JP5414449B2 - Coating composition - Google Patents

Description

  The present invention provides a coating that provides a transparent film excellent in durability such as adhesion and scratch resistance, chemical resistance, hot water resistance, heat resistance, and weather resistance on the surface of a plastic optical substrate such as a plastic lens. It relates to a composition. Especially, it is related with the coating composition for forming the optimal hard-coat layer on the surface of the optical base material containing pigment | dyes, such as a dyeing lens and 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.

  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. This silicone-based coating layer is composed of a silica fine particle, an organosilicon compound having a hydrolyzable group, a curing catalyst, an acid aqueous solution, and a water-soluble solvent as a main component (hereinafter referred to as “low-coating using silica fine particles”). (Which may be referred to as a “refractive index coating composition”) is applied to the surface of a plastic lens and then heated to cure the applied film and volatilize the contained solvent (Patent Document). 1).

  However, when a high refractive index plastic lens having a refractive index exceeding 1.50 is coated with the low refractive index coating composition, interference fringes are generated due to the difference in refractive index between the plastic lens and the coating layer. , Causing poor appearance.

  Various studies have been made to solve this problem. For example, a coating composition in which silica fine particles, which are one component of the coating composition, are replaced with a composite metal oxide such as Sb, Ti, Zr, or Sn having a high refractive index is known (see, for example, Patent Document 2). This coating composition can be suitably used for a high refractive index plastic lens. However, those containing titanium oxide have room for improvement in terms of weather resistance because the coating layer itself deteriorates due to the photocatalytic ability of titanium oxide.

  In order to avoid the photocatalytic ability of titanium oxide, a coating composition for high refractive index that does not use titanium oxide has been developed (see, for example, Patent Document 3). This coating composition can prevent deterioration of the coating layer itself. However, since the ultraviolet absorbing ability by titanium oxide is not exhibited, the light deterioration mechanism between the coating layer and the plastic lens cannot be suppressed, and the coating layer and the plastic are exposed to light for a long time. In some cases, the adhesion with the lens was lowered (hereinafter, the adhesion between the coating layer after being exposed to light and the plastic lens may be referred to as weather resistance adhesion).

  Furthermore, a method for improving weather resistance adhesion by adding cerium oxide fine particles surface-treated with a surfactant in the coat layer to give the coat layer ultraviolet absorption ability has been studied (for example, , See Patent Document 4). By using this coating composition, weather resistance adhesion can be improved. However, the coating composition described in Patent Document 4 has room for improvement in that a coating layer that satisfies high scratch resistance cannot be formed. Furthermore, in the method described in Patent Document 4, when adjusting the coating agent, the inorganic oxide fine particles to be used may be colored, and there is room for improvement.

Japanese Patent Publication No.57-2735 JP-A-5-264805 JP 2004-224965 A JP 2006-70078 A

  In recent years, the performance required for the coating layer has increased, and in addition to the above physical properties, a coating composition that satisfies the following performance is desired. Specifically, an antireflection film may be provided on the coating layer formed from the coating composition in order to further enhance the function of the plastic lens. Before the antireflection film is provided, alkali cleaning is performed. However, the performance that the coating layer is difficult to peel off is required (hereinafter, this performance may be regarded as chemical resistance).

  In addition, plastic lenses may come into contact with hot water depending on their usage, but in this case as well, performance that does not cause cracks in the coating layer is required (hereinafter, this performance is referred to as hot water resistance). There is also.)

  Further, when the plastic lens expands due to heat, the coating layer is capable of following the expansion and is required to have a performance such that cracks do not occur (hereinafter, this performance may be referred to as heat resistance). In particular, for this heat resistance, not only the performance as a coating layer as described above, but also the performance is required when the coating layer is formed. That is, heating is required when forming the coat layer. Under the present circumstances, the coating composition excellent in the moldability which can suppress generation | occurrence | production of the crack which arises by shrinkage | contraction of this coating layer and expansion | swelling of a plastic lens is calculated | required.

  Therefore, the object of the present invention is that the initial coloration is small, the hard coat layer does not peel off due to the occurrence of cracks and the like even after long-term use, and the adhesiveness to an optical substrate such as a plastic lens is good. An object of the present invention is to provide a coating composition that can form a hard coat layer that has high chemical resistance, hot water resistance, and heat resistance, and that is particularly excellent in heat resistance during the formation of the hard coat layer.

  Among others, it is to provide a coating composition that can be effectively used as a hard coat layer of a plastic lens containing a dye or a photochromic compound.

  Another object of the present invention is to provide a method capable of stably producing a coating agent obtained by mixing the above coating composition.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, in the hard coat layer-forming coating composition containing the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B) as essential components, a specific amount of cerium oxide is blended, and a specific disilane compound The present inventors have found that a coating composition containing a specific amount of can solve the above-mentioned problems, and has completed the present invention.

That is, the present invention provides 20.00 parts by mass to 60.00 parts by mass of inorganic oxide fine particles (A) containing cerium oxide,
Following formula (1)

(In the formula, R ¹ represents a methyl group or an ethyl group, and X represents an alkylene group having 2 to 5 carbon atoms.)
A hard coat layer forming coating composition containing 40.00 parts by mass to 80.00 parts by mass of a hydrolyzable organosilicon compound (B) containing a disilane compound (B1) represented by:
The total amount of the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B) is 100 parts by mass,
The 0.25 weight parts to 15.00 parts by mass of cerium oxide, and the disilane compound (B1) 3.50 part by mass to 25.00 mass parts <br/> seen including, the hydrolyzable organosilicon compound But,

Under following formula (2)

{Where,
R ² is an alkyl group having 1 to 3 carbon atoms,
R ³ represents the following formula (3)

(Where
R ⁵ is an alkylene group having 1 to 8 carbon atoms. Or a group represented by the following formula (4)

(Where
R ⁶ is an alkylene group having 1 to 8 carbon atoms. )
R ⁴ is an alkyl group having 1 to 3 carbon atoms, and each R ⁴ may be the same group or a different group. }
And an epoxy group-containing organosilicon compound (B2) represented by formula (5):

(Where
R ³ and R ⁴ have the same meaning as in the formula (2). )
An epoxy group-containing organosilicon compound (B3) represented by the formula (1), with respect to 1 mol of the disilane compound (B1):
0.30 to 3.00 mol of an epoxy group-containing organosilicon compound (B2) represented by the formula (2),
2. A coating composition comprising 2.50 to 20.00 mol of an epoxy group-containing organosilicon compound (B3) represented by the formula (5).

  In the present invention, it is preferable that the inorganic oxide fine particles (A) do not contain titanium oxide, and the inorganic oxide fine particles (A) are particles other than the cerium oxide fine particles (A1) and the cerium oxide fine particles. It is preferably composed of one inorganic oxide fine particle (A2).

  Furthermore, in the present invention, 20.00 parts by mass to 70 parts by mass of water (C) per 100 parts by mass of the total amount of the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B). It is preferable to contain 0.000 parts by mass, 0.20 to 5.00 parts by mass of the curing catalyst (D), and 60.00 to 180.00 parts by mass of the water-soluble organic solvent (E).

Further, the present invention is a method for producing a coating agent by mixing the coating composition,
The inorganic oxide fine particles (A) are composed of cerium oxide fine particles (A1) and first inorganic oxide fine particles (A2),
As the cerium oxide fine particles (A1), cerium oxide fine particles dispersed in an acid aqueous solution are used, and the hydrolyzable organosilicon compound (B) and the cerium oxide fine particles (A1) dispersed in the acid aqueous solution are mixed. Then, after hydrolyzing the hydrolyzable organosilicon compound (B), the obtained mixture and the curing catalyst (D) are mixed, and then the first inorganic oxide fine particles (A2) are mixed. Is a method for producing a coating agent. According to this method, the coating agent can be produced without coloring.

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

  Moreover, this optical article exhibits an excellent effect 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 composition of the present invention is characterized in that a specific amount of cerium oxide and a disilane compound (B1) represented by the formula (1) is blended. These blends form a hard coat layer with little initial coloration, good appearance and good weather resistance, good adhesion to plastic optical substrates without causing poor appearance such as cracks even after long-term use. I can do it. Furthermore, it is possible to form a hard coat layer having high chemical resistance and high hot water resistance, and it is also possible to suppress the occurrence of cracks due to thermal history during the formation of the coat layer.

  Therefore, if the coating composition of the present invention is used, the appearance of the hard coat layer will not be deteriorated, so that the lifetime of optical articles such as plastic lenses can be dramatically extended.

