JP2002363442A - Composite oxide particle including antimony oxide- covered titanium oxide, dispersion sol of the particle, coating liquid for forming transparent film containing the fine particle, and substrate having transparent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a composite oxide particle suitably usable for a coating liquid capable of providing a high refractive index film having colorless transparency and high refraction index, further having excellent hot-water resistance, sweat resistance, weather resistance, light resistance, chemical resistance, scratch resistance, abrasion resistance, impact resistance, flexibility, dyeability, discoloration resistance and adhesion to a substrate, and further to prepare a dispersion sol of the particle, and the coating liquid containing the particle. SOLUTION: The composite oxide particle comprising antimony oxide-covered titanium oxide is regulated so that the content of the titanium oxide expressed in terms of TiO2 in the nuclear particle containing the titanium oxide may be >=10 wt.%, and the amount of the covering layer comprising the antimony oxide expressed in terms of Sb2 O5 may be 1-90 wt.% based on the amount of the composite oxide particle comprising the antimony oxide- covered titanium oxide. The dispersion sol of the particle is obtained by dispersing the composite oxide particle comprising the antimony oxide-covered titanium oxide in water and/or an organic solvent. The coating liquid for forming the transparent coating film contains the composite oxide particle comprising the antimony oxide-covered titanium oxide, and a matrix-forming component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antimony oxide-coated titanium oxide-containing composite oxide particle comprising a titanium oxide-containing core particle and an antimony oxide-coated layer, an aqueous dispersion sol of the fine particles, an organosol of the fine particles, and The present invention relates to a coating solution for forming a transparent film using fine particles, and a substrate with a transparent film formed using the coating solution. More specifically, it has a high refractive index, high transmittance, no interference fringes, scratch resistance, abrasion resistance, impact resistance, hot water resistance, sweat resistance, chemical resistance, weather resistance, light resistance Contains antimony oxide-coated titanium oxide, which is excellent in flexibility, adhesion to substrates such as glass and plastics, and can be used to further improve dimming properties, dyeing properties, fading resistance, etc. The present invention relates to composite oxide particles, a coating solution for forming a transparent film using the fine particles, and a substrate with a transparent film formed using the coating solution.

[0002]

BACKGROUND OF THE INVENTION Conventionally, various high-refractive-index hard films have been formed on a surface of a base material such as a transparent plastic or glass to form a hard coat film having a refractive index equivalent to that of the base material. A method for forming a coat film has been proposed. In this connection, diethylene glycol bis (allyl carbonate) resin lenses are particularly superior in safety, workability, fashionability, and the like as compared with glass lenses. Due to the development of coating technology and anti-reflection technology, it has spread rapidly. However, since the refractive index of diethylene glycol bis (allyl carbonate) resin is 1.50, which is lower than that of a glass lens, there is a defect that the outer peripheral portion of a myopic lens is thicker than that of a glass lens. For this reason, in the field of spectacle lenses made of synthetic resin, attempts are being actively made to reduce the thickness using a high refractive index resin material. As such an attempt, JP-A-59-13
JP-A-3211, JP-A-63-46213, JP-A-2-270859 and the like propose a high refractive index resin material having a refractive index of 1.60 or more.

On the other hand, plastic spectacle lenses have a drawback that they are easily scratched. Therefore, a method of providing a silicon-based hard coat film on the surface of a plastic lens is generally used. However, when the same method is applied to a high-refractive-index resin lens having a refractive index of 1.54 or more, interference fringes may occur due to a difference in the refractive index between the resin lens and the coating film, which may cause poor appearance. To solve this problem, Japanese Patent Publication No. Sho 61-54331 and Japanese Patent Publication No. Sho 63-3
No. 7142 discloses a colloidal dispersion of fine particles of silicon dioxide used in a coating solution for forming a silicon-based film (hereinafter, the coating solution for forming a film may be referred to as a coating composition) having a high refractive index. Al, Ti, Zr, S
There is disclosed a technique of replacing the inorganic oxide fine particles of n and Sb with a colloidal dispersion. Also, JP-A-1-301
No. 517 discloses a method for producing a composite sol of titanium oxide and cerium dioxide.
No. 4902 discloses a composite inorganic oxide fine particle of Ti and Ce, and JP-A-3-68901 discloses T
A coating composition containing fine particles obtained by treating a composite oxide of i, Ce and Si with an organosilicon compound is disclosed.

Japanese Patent Application Laid-Open Nos. 5-2102 and 7-76671 disclose composite oxide fine particles of Ti and Fe and composite oxide fine particles of Ti, Fe and Si treated with an organosilicon compound. And cured coatings containing the same. Further, the present applicant has disclosed in Japanese Patent Application Laid-Open No. 8-48940 that Ti, Si and Z
Disclosed are a coating composition containing fine particles obtained by treating a composite inorganic oxide of r with an organosilicon compound, and a cured film.

However, the coating compositions described in JP-B-61-54331 and JP-B-63-37142 have the following problems. For example, when a colloidal dispersion of oxide fine particles of Al, Zr, Sn, and Sb is used as a coating composition for a high-refractive-index resin lens having a refractive index of 1.54 or more, the coating and curing of the resin are higher than that of a silicon-based coating composition. The degree of subsequent interference fringes can be improved. However, when inorganic oxide fine particles of Al and Sb are used, the refractive index as a coating film is limited, so that it is impossible to completely suppress interference fringes for a lens substrate of 1.60 or more. Met. This is because although the inorganic oxide fine particles alone have a high refractive index of 1.60 or more, when they are generally used as a coating material, an organosilicon compound, an epoxy resin, or the like is mixed, so that the filling rate is reduced, and the coating of the coating is reduced. This is because the refractive index is lower than that of the base lens. Also, when inorganic oxide fine particles of Zr and Sn were used, their dispersibility was unstable, so that when used in large amounts, a transparent coating could not be obtained.

On the other hand, when a colloidal dispersion of Ti inorganic oxide fine particles is used as a coating composition,
Since TiO ₂ itself has a higher refractive index than the inorganic oxide, the formed film shows a refractive index of around 1.60 or more, and the range of the refractive index of the film that can be set is widened. There is an advantage. However, T
Because iO ₂ is inferior weatherability is very, decomposition of the organic silicon compounds and organic components in the coating with a film formed from a coating composition containing TiO _2, decomposition of the epoxy resin component, more coating a resin substrate surface Degradation occurred, and there was a problem in coating durability. In addition, there is also a problem that this coating is inferior in adhesion to a substrate.

For this reason, a coating composition containing composite oxide fine particles of titanium dioxide and cerium dioxide described in JP-A-2-264909 and JP-A-3-68901, or JP-A-5-2102 is disclosed. A coating composition comprising the described composite oxide microparticles of titanium dioxide and iron oxide has been proposed. However, when cerium dioxide or iron oxide is combined with titanium dioxide to improve the weather resistance of titanium dioxide, the coatings obtained from these coating compositions are not always satisfactory in terms of fading resistance. Further, there is also a problem that the cured coating obtained from these composite sols is more or less colored.

In recent years, plastic lenses have become thinner as the refractive index of plastic lenses has increased. A hard coat layer (film) is formed on the surface of the plastic lens having a high refractive index, and an antireflection film is further formed on the hard coat film for the purpose of preventing reflection, thereby forming a multi-coat layer. The plastic lens substrate is distorted during the formation process, and is easily broken by impacts such as falling.However, in order to eliminate such defects, use a flexible primer layer between the plastic lens and the hard coat film to absorb the impact. Provision has been made.

However, if the refractive index of the primer film is not equal to the refractive index of the base material, there is a problem that interference fringes occur, and it is desired to form a primer film having the same refractive index as the base material. The present applicant has disclosed Japanese Patent Application Laid-Open No. 8-4894.
No. 0, the refractive index is 1.54 or more (specifically, 1.5
9-9. 1.66) has proposed a coating liquid for forming a film containing titanium, which can be suitably used for a lens substrate, fine particles of a composite oxide composed of oxides of silicon, zirconium and / or aluminum, and a matrix.

[0010] Further, JP-A-9-71580, JP-A-9-110979 and JP-A-9-255798 disclose that the refractive index is as high as 1.67 to 1.70 and the Abbe number is 30. A lens substrate (optical material) obtained from the above ebisulphide compound has been proposed. For this reason,
The present applicants have proposed in JP-A-2000-204301 a coating liquid for forming a coating film which can be suitably used for such a lens substrate having a high refractive index and a high Abbe number.
At this time, titanium oxide fine particles or titanium oxide fine particles containing zirconium oxide or silicon oxide are used as core particles, and fine particles having a coating layer formed of at least one of silicon oxide, zirconium oxide, and aluminum oxide can be suitably used. Is disclosed.

Further, in recent years, the refractive index of plastic lenses (organic glass) has been further increased, and for example, high refractive index plastic lenses having a refractive index of 1.71-1.74 are commercially available. However, such a high-refractive-index lens has a drawback that the dyeability and the impact resistance are inferior to those having a refractive index of 1.54 to less than 1.71. For this reason, there is a method of directly dyeing a high-refractive-index lens by a transfer method.

In addition, since the impact resistance is low as described above, it is necessary to provide a primer layer between the lens substrate and the hard coat layer in order to improve the impact resistance. JP-A-6-82604, JP-A-6-13
No. 8301 is disclosed. Therefore, it has been proposed to dye such a hard coat layer or a primer layer. However, in the above-mentioned conventionally known composite particles containing titanium oxide, the dyeing may be faded. there were.

[0013]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and is colorless and transparent, has a high refractive index, and further has hot water resistance, sweat resistance, weather resistance, and the like. High refractive index with excellent light resistance, chemical resistance, scratch resistance, abrasion resistance, impact resistance, flexibility, excellent dyeing and fading resistance, and excellent adhesion to the substrate It is an object of the present invention to provide a composite oxide particle which can be suitably used in a coating solution capable of forming a film, the particle-dispersed sol, and a coating solution.

Further, the present invention provides a colorless, transparent and durable resin lens having a refractive index of 1.54 or more, more preferably 1.60 or more, further 1.67 or more, especially 1.70 or more. Excellent in hot water resistance, sweat resistance, weather resistance, chemical resistance, abrasion resistance, abrasion resistance, impact resistance, flexibility, and also excellent dyeing and fading resistance, and interference fringes It is another object of the present invention to provide a transparent-coated substrate having excellent anti-fading properties, such as a synthetic resin lens having a small thickness, on which a high-refractive-index hard coat film that does not occur is formed.

[0015]

SUMMARY OF THE INVENTION The antimony oxide-coated titanium oxide-containing composite oxide particles according to the present invention are characterized by comprising titanium oxide-containing core particles and a coating layer made of antimony oxide. The titanium oxide content in the titanium oxide-containing core particles is 10% by weight or more in terms of TiO ₂ , and the amount of the coating layer made of the antimony oxide oxide is more than that of the antimony oxide-coated titanium oxide-containing composite oxide particles. ,
Sb ₂ O ₅ is preferably in the range of 1 to 90% by weight.

The titanium oxide-containing core particles are Si, Al,
1 selected from Sn, Zr, Zn, Sb, Nb, Ta and W
It preferably contains oxides of more than one element. Further, Si, Al, Sn, Zr, Zn, Sb, Nb,
One or more intermediate thin film layers made of any one of oxides, composite oxides, and mixtures of one or more elements selected from Ta and W may be formed.

