Coating liquid for forming transparent film and substrate having transparent coating film

The present invention relates to a novel coating liquid for forming a transparent film and a substrate with a transparent film having a transparent film formed from the coating liquid for forming a transparent film.

Optical plastic molded products made of transparent resin have come to be used in applications where glass has been conventionally used due to their characteristics such as light weight, excellent workability and impact resistance. The refractive index of the transparent resin is appropriately selected and used according to the intended use.

For example, in the field of spectacle lenses, when a low refractive index resin material is used, the outer peripheral portion tends to be thicker than that of a glass lens. There is. As such an attempt, Japanese Patent Application Laid-Open No. 59-133211 (Patent Document 1), Japanese Patent Application Laid-Open No. 63-46213 (Patent Document 2), Japanese Patent Application Laid-Open No. 2-270859 (Patent Document 3), etc. Has proposed a high refractive index resin material having a refractive index higher than that.

On the other hand, plastic spectacle lenses have a drawback that they are easily scratched. For this reason, a method of providing a silicone-based hard coat film on the surface of a plastic lens is generally performed. However, when the same method is applied to a high-refractive index resin lens of 1.54 or more, interference fringes may occur due to the difference in refractive index between the resin lens and the coating film, which may cause a poor appearance. In order to solve this problem, as a high refractive index hard coating with a small difference in refractive index from the transparent resin, Japanese Patent Application Laid-Open No. 2-264902 (Patent Document 4) describes composite inorganic oxide fine particles of titanium oxide and cerium oxide. Is disclosed, and Japanese Patent Application Laid-Open No. 3-68901 (Patent Document 5) discloses a coating composition containing fine particles obtained by treating oxide particles containing titanium oxide and, if necessary, cerium oxide with an organic silicon compound. ing.

Further, Japanese Patent Application Laid-Open No. 5-2102 (Patent Document 6) discloses a hard coat film using titanium oxide and iron oxide composite oxide fine particles, and Japanese Patent Application Laid-Open No. 7-76671 (Patent Document 7) discloses. Discloses a coating composition containing particles obtained by treating composite oxide fine particles of titanium oxide and iron oxide with an organic silicon compound, and a thermosetting catalyst such as unsaturated polyvalent carboxylic acid and imidazole, and a cured film.

Further, Japanese Patent Application Laid-Open No. 8-48940 (Patent Document 8) discloses a coating composition for a lens composed of a composite inorganic oxide of Ti, Si, Zr and / or Al and a matrix.

Further, as such a base material for a lens, JP-A-9-71580, JP-A-9-110979, and JP-A-9-255781 have a high refractive index of 1.67 to 1.70 and an Abbe number. Optical materials consisting of more than 30 shrimp sulfide compounds have been proposed. As a hard coat film used for such an optical material, in Japanese Patent Application Laid-Open No. 2000-204301 (Patent Document 9), nuclear particles made of a composite solid solution oxide of titanium oxide and tin oxide, and silicon oxide, which are nuclear particles made of a composite solid solution oxide of titanium oxide and tin oxide, are used. , A fine particle having a coating layer made of a composite oxide of zirconium oxide and / or aluminum oxide can be preferably used.

Further, in Japanese Patent Application Laid-Open No. 2002-363442 (Patent Document 10), the applicant uses metal oxide fine particles composed of titanium oxide-containing nuclear particles and an antimony oxide coating layer for a hard coat film such as a lens. I'm proposing to do it.<patcit num="1"><text>JP-A-59-133211</text></patcit><patcit num="2"><text>JP-A-63-46213</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 2-270859</text></patcit><patcit num="4"><text>Japanese Patent Application Laid-Open No. 2-264902</text></patcit><patcit num="5"><text>Japanese Unexamined Patent Publication No. 3-68901</text></patcit><patcit num="6"><text>Japanese Patent Application Laid-Open No. 5-2102</text></patcit><patcit num="7"><text>Japanese Unexamined Patent Publication No. 7-76671</text></patcit><patcit num="8"><text>Japanese Unexamined Patent Publication No. 8-48940</text></patcit><patcit num="9"><text>Japanese Unexamined Patent Publication No. 2000-204301</text></patcit><patcit num="10"><text>Japanese Unexamined Patent Publication No. 2002-363442</text></patcit>

<p> When titanium oxide is used as the coating composition, TiO₂Since it has a higher refractive index than other inorganic oxides, the formed film has an advantage that it exhibits a refractive index of around 1.60 or even higher, and at the same time, the range of choice of the refractive index of the film is widened. is there. But TiO₂Is extremely inferior in weather resistance, so TiO₂In the coating film formed from the coating composition containing, the organic components such as the organosilicon compound in the coating film are decomposed, the epoxy resin component used for the coating film forming component is decomposed, and further, the coating film on the surface of the resin base material is used. Deterioration occurred, and there was a problem in film durability. Further, this film has a problem that the adhesion to the base material is inferior.</p><p> Therefore, as proposed in Patent Documents 3 to 6, it has been attempted to improve the weather resistance by combining titanium oxide with cerium oxide or the like, but the obtained film is in terms of weather resistance. It was inadequate. Further, there is also a problem that the cured film obtained from these composite sols is colored to some extent.</p><p> Further, such a hard coat layer or a primer layer has been dyed as needed, but in the above-mentioned conventionally known titanium-based composite particles and the like, the dyeing may fade due to the action of titanium oxide. In other words, the fading resistance may be reduced.</p><p> Therefore, the applicant proposes the use of titanium oxide-based fine particles having an antimony oxide coating layer in Patent Document 10. By doing so, the weather resistance, the adhesiveness, and the weather fading resistance of the dyed product are improved, and a hard coat film superior to the conventional one can be obtained. However, there is a problem that the hard coat film itself is discolored (yellowed) by ultraviolet rays.</p><p> By the way, a shrimp sulfide compound or the like has been proposed as a lens base material, but in the United States and the like, a polycarbonate lens is the mainstream as a high refractive index lens from the viewpoint of safety. However, there is a drawback that the hard coat and the transparent film, which have been conventionally proposed, have poor adhesion to the polycarbonate base material. Therefore, a primer film has been formed between the polycarbonate base material and the transparent film. However, in this case, although the adhesion is improved, there are problems that it takes time to form the film and the cost is high. Therefore, the appearance of a hard coat or a transparent film having excellent adhesion to the polycarbonate base material has been desired.</p>

<p> Under such circumstances, as a result of diligent studies to solve the above problems, metal oxide fine particles composed of metal oxide nuclei particles and a coating layer made of antimony oxide are used, and an organic silicon compound is used. By using two specific hardeners (coating-forming components) in combination, the above problems can be solved, and even a polycarbonate base material has high adhesion, high refractive index, and weather resistance. The present invention has been completed by finding that a transparent film having improved weather fading resistance, excellent scratch resistance, dyeing property, and weather resistance, and which is not discolored by ultraviolet rays can be obtained. (1) That is, the coating liquid for forming a transparent film according to the present invention is characterized by containing the following components (A) to (D); (A) an organic silicon compound and / or a hydrolyzate of the organic silicon compound. , (B) Metal oxide fine particles composed of (B) metal oxide nuclei particles and a coating layer composed of antimony oxide, (C) polythiol compound, organic polyvalent carboxylic acid, selected from the group consisting of acetylacetone metal complex. A curing agent consisting of one or more curing agents (hardening agent A) and (D) a compound containing basic nitrogen (hardening agent B). (2) The metal oxide fine particles (B) are surface-modified with an organosilicon compound or an amine compound. (3) At least a part of the organosilicon compound (A) is an epoxy group-containing organosilicon compound, and the content of the epoxy group-containing organosilicon compound in the total organosilicon compound is 60% by weight or more as a solid content. (4) The antimony oxide constituting the coating layer has an oxidation number of antimony in the range of 3 to 5. (5) The ratio of the coating layer is Sb₂O₅In terms of conversion, it is in the range of 1 to 90% by weight. (6) Metal oxide nuclei particles contain antimony pentoxide or titanium oxide as the main component. (7) The metal oxide nuclei particles contain titanium oxide as a main component, and one or more elements selected from the group consisting of Si, Al, Sn, Zr, Fe, Sb, Nb, Ta, and W. Contains oxides in a proportion of less than 10% by weight in terms of oxides. (8) An intermediate thin film composed of oxides of one or more elements selected from the group consisting of Si, Al, Sn, Zr, Sb, Nb, Ta, and W between the metal oxide nuclei particles and the coating layer. One or more layers are formed. (9) A base material with a transparent film having a transparent film formed on the surface of a polycarbonate base material using the coating liquid for forming a transparent film. (10) The refractive index of the transparent film is 1.54 or more. (11) It has a primer film between the polycarbonate base material and the transparent film. (12) An antireflection film is further provided on the transparent film.</p>

