JP4757795B2 - Laminated body - Google Patents

Description

  The present invention relates to a laminate in which a cured product layer of a coating composition is formed on the surface of a thiourethane resin substrate or an allyl resin substrate, and more specifically, adhesion, scratch resistance, weather resistance, etc. It is related with the laminated body which is excellent in and suitable as a spectacle lens.

  Synthetic resin lenses have characteristics that are not found in glass lenses, such as lightness, safety, ease of processing, and fashionability, and have been rapidly spreading in recent years, but have the disadvantage of being easily scratched. In general, a silicone-based coat layer (called a so-called hard coat layer) is provided on the surface.

  Conventionally, such a silicone-based coating layer is obtained by applying a coating composition mainly composed of silica fine particles, a polymerizable organic silane compound, a polymerization catalyst, an acid aqueous solution, and a solvent to the surface of a synthetic resin lens and heating. The composition was cured and the solvent was volatilized (see, for example, Japanese Patent Publication No. 57-2735). However, the hard coat layer formed by curing such a coating composition has a low refractive index, and when formed on the surface of a synthetic resin lens having a high refractive index, it interferes with the difference in refractive index from the synthetic resin lens. There is a problem that streaks are generated, resulting in poor appearance, and there is a need for improvement.

  In order to solve this problem, various coating compositions for forming a hard coating layer having a high refractive index have been proposed. For example, silica fine particles blended in the coating composition described above can be used in various types having a high refractive index. A coating composition in which the composite metal oxide is replaced with a coating composition, specifically, the following coating composition has been proposed.

(1) Coating composition replaced with composite metal oxide containing Sb, Ti, Zr, Sn, etc. (Japanese Patent Laid-Open No. 5-264805)
(2) Coating composition replaced with composite oxide containing Ti, Ce, Sn, etc. (Japanese Patent Laid-Open No. 10-245523)
(3) Coating composition replaced with composite metal oxide containing Ti, Sn and Zr (Japanese Patent Laid-Open No. 9-49215)
(4) Coating composition replaced with composite metal oxide containing Ti and Sb (Japanese Patent Laid-Open No. 2002-363442)
(5) Coating composition replaced with composite metal oxides such as Sn, Zr, W, and Si (Japanese Patent Laid-Open No. 2000-281973)

  However, the coating compositions using the composite metal oxides of Patent Documents 1 to 5 have high sensitivity to moisture, and thus a phenomenon that the formed hard coat layer is whitened (white turbidity) is observed. Moreover, the weather resistance (or durability) of the hard coat layer to be formed is low, and there arises a problem that, for example, the adhesion between the hard coat layer and the synthetic resin lens is lowered with time.

  Therefore, the present invention is a laminate in which a cured product layer of a coating composition is formed on the surface of a resin substrate, and whitening (white turbidity) of the cured product layer due to moisture is effectively suppressed, and weather resistance An object of the present invention is to provide a laminate that is excellent in properties and in which a decrease in adhesion with time is effectively suppressed.

The present inventors have intensively studied to solve the above problems. As a result, a thiourethane resin base or an allyl resin base was selected as the resin base, and a composite metal oxide composed of tin oxide and zirconium oxide was coated with antimony pentoxide and silicon oxide as the coating composition. By using composite metal oxide fine particles that do not contain titanium and those containing other specific components, by combining such a resin base material with a coating composition, whitening of the cured layer caused by moisture (white turbidity) ) Is suppressed, and a laminate having excellent weather resistance or durability can be obtained, and the present invention has been completed.

That is, according to the present invention, in the laminate in which the cured product layer of the coating composition is formed on the resin substrate surface,
The coating composition comprises the following components (A) to (D):
(A) Composite metal oxide fine particles not containing titanium oxide , coated with a composite metal oxide composed of tin oxide and zirconium oxide with antimony pentoxide and silicon oxide ;
(B) an epoxy group-containing silicon compound or a partial hydrolyzate thereof;
(C) an organic solvent;
(D) an acetylacetonate complex;
And a laminated body characterized in that the resin substrate is a thiourethane resin substrate or an allyl resin substrate.

  In the laminate of the present invention, the coating composition comprises 25 to 250 parts by mass of the composite metal oxide fine particles of the component (A) per 100 parts by mass of the component (B), and the organic solvent of the component (C). 100 to 2500 parts by mass and the acetylacetonate complex of the component (D) is preferably contained in an amount of 0.1 to 15 parts by mass.

