C. Etching was performed by immersing in a KOH aqueous solution having a concentration of 2% for 2 minutes. Further, these were taken out, washed with water, and then sufficiently dried.

(2) Formation of hard coat layer film The coating composition (1) prepared in this example was applied to the surface of the plastic lens substrate to form a hard coat layer coating film. In addition, application | coating of this coating composition was performed using the dipping method (lifting speed 300 minutes).
Next, after drying the said coating film for 10 minutes at 90 degreeC, it heat-processed for 2 hours at 110 degreeC, and hardened | cured the coating film (hard-coat layer).
In addition, the film thickness after hardening of the said hard-coat layer film | membrane formed in this way was about 2.5-3.0 micrometers.

(3) Formation of antireflection film layer An example substrate HX-1 with a coating film was obtained by depositing an inorganic oxide component having the following constitution on the surface of the hard coat layer film by vacuum deposition. . Here, the order of SiO ₂ : 0.06λ, ZrO ₂ : 0.15λ, SiO ₂ : 0.04λ, ZrO ₂ : 0.25λ, and SiO ₂ : 0.25λ from the hard coat layer side toward the atmosphere side. Each of the layers of the antireflection layer film laminated in (1) was formed. The design wavelength λ was 520 nm.
For this example substrate HX-1, the appearance (interference fringes), appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance and light resistance were tested and evaluated using the above-described evaluation test method. . The results are shown in Table 1.

[Example 2]
Preparation of coating composition (2)
41.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) 13 A plurality of containers each containing 0.7 g of a mixed solution were prepared, and 36.1 g of a 0.1N hydrochloric acid aqueous solution was dropped into the mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, 0.8 g of a complex oxide fine particle methanol dispersion (SM1) containing silicon and aluminum as main components, prepared in Example 1, in a container containing these hydrolyzed solutions, and further inorganic oxide fine particles -Dispersed methanol-containing sol (manufactured by JGC Catalysts & Chemicals Co., Ltd. Optolake 1120Z (8RS-25 · A17), solid content concentration 20% by weight, average particle size 15 nm, core TiO ₂ , SnO ₂ , SiO ₂ , K ₂ O Inorganic oxide fine particles containing SiO ₂ and ZrO ₂ in the shell) 313.2 g, propylene glycol monomethyl ether (PGM) 6.6 g, tris (2.4-pentanedionate) aluminum III (Tokyo Chemical Industry Co., Ltd.) 1.4g) and a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7001). g was added and stirred overnight at room temperature, paint compositions as a hard coat layer film-forming coating material for optical substrate (2) was prepared. At this time, the content of the composite oxide fine particles was 0.2 parts by weight with respect to 100 parts by weight of components other than the composite oxide.

Creation of plastic lens substrate (2)
Next, in the step (1) for producing the plastic lens substrate of Example 1, the same procedure as in Example 1 was used except that the coating composition (2) prepared in this example was used instead of the coating composition (1). Thus, Example substrate HX-2 was obtained.
About this Example board | substrate HX-2, it evaluated by testing external appearance (interference fringe), external appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance, and light resistance using the above-described evaluation test method. . The results are shown in Table 1.

[Example 3]
Preparation of coating composition (3)
41.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) 13 A plurality of containers each containing 0.7 g of a mixed solution were prepared, and 36.1 g of a 0.1N hydrochloric acid aqueous solution was dropped into the mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, 19.2 g of a methanol dispersion (SM1) of composite oxide fine particles containing silicon and aluminum as main components, prepared in Example 1, in a container containing these hydrolyzed solutions, and further inorganic oxide fine particles -Dispersed methanol-containing sol (manufactured by JGC Catalysts & Chemicals Co., Ltd. Optolake 1120Z (8RS-25 · A17), solid content concentration 20% by weight, average particle size 15 nm, core TiO ₂ , SnO ₂ , SiO ₂ , K ₂ O Inorganic oxide fine particles containing SiO ₂ and ZrO ₂ in the shell) 313.2 g, propylene glycol monomethyl ether (PGM) 6.6 g, tris (2.4-pentanedionate) aluminum III (Tokyo Chemical Industry Co., Ltd.) )) 1.4g and silicone surfactant as leveling agent (Toray Dow Corning Co., Ltd., L-7001) 0 2g was added and stirred overnight at room temperature, paint compositions as a hard coat layer film-forming coating material for optical base material (3) was prepared. At this time, the content of the composite oxide fine particles was 4.8 parts by weight with respect to 100 parts by weight of components other than the composite oxide.