<p> According to the present invention, it has a high refractive index, high transmittance, no interference fringes, scratch resistance, abrasion resistance, impact resistance, heat resistance, water resistance, sweat resistance, chemical resistance, weather resistance, A transparent film having excellent light resistance and flexibility can be formed on a base material such as plastic, particularly on the surface of a polycarbonate base material, which has been difficult in the past, with good adhesion. Moreover, the obtained transparent film has a characteristic that the dyeability can be improved and the discoloration due to ultraviolet rays is particularly small.</p><p> The coating liquid for forming a transparent film according to the present invention contains metal oxide fine particles composed of metal oxide nuclei particles and a coating layer composed of antimony oxide, a polythiol compound as a curing agent [a], and an organic polyvalent carboxylic acid. , One or more compounds selected from the acetylacetone metal complex and a compound containing basic nitrogen as a curing agent [b] are contained, so that the curing catalytic action is amplified, and the reason is not clear. Discoloration of the guard coat film due to ultraviolet rays is also suppressed, so that a transparent film having excellent weather resistance, light resistance, chemical resistance, flexibility and dyeability can be formed. Further, when the metal oxide fine particles are surface-modified, the adhesion to the base material, particularly the polycarbonate base material, is excellent and the surface hardness is high. Therefore, the scratch resistance and the abrasion resistance are excellent, and if necessary. It is possible to suppress discoloration, fading, and fading of the dyeing even when the dyeing is performed.</p>

Hereinafter, the coating liquid for forming a transparent film according to the present invention will be specifically described.<u style="single">Coating liquid for forming a transparent film</u> The coating liquid for forming a transparent film according to the present invention contains the following components (A) to (D). (A) Organic silicon compound and / or hydrolyzate of the organic silicon compound, (B) Metal oxide fine particles composed of (B) metal oxide nuclei particles and a coating layer composed of antimony oxide, (C) polythiol. A curing agent consisting of one or more curing agents (curing agent A) selected from the group consisting of a compound, an organic polyvalent carboxylic acid, and an acetylacetone metal complex, and (D) a compound containing basic nitrogen (curing agent B).

[Organosilicon compound and / or hydrolyzate of the organosilicon compound]

The organosilicon compound functions as a film-forming component of the transparent film, and is not particularly limited as long as it can be hydrolyzed to form a silica-based film and cured. Specifically, the organosilicon compounds shown below and their hydrolysates are used.

As the organosilicon compound, an organosilicon compound represented by the following formula is used. R¹_aR²_{b b}Si (OR³)_{4- (a + b)} R¹_aR²_{b b}SiX_{4- (a + b)}(Here, R¹Is an alkyl group having 1 to 6 carbon atoms having an organic group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a vinyl group, an epoxy group, a methacryloxy group, a mercapto group, and an amino group.²Is an alkyl group having 1 to 3 carbon atoms, an alkylene group, a cycloalkyl group, an alkyl halide group, an aryl group, and R³Is an alkyl group having 1 to 4 carbon atoms, an alkylene group, a cycloalkyl group, an alkoxyalkyl group, and an arylalkyl group. X is a halogen atom. Also, a = 0 or 1, b = 0, 1 or 2).

Specific examples of the organic silicon compound represented by the above formula include tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, trimethylchlorosilane, and α-glusideoxymethyltri. Methoxysilane, α-glycidoxyethyl trimethoxysilane, β-glycidoxyethyl trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epylcyclohexyl) -ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) -ethyltriethoxysilane, γ-aminopropyl Trimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxylan, N-β (aminoethyl) -γ-aminopropylmethyldietoxylan and the like can be mentioned. it can. These can be used alone or in combination of two or more.

The organosilicon compound may be an unhydrolyzate or a hydrolyzate. Hydrolysis is preferably carried out in the presence of an acid in a polar organic solvent such as alcohol or in the absence of a solvent. When a hydrolyzate is used, the organosilicon compound may be hydrolyzed in advance and then mixed with the metal oxide fine particles described later. However, after mixing the metal oxide fine particles and the organosilicon compound, the organosilicon The compound may be hydrolyzed. In this way, surface modification can be substantially performed at the same time, so that the number of production steps can be reduced and the production efficiency is excellent.

In the present invention, it is preferable to use an epoxy group-containing organosilicon compound as the organosilicon compound, and at this time, the content of the epoxy group-containing organosilicon compound is 60% by weight or more as a solid content among all the organosilicon compounds. Is preferable. Examples of such an epoxy group-containing organic silicon compound include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane. It is preferably used.

Such an epoxy group-containing organosilicon compound may be used alone or in combination with other organosilicon compounds. When used in combination, it is desirable that the content of the epoxy group-containing organosilicon compound is 60% by weight or more as the solid content of the total organosilicon compound. Can be raised.

In the transparent film, the organosilicon compound forms a film-forming component (also referred to as a matrix, a binder, or a vehicle), and silanol produced by hydrolysis is polycondensed. Further, when the epoxy group is contained, the epoxy group undergoes ring-opening polymerization, so that a transparent film having excellent scratch resistance, weather resistance, and weather fading resistance can be formed.

[Metal oxide fine particles]

The metal oxide fine particles are composed of metal oxide nuclei particles and a coating layer made of antimony oxide. Although the average particle size of the metal oxide fine particles is not particularly limited, it is preferably in the range of 1 to 100 nm, preferably 2 to 60 nm.

Within such an average particle size range, the obtained transparent film has high hardness, excellent scratch resistance, and the refractive index of the transparent film can be sufficiently increased. When the average particle size is smaller than the lower limit of the above range, the transparent film obtained by using the coating liquid containing the metal oxide fine particles has insufficient hardness, is inferior in scratch resistance, and has a sufficiently high refractive index of the transparent film. There are things you can't do. Further, when the average particle size exceeds the upper limit of the above range, the obtained film may appear cloudy due to light scattering.

<u style="single">Metal oxide nuclei particles</u> The nuclear particles have a refractive index in the range of 1.7 to 3.0, and are not particularly limited as long as they can form a coating layer of antimony oxide, which will be described later. Preferably, those containing antimony pentoxide or titanium oxide as a main component are desirable.

In the case of antimony pentoxide nuclei particles, they may be composed of antimony pentoxide or may contain other antimony oxides (those having different oxidation numbers). Antimony pentoxide nuclei particles are easy to coat with antimony oxide, and the refractive index of the obtained metal oxide fine particles is in a narrow range of about 1.6 to 1.7, and the transparent film obtained by using this is dyeable. It is excellent and can suppress fading due to ultraviolet rays after dyeing.

Further, the titanium oxide-based nuclear particles may contain oxides of one or more elements selected from Si, Al, Sn, Zr, Fe, Sb, Nb, Ta and W in addition to titanium oxide or Ti. When other oxides are contained, the titanium oxide content in the titanium oxide-based nuclear particles is TiO.₂It is desirable that the weight is 10% by weight or more, and further 20% by weight or more. With such a content, the refractive index of the transparent film can be increased and interference fringes are not formed.

Such components other than titanium oxide and titanium oxide may be in a mixture, in a solid solution state with each other, or in another composite state. Further, titanium oxide may be amorphous or crystalline such as anatas type, rutile type and brookite type. Furthermore, barium titanate (BaTiO)₃Or BaOTiO₂) May be a perovskite type titanium compound.

When the titanium oxide-based nuclear particles contain a component other than titanium oxide, composite nuclear particles containing tin oxide can be mentioned. When these composite nuclei particles are used, a transparent film having a high refractive index suitable for use in a high refractive index lens substrate can be obtained. Further, the titanium oxide-based nuclear particles may contain silica or zirconia in addition to tin oxide.

The average particle size of the nuclear particles is appropriately selected depending on the particle size of the metal oxide particles to be finally used, but is preferably in the range of 1 to 100 nm, preferably 2 to 50 nm.<u style="single">Antimony oxide coating layer</u> A coating layer made of antimony oxide is formed on the surface of the nuclear particles.

The thickness of the antimony oxide coating layer is not particularly limited and varies depending on the particle size of the nuclear particles, but is usually preferably in the range of 1/200 to 1/5 of the particle size of the nuclear particles. In addition, the content of antimony oxide constituting the coating layer in the metal oxide fine particles is Sb.₂O₅It may be formed so as to be in the range of 1 to 90% by weight, preferably 5 to 70% by weight. Within such a range, the particle size of the metal oxide particles is uniform, the fading resistance is high, and a transparent film can be formed. By providing such an antimony oxide coating layer, it is possible to enhance the weather resistance, and further, since the original action of titanium oxide is suppressed by the antimony oxide coating layer, the color fading resistance is also excellent, and further. Since the refractive index can be arbitrarily changed depending on the thickness of the antimony oxide coating layer, a transparent film without interference fringes can be formed according to the refractive index of the base material.

If the content of the antimony oxide coating layer in the metal oxide fine particles is less than the above lower limit in terms of oxide, the above-mentioned fading resistance may be insufficient. If the content of the antimony oxide coating layer exceeds the above upper limit, the particle size of the obtained metal oxide fine particles may become non-uniform or aggregate, and the transparency of the obtained transparent film may decrease.

Here, the antimony oxide constituting the coating layer is "Sb.₂O₅Is not limited to "usually Sb₂O₃~ Sb₂O₅That is, it means an oxide in which the oxidation number of antimony is in the range of 3 to 5. When such an antimony oxide coating layer is provided, when the transparent film contains a dye, the obtained transparent film has improved fading resistance as compared with the case where only the nuclear particles are used.