  The laminate of the present invention is useful as a plastic lens, but particularly when used for plastic lenses, the refractive index of the thiourethane resin substrate or the allyl resin substrate is 1.55 or more, or It is preferable that the urethane resin base material or the allyl resin base material contains a pigment.

  According to the present invention, the coating composition containing the components (A) to (D) is applied to the surface of the thiourethane resin substrate or the allyl resin substrate, and heated to a temperature of 80 ° C. or higher. There is provided a method for producing a laminate, wherein the coating composition is cured to form a cured product layer.

  The laminate of the present invention has a characteristic that the cured product layer of the above coating composition is formed on the surface of the thiourethane resin substrate or the allyl resin substrate, so that the sensitivity to moisture is low and the weather resistance is excellent. For example, even when the coating composition is applied under high humidity or in a state of absorbing water, a transparent cured product layer without white turbidity can be obtained. In addition, as shown in the examples described later, even after a long time (200 hours) deterioration acceleration test, the adhesiveness does not deteriorate between the cured product layer and the resin base material, and high adhesiveness is achieved. Is retained. Thus, the laminate of the present invention is extremely excellent with respect to both moisture sensitivity and weather resistance.

  For example, when a cured product layer is formed on the surface of a thiourethane resin substrate or an allyl resin substrate using a coating composition of another composition, the sensitivity to moisture is low and the cured product layer becomes cloudy due to the influence of moisture. However, the weather resistance is poor, and the adhesion between the cured product layer and the resin base material is greatly reduced after the deterioration acceleration test. Moreover, even if it uses the coating composition containing (A)-(D) component, when using resin bases other than a thiourethane resin base material and an allyl resin base material, for example, a polycarbonate resin base material, The surface of the polycarbonate resin base material is dissolved by contact with the epoxy group-containing silicon compound which is component B) or a partial hydrolyzate thereof, and the resin base material itself is slightly clouded. In addition, the solvent resistance, scratch resistance, and adhesion are insufficient, making it unsuitable for use as a plastic lens.

  In addition, in this invention, the presence or absence of the cloudiness (or whitening) of a laminated body is observed visually by irradiating light to a laminated body along the layer direction of a hardened | cured material layer. When light is irradiated in the direction perpendicular to the layer direction of the cured product layer, the white turbid layer is very thin, so the optical path of the light passing through the white turbid layer is extremely short. Because you can't.

  As described above, the laminate of the present invention is excellent in both moisture sensitivity characteristics and weather resistance, and excellent characteristics such as transparency, adhesion, and scratch resistance are maintained over a long period of time, particularly as a plastic lens. , Its industrial value is high.

[Coating composition]
The coating composition used for manufacturing the laminate of the present invention contains the components (A) to (D) described above.

<(A) component>
The component (A) is a composite metal oxide fine particle containing no titanium oxide, in which a composite metal oxide composed of tin oxide and zirconium oxide is coated with antimony pentoxide and silicon oxide . The composite metal oxide fine particles are usually used in a colloidal dispersion using water, an alcohol-based or other organic solvent as a dispersion medium.

  Such composite metal oxide fine particles contain 70 to 99 mass% of the composite metal oxide composed of tin oxide and zirconium oxide, and 1 to 30 mass% in total of antimony pentoxide and silicon oxide. More preferably, tin oxide is 50 to 96% by mass, zirconium oxide is 3 to 49% by mass, antimony pentoxide is 1 to 29.9% by mass, and silicon oxide is 0.1 to 29% by mass. It is good to contain.

  The composite metal oxide fine particles may contain a trace amount of other metal oxide components other than tin and zirconium, but are preferably substantially free of titanium oxide. Titanium oxide has a high sensitivity to moisture, tends to cause whitening of the cured product layer of the coating composition, and tends to reduce the weather resistance of the cured product layer.

  As the dispersion medium for the composite metal oxide fine particles, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, t-butyl alcohol, and n-butyl alcohol are preferable, and methanol and 2-propanol are particularly preferable. In addition, the ratio of the composite metal oxide fine particles in the dispersion medium at this time increases the refractive index of the cured layer of the coating composition, and the composite metal oxide fine particles become unstable in the dispersion medium. In order to prevent this, 10 mass%-50 mass% are preferable.