  This effect is particularly effective when the disilane compound (B1) is an epoxy group-containing organosilicon compound (B2) having two hydrolyzable groups and an epoxy group-containing organosilicon compound (B3) having three hydrolyzable groups. When a specific amount is used and inorganic oxide fine particles not containing titanium oxide are used, this becomes remarkable.

  The reason why the coating composition of the present invention exhibits such excellent effects is not clear, but the present inventors presume as follows.

  In other words, by containing cerium oxide, the ability to absorb ultraviolet rays is exerted, and ultraviolet rays that reach the plastic optical substrate can be cut, and the optical deterioration of the interface portion between the hard coat layer and the plastic optical substrate is prevented. It is thought to suppress.

  In addition, by using the disilane compound represented by the above formula (1), since it has a portion in which silicon atoms are bonded by hydrocarbon instead of siloxane bond, it has excellent chemical resistance, particularly alkali resistance, and hardness. It is considered that flexibility can be imparted without impairing the properties, the hot water resistance is high, and a coat layer having excellent heat resistance can be formed.

  Furthermore, the use of the disilane compound is considered to improve the adhesion at the interface between the coating layer and the plastic optical substrate. Therefore, a synergistic effect due to the effect of using the cerium oxide and the effect of improving the adhesion at the interface between the coat layer and the plastic optical substrate is exhibited. In the use of optical articles over a long period of time, the coat layer and the plastic It is considered that stress generated between the optical substrate and the optical base material can be relaxed, and excellent effects, particularly weather resistance adhesion can be improved.

  This effect is considered to be exhibited more significantly by using inorganic oxide fine particles not containing titanium oxide and by using a specific amount of the epoxy group-containing organosilicon compounds (B2) and (B3). .

  In the present invention, the cerium oxide fine particles (A1) dispersed in the acid aqueous solution are first mixed with the hydrolyzable organosilicon compound (B) to hydrolyze the hydrolyzable organosilicon compound (B). After that, the method of mixing the obtained mixture and the curing catalyst (D) and then mixing the first inorganic oxide fine particles (A2) is provided. According to this method, the coating agent can be produced without coloring. Although the reason for this is not clear, it is conceivable that the mixing order can prevent oxidation or reduction of cerium oxide and other inorganic oxides and prevent them from being colored.

  The coating composition of the present invention comprises 20.00 parts by mass to 60.00 parts by mass of inorganic oxide fine particles (A) containing cerium oxide and a hydrolyzable organosilicon compound containing a disilane compound represented by the formula (1). A hard coat layer forming coating composition containing 40.00 parts by mass to 80.00 parts by mass of (B). Hereinafter, each component will be described.

<Inorganic oxide fine particles (A)>
The inorganic oxide fine particles used in the present invention are not particularly limited as long as they contain cerium oxide, and known ones can be used. Also, one type can be used, or two or more types can be mixed and used.

  From the viewpoint that the inorganic oxide fine particles (A) can be uniformly dispersed in the hard coat layer, the inorganic oxide fine particles (A) are colloidal using water, an alcohol or other organic solvent as a dispersion medium. It is used in the form of a sol in which the inorganic oxide fine particles (A) are dispersed. Hereinafter, the inorganic oxide fine particles (A) may be simply used as the component (A).

  Specific examples of the dispersion medium include alcohol solvents such as isopropanol, ethanol, methanol, and ethylene glycol, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide, or water, and a mixed solvent thereof. Among these, it is preferable to use an alcohol solvent or water.

  When these dispersion media are used, the solid content concentration of the inorganic oxide fine particles (A) (the concentration of the inorganic oxide fine particles (A) contained in the sol) is 10% by mass to 50% in view of operability. It is preferable that it is mass%.

  As the inorganic oxide fine particles (A), those having a primary particle diameter of about 1 to 300 nm observed with an electron microscope (TEM) can be suitably used. As will be described in detail below, the inorganic oxide fine particles (A) may include a plurality of fine particles such as cerium oxide fine particles and first inorganic oxide fine particles (A2). Also, all the particles preferably have a primary particle diameter of about 1 to 300 nm.

  The blending amount of such inorganic oxide fine particles (A) is 20.00 parts by mass to 60.00 parts by mass as a total amount of 100 parts by mass with the hydrolyzable organosilicon compound (B) described in detail below. is there. In addition, this mass part is the compounding quantity of solid content (inorganic oxide microparticles | fine-particles (A)) except a dispersion medium. When the amount of the inorganic oxide fine particles (A) is less than 20.00 parts by mass, the hardness of the coat layer is reduced, which is not preferable. On the other hand, when the amount exceeds 60.00 parts by mass, the heat resistance of the coat layer is lowered, the flexibility is further lowered, and the coat layer becomes brittle. Therefore, when the hardness, heat resistance, and flexibility of the coating film are taken into account, the blending amount of the inorganic oxide fine particles (A) is more preferably 30.00 parts by mass to 50.00 parts by mass.

  In general, the amount of inorganic oxide fine particles in the finally formed hard coat layer is 30% to 70% by mass, preferably 40% to 60% by mass, and the like. 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 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 ask for.

  In the present invention, the inorganic oxide fine particles (A) contain cerium oxide. Therefore, composite oxide fine particles containing cerium oxide, cerium oxide fine particles (A1) and those containing the composite oxide fine particles, or cerium oxide fine particles (A1) and first inorganic oxide fine particles not containing cerium oxide (A2) As long as it contains.

  Composite oxide fine particles containing cerium oxide include silicon (Si), aluminum (Al), iron (Fe), indium (In), zirconia (Zr), tin (Sn), antimony (Sb), and titanium (Ti). And at least one element selected from tungsten (W) and composite oxide fine particles comprising an oxide of cerium (Ce). Among these, composite oxide fine particles composed of at least one element selected from Si, Zr, Sn, Sb, and W, and an oxide of Ce are particularly preferable. In particular, in consideration of the weather resistance of the obtained hard coat layer, it is preferable to use composite oxide fine particles not containing titanium oxide. As described above, the composite oxide fine particles are also preferably used in a state of being dispersed in water, an alcohol-based or other organic solvent. It is preferable that the solid content concentration and the primary particle diameter also satisfy the above range.

  The ratio of cerium oxide in the composite oxide fine particles is such that the cerium oxide component is 0.25 when the total amount of the hydrolyzable organosilicon compound (B) and the composite oxide fine particles described below is 100 parts by mass. If it becomes a mass part thru | or 15.00 mass part, it will not restrict | limit in particular. When the cerium oxide component does not satisfy the above range only by using the composite oxide fine particles, the cerium oxide component can be prepared by blending the cerium oxide fine particles (A1). In the composite oxide fine particles, the ratio of oxides other than cerium oxide is not particularly limited, and may be determined as appropriate according to the refractive index of the plastic optical substrate.

  In the present invention, it will be described in detail below. However, since it becomes easy to adjust the blending amount of cerium oxide, in order to apply to plastic optical substrates of various refractive indexes, cerium oxide fine particles (A1), It is preferable to use inorganic oxide fine particles (A) containing the first inorganic oxide fine particles (A2) not containing cerium oxide. First, the first inorganic oxide fine particles (A2) will be described.

<First inorganic oxide fine particles (A2)>
In this case, the first inorganic oxide fine particles (A2) are not particularly limited, and are oxides of at least one element selected from Si, Al, Fe, In, Zr, Sn, Sb, Ti, and W. Oxide fine particles made of Among these, oxide fine particles made of an oxide of at least one element selected from Si, Zr, Sn, and Sb are preferable. In particular, considering the weather resistance of the resulting hard coat layer, it is preferable to use oxide fine particles not containing titanium oxide. Specifically, the first inorganic oxide fine particles (A2) may be antimony oxide fine particles, silicon oxide fine particles (silica fine particles), or composite inorganic oxide fine particles containing a plurality of oxides of the above elements. Hereinafter, the first inorganic oxide fine particles may be simply used as the component (A2).

  These 1st inorganic oxide fine particles (A2) should just determine suitably the compounding quantity of the oxide contained according to the use application.

  For example, when applied to a low refractive index plastic optical substrate having a refractive index of 1.50 or less, silica fine particles may be used. The silica fine particles are not particularly limited, and known ones can be used. Specifically, in a state of being dispersed in water, alcohol, or other organic solvent, the solid content concentration is 10.00 mass% to 50.00 mass%, and the primary particle diameter is 1 to 300 nm. It is preferable to use it. Commercially available silica fine particles can be used. As the silica fine particles, silica sol using water as a dispersion medium such as Snowtex OXS, Snowtex OS, Snowtex O, Snowtex O-40, etc., sold by Nissan Chemical Industries, Ltd., MA-ST-MS A silica sol using an alcohol such as (dispersion medium; methanol) or IPA-ST (dispersion medium; isopropanol) as a dispersion medium can be used.