Preferred antimony oxides are oxides with an oxidation number of less than 5. When the oxidation number is less than 5, the dyed product has better fading resistance. In the present invention, the antimony oxide may be amorphous or crystalline, and may contain water of hydration or water of crystallization.

<u style="single">Intermediate thin film layer</u> Further, the metal oxide fine particles according to the present invention are one or more selected from Si, Al, Sn, Zr, Zn, Sb, Nb, Ta and W between the nuclear particles and the antimony oxide coating layer. One or more intermediate thin film layers composed of at least one of an oxide of the element, a composite oxide, and a mixture thereof may be formed. The intermediate thin film layer may be one layer or two or more layers.

By forming at least one intermediate thin film layer between the nuclear particles and the antimony oxide coating layer, the refractive index of the metal oxide fine particles can be adjusted, and the light resistance and weather resistance of the obtained transparent coating film ( Resistance to film deterioration due to decomposition of vehicle components due to the activity of titanium oxide-based nuclear particles, etc.), adhesion between the transparent film and the substrate can be improved, and coloration of the particles can be suppressed or colorless. , The transparency of the transparent film can be improved.

In addition, the number of intermediate thin film layers and the thickness of at least one intermediate thin film layer are such that the ratio of nuclear particles in the metal oxide fine particles is in the range of 10 to 99% by weight, and the ratio of the antimony oxide coating layer is Sb.₂O₅There is no particular limitation as long as it is formed so as to be in the range of 1 to 90% by weight.

As the intermediate thin film layer, a composite oxide composed of silicon oxide and zirconium oxide and / or aluminum oxide is particularly preferable, and as the composite form thereof, silicon oxide, zirconium oxide, and aluminum oxide are laminated for each single component to form a thin film. A layer may be formed, or a thin film layer may be formed by a component of silica / zirconia, silica / alumina, or silica / zirconia / alumina. When such an intermediate thin film layer is formed, metal oxide fine particles capable of forming a transparent film having excellent weather resistance, light resistance, adhesion to a base material, film hardness, scratch resistance, and the like can be formed. Can be obtained.

Further, by using silicon oxide for the intermediate thin film layer, the stability of the metal oxide fine particle dispersion liquid is improved, and the pot life of the coating liquid obtained by using the silicon oxide is extended. Then, it is possible to improve the hardness of the transparent film obtained by applying the coating liquid containing such metal oxide fine particles and the adhesion to the antireflection film formed on the transparent film. As a result, in this case as well, weather resistance, light resistance, adhesion to the base material, film hardness, scratch resistance and the like are further improved.

The method for preparing such metal oxide fine particles is not particularly limited as long as the above-mentioned metal oxide fine particles can be obtained, and a conventionally known method can be adopted. In particular, the method for producing titanium oxide-containing composite oxide particles coated with antimony oxide disclosed in JP-A-2002-363442, which was filed by the applicant of the present application, can be preferably adopted.

As the titanium oxide-based nuclear particles, the composite oxide particles disclosed in Japanese Patent Application Laid-Open No. 8-48940, etc. filed by the applicant of the present application are preferably used. For example, a method of hydrolyzing an aqueous solution of peroxotitanic acid and a method of hydrolyzing titanium alkoxide and a titanium salt can be mentioned. Of these, it is desirable to use peroxotitanic acid (titanium peroxide) in terms of controlling the particle size and crystallinity.

As the antimony pentoxide particles, antimony pentoxide particles disclosed in JP-A-2-180717, etc. filed by the applicant of the present application are preferably used. For example, an antimony oxide sol obtained by dissolving antimony trioxide in an oxidizing agent and an alkali and then reacting them is preferably used.

When forming the intermediate thin film layer, the intermediate thin film layer may be formed by the same method as the method for forming the coating layer on the nuclear particles. As a method for forming the antimony oxide coating layer, first, an aqueous dispersion of nuclear particles or nuclear particles provided with an intermediate thin film layer is prepared. The concentration of this 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. Within this range, it can be formed efficiently and the dispersibility of the dispersion is high.

Then, the antimony compound is added to the above dispersion. As for the amount of antimony compound added, the ratio of the antimony oxide coating layer in the finally obtained metal oxide fine particles is Sb.₂O₅It should be in the range of 1 to 90% by weight.

The antimony compound used in the present invention is not particularly limited, and antimony mineral salts such as antimony chloride, organic acid salts such as antimony tartrate, alkali antimony such as sodium antimonate and potassium antimonate, and antimony alkoxide are used. be able to.

A solution prepared by dissolving the antimony compound in water and / or an organic solvent is added to the aqueous dispersion of the nuclear particles or the nuclear particles provided with the intermediate thin film layer while appropriately adjusting the pH and temperature of the solution, if necessary. Then, a coating layer can be formed by adding an oxidizing agent. After mixing the nuclear particles and the antimony compound, aging may be carried out. Further, the oxidizing agent may be added to the antimony compound in advance and reacted, or the antimony compound may contain an oxidizing agent.

By coating in this way, the antimony compound is oxidized and a coating layer made of antimony oxide is formed. The obtained particles may be washed to remove unnecessary substances, if necessary. The oxidizing agent is not particularly limited as long as the oxidation number of antimony can be maintained at 3 to 5 valences, and specifically, oxygen, ozone, hydrogen peroxide, hypochlorous acid and the like can be used. Examples of the cleaning method include an ultrafiltration membrane method and a deionization method using an ion exchange resin.

[Surface modification treatment]

It is preferable that the surface of the metal oxide fine particles according to the present invention is modified by treating the surface with an organosilicon compound or an amine compound. When the modification treatment is performed, the dispersed state of the metal oxide fine particles in the coating liquid for forming a transparent film becomes stable for a long period of time.

Further, the surface-modified metal oxide fine particles have low reactivity with the matrix (organosilicon compound and / or its hydrolyzate) and have a high affinity with the matrix. Therefore, the obtained transparent film has a higher hardness than the one not subjected to the surface modification treatment, and also has a higher affinity with the base material. It is possible to form a transparent film having excellent adhesion, scratch resistance, flexibility, dyeability and the like on a polycarbonate base material which has been difficult to form.

As the organosilicon compound used in the surface modification treatment, an organosilicon compound known as a silane coupling agent can be used, and the type thereof is appropriately selected according to the application, the type of solvent, and the like. Specifically, the following are used. Formula: R₃Monofunctional silane represented by SiX Formula: R₂SiX₂Bifunctional silane represented by: Formula: RSiX₃Trifunctional silane represented by: Formula: SiX₄A tetrafunctional silane represented by. (R is an alkyl group having an alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group or an epoxy group, and X is a hydrolyzable group (alkoxy group or halogen or hydrogen). Is a monofunctional silane such as trimethylsilane, dimethylphenylsilane and dimethylvinylsilane, a bifunctional silane such as dimethylsilane and diphenylsilane, a trifunctional silane such as methylsilane and phenylsilane, and a tetrafunctional silane such as tetraethoxysilane. In the surface modification treatment, the hydrolyzable group may be untreated or hydrolyzed. After the treatment, the hydrolyzable group reacts with the -OH group on the surface of the fine particles. It is preferable to use the above state, but there is no problem even if a part of the state remains.

Such an organosilicon compound may be the same as the above-mentioned (A) organosilicon compound and its hydrolyzate as a film-forming component. If the same material is used, a more stable coating liquid having high affinity in the coating liquid for forming a transparent film can be obtained.

Examples of amine-based compounds include alkylamines such as ammonium or ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, monoethanolamine and triethanolamine. There are quaternary ammonium salts such as alkanolamines, tetramethylammonium salts, and tetramethylammonium hydroxides, and quaternary ammonium hydroxides.

To modify the surface of the metal oxide fine particles with an organosilicon compound or an amine compound, for example, the metal oxide fine particles were mixed in an alcohol solution of these compounds, and a predetermined amount of water and a catalyst were added if necessary. After that, it is advisable to leave it at room temperature for a predetermined time or to perform heat treatment.

The surface of the metal oxide fine particles can also be modified with these compounds by adding the hydrolyzate of these compounds and the metal oxide fine particles to a mixed solution of water and alcohol and heat-treating the mixture.

The metal oxide fine particles obtained by the above method are usually obtained with a dispersion liquid dispersed in a solvent. Examples of the solvent include those described later. When blended in the coating liquid, the metal oxide fine particles may be blended as a solid-liquid separated / dried powder from the dispersion liquid, but usually, the dispersion liquid may be blended as it is. Moreover, you may replace the dispersion liquid with a solvent if necessary.

[Hardener [a]]

As the curing agent [a] used in the coating liquid for forming a transparent film of the present invention, one or more compounds selected from polythiol compounds, organic polyvalent carboxylic acids, and acetylacetone metal complexes are used. These compounds function as ring-opening polymerization curing agents for epoxy groups and / or condensation catalysts for silanol groups.