Creation of plastic lens substrate (3)
Next, in the step (1) of producing the plastic lens substrate of Example 1, the same procedure as in Example 1 was used except that the coating composition (3) prepared in this example was used instead of the coating composition (1). Thus, Example substrate HX-3 was obtained.
About this example substrate HX-3, the above-described evaluation test method was used to test and evaluate the appearance (interference fringes), appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance, and light resistance. . The results are shown in Table 1.

[Example 4]
Preparation of aqueous dispersion of composite oxide fine particles containing silicon and aluminum as main components (2)
Preparation of aqueous dispersion of composite oxide fine particles containing silicon and aluminum as main components in Example 1 (1) In step (1), an aqueous solution of sodium aluminate (concentration: 0.9% by weight) added to alkaline silica sol Except for changing the amount from 2712 g to 611 g, an aqueous dispersion (SW2) of composite oxide fine particles containing silicon and aluminum as main components and having a solid content concentration of 30% by weight was obtained in the same manner as in Example 1.
At this time, the Al ₂ O ₃ / SiO ₂ molar ratio when the sodium aluminate aqueous solution was mixed with the alkaline silica sol in step (1) was 0.2.
Further, the SiO ₂ concentration of the aqueous dispersion of the composite oxide fine particles is 30.32% by weight, the Al ₂ O ₃ concentration is 0.05% by weight, the Na ₂ O concentration is 0.03% by weight, Al ₂ O ₃ / The SiO ₂ molar ratio was 9.7 × 10 ⁻⁴ and the pH was 6.3.

The composite oxide fine particles contained in the aqueous dispersion (SW2) of the composite oxide fine particles have an average particle size of 16.7 nm, a specific surface area of 160 m ² / g, and a negative charge amount per unit surface area of 0.12 μeq. / m ^2, modification amount of aluminum per unit surface area was 9.7 × 10 ^-4 mol / m ^2.

Preparation of methanol dispersion of composite oxide fine particles containing silicon and aluminum as main components (2)
Example 1 except that the composite oxide fine particle aqueous dispersion (SW2) prepared in this example was used instead of the composite oxide fine particle aqueous dispersion (SW1) containing silicon and aluminum as main components. A methanol dispersion (SM2) of composite oxide fine particles containing silicon and aluminum as main components was prepared in the same manner as the preparation (1) of a methanol dispersion of composite oxide fine particles containing silicon and aluminum as main components.
The water content of the resulting composite oxide fine particle methanol dispersion (SM2) is about 10% by weight, the solids concentration is 30% by weight, the solids concentration on the basis of SiO ₂ is 30.32% by weight, When diluted 10 times with distilled water, the pH was 5.2 and the viscosity was 1.5 mPa · s. The composite oxide fine particles contained in the methanol dispersion have an average particle diameter of 16.7 nm and a specific surface area of 160 m ² / g. The amount of aluminum modified into the composite oxide fine particles is based on Al ₂ O _3. unit surface area converted at 9.7 × 10 ^-4 mol / m ² of the negative charge amount present in the unit specific per surface area of the composite oxide particles was 0.12Myueq / m ^2.

Preparation of coating composition (4)
41.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) 13 A plurality of containers each containing 0.7 g of a mixed solution were prepared, and 36.1 g of a 0.1N hydrochloric acid aqueous solution was dropped into the mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, 16.8 g of a methanol dispersion (SM2) of composite oxide fine particles containing silicon and aluminum as main components, prepared in this example, and inorganic oxide fine particles prepared in this example were placed in a container containing these hydrolysis solutions. Methanol-dispersed sol (manufactured by JGC Catalysts & Chemicals Co., Ltd. Optolake 1120Z (8RS-25 / A17), solid content concentration 20% by weight, average particle size 15 nm, TiO ₂ , SnO ₂ , SiO ₂ , K ₂ O in the core Inorganic oxide fine particles containing SiO ₂ and ZrO ₂ in the containing shell) 313.2 g, 6.6 g of propylene glycol monomethyl ether (PGM), Tris (2.4-pentanedionate) aluminum III (Tokyo Chemical Industry Co., Ltd.) 1.4 g) and a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7001). g was added and stirred overnight at room temperature, paint compositions as a hard coat layer film-forming coating material for optical substrate (4) was prepared. At this time, the content of the composite oxide fine particles was 4.3 parts by weight with respect to 100 parts by weight of components other than the composite oxide.