The surface of the titanium oxide-containing composite oxide particles coated with antimony oxide according to the present invention is preferably modified with an organosilicon compound or an amine compound. The antimony oxide-coated titanium oxide-containing composite oxide particle dispersion sol according to the present invention is obtained by dispersing the above-described antimony oxide-coated titanium oxide-containing composite oxide particles in water and / or an organic solvent.

The coating liquid for forming a transparent film according to the present invention comprises an antimony oxide-coated titanium oxide-containing composite oxide particle as described above, an organosilicon compound represented by the following formula (A) as a matrix-forming component, and an organosilicon compound. It is characterized by containing at least one hydrolyzate and / or partial condensate of the compound.

R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (A) wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group,
A methacryloxy group, a mercapto group, an organic group having an amino group or an epoxy group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a hydrocarbon group or an acyl group having 1 to 8 carbon atoms,
a and b represent 0 or 1. Further, the second coating liquid for forming a transparent film according to the present invention comprises the above-described antimony oxide-coated titanium oxide-containing composite oxide particles, and a thermosetting resin as a matrix-forming component.
It is characterized by containing at least one resin selected from a thermoplastic resin and an ultraviolet curable resin. In particular, it is preferable that the matrix forming component is made of a polyester resin or a urethane resin.

The substrate with a transparent film according to the present invention is characterized in that the substrate has a transparent film formed on the surface of the substrate using the first or second coating liquid for forming a transparent film.
A hard coat formed on the surface of the base material using a primer film formed using the second transparent film forming coating solution and further using the first transparent film forming coating solution thereon It is characterized by having a film.

An antireflection film may be further provided on the transparent film or the hard coat film.

[0022]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. First, the antimony oxide-coated titanium oxide-containing composite oxide particles according to the present invention will be described. The antimony oxide-coated titanium oxide-containing composite oxide particles according to the present invention are characterized by comprising titanium oxide-containing core particles and a coating layer made of antimony oxide. Although the average particle size of such an antimony oxide-coated titanium oxide-containing composite oxide particle is not particularly limited, it is desirably in the range of 1 to 100 nm, preferably 2 to 60 nm.

When the average particle diameter is less than 1 nm, the coating obtained using a coating solution containing these particles has insufficient hardness, poor scratch resistance and abrasion resistance, and has a sufficient refractive index of the coating. And the average particle diameter is 10
If it exceeds 0 nm, the resulting coating may become cloudy and opaque. [Titanium oxide-containing core particles] The titanium oxide-containing core particles may be made of only titanium oxide or may be made of titanium oxide and components other than titanium oxide. When components other than titanium oxide are contained, oxides of one or more elements selected from Si, Al, Sn, Zr, Zn, Sb, Nb, Ta and W are preferable as components other than titanium oxide.
Such titanium oxide and components other than titanium oxide may be in a mixture, in a solid solution state with each other, or in another composite state. The titanium oxide may be amorphous or crystalline such as anatase, rutile, or brookite. Furthermore, barium titanate (B
a perovskite type titanium compound such as aTiO ₃ or BaO.TiO ₂ ).

The content of titanium oxide in the core particles containing titanium oxide is 10% by weight or more, preferably 20% by weight or more in terms of TiO ₂ . (The upper limit is 100% by weight.) When the content of titanium oxide is less than 10% by weight, the refractive index of the transparent film obtained by using the coating liquid containing these particles does not increase, and depending on the refractive index of the substrate, interference occurs. Streaks may form.

As an example of the case where components other than titanium oxide are contained in the above-mentioned titanium oxide-containing core particles, there are particles made of titanium oxide and tin oxide. When a composite core particle of titanium oxide and tin oxide is used, a transparent film having a high refractive index suitable for use in a high refractive index lens substrate can be obtained. Further, as the titanium oxide-containing core particles, particles containing an oxide of Si or Zr in addition to tin oxide can also be suitably used.
When tin oxide, silica, and zirconia are contained as described above, the ratio of titanium oxide and oxides other than titanium oxide in the titanium oxide-containing core particles is calculated as oxides other than titanium oxide (MO _x ), and TiO ₂ / (MO _x ) 50/50 by weight ratio
It is preferably in the range of 90/10. 50/50
When the weight ratio is less than 90/10, the refractive index of the transparent coating may be low, and when the weight ratio is more than 90/10, the stability when used as titanium oxide-containing core particles may be insufficient.

The refractive index of the titanium oxide-containing core particles used in the present invention varies depending on the crystallinity and composition of the particles, but is generally 1.7 to 3.0, and in many cases 2.2 to 2.0.
It shows a value in the range of 2.7, which is higher than the refractive index of oxides of Al, Zr, Sn and Sb. The average particle diameter of such titanium oxide-containing core particles is not particularly limited, but is generally about 1 to 100.
nm, preferably in the range of 2 to 50 nm.

[Antimony Oxide Coating Layer] The antimony oxide-coated titanium oxide-containing composite oxide particles according to the present invention comprise:
A coating layer made of antimony oxide is formed on the surface of the titanium oxide-containing core particles. The thickness of the antimony oxide coating layer is not particularly limited, and varies depending on the particle diameter of the titanium oxide-containing core particles.
It is desirable to be in the range of 00 to 1/5. Further, 1 to 90 wt% content of the Sb ₂ O ₅ of antimony oxide constituting the coating layer of antimony oxide coated titanium oxide-containing composite oxide particles, so that preferably in the range of 5 to 50 wt% What is necessary is just to be formed.

With such an antimony oxide coating layer, compared to the case of using only titanium oxide-containing core particles,
The fading resistance of the coating obtained from the coating liquid containing these particles is improved. The content of the antimony oxide coating layer in the antimony oxide-coated titanium oxide-containing composite oxide particles is Sb ₂
If the O ₅ less than 1 wt%, the fading resistance is insufficient that the proportion is less of the titanium oxide-containing core particle content of antimony oxide exceeds 90% by weight as Sb ₂ O _5, The refractive index of the antimony oxide-coated titanium oxide-containing composite oxide particles decreases, the refractive index of the obtained transparent coating decreases, and interference fringes may occur depending on the refractive index of the substrate.

In the present invention, the antimony oxide is
It may be amorphous, crystalline such as a pyrochlore structure, or crystalline not specified as a pyrochlore structure, or the like, and may contain water of hydration or water of crystallization. [Intermediate thin film layer] Further, Si, Al, Sn, Zr, Z
One or more intermediate thin film layers made of at least one of oxides, composite oxides, and mixed oxides of one or more elements selected from n, Sb, Nb, Ta and W may be formed. The intermediate thin film layer may be a single layer or a multilayer of two or more layers.

By forming at least one intermediate thin film layer between the titanium oxide-containing core particles and the antimony oxide coating layer, the refractive index of the antimony oxide-coated titanium oxide-containing composite oxide particles can be adjusted. In addition, the light resistance and weather resistance of the coating obtained using a coating solution containing these particles (such as resistance to the deterioration of the film due to the decomposition of the vehicle component due to the activity of the core particles containing titanium oxide), the film and the base The adhesion to the material can be improved, the coloring of the particles can be suppressed, and the particles can be made colorless, and the transparency of the film can be improved.

The number and thickness of the intermediate thin film layers provided in at least one layer are such that the proportion of the titanium oxide-containing core particles in the antimony oxide-coated titanium oxide-containing composite oxide particles is 10 to 99% by weight. There is no particular limitation as long as it is formed so that the proportion of the antimony oxide coating layer is in the range of 1 to 90% by weight. As the intermediate thin film layer, a composite oxide composed of silicon oxide, zirconium oxide, and / or aluminum oxide is particularly preferable. As the composite form, silicon oxide, zirconium oxide, and aluminum oxide are laminated for each single component. The thin film layer may be formed, or the thin film layer may be formed of silica-zirconia, silica-alumina, and silica-zirconia-alumina components.

In this case, when silicon oxide and zirconium oxide and / or aluminum oxide are used as the intermediate thin film layer, excellent weather resistance, light resistance, adhesion to a substrate,
Antimony oxide-coated titanium oxide-containing composite oxide particles capable of forming a transparent film having film hardness, scratch resistance, flexibility and the like can be obtained. In addition, by including silicon oxide in the thin film layer, the stability of the composite oxide fine particle-dispersed water sol is improved, and the pot life of the coating solution described later is increased, and the hardness of the obtained transparent film is improved and the transparency of the transparent film is improved. Adhesion with the anti-reflection film formed thereon can be improved, and also in this case, weather resistance, light resistance, adhesion to the substrate, film hardness, abrasion resistance, flexibility, etc. are improved. I do.

[Preparation of antimony oxide-coated titanium oxide-containing composite oxide particles] The antimony oxide-coated titanium oxide-containing composite oxide particles are prepared by the above-described antimony oxide-coated titanium oxide-containing composite oxide particles. There is no particular limitation as long as the particles can be obtained, and a conventionally known method can be employed. As the titanium oxide-containing core particles, the composite oxide particles disclosed in JP-A-8-48940 filed by the present applicant can be preferably used. When obtaining an antimony oxide-coated titanium oxide-containing composite oxide particle having an (intermediate) thin film layer, a composite oxide particle having an intermediate thin film layer formed by the same method as that for forming a coating layer on core particles is used. Just fine.

As a method of forming the antimony oxide coating layer, first, an aqueous dispersion of titanium oxide-containing core particles or titanium oxide-containing core particles provided with an intermediate thin film layer is prepared. The concentration of the dispersion is preferably in the range of 0.01 to 40% by weight, more preferably 0.1 to 30% by weight as a solid content. When the solids concentration of the dispersion is less than 0.01% by weight, the productivity is low and the method is not industrially effective. In some cases, a transparent film excellent in film strength and the like cannot be obtained.

Next, an antimony compound is added to the dispersion. The addition amount of the antimony compound is 1 ratio of antimony oxide antimony oxide coated titanium oxide-containing composite oxide fine particles finally obtained as Sb ₂ O ₅
It is in the range of 90% by weight. The antimony compound used in the present invention is not particularly limited, and examples thereof include antimony mineral salts such as antimony chloride, organic acid salts such as antimony tartrate, and alkali antimonates such as sodium antimonate.

The solution prepared by dissolving the antimony compound in water and / or an organic solvent is added to the aqueous dispersion of the titanium oxide-containing core particles or the titanium oxide-containing core particles provided with the intermediate thin film layer, if necessary. The coating layer can be formed by adding while appropriately adjusting pH and temperature, then adding an oxidizing agent, and aging as needed.
After the formation of the coating layer, the impurities may be removed by a washing treatment as necessary.

The oxidizing agent is not particularly limited as long as the oxidation number of antimony can be maintained in a pentavalent or peroxidized state, and specifically, oxygen, ozone, hydrogen peroxide, hypochlorous acid and the like can be used. Examples of the washing method include an ultrafiltration membrane method and a deionization method using an ion exchange resin. [Surface Modification Treatment] The surface of the antimony oxide-coated titanium oxide-containing composite oxide particles according to the present invention may be modified by treating the surface with an organosilicon compound or an amine compound. When the modification treatment is performed as described above, the dispersion state of the antimony oxide-coated titanium oxide-containing composite oxide particles in the coating liquid containing the antimony oxide-coated titanium oxide-containing composite oxide particles and the matrix described below is long. And the dispersion state of the antimony oxide-coated titanium oxide-containing composite oxide particles in the coating liquid becomes stable even when an ultraviolet curable resin is used as the matrix. In addition, antimony oxide-coated titanium oxide-containing composite oxide particles whose surface is modified with an organosilicon compound or an amine-based compound have low reactivity with the matrix and good affinity with the matrix. The resulting film is higher in hardness and transparency than the film obtained from the coating solution containing the untreated antimony oxide-coated titanium oxide-containing composite oxide particles,
It is also excellent in abrasion resistance, adhesion to a substrate, abrasion resistance, flexibility and dyeing properties. Further, the affinity between the antimony oxide-coated titanium oxide-containing composite oxide particles and the solvent in the coating solution is further improved as compared with the case where the antimony oxide-coated titanium oxide-containing composite oxide particles are not surface-treated. Therefore, a coating liquid having excellent dispersibility can be prepared.