  Moreover, in order to improve dispersion stability, it is also possible to use the composite metal oxide fine particles whose surface is treated with an amine compound and / or carboxylic acid. Examples of amine compounds used here include ammonium or ethylamine, triethylamine, isopropylamine, n-propylamine, dimethylamine, diethylamine, diisopropylamine, dipropylamine and other alkylamines, benzylamine and other aralkylamines, morpholine, piperidine and the like. Examples thereof include alkanolamines such as alicyclic amine, monoethanolamine, diethanolamine, triethanolamine, and isopropanolamine. Examples of the carboxylic acid include acetic acid, oxalic acid, lactic acid, malic acid, citric acid, tartaric acid, salicylic acid, glycolic acid, benzoic acid, phthalic acid, malonic acid, and mandelic acid. Such a surface treatment agent is preferably in the range of 0.01 to 5 parts by mass per 100 parts by mass of the composite metal oxide fine particles.

  The particle diameter of the composite metal oxide fine particles is not particularly limited, but the average particle diameter is preferably in the range of 1 to 300 nm in order not to impair the transparency of the obtained cured product layer.

  As described above, the composite metal oxide fine particles are generally used as a dispersion liquid dispersed in a dispersion medium, and the dispersion liquid pH is preferably 4.0 to 9.5. By setting the pH within such a range, it is possible to prevent a decrease in the transmittance of the dispersion liquid due to a decrease in the dispersibility of the composite metal oxide fine particles, and a storage stability of the coating composition due to a decrease in the dispersion stability of the composite metal oxide fine particles. The fall of property can be prevented.

  The compounding amount of the composite metal oxide fine particles described above may be appropriately determined depending on the composition ratio of the metal oxide and the desired physical properties according to the purpose of the finally obtained cured product layer. (Group-containing silicon compound or partial hydrolyzate thereof) It is preferably in the range of 25 to 250 parts by mass, particularly 40 to 200 parts by mass, per 100 parts by mass. When the composite metal oxide fine particles are used in the above range, the amount of the composite metal oxide fine particles is 20 to 70 parts by mass, particularly 30 to 65 parts by mass, per 100 parts by mass of the finally formed cured product layer. Become. If the amount of the composite metal oxide fine particles per cured product layer is less than 20 parts by mass, the scratch resistance of the cured product layer, the refractive index of the cured product layer, and the like may be insufficient. Moreover, when forming an inorganic vapor deposition film (antireflection film) on a hardened | cured material layer, there exists a possibility that adhesiveness with this vapor deposition film may also fall. Furthermore, when the amount of the composite metal oxide fine particles per 70 parts by mass exceeds 70 parts by mass, the cured product layer tends to crack.

  The mass of the cured product layer finally formed is the mass of the composite metal oxide fine particles, (B) an epoxy group-containing silicon compound described later or a partial hydrolyzate thereof, and further blended as necessary ( It is the total mass of solid content when the organosilicon compound other than B) and further the epoxy compound are polymerized and condensed. Since the organic solvent such as methanol added to the coating composition volatilizes during the formation of the cured product layer, it is not included in the mass of the finally obtained cured product layer.

<(B) component>
The epoxy group-containing silicon compound of component (B) has a function as a binder, and as such an epoxy group-containing silicon compound, a known compound per se can be used without any limitation. Specific examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane and those partially or wholly hydrolyzed or partially condensed. Among these, from the viewpoint of adhesion to a thiourethane resin substrate or an allyl resin substrate described later, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and some or all of these It is preferable to use a hydrolyzed or partially condensed product. In addition, an epoxy group containing silane compound may use only 1 type, or may use 2 or more types together.

  What is necessary is just to determine suitably the compounding quantity of the said epoxy-group containing silicon compound according to the physical property etc. which are desired according to the objective of the hardened | cured material layer finally obtained, and it is 30-per 100 mass parts of hardened | cured material layers finally formed. It is preferable that it is 80 mass parts, and also 35-70 mass parts. If the amount of the epoxy group-containing silicon compound is less than 30 parts by mass, the cured product layer tends to crack, and if it exceeds 80 parts by mass, the scratch resistance and refractive index tend to be insufficient. When forming an inorganic vapor deposition film on a physical layer, there exists a possibility that both adhesiveness may fall.

<(C) component>
The (C) component organic solvent dissolves the (B) epoxy group-containing silicon compound and the binder component (for example, an organosilicon compound) other than the component (B) blended as necessary, and the composite metal oxide. A known organic solvent can be used without any limitation as long as it is a solvent that can disperse fine particles well and has volatility. Examples of such organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