Creation of plastic lens substrate (4)
Next, in the step (1) for producing the plastic lens substrate of Example 1, the same procedure as in Example 1 was used, except that the coating composition (4) prepared in this example was used instead of the coating composition (1). Example substrate HX-4 was obtained by this method.
This Example Substrate HX-4 was tested and evaluated for appearance (interference fringes), appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance, and light resistance using the above-described evaluation test method. . The results are shown in Table 1.

[Comparative Example 1]
Preparation of coating composition (5)
41.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) 13 A plurality of containers each containing 0.7 g of a mixed solution were prepared, and 36.1 g of a 0.1N hydrochloric acid aqueous solution was dropped into the mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, in a container containing these hydrolysates, a methanol-dispersed sol containing inorganic oxide fine particles (Optical 1120Z (8RS-25 · A17) manufactured by JGC Catalysts & Chemicals Co., Ltd.), solid content concentration 20% by weight, average Particle diameter 15 nm, inorganic fine particles containing TiO ₂ , SnO ₂ , SiO ₂ , K ₂ O in the core and SiO ₂ , ZrO ₂ in the shell) 313.2 g, 6.6 g of propylene glycol monomethyl ether (PGM), 1.4 g of tris (2.4-pentanedionato) aluminum III (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.2 g of a silicone surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) as a leveling agent And stirred at room temperature all day and night to prepare a coating composition (R1) as a coating composition for forming a hard coat layer film for an optical substrate. At this time, the content of the composite oxide fine particles was 0 part by weight with respect to 100 parts by weight of components other than the composite oxide.

Making a plastic lens substrate (5)
Next, in the process (1) for producing the plastic lens substrate of Example 1, the same procedure as in Example 1 was used except that the coating composition (R1) prepared in this Comparative Example was used instead of the coating composition (1). Thus, a comparative substrate HR-1 was obtained.
About this comparative example board | substrate HR-1, using said evaluation test method, the external appearance (interference fringe), external appearance (cloudiness), scratch resistance, film | membrane hardness, adhesiveness, weather resistance, and light resistance were tested and evaluated. . The results are shown in Table 1.

[Comparative Example 2]
Preparation of coating composition (6)
41.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) 13 A plurality of containers each containing 0.7 g of a mixed solution were prepared, and 36.1 g of a 0.1N hydrochloric acid aqueous solution was dropped into the mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, in a container containing these hydrolysis solutions, an aqueous dispersion of composite oxide fine particles containing only silicon as a main component (cataloid SI-40 manufactured by JGC Catalysts & Chemicals Co., Ltd., solid content concentration 40% by weight, average particle size 17 nm, SiO ₂ content of 99.0 wt%) 12.6 g, further methanol dispersion sol containing inorganic oxide fine particles (JGC catalysts and Chemicals Ltd. Optolake 1120Z (8RS-25 · A17) , the concentration solids 203.2% by weight, average particle diameter 15 nm, 313.2 g of inorganic oxide fine particles containing TiO ₂ , SnO ₂ , SiO ₂ , K ₂ O in the core and SiO ₂ , ZrO ₂ in the shell), and propylene glycol monomethyl ether (PGM) 6.6 g, Tris (2.4-pentandionato) aluminum III (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.4 g and Siri Coating composition as a coating composition for forming a hard coat layer film for an optical substrate by adding 0.2 g of an organic surfactant (manufactured by Toray Dow Corning Co., Ltd., L-7001) and stirring the mixture overnight at room temperature. (R2) was prepared. At this time, the content of the composite oxide fine particles was 4.3 parts by weight with respect to 100 parts by weight of components other than the composite oxide.
Next, in the step (1) for producing the plastic lens substrate of Example 1, the same procedure as in Example 1 was used, except that the coating composition (R2) prepared in this Comparative Example was used instead of the coating composition (1). Thus, a comparative substrate HR-2 was obtained.
About this comparative example board | substrate HR-2, using said evaluation test method, the external appearance (interference fringe), external appearance (cloudiness), scratch resistance, film | membrane hardness, adhesiveness, weather resistance, and light resistance were tested and evaluated. . The results are shown in Table 1.