As the organosilicon compound to be used, a known organosilicon compound known as a silane coupling agent can be used, and its type is appropriately selected according to the use and the type of the solvent. The following are specifically used as the organosilicon compound. A monofunctional silane represented by the formula: R ₃ SiX (R is an organic group having an alkyl group, phenyl group, vinyl group, methacryloxy group, mercapto group, amino group, epoxy group, X
Is a hydrolyzable group). Examples of such a monofunctional silane include trimethylsilane, dimethylphenylsilane, dimethylvinylsilane and the like.

A bifunctional silane represented by the formula: R ₂ SiX ₂ (R and X are the same as monofunctional silane). Examples of such a bifunctional silane include dimethylsilane, diphenylsilane and the like. A trifunctional silane of the formula: RSix ₃ (R and X
Is the same as monofunctional silane). Examples of such a trifunctional silane include methylsilane, phenylsilane and the like.

Tetrafunctional silane represented by the formula: SiX ₄ (X is the same as monofunctional silane). Examples of such tetrafunctional silanes include tetraalkoxysilanes such as tetraethoxysilane. These may be used alone or as a mixture of two kinds. In performing the surface modification treatment, the hydrolyzable group may be untreated or partially hydrolyzed. Also,
After the treatment, a state in which the hydrolyzable group has reacted with the —OH group of the fine particles is preferable, but a state in which a part remains may be acceptable.

Examples of the amine compound include alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, monoethanolamine, triethanolamine and the like. And quaternary ammonium salts and quaternary ammonium hydroxides such as tetramethylammonium salts and tetramethylammonium hydroxides of these amines.

In order to modify the surface of the antimony oxide-coated titanium oxide-containing composite oxide particles with an organosilicon compound or an amine compound, for example, antimony oxide-coated titanium oxide-containing titanium oxide-containing composite oxide particles are dissolved in an alcohol solution of these compounds. Are mixed, and after adding a predetermined amount of water and a catalyst as necessary, it is preferable to leave the mixture at room temperature for a predetermined time or to perform a heat treatment.

The antimony oxide-coated titanium oxide-containing composite oxide can also be prepared by adding a hydrolyzate of these compounds and antimony oxide-coated titanium oxide-containing composite oxide particles to a mixture of water and alcohol and subjecting the mixture to heat treatment. The surface of the particles can be modified with these compounds. The amount of the organosilicon compound or amine compound used at this time is appropriately set according to the amount of hydroxyl groups present on the surface of the antimony oxide-coated titanium oxide-containing composite oxide particles.

Antimony oxide-coated composite containing titanium oxide
Oxide particle dispersion sol The antimony oxide-coated titanium oxide-containing composite oxide particle dispersion sol according to the present invention is the above-described antimony oxide-coated titanium oxide-containing composite oxide particle, in which water, an organic solvent, or a mixture of water and an organic solvent. Dispersed in mixed solvent. The antimony oxide-coated titanium oxide-containing composite oxide particle dispersion sol according to the present invention contains titanium oxide-containing core particles containing an oxide other than titanium oxide, or is provided with the above-mentioned (intermediate) thin film layer as necessary. Therefore, it is excellent in monodispersibility and dispersion stability as compared with conventionally known titanium oxide sol and antimony oxide sol, or conventionally known composite oxide sol containing other oxides.

The concentration of the antimony oxide-coated titanium oxide-containing composite oxide particles in the water sol in which the antimony oxide-coated titanium oxide-containing composite oxide particles are dispersed in water is approximately 0.01 to 40% by weight as a solid concentration. , Preferably 0.5 to
It is desirably in the range of 20% by weight. When the solid content concentration is less than 0.01% by weight, the concentration is too low, so that the concentration of the coating solution obtained by blending with other components becomes too low, and the thickness of the obtained coating film is reduced by one time. The desired thickness may not be achieved by coating. If the solid concentration exceeds 40% by weight, the stability of the sol may be insufficient.

In the case of an organosol in which antimony oxide-coated titanium oxide-containing composite oxide particles are dispersed in an organic solvent,
The antimony oxide-coated titanium oxide-containing composite oxide particles preferably have been surface-modified with an organosilicon compound or an amine compound. The surface-modified one is excellent in dispersibility in an organic solvent because the surface is hydrophobicized. The concentration of the antimony oxide-coated titanium oxide-containing composite oxide particles in the organosol is desirably approximately 1 to 60% by weight, preferably 2 to 30% by weight as a solid concentration. Solid content concentration 1% by weight
If the concentration is less than 1, the concentration of the coating solution obtained by blending with other components is too low because the concentration is too low, and the thickness of the obtained coating film cannot be attained to a desired thickness by one application. There is. If the solid concentration exceeds 60% by weight, the stability of the sol becomes insufficient.

Examples of the organic solvent used in the organosol of the present invention include alcohols such as methanol, ethanol and isopropyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, glycols such as ethylene glycol, methyl acetate, and the like. Esters such as ethyl acetate, ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as dichloroethane, aromatic hydrocarbons such as toluene and xylene, carboxylic acids and N, N -Dimethylformamide and the like. These solvents may be used as a mixture of two or more kinds.

First, the coating liquid for forming a high refractive index transparent film according to the present invention will be described. The coating solution for forming a high refractive index transparent film according to the present invention comprises a matrix forming component and titanium oxide-containing composite oxide particles coated with antimony oxide. [Matrix-forming component] In the first coating liquid for forming a high-refractive-index transparent film according to the present invention, an organosilicon compound represented by the following formula (A) as a matrix-forming component, its hydrolyzate, It contains at least one selected from partial condensates and mixtures thereof (hereinafter sometimes simply referred to as organosilicon matrix forming components).

R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (A) wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group,
A methacryloxy group, a mercapto group, an organic group having an amino group or an epoxy group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a hydrocarbon group or an acyl group having 1 to 8 carbon atoms,
a and b represent 0 or 1. As the organosilicon compound represented by the above formula, specifically, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltriethoxysilane,
Methyltriethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy)
Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, γ-
Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxy Examples include silane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like. These can be used alone,
You may mix and use 2 or more types. Further, these are preferably used in the absence of a solvent or in a polar organic solvent such as alcohol in the presence of an acid. Further, after the hydrolysis, it may be mixed with the above-mentioned antimony oxide-coated titanium oxide-containing composite oxide particles, or after being mixed with the antimony oxide-coated titanium oxide-containing composite oxide particles, the hydrolysis may be carried out. The hydrolysis may be all hydrolyzed or partially hydrolyzed.

The proportion of the coating component derived from the organosilicon matrix-forming component in the cured coating is 10%.
It is appropriate that the content is in the range of 90 to 90% by weight, preferably 20 to 80% by weight. If this ratio is 10% by weight or less,
The adhesion between the substrate and the coating may be reduced,
If the content is 0% by weight or more, a coating having a high refractive index may not be obtained.

The matrix forming components contained in the second coating liquid for forming a high-refractive-index transparent film according to the present invention include acrylic resins, melamine resins, ultraviolet curable resins, urethane resins, polyester resins, and phosphorous resins. General paint resins such as phagen resins are used. In the case of the second coating liquid, the proportion of the coating component derived from the resin component in the cured coating is appropriately in the range of 10 to 90% by weight, preferably 20 to 80% by weight. . If the proportion is less than 10% by weight, the adhesion between the substrate and the coating may be reduced. If the proportion is more than 90% by weight, a coating having a high refractive index may not be obtained.

Usually, the first coating liquid is used for forming a hard coat film, and the second coating liquid is used for forming a primer film. [Complex oxide particles containing titanium oxide coated with antimony oxide]
As the antimony oxide-coated titanium oxide-containing composite oxide particles, the same antimony oxide-coated titanium oxide-containing composite oxide particles as described above can be used.

The surface of the above-described antimony oxide-coated titanium oxide-containing composite oxide particles is preferably treated with an organosilicon compound or an amine.
When the surface of the antimony oxide-coated titanium oxide-containing composite oxide particles is modified by treating it with an organosilicon compound or an amine, the coating liquid containing the antimony oxide-coated titanium oxide-containing composite oxide particles and the matrix contains antimony. The dispersed state of the oxide-coated titanium oxide-containing composite oxide particles becomes stable over a long period of time, and even when an ultraviolet curable resin is used as a matrix-forming component, the antimony oxide-coated titanium oxide-containing composite oxide-containing composite oxide The dispersed state of the material particles becomes stable. Also,
Antimony oxide-coated titanium oxide-containing composite oxide particles whose surface has been modified with organosilicon compounds or amines have improved reactivity and affinity with matrix-forming components,
As a result, the coating obtained from the coating liquid containing the surface-treated antimony oxide-coated titanium oxide-containing composite oxide particles was obtained from the coating liquid containing the antimony oxide-coated titanium oxide-containing composite oxide particles that were not surface-treated. The hardness is higher than that of the resulting coating, and it is also excellent in light resistance, weather resistance, transparency, abrasion resistance, adhesion to a substrate, abrasion resistance, flexibility and dyeing properties. Further, the affinity between the antimony oxide-coated titanium oxide-containing composite oxide particles and the solvent in the coating solution is further improved as compared with the case where the composite oxide particles are not surface-treated.

In the coating liquid according to the present invention, the matrix forming component and the solid component (in terms of oxide) or 100 parts by weight of the resin are converted to 100 parts by weight when converted to resin.
It is desirable that the titanium oxide-containing composite oxide particles coated with antimony oxide be contained in an amount of 5 to 1000 parts by weight, preferably 10 to 600 parts by weight. [Other Coating Solution Components] The coating solution according to the present invention contains the following components (C) to (c) together with antimony oxide-coated titanium oxide-containing composite oxide particles and a matrix forming component.
The component (G) may optionally be included.

Component (C), that is, at least one hydrolyzate and / or partial condensate of the organosilicon compound represented by the formula: Si (OR ⁴ ) ₄ (where R ⁴ has 1 to 8 carbon atoms)
Represents a hydrocarbon group, an alkoxyalkyl group or an acyl group. ). The organosilicon compound represented by the above formula is capable of easily adjusting the refractive index of the formed transparent film while maintaining the transparency of the transparent film, further increasing the curing speed of the film after application of the coating solution, It is used for the purpose of improving the hardness of the steel. By using the component (C), the refractive index of the cured film can be appropriately adjusted according to the refractive index of the base lens, and the content of the antimony oxide-coated titanium oxide-containing composite oxide particles is reduced to some extent. Even with this, the adhesion of the antireflection film can be obtained. Further, by blending the tetrafunctional organosilicon compound in the component (C) into the coating composition, the curing speed at the time of forming a cured film is increased, and in particular, the sulfur-containing urethane-based resin in which the dye is easily removed from the fabric lens. When a coating is formed on such a substrate, the amount of detachment can be suppressed, and the change in color tone of the dyed lens before and after the formation of the coating can be reduced. Specific examples of the tetrafunctional organosilicon compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraaryloxysilane, tetrakis (2 -Methoxyethoxy) silane, tetrakis (2-ethylbutoxysilane), tetrakis (2
-Ethylhexyloxy) silane and the like. These may be used alone or as a mixture of two or more.
In addition, it is preferable that these are hydrolyzed in the absence of a solvent or in an organic solvent such as an alcohol in the presence of an acid. The proportion of the coating component derived from the hydrolyzate of the tetrafunctional organosilicon compound (C) in the cured coating is suitably from 0 to 50% by weight. This is 5
If the content is 0% by weight or more, cracks easily occur in the cured film.

