JP2018027992A - Coating composition, and optical article having coat layer made of the coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition forming a coat layer excellent in appearance, excoriation resistance, boiling adhesion and weather-resistant adhesion.SOLUTION: Provided is a coating composition comprising: inorganic oxide particles (A); a hydrolyzable group-containing organic silicon compound (B); water or an acid aqueous solution (C); a hardening catalyst (D); an organic solvent (E); and aromatic alcohols (F). In the coating composition, the aromatic alcohols (F) are included in an amount of 3 to 100 pts.mass to 100 pts.mass of the total of the inorganic oxide particles (A) and the hydrolyzable group-containing organic silicon compound (B).SELECTED DRAWING: None

Description

  The present invention relates to a novel coating composition and a novel laminate having a hard coat layer (cured product layer) formed from the coating composition. Specifically, the present invention relates to a coating composition for forming an optimum hard coat layer on the surface of a high refractive index resin substrate (lens) having a refractive index exceeding 1.50 or the surface of a photochromic optical substrate such as a photochromic plastic lens. .

  Plastic lenses have features that are not found in glass lenses, such as lightness, safety, ease of processing, and fashionability, and are currently mainstream in the field of eyeglass lenses. However, for example, a diethylene glycol bisallyl carbonate resin lens that is generally used has a disadvantage that its refractive index is 1.50, which is lower than that of glass, and the outer periphery of the lens becomes thick. For this reason, in the field of resin lenses, thinning is performed with synthetic resin lenses having a higher refractive index. In addition, lenses that have been given anti-mold properties by dyeing plastic lenses (hereinafter also referred to as dye lenses) are also used.

  On the other hand, since the plastic lens has a defect that is easily scratched, this defect is improved by providing a silicone-based hard coat layer on the surface. The hard coat film forming the hard coat layer is usually a coating composition mainly composed of inorganic oxide fine particles, polymerizable organic silane compound (hydrolyzable organosilicon compound), polymerization catalyst, water and organic solvent. Is applied to the surface of a plastic lens and heated to remove the organic solvent and polymerize and cure (Patent Document 1). Further, in such a coating composition, various improvements have been made for the purpose of increasing the refractive index and improving the storage stability (Patent Document 2). It is no different from what is proposed in. Furthermore, a coating composition to which N-methylpyrrolidone or the like is added in order to improve adhesion to a plastic lens has also been proposed (Patent Document 3).

Japanese Patent Publication No.57-2735 International Publication No. 01/42381 Pamphlet International Publication No. 2010/122912 Pamphlet

  By the way, since the hard coat film as described above contains a large amount of inorganic oxide fine particles, there is a drawback that the adhesion to an optical substrate such as a plastic lens is essentially poor. Furthermore, since the thermal expansion coefficient of the hard coat film is significantly different from that of the substrate, there is also a problem that cracks are likely to occur in the hard coat film due to heating during curing of the coating composition (usually about 120 ° C.).

  Conventionally, as a means for solving the above-mentioned problems, the surface of a substrate such as a plastic lens is further subjected to polishing treatment, corona discharge treatment, plasma discharge treatment, UV ozone treatment, etc. in addition to chemical treatment with a simple alkaline solution in order to improve adhesion. Have been subjected to physical surface treatment or chemical surface treatment such as primer treatment. However, performing such a surface treatment process brings about a decrease in productivity and an increase in production cost. Therefore, it has been desired to simplify the process as much as possible.

  In addition, plastic lenses may come into contact with warm water depending on the intended use, but hard coat films have low warm water resistance, and may be partially peeled off the plastic substrate when in contact with warm water. May have occurred.

  In addition, when a hard coat film is laminated on a dyed lens, the hard coat film may be peeled off in a short period of time, and there is still room for improvement.

  Therefore, the object of the present invention is that it has good adhesion to optical substrates such as plastic lenses including dyed lenses, has high warm water resistance, and generates cracks due to thermal history during curing. An object of the present invention is to provide a coating composition for forming a hard coat film in which the above is effectively prevented.

  Also, a coating composition that can be used effectively as a hard coat film in which a photochromic compound is dispersed inside a plastic substrate or a photochromic coating layer in which a photochromic compound is dispersed is formed on the substrate surface. It is to provide.

  According to the present invention, inorganic oxide fine particles (A), hydrolyzable group-containing organosilicon compound (B), water or acid aqueous solution (C), curing catalyst (D), organic solvent (E), and aromatic alcohol Provided is a coating composition for forming a hard coat film, which contains the compound (F) as an essential component.

In the coating composition of the present invention,
(1) The aromatic alcohol (F1) is contained in an amount of 3 to 100 parts by mass per 100 parts by mass of the total amount of the inorganic oxide fine particles (A) and the hydrolyzable group-containing organosilicon compound (B). Doing things,
(2) The aromatic alcohol (F) is a compound containing at least one aromatic ring and at least one hydroxyl group,
(3) The hydrolyzable group-containing organosilicon compound (B) is 40 to 90 masses per 100 parts by mass of the total amount of the inorganic oxide fine particles (A) and the hydrolyzable group-containing organosilicon compound (B). Contained in the amount of parts,
Is preferred.

  According to the present invention, there is provided an optical article having a hard coat layer obtained by curing the coating composition on a plastic optical substrate.

  In the invention of the optical article, an excellent effect is exhibited when the plastic optical substrate is a photochromic optical substrate. Among them, the photochromic optical substrate has a photochromic coat layer obtained by curing a polymerizable curable composition containing a polymerizable monomer and a photochromic compound on a plastic optical substrate, In the case of an optical article in which a hard coat layer is formed on a photochromic coat layer, a particularly excellent effect is exhibited.

  Similarly, this optical article exhibits excellent effects even when the plastic optical substrate is an optical substrate containing a dye.

  The coating agent composition of the present invention has an important feature that an aromatic alcohol (F) is blended. By blending such an aromatic alcohol (F), a plastic optical material such as a plastic lens can be obtained. A hard coat film having excellent adhesion to a substrate can be formed, and this hard coat film is also excellent in resistance to thermal history, and also effectively generates cracks due to thermal history such as curing. Can be prevented.

  According to this coating composition, it is possible to form a hard coat film having good adhesion to a substrate only by chemical treatment using an alkali solution that has been conventionally used for general purposes. Furthermore, the hot water resistance is also improved, and even when contacted with warm water, there is little decrease in adhesion, and industrial utility is extremely high.

  The reason why the hard coat film having the above characteristics is formed by blending the aromatic alcohols (F) is not clearly clarified, but the present inventors presume as follows. doing.

  That is, the aromatic alcohol (F) has a high boiling point and a low vapor pressure, and a polymer forming a plastic optical substrate such as a plastic lens, such as poly (meth) acrylate ((meth)). It is a compound that has a high affinity for acrylate resins) and poly (thio) urethanes ((thio) urethane resins) and can dissolve or swell these polymers. Accordingly, when the coating composition is applied to a substrate and cured by heating, the aromatic alcohols (F) are not all evaporated and volatilized, but a part thereof is a surface portion of the substrate. The hard coat film is formed in a state where the surface portion of the base material swells and the aromatic alcohol (F) remains in the hard coat film. Therefore, the formed hard coat film is considered to exhibit excellent adhesion and hot water resistance to the plastic optical substrate. Furthermore, since the aromatic alcohol (F) remains in the hard coat film to be formed, this hard coat film is imparted with appropriate flexibility and has high followability to the substrate surface. As a result, it is considered that high resistance to thermal history (difference in thermal expansion) is exhibited.

The coating composition of the present invention comprises inorganic oxide fine particles (A), hydrolyzable group-containing organosilicon compound (B), water or acid aqueous solution (C), curing catalyst (D), organic solvent (E), and aroma. A group alcohol (F) is contained as an essential component. Thus, by including the components (A) to (F), particularly the aromatic alcohols (F), the excellent effects (particularly adhesion) of the present invention can be exhibited.
Hereinafter, each component which comprises the coating composition of this invention is demonstrated.