<u style="single">Polythiol compound</u> The polythiol compound used in the present invention is not particularly limited as long as it has two or more thiol groups in one molecule. For example, a thiol compound having two thiol groups in the molecule obtained by an esterification reaction between a polyol such as ethylene glycol dithioglycolate and a mercapto organic acid, trimethylol propanthris (thioglycolate), pentaerythritol tetrakis (thio). A thiol compound having three or more thiol groups in the molecule obtained by an esterification reaction between a polyol such as Glycolate) and a mercapto organic acid, a terminal thiol group-containing thiol compound obtained by a reaction between an epoxy compound and hydrogen sulfide, 1 , 4-Butandithiol, 1,6-hexanedithiol, 1,10-decandithiol and other alkylpolythiol compounds and the like can be mentioned.

Of these, a thiol compound obtained by an esterification reaction between a polyol and a mercapto organic acid is preferable, and a thiol compound having three or more thiol groups in the molecule is particularly preferable.

When an alkali metal compound (basic substance) is used as a catalyst when synthesizing this polythiol compound, it is desirable to perform dealkali treatment in the purified polythiol compound to reduce the alkali metal ion concentration to 50 ppm or less. In particular, it is desirable to set it to 10 ppm or less.

If the alkali metal ion concentration in the polythiol compound is high, the viscosity of the coating liquid may increase.<u style="single">Organic multivalent carboxylic acid</u> Examples of the organic polyvalent carboxylic acid used in the present invention include maleic acid, phthalic acid, fumaric acid, adipic acid, itaconic acid, malic acid, hexahydrophthalic acid, tetrahydrophthalic acid, het acid, phthalic anhydride, phthalic anhydride, and the like. Fumaric anhydride, adipic anhydride, malic anhydride, nagic anhydride, trimeritic anhydride, pyromelitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, benzophenone tetracarboxylic Acid anhydride and the like can be mentioned.

Among them, adipic acid, itaconic acid, hetic acid, phthalic anhydride, trimellitic anhydride, and pyromeritic anhydride can be suitably used as a condensation catalyst for a compound having a silanol group and a curing agent for a compound having an epoxy group.

<u style="single">Acetylacetone metal complex</u> As the acetylacetone metal complex used in the present invention, a compound represented by the following general formula is used.

M (CH₂COCH₂COCH₃)_n(However, M is an element selected from Al (III), Cr (III), Co (III), Cu (II), and Fe (III).) Specifically, aluminum acetylacetone and chromium acetyl. Examples thereof include acetylacetone metal complexes such as acetonate, titanylacetylacetonate and cobalt acetylacetonate. Among them, the acetylacetone metal complex of Al (III) and Fe (III) can be preferably used. These acetylacetone metal complexes are useful for curing a condensation catalyst of a compound having a silanol group, an organosilicon compound having an epoxy group and / or a hydrolyzate of the organosilicon compound.

[Hardener [b]]

Next, the curing agent [b] used for the coating for forming a transparent film of the present invention is composed of a compound containing basic nitrogen.

Examples of the basic nitrogen-containing compound include amine compounds having a tertiary amino group in the molecule, hydrazide compounds, amide compounds and the like. These compounds act as a curing agent by themselves, and can further accelerate curing when used in combination with the curing agent [a]. Then, when used in combination with the curing agent [a], although the reason is not clear, the reaction of the silanol group of the compound having a silanol group and the hydrolyzate of the organosilicon compound and the epoxy group of the organosilicon compound having an epoxy group Since the reaction of the above can be promoted in a well-balanced manner, a transparent film having better weather resistance, adhesion and scratch resistance than the conventional one can be obtained. Moreover, the problem of discoloration (yellowing) of the film due to ultraviolet rays has been solved, and the transparent film with excellent transparency adheres to a base material such as polycarbonate, which was difficult to form in the past. Can be formed well.

Examples of the amine compound include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine-n-methylpiperazin, 2-methylimidazole, 2 -Primary amines or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as ethyl imidazole, 2-ethyl-4-methyl imidazole and 2-phenyl imidazole. 2-Dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-) Hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2- Phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazolin, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, Nn-dimethylaminobenzoic acid , Isonicotinic acid, picolinic acid and the like, alcohols having a tertiary amino group in the molecule, phenols, carboxylic acids and the like can be mentioned.

Among them, primary amines or secondary amines can be preferably adopted. Examples of the hydrazide compound and amide compound include carboxylic acid dihydrazide such as adipic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and P-oxybenzoic acid dihydrazide, and dicyandiamide. Among them, adipic acid dihydrazide and dicyandiamide can be preferably adopted.

[solvent]

The coating liquid according to the present invention has the purpose of imparting fluidity to the coating liquid, adjusting the solid content concentration contained in the coating liquid, and adjusting the surface tension, viscosity, evaporation speed, etc. of the coating liquid. A solvent is used. As the solvent, water or an organic solvent is used, and as the organic solvent, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, glycols such as ethylene glycol, methyl acetate, etc. Esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran, aromatic hydrocarbons such as toluene and xylene, carboxylic acids and N, N-dimethylformamide may be used. it can. Two or more of these organic solvents can be mixed and used.

[Composition of coating liquid]

The coating liquid for forming a transparent film according to the present invention can be obtained by mixing the above-mentioned components (A), (B), (C) and (D) with other components as necessary.

The solid content concentration of the coating liquid for forming a transparent film is 1 to 70% by weight, and further 5 to 50% by weight, including the solid content derived from other components used by mixing as necessary. It is preferably in the range.

The content of the (A) organosilicon compound and / or the hydrolyzate of the organosilicon compound in the coating liquid is such that the content in the obtained transparent film (in other words, the content in the total solid content) is the solid content. It is preferably in the range of 20 to 70% by weight, more preferably 30 to 60% by weight (in terms of silica). Within this range, it is possible to obtain a film having high adhesion to the base material and the antireflection film and further having excellent scratch resistance. If the content of the component (A) is low, the adhesion to the base material and the antireflection film is lowered, and even if the content is high, the scratch resistance is insufficient and the film may be easily damaged.

Regarding the content of (B) metal oxide fine particles in the coating liquid, the content in the obtained transparent film (in other words, the content in the total solid content) is 20 to 80 in terms of solid content (oxide equivalent). It is preferably in the range of% by weight, more preferably 30 to 70% by weight. Within this range, scratch resistance is high, and the refractive index can be changed according to the refractive index of the base material, so that a transparent film with less interference fringes can be obtained.

If the content of the metal oxide fine particles is small, the scratch resistance may be insufficient, and the refractive index cannot be as high as that of the base material, so that interference fringes may not be suppressed. The refractive index of the transparent film can be adjusted by changing the amount ratio of (A) the organosilicon compound and (B) the metal oxide fine particles, and (B) the thickness of the antimony coating layer constituting the metal oxide fine particles. It can also be prepared by changing the thickness of the intermediate layer and the oxide species. For example, (B) increasing the amount of metal oxide fine particles increases the refractive index, and increasing the thickness of the antimony coating layer or using a middle layer having a high refractive index increases the refractive index. Can be enhanced.

If the content of the metal oxide fine particles in the transparent film is too large, the adhesion to the base material and the antireflection film may be lowered, and the coating film may be whitened or cracks may occur. Appearance problems may occur and the strength of the film may decrease.

The amount of the polythiol compound used as the curing agent [a] in the coating liquid for forming a transparent film is (A) per part by weight of the organosilicon compound and / or the hydrolyzate of the organosilicon compound as a solid content. , 0.01 to 0.2 parts by weight, more preferably 0.01 to 0.1 parts by weight. Within this range, the coating film can be sufficiently cured and the adhesion to the substrate can be improved. If the amount of the polythiol compound is small, the amount of the catalyst is small, so that the curing is insufficient, the adhesion to the base material is insufficient, and if the amount is large, the odor is strong, which may be unfavorable in the working environment.

The amount of the organopolycarboxylic acid used as the curing agent [a] is (A) the organosilicon compound and / or the organopolycarboxylic acid per part by weight of the hydrolyzate of the organosilicon compound as a solid content. Is preferably in the range of 0.03 to 0.4 parts by weight, more preferably 0.1 to 0.3 parts by weight. Within this range, the coating film can be sufficiently cured and the adhesion to the substrate can be improved. If the amount of the organic polyvalent carboxylic acid is small, the action as a condensation catalyst and a curing catalyst becomes insufficient, and a film having sufficient scratch resistance and heat resistance may not be obtained. Pot life may be reduced, and depending on the type of organic polyvalent carboxylic acid, it may precipitate during curing and cause poor appearance.

The amount of the acetylacetone metal complex used as the curing agent [a] is 0.005 to 0.07 per part by weight of the (A) organosilicon compound and / or the hydrolyzate of the organosilicon compound as a solid content. It is by weight, preferably 0.01 to 0.05 parts by weight. Within this range, the coating film can be sufficiently cured and the adhesion to the substrate can be improved. If the amount of acetylacetone metal complex is small, the action as a condensation catalyst and curing catalyst becomes insufficient, and a film having scratch resistance and heat resistance cannot be obtained. Even if the amount of acetylacetone metal complex is large, it can be obtained depending on the type of acetylacetone metal complex. The transparent film (cured product) to be formed may be colored.