(D) component: Si component, Al,
Sn, Sb, Ta, Ce, La, Fe, Zn, W, N
b. Colloidal (sol) -like dispersion of fine particles composed of an oxide of one or more elements selected from Zr and In
Or more and / or Si, Al, Sn, Sb, Ta,
One or more colloidal dispersions of composite oxide fine particles composed of oxides of two or more elements selected from the group consisting of Ce, La, Fe, Zn, W, Zr, Nb, In, and Ti, It is used to optimize the refractive index, adhesion to the substrate, dyeability, heat resistance, etc. depending on the type of the substrate lens. These are specifically SiO ₂ , Al ₂ O ₃ , Sn
O ₂ , Sb ₂ O ₅ , Ta ₂ O ₅ , CeO ₂ , La ₂ O ₃ , Fe ₂
Inorganic oxide fine particles such as O ₃ , ZnO, WO ₃ , ZrO ₂ , In ₂ O ₃ , and Nb ₂ O ₅ are colloidally dispersed in water or an organic solvent. Alternatively, composite oxide fine particles composed of oxides containing two or more of these oxide component elements are colloidally dispersed in water or an organic solvent. In any case, the particle size is about 1 to 30.
nm is suitable, and the kind and amount of application to the coating solution of the present invention are determined by the intended film performance.

Further, in order to enhance the dispersion stability of these fine particles in a coating solution, it is possible to use those obtained by treating the surface of the fine particles with an organosilicon compound or an amine compound in the same manner as described above. Component (E): at least one selected from the group consisting of a polyfunctional epoxy compound, a polyhydric alcohol, a polycarboxylic acid and a polycarboxylic anhydride, which is a component (E), improves the dyeability of a formed film; Alternatively, it is used for the purpose of improving various durability.

Examples of the polyfunctional epoxy compound include diglycidyl ethers of difunctional alcohols such as (poly) ethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol, glycerin, trimethylolpropane and the like. And di- or triglycidyl ethers of trifunctional alcohols.

Examples of the polyhydric alcohol include: difunctional alcohols such as (poly) ethylene glycol, propylene glycol, polypropylene glycol, neopentyl glycol, catechol, resorcinol, and alkylene glycol; trifunctional alcohols such as glycerin and trimethylolpropane; Polyvinyl alcohol and the like.

Examples of the polycarboxylic acid include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, orthophthalic acid, terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid and the like. Examples of the polycarboxylic anhydride include succinic anhydride, maleic anhydride, itaconic anhydride, 1.2-dimethylmaleic anhydride, and phthalic anhydride.

The proportion of the coating component derived from the component (E) in the cured coating is suitably from 0 to 40% by weight. This is because when the content is 40% by weight or more, the adhesion between the cured film and the antireflection film formed thereon is reduced. Component (F): The hindered amine compound as the component (F) is used for the purpose of improving the dyeability of the formed film. As the component (F), specifically, bis (2,2,6,
6-tetramethyl-4-piperidyl) sebacate, 1- ｛2- [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl {-4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2, 2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4 -Benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,
7,9,9-Tetramethyl-1,3,8-triazaspiro [4,5]
Undecane-2,4-dione, dimethyl succinate / 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly {[(6- (1,1 , 3,3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl]
[2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl)
Imino]｝, N, N'-bis (3-aminopropyl) ethylenediamine.2,4-bis [N-butyl- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6- Chloro-1,3,5-triazine condensate, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6- Pentamethyl-4-piperidyl) and the like.

The upper limit of the use amount of this component is desirably 3% by weight or less based on the total solid content in the coating solution. And not desirable. Component (G): One or more selected from amines, amino acids, metal acetylacetonates, metal salts of organic acids, perchloric acids, salts of perchloric acids, acids and metal chlorides of component (G) are silanols. It is a curing catalyst used for accelerating the curing of (organosilicon matrix forming component) or epoxy group. By using these curing catalysts, it is possible to accelerate the film forming reaction. Specific examples thereof include n-butylamine, triethylamine, guanidine, amines such as biguanide, amino acids such as glycine, aluminum acetylacetonate, chromium acetylacetonate, titanyl acetylacetonate, and metal acetyl such as cobalt acetylacetonate. Organic acid metal salts such as acetonate, sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, tin octylate, perchloric acids such as perchloric acid, ammonium perchlorate, magnesium perchlorate or salts thereof, Acids such as hydrochloric acid, phosphoric acid, nitric acid, paratoluenesulfonic acid, or SnCl ₂ , AlCl ₃ , FeCl ₃ , TiCl ₄ ,
Examples thereof include metal chlorides which are Lewis acids such as ZnCl ₂ and SbCl ₃ .

These curing catalysts can be used after adjusting the kind and amount of use according to the composition of the coating solution and the like. The upper limit of the amount used is preferably 5% by weight or less based on the solid content in the coating solution. Further, the coating liquid according to the present invention, coating properties, in order to improve the performance of the coating film formed on the substrate from the coating liquid, if necessary, a small amount of a surfactant,
Antistatic agents, ultraviolet absorbers, antioxidants, disperse dyes, oil-soluble dyes, fluorescent dyes, pigments, photochromic compounds, thixotropic agents, and the like may be added.

Solvent: The purpose of the coating solution according to the present invention is to impart fluidity to the coating solution, adjust the concentration of solids contained therein, and adjust the surface tension, viscosity, evaporation speed, etc. of the coating solution. And a solvent is used. As the solvent, water or an organic solvent is used, and examples of the organic solvent include those similar to those exemplified in the organosol. When a dispersion sol of antimony oxide-coated titanium oxide-containing composite oxide particles is used, the solvent to be added may be the same as or different from the dispersion medium of the dispersion sol.

[Production Method of Transparent Film Forming Coating Solution] The coating solution according to the present invention comprises the antimony oxide-coated titanium oxide-containing composite oxide particles obtained as described above, a matrix forming component, and By mixing with other components. When producing the coating liquid according to the present invention, the antimony oxide-coated titanium oxide-containing composite oxide particle dispersion sol according to the present invention described above can be suitably used.

The solid content concentration of the coating solution is in the range of 1 to 70% by weight, preferably 2 to 50% by weight in total including the solid content derived from other components used by mixing if necessary. . In producing the coating solution according to the present invention, the antimony oxide-coated titanium oxide-containing composite oxide particle dispersion sol as described above is preferably used. If it can be monodispersed in a coating solution, fine powdery antimony oxide-coated titanium oxide-containing composite oxide particles may be used, and the dispersion sol may be dried and used.

Substrate with Transparent Coating Next, the substrate with a transparent coating according to the present invention will be described. The substrate with a transparent coating according to the present invention has a substrate and a high-refractive-index transparent coating formed on the surface of the substrate, and the transparent coating is the first coating liquid or the second coating liquid according to the present invention. It is formed from liquid.

Among the above substrates, various substrates made of glass, plastic, and the like are used. Specifically, various optical lenses such as spectacle lenses and cameras, various display element filters, looking glasses, window glasses, automobiles, etc. And light covers used in automobiles and the like. On this surface, a transparent film is formed as a hard coat film.

Further, in addition to the hard coat film, a transparent film may be formed as a primer film for a plastic lens. The thickness of the film formed on the surface of these substrates varies depending on the use of the substrate with a film,
5 to 30 μm is preferred. The substrate with a transparent coating according to the present invention is obtained by applying the coating solution according to the present invention to a substrate surface as described above by a conventionally known method such as a dip pink method, a spinner method, a spray method, a roll coater method or a flow method. The film can be produced by drying to form a film, and then heating the film formed on the surface of the substrate to a temperature not higher than the heat resistant temperature of the substrate. Especially heat deformation temperature is 100 ℃
The spinner method which does not need to fix the lens base material with a jig for a lens base material less than the above is preferable. When the substrate for forming a film is a resin lens, it is preferable to form a film by applying a coating solution on the substrate and then heating and drying at a temperature of 40 to 200 ° C. for several hours.

When an ultraviolet curable resin is used as a matrix-forming component of the coating solution, the coating solution is applied to the surface of the substrate and then dried, and a predetermined amount is applied to the surface of the substrate on which the coating solution is applied. The coated substrate according to the present invention can be manufactured by a method such as irradiating ultraviolet rays having a wavelength and curing. Further, in producing the coated substrate according to the present invention, in order to improve the adhesion between the substrate, for example, a lens substrate and the coating, the surface of the substrate is previously treated with an alkali, an acid or a surfactant. Alternatively, a polishing treatment with inorganic or organic fine particles, a primer treatment or a plasma treatment may be performed.

The coated substrate according to the present invention includes:
A primer film may be provided between the substrate and the hard coat layer. In this case, the primer film may be formed using the second coating solution, and the hard coat film may be formed using the first coating solution. In the case of a plastic lens using an optical material having a high refractive index, the thickness of the lens is also reduced, and a hard coat layer (film) as described above is formed on the surface. Is formed. In the multi-coat layer forming process, the plastic lens substrate is distorted, and the lens may be easily broken due to impact such as dropping. Therefore, a flexible primer film that absorbs impact between the plastic lens and the hard coat film is formed. Is provided.

If the refractive index of the primer film is not equal to the refractive index of the base material, interference fringes may occur. However, in the coating solution for forming a film according to the present invention, as a matrix component,
As described above, the use of the second coating liquid containing a coating resin enables the formation of a primer film having a refractive index similar to that of the base material. In the case of forming such a primer film, the coating solution may be applied by the method described above, and then the coating may be cured.

[Synthetic Resin Lens] Next, the case where the base material is a synthetic resin lens will be described. When the substrate is a lens made of a synthetic resin, the surface of the synthetic resin lens substrate contains the antimony oxide-coated titanium oxide-containing composite oxide particles and a matrix-forming component, and further includes the components (C) to (G) described above. ) A high refractive index coating (also referred to as a transparent coating or a hard coating layer) formed from a coating solution containing at least one or more components.

The lens made of a synthetic resin preferably has a refractive index of the lens substrate of 1.54 or more, and further has transparency, dyeability, heat resistance, water absorption, bending strength, impact resistance, weather resistance, and light resistance. As a base lens which can satisfy desired characteristics in terms of flexibility, workability, and the like, a sulfur-containing urethane-based, (meth) acryl-based, or episulfide-based lens base material is preferable. JP-A-9-110979 and JP-A-9-255781 disclose a lens substrate obtained from an Ebisulphide compound having a high refractive index of 1.67 to 1.70 and an Abbe number of more than 30. It is suitable. Also. The recently marketed refractive index is 1.60
When a transparent film (primer layer and / or hard coat layer) is formed on a high refractive index lens substrate having a refractive index of about 1.80 to about 1.80, particularly about 1.71 to 1.80, and the transparent film is dyed, Since the coating contains the antimony oxide-coated titanium oxide-containing composite oxide particles of the present invention, the dyeing is not discolored or faded, that is, a thin synthetic resin lens excellent in fading resistance can be obtained. it can.