<Inorganic oxide fine particles (A)>
As the inorganic oxide fine particles in the coating composition of the present invention, known inorganic oxide fine particles used in conventional low refractive index or high refractive index coating agents can be used without any limitation. In the low refractive index coating agent, it is preferable to use inorganic oxide fine particles mainly composed of silica fine particles. Further, the high refractive index coating agent is composed of an oxide or a composite inorganic oxide containing at least one element selected from Si, Al, Ti, Fe, In, Zr, Au, Sn, Sb, W and Ce. It is preferable to use fine particles, particularly oxide or composite inorganic oxide fine particles containing at least one element selected from the group consisting of Si, Al, Ti, Fe, Zr, Sn, Sb and W. The inorganic oxide fine particles need only contain one or more oxides of elements selected from the above element group, and may include composite oxide fine particles containing the above elements, or a plurality of the above inorganic oxide fine particles. You may mix and use a thing particle.

  Furthermore, when cerium oxide fine particles are included as part of such inorganic oxide fine particles, the durability and appearance of the hard coat layer to be formed can be improved.

  Further, the particle diameter of the inorganic oxide fine particles is not particularly different from that used in the conventional coating agent, and those having a primary particle diameter of about 1 to 300 nm observed with an electron microscope (TEM) can be preferably used. Fine particles having such a particle size are usually used in the form of being dispersed in water or a part of an organic solvent described below (particularly an alcohol solvent) as a dispersion medium. Generally, the particles are aggregated by colloidal dispersion. Is prevented. For example, in the present invention, as the inorganic oxide fine particles, the coating composition may be in the form of a water-soluble organic solvent or a sol dispersed in water from the viewpoint that it can be finely and uniformly dispersed in the hard coat film. Silica fine particles (ie, silica sol) or composite inorganic oxide fine particles blended therein are suitable.

  When the inorganic oxide fine particles are used in the form of sol, in order to further improve the operability, the inorganic oxide fine particles contained in the sol have a concentration (solid content concentration) of 10 to 50% by mass. It is preferable to do.

  Specific examples of the organic solvent used for the dispersion medium of the inorganic oxide fine particles in the present invention include alcohols such as n-butanol, 2-butanol, t-butanol, isopropanol, ethanol, methanol, and ethylene glycol; propylene glycol monomethyl ether Cellsolves such as propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide and the like. These organic solvents may be used alone, as a mixed solvent of a plurality of organic solvents, or as a mixed solvent of an organic solvent and water. Among the above dispersion media, it is preferable to use water, alcohols, or a mixed solvent of water and alcohols.

  Silica sols used for low refractive index coating agents are commercially available. For example, sols containing water as a dispersion medium are available from Nissan Chemical Industries, Ltd. Snowtex OXS, Snowtex OS, Snowtex O, Snowtex O. It is marketed under a trade name such as -40. Sols using an organic solvent as a dispersion medium are commercially available from Nissan Chemical Industries, Ltd. as methanol silica sol, MA-ST-MS (dispersion medium; methanol), IPA-ST (dispersion medium; isopropanol), and the like.

  Further, the composite inorganic oxide fine particles used for the high refractive index coating agent contain two or more kinds of inorganic oxides. Specifically, Si, Al, Ti, Fe, In, Zr, Au, Sn , Sb, W and Ce are preferably composite inorganic oxide fine particles containing at least two kinds of inorganic oxides.

  What is necessary is just to determine suitably the compounding quantity of the oxide in the case of using complex oxide microparticles | fine-particles as the inorganic oxide microparticles | fine-particles in the said invention according to the use use. Among them, the composite inorganic oxide fine particles used in the present invention preferably contain zirconium oxide. Specifically, titanium oxide is 0 to 80% by mass, zirconium oxide is 1 to 25% by mass, and tin oxide is 0 to 0%. It is preferable that 80% by mass, 0 to 20% by mass of antimony pentoxide, 0 to 10% by mass of tungsten oxide, and 0 to 25% by mass of silicon dioxide.

  The composite inorganic oxide fine particles as described above are commercially available in the form of a sol using an organic solvent as a dispersion medium in the same manner as the silica sol. For example, the HX series, HIT series, HT series and Nissan Chemical Industries, Ltd. Examples include OPTRAK series manufactured by JGC Catalysts & Chemicals.

  Further, as the inorganic oxide fine particles used in the high refractive index coating agent, antimony pentoxide fine particles can be used from the viewpoint of easy availability. Even when antimony pentoxide fine particles are used, it is preferably used in the coating composition in the form of a sol dispersed in a water-soluble organic solvent or water. Moreover, it is preferable to use an antimony pentoxide sol having a solid content concentration of 10 to 50% by mass. Such antimony pentoxide fine particles are commercially available in the form of a sol using an organic solvent as a dispersion medium in the same manner as the silica sol, for example, Sun Colloid AMT-330S and AMT-332S, manufactured by Nissan Chemical Industries, Ltd. AMT series such as NV can be mentioned.

  The blending amount of the inorganic oxide fine particles in the coating composition of the present invention is the hydrolyzability described later from the viewpoint of the kind of inorganic oxide, the hardness of the finally obtained hard coat layer, heat resistance, and flexibility. As a total amount of 100 parts by mass with the group-containing organosilicon compound (B), 20.0 parts by mass to 60.0 parts by mass, particularly 30.0 parts by mass to 50.0 parts by mass are preferable. In addition, this mass part is the compounding quantity of solid content (inorganic oxide microparticles | fine-particles) except the dispersion medium.

  In general, the amount of inorganic oxide fine particles in the finally formed hard coat layer is 30% by mass to 70% by mass, preferably 40% by mass to 60% by mass. It is better to set according to the amount of ingredients used. The mass of the hard coat layer is obtained by hydrolyzing the following hydrolyzable group-containing organosilicon compound and then weighing the mass of the solid component remaining after heating the resulting coating composition at 120 ° C. for 3 hours. It can be obtained by doing.

  When a plurality of types of inorganic oxide fine particles are used in the blending ratio, the total mass thereof corresponds to the blending amount of the inorganic oxide fine particles. Moreover, when using several types of hydrolysable organosilicon compounds, those total mass corresponds to the compounding quantity of a hydrolysable group containing organosilicon compound.

In the present invention, in order to further improve the durability and appearance of the hard coat layer, when cerium oxide fine particles are used, the amount used is 1 to 20% by mass of the inorganic oxide fine particles. Good.
Next, the hydrolyzable group-containing organosilicon compound (B) will be described.

<Hydrolyzable group-containing organosilicon compound (B)>
The hydrolyzable group-containing organosilicon compound (hereinafter also simply referred to as organosilicon compound) in the coating composition of the present invention is a transparent cured body that becomes a matrix when the coating composition is cured to form a hard coat layer. It is a component to be formed and has a function as a binder for the inorganic oxide fine particles.

  As the organosilicon compound, a known organosilicon compound can be used without any limitation, but a compound having an alkoxy group as a hydrolyzable group is preferable, and two or more alkoxy groups, a silicon atom A compound bonded to is more preferable.