The amount of the basic nitrogen-containing compound used as the curing agent [b] is 0.001 to 0.1 per part by weight based on (A) the organosilicon compound and / or the hydrolyzate of the organosilicon compound as a solid content. It is preferably in the range of 0.002 to 0.08 parts by weight, more preferably 0.002 to 0.08 parts by weight. Within this range, the coating film can be sufficiently cured, the adhesion to the substrate is high, and the discoloration of the transparent coating film due to ultraviolet rays can be controlled. If the amount of the basic nitrogen-containing compound used is small, the adhesion between the obtained transparent film and the substrate may decrease, or the discoloration of the transparent film due to ultraviolet rays may not be controlled. When the amount of the basic nitrogen-containing compound increases, the number of ions increases as a whole, so that the stability of the coating liquid decreases, which leads to a decrease in pot life, and in some cases, the coating liquid for forming a transparent film gels. Sometimes.

In the coating liquid for forming a transparent film according to the present invention, the above-mentioned components are dissolved or dispersed in a solvent, and can be used by diluting with a diluting solvent, if necessary. As the diluting solvent, alcohols, ketones, esters, ethers, cellosolves and the like can be used. Further, when it is desired to impart dyeability to the transparent film or to obtain further adhesion, it is possible to add a polyhydric alcohol or an epoxy resin.

Further, in order to improve the coatability and the performance of the transparent film, it is also useful to add a silicone-based or fluorine-based surfactant, an antistatic agent, an ultraviolet absorber, or the like, if necessary. The coating method of the coating liquid is selected from known methods such as a dipping method and a spin coating method. The curing is performed by heat treatment, and it is desirable that the curing conditions are 50 ° C to 150 ° C, preferably 80 ° C to 130 ° C for 0.5 hours to 5 hours. At this time, it is preferable to control the transparent film forming conditions so that the film thickness of the coating liquid for forming a transparent film after curing is in the range of 0.5 to 10 μm, more preferably 1.0 to 5.0 μm. If the film thickness of the transparent film is thin, sufficient scratch resistance may not be obtained, and if the film thickness of the transparent film is thick, the smoothness of the surface may be lowered and problems such as cracks may occur.

<u style="single">Substrate with transparent coating</u> The substrate with a transparent film according to the present invention has a transparent film (hereinafter, may be referred to as a hard coat film) formed on the surface of the substrate by using the coating liquid for forming a transparent film.

Examples of the base material used in the present invention include various base materials made of plastics such as polycarbonate, polythiourethane, and aliphatic allyl carbonate. These base materials are used for various optical lenses such as spectacle lenses and cameras, various display element filters, looking glasses, window glasses, paint films for automobiles, and light covers used for automobiles. The refractive index of these substrates is usually in the range of 1.55 to 1.74.

The refractive index of the transparent film formed on the surface of such a transparent substrate is preferably 1.55 or more. When the refractive index of the transparent film is 1.55 or more, the difference in refractive index from the base material is small, so that interference fringes can be suppressed.

In order to suppress the interference fringes, it is desirable that the difference in refractive index is within 0.03, preferably within 0.01. The film thickness of the transparent film varies depending on the use of the coated substrate, but is preferably 0.5 to 10 μm.

In the base material with a transparent coating according to the present invention, the coating liquid according to the present invention is applied to the surface of the base material as described above by a conventionally known method such as a dipping method, a spinner method, a spray method, a roll coater method or a flow method. It can be produced by drying to form a transparent film, and then heating the transparent film thus formed on the surface of the substrate to a temperature below the heat resistant temperature of the substrate. In particular, for a lens base material having a thermal deformation temperature of less than 100 ° C, the spinner method, which does not require fixing the lens base material with a jig or tool, is suitable. When the base material is a resin lens, the coating liquid may be applied onto the base material and then heated and dried at a temperature of 40 to 200 ° C. for several hours.

Further, in producing the base material with a transparent coating according to the present invention, the surface of the base material is treated with an alkali, an acid or a surfactant in advance for the purpose of improving the adhesion between the base material, for example, the lens base material and the transparent coating. It may be subjected to polishing treatment with inorganic or organic fine particles, primer treatment or plasma treatment.

[Synthetic resin lens]

When the base material is a synthetic resin lens, it is a typical example of the base material with a transparent film according to the present invention, and a transparent film formed from the coating liquid for forming a transparent film is formed on the surface of the resin lens base material. It is characterized by having.

The transparent film formed from the coating liquid according to the present invention can be widely formed on a thin synthetic resin lens made of a high-refractive resin material. Specifically, it can be applied to a high-refractive index lens having a refractive index of 1.54 or more, and is particularly suitable for a polycarbonate lens.

Even if a transparent thin film is provided on a polycarbonate lens using a conventional coating liquid, the adhesiveness is low, so that the strength is weak and the polycarbonate lens may be immediately peeled off or damaged. On the other hand, if the coating liquid according to the present invention is used, although the reason is not clear, the reaction of the silanol group of the compound having a silanol group and the hydrolyzate of the organosilicon compound with the organosilicon compound having an epoxy group Since the reaction of the epoxy group can be promoted in a well-balanced manner, a transparent film having excellent weather resistance, adhesion and scratch resistance can be obtained as compared with the conventional ones. Then, conventionally, a primer film has been formed, but if the coating liquid of the present invention is used, the primer film is not always required. It is possible to form two or more types of transparent coatings with different refractive indexes for the purpose of antireflection, and the refractive index of the transparent coating can be adjusted by (, (A) organic silicon compound and (B) metal oxide fine particles. It can be prepared by changing the amount ratio with and (B) the thickness of the antimony coating layer constituting the metal oxide fine particles, and changing the thickness of the intermediate layer and the oxide species. Further, the transparent film may be laminated so as to gradually reduce the difference in the refractive index between the lens base material and the transparent film, and this is more effective in eliminating the interference fringes.

In addition to polycarbonate lenses, it is a high-refractive-index lens that can be used as a lens base material in terms of transparency, dyeability, heat resistance, bending strength, impact resistance, weather resistance, light resistance, flexibility, workability, etc. The coating liquid of the present invention can be preferably used for sulfur-containing urethane-based, (meth) acrylic-based, episulfide-based lens base materials, lens base materials obtained from episulfide compounds, and the like.

Further, by providing a single-layer / multi-layer antireflection film made of an inorganic substance on the transparent film, it is possible to reduce reflection and improve transmittance, and further improve the function as a spectacle lens. it can. Inorganic substances include SiO, SiO₂, Si₃N₄, TiO₂, ZrO₂, Al₂O₃, MgF₂, Ta₂O₅, CaF₂The antireflection film can be formed by a thin film forming method such as a vacuum vapor deposition method. It is also possible to prepare a coating liquid containing the above components and form an antireflection film by a wet method.

Further, in the present invention, there is no problem even if a primer film is provided between the lens base material and the transparent film (hard coat film). If a primer film is provided, the dyeability can be improved and uneven dyeing can be prevented. The primer film can be formed by a coating liquid for forming a film containing a conventionally known paint resin as a matrix, preferably a polyester resin or a urethane resin.

Further, according to the present invention, when the transparent film is dyed, the transparent film contains specific metal oxide fine particles, so that the dyeing does not discolor or fade, that is, it has excellent fading resistance. It is possible to obtain a thin synthetic resin lens, which is also suitable for, for example, colored spectacle lenses and sunglasses.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[Example 1]<u style="single">Preparation of Titanium-based Nuclear Particle (TN-1) Dispersion Sol</u> TiO₂While stirring 250 kg of an aqueous solution of titanium sulfate having a concentration of 0.4% by weight, the titanium sulfate was hydrolyzed by gradually adding aqueous ammonia having a concentration of 15% by weight to obtain a white slurry solution having a pH of 8.5. It was. This slurry was filtered and then washed to obtain 11.11 kg of a hydrous titanate gel cake having a solid content concentration of 9% by weight.

To 5.55 kg of this cake, 6.06 kg of hydrogen peroxide solution having a concentration of 33% by weight and 13.4 kg of water were added, and then heated at 80 ° C. for 5 hours to obtain TiO.₂As a result, 25 kg of a 2.0 wt% titanium peroxide aqueous solution was obtained. This aqueous solution of titanium peroxide was yellowish brown transparent and had a pH of 8.1.

Average particle size is 7 nm and SiO₂750 g of silica sol having a concentration of 15% by weight, 22.5 kg of the above-mentioned aqueous titanic acid solution, and 27.25 kg of pure water were mixed and heated at 200 ° C. for 96 hours in an autoclave. The colloidal solution obtained after heating was concentrated to obtain a titanium-based nuclear particle (TN-1) dispersed sol having a solid content concentration of 10% by weight.

<u style="single">Formation of intermediate thin film layer</u> ZrO in which 5.26 kg of zirconium oxychloride is dissolved in 9.474 kg of water₂An aqueous solution of zirconium oxychloride having a concentration of 2% by weight was hydrolyzed by adding aqueous ammonia having a concentration of 15% by weight to obtain a slurry having a pH of 8.5. This slurry is filtered and washed to ZrO₂A cake with a concentration of 10% by weight was obtained.