Further, on such a hard coat layer,
A single-layer or multi-layer antireflection film made of inorganic material may be provided.
In addition, by forming an anti-reflection film,
The function as a spectacle lens can be improved
Can be further improved. As inorganic substances, S
iO, SiO_Two, Si_ThreeN_Four, TiO_Two, ZrO_Two, Al_TwoO
_Three, MgF_Two, Ta_TwoO_ThreeThin film type such as vacuum evaporation method
An antireflection film can be formed by a forming method.

Further, when a transparent film / anti-reflection film is provided on the hard coat layer, a primer film is provided between the substrate and the hard coat layer to improve impact resistance and adhesion. be able to. In this case, the primer film can be formed by a coating liquid for forming a coating film containing a resin for paint, preferably a resin for urethane paint or a resin for polyester paint, as a matrix.

Further, when a transparent film (anti-reflection film) is provided on the hard coat layer, the impact resistance and the adhesion are improved by providing a primer layer between the substrate and the hard coat layer. Can be. At this time, the primer film is formed of a second resin containing the above-mentioned coating resin as a matrix, preferably a polyester resin or a urethane resin.
Can be formed by a transparent coating solution for forming a transparent film.

[0078]

According to the present invention, when forming a transparent film on a substrate such as a synthetic resin lens, fine particles are blended, and when the transparent film is dyed, the dyeing does not discolor or fade. It is possible to provide antimony oxide-coated titanium oxide-containing composite fine particles capable of obtaining a thin synthetic resin lens excellent in fading resistance.

Further, according to the present invention, the ratio of the matrix forming component to the antimony oxide-coated titanium oxide-containing composite oxide particles in the coating solution and the composition of the antimony oxide-coated titanium oxide-containing composite oxide particles are changed. Thereby, the refractive index of the transparent film formed on the base material can be freely controlled. When the refractive index of the transparent film is made equal to the refractive index of the substrate in this manner, interference fringes caused by the difference in the refractive index between the two can be eliminated. On the other hand, when the refractive index of the coating is very high compared to the refractive index of the substrate, the gloss of the surface of the substrate becomes very high. Such a film having a very high refractive index formed on a substrate using the coating solution for forming a film according to the present invention contains titanium oxide as a main component in the composite oxide fine particles in the film. Excellent ultraviolet shielding effect,
It is suitable as a paint film and / or a top coat film for automobiles and the like.

The film formed on the substrate using the coating solution for forming a film according to the present invention is colorless and transparent,
Glasses with excellent adhesion to the substrate, weather resistance, light resistance, chemical resistance, flexibility and dyeability, and high surface hardness, and therefore excellent scratch and abrasion resistance. It is suitable for providing various optical lenses such as lenses and cameras, various display element filters, looking glasses and the like. Then, on the surface of a base material such as a looking glass, a window glass and various display element filters, a coating liquid for forming a high refractive index layer for forming a multilayer antireflection film having high surface hardness and being colorless and transparent according to the present invention. If formed, the contents will be clearly visible. If such an anti-reflection film is formed on various display element surfaces, a fluorescent lamp or the like will not be reflected on these display element surfaces, so that images will be clear and eyestrain will be eliminated.

Further, the coating liquid for forming a film according to the present invention, wherein the high refractive index film formed on a substrate using a coating liquid containing a coating resin as a matrix-forming component is colorless and transparent. No coloration of cured film, excellent weather resistance, light resistance, excellent adhesion to substrate, flexibility
In addition, since the film has excellent discoloration resistance and the refractive index of the film can be made equal to the refractive index of the substrate as described above, a hard coat film (cured film), a transparent film and an antireflection film are formed on the high refractive index film. It can be suitably used as a primer film for a plastic lens or the like, and the obtained plastic lens has excellent impact resistance. When used as such a primer film, a polyester resin, a urethane resin, or the like is preferably used as the coating resin.

Furthermore, by providing a cured resin film formed from the first coating liquid according to the present invention on a synthetic resin lens substrate having a refractive index of 1.54 or more, interference fringes and coloring of the cured film are eliminated. It is possible to provide a lightweight and thin synthetic resin lens having excellent heat resistance, light resistance, adhesion to a substrate, flexibility, chemical resistance, abrasion resistance, abrasion resistance, dyeability and various durability. it can.

By laminating an antireflection film made of an inorganic material on the cured film, surface reflection can be suppressed and the function as a spectacle lens can be further improved. In this case, when the primer film formed from the second coating solution is provided on the plastic lens substrate, and the primer film and / or the cured film is dyed, the dyeing may be discolored or faded. No, that is, a thin synthetic resin lens excellent in fading resistance can be obtained. It is particularly effective for obtaining a thin synthetic resin lens having a high refractive index, which is difficult to dye by a conventional method.

[0084]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0085]

Example 1 Core particles containing titanium oxide (TN-1) dispersed
While the concentration in terms of preparing TiO ₂ Le is stirred for 0.4 wt% aqueous solution of titanium sulfate 250 kg, this was hydrolyzed by adding gradually concentration of 15 wt% ammonia water, pH 8.5
Was obtained as a white slurry. The slurry was filtered and washed to obtain 11.11 kg of a cake of hydrous titanate gel having a solid content of 9% by weight.

To 5.55 kg of this cake, 6.06 kg of a hydrogen peroxide solution having a concentration of 33% by weight and 13.4 kg of water were added, and the mixture was heated at 80 ° C. for 5 hours to obtain TiO ₂ of 2.0%.
25 kg of a weight% (peroxide) titanic acid aqueous solution were obtained. This (peroxide) titanic acid aqueous solution was yellow-brown and transparent, and had a pH of 8.1. Next, when the average particle diameter is 7 nm and Si
333.3 g of a silica sol having an O ₂ concentration of 15% by weight, 22.5 kg of the above titanic acid aqueous solution, and 27.25 k of pure water
and heated in an autoclave at 200 ° C. for 96 hours. After heating, the obtained colloid solution was concentrated to obtain a titanium oxide-containing core particle (TN-1) dispersion sol having a solid content of 10% by weight.

Formation of Intermediate Thin Film Layer 5.26 kg of zirconium oxychloride was added to 9.474 k of water.
Aqueous ammonia having a concentration of 15% by weight was added to an aqueous solution of zirconium oxychloride having a ZrO ₂ concentration of 2% by weight and dissolved therein to hydrolyze, thereby obtaining a slurry having a pH of 8.5. This slurry was filtered and washed, and the concentration was 10% by weight as ZrO2.
Got a cake. 1.22 kg of this cake has 3.08 water
After adding 9.0 kg of KOH aqueous solution to make the mixture alkaline, 9.0 kg of hydrogen peroxide was added thereto, followed by dissolving by heating. 1 kg was prepared.

[0088] Separately, after diluting the commercially available water glass with water, dealkalized with a cation exchange resin, SiO ₂ concentration 2
18.9 kg of a weight% silicic acid solution was prepared. 20 kg of water was added to 5 kg of a dispersion sol of titanium oxide-containing core particles (TN-1) to make a solid content concentration of 2% by weight, and then heated to 90 ° C.
89 g were added. Next, this mixed solution was subjected to heat treatment in an autoclave at 200 ° C. for 18 hours, and then concentrated by an ultrafiltration membrane method. An aqueous dispersion sol of titanium oxide-containing core particles having a thin film layer was obtained.
The average particle size of this sol was 9 nm.

Formation of Antimony Oxide Coating Layer Antimony trioxide (Nippon Seimitsu Co., Ltd.) was dissolved in a solution prepared by dissolving 285 g of caustic potassium (purity: 85% by weight) in 9000 g of water.
(ATOX-R, purity: 99% by weight) was suspended. The suspension is heated to 100 ° C. and then water 1100
The aqueous solution diluted with g was added over 14 hours to prepare an antimonic acid compound aqueous solution.

20 kg of water was added to 5 kg of an aqueous dispersion sol of titanium oxide-containing core particles having an intermediate thin film layer composed of silicon oxide and zirconium oxide so that the solid content concentration became 2% by weight. 1.768 kg of water was added to 1.010 kg of the aqueous solution, and an antimonic acid compound aqueous solution having a concentration of 2% by weight in terms of Sb ₂ O ₅ was added thereto. .

After deionization treatment, the solid content concentration was 1% by weight.
Water and then autoclaved to 98
Heat treatment was performed at 18 ° C. for 18 hours. The obtained colloid solution was concentrated to prepare an antimony oxide-coated titanium oxide-containing composite oxide particle (AT-1) -dispersed aqueous sol having a solid content of 10% by weight. The average particle diameter of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) was 9.1 nm.

Further, the water of the dispersion medium of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) was replaced with methanol, and concentrated until the solid content concentration became 20% by weight. Titanium-containing composite oxide particles (AT
An organosol of -1) was prepared. Preparation of Transparent Coating Liquid (FS-1) Ethyl cellosolve 4 was placed in a flask equipped with a stirrer.
1.15 g, 35.45 g of γ-glycidoxypropyltrimethoxysilane, 11.82 g of γ-glycidoxypropylmethyldimethoxysilane, and 4.56 g of tetramethoxysilane were added successively, and then 0.05N hydrochloric acid solution 1 was added.
2.9 g was added and the mixture was stirred for 30 minutes. Subsequently, a silicone surfactant (L-7604, manufactured by Nippon Unicar Co., Ltd.) was added.
After adding 04 g, the mixture was aged at 5 ° C. for 24 hours to prepare a liquid containing a matrix-forming component.

231 g of the organosol of the above-mentioned antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) was added to the liquid containing the matrix-forming component, and 1 g of aluminum acetylacetonate was further added. After aging at 0 ° C. for 48 hours, a coating solution (FS-1) for forming a transparent film was prepared.

[0094]

Example 2 In Example 1, an aqueous dispersion sol of core particles containing titanium oxide having an intermediate thin film layer was prepared.
The amount of the solution of zirconium in hydrogen peroxide was 427 g, and the amount of the silicic acid solution was 1323 g. 2.273kg
A water sol in which antimony oxide-coated titanium oxide-containing composite oxide particles (AT-2) were dispersed in water and an organosol in which methanol was dispersed were prepared in the same manner as in Example 1 except that 3.977 kg of water was added. Then, a coating liquid (FS-2) for forming a transparent film was prepared.

The average particle size of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-2) was 9.3 nm.

[0096]

Example 3 In Example 1, the amount of silica sol was 750 when preparing a dispersion sol of titanium oxide-containing core particles (TN-1).
g when preparing an aqueous dispersion sol of titanium oxide-containing core particles having an intermediate thin film layer, the amount of zirconium hydrogen peroxide solution is 1.525 kg, and the amount of silicic acid solution is 4.725 k.
g of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) -dispersed aqueous sol, the amount of the aqueous solution of the antimonate compound was adjusted to 9.09 kg, and water was further reduced to 1 g.
Except for adding 5.91 kg, antimony oxide-coated titanium oxide-containing composite oxide particles (AT-
The aqueous dispersion sol and organosol of 3) were prepared, and then a coating liquid (FS-3) for forming a transparent film was prepared. In addition, composite oxide particles (AT-
The average particle diameter of 3) was 7.6 nm.