If this (B) component is illustrated in a specific example, the following can be illustrated.
γ-glycidoxypropyltrimethoxysilane γ-glycidoxypropylmethyldimethoxysilane γ-glycidoxypropylmethyldiethoxysilane γ-glycidoxypropyltriethoxysilane 5,6-epoxyhexyltriethoxysilane β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane tetraethoxysilane tetramethoxysilane tetramer tetraethoxysilane pentamer vinyltrimethoxysilane silane vinyltriethoxysilane vinyltriacetoxysilane methyltrimethoxysilane methyltriethoxysilane methyltri Phenoxysilane Dimethyldimethoxysilane Trimethylmethoxysilane Phenyltrimethoxysilane Diphenyldimethoxysilane Cyclohexylmethyldimethoxysilane 1,2-Bis ( Limethoxysilyl) ethane 1,2-bis (triethoxysilyl) ethane 1,3-bis (trimethoxysilyl) propane 1,3-bis (triethoxysilyl) propane 1,6-bis (trimethoxysilyl) hexane 1 , 6-bis (triethoxysilyl) hexane n-propyltrimethoxysilane n-butyltrimethoxysilane isobutyltrimethoxysilane isobutyltriethoxysilane n-hexyltrimethoxysilane n-hexyltriethoxysilane n-octyltriethoxysilane n- Decyltrimethoxysilane 3-ureidopropyltriethoxysilane bis [3- (diethoxymethylsilyl) propyl] carbonate trifluoropropyltrimethoxysilane perfluorooctylethyltriethoxysilane γ-chlorop Pyrtrimethoxysilane Vinyltri (β-methoxy-ethoxy) silane Allyltrimethoxysilane γ-acryloxypropyltrimethoxysilane γ-acryloxypropyltriethoxysilane γ-methacryloxypropyltrimethoxysilane γ-methacryloxypropyltriethoxysilane γ -Methacryloxypropyldimethoxymethylsilane γ-mercaptopropyltrialkoxysilane γ-aminopropyltrimethoxysilane γ-aminopropyltriethoxysilane N-phenyl-γ-aminopropyltrimethoxysilane N-2 (aminoethyl) 3-aminopropyl Triethoxysilane N-2 (aminoethyl) 3-aminopropyltrimethoxysilane N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane p-styryl Trimethoxysilane 3- isocyanatopropyltriethoxysilane those described above some of the hydrolyzable groups in the organosilicon compound or all fused ones or partially hydrolyzed.

  In the present invention, among the above, as an organosilicon compound that improves adhesion and crosslinkability with a plastic optical substrate, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like are preferably used.

  In addition, there are four alkoxy groups capable of hydrolysis, such as tetraethoxysilane and tetramethoxysilane, as organosilicon compounds that make the hard coat film dense and improve the scratch resistance of plastic optical substrates. , Tetraethoxysilane, or tetramethoxysilane dimer or tetramer (in the case of tetramer, 10 alkoxy groups exist in one molecule), methyltriethoxysilane, 1,2-bis (trimethoxy Silyl) ethane, 1,2-bis (triethoxysilyl) ethane and the like are preferably used.

  In addition, the said organosilicon compound can also use only 1 type, and can also use it in combination of 2 or more types. In particular, among these, it is preferable to use a combination of the compound exemplified as the preferred organosilicon compound that improves the adhesion and crosslinkability and the compound exemplified as the preferred organosilicon compound that improves the scratch resistance. In this case, in order to enhance the effect of using an aromatic alcohol and to form a hard coat layer that exhibits better performance, the organosilicon compound effective for improving the crosslinkability is improved for improving the scratch resistance. It is preferable to use it in an amount of 2.0 to 7.0 times by mass with respect to the effective organosilicon compound.

In this invention, the compounding quantity of a hydrolysable group containing organosilicon compound (B) makes the total amount with the said oxide fine particle (A) 100 mass parts, and is the range of 40.0 mass parts-90.0 mass parts. It is preferable to use in. In addition, the compounding quantity of this (B) is the quantity of the hydrolysable group containing organosilicon compound which is not hydrolyzed. If the amount of the hydrolyzable group-containing organosilicon compound is small, the heat resistance and flexibility of the hard coat layer tend to be lowered, and the hard coat layer itself tends to be brittle. On the other hand, when the amount of the hydrolyzable group-containing organosilicon compound increases, the hardness of the hard coat layer tends to decrease. Considering the hardness, heat resistance, flexibility and the like of the obtained hard coat layer, the blending amount of the hydrolyzable group-containing organosilicon compound is 50. The total amount with the oxide fine particles (A) is 100 parts by mass. It is particularly preferable to use in the range of 0 to 70.0 parts by mass.
Next, water or acid aqueous solution (C) is demonstrated.

<Water or acid aqueous solution (C)>
In the coating composition of the present invention, the hydrolyzable group-containing organosilicon compound (B) is hydrolyzed, and the hydrolyzate is polymerized and cured (polycondensation) in the form of incorporating the inorganic oxide fine particles (A). Thus, a hardened layer is formed as a matrix, and the inorganic oxide fine particles (A) are finely dispersed in the matrix. In order to promote the hydrolysis of the hydrolyzable group-containing organosilicon compound (B) for forming the cured body, it is necessary to add water or an acid aqueous solution.

  The amount of water or acid aqueous solution (C) used is such that the inorganic oxide fine particles (A) and the hydrolyzable groups are used from the viewpoint of efficiently hydrolyzing the hydrolyzable group-containing organosilicon compound (B). 1.0 part by mass to 50.0 parts by mass, preferably 5.0 parts by mass to 30.0 parts by mass, and more preferably 15.0 parts by mass to 100 parts by mass of the total mass of the organosilicon compound (B). The amount is preferably 25.0 parts by mass. That is, when the amount of water is small, the hydrolysis of the hydrolyzable group-containing organosilicon compound (B) does not proceed sufficiently, and the scratch resistance of the resulting hard coat layer is lowered, or the resulting coating agent There is a risk that the characteristics such as storage stability of the product will deteriorate. If the amount of water is too large, it is difficult to form a hard coat layer having a uniform thickness, which may adversely affect the appearance. In addition, the compounding quantity of the said water is based on the thing of the state in which the hydrolysable group containing organosilicon compound (B) is not hydrolyzed.

  As already mentioned, the inorganic oxide fine particles (A) may be used in the form of a dispersion (sol) dispersed in water. In such a case, the blending amount of water includes the amount of water used in the dispersion medium. For example, when the inorganic oxide fine particles (A) are used, if the amount of water contained in the dispersion satisfies the range of the amount of water, it is necessary to further mix water with the coating composition. Absent. If the amount of water is less than the range, water may be further mixed.

In addition, when an acid aqueous solution is used in the present invention, hydrolysis of the hydrolyzable group-containing organosilicon compound (B) can be further promoted. In this case, since the acid content is small, the blending amount is the amount of the acid aqueous solution. To specifically illustrate the acid content, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or an aqueous solution of an organic acid such as acetic acid or propionic acid can be used. Among these, hydrochloric acid and acetic acid are preferably used from the viewpoints of storage stability and hydrolyzability of the coating composition. The concentration of the acid aqueous solution is preferably 0.001 to 0.5N, particularly 0.01 to 0.1N.
Next, the curing catalyst (D) will be described.

<Curing catalyst (D)>
The curing catalyst (D) in the coating composition of the present invention is used to promote condensation (polymerization curing) of the hydrolyzate of the hydrolyzable group-containing organosilicon compound (B). Specific examples of the curing catalyst include acetylacetonate complexes, perchlorates, organometallic salts, and various Lewis acids. These can use 1 type of curing catalysts independently, and can also use 2 or more types together. By using these curing catalysts, the coat layer can be made harder.

Specifically, as an acetylacetonate complex,
Aluminum acetylacetonate,
Lithium acetylacetonate,
Indium acetylacetonate,
Chromium acetylacetonate,
Nickel acetylacetonate,
Titanium acetylacetonate,
Iron acetylacetonate,
Zinc acetylacetonate,
Cobalt acetylacetonate,
Copper acetylacetonate,
A zirconium acetylacetonate etc. can be illustrated. Among these, aluminum acetylacetonate and titanium acetylacetonate are preferable.

  Examples of the perchlorate include magnesium perchlorate, aluminum perchlorate, zinc perchlorate, and ammonium perchlorate.