Add 3.08 kg of water to 1.22 kg of this cake, add 9.0 kg of hydrogen peroxide to make it alkaline, and then heat to dissolve it, and then add ZrO.₂As a result, 6.1 kg of a zirconium hydrogen peroxide solution having a concentration of 2% by weight was prepared.

Separately, after diluting commercially available water glass with water, dealkaliate with a cation exchange resin, and SiO₂18.9 kg of a silicic acid solution having a concentration of 2% by weight was prepared. To 5 kg of titanium-based nuclear particle (TN-1) dispersed sol, 20 kg of water was added to bring the solid content concentration to 2% by weight, and then heated to 90 ° C. 1.525 kg of zirconium hydrogen peroxide solution and silicic acid were added to this. 4.725 kg of liquid was added.

Then, this mixed solution was heat-treated at 200 ° C. for 18 hours in an autoclave, concentrated by an ultrafiltration membrane method, and composed of transparent silicon oxide and zirconium oxide having a solid content concentration of 10% by weight and having a pale milky white color. An aqueous dispersion sol of titanium-based nuclear particles (TN-1) having an intermediate thin film layer was obtained. The average particle size of this sol was 9.0 nm.

<u style="single">Formation of antimony oxide coating layer</u> Antimony trioxide (manufactured by Nihon Seiko Co., Ltd .: ATOX-R, purity weight 99%) 555 g is suspended in an aqueous solution in which 285 g of caustic potash (manufactured by Asahi Glass Co., Ltd .: purity 85% by weight) is dissolved in 9000 g of water. It was. This suspension was heated to 100 ° C., and then an aqueous solution of an oxidizing agent (146.5 g of hydrogen peroxide solution having a concentration of 35% by weight) diluted with 1100 g of water was added over 14 hours to prepare an aqueous antimonic acid compound solution.

20 kg of water was added to 5 kg of the aqueous dispersion sol of the titanium-based nuclear particles (TN-1) having the intermediate thin film layer so that the solid content concentration was 2% by weight, and water was added to 9.09 kg of the antimonic acid compound aqueous solution. 15.91kg plus Sb₂O₅An aqueous antimonic acid compound solution having a converted concentration of 2% by weight was added, deionized with an ion exchange resin, and the nuclear particles were coated with the antimonic acid compound.

Then, water was added so that the solid content concentration became 1% by weight, and then heat treatment was performed in an autoclave at 98 ° C. for 18 hours (the antimony acid compound was oxidized by an oxidizing agent and coated with antimony oxide. Layers are formed). The obtained colloidal solution was concentrated to prepare an antimony oxide-coated titanium-based composite oxide particle (AT-1) dispersed aqueous sol having a solid content concentration of 10% by weight.

The average particle size of the antimony oxide-coated titanium-based composite oxide particles (AT-1) was 9.1 nm. Further, the water of the dispersion medium of the antimony oxide-coated titanium-based composite oxide particles (AT-1) was replaced with methanol and concentrated until the solid content concentration reached 20% by weight, and the antimony oxide-coated titanium-based composite oxide was concentrated. An organosol of particles (AT-1) was prepared.

<u style="single">Surface modification treatment</u> 1000 g of an organosol of antimony oxide-coated titanium-based composite oxide particles (AT-1) was placed in a reaction vessel, 56 g of methyltrimethoxysilane and 20 g of water were added while stirring the mixture, and the mixture was heated to 50 ° C. Then, it was concentrated to prepare an organosol of antimony oxide-coated titanium-based composite oxide particles (ST-1) surface-modified with methyltrimethoxysilane having a solid content concentration of 20% by weight.

The refractive index of the particles was determined by measuring the refractive index of the aqueous dispersion sol of the particles with a refractive index meter (manufactured by Atago Co., Ltd .: RX-5000α), and separately measuring the specific gravity of the sol. ..<u style="single">Preparation of coating liquid (FS-1) for forming a transparent film</u> In a flask equipped with a stirrer, 110.5 g of γ-glycidoxypropyltrimethoxysilane, 11.3 g of tetramethoxysilane, and 30.1 g of methyl alcohol were sequentially added, and then 39.19 g of 0.05N hydrochloric acid water was added and stirred for 30 minutes. Subsequently, 0.4 g of a silicone-based surfactant (manufactured by Nippon Unicar Co., Ltd .: L-7001) was added and aged at 5 ° C. for 24 hours to prepare a liquid containing a matrix-forming component.

To the liquid containing this matrix-forming component, 280 g of the organosol of the antimony oxide-coated titanium-based composite oxide particles (ST-1) was added, and a polythiol compound (manufactured by Toray Fine Chemicals Co., Ltd.) was added as a curing agent [a]. Polythiol QE-340M ") 1.5 g, pyromeritic anhydride 15 g, and 2-ethyl-4-methylimidazole 2 g as a curing agent [b] are added, and after thorough stirring, aging at 0 ° C for 48 hours to form a transparent film. A coating solution (FS-1) for use was prepared.

<u style="single">Creation of base material with transparent coating (PL-1)</u> After cleaning a commercially available polycarbonate plate (Iupilon sheet manufactured by Mitsubishi Engineering Plastics Co., Ltd.), refractive index = 1.59), apply the coating liquid for forming a transparent film (FS-1) by the dipping method (pulling speed 160 mm / min). It was applied, air-dried for 1 minute, and then heated at 120 ° C. for 2 hours to be cured to prepare a substrate with a transparent film (PL-1-1).

A base material with a transparent coating (PL-1-1) is set in a vacuum vapor deposition apparatus, and the pressure is 1.33 × 10 while heating the vacuum chamber to 60 ° C.^-3After exhausting to, and performing oxygen ion cleaning, SiO manufactured by Optron Co., Ltd. as a silica source₂M1, as a source of zirconia ZrO manufactured by Optron Co., Ltd.₂Using G, first form a silica and zirconia layer (thickness 1 / 4λ (λ = 520nm)), then a zirconia layer (thickness 1 / 2λ), and then a silica layer (thickness 1 / 4λ) on the transparent coating. An antireflection film was formed on the silica to prepare a base material with a transparent film (PL-1).

The following characteristics were evaluated for the obtained transparent coated base material (PL-1), and the results are shown in Table 1.<u style="single">(1) Appearance</u> A fluorescent lamp (Toshiba Litec Co., Ltd .: Mellow 5N, three-wavelength neutral white fluorescent lamp) is placed in a black background, and the light of the fluorescent lamp is reflected by the antireflection film surface of the test piece due to light interference. The occurrence of rainbow patterns (interference fringes) was visually confirmed. : No interference fringes are observed. : Interference fringes are slightly observed but not noticeable. Δ: Interference fringes are recognized and conspicuous. ×: There are glaring interference fringes.<u style="single">(2) Scratch resistance test</u> A load of 700 g was applied to Bonstar Steel Wool # 0000 (manufactured by Nippon Steel Wool Co., Ltd.), and the surface of the test piece was rubbed with 30 strokes / 60 seconds to visually determine the degree of scratches. : Scratched area is less than 10% : Scratched area is 10% or more and less than 20% : Scratched area is 20% or more and less than 50% ×: Scratched area is 50% or more<u style="single">(3) Adhesion test</u> Make cuts on the lens surface at 1 mm intervals with a knife to form 100 squares of 1 mm2, press the cellophane adhesive tape strongly, then pull sharply in the 90 degree direction and count the number of squares that do not peel off. , Evaluated according to the following criteria. : Remaining mass 100 : Remaining mass 90-99 : Remaining mass 80-89 ×: Remaining mass less than 80<u style="single">(4) Heat and water resistance test</u> After immersing the test piece in hot water at 80 ° C. for 10 minutes, the adhesion test was performed and evaluated according to the following criteria. : Remaining mass 100 : Remaining mass 90-99 : Remaining mass 80-89 ×: Remaining mass less than 80<u style="single">(5) Weather resistance test (appearance)</u> The xenon weather meter (manufactured by Suga Test Instruments Co., Ltd .: SX75 type) was used for 100 hours of exposure, and the appearance (crack occurrence status) was observed and evaluated according to the following criteria. : No crack is observed. Δ: Slight cracks are observed but not noticeable. ×: Cracks are recognized and conspicuous.<u style="single">(6) Weather resistance test (adhesion)</u> The exposure was carried out for 100 hours with a xenon weather meter (manufactured by Suga Test Instruments Co., Ltd .: SX75 type), the adhesion test was carried out, and the evaluation was made according to the following criteria. : Residual mass 91 or more : Residual mass 70-90 : Residual mass 50-69 ×: Residual mass less than 50 (7) Weather resistance test (discoloration) QUV test equipment (Q-Panel Lab Products) Manufactured by: UVA lamp used) was exposed to ultraviolet rays for 70 hours, and discoloration of the substrate with a transparent coating was visually observed under a three-wavelength fluorescent lamp. Then, it was evaluated according to the following criteria. : Slight discoloration is observed : Clear discoloration is observed ×: Significant discoloration is observed [Example 2]<u style="single">Preparation of Titanium-based Nuclear Particle (TN-2) Dispersion Sol</u> TiO₂A white slurry was prepared by mixing 93.665 kg of a titanium tetrachloride solution having a concentration of 7.75% by weight and 36.295 kg of aqueous ammonia having a concentration of 15% by weight. This slurry was filtered and then washed to obtain 54.579 kg of a hydrous titanate gel cake having a solid content concentration of 13.3% by weight.