FIG. 1 shows an X-ray diffraction pattern of the composite oxide fine particles prepared in Example 3.

[0098]

Example 4 93.665 kg of a titanium tetrachloride solution having a concentration of 7.75% by weight in terms of TiO ₂ and a concentration of 15
A white slurry was prepared by mixing and neutralizing 36.295 kg of aqueous ammonia of 36% by weight. The slurry was filtered and washed to obtain 54.579 kg of a cake of hydrous titanate gel having a solid content of 13.3% by weight.

To 7.519 kg of this cake, 11.429 kg of a hydrogen peroxide solution having a concentration of 35% by weight and 59.148 of water were added.
After adding 2 kg and heating at 80 ° C. for 2 hours to dissolve,
21.9 kg of water was added thereto to prepare an aqueous solution of titanic oxide having a concentration of 1.0% by weight as TiO ₂ . A concentration of 1.02% by weight as SnO ₂ was added to the obtained aqueous solution of titanic peroxide.
8.906 kg of an aqueous potassium stannate solution was added, and the mixture was sufficiently stirred, and then deionized with a cation exchange resin. After deionization treatment, 272.7 g in terms of SiO ₂
1818 g of silica sol (silica concentration: 15
Wt.) And then 25.6 kg of water so that the solid concentration becomes 1 wt.%.
The obtained colloid solution was concentrated by heating at 40 ° C. for 18 hours to hydrolyze, and a titanium oxide-containing core particle (TN-4) dispersion sol having a solid content of 10% by weight was obtained. The average particle size of the titanium oxide-containing core particles (TN-4) was 12.8 nm.

Next, dispersion of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-4) was carried out in the same manner as in Example 2, except that a titanium oxide-containing core particle (TN-4) dispersion sol was used. A water sol and an organosol were prepared.
The average particle diameter of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-4) was 13.1 nm. Preparation of Transparent Film Forming Coating Solution (FS-4) A transparent film forming coating solution (FS-4) was prepared in the same manner as in Example 1 except that an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-4) was used. FS-4) was prepared.

[0101]

Example 5 The procedure of Example 4 was repeated, except that the antimony oxide coating layer was formed with the addition of 9.09 kg of an aqueous solution of an antimonate compound and 15.91 kg of water, followed by heat treatment at 175 ° C. An aqueous sol and an organosol were prepared by dispersing titanium oxide-containing composite oxide particles (AT-5) coated with antimony oxide. The average particle diameter of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-5) is 13.4 n.
m.

Preparation of Transparent Film Forming Coating Solution (FS-5) Example 1 was repeated except that an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-5) was used.
In the same manner as in the above, a coating liquid for forming a transparent film (FS-5) was prepared. FIG. 2 shows an X-ray diffraction diagram of the composite oxide fine particles prepared in Example 5.

[0103]

Example 6 Based on Example 2 of JP-A-10-245224, core particles containing titanium oxide (T
N-6) A dispersion sol was prepared. Step (a): titanium tetrachloride (manufactured by Sumitomo Citix Corporation:
27.2% by weight in terms of TiO _2, Cl 32.0% by weight)
293.8 g (79.8 g in terms of TiO ₂ ) and water 37
1.6 g was placed in a 3-liter separable glass-made flask with a jacket, and 665 g of an aqueous titanium chloride solution (Ti
(12.0% by weight in terms of O ₂ ). This aqueous solution was heated to 50 ° C. while stirring with a glass stirring rod, and then cooled and cooled to a concentration of 35% by weight of a hydrogen peroxide solution 95%.
0.8 g and metallic tin powder (manufactured by Yamaishi Metal Co., Ltd .: trade name A)
T-Sn, No. 200) 566.4 g were added.

For the addition of the aqueous hydrogen peroxide and the metallic tin, 31.5 g (0.265 mol) of metallic tin was added first, and then 53.8 g (0.554 mol) of aqueous hydrogen peroxide were gradually added.
Wait for this reaction to end, then 31.5 g of metallic tin
(0.265 mol) and then 53.8 g of aqueous hydrogen peroxide
(0.554 mol) was added slowly. In this way, the addition of the metal peroxide followed by the addition of the hydrogen peroxide solution is repeated a total of 17 times at intervals of 5 to 10 minutes (31.5 g of metal tin and 53.8 g of hydrogen peroxide solution). After performing × 17 divided additions, finally, 30.9 g of metal tin and then 36.2 g of hydrogen peroxide were added, and a total of 18 divided additions were performed.

The reaction is exothermic and reaches 70-75 ° C. by the addition of metallic tin.
The temperature dropped to 0 to 60 ° C. Therefore, the reaction temperature is 50-75 ° C
Met. The ratio of hydrogen peroxide and metallic tin at the time of addition is H ₂
The molar ratio of O ₂ / Sn was 2.09. The time required for adding the hydrogen peroxide solution and the metal tin was 3.0 hours. After completion of the reaction, a basic titanium chloride-tin complex salt aqueous solution 319
5.6 g were obtained.

The concentration at this time was 25% by weight as a total concentration in terms of TiO ₂ + SnO ₂ . Step (b): the basic titanium chloride obtained in step (a)
11269 g of water in 2870 g of tin complex salt aqueous solution, concentration 2
After adding 211 g of 8% by weight aqueous ammonia, TiO2 + S
It was diluted to 5% by weight in a concentration converted to nO2. This aqueous solution was hydrolyzed at 95 ° C. for 10 hours to obtain an aggregate slurry of a titanium oxide-tin oxide composite colloid having an average particle diameter of 5.9 nm. Step (C): The agglomerated slurry of the titanium oxide-tin oxide composite colloid obtained in step (b) was treated with about 1
The operation of concentration → water injection → concentration was repeated using 5 liters to wash and remove excess electrolyte, followed by peptization to obtain 14,350 g of an acidic titanium oxide-tin oxide composite aqueous sol. The average particle diameter of the titanium oxide-tin oxide composite colloid particles was 5.9 nm. Step (d): isopropylamine 137 was added to 14350 g of the acidic titanium oxide-tin oxide composite sol obtained in step (C).
g, the mixture was made alkaline by using an ultrafiltration apparatus, and the operation of concentration → water injection → concentration was repeated using about 24 liters of water, and excess electrolyte was washed away to remove the alkaline titanium oxide-tin oxide composite aqueous solution. 14,600 g of sol was obtained. Further, the solution was passed through a column packed with 200 milliliters of an anion exchange resin (Amberlite IRA-410, manufactured by Organo Corporation) to obtain 15,500 g of an alkaline titanium oxide-tin oxide composite aqueous sol having a small anion content. This sol is concentrated under reduced pressure by a rotary evaporator,
7 Kg of a dispersion sol of titanium oxide-containing core particles (TN-6) was obtained.

The concentration at this time was 10% by weight as a total concentration in terms of TiO ₂ + SnO ₂ . The average particle size of the titanium oxide-containing core particles (TN-6) was 5.9 nm. Next, in Example 1, titanium oxide-containing core particles (TN-) having an intermediate thin film layer composed of silicon oxide and zirconium oxide were used.
Using titanium oxide-containing core particles (TN-6) instead of 1)
At the time of preparing the aqueous sol in which the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) were dispersed, the amount of the antimonic acid compound aqueous solution was 2.273 kg, and the water was 3.977 kg.
Except for adding, an antimony oxide-coated titanium oxide-containing composite oxide particle (AT-6) -dispersed aqueous sol and organosol were prepared in the same manner as in Example 1. The average particle diameter of the titanium oxide-containing composite oxide particles (AT-6) coated with antimony oxide was 6.1 nm.

Preparation of Coating Solution (FS-6) for Forming Transparent Film Example 1 was repeated except that the organosol of the obtained antimony oxide-coated titanium oxide-containing composite oxide particles (AT-6) was used.
In the same manner as in the above, a coating liquid for forming a transparent film (FS-6) was prepared.

[0109]

Example 7 Based on Example 3 of JP-A-10-245224, core particles containing titanium oxide (T
N-7) A dispersion sol was prepared. Step (a): titanium tetrachloride (manufactured by Sumitomo Citix Corporation:
27.2% by weight in terms of TiO _2, Cl 32.0% by weight)
1175 g (319.6 g in terms of TiO ₂ ) and water 14
88.4 g was placed in a 3 liter jacketed glass separable flask with a titanium chloride aqueous solution.
(12.0% by weight in terms of TiO ₂ ).

The aqueous solution was heated to 50 ° C. while being stirred with a glass stirring rod, and then cooled and cooled with 510 g of 35% by weight aqueous hydrogen peroxide and metallic tin powder (trade name AT manufactured by Yamaishi Metal Co., Ltd.). -Sm, No. 200) 237.4.
g was added. For the addition of the aqueous hydrogen peroxide and the metal tin, first, 102 g (1.05 mol) of the aqueous hydrogen peroxide and then 47.5 g (0.4 mol) of the metal tin were gradually added. Wait for this reaction to end, and then add 102 g of hydrogen peroxide solution
(1.05 mol) followed by 47.5 g of metal tin (0.
4 mol) was added slowly. By repeating the addition of the metal tin subsequent to the addition of the hydrogen peroxide solution a total of 5 times at intervals of 3 to 7 minutes, (102 g of the hydrogen peroxide solution and 47.5 g of metal tin) × 5 times Was added in portions.

The reaction reached 70 to 75 ° C. by the addition of metallic tin due to an exothermic reaction, and dropped to 50 to 60 ° C. upon cooling when the reaction was completed. Therefore, the reaction temperature is 50-75.
° C. The ratio of the aqueous solution of hydrogen peroxide to metallic tin at the time of addition was 2.63 in terms of a H ₂ O ₂ / Sn molar ratio. The time required for adding the hydrogen peroxide solution and the metal tin was 1 hour. After completion of the reaction, an aqueous solution of basic titanium chloride-tin complex salt 413
9.3 g were obtained.

The concentration at this time was 15% by weight as a total concentration in terms of TiO ₂ + SnO ₂ . Step (b): the basic titanium chloride obtained in step (a)
7798.7 g of water was added to 4139.3 g of a tin complex salt aqueous solution,
480 g of aqueous ammonia having a concentration of 28% by weight was added, and Ti was added.
It was diluted to 5% by weight in a concentration converted to O ₂ + SnO ₂ .
This aqueous solution was hydrolyzed at 94 ° C. for 10 hours to obtain an aggregate slurry of a titanium oxide-tin oxide composite colloid having an average particle size of 5.9 nm. Step (c): The aggregate slurry of the titanium oxide-tin oxide composite colloid obtained in step (b) was treated with about 3
The operation of concentration → water injection → concentration was repeated using 0 liter, and excess electrolyte was washed and removed, followed by peptization to obtain 31,000 g of an acidic titanium oxide-tin oxide composite aqueous solution. The average particle diameter of the titanium oxide-tin oxide composite colloid particles is
It was 5.9 nm. Step (d): isopropylamine 274 is added to 15500 g of the acidic titanium oxide-tin oxide composite sol obtained in step (c).
g, the mixture was made alkaline, and the operation of concentration → water injection → concentration was repeated using about 48 liters of water in an ultrafiltration apparatus, and excess electrolyte was washed away to remove the alkaline titanium oxide-tin oxide composite aqueous solution. 30500 g of sol were obtained. Further, the solution was passed through a column packed with 1200 ml of an anion exchange resin (Amberlite IRA-410, manufactured by Organo Corporation) to obtain 31,000 g of an alkaline titanium oxide-tin oxide composite aqueous sol having a small anion content. This sol was concentrated under reduced pressure using a rotary evaporator, and titanium oxide-containing core particles (TN-7) dispersed sol 6.085.
Kg was prepared.