  Examples of the organic metal salt include sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate and the like.

  Examples of the Lewis acid include stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, and antimony chloride.

  In the present invention, a hard coat layer having high scratch resistance can be obtained in a short time even at a relatively low temperature, and from the viewpoint of excellent storage stability of the coating composition, an acetylacetonate complex or perchlorate is used as a curing catalyst. It is preferable to use it. Among them, it is preferable that the curing catalyst is 50% by mass or more, particularly 70% by mass or more, and optimally the entire amount of the curing catalyst is an acetylacetonate complex or a perchlorate.

From the viewpoint of obtaining a hard coat layer, the curing catalyst is 0.10 parts by mass to 5 parts per 100 parts by mass of the total amount of the inorganic oxide fine particles (A) and the hydrolyzable group-containing organosilicon compound (B). It is preferably used in an amount in the range of 0.000 parts by weight, especially 1.50 parts by weight to 3.50 parts by weight. In addition, the compounding quantity of the said curing catalyst is based on the thing of the state in which the (B) component is not hydrolyzed.
Next, the organic solvent (E) will be described.

<Organic solvent (E)>
In the coating composition of the present invention, the organic solvent (E) serves as a solvent for the hydrolyzable group-containing organosilicon compound (B) and serves as a dispersion medium for the inorganic oxide fine particles (A). A known organic solvent other than the aromatic alcohol (F) can be used as long as it has a function and is volatile. As will be described later, the aromatic alcohol (F) is blended separately from the organic solvent (E), and the aromatic alcohol is not included in the organic solvent in the present invention. As a specific example of such an organic solvent,
Methanol, ethanol, propanol, isopropanol, n-butanol, 2-
Alcohols such as butanol, t-butanol, diacetone alcohol;
Lower carboxylic acid esters such as methyl acetate;
Ethers such as dioxane, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether;
Ketones such as acetone, methyl ethyl ketone, acetylacetone;
Halogenated hydrocarbons such as methylene chloride and chloroform;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Etc. These organic solvents can be used alone or in admixture of two or more.

  Among these organic solvents (E), methanol, isopropanol, t-butanol, diacetone alcohol are particularly preferred from the viewpoint that when a coating agent is applied and cured, it easily evaporates and a smooth hard coat layer is formed. , Ethylene glycol monoisopropyl ether, propylene glycol monomethyl ether, and acetylacetone are preferably used. In addition, as described above, a part of the organic solvent can be mixed with the inorganic oxide fine particles (A) in advance as a dispersion medium of the inorganic oxide fine particles (A).

The amount of the organic solvent (E) used is not particularly limited, but in order to obtain good storage stability, appearance, etc., the total of the inorganic oxide fine particles (A) and the hydrolyzable group-containing organosilicon compound (B) The amount is preferably 50 to 500 parts by mass, more preferably 120 to 250 parts by mass per 100 parts by mass. In addition, the compounding quantity of the said organic solvent (E) is based on the thing of the state which the hydrolysable group containing organosilicon compound (B) has not hydrolyzed, This hydrolysable group containing organosilicon compound It does not include alcohol produced by hydrolysis.
Next, the aromatic alcohols (F) will be described.

<Aromatic alcohols (F)>
In the coating composition of the present invention, aromatic alcohols (F) are used in addition to the components (A) to (E). Aromatic alcohols are compounds containing at least one aromatic ring and at least one hydroxyl group in the molecule, and are particularly used to enhance the adhesion of the hard coat layer to a plastic lens.

  As described above, the aromatic alcohol (F) of the present invention has a high boiling point and a low vapor pressure. Therefore, although it is estimated, it is not volatilized by heating at the time of curing, and a part of the film remains in the hard coat film. As a result, the followability of the film to the plastic substrate is improved, and the heat history (hard coat film) It is considered that the occurrence of cracks in the hard coat film due to the difference in thermal expansion coefficient between the substrate and the substrate is prevented. In addition, since it has the property of having a high affinity for the plastic that forms the base material to which the hard coat film is applied, it shows the function of swelling the surface portion of the plastic optical base material during curing. It is considered that the adhesion between the obtained hard coat film and the plastic optical substrate can be remarkably improved. And since the adhesiveness of a hard-coat film | membrane can be improved, warm water resistance is also improved and even if it contacts with warm water, it is thought that the adhesiveness does not fall so much.

  Such aromatic alcohols (F) are not particularly limited as long as they are uniformly mixed with the organic solvent (E) described above, but the boiling point is 100 to 300 ° C. from the viewpoint of remaining in the hard coat film. It is preferable that it is 160-240 degreeC, and it is most preferable that it is 200-210 degreeC. When the boiling point of the aromatic alcohol (F) is less than 100 ° C., after the coating composition of the present invention is applied to the plastic substrate, before it penetrates into the plastic substrate when heated for drying and curing, Therefore, the adhesion improving effect tends to be low. Further, when the boiling point of the aromatic alcohol (F) exceeds 300 ° C., the amount remaining in the finally obtained hard coat film increases, so that the film hardness (scratch property) tends to decrease. .

  Specific examples of the aromatic alcohols (F) include 4-methoxybenzyl alcohol, 4-isopropylbenzyl alcohol, α, α, 4-trimethylbenzenemethanol, 2-methyl-3-phenylpropanol, 3-phenylpropanol, 2,4-dimethylbenzyl alcohol, 1-phenyl-2-methyl-2-propanol, 1- (4-methylphenyl) ethanol, 2-ethoxybenzyl alcohol, 4-ethoxybenzyl alcohol, furfuryl alcohol, 2-phenylpropanol 4-methyl-1-phenyl-2-pentanol, 2-methoxybenzyl alcohol, 3- (4-methoxyphenyl) propanol, 4-methyl-2-phenylpentanol, 2-methyl-4-phenyl-2- Butanol, 4-methylbenzyla Lucol, 5-methylfurfuryl alcohol, phenethyl alcohol, 3-methyl-1-phenyl-3-pentanol, 2-phenoxyethanol, 1-phenylpropanol, 2-phenyl-2-propanol, 4-phenylbutan-2-ol , Piperonyl alcohol, 1-phenylethanol, 2- (4-methyl-5-thiazolyl) ethanol, 2-thienylmethanol, 3,4-dimethoxybenzyl alcohol, 2,3-dimethoxybenzyl alcohol, 4-phenyl-3 -Buten-2-ol, 1-phenyl-2-pentanol, benzyl alcohol, 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-nitrophenylethanol, 3-chlorobenzyl alcohol, 3,4-dichlorobenzyl alcohol 2,3,5,6-tetrafluorophenylethanol, 3-methoxybenzyl alcohol, 3-phenoxybenzyl alcohol, 2-chlorobenzyl alcohol, o-chlorobenzyl alcohol, isopropylbenzyl alcohol, 3,4,5-trimethoxy Examples include benzyl alcohol.

  Among these, benzyl alcohol, phenethyl alcohol, furfuryl alcohol, 2-phenyl alcohol, phenethyl alcohol, 2-furyl alcohol are particularly preferred because they have a high affinity for optical substrates made of plastic and greatly improve the adhesion between the hard coat film and the plastic optical substrate. Phenyl-2-propanol, 1-phenyl-2-methyl-2-propanol, and 4-methylbenzyl alcohol are preferably used, and benzyl alcohol is most preferably used among them.

  As understood from the above description, the above aromatic alcohol has a high boiling point and is used from the viewpoint of partially penetrating a plastic optical substrate, and is a general organic solvent. Is not intended to be used. The amount of aromatic alcohol used is small compared to the organic solvent used as a dispersion medium. Specifically, the total amount of inorganic oxide fine particles (A) and hydrolyzable organosilicon compound (B) is 100. It is preferable to use in the range of 3 to 100 parts by mass, more preferably in the range of 9 to 60 parts by mass, and most preferably in the range of 20 to 45 parts by mass. In addition, the usage-amount of aromatic alcohol is based on the thing in the state which the hydrolysable organosilicon compound (B) has not hydrolyzed. When the amount used exceeds 100 parts by mass, the scratch resistance tends to decrease. On the other hand, when the amount used is less than 3 parts by mass, the adhesion between the hard coat film and the plastic optical substrate tends to decrease.