To 7.519 kg of this cake, 11.429 kg of hydrogen peroxide solution having a concentration of 35% by weight and 59.148 kg of water were added, heated at 80 ° C for 2 hours to dissolve, and then 21.9 kg of water was added to TiO.₂An aqueous solution of titanium peroxide having a concentration of 1.0% by weight was prepared.

SnO in the obtained titanium peroxide aqueous solution₂8.906 kg of an aqueous potassium succinate solution having a concentration of 1.02% by weight was added, and the mixture was sufficiently stirred and then deionized with a cation exchange resin. After deionization, SiO₂Add 1818 g of silica sol (silica concentration 15% by weight) so that it becomes 272.7 g, then add 25.6 kg of water so that the solid content concentration becomes 1% by weight, and then in an autoclave at 140 ° C 18 The mixture was heated for a period of time to hydrolyze, and then the obtained colloidal solution was concentrated to obtain a titanium-based nuclear particle (TN-2) dispersed sol having a solid content concentration of 10% by weight. The average particle size of titanium-based nuclear particles (TN-2) was 12.8 nm.

<u style="single">Adjustment of coating liquid (FS-2) for forming a transparent film</u>The titanium-based nuclear particles (TN-2) were used as the titanium-based nuclear particles, and in Example 1, when preparing an aqueous dispersion sol of the titanium-based nuclear particles (TN-1) having an intermediate thin film layer, The amount of the hydrogen peroxide solution of zirconium was 427 g, the amount of silicic acid solution was 1323 g, the amount of the antimonic acid compound aqueous solution at the time of forming the antimony oxide coating layer was 9.09 kg, 15.91 kg of water was added, and the temperature was 175 ° C. An antimony oxide-coated titanium-based composite oxide particle (AT-2) dispersed water sol, an organosol, and a surface-modified treated sol (ST-2) were prepared in the same manner as in Example 1 except that they were heated, and then a transparent film was prepared. A coating solution for forming (FS-2) was prepared. The average particle size after forming the intermediate thin film layer was 12.8 nm. The average particle size of the antimony oxide-coated titanium-based composite oxide particles (ST-2) was 13.4 nm.

<u style="single">Creation of base material with transparent coating (PL-2)</u> In Example 1, a base material with a transparent film (PL-2) was prepared in the same manner except that the coating liquid for forming a transparent film (FS-2) was used, and each of the base materials with a transparent film (PL-2) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Example 3]<u style="single">Preparation of coating liquid (FS-3) for forming a transparent film</u> Titanium-based nuclear particles (TN) composed of titanium oxide and tin oxide having a solid content concentration of 10% by weight, in accordance with the methods described in Examples 3 of JP-A-10-245224, steps (a) to (d). -3) A dispersed sol (average particle size 5.9 nm) was obtained.

Then, in Example 1, instead of the titanium-based nuclear particle (TN-1) dispersed sol having an intermediate thin film layer composed of silicon oxide and zirconium oxide, a titanium-based nuclear particle (TN-3) dispersed sol was used. An antimony oxide-coated layer is formed in the same manner as in 1, and an antimony oxide-coated titanium-based composite oxide particle (AT-3) dispersed aqueous sol, an organosol, and a surface-modified treated sol (ST-3) are prepared. Next, a coating solution for forming a transparent film (FS-3) was prepared. The average particle size of the antimony oxide-coated titanium-based composite oxide particles (AT-3) was 6.3 nm.

<u style="single">Creation of base material with transparent coating (PL-3)</u> In Example 1, a base material with a transparent film (PL-3) was prepared in the same manner except that the coating liquid for forming a transparent film (FS-3) was used, and each of the base materials with a transparent film (PL-3) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Example 4]<u style="single">Preparation of antimony trioxide nuclear particle (TN-1) dispersion sol</u> Antimony trioxide (manufactured by Nihon Seiko Co., Ltd .: ATOX-R, purity weight 99%) 5.56 kg is suspended in a solution in which 2.86 kg of caustic potash (manufactured by Asahi Glass Co., Ltd .: purity 85% by weight) is dissolved in 89 kg of water. It became cloudy. This suspension is heated to 100 ° C, then an aqueous solution of an oxidizing agent (2.93 kg of hydrogen peroxide solution having a concentration of 35% by weight) diluted with 9.65 kg of water is added in 7 hours, and the suspension is added at 98 ° C for 10 hours. After aging, the mixture was cooled and filtered to prepare an aqueous solution of potassium antimonate having a solid content concentration of 7%. The pH of the aqueous solution at this time was 12.5.

Next, while cooling and stirring 55 kg of this aqueous solution, 243 kg of water was added to dilute it, dealkalized with a cation exchange resin, heated at 98 ° C for 20 hours, concentrated, and antimony pentoxide having a solid content concentration of 14.5%. A system core particle (TN-4) dispersed aqueous sol was prepared.

The average particle size of antimony pentoxide nuclear particles (TN-4) was 21.2 nm.<u style="single">Formation of antimony oxide coating layer</u> Antimony trioxide (manufactured by Nihon Seiko Co., Ltd .: ATOX-R, purity weight 99%) 555 g was suspended in a solution in which 285 g of caustic potash (manufactured by Asahi Glass Co., Ltd .: purity 85% by weight) was dissolved in 9000 g of water. This suspension was heated to 100 ° C., and then an aqueous solution obtained by diluting an oxidizing agent (146.5 g of hydrogen peroxide solution having a concentration of 35% by weight) with 1100 g of water was added in 14 hours to prepare an aqueous antimonic acid compound solution.

Antimony trioxide nuclear particles (TN-4) dispersed water 21.75 kg of water is added to 3 kg of sol to make the solid content concentration 2% by weight, and 15.91 kg of water is added to 9.09 kg of an aqueous antimony acid compound solution to make Sb.₂O₅An aqueous antimony compound solution having a converted concentration of 2% by weight was added, and antimony oxide precursor coating treatment was performed while deionizing with an ion exchange resin.

Water was added so that the solid content concentration became 1% by weight, and then heat treatment was performed in an autoclave at 98 ° C. for 18 hours. The obtained colloidal solution was concentrated to prepare an antimony oxide-coated antimony pentoxide fine particle (AT-4) dispersed aqueous sol having a solid content concentration of 10% by weight. The average particle size of the antimony oxide-coated antimony pentoxide fine particles (AT-4) was 22.5 nm.

Further, the water of the dispersion medium of the antimony oxide-coated antimony trioxide fine particles (AT-4) was replaced with methanol and concentrated until the solid content concentration reached 20% by weight, and the antimony oxide-coated antimony trioxide fine particles (AT- The organosol of 4) was prepared.

<u style="single">Implementation of surface modification treatment</u> 1000 g of an organosol of antimony oxide-coated antimony pentoxide fine particles (AT-4) was placed in a reaction vessel, 56 g of methyltrimethoxysilane and 20 g of water were added while stirring the mixture, and then the mixture was heated to 50 ° C. Then, it was concentrated to prepare an organosol of antimony oxide-coated antimony pentoxide fine particles (ST-4) surface-modified with methyltrimethoxysilane having a solid content concentration of 20% by weight.<u style="single">Preparation of coating liquid (FS-4) for forming a transparent film</u> Example 1 and Example 1 except that 510 g of antimony oxide-coated antimony pentoxide fine particles (ST-4) organosol was used instead of 280 g of antimony oxide-coated titanium-based composite oxide particles (ST-1) organosol. In the same manner, a coating liquid (FS-4) for forming a transparent film was prepared.

<u style="single">Creation of base material with transparent coating (PL-4)</u> In Example 1, a base material with a transparent film (PL-4) was prepared in the same manner except that the coating liquid for forming a transparent film (FS-4) was used, and each of the base materials with a transparent film (PL-4) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Example 5]<u style="single">Preparation of Titanium-based Composite Oxide Particles (ST-5) Coated with Antimony Oxide</u> Example 1 except that methyltrimethoxysilane was replaced with tetraethoxysilane when the surface modification treatment was performed using the antimony oxide-coated titanium-based composite oxide particles (ST-1) prepared in Example 1. In the same manner as above, antimony oxide-coated titanium-based composite oxide particles (ST-5) surface-modified with tetraethoxysilane were prepared.

<u style="single">Preparation of coating liquid (FS-5) for forming a transparent film</u> Then, instead of the antimony oxide-coated titanium-based composite oxide particles (ST-1) surface-modified with methyltrimethoxysilane, the antimony oxide-coated titanium-based composite oxide surface-modified with tetraethoxysilane. A coating liquid (FS-5) for forming a transparent film was prepared in the same manner as in Example 1 except that particles (ST-5) were used.