  In addition, when applied to a high refractive index plastic optical substrate having a refractive index exceeding 1.50, antimony oxide fine particles or composite inorganic oxide fine particles containing a plurality of oxides of the above elements may be used. Among these, when applied to an optical substrate made of a high refractive index plastic, it is preferable to use composite inorganic oxide fine particles made of oxides of Si, Zr, Sn, and Sb. When this composite inorganic oxide fine particle is used, the blending amount of each component may be appropriately determined according to the application to be used, but tin oxide is 50 mass% to 96 mass%, zirconium oxide is 3 mass% to 49 mass%. It is preferable to satisfy 1% by mass to 29.9% by mass of antimony oxide and 0.1% by mass to 29% by mass of silicon oxide. Both the antimony oxide fine particles and the composite inorganic oxide fine particles are dispersed in water, alcohol or other organic solvent, and the solid content concentration is 10.00 mass% to 50.00 mass%, primary particles. It is preferable to use one having a diameter of 1 to 300 nm. As these first inorganic oxide fine particles (A2), commercially available ones can be used. Specifically, antimony pentoxide such as AMT-332S · NV (dispersion medium: methanol) manufactured by Nissan Chemical Industries, Ltd. HX series (dispersion medium: methanol), which is a composite inorganic oxide fine particle of sol, zirconium oxide or tin oxide, can be suitably used.

  When using the first inorganic oxide fine particles (A2), the cerium oxide fine particles (A1) must be used. Therefore, the usage amount of the first inorganic oxide fine particles (A2) may be appropriately determined within the range satisfying the scope of the present invention, depending on the usage amount of the cerium oxide fine particles. Specifically, the total amount of the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B) is 100 parts by mass, and the inorganic oxide fine particles (A) are 20.00 parts by mass to 60.00 parts by mass. Since the cerium oxide contained in the inorganic oxide fine particles (A) is 0.25 part by mass to 15.00 parts by mass, the first inorganic oxide fine particles (A2) contained in the inorganic oxide fine particles (A) May be used in an amount of 5.00 parts by mass to 59.75 parts by mass. As a matter of course, if the range of suitable inorganic oxide fine particles (A) and cerium oxide is changed, the range of the first inorganic oxide fine particles (A2) is changed accordingly.

  Next, the cerium oxide fine particles (A1) will be described.

<Cerium oxide fine particles (A1)>
In the present invention, when cerium oxide fine particles are used, it is not particularly limited, and known ones can be used. In particular, considering the operability of the coating composition and the uniform dispersion in the coating layer, the sol in which cerium oxide fine particles (A1) are dispersed colloidally with water or an alcohol solvent as a dispersion medium. It is preferable to use in a state. In this case, those having a primary particle diameter of about 1 to 300 nm can be suitably used. Further, the solid content concentration (concentration of the cerium oxide fine particles (A1) contained in the sol) is preferably 10% by mass to 50% by mass, and particularly preferably 10% by mass to 40% by mass. Hereinafter, the cerium oxide fine particles may be simply used as the component (A1).

  Among such cerium oxide fine particles, it is preferable to use cerium oxide fine particles (sol) dispersed in an acid aqueous solution. By using the cerium oxide fine particles dispersed in the acid aqueous solution, the dispersion of the cerium oxide fine particles themselves can be further stabilized, and the storage stability of the coating agent itself can be improved. As estimated, by using cerium oxide fine particles dispersed in an acid aqueous solution, the hydrolyzed organosilicon compound is bonded to the surface of cerium oxide, and as a result, the storage stability of the coating agent is improved. It is thought that there is not.

  In order to make the acid aqueous solution, it is preferable to blend a known acidic compound, specifically, sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid, phthalic acid, malic acid, maleic acid, oxalic acid, lactic acid, malic acid, Citric acid, tartaric acid, salicylic acid, glycolic acid, benzoic acid, malonic acid, mandelic acid and the like can be used. Among these, it is preferable to use acetic acid. Such an acid aqueous solution is not particularly limited, but preferably has a pH of 2 to 6, and when acetic acid is used, 1% by mass to 10% by mass in the acid aqueous solution containing cerium oxide fine particles. The concentration of acetic acid may be adjusted within a range of%.

  Commercially available cerium oxide fine particles dispersed in such an acid aqueous solution can be used. Specific examples include Niedral U-15 sold by Taki Chemical Industry.

  Next, the blending amount of cerium oxide will be described.

<Cerium oxide content>
In the present invention, the blending amount of cerium oxide is 0.25 with the total amount of inorganic oxide fine particles (A) containing cerium oxide and the hydrolyzable organosilicon compound (B) described in detail below as 100 parts by mass. Must be in the range of parts by weight to 15.00 parts by weight. When the blending amount of cerium oxide is less than 0.25 parts by mass, the ultraviolet absorption ability of the hard coat layer is reduced, and the ultraviolet rays reach the plastic optical substrate. Adhesiveness with a base material falls. In addition, when an optical substrate containing a dye, a photochromic compound, or the like is used, the photodegradation of the dye or photochromic compound present at the interface between the hard coat layer and the plastic optical substrate cannot be suppressed. On the other hand, when the blending amount of cerium oxide exceeds 15.00 parts by mass, the hard coat layer itself is colored, which is not preferable. In consideration of the initial coloration, weather resistance, and weather resistance adhesion of the hard coat layer, the amount of cerium oxide is preferably 0.85 in order to exert the effect of using the disilane compound described in detail below. The range is from mass parts to 12.60 mass parts, more preferably from 0.85 mass parts to 5.50 mass parts.

  In addition, when the inorganic oxide fine particle (A) to be used consists of only the complex oxide fine particle containing cerium oxide, the compounding amount of the composite oxide fine particle corresponds to the compounding amount of the inorganic oxide fine particle (A). The blending amount of the cerium oxide corresponds to the amount of cerium oxide contained in the composite oxide fine particles.

  When the inorganic oxide fine particles (A) are composed of the cerium oxide fine particles (A1) and the composite oxide fine particles, the total amount of the component (A1) and the composite oxide fine particles It corresponds to the blending amount of (A). The blending amount of the cerium oxide corresponds to the total amount of the blending amount of the component (A1) and the amount of cerium oxide contained in the composite oxide fine particles.

  Furthermore, when the inorganic oxide fine particles (A) are composed of the cerium oxide fine particles (A1) and the first inorganic oxide fine particles (A2), the total amount of the components (A1) and (A2) is inorganic. This corresponds to the amount of oxide fine particles (A). And the compounding quantity of the said cerium oxide corresponds to the compounding quantity of (A1) component.

  Next, the hydrolyzable organosilicon compound (B), which is another essential component, will be described.

<(B) Hydrolyzable organosilicon compound>
In the coating composition of the present invention, the hydrolyzable organosilicon compound (B) is a component that forms a transparent cured body that becomes a matrix when the hard coating layer is formed by curing the coating agent, and the inorganic oxidation compound The fine particles (A) have a function as a binder. Hereinafter, this hydrolyzed organosilicon compound may be simply used as the component (B).

  In the present invention, the amount of the hydrolyzable organosilicon compound (B) is 100 parts by mass with respect to the total amount of the inorganic oxide fine particles (A) (the total amount of the (A) component and the (B) component). 40.00 parts by mass to 80.00 parts by mass. When the hydrolyzable organosilicon compound (B) is less than 40.00 parts by mass, the heat resistance of the coat layer is lowered, the flexibility is further lowered, and the coat layer itself becomes brittle. On the other hand, when the amount exceeds 80.00 parts by mass, the hardness of the coat layer is reduced, which is not preferable. Considering the hardness, heat resistance, flexibility, etc. of the coat layer, the blending amount of the hydrolyzable organosilicon compound (B) is preferably 50.00 parts by mass to 70.00 parts by mass.

  In addition, the compounding quantity of this (B) component is the quantity of the hydrolysable organosilicon compound (B) which is not hydrolyzed.

  In addition, the present invention is characterized in that the coating composition contains a specific amount of cerium oxide, and the following formula (1):

(In the formula, R ¹ represents a methyl group or an ethyl group, and X represents an alkylene group having 2 to 3 carbon atoms.)
A specific amount of the disilane compound (B1) represented by Next, this disilane compound will be described.