  In addition, as will be described in detail below, for example, in a plastic optical base material (photochromic optical base material) containing a photochromic compound, a hindered amine-based weathering agent is included to impart weather resistance, and the photochromic compound exhibits its effect. A plastic optical substrate having a large amount of free space is used in order to exert its effect (in order to perform molecular motion). In this case, the weathering agent easily moves to the surface of the plastic optical substrate, which may affect the formation of the hard coat film. This photochromic optical substrate includes a photochromic optical substrate obtained by a kneading method and a photochromic optical substrate obtained by a coating method.

  In addition, the plastic optical base material (photochromic optical base material obtained by a kneading method) obtained by directly curing a polymerization curable composition containing a photochromic compound and a polymerizable monomer is usually a polymerizable monomer. The photochromic compound is blended in an amount of 0.005 to 1.00 parts by mass and the weathering agent is blended in an amount of 0.01 to 2.00 parts by mass with respect to 100 parts by mass of the body. On the other hand, an optical substrate having a photochromic coating layer obtained by applying a polymer curable composition containing a photochromic compound and a polymerizable monomer on a plastic optical substrate and curing the coating film (by a coating method) The resulting photochromic optical substrate) usually has a photochromic compound of more than 1.00 parts by mass and not more than 10.00 parts by mass, and the weathering agent has 2.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer. More than 15.00 parts by mass is blended and manufactured.

  In addition, the coating composition of the present invention is effective from the viewpoint of adhesion even in a plastic optical substrate (colored optical substrate) colored with a dye or pigment described later. When a hard coat film is formed on the photochromic optical substrate as described above, the scratch resistance tends to decrease when the amount of aromatic alcohol used increases, and the adhesiveness tends to decrease when the amount used decreases. is there. In addition, when a hard coat film is formed on the above-described colored optical substrate, a phenomenon that the adhesion is easily lowered when used for a long time as compared with an uncolored optical substrate is observed. The cause of this is not clear, but dyes or pigments bleed out at the interface between the colored optical substrate and the hard coat layer, or the dye or pigment near the interface deteriorates due to ultraviolet rays, etc. It is estimated that adhesion will be reduced.

  As described above, this aromatic alcohol is not used as an organic solvent (dispersion medium). Therefore, in order to satisfy the above range and maintain the excellent scratch resistance of the hard coat film to be formed, per 100 parts by mass of the total amount of the water or acid aqueous solution (C) and the organic solvent (E). 50 parts by mass or less, and preferably 20 parts by mass or less. In addition, the said organic solvent (E) shall not contain the organic solvent produced by hydrolyzing the hydrolysable organosilicon compound (B).

<Other additives>
The coating composition of the present invention can optionally contain known additives in addition to the various components described above.

  In the coating agent composition of the present invention, an additive known per se can be optionally blended as long as the object of the present invention is not impaired. Examples of such additives include surfactants, antioxidants, radical scavengers, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, and fragrances. And plasticizers.

For example, as the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but a nonionic surfactant is preferably used from the viewpoint of wettability to a plastic lens substrate. Specific examples of nonionic surfactants that can be suitably used include:
Sorbitan fatty acid ester,
Glycerin fatty acid ester,
Decaglycerin fatty acid ester,
Propylene glycol pentaerythritol fatty acid ester,
Polyoxyethylene sorbitan fatty acid ester,
Polyoxyethylene sorbite fatty acid ester,
Polyoxyethylene glycerin fatty acid ester,
Polyethylene glycol fatty acid ester,
Polyoxyethylene alkyl ether,
Polyoxyethylene phytosterol phytostanol,
Polyoxyethylene polyoxypropylene alkyl ether,
Polyoxyethylene alkylphenyl ether,
Polyoxyethylene castor oil / hardened castor oil,
Polyoxyethylene lanolin, lanolin alcohol, beeswax derivatives,
Polyoxyethylene alkylamine / fatty acid amide,
Polyoxyethylene alkylphenyl formaldehyde condensate,
Single chain polyoxyethylene alkyl ether,
Etc.

  In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is 0.001 to 1 part by mass per 100 parts by mass of the above-mentioned essential components (total amount of the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B)). The range of is preferable.

  In addition, as antioxidants, radical scavengers, UV stabilizers, UV absorbers, hindered phenol antioxidants, phenol radical scavengers, sulfur antioxidants, benzotriazole compounds, benzophenone compounds, etc. It can be used suitably. The addition amount of these compounding agents is 0.1 to 20 masses per 100 parts by mass of the above-mentioned essential components (total amount of inorganic oxide fine particles (A) and hydrolyzable organosilicon compound (B)). A range of parts is preferred.

  Dyes and pigments are used for coloring. Nitroso dyes, nitro dyes, azo dyes, stilbenzoazo dyes, ketimine dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, quinoline dyes, methine dyes, Polymethine dye, thiazole dye, indamine dye, indophenol dye, azine dye, oxazine dye, thiazine dye, sulfur dye, aminoketone dye, oxyketone dye, anthraquinone dye, perinone dye, indigoid dye, phthalocyanine dye, azo pigment, anthraquinone dye Examples thereof include pigments, phthalocyanine pigments, naphthalocyanine pigments, quinacridone pigments, dioxazine pigments, indigoid pigments, triphenylmethane pigments, and xanthene pigments. In using a dye or a pigment, it is appropriately determined depending on the color density of the substrate to be colored.

<Preparation of coating agent>
In this invention, a coating agent is manufactured from the said coating composition, this hardener layer is formed by apply | coating this coating agent on the surface of plastic optical base materials, such as a plastic lens, and drying and hardening. In the present invention, the coating agent obtained from the coating composition can be produced by weighing and mixing a predetermined amount of each component. The order of mixing the components is not particularly limited, and all the components can be mixed at the same time. However, water or an acid aqueous solution (C) is added to the hydrolyzable group-containing organosilicon compound (B) and hydrolyzable. After hydrolyzing the group-containing organosilicon compound (B), it is preferable to mix the inorganic oxide fine particles (A) from the viewpoint of dispersion stability of the inorganic oxide fine particles (A).

  The mixing order of the curing catalyst (D), the organic solvent (E), and the aromatic alcohol (F) is not particularly limited, and all the components are combined simultaneously with (A), (B), and (C). Among them, it is possible to mix them, but among them, as a preferred embodiment, when (B) is hydrolyzed with (C), (E) and (F) are weighed together with (B). And then mixing in (C) and then adding and mixing (A) and (D) in this order. In this case, the hydrolysis is preferably performed at a temperature of 10 to 40 ° C. so as not to adversely affect the physical properties of the hard coat film and to reduce the storage stability.

The coating agent obtained by mixing in this way is not particularly limited, but the solid content concentration of the hydrolyzate (A) and (B) is 15% in the total mass of the coating agent. It is preferable to be in the range of ˜50% by mass, particularly 20 to 40% by mass.
Next, a plastic optical substrate to which the obtained coating agent is applied will be described.

<Optical substrate made of plastic>
The coating composition of the present invention is applied to the formation of a hard coat layer on the surface of a plastic optical substrate such as an eyeglass lens, a camera lens, a liquid crystal display, a house or an automobile window, and is particularly suitable for use as an eyeglass lens. Preferably used. Also, the type of plastic forming the optical substrate is not limited. For example, known resins such as (meth) acrylic resins, polycarbonate resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins The present invention can be applied to the formation of a hard coat film on the surface of the optical substrate without any limitation.