<u style="single">Creation of base material with transparent coating (PL-5)</u> In Example 1, a base material with a transparent film (PL-5) was prepared in the same manner except that the coating liquid for forming a transparent film (FS-5) was used, and each of the base materials with a transparent film (PL-5) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Example 6]<u style="single">Preparation of Antimony Trioxide Fine Particles (ST-6) Coated with Antimony Oxide</u> Antimons surface-modified with γ-glycidoxypropyltrimethoxysilane in the same manner as in Example 4 except that 56 g of methyltrimethoxysilane was replaced with 82 g of γ-glycidoxypropyltrimethoxysilane in Example 4. Antimonate pentoxide fine particles (ST-6) coated with oxide were prepared.

<u style="single">Preparation of coating liquid (FS-6) for forming a transparent film</u> Then, the coating liquid for forming a transparent film was obtained in the same manner as in Example 4 except that the antimony oxide-coated antimony pentoxide fine particles (ST-6) were used instead of the antimony oxide-coated antimony pentoxide fine particles (ST-4). (FS-6) was prepared.

<u style="single">Creation of base material with transparent coating (PL-6)</u> In Example 1, a base material with a transparent film (PL-6) was prepared in the same manner except that the coating liquid for forming a transparent film (FS-6) was used, and each of the base materials with a transparent film (PL-6) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Example 7]<u style="single">Preparation of coating liquid (FS-7) for forming a transparent film</u> In Example 1, when preparing the coating liquid for forming a transparent film (FS-1), 20 g of trimellitic anhydride (that is, no polythiol compound was used) as the curing agent [a] and 2-ethyl as the curing agent [b]. A coating solution for forming a transparent film (FS-7) was prepared in the same manner as in Example 1 except that the mixture was changed to 2 g of imidazole.

<u style="single">Creation of base material with transparent coating (PL-7)</u> In Example 1, a base material with a transparent film (PL-7) was prepared in the same manner except that the coating liquid for forming a transparent film (FS-7) was used, and each of the base materials with a transparent film (PL-7) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Example 8]<u style="single">Preparation of coating liquid (FS-8) for forming a transparent film</u> In Example 7, when preparing the coating liquid for forming a transparent film (FS-7), the curing agent [a] was changed to 3.5 g of ferric acetylacetone (that is, trimellitic anhydride was not used). A coating liquid (FS-8) for forming a transparent film was prepared in the same manner as in Example 7.

<u style="single">Creation of base material with transparent coating (PL-8)</u> Organosol of titanium-based composite fine particles surface-modified with tetraethoxysilane (manufactured by Catalysis Chemical Industry Co., Ltd .: Optreak 1130Z (S-7 / A8), average particle size 9 nm, solid content concentration 30% by weight, dispersion medium: 70 g of methyl alcohol, 100 g of an aqueous dispersion of urethane elastomer with a concentration of 30% by weight (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Superflex 150), 400 g of methyl alcohol, and a silicone-based surfactant (manufactured by Nippon Unicar Co., Ltd .: L-7604) 0.2 g was added and mixed to prepare a coating solution for forming a primer film. First, after cleaning a commercially available polycarbonate plate (manufactured by Mitsubishi Engineering Plastics Co., Ltd .: Iupilon sheet, refractive index = 1.59), a coating solution for forming a primer film is applied by a dipping method (pulling speed 120 mm / min), and 1 After air-drying for 1 minute, it was heated at 90 ° C. for 20 minutes and cured to form a primer film. Next, the coating liquid for forming a transparent film (FS-8) is applied by the dipping method (pulling speed 160 mm / min) in the same manner as in Example 1, air-dried for 1 minute, and then heated at 120 ° C. for 2 hours. To prepare a base material with a transparent film (PL-8-1), and then to form an antireflection film on the transparent film in the same manner as in Example 1 to form a base material with a transparent film (PL-8). Each characteristic was evaluated for the substrate with a transparent coating (PL-8), and the results are shown in Table 1.

[Example 9]<u style="single">Preparation of coating liquid (FS-9) for forming a transparent film</u> In Example 7, the transparent film-forming coating solution (FS-7) was prepared in the same manner as in Example 7 except that the curing agent [b] was changed to 4.7 g of dicyandiamide. FS-9) was prepared.

<u style="single">Creation of base material with transparent coating (PL-9)</u> In Example 8, a substrate with a transparent film (PL-) was used in the same manner as in Example 8 except that the coating liquid for forming a transparent film (FS-9) was used instead of the coating liquid for forming a transparent film (FS-8). 9) was prepared, each characteristic of the transparent coated substrate (PL-9) was evaluated, and the results are shown in Table 1.

[Example 10]<u style="single">Coating liquid for forming a transparent film (FS-10)</u> In Example 4, when the coating liquid for forming a transparent film (FS-4) was prepared, antimony oxide-coated titanium-based composite oxide particles (instead of antimony oxide-coated antimony pentoxide fine particles (ST-4) organosol) ( A coating liquid (FS-10) for forming a transparent film was prepared in the same manner as in Example 4 except that AT-4) dispersed organosol (that is, not subjected to surface modification treatment) was used. The coating liquid slightly became cloudy, and agglutination was confirmed.<u style="single">Creation of base material with transparent coating (PL-10)</u> In Example 1, a base material with a transparent film (PL-10) was prepared in the same manner except that the coating liquid for forming a transparent film (FS-10) was used, and each of the base materials with a transparent film (PL-10) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Comparative example 1]<u style="single">Coating liquid for forming a transparent film (CFS-1)</u> In Example 1, a coating liquid for forming a transparent film (CFS-1) was prepared in the same manner as in Example 1 except that antimony oxide-coated titanium-based composite oxide particles (ST-1) were not added.<u style="single">Creation of transparent coated base material (CPL-1)</u> In Example 1, a base material with a transparent film (CPL-1) was prepared in the same manner except that the coating liquid for forming a transparent film (CFS-1) was used, and each of the base materials with a transparent film (CPL-1) was prepared. The characteristics were evaluated and the results are shown in Table 1.

[Comparative example 2]<u style="single">Coating liquid for forming a transparent film (CFS-2)</u> In Example 2, instead of the antimony oxide-coated titanium-based composite oxide particles (ST-1), the organosol (catalyst) of the titanium-based composite fine particles not coated with antimony oxide and surface-modified with tetraethoxysilane. Kasei Kogyo Co., Ltd .: Optreak 1120Z (S-7 / A8), average particle size 9 nm, solid content concentration 30% by weight, dispersion medium: methyl alcohol) diluted with methyl alcohol to a solid content concentration of 20% by weight. A coating solution for forming a transparent film (CFS-2) was prepared in the same manner except that it was used, but gelation occurred at the time of preparation. Therefore, a base material with a transparent film was not prepared. (Note that titanium oxide-containing nuclear particles of Optreak 1120Z (S-7 / A8): TiO₂/ ZrO₂= 51.2, Intermediate thin film layer: SiO₂+ ZrO₂/ Titanium oxide-containing composite oxide particles = 4.88) [Comparative Example 3]<u style="single">Coating liquid for forming a transparent film (CFS-3)</u> In Example 3, a transparent film was formed in the same manner as in Example 3 except that only 2.2 g of the curing agent [a] acetylacetone aluminum was used as a curing agent when preparing the coating liquid (FS-3) for forming a transparent film. A coating solution for use (CFS-3) was prepared.<u style="single">Creation of transparent coated base material (CPL-3)</u> In Example 1, a base material with a transparent film (CPL-3) was prepared in the same manner except that the coating liquid for forming a transparent film (CFS-3) was used, and each characteristic of the base material with a transparent film (CPL-3) was obtained. The results are shown in Table 1.

[Comparative example 4]<u style="single">Coating liquid for forming a transparent film (CFS-5)</u> In Example 8, it is transparent in the same manner as in Example 8 except that only 2.0 g of the curing agent [b] 2-ethylimidazole was used as the curing agent when preparing the coating liquid (FS-8) for forming a transparent film. A coating liquid for film formation (CFS-5) was prepared.<u style="single">Creation of base material with transparent coating (CPL-5)</u> In Example 1, a base material with a transparent film (CPL-5) was prepared in the same manner except that the coating liquid for forming a transparent film (CFS-5) was used, and each of the base materials with a transparent film (CPL-5) was prepared. The characteristics were evaluated and the results are shown in Table 1.

<tables num="1"><img file="JP2006070144A_D0001.tif" /></tables>

As can be discerned from the results in Table 1, the transparent film-coated substrates (Examples 1 to 8) using the transparent film-forming coating containing the essential components, which are the features of the present invention, have a good appearance and excellent resistance. It has scratch resistance, adhesion, heat resistance and weather resistance.

Compared with these, Comparative Example 1 which does not contain the metal oxide fine particles composed of the metal oxide nuclei particles and the coating layer made of antimony oxide has good adhesion, heat resistance and weather resistance, but Poor appearance and scratch resistance.

Comparative Example 2 using titanium-based composite fine particles not coated with antimony oxide caused gelation during preparation. Comparative Example 3 containing only the curing catalyst (A) is inferior in adhesion, heat resistance and weather resistance. Comparative Example 4, which contains only the curing catalyst (B), is inferior in scratch resistance.