<Disilane compound (B1) represented by the formula (1)>
In the present invention, the hydrolyzable organosilicon compound (B) includes the disilane compound (B1) represented by the formula (1). By including this disilane compound (B1), the heat resistance, chemical resistance and hot water resistance of the resulting hard coat layer can be improved. Further, it is considered that the adhesion at the interface between the hard coat layer and the plastic optical substrate can be improved, but the weather resistance adhesion can be dramatically improved by a synergistic effect with the effect of using cerium oxide.

  The disilane compound (B1) basically has the same role as described in the organosilicon compound (B). Hereinafter, this disilane compound may be simply used as the component (B1).

In the formula (1), R ¹ is a methyl group or an ethyl group. X is an alkylene group having 2 to 3 carbon atoms. When the number of carbon atoms exceeds 3, the chemical resistance, the hot water resistance and the heat resistance are excellent, but the hardness of the hard coat layer is lowered and the scratch resistance is deteriorated, which is not preferable. Therefore, in order to satisfy chemical resistance, hot water resistance, heat resistance, scratch resistance, and weather resistance adhesion, X is preferably an ethylene group.

  Specific examples of the disilane compound (B1) include 1,2-bis (triethoxysilyl) ethane and 1,2-bis (trimethoxysilyl) ethane. In particular, 1,2-bis (trimethoxysilyl) ethane. Ethoxysilyl) ethane is preferred.

  The amount of the disilane compound (B1) is 3.50 parts by mass to 25.00 parts by mass with respect to 100 parts by mass as the total of the component (A) and the hydrolyzable organosilicon compound (B). Must. When the compounding amount of the disilane compound (B1) is less than 3.50 parts by mass, chemical resistance and weather resistance adhesion cannot be sufficiently improved, and cracks due to thermal history during curing occur. It becomes easy to do. Moreover, when the compounding quantity of a disilane compound (B1) exceeds 25.00 mass parts, since abrasion resistance will fall, it is unpreferable. Therefore, when the physical properties of the obtained hard coat layer and the moldability of the hard coat layer are taken into consideration, the amount of the disilane compound (B1) is more preferably 5.00 parts by mass to 20.00 parts by mass.

  In addition, the compounding quantity of this (B1) component is the quantity of the disilane compound which is not hydrolyzed.

  This disilane compound (B1) is included in the hydrolyzable organosilicon compound (B). Therefore, for example, the total amount of the component (A) and the component (B) is 100 parts by mass, the component (B) is 40.00 parts by mass to 80.00 parts by mass, and the (B1) is 3 In the case of .50 parts by mass to 25.00 parts by mass, 15.00 parts by mass to 76.50 parts by mass of the hydrolyzable organosilicon compound other than the component (B1) are included. Of course, when the component (B) satisfies the above range and the component (B1) is 5.00 parts by mass to 20.00 parts by mass, the hydrolyzability other than the component (B1) It shall contain 20.00 parts by mass to 75.00 parts by mass of an organosilicon compound.

  In addition, the compounding quantity of hydrolysable organosilicon compounds other than this (B1) component is the quantity of the state which is not hydrolyzed.

  Next, hydrolyzable organosilicon compounds other than the component (B1) will be described.

<Hydrolyzable organosilicon compound other than (B1) component>
(B1) The hydrolyzable organosilicon compound other than the component, under following formula (2)

{Where,
R ² is an alkyl group having 1 to 3 carbon atoms,
R ³ represents the following formula (3)

(Where
R ⁵ is an alkylene group having 1 to 8 carbon atoms. Or a group represented by the following formula (4)

(Where
R ⁶ is an alkylene group having 1 to 8 carbon atoms. )
R ⁴ is an alkyl group having 1 to 3 carbon atoms, and each R ⁴ may be the same group or a different group. }
And an epoxy group-containing organosilicon compound (B2) represented by formula (5):

(Where
R ³ and R ⁴ have the same meaning as in the formula (2). )
To use in the epoxy group-containing organic silicon compound represented the (B3).

  Hereinafter, the epoxy group-containing organosilicon compound represented by the formula (2) having the two hydrolyzable groups is simply used as the component (B2), and the formula (5) has the three hydrolyzable groups. The epoxy group-containing organosilicon compound shown may be simply used as the component (B3).

  Next, the components (B2) and (B3) will be described.

<Epoxy group-containing hydrolyzable organosilicon compound (B2), (B3)>
These components (B2) and (B3) basically have the same role as described in the organosilicon compound (B).

  Specific examples of the component (B2) include γ-glycidoxypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane. Among them, it is preferable to use γ-glycidoxypropylmethyldimethoxysilane.

  Specific examples of the component (B3) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, β- (3,4- (Epoxycyclohexyl) ethyltrimethoxysilane. Among them, it is preferable to use γ-glycidoxypropyltrimethoxysilane.

  The blending amount of these (B2) component and (B3) component is appropriately determined depending on the blending amount of the (B) component and the (B1) component as described above, and among them, it is blended in the following proportions. Is particularly preferred.

  Specifically, it is blended so that the component (B2) is 0.30 to 3.00 mol and the component (B3) is 2.50 to 20.00 mol with respect to 1 mol of the component (B1). It is preferable. When the blending amount of the component (B2) and the component (B3) satisfies the above range, the hardness, heat resistance, and hot water resistance of the coat layer can be improved. Among them, in order to improve the hardness of the coat layer while maintaining heat resistance and hot water resistance, the component (B2) is preferably 0.30 mol to 2.50 mol, more preferably 0.30 mol to 2. It is preferable to be 00 mol. In order to maintain the hardness of the coat layer higher, the component (B3) is preferably 2.50 mol to 15.00 mol, more preferably 2.50 mol to 10.00 mol. This blending amount is the amount of the (B1) component, the (B2) component, and the (B3) component that are not hydrolyzed.

  In consideration of adhesion, the component (B2) and the component (B3) satisfy the above range, and the total amount of the component (B2) and the component (B3) is 1 mol of the component (B1). The amount is preferably 3.00 mol or more, more preferably 4.00 mol or more, still more preferably 5.0 mol or more, and particularly preferably 6.00 mol or more. In addition, the upper limit of the total amount of the component (B2) and the component (B3) may be appropriately determined within the range in which the component (B2) and the component (B3) satisfy the above range. Is preferably 20.0 mol or less, more preferably 15.0 mol or less.

  In addition, the compounding quantity of these (B2) component and (B3) component is, of course, the total amount (mass conversion) of (B1) component, (B2) component, and (B3) component is (B) component. It shall be the same as the blending amount or less.

  As described above, when the total amount of the component (B1), the component (B2), and the component (B3) is less than the blending amount of the component (B), (B1), (B2), (B3 Other organosilicon compounds other than) can be blended.

  Next, other organosilicon compounds will be described.

<Hydrolyzable organosilicon compounds other than (B1), (B2), (B3)>
As other hydrolyzable organosilicon compounds, known organosilicon compounds that can be used in coating compositions can be used. Specifically, tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, phenyltri Methoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, 3-ureidopropyltriethoxysilane, trifluoropropyltrimethoxysila Perfluorooctylethyltriethoxysilane, γ-chloropropyltrimethoxysilane, 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, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-2 (aminoethyl) 3-aminopropyl Examples include reethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, p-styryltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. It is done.

The compounding amount of these other organosilicon compounds is appropriately determined depending on the compounding amounts of the component (B), the component (B1), the component (B2), and the component (B3) .

  Next, other components that can be blended in the coating composition of the present invention, specifically, water (C), curing catalyst (D), and water-soluble organic solvent (E) will be described. First, the water (C) component will be described.

<Water (C)>
In the coating composition of the present invention, the component (B) is hydrolyzed, and the hydrolyzate is polymerized and cured (polycondensation) in the form of incorporating the component (A) to form a cured body as a matrix, A) A hard coat layer in which components are finely dispersed in a matrix is formed. In order to form this coat layer, it is preferable to add water in order to promote hydrolysis of the hydrolyzable organosilicon compound.

  Such water is 20.00 parts by mass to 70.00 parts by mass, preferably 30.00 parts by mass to 70.00 parts by mass per 100 parts by mass of the total mass of the components (A) and (B). More preferably, the amount is 35.00 parts by mass to 60.00 parts by mass. That is, when the amount of water is small, the hydrolysis of the component (B) does not proceed sufficiently, and the scratch resistance of the resulting hard coat layer tends to decrease, and the storage stability of the resulting coating agent is stable. There is a risk that the characteristics such as On the other hand, 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 optical properties. In addition, the blending amount of the water is based on that in which the component (B) is not hydrolyzed.