  In particular, the coating agent obtained from the coating composition of the present invention has higher adhesion to the (meth) acrylic resin. Therefore, it can be suitably used for a hard coat layer on an optical substrate made of a (meth) acrylic resin containing a photochromic compound. Among them, there is a lot of free space, and in particular, a hard optical substrate (photochromic optical substrate) made of a (meth) acrylic resin containing a photochromic compound and a hindered amine-based weathering agent that affects the formation of a hard coat layer. It can be suitably used when forming a coat layer. The (meth) acrylic resin having a large amount of free space includes, in particular, a polyfunctional acrylate having a tri- or more functional (meth) acrylate group and a di (meth) acrylate having an alkylene glycol chain having 2 to 15 repeating units. A (meth) acrylic resin obtained by curing the composition containing the resin is preferable.

Specific examples of such polyfunctional acrylates having a tri- or higher functional (meth) acrylate group are as follows:
Trimethylolpropane trimethacrylate,
Trimethylolpropane triacrylate,
Tetramethylol methane trimethacrylate,
Tetramethylol methane triacrylate,
Is mentioned.
In addition, as di (meth) acrylate having an alkylene glycol chain having 2 to 15 repeating units,
Polyethylene glycol dimethacrylate having an average molecular weight of 536,
Polytetramethylene glycol dimethacrylate having an average molecular weight of 736,
Polypropylene glycol dimethacrylate having an average molecular weight of 536,
Polyethylene glycol diacrylate having an average molecular weight of 258,
Polyethylene glycol diacrylate having an average molecular weight of 308,
Polyethylene glycol diacrylate having an average molecular weight of 522,
Polyethylene glycol methacrylate acrylate having an average molecular weight of 272,
Polyethylene glycol methacrylate acrylate having an average molecular weight of 536,
2,2-bis [4-methacryloxy polyethoxy) phenyl] propane,
2,2-bis [4-acryloxydiethoxy) phenyl] propane,
2,2-bis [4-acryloxy polyethoxy) phenyl] propane,
Is mentioned.

  Further, the composition containing a polyfunctional acrylate having a (meth) acrylate group having 3 or more functional groups and a di (meth) acrylate having an alkylene glycol chain having 2 to 15 repeating units has other polymerizable monomers. For example, (meth) acrylates such as glycidyl methacrylate and urethane acrylate may be added.

  The plastic optical substrate containing the photochromic compound (hereinafter referred to as a photochromic optical substrate) has a photochromic coating layer in which the photochromic compound is dispersed inside the substrate or the photochromic compound is dispersed on the substrate surface. It may be. More specifically, the coating composition of the present invention is obtained by polymerizing a curable composition containing the above (meth) acrylate monomer and a photochromic compound to form a photochromic optical substrate, the surface of a plastic optical substrate A curable composition containing the (meth) acrylate monomer and a photochromic compound is applied to the substrate, and then cured to form a photochromic coat layer, which is suitable for forming a hard coat layer for a photochromic optical substrate. Can be used. The photochromic coat layer usually contains a large amount of photochromic compound. Therefore, the photochromic optical base material on which the photochromic coating layer is formed has a case where the adhesion of the hard coating layer may be lowered due to the deterioration of the photochromic compound due to the use for a long time, but the coating composition of the present invention is used. By forming the hard coat layer on the photochromic coat layer, the adhesion of the initial hard coat layer is improved, so that the adhesion of the hard coat layer on the photochromic optical substrate can also be improved.

  Furthermore, a dye lens is mentioned as a base material with which the coating composition of this invention is useful. In particular, it is suitable for dyeing lenses of high refractive index plastic lenses such as thiourethane resins and thioepoxy resins. The dyeing lens usually contains the aforementioned dye, but this dye is deteriorated by ultraviolet rays. Therefore, degradation of the dye causes a problem that the adhesion between the hard coat layer and the plastic lens base material interface is remarkably lowered, but the hard coat layer is laminated on the surface of the dyed lens using the coating composition of the present invention. Thus, by improving the initial adhesion, it is possible to suppress the problem of deterioration in adhesion due to long-term use.

  In addition, although shown in the following Example, dye and a photochromic compound are easy to deteriorate a dyeing | staining lens and a photochromic optical base material for said reason. Therefore, in these optical base materials, the weather resistance adhesion between the hard coat layer and the plastic lens base material interface tends to be lowered. Therefore, when this optical substrate is used, the difference in weather resistance adhesion between the coating composition of the present invention and the other coating compositions becomes remarkable. In particular, the above-described effect is remarkably exhibited particularly when a dyed lens (lens containing a dye) is targeted.

  Next, a method for producing an optical article having a hard coat layer by laminating a hard coat layer on a plastic optical substrate using the coating agent obtained from the coating composition of the present invention will be described.

<Optical article manufacturing method, optical article>
The coating agent produced as described above is hardened by applying filtration to the surface of a plastic optical substrate such as a plastic lens after drying to remove foreign substances as necessary, drying and curing. A coat layer is formed. As this plastic optical substrate, the above-mentioned optical substrate is used.

  The coating agent can be applied by a known coating method such as dipping method, spin coating method, dip spin coating method, spray method, brush coating or roller coating. What is necessary is just to perform the drying after apply | coating a coating agent suitably on the conditions which can remove the solvent in a coating agent. Curing after drying may be performed until the coating layer to be formed has sufficient strength, but it is initially 5 to 30 at 60 to 80 ° C. from the viewpoint of laminating a hard coat layer that prevents rapid shrinkage and has a good appearance. It is preferable to perform pre-curing for about 1 minute, and then perform curing for about 1 to 3 hours at a temperature of 90 ° C. to 120 ° C., depending on the substrate. In particular, since the coating agent obtained from the coating composition of the present invention exhibits excellent adhesion, the temperature after preliminary curing can be made relatively low. Specifically, the temperature after preliminary curing can be 95 to 115 ° C, and further 100 to 110 ° C. Thus, since it can be cured at a relatively low temperature, it is possible to prevent yellowing and thermal deformation of the plastic lens.

  The hard coat layer formed as described above may have a thickness of about 0.1 to 10 μm, and generally a thickness of 1 to 5 μm is suitable for a spectacle lens. By employing the above method, an optical article in which a hard coat layer is formed on a plastic optical substrate can be obtained.

  The coating composition of the present invention not only provides a hard coat layer having excellent scratch resistance, but also prevents appearance defects due to light deterioration such as cracks and peeling of the hard coat layer even when used for a long period of time. be able to. Furthermore, it is possible to prevent the occurrence of cracks in the hard coat layer resulting from the thermal history during curing, specifically, the cracks in the hard coat layer caused by the shrinkage of the hard coat layer and the expansion of the plastic optical substrate. Moreover, it is excellent also in hot water resistance, and it can improve that a crack generate | occur | produces or adhesiveness falls even if it makes it contact with warm water.

  Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. In addition, about the plastic optical base material (lens base material) and each component which were used in the present Example, it is as follows.

(1) Plastic optical substrate (lens substrate)
MRA: Thiourethane resin plastic lens, refractive index = 1.60.
MRB: Thiourethane resin plastic lens, refractive index = 1.67.
MRC: Thiourethane resin plastic lens dyed brown with luminous transmittance of about 75%, refractive index = 1.67.
MRD: thiourethane resin plastic lens dyed brown with a luminous transmittance of about 15%, refractive index = 1.67.
PC1: A lens (photochromic optical substrate) having a coating layer made of a methacrylic resin on the surface of a plastic lens MRA.

[Method for producing PC1]
2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane / polyethylene glycol diacrylate having an average molecular weight of 776, which is a radical polymerizable monomer, an average molecular weight of 532) / trimethylolpropane trimethacrylate / polyester oligomer hexaacrylate / glycidyl methacrylate Were blended at a blending ratio of 40 parts by mass / 15 parts by mass / 25 parts by mass / 10 parts by mass / 10 parts by mass, respectively. Next, 3 parts by weight of the following photochromic compound was added to 100 parts by mass of the radical polymerizable monomer mixture, and ultrasonic dissolution was performed at 70 ° C. for 30 minutes.

  Thereafter, Irgacure 1870 manufactured by BASF Corporation, which is a polymerization initiator, is a mixture of the resulting composition with 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. (Weight ratio 3: 7) is 0.35 parts by mass, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as a stabilizer is 5 parts by mass, triethylene glycol-bis [3- 3 parts by mass of (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 7 parts by mass of γ-methacryloyloxypropyltrimethoxysilane as a silane coupling agent, and Toray Dow Corning as a leveling agent Add 0.1 parts by mass of silicone surfactant L-7001 made by Co., Ltd. and mix thoroughly. The photochromic curable composition was prepared by combining.

  MRA (thiourethane resin plastic lens, refractive index = 1.60) was used as an optical substrate made of plastic, and this plastic optical substrate was sufficiently degreased with acetone and washed with a 5% aqueous sodium hydroxide solution at 50 ° C. After washing for 4 minutes, washing with running water for 4 minutes, and washing with distilled water at 40 ° C for 4 minutes, drying was performed at 70 ° C.

  Next, as a primer coating solution, a moisture curing type primer Takeseal PFR402TP-4 and ethyl acetate manufactured by Takebayashi Chemical Industry Co., Ltd. and ethyl acetate were respectively prepared to be 50 parts by mass. A liquid that was added 0.03 parts by mass of leveling agent FZ-2104 and was sufficiently stirred until uniform in a nitrogen atmosphere was used.

  This primer solution was spin-coated on the surface of the lens MRA using a spin coater 1H-DX2 manufactured by MIKASA. By leaving this lens at room temperature for 15 minutes, a lens substrate having a primer layer with a thickness of 7 μm was prepared.

Next, about 1 g of the above-described photochromic curable composition was spin-coated on the surface of the lens substrate having the primer layer. A D-valve manufactured by Fusion UV Systems Co., Ltd., adjusted so that the lens surface coated with a coating film made of the photochromic curable composition has an output at 405 nm of 150 mW / cm ² on the lens surface in a nitrogen gas atmosphere. The coating film was cured by irradiating with light for 3 minutes using F3000SQ equipped with. Then, the photochromic coating layer was formed by performing heat processing for 1 hour with a 110 degreeC thermostat further. The film thickness of the resulting photochromic coating layer can be adjusted depending on the spin coating conditions. The film thickness of the photochromic coat layer was adjusted to be 40 ± 1 μm.

(2) Component for coating composition [inorganic oxide fine particles (A)]
A1: Methanol dispersion sol of antimony pentoxide. Solid concentration (concentration of antimony pentoxide fine particles) 30.5% by mass. pH (1 + 1) 5.3.
A2: Tin oxide 17.7 mass%, zirconium oxide 12.7 mass%, silicon dioxide 1
A methanol-dispersed sol of fine composite inorganic oxide particles containing 5.4% by mass and 54.2% by mass of titanium oxide (rutile type). Solid content concentration (concentration of composite inorganic oxide fine particles) 30.0 mass%. p
H (1 + 1) 5.0.
A3: Methanol-dispersed sol of fine composite inorganic oxide particles containing 77.6% by mass of tin oxide, 11.7% by mass of zirconium oxide, 7.0% by mass of antimony pentoxide, and 3.7% by mass of silicon dioxide. Solid content concentration (concentration of composite inorganic oxide fine particles) 30.6% by mass. pH (1 + 1
8.3.
A4: Tin oxide 14.2 mass%, zirconium oxide 74.6 mass%, silicon dioxide 1
A methanol-dispersed sol of composite inorganic oxide fine particles containing 1.1% by mass. Solid concentration (concentration of composite inorganic oxide fine particles) 38.5% by mass. pH (1 + 1) 5.0.
A5: Methanol-dispersed sol of fine particles consisting only of silicon dioxide. Solid content concentration (concentration of silicon dioxide fine particles) 30.0% by mass. pH (1 + 1) 4.8.
A6: Water-dispersed cerium oxide fine particles (Nydral U-15 manufactured by Taki Chemical). Solid concentration (concentration of cerium oxide fine particles) 15.0% by mass (containing 2% by mass of acetic acid and 83% by mass of water).
pH (1 + 1) 3.0.

[Hydrolyzable group-containing organosilicon compound (B)]
BSE: 1,2-bis (triethoxysilyl) ethane.
GTS: γ-glycidoxypropyltrimethoxysilane.
GDS: γ-glycidoxypropylmethyldimethoxysilane.
TEOS: Tetraethoxysilane [Water or acid aqueous solution (C)]
C1: 0.05N hydrochloric acid aqueous solution.
C2: distilled water.

[Curing catalyst (D)]
Complex having aluminum as central metal D1: Tris (2,4-pentanedionato) aluminum (III) (acetylacetonate complex).

[Organic solvent (E)]
E1: methanol.
E2: t-butanol.
E3: diacetone alcohol.
E4: ethylene glycol isopropyl ether.
E5: Propylene glycol monomethyl ether.
E6: Acetylacetone.

[Aromatic alcohol (F)]
F1: 2-methyl-4-phenyl-2-butanol (boiling point: 121 ° C.)
F2: 3,4-dichlorobenzyl alcohol (boiling point: 148-151 ° C.)
F3: Furfuryl alcohol (boiling point; 170 ° C.)
F4: 2-phenyl-2-propanol (boiling point; 202 ° C.)
F5: benzyl alcohol (boiling point; 204.7 ° C.)
F6: 1-phenyl-2-methyl-2-propanol (boiling point; 215 ° C.)
F7: 4-methylbenzyl alcohol (boiling point: 217 ° C.)
F8: Phenethyl alcohol (boiling point: 219-221 ° C.)
F9: 2-chlorobenzyl alcohol (boiling point: 230 ° C.)
F10: o-chlorobenzyl alcohol (boiling point; 230 ° C.)
F11: 2-phenoxyethanol (boiling point: 245.2 ° C.)
F12: 4-methoxybenzyl alcohol (boiling point: 259 ° C.)

Example 1
[Manufacture of coating agent 1]
GTS 56.3 parts by mass as the hydrolyzable group-containing organosilicon compound (B), E2 17.0 parts by mass, E3 56.0 parts by mass as organic solvent (E), and F1 30.0 as aromatic alcohol (F) 0.16 parts by mass of a silicone surfactant (L7001 manufactured by Toray Dow Corning Co., Ltd.) was further added and mixed with stirring. While stirring the resulting solution, 13.0 parts by mass of C1 and 8.0 parts by mass of C2 as water or acid aqueous solution (C) were added with care so that the liquid temperature does not exceed 50 ° C. Stirring was continued for 3 hours. Thereafter, 3.0 parts by mass of D1 was added as a curing catalyst (D) and mixed with stirring for 1 hour. Next, 150 parts by mass of A1 (45.8 parts by mass of antimony pentoxide fine particles, 104.2 parts by mass of methanol) were added as inorganic oxide fine particles (A), and the mixture was stirred and mixed at room temperature for 24 hours.

Examples 2-31 and Comparative Example 1
[Manufacture of coating agents 2-32]
Inorganic oxide fine particles (A), hydrolyzable group-containing organosilicon compound (B), water or acid aqueous solution (C), curing catalyst (D), organic solvent (E), aromatic shown in Table 1 and Table 2 It was produced in the same manner as coating agent 1 except that alcohol (F) was used. The composition of the formulation is shown in Tables 1 and 2. The coating agents 2-31 correspond to Examples 2-31, and the coating agent 32 corresponds to Comparative Example 1, respectively.

Example 32
An optical base material (lens base material) MRA having a thickness of about 2 mm was immersed in a 10 mass% sodium hydroxide aqueous solution at 50 ° C., and alkali etching was performed for 5 minutes using an ultrasonic cleaner. After alkali etching, the substrate was washed successively with tap water and distilled water at 50 ° C. to remove the remaining alkali and then left for about 10 minutes until the temperature reached room temperature. This lens substrate was dip coated with the coating agent 1 at 25 ° C. at a pulling rate of 15 cm / min. Then, after pre-curing for 15 minutes in an oven at 70 ° C., curing is performed at 110 ° C. for 2 hours, and a hard coat layer is formed with a thickness of 2.1 μm on both surfaces of the optical substrate (lens substrate) MRA. A formed optical article (hard coat lens) was obtained. The refractive index of the hard coat layer was 1.57.

[Evaluation results of optical articles]
When this optical article (hard coat lens) was evaluated for appearance, boiling adhesion test, steel wool scratch resistance, and weather resistance adhesion, appearance A, boiling adhesion: 5 hours or more, steel wool scratch resistance: A, Weather-resistant adhesion: 288 hours or longer. The results are shown in Table 6. About each evaluation, it performed by the following method.

(appearance)
Visual observation evaluated the liquid pool of the lower part of a lens produced at the time of dip-coating a coating liquid on a plastic lens, and the repelling seen in the contact part of a lens and a lens holding jig. As the lens holding jig, a three-point fixed jig having one holding part on each of the left and right with the lower end of the lens as the center and one holding part on the upper part was used. The evaluation criteria are as follows.
A: Liquid pool and repelling are hardly seen.
B: Liquid pool and repelling are observed within 0.5 mm from the lens edge.
C: Liquid pool and repelling are observed within 1.0 mm from the lens edge.
D: Liquid pool and repelling are observed within 1.5 mm from the lens edge.
E: Liquid pool and repellency are observed at a portion exceeding 1.5 mm from the lens edge.

(Boil adhesion test)
The obtained optical article (hard coat lens) was put into boiling distilled water, and the adhesion of the hard coat lens was evaluated every hour. In the test evaluation, the adhesion between the hard coat film and the lens was evaluated by a cross-cut tape test according to JISD-0202 before the test and every hour of the test. That is, using a cutter knife, cuts are made at intervals of about 1 mm on the hard coat film surface to form 100 squares. A cellophane adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) was strongly pasted thereon, and then pulled and peeled at a stretch from the surface in a direction of 90 °, followed by measuring the squares on which the hard coat film remained. As the evaluation result, the test time when the remaining square is less than 90 is described. For example, when it is described as 3 hours, it means that the number of grids remaining in the crosscut tape test after 3 hours of acceleration is less than 90. Moreover, when the number of cells remaining in the promotion 5 hours was 90 or more, it was described as 5 hours or more.

(Steel wool scratch resistance)
Using steel wool (Bonstar # 0000 manufactured by Nippon Steel Wool Co., Ltd.), the surface of the optical article (hard coat film surface) was rubbed for 10 reciprocations while applying a load of 3 kg, and the degree of damage was visually evaluated. The evaluation criteria are as follows.
A: Scratches are not found (when scratches could not be confirmed visually).
B: Scratches are scarcely observed (when there are 1 or more and less than 5 scratches visually).
C: Slightly scratched (when there are 5 or more and less than 10 scratches visually).
D: Scratches (when there are 10 or more scratches visually).
E: Peeling of the hard coat film has occurred.

(Weather resistance adhesion test)
The obtained optical article (hard coat lens) was allowed to stand for 8 hours under a radiant intensity of 0.89 W / cm 2 (340 nm) using a Q-LAB QUV Accelerated Weathering Tester (lens surface temperature of about 60 ° C.). The sample was allowed to stand for 4 hours under humidification (lens surface temperature of about 60 ° C.), and this test was evaluated every two cycles (total 24 hours), and the test was conducted for a maximum of 288 hours. In the test evaluation, the adhesion between the hard coat film and the lens was evaluated by a cross-cut tape test according to JISD-0202 before the test and every 24 hours of the test. That is, using a cutter knife, cuts are made at intervals of about 1 mm on the hard coat film surface to form 100 squares. A cellophane adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) was strongly pasted thereon, and then pulled and peeled at a stretch from the surface in a direction of 90 °, followed by measuring the squares on which the hard coat film remained. As the evaluation result, the test time when the remaining square is less than 90 is described. For example, when it is described as 100 hours, it means that the number of grids remaining in the crosscut tape test after 100 hours of acceleration is less than 90. In addition, when the number of cells remaining after the promotion of 288 hours was 90 or more, it was described as 288 hours or more.
The above results are shown in Table 3.

Examples 33-186
A hard coat lens having a hard coat layer in the same manner as in Example 1 using coating agents 2-31 obtained from the compositions shown in Table 1 and Table 2, and an optical base material (lens base material) Were prepared and evaluated. The evaluation results are shown in Tables 3 to 7.

Comparative Examples 2-6
Using the coating agent 32 shown in Table 2 and the optical base material (lens base material), a hard coat lens having a hard coat layer was produced in the same manner as in Example 1 and evaluated. The evaluation results are shown in Table 8.

  As apparent from the above examples, the inorganic oxide fine particles (A), hydrolyzable group-containing organosilicon compound (B), water or acid aqueous solution (C), curing catalyst (D), water-soluble organic solvent of the present invention. By blending (E) and the aromatic alcohol (F), it was possible to form a hard coat layer excellent in appearance, boiling adhesion, scratch resistance, and weather resistance adhesion. On the other hand, in Comparative Examples 1-5, since aromatic alcohol (F) was not included, sufficient weather-resistant adhesion could not be obtained.

Claims (10)

  Inorganic oxide fine particles (A), hydrolyzable group-containing organosilicon compound (B), water or acid aqueous solution (C), curing catalyst (D), organic solvent (E), and aromatic alcohols (F) Coating composition.   The aromatic alcohol (F) is in an amount of 3 to 100 parts by mass with respect to 100 parts by mass of the total amount of the inorganic oxide fine particles (A) and the hydrolyzable group-containing organosilicon compound (B). The coating composition according to claim 1, which is contained.   The coating composition according to claim 1, wherein the aromatic alcohol (F) has a boiling point of 100 to 300 ° C.   The coating composition according to claim 1, wherein the aromatic alcohol (F) is benzyl alcohol or 2-phenyl-2-propanol.   The inorganic oxide fine particles (A) are inorganic oxide fine particles containing at least one element selected from the group consisting of Ti, Zr, Sn, and Sb. A coating composition according to claim 1.   1 to 50 parts by mass of water or an aqueous acid solution (C) and a curing catalyst (D) per 100 parts by mass of the total amount of the inorganic oxide fine particles (A) and the hydrolyzable group-containing organosilicon compound (B). The organic solvent (E) is contained in an amount of 0.1 to 5.0 parts by mass, the organic solvent (E) is contained in an amount of 3 to 100 parts by mass, and the aromatic alcohol (F) is contained in an amount of 3 to 100 parts by mass. The coating composition as described.   An optical article having a hard coat layer obtained by curing the coating composition according to any one of claims 1 to 6 on a plastic optical substrate containing sulfur.   The optical article according to claim 7, wherein the plastic optical substrate is a photochromic optical substrate.   The photochromic optical substrate has a photochromic coating layer obtained by curing a polymerization curable composition containing a polymerizable monomer and a photochromic compound on a plastic optical substrate, and the photochromic coating layer The optical article according to claim 8, wherein a hard coat layer is formed thereon.   The optical article according to claim 7, wherein the plastic optical substrate is an optical substrate containing a dye.