The concentration at this time was 10% by weight as a total concentration in terms of TiO ₂ + SnO ₂ . The average particle size of the titanium oxide-containing core particles (TN-6) was 5.9 nm. Next, in Example 6, instead of titanium oxide-containing core particles (TN-6) dispersion sol, titanium core particles (TN-7) dispersion sol was used,
Example 1 Example 1 was repeated except that the amount of the antimonic acid compound aqueous solution was adjusted to 9.09 kg and water was added to 15.91 kg when preparing the aqueous sol of the dispersion of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-6). In the same manner as in the above, an aqueous sol and an organosol dispersed with antimony oxide-coated titanium oxide-containing composite oxide particles (AT-7) were prepared.

The average particle diameter of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-7) was 6.3 nm. Preparation of Coating Solution for Transparent Film Formation (FS-7) Example 1 except that the organosol of the obtained antimony oxide-coated titanium oxide-containing composite oxide particles (AT-7) was used.
In the same manner as in the above, a coating liquid for forming a transparent film (FS-7) was prepared.

[0115]

Example 8 1000 g of an organosol of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) prepared in Example 1 was placed in a reaction vessel, and while stirring, 56 g of methyltrimethoxysilane and 20 g of water were added. And then warmed to 50 ° C. And then concentrated to a solids concentration of 20.
Weight percent methyltrimethoxysilane-coated antimony oxide-coated titanium oxide-containing composite oxide particles (AT
-8) was prepared.

Preparation of Transparent Film Forming Coating Solution (FS-8) Example 1 was repeated except that an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-8) was used.
In the same manner as in the above, a coating liquid for forming a transparent film (FS-8) was prepared.

[0117]

Example 9 Antimony oxide-coated titanium oxide-containing composite oxide particles (AT-9) surface-treated with vinyltrimethoxysilane in the same manner as in Example 8 except that methyltrimethoxysilane was replaced with vinyltrimethoxysilane. ) Was prepared. Preparation of Coating Solution for Transparent Film Formation (FS-9) Example 1 was followed by using an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-9).
In the same manner as in the above, a coating liquid for forming a transparent film (FS-9) was prepared.

[0118]

Example 10 In Example 8, instead of the organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1), antimony oxide-coated titanium oxide-containing titanium oxide-containing composite oxide particles prepared in Example 2 ( AT-2) An antimony oxide-coated titanium oxide-containing composite oxide particle surface-treated with tetraethoxysilane in the same manner as in Example 8 except that tetraethoxysilane was used instead of methyltrimethoxysilane using the organosol of AT-2). An organosol of (AT-10) was prepared.

Preparation of Coating Solution (FS-10) for Forming a Transparent Coating A transparent coating was prepared in the same manner as in Example 1 except that the organosol of the obtained antimony oxide-coated titanium oxide-containing composite oxide particles (AT-10) was used. A coating solution for forming a film (FS-10) was prepared.

[0120]

Example 11 A surface treatment with γ-glycidoxypropyltrimethoxysilane was performed in the same manner as in Example 10 except that γ-glycidoxypropyltrimethoxysilane was used instead of tetraethoxysilane. Antimony oxide-coated titanium oxide-containing composite oxide particles (AT
-11) was prepared.

Preparation of Coating Solution (FS-11) for Forming Transparent Coating A transparent coating was prepared in the same manner as in Example 1 except that the organosol of the obtained antimony oxide-coated titanium oxide-containing composite oxide particles (AT-11) was used. A coating solution for coating formation (FS-11) was prepared.

[0122]

Example 12 In Example 8, instead of the organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1), an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-3) was used. An organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-12) surface-treated with methyltrimethoxysilane was prepared in the same manner as in Example 8 except for using.

Preparation of Coating Solution (FS-12) for Formation of Transparent Coating A transparent coating was prepared in the same manner as in Example 1 except that the organosol of the obtained antimony oxide-coated titanium oxide-containing composite oxide particles (AT-12) was used. A coating solution for forming a film (FS-12) was prepared.

[0124]

Example 13 In Example 8, an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-4) was used in place of the organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1). An organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-13) surface-treated with methyltrimethoxysilane was prepared in the same manner as in Example 8 except for using the same.

Preparation of Coating Solution (FS-13) for Forming Transparent Coating A transparent coating was prepared in the same manner as in Example 1 except that the organosol of the obtained antimony oxide-coated titanium oxide-containing composite oxide particles (AT-13) was used. A coating solution for film formation (FS-13) was prepared.

[0126]

Example 14 In Example 8, an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-5) was used instead of the organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1). Organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-14) surface-treated with tetraethoxysilane in the same manner as in Example 8 except that tetraethoxysilane was used instead of methyltrimethoxysilane. Was prepared.

Preparation of Coating Solution (FS-14) for Forming Transparent Film Next, a transparent film was prepared in the same manner as in Example 1 except that an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-14) was used. A coating solution for formation (FS-14) was prepared.

[0128]

Example 15 1000 g of an organosol of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-6) prepared in Example 6 was collected on a rotary evaporator, and 4000 g of methyl cellosolve was added, followed by distillation under reduced pressure. An organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-15) using methyl cellosolve having a solid content of 20% by weight as a dispersion medium was prepared.

Preparation of Coating Solution (FS-15) for Forming a Transparent Film Next, a transparent film was prepared in the same manner as in Example 1 except that an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-15) was used. A coating solution for formation (FS-15) was prepared.

[0130]

Example 16 In Example 8, an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-7) was replaced with an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1). An organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-16) surface-treated with methyltrimethoxysilane was prepared in the same manner as in Example 8 except for using the same.

Preparation of Transparent Film Forming Coating Solution (FS-16) Next, a transparent film was prepared in the same manner as in Example 1 except that an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-16) was used. A coating solution for formation (FS-16) was prepared.

[0132]

Example 17 Preparation of a Coating Solution (FS-17) for Forming a Transparent Film Ethyl cellosolve was placed in a flask equipped with a stirring device.
5 g, γ-glycidoxypropyltrimethoxysilane 1
5.26 g, 32.00 g of γ-glycidoxypropylmethyldimethoxysilane, 8.45 tetramethoxysilane
g in order, and then 12.90 of 0.05 N hydrochloric acid.
After stirring for 30 minutes, the mixture was aged at 5 ° C. for 24 hours to prepare a liquid containing a matrix-forming component. Subsequently, a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd .: L-70)
01), 231.0 g of an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) prepared in Example 1, glycerin diglycidyl ether (Denacol EX manufactured by Nagase & Co., Ltd.) -313)
5.1 g, magnesium perchlorate 0.4 as curing catalyst
11 g was added in this order and dissolved, and then aging was performed at 0 ° C. for 48 hours to prepare a coating solution (FS-17) for forming a transparent film.

[0133]

Example 18 Preparation of Transparent Film Forming Coating Solution (FS-18) In Example 1, when preparing the transparent film forming coating solution (FS-1), the amount of tetramethoxysilane was changed to 7.6 g. And a coating liquid for forming a transparent film (FS-18) in the same manner as in Example 1 except that the amount of the organosol of the titanium oxide-containing composite oxide particles (AT-1) coated with antimony oxide was 225 g.
Was prepared.

[0134]

Example 19 Substrates with Transparent Coating (PL-1, PL-8, PL-9, PL
-17, PL-18) commercially available resin lens (R1) as a base material (Mitsui Chemicals, Inc.)
Manufactured by N = 1.74), and this was mixed with N at a concentration of 13% by weight.
After being immersed in an aOH aqueous solution for 5 minutes, it was sufficiently washed with water and dried. Next, each of the coating liquids for forming a transparent film prepared in Examples 1, 8, 9, 17, and 18 was applied by a spin coating method. Spin coating conditions are as follows: after applying a hard coat liquid during low rotation, rotation speed: 2500 rpm, rotation time: 1
The ball was shaken off under the condition of seconds. After the application, the coating was temporarily dried at 90 ° C. for 18 minutes, and then heat-cured at 106 ° C. for 30 minutes.
Heating and curing were performed at 106 ° C. for 120 minutes to form substrates with transparent coatings (PL-1, PL-8, PL-9, PL-17, PL-18). At this time, the thickness of the transparent coating was 2.3 μm.

The lens on which each transparent film was formed was prepared using a commercially available dye (Amber D for Seiko Plux).
Dyeing (fabric) was carried out in a dyeing bath at a temperature of 3 ° C. for 3 minutes. Preparation of Transparent Coated Substrates (PL-2, PL-10, PL-11) A commercially available resin lens (R2) (manufactured by Mitsubishi Gas Chemical Co., Ltd .: n = 1.71) was used as a substrate. It was immersed in a 13% by weight aqueous solution of NaOH for 5 minutes, washed sufficiently with water, and dried.

Next, Example 2, Example 10, and Example 1
Using the coating solution for forming a transparent film prepared in Step 1, the substrate with a transparent film (PL-2, PL) was prepared in the same manner as the substrate with a transparent film (PL-1).
-10, PL-11). The thickness of the transparent coating is 2.3 μm
Met. The lens on which each transparent film was formed was a commercially available dye (Sumicaron Blue ER, manufactured by Sumitomo Chemical Co., Ltd.).
PD 2.0g, Sumicaron Red E-RPD
8 g, Sumicaron Yellow E-RPD 0.4 g) was mixed with 1 L of water in a 65 ° C. dyeing bath, and then dried at 110 ° C. for 1 hour.

Preparation of Transparent Coated Substrates (PL-4, PL-13) Commercially available resin lens (R3) (Mitsui Chemicals, Inc.) as a substrate
(N = 1.66) manufactured by N.
After being immersed in an aOH aqueous solution for 5 minutes, it was sufficiently washed with water and dried. Then, using the coating liquid for forming a transparent film prepared in Example 4 and Example 13, in the same manner as the substrate with a transparent film (PL-1), the substrate with a transparent film (PL-4, PL-13, ) Formed. The thickness of the transparent coating was 2.3 μm.

The lens on which each transparent film was formed was prepared using a commercially available dye (Amber D for Seiko Plux).
Dyeing (fabric) was carried out in a dyeing bath at a temperature of 3 ° C. for 3 minutes. Substrate with transparent coating (PL-3, PL-5, PL-6, PL-7, PL-12, PL-
Commercially available resin lens (R4) as a base material for preparation of 14, PL-15, PL-16 ) (Mitsui Chemicals, Inc.)
(N = 1.60).
After being immersed in an aOH aqueous solution for 5 minutes, it was sufficiently washed with water and dried.

Next, Example 3, Example 5, Example 6,
Using each of the coating liquids for forming a transparent film prepared in Example 7, Example 12, Example 14, Example 15, and Example 16,
Substrate with a transparent coating (PL-3, PL-5, PL-6, PL-7, PL-12, PL-14, PL-15, PL-
16) formed. The thickness of the transparent coating was 2.3 μm.

The lens on which each transparent film was formed was prepared using a commercially available dye (Sumicaron Blue E-manufactured by Sumitomo Chemical Co., Ltd.).
RPD 2.0g, Sumicaron Red E-RPD
0.8 g, Sumicaron Yellow E-RPD 0.4
g) in a dye bath at 65 ° C. mixed with 1 L of water.
Drying was performed at 0 ° C. for 1 hour. The following characteristics were evaluated for the substrate with a transparent coating obtained as described above.