[Comparative Example 3]
Preparation of coating composition (7)
41.0 g of γ-glycidoxypropyltrimethoxysilane (Z-6040 manufactured by Toray Dow Corning Co., Ltd.), γ-glycidoxypropylmethyldiethoxysilane (Z-6042 manufactured by Toray Dow Corning Co., Ltd.) 13 A plurality of containers each containing 0.7 g of a mixed solution were prepared, and 36.1 g of a 0.1N hydrochloric acid aqueous solution was dropped into the mixed solution while stirring. Furthermore, this liquid mixture was stirred at room temperature all day and night to hydrolyze the silane compound.
Next, in a container containing these hydrolyzed solutions, 39.0 g of a complex oxide fine particle methanol dispersion (SM1) prepared mainly in Example 1 containing silicon and aluminum as main components, and further inorganic oxide fine particles were added. Methanol-dispersed sol (manufactured by JGC Catalysts & Chemicals Co., Ltd. Optolake 1120Z (8RS-25 / A17), solid content concentration 20% by weight, average particle size 15 nm, TiO ₂ , SnO ₂ , SiO ₂ , K ₂ O in the core Inorganic oxide fine particles containing SiO ₂ and ZrO ₂ in the containing shell) 313.2 g, 6.6 g of propylene glycol monomethyl ether (PGM), Tris (2.4-pentanedionate) aluminum III (Tokyo Chemical Industry Co., Ltd.) 1.4 g) and a silicone surfactant as a leveling agent (manufactured by Toray Dow Corning Co., Ltd., L-7001). g was added and stirred overnight at room temperature, paint compositions as a hard coat layer film-forming coating material for optical base material (R3) was prepared. At this time, the content of the composite oxide fine particles was 10.0 parts by weight with respect to 100 parts by weight of components other than the composite oxide.

Next, in the step (1) for producing the plastic lens substrate of Example 1, the same procedure as in Example 1 was used, except that the coating composition (R3) prepared in this Comparative Example was used instead of the coating composition (1). In this way, a comparative substrate HR-3 was obtained.
About this comparative example board | substrate HR-3, it evaluated by testing external appearance (interference fringe), external appearance (cloudiness), scratch resistance, film hardness, adhesion, weather resistance, and light resistance using the above-described evaluation test method. . The results are shown in Table 1.

  As shown in Table 1, using a coating composition containing composite oxide fine particles containing silicon and aluminum as main components in a range of 0.1 to 5 parts by weight with respect to 100 parts by weight of other components. It turned out that the film | membrane hardness of the Example board | substrate which formed the hard-coat layer film | membrane improves dramatically. Further, it was found that the substrate of this example was excellent in scratch resistance, had no interference fringes, and had excellent adhesion, light resistance and weather resistance. From these, it was shown that the coating composition according to the present invention has excellent performance as a coating composition for forming a coating film for a high refractive index substrate.

Claims (4)

(C) a composite oxide particles molar ratio of unrealized silicon and aluminum as main components silicon and aluminum in the range of 0.0005 to 0.05 with Al ₂ O ₃ / SiO ₂ equivalent value,
(F) Core-shell type in which the core is a composite oxide fine particle containing one or more selected from zirconium, tin, titanium, niobium, tungsten, antimony, and indium, and the shell is an oxide or composite oxide containing silicon A filler comprising inorganic oxide fine particles, and
(M) A coating composition containing a matrix-forming component comprising an organosilicon compound and / or a hydrolyzate thereof ,
The content of the composite oxide fine particles (C) is, when the total weight 100 parts by weight of the filler (F) and the matrix forming component (M), and being in the range of 0.1 to 5 parts by weight A coating composition for forming a hard coat layer film . When silicon and aluminum contained in the composite oxide fine particles are combined with each other in terms of SiO ₂ and Al ₂ O ₃ , 70 to 100% by weight based on the total weight of the composite oxide fine particles. The coating composition for forming a hard coat layer film according to claim 1, wherein the coating composition is in the range of. The content of the composite oxide fine particles (C) is in the range of 0.1 to 3.0 parts by weight when the total weight of the filler (F) and the matrix forming component (M) is 100 parts by weight. 3. The coating composition for forming a hard coat layer film according to claim 1 or 2 . The surface negative charge density of the composite oxide fine particles is in the range of 0.5 to 1.1 μeq / m ² when the pH of the dispersion sol containing the composite oxide fine particles is 5.0. The coating composition for hard-coat layer film formation in any one of Claims 1-3 .