  As already described, the component (A) may be used in the form of a dispersion (sol) dispersed in water. Of course, the case where the cerium oxide fine particles are used in a state dispersed in water is also included. In such a case, the blending amount of water includes the amount of water used in the dispersion medium. For example, when the component (A) is used, if the amount of water contained in the dispersion satisfies the range of the amount of water, it is not necessary to further mix water with the coating composition. If the amount of water is less than the range, water may be further mixed.

  Moreover, since the water used here accelerates | stimulates hydrolysis of (B) component, it can also be made into acid aqueous solution. 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. As a matter of course, this acid aqueous solution includes the acid aqueous solution when a dispersion liquid in which the cerium oxide fine particles (B1) are dispersed in the acid aqueous solution is used.

  Next, the curing catalyst (D) will be described.

<Curing catalyst (D)>
The curing catalyst (D) is used for promoting the condensation (polymerization curing) of the hydrolyzate of the component (B). Specifically, an acetylacetonate complex, a perchlorate, an organic metal salt, and various Lewis acids are used, and these can be used alone or in combination of two or more. By using these curing catalysts, the coat layer can be made harder.

  Examples of the acetylacetonate complex include those described in JP-A-11-119011, specifically, aluminum acetylacetonate, lithium acetylacetonate, indium acetylacetonate, chromium acetylacetonate, nickel acetylacetate. Examples thereof include narate, titanium acetylacetonate, iron acetylacetonate, zinc acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, and zirconium acetylacetonate. 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, an acetylacetonate complex or perchlorate is used from the viewpoint that a hard coat layer having high scratch resistance can be obtained in a short time even at a relatively low temperature, and the storage stability of the coating composition is excellent. Is preferred. 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 0.25 parts by mass to 5.00 parts by mass, particularly 2.00 parts by mass, per 100 parts by mass of the total amount of the component (A) and (B). It is preferably used in an amount ranging from 4.00 parts by mass. In addition, the compounding quantity of the said curing catalyst is based on the thing of the state in which (B) component is not hydrolyzed.

  Next, the water-soluble organic solvent (E) will be described.

<Water-soluble organic solvent (E)>
In the present invention, the water-soluble organic solvent (E) refers to an organic solvent having a solubility in water at 25 ° C. of 10% by mass or more, preferably 50% by mass or more.

  The water-soluble organic solvent (E) is a solvent for the component (B) and a dispersion medium for the component (A). Specific examples of such water-soluble organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, t-butyl alcohol, 2-butanol and diacetone alcohol; lower alcohol esters of lower carboxylic acids such as methyl acetate. Ethers such as cellosolve, dioxane and ethylene glycol monoisopropyl ether; ketones such as acetone, methyl ethyl ketone and acetylacetone. These organic solvents can be used alone or in admixture of two or more.

  Among these water-soluble organic solvents (E), methanol, isopropanol, t-butyl alcohol, in particular, from the viewpoint that when a coating agent is applied and cured, it easily evaporates and a smooth hard coat layer is formed. It is preferable to use diacetone alcohol, ethylene glycol monoisopropyl ether, or acetylacetone. Further, as described above, a part of such a water-soluble organic solvent can be mixed with inorganic oxide fine particles in advance as a dispersion medium for the component (A).

  The amount of the water-soluble organic solvent (E) used is not particularly limited, but is preferably per 100 parts by mass of the total amount of the component (A) and the component (B) in order to obtain storage stability and sufficient scratch resistance. Is preferably in the range of 60.00 parts by mass to 200.00 parts by mass, more preferably 60.00 parts by mass to 180.00 parts by mass. The blending amount of the water-soluble organic solvent (E) is based on the hydrolyzable organosilicon compound (B) that is not hydrolyzed, and the hydrolyzable organosilicon compound is hydrolyzed. It does not include alcohol produced by decomposition.

  Next, additional components other than the components (A), (B), (C), (D), and (E) will be described.

<Other additive components>
In the present invention, in addition to the above components, the following additional components can be blended within a range that does not impair the effects of the present invention.

  A cyclic ketone compound can also be added to the coating composition of the present invention for the purpose of improving and stabilizing the adhesion between the hard coat layer and the plastic optical substrate. Specific examples include N-methylpyrrolidone, ε-caprolactam, γ-butyrolactone, 1-vinyl-2-pyrrolidone, isophorone, cyclohexanone, methylcyclohexanone, and the like. It is preferable that the compounding quantity of these cyclic ketone compounds shall be 0.10 mass part thru | or 5.00 mass part per 100 mass parts of total amounts of (A) component and (B) component.

  Moreover, the additive normally mix | blended with a coating composition can be used unless the objective of this invention is 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 sorbit 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 / cured Castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, poly Alkoxy polyoxyethylene alkyl amine fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensates, can be mentioned a single-chain polyoxyethylene alkyl ethers. In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is 0.001 to 1.00 per 100 parts by mass of the total amount of the essential components described above (total amount of the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B)). A range of parts by mass is preferred.

  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 suitably used. The addition amount of these compounding agents is 0.10-20.100 parts by mass 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 00 parts by mass 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.

  Next, a method for producing a coating agent by mixing a coating composition containing the above components will be described.

<Manufacturing method of coating agent>
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, in order to obtain a coating agent with less coloring, it is preferable to employ the following method. In particular, when the cerium oxide fine particles (A1) are used, it is preferable to employ the following method.

  That is, first, the dispersion of the cerium oxide fine particles (A1) and the component (B) are mixed, the component (B) is hydrolyzed, and then the resulting mixture and the first inorganic oxide fine particles (A2) are mixed. It is preferable to do. When the curing catalyst is used, the dispersion of the cerium oxide fine particles (A1) and the component (B) are mixed, the component (B) is hydrolyzed, and the resulting mixture and the curing catalyst (D ) And then the first inorganic oxide fine particles (A2) are preferably mixed. Therefore, it is preferable to use the component (A1) dispersed in the acid aqueous solution. Although the reason is not clear, when the component (A1) is used, the color of the coating agent can be minimized by adopting the above method.

  The method will be described in more detail. First, component (B) is hydrolyzed by mixing component (B) and water-dispersed cerium oxide fine particles (A1), particularly component (A1) dispersed in an acid aqueous solution. In this case, in order to prevent the component (B) from having a high molecular weight, it is preferable to add the component (A1) to the component (B). Moreover, in order to make hydrolysis of (B) component quicker, acid aqueous solution like hydrochloric acid can also be added separately. Hydrolysis is preferably carried out at a temperature of 10 to 40 ° C. for 1 to 48 hours so as not to adversely affect the physical properties of the hard coat layer and to reduce the storage stability of the obtained coating agent. In addition, when mixing (B) component, the addition order in particular of (B1), (B2), (B3) component is not restrict | limited.

  The hydrolysis of the component (B) is performed until all the components (B) are hydrolyzed. Regarding the end of the hydrolysis, in the obtained coating agent, the amount of the organic solvent (alcohol solvent) generated from the component (B) used does not change because the amount of the organic solvent is determined by gas chromatography. What is necessary is just to confirm that it corresponds with the quantity of an organic solvent.

  Next, the mixture (mixture containing the component (A1) and the hydrolyzate of the component (B)) obtained by the above method and the component (A2) are mixed. This mixing is preferably performed by stirring at a temperature of 10 to 40 ° C. for 1 to 48 hours. In addition, when the curing catalyst (D) is used, it is preferable to mix the mixture and the curing catalyst (D) before mixing the mixture and the component (A2). It is preferable to stir and mix in the temperature range of 5 ° C. for 5 minutes to 12 hours. When the curing catalyst (D) is used, in particular, when the first inorganic oxide fine particles (A2) containing antimony oxide are used, the coloration of the resulting coating agent can be further reduced by employing the above mixing method. it can.

  By adopting the method as described above, coloring is small, the cerium oxide fine particles (A1) are sufficiently dispersed, and the storage stability of the coating agent itself can be improved. It is estimated that this is because the hydrolyzate is bonded to the surface of cerium oxide and the cerium oxide fine particles (A1) are stabilized by mixing the component (A1) and the component (B) first.

  The order of mixing the other components is not particularly limited, but the water-soluble organic solvent (E) is preferably mixed as a dispersion medium for the component (A2). Further, other additives are not particularly limited, but are preferably further mixed while the mixture and the component (A2) are being mixed.

  The coating agent obtained by mixing in this way is not particularly limited, but the solid content concentration consisting of the hydrolyzate of the component (A) and the component (B) is in the total mass of the coating agent. The amount may be 15 to 50% by mass, preferably 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 is, in particular, a polyfunctional acrylate having a tri- or higher 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 a composition containing is preferable.

  Specific examples of such polyfunctional acrylates having a tri- or higher functional (meth) acrylate group include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, and tetramethylolmethane triacrylate. It is done. Examples of the di (meth) acrylate having an alkylene glycol chain having 2 to 15 repeating units include polyethylene glycol dimethacrylate having an average molecular weight of 536, polytetramethylene glycol dimethacrylate having an average molecular weight of 736, and polypropylene glycol dimethacrylate having an average molecular weight of 536. Methacrylate, 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-act Proxy-diethoxy) phenyl] propane, 2,2-bis [4- acryloxy polyethoxy) phenyl] propane.

  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 base material (photochromic optical base material) containing the photochromic compound is one in which a photochromic compound is dispersed inside the base material or a photochromic coating layer in which the photochromic compound is dispersed is formed on the base material surface. May be. More specifically, the coating composition of the present invention is suitable for forming a hard coat layer of a photochromic lens obtained by kneading a polymerization curable composition containing the (meth) acrylate monomer and a photochromic compound. Can be used. In addition, a hard coat layer is formed by applying a polymerization curable composition containing the (meth) acrylate monomer and a photochromic compound to the surface of a plastic optical substrate and then curing to form a photochromic coat layer. Can be suitably used.

  In addition, since the photochromic coating layer usually contains a large amount of photochromic compound, the plastic optical substrate may have a low weather resistance (such as yellowing after long-term use). By forming a hard coat layer comprising the coating composition on the photochromic coat layer, the weather resistance can 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, the color tone of the dyed lens changes when used for a long time. Furthermore, there is a problem that the adhesion between the hard coat layer and the plastic lens base material is remarkably lowered due to the deterioration of the dye, but the coat layer made of the coating composition of the present invention is laminated to give the ultraviolet absorbing ability. By doing so, it is possible to suppress problems such as the above-described change in color tone and a decrease in adhesion.

  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, these optical base materials tend to have the lowest weather resistance adhesion particularly of the hard coat layer. 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, the manufacturing method of the optical article which apply | coats the coating agent obtained by the said method on the plastic optical base material, and has a hard-coat layer is demonstrated.

<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 dipping, spin coating, dip spin coating, spraying, brushing or roller coating.

  Drying after coating is performed by first performing preliminary curing at 60 to 80 ° C. for about 5 to 30 minutes, and then performing curing for about 1 to 3 hours at a temperature of 90 to 120 ° C., depending on the substrate. Is good. 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 chemical resistance and hot water resistance, and even if it is brought into contact with a chemical (particularly an alkaline aqueous solution) or warm water, it is possible to improve the occurrence of cracks or the decrease in adhesion.

  Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples.

  The optical substrate (lens substrate) and each component used in this example will be described.

(1) Plastic optical substrate (lens substrate)
CR: allyl resin plastic lens, refractive index = 1.50.
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.
TE: Thioepoxy resin plastic lens, refractive index = 1.71.
PC1: A lens (photochromic optical substrate) having a coating layer made of a methacrylic resin on the surface of a plastic lens substrate.

[Production method of PC1 Photochromic optical substrate by coating method]
2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane / polyethylene glycol diacrylate (average molecular weight 532) / trimethylolpropane trimethacrylate / polyester oligomer hexaacrylate / glycidyl having an average molecular weight of 776 which is a radical polymerizable monomer Methacrylate was 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 photochromic compound (1) was added to 100 parts by weight of the radical polymerizable monomer mixture, and ultrasonic dissolution was performed at 70 ° C. for 30 minutes. Thereafter, a mixture of the polymerization initiator CGI1870: 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (weight ratio 3) was added to the obtained composition. 7) 0.35 parts by mass, stabilizer bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 5 parts by mass, triethylene glycol-bis [3- (3-t -Butyl-5-methyl-4-hydroxyphenyl) propionate, 3 parts by mass, 7 parts by mass of γ-methacryloyloxypropyltrimethoxysilane, which is a silane coupling agent, and silicone produced by Toray Dow Corning Co., Ltd., which is a leveling agent 0.1 part by mass of a surfactant L-7001 and mixing thoroughly, photochromic The polymerizable curable composition was prepared.

  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, it was dried at 70 ° C. Next, as a primer coating solution, the moisture curing type primer “Takeseal PFR402TP-4” manufactured by Takebayashi Chemical Industry Co., Ltd. and ethyl acetate are prepared to be 50 parts by mass, respectively, and Toray Dow Corning Co., Ltd. is further added to this mixed solution. 0.03 parts by mass of a company leveling agent FZ-2104 was added, and a liquid that was sufficiently stirred until uniform in a nitrogen atmosphere was used. This primer solution was spin-coated on the surface of the lens B 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-mentioned photochromic polymerization curable composition was spin-coated on the surface of the lens substrate having the primer layer. D manufactured by Fusion UV Systems Co., Ltd., adjusted so that the output at 405 nm of the lens surface was 150 mW / cm ² in a nitrogen gas atmosphere on a lens coated with a coating film comprising the photochromic polymerization curable composition. Using F3000SQ equipped with a valve, light was irradiated for 3 minutes to cure the coating film. 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 [component A; inorganic oxide fine particles containing cerium oxide (A)]
A2 (1): A methanol-dispersed sol of composite metal oxide fine particles containing 11.7% by mass of zirconium oxide, 77.6% by mass of tin oxide, 7.0% by mass of antimony oxide, and 3.7% by mass of silicon dioxide. Solid content concentration (concentration of composite metal oxide fine particles) 40% by mass.
A2 (2): Methanol-dispersed antimony pentoxide fine particles (Sun colloid AMT-332S · NV manufactured by Nissan Chemical Industries, Ltd., solid content (concentration of antimony pentoxide fine particles); 30% by mass
A2 (3): Water-dispersed silica fine particles (Snowtex O-40 manufactured by Nissan Chemical Industries, Ltd., solid content concentration (silica fine particle concentration); 40% by mass)
A1: Water-dispersed cerium oxide fine particles (Nidral U-15, manufactured by Taki Chemical Co., Ltd., solid content (concentration of cerium oxide fine particles): 15% by mass, containing 3% by mass of acetic acid)
[Component B; hydrolyzable group-containing organosilicon compound]
(B1 component): Disilane compound BSE: 1,2-bis (triethoxysilyl) ethane.
In addition, as a comparison of the component (B1),
BSH: 1,6-bis (triethoxysilyl) hexane.
Was used.
(B2 component): Epoxy group-containing hydrolyzable organosilicon compound GDS: γ-glycidoxypropylmethyldimethoxysilane.
(B3 component): Epoxy group-containing hydrolyzable organosilicon compound GTS: γ-glycidoxypropyltrimethoxysilane.

[C component; water]
A 0.001N to 1N aqueous hydrochloric acid solution was used.

[D component; curing catalyst]
Complex D1 having aluminum as a central metal: Tris (2,4-pentanedionato) aluminum (III).

[E component; water-soluble organic solvent]
MeOH: methanol.
TBA: t-butanol.
DAA: diacetone alcohol.
EGiPrE: ethylene glycol isopropyl ether.
AcAc: acetylacetone.

[Other additives]
Silicone surfactant L1: Silicone surfactant L7001 manufactured by Toray Dow Corning Co., Ltd.
Cyclic ketone compound NMP: N-methylpyrrolidone.

Production of coating agent 1 (coating agent 1 obtained from composition 1)
γ-glycidoxypropyltrimethoxysilane 42.96 parts by mass, γ-glycidoxypropylmethyldimethoxysilane 4.79 parts by mass, 1,2-bis (triethoxysilyl) ethane 10.19 parts by mass, silicone-based interface Activator (silicone surfactant L7001 manufactured by Toray Dow Corning Co., Ltd.) 0.28 parts by mass, 55.50 parts by mass of diacetone alcohol, 16.87 parts by mass of t-butyl alcohol, 0.82 parts by mass of N-methylpyrrolidone The parts were mixed. While sufficiently stirring this liquid, a mixed liquid of 17.84 parts by mass of 0.038N hydrochloric acid aqueous solution and 27.45 parts by mass of water-dispersed cerium oxide fine particles (Nidaral U-15 manufactured by Taki Chemical Industry, solid content: 15% by mass). After the addition was completed, stirring was continued at 15 to 30 ° C. for 20 hours. Next, after adding 3.01 parts by mass of tris (2,4-pentanedionato) aluminum (III), the mixture was stirred for 1 hour at 20 to 25 ° C. (Composite inorganic oxide fine particles 37.94 parts by mass, methanol 56.91 parts by mass) were mixed and stirred for 24 hours to obtain coating agent 1. It should be noted that the hydrolysis of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and 1,2-bis (trimethoxysilyl) ethane indicates that the hydrolysis was completed by gas chromatography. confirmed. Table 1 shows the amount of each component (the amount of composition 1) before the coating agent 1 was prepared. In addition, what mixed the thing of the mixture ratio of the composition 1 in Table 1 by the said method corresponds to the coating agent 1. FIG.

Production of Coating Agents 2-24, 26, Comparative Coating Agents 1-7 (Coating Agents 2-24, 26 Obtained from Compositions 2-24, 26, and Comparative Coating Agents 1- 1 Obtained from Comparative Compositions 1-7 7)
A component shown in Tables 1 to 5; inorganic oxide fine particles, B component; hydrolyzable group-containing organosilicon compound, C component; water, D component; curing catalyst, E component; water-soluble organic solvent, additive; It was produced by the same method as coating agent 1 except that a surfactant and a cyclic ketone compound were used. The composition of the formulation is shown in Tables 1-5. In addition, what mixed the thing of the mixing | blending ratio of the compositions 2-24 and 26 in Table 1-Table 5 by the said method corresponds to the coating agents 2-24,26. Moreover, what mixed the thing of the comparative compositions 1-7 by the said method corresponds to the comparative coating agents 1-7.

Coating agent 25
(Coating agent 25 obtained from composition 25)
γ-glycidoxypropyltrimethoxysilane 54.20 parts by mass, γ-glycidoxypropylmethyldimethoxysilane 5.39 parts by mass, silicone surfactant (silicone surfactant Toray Dow Corning L7001) 0.29 parts by mass, 13.19 parts by mass of t-butyl alcohol, and 1.17 parts by mass of N-methylpyrrolidone were mixed. While sufficiently stirring this liquid, a mixed liquid of 31.06 parts by mass of water-dispersed cerium oxide fine particles (Nidaral U-15 manufactured by Taki Chemical Industry Co., Ltd., solid content: 15% by mass) was added, and then water-dispersed silica fine particles (A2 (3), Nissan Chemical Industries, Ltd. Snowtex O-40, solid content concentration: 40% by mass) 52.73 parts by mass of a mixed solution was added, and after the addition was completed, the mixture was added at 15-20 ° C. for 12-24 hours. Stirring was continued. Subsequently, a mixed solution of 2.46 parts by mass of tris (2,4-pentanedionato) aluminum (III), 9.97 parts by mass of ethylene glycol isopropyl ether, 13.19 parts by mass of acetylacetone, and 44.44 parts by mass of methanol was added. Thereafter, the mixture was stirred at 20 to 25 ° C. for 3 hours to obtain a coating agent 25. Note that the hydrolysis of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and 1,2-bis (trimethoxysilyl) ethane indicates that the hydrolysis was completed by gas chromatography. confirmed. Table 4 shows the blending amount of each component (the blending amount of the composition 25) before making the coating agent 25. In addition, what mixed the thing of the mixture ratio of the composition 25 in Table 4 by the said method corresponds to the coating agent 25. FIG.

実施例１
厚さが約２ｍｍの光学基材（レンズ基材）ＣＲを、５０℃の１０質量％水酸化ナトリウム水溶液に浸漬し、超音波洗浄器を用いて、５分間アルカリエッチングを行った。アルカリエッチング後、水道水、及び５０℃の蒸留水で順次洗浄し、残余のアルカリ分を取り除いた後、室温になるまで約１０分間放置した。このレンズ基材に、コーティング剤１を２５℃で、引き上げ速度１５ｃｍ／分の速さで、ディップコートした。この後、７０℃のオーブンにて１５分間予備硬化した後、１１０℃で２時間の硬化を行い、光学基材（レンズ基材）ＣＲの両面に、それぞれ２．８μｍの厚みでハードコート層が形成された光学物品（ハードコートレンズ）を得た。

Example 1
An optical substrate (lens substrate) CR having a thickness of about 2 mm was immersed in a 10% by mass aqueous sodium hydroxide 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 on each side of the optical substrate (lens substrate) CR with a thickness of 2.8 μm. A formed optical article (hard coat lens) was obtained.

(Evaluation results of optical articles)
When this optical article (hard coat lens) was evaluated for alkali resistance test, heat resistance test, yellowness (YI), Bayer test, steel wool scratch resistance, weather resistance adhesion, alkali resistance test: alkali concentration 1 0.0 wt%, temperature of occurrence of cracks due to thermosetting: 140 ° C. or higher, hot water resistance: 3 hours, Bayer value: 6.5, steel wool scratch resistance: A, weather resistance adhesion: 400 hours or more. The results are shown in Table 6. About each evaluation, it performed by the following method.

(Alkali resistance test)
The obtained optical article (hard coat lens) was immersed in a 0.1 mass% (0.1 wt%) sodium hydroxide aqueous solution at 50 ° C., and ultrasonic waves were applied for 5 minutes using an ultrasonic cleaner. Next, this alkali-treated lens is immersed in ion-exchanged water at 50 ° C. and subjected to ultrasonic waves for 5 minutes using an ultrasonic cleaner, and then the appearance of the hard coat film (the presence or absence of cracks and peeling of the hard coat film) ) Was evaluated visually. If no crack was confirmed, the concentration of sodium hydroxide was increased by 0.1% by mass, and the same alkali treatment and ion exchange water treatment were carried out until an appearance defect occurred. The evaluation result was shown by the density | concentration of the sodium hydroxide aqueous solution processed at the end when a crack was confirmed. For example, when 0.3 wt% is described in the table, the optical article (hard coat lens) is further treated with 0.1 wt% sodium hydroxide aqueous solution treatment, then with 0.2 wt% sodium hydroxide aqueous solution treatment, and further with a. This means that cracking or peeling of the hard coat film was confirmed for the first time after treatment with a 3 wt% sodium hydroxide aqueous solution.

(Heat resistance test)
In the test method, 10 optical articles (hard coat lenses) obtained were heated in a forced convection oven at 115 ° C. to 140 ° C. every 5 ° C. for 1 hour. The evaluation result described the temperature at which cracks were generated by heating even one sheet, and when cracks were not confirmed in a heating test at 140 ° C. for 1 hour, it was described as 140 ° C. or higher. Those having a high temperature are less likely to cause cracks due to shrinkage of the coating layer and expansion of the plastic lens, and can be judged as a coating composition having good moldability.

(Heat resistance test)
In the test method, 10 optical articles (hard coat lenses) obtained were placed in boiling distilled water, and the presence or absence of cracks in the hard coat lenses was visually evaluated every hour, and the test time was 3 hours.

  The evaluation result described the test time when crack generation was confirmed by hot water even with one sheet. For example, when occurrence of a crack was confirmed at a test time of 2 hours, it was expressed as 2 hours, and when no crack was confirmed even after 3 hours of the upper limit of the test time, it was expressed as 3 hours or more.

(Yellowness measurement)
In the test method, the yellowness (YI) of the obtained optical article (hard coat lens) was determined using an SM color computer (SM-T) manufactured by Suga Test Instruments Co., Ltd.

(Bayer test)
Based on the Bayer test method (ASTM D-4060 or ASTM F735-81), the surface of the lens substrate (non-coated lens) on which the hard coat layer is not formed and the surface of the hard coat layer formed on the lens substrate (hard The surface of the coated lens was scratched by the following method.

  That is, a non-coated lens and a hard-coated lens were mounted on an abrasive holding body having two Φ50 mm holes from below the holes, with their convex surfaces facing upward. Next, 500 g of a commercially available abrasive (abrasive made of alumina-zirconia manufactured by SAINT-GOBAIN CERAMIC MATERIALS CANADA INC.) Was put in an abrasive holder, and two lenses mounted in this state were 150 per minute. The surface of the two lenses was scratched by oscillating at a stroke frequency for a total of 2 minutes with a stroke width of 4 inches.

  Next, for these lenses, the haze was measured with a spectrometer (Haze meter manufactured by Suga Test Instruments Co., Ltd.), and the difference between the haze values before and after scratching was obtained. Was calculated.

Bayer value = ΔHaze (non-coated) / ΔHaze (hard-coated)
In the formula, ΔHaze (non-coated) is a value obtained by subtracting the Haze value before the test from the Haze value after the test for the non-coated lens. The value obtained by subtracting the previous Haze value. The larger the value, the higher the surface hardness and the better the scratch resistance. Usually, the hardness is 4 or higher, the hardness is comparable to glass at 6 or higher, and the scratch resistance is remarkably excellent. means.

(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 10 times while applying a load of 3 kg, and the degree of damage was visually evaluated. The evaluation criteria are as follows.
A: It is not scratched or not attached (when the scratch 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.
Further, when the surface of the hard coat layer became cloudy (ground glass) due to the fragile outermost layer, it was also written as “Suri”.

(Weather resistance adhesion test)
The obtained optical article (hard coat lens) was used under the conditions of a radiation intensity of 40 W / m ² and a lens surface temperature of 50 ° C. using a xenon weather meter X25 (2.5 kW xenon arc lamp) manufactured by Suga Test Instruments Co., Ltd. The test was conducted for up to 400 hours below.

  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 25 hours of the test. That is, a cutter knife is used to cut 100 squares on the hard coat film surface at intervals of about 1 mm. A cellophane pressure-sensitive adhesive tape (cello tape (registered trademark) manufactured by Nichiban Co., Ltd.) was strongly pasted thereon, and then pulled from the surface in a 90 ° direction and peeled off at a stretch. Then, the square where the hard coat film remained was measured.

  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 400 hours was 90 or more, it was described as 400 hours or more.

  The above results are shown in Table 6.

Examples 2-49
Using the coating agents 2 to 26 obtained from the compositions shown in Tables 1 to 4 and an optical substrate (lens substrate), 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 Tables 6-8.

Comparative Examples 1-8
Using the comparative coating agents 1 to 7 obtained from the comparative compositions shown in Table 5 and the optical substrate (lens substrate), a hard coat lens having a hard coat layer was produced in the same manner as in Example 1. And evaluated. Further, Comparative Example 7 was not evaluated except for the heat resistance test because there was no initial adhesion. The evaluation results are shown in Table 9.

Example 50
The photochromic optical substrate PC1 was immersed in a 20 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 on each side of the optical substrate (lens substrate) CR with a thickness of 2.8 μm. A formed optical article (hard coat lens) was obtained.

(Evaluation results of optical articles)
When this optical article (hard coat lens) was evaluated for Bayer test, alkali resistance test, yellowing degree (ΔYI), and steel wool scratch resistance, Bayer value was 7.6, alkali resistance test: alkali concentration 1 0.0 wt%, yellowing degree (ΔYI): 1.5, and steel wool scratch resistance: A ′. The results are shown in Table 10.

(Evaluation of weather resistance test ΔYI)
Since the optical base material (lens PC1) having a photochromic coating layer contains a large amount of the photochromic compound on the coating layer, the weather resistance may be inferior. However, when a hard coat layer comprising the coating composition of the present invention is formed on the photochromic coat layer, the weather resistance can be improved. This weather resistance was evaluated by the following method.

A lens having a photochromic coating layer of a sample under the conditions of a radiation intensity of 40 W / m ² and a lens surface temperature of 50 ° C. using a xenon weather meter X25 (2.5 kW xenon arc lamp) manufactured by Suga Test Instruments Co., Ltd. The lens using PC1 was irradiated with light for 100 hours to accelerate deterioration.

Next, using SM color computer (SM-T) manufactured by Suga Test Instruments Co., Ltd., YI (YI ₀ ) before accelerated deterioration and YI (YI ₁₀₀ ) after accelerated deterioration were measured. And yellowing was evaluated.
Yellowing degree (ΔYI) = YI ₁₀₀ −YI ₀
The smaller the degree of yellowing (ΔYI), the lower the degree of yellowing of the lens after deterioration, and the better the weather resistance. The results are shown in Table 9.

Examples 51-54
Using the coating agents 1 and 6 to 9 obtained from the compositions shown in Tables 1 and 2 and the photochromic optical substrate PC1, plastic lenses having a hard coat layer were produced in the same manner as in Example 50. The evaluation was performed. The evaluation results are shown in Table 9.

Comparative Example 9
Using the comparative coating agent 3 obtained from the comparative composition 3 and the photochromic optical substrate PC1, a plastic lens having a hard coat layer was produced in the same manner as in Example 50 and evaluated. The evaluation results are shown in Table 10.

As is apparent from the above examples, the weather resistance adhesion can be obtained by blending the disilane compound (B1) represented by the formula (1), cerium oxide, and further the components (B2) and (B3) at a desired ratio. It was possible to form a hard coating layer having high hardness having alkali resistance, hot water resistance and heat resistance. On the other hand, in Comparative Examples 1-7, since it remove | deviated from a suitable composition, it was not able to satisfy at least 1 or more physical property of a weather-resistant adhesiveness, alkali resistance, hot water resistance, heat resistance, and hardness.

  Furthermore, when a photochromic optical substrate by a coating method was used, weather resistance adhesion, alkali resistance, hot water resistance, and heat resistance were satisfied, and yellowing of the lens after the weather resistance test could be reduced.

Claims (9)

20.00 parts by mass to 60.00 parts by mass of inorganic oxide fine particles (A) containing cerium oxide,
Following formula (1)

(Where
R ¹ is a methyl group or an ethyl group,
X is a C2-C3 alkylene group. )
A hard coat layer forming coating composition containing 40.00 parts by mass to 80.00 parts by mass of a hydrolyzable organosilicon compound (B) containing a disilane compound (B1) represented by:
The total amount of the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B) is 100 parts by mass,
The 0.25 weight parts to 15.00 parts by mass of cerium oxide, and the disilane compound (B1) 3.50 part by mass to look 25.00 parts by <br/> containing the hydrolyzable organic silicon compound ,
Following formula (2)

{Where,
R ² is an alkyl group having 1 to 3 carbon atoms,
R ³ represents the following formula (3)

(Where
R ⁵ is an alkylene group having 1 to 8 carbon atoms. Or a group represented by the following formula (4)

(Where
R ⁶ is an alkylene group having 1 to 8 carbon atoms. )
R ⁴ is an alkyl group having 1 to 3 carbon atoms, and each R ⁴ may be the same group or a different group. }
An epoxy group-containing organosilicon compound (B2) represented by:
Following formula (5)

(Where
R ³ and R ⁴ have the same meaning as in the formula (2). )
An epoxy group-containing organosilicon compound (B3) represented by the formula (1), with respect to 1 mol of the disilane compound (B1):
0.30 to 3.00 mol of an epoxy group-containing organosilicon compound (B2) represented by the formula (2),
2.50 to 20.00 mol of the epoxy group-containing organosilicon compound (B3) represented by the formula (5)
Coating composition characterized contains Mukoto. The coating composition according to claim 1, wherein the inorganic oxide fine particles (A) do not contain titanium oxide. The coating composition according to claim 1 or 2 , wherein the inorganic oxide fine particles (A) include cerium oxide fine particles (A1) and first inorganic oxide fine particles (A2) other than the cerium oxide fine particles. object. From 100 parts by mass of the total amount of the inorganic oxide fine particles (A) and the hydrolyzable organosilicon compound (B), 20.00 parts by mass to 70.00 parts by mass of water (C), and a curing catalyst (D) The coating according to any one of claims 1 to 3 , comprising 0.20 parts by mass to 5.00 parts by mass and 60.00 parts by mass to 180.00 parts by mass of a water-soluble organic solvent (E). Composition. By mixing the coating composition according to any one of claims 1-4, a method for producing a coating agent,
The inorganic oxide fine particles (A) are composed of cerium oxide fine particles (A1) and first inorganic oxide fine particles (A2),
As the cerium oxide fine particles (A1), cerium oxide fine particles dispersed in an acid aqueous solution are used, and the hydrolyzable organosilicon compound (B) and the cerium oxide fine particles (A1) dispersed in the acid aqueous solution are mixed. Then, after hydrolyzing the hydrolyzable organosilicon compound (B), the obtained mixture and the curing catalyst (D) are mixed, and then the first inorganic oxide fine particles (A2) are mixed. The manufacturing method of the coating agent characterized. An optical article having a hard coat layer obtained by curing the coating composition according to any one of claims 1 to 4 on a plastic optical substrate. The optical article according to claim 6 , 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 7 , wherein a hard coat layer is formed thereon. The optical article according to claim 6 , wherein the plastic optical substrate is an optical substrate containing a dye.