Table 1 shows the results. Fading property Each of the dyed lenses obtained above was subjected to an ultraviolet irradiation device (Q-Pa
(Nel Lab Products: QUV) for 20 hours, and the change in the color tone before and after the exposure was visually observed, and the judgment was made according to the following criteria.

：: Little difference is observed. Δ: A slight difference is observed. X: A clear difference is seen. Interference fringes Regarding the presence or absence of the occurrence of interference fringes, the light of the fluorescent lamp was reflected on the lens surface in a state where the background was blackened, and the occurrence of a rainbow pattern due to the interference of light was visually observed.

：: No rainbow pattern is observed. Δ: A slight rainbow pattern is observed. ×: A rainbow pattern is clearly observed. Scratch resistance The state of the coating film after 10 reciprocations with a load of 1 kg / cm2 using # 0000 steel wool was observed, and the judgment was made according to the following criteria.

A: No damage at all. B: Almost no damage. C: Slightly scratched. D: Many scratches are made. Adhesion After immersion in warm water of 70 ° C for 2 hours, 11 parallel line-shaped scratches are made on the lens surface with a knife at 1 mm intervals vertically and horizontally each to make 100 squares, and a cellophane tape is adhered and peeled off to form a film. The number of squares remaining without peeling was checked.
(Hereinafter, it may be referred to as a cross-cut tape test.) After exposing for 200 hours using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.) having a weather-resistant carbon arc electrode, the cross-cut tape test was performed. I went about.

Long-term stability After storing each coating liquid for forming a transparent film at 10 ° C. for 25 days and 45 days, a transparent film is formed as described above, and the weather resistance is evaluated from the fading property. ○, △, the difference from the transparent film formed immediately after preparing the coating solution for
The evaluation was made in three stages of x.

○: No difference was observed. Δ: A slight decrease in performance was observed. X: Performance was clearly reduced.

[0147]

Comparative Example 1 In Example 1, the dispersion medium of the aqueous dispersion sol of the titanium oxide-containing core particles having an intermediate thin film layer composed of silicon oxide and zirconium oxide was replaced with methanol, and the solid content was reduced to 20% by weight. Concentration was performed to obtain an organosol of titanium oxide-containing core particles. This sol is mixed with antimony oxide-coated titanium oxide-containing composite oxide particles (AT-
A coating solution for forming a transparent film (CFS-1) was prepared in the same manner as in Example 1 except that the coating solution was used in place of 1). Using this coating solution, a transparent film was formed on the resin lens (R1) in the same manner as in Example 19, and the characteristics of the obtained substrate with a transparent film were evaluated. Table 1 shows the results.

[0148]

Comparative Example 2 In Example 4, the dispersion medium of the aqueous dispersion sol of titanium oxide-containing core particles having an intermediate thin film layer composed of silicon oxide and zirconium oxide was replaced with methanol and concentrated until the solid content concentration became 20% by weight. Thus, an organosol of titanium oxide-containing core particles was obtained. A coating solution for forming a transparent film (CFS-2) was prepared in the same manner as in Example 4, except that this sol was used in place of the antimony oxide-coated titanium oxide-containing composite oxide particles (AT-4). Using this coating solution, a transparent film was formed on the resin lens (R2) in the same manner as in Example 19, and the characteristics of the obtained substrate with a transparent film were evaluated.
Table 1 shows the results.

[0149]

Comparative Example 3 In Example 6, the water in the dispersion medium of the dispersion sol of titanium oxide-containing core particles (TN-6) composed of titanium oxide and tin oxide was replaced with methanol, and the solid content concentration was 20% by weight.
To obtain an organosol of titanium oxide-containing core particles. Except for using this sol instead of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-6),
Coating solution for forming a transparent film (CFS-3) in the same manner as in Example 6.
Was prepared. Using this coating solution, a transparent film was formed on the resin lens (R4) in the same manner as in Example 19, and the characteristics of the obtained substrate with a transparent film were evaluated. Table 1 shows the results.

[0150]

[Table 1]

[0151]

Example 20 Preparation of a coating liquid for primer film formation (PFS-20)
In Preparation Example 11, except that an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-1) was used instead of the organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-2). In the same manner as in Example 11, an organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-19) surface-treated with γ-glycidoxypropyltrimethoxysilane was prepared.

A concentration of 30 was added to 2000 g of this organosol.
By mixing 500 g of an aqueous dispersion of urethane elastomer (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Superflex 150) by weight, a coating liquid for forming a primer film (PFS-20) was prepared. Commercially available resin lens (R1) as a base material for forming a primer film (Mitsui Chemicals, Inc.)
(N = 1.74), which was used at a concentration of 5% by weight of Na.
After being immersed in an OH aqueous solution for 5 minutes, it was sufficiently washed with water and dried.

Next, this resin lens (R1) was immersed in the primer film-forming coating solution (PFS-20), pulled up at a pulling rate of 95 mm / min, and heated at 85 ° C. for 120 min.
The film was cured by heating at 04 ° C. for 60 minutes to form a primer film on the lens surface. Formation of Transparent Coating Next, a substrate with a transparent coating was formed on this lens in the same manner as in Example 19, using the coating liquid for forming a transparent coating (FS-8) prepared in Example 8.

Formation of Antireflection Film Next, the resin film (R1) with the primer film and the transparent film was exposed to argon gas plasma of 200 W output in vacuum for 30 seconds, and then from the lens side to the air side by vacuum evaporation. Toward SiO ₂ , ZrO ₂ , SiO ₂ , Z
Five thin films of rO ₂ and SiO ₂ were formed. The optical film thickness of the formed anti-reflection film is about λ / 4 for SiO ₂ ,
The total film thickness of O ₂ and SiO ₂ is about λ / 4, and the next ZrO ₂ is about λ
/ 4, and the uppermost SiO ₂ is about λ / 4. (Design wavelength λ is 510 nm) An antireflection film was formed.

[0155] impact resistance test obtained as described above primer film, was subjected to impact testing using the transparent film and the antireflection film-coated plastic lens. The test method of the impact resistance was 16.2 g, 100 g, 200 g, and 400 g from the height of 126 cm.
The four types of steel balls were vertically dropped on a plastic lens, and the presence or absence of cracks was judged. No cracking ... ○ Cracking ... ×

Further, assuming that the primer film was not formed, the coating solution for forming a transparent film (FS) prepared in Example 8 was used.
-8), a substrate with a transparent coating was formed on the lens (R1) in the same manner as in Example 19, and then an antireflection film was formed by a vacuum deposition method in the same manner, and an impact resistance test was performed. Table 2 shows the results.

[0157]

Embodiment 21 In Embodiment 20, a resin lens (R
Using a resin lens (R4) with n = 1.60 instead of 1), the amount of organosol of antimony oxide-coated titanium oxide-containing composite oxide particles (AT-19) in preparing a coating solution for forming a primer film Was replaced with 1200 g of methanol 80
By adding 0 g, a coating solution for forming a primer film (PFS-22) was prepared, and a primer film was formed on the lens surface.

Next, the coating liquid (FS) prepared in Example 12 was applied to the lens on which the primer film was formed.
-12), a substrate with a transparent film was formed in the same manner as in Example 20, then an antireflection film was formed by a vacuum evaporation method, and an impact resistance test was performed. Further, assuming that the primer film was not formed, the transparent lens-forming coating solution (FS-12) prepared in Example 12 was used. To form
An antireflection film was formed by a vacuum evaporation method in the same manner as in Example 20, and an impact resistance test was performed.

Table 2 shows the results.

[0160]

[Table 2]

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of the composite oxide fine particles prepared in Example 3.

FIG. 2 is an X-ray diffraction diagram of the composite oxide fine particles prepared in Example 5.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 17/00 C09D 17/00 167/00 167/00 175/04 175/04 183/02 183/02 183 / 04 183/04 201/00 201/00 F-term (reference) 4J037 AA18 AA22 AA30 CA15 CB09 CB16 CC28 DD05 EE03 EE04 EE14 EE19 EE43 FF30 4J038 DL021 DL031 DL051 DL081 DL091 DL111 DL121 HA166 HA216 JB02 KA03 LA04 NA11 NA12 NA14 NA17 PA17 PA19 PB01 PB07 PB08 PC03 PC08

Claims (12)

[Claims] 1. An antimony oxide-coated titanium oxide-containing composite oxide particle comprising a titanium oxide-containing core particle and a coating layer made of antimony oxide. 2. The titanium oxide content in the titanium oxide-containing core particles is 10% by weight or more in terms of TiO ₂ , and the amount of the coating layer made of antimony oxide is the same as that of the titanium oxide-containing composite oxide particles. In contrast, 1 as Sb ₂ O ₅
The antimony oxide-coated titanium oxide-containing composite oxide particles according to claim 1, wherein the content is in the range of from 90 to 90% by weight. 3. The method according to claim 2, wherein the titanium oxide-containing core particles are Si, Al,
1 selected from Sn, Zr, Zn, Sb, Nb, Ta and W
The titanium oxide-containing composite oxide particles coated with antimony oxide according to claim 1, comprising an oxide of at least one kind of element. 4. Si, Al, Sn, Zr, Zn, Sb, between the titanium oxide-containing core particles and the antimony oxide coating layer.
2. An intermediate thin film layer comprising one or more oxides, composite oxides, or mixtures of one or more elements selected from Nb, Ta, and W. 3. The composite oxide particles containing titanium oxide coated with antimony oxide according to any one of 3. 5. The surface is modified with an organosilicon compound or an amine compound.
5. The composite oxide particles containing titanium oxide coated with antimony oxide according to any one of 4. 6. An antimony oxide-coated titanium oxide-containing composite oxide particle obtained by dispersing the antimony oxide-coated titanium oxide-containing composite oxide particle according to any one of claims 1 to 5 in water and / or an organic solvent. Dispersed sol. 7. An antimony oxide-coated titanium oxide-containing composite oxide particle according to claim 1, and an organosilicon compound represented by the following formula (A) as a matrix-forming component: A coating liquid for forming a transparent film, comprising at least one hydrolyzate and / or partial condensate. R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)} (A) wherein R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, a vinyl group,
A methacryloxy group, a mercapto group, an organic group having an amino group or an epoxy group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, R ³ is a hydrocarbon group or an acyl group having 1 to 8 carbon atoms,
a and b represent 0 or 1. ) 8. An antimony oxide-coated titanium oxide-containing composite oxide particle according to any one of claims 1 to 5, and a thermosetting resin or a thermoplastic resin as a matrix-forming component.
A coating liquid for forming a transparent film, comprising at least one resin selected from ultraviolet curable resins. 9. The coating liquid for forming a transparent film according to claim 8, wherein the matrix forming component is made of a polyester resin or a urethane resin. 10. A substrate with a transparent coating, comprising a transparent coating formed on the surface of the substrate using the coating liquid for forming a transparent coating according to claim 7. 11. A transparent film for forming a transparent film according to claim 7, further comprising a primer film formed on the surface of the base material using the coating liquid for forming a transparent film according to claim 8 or 9. A substrate with a transparent coating, comprising a hard coat film formed using a coating solution. 12. The method according to claim 1, further comprising an antireflection film on the transparent film or the hard coat film.
12. The substrate with a transparent coating according to 0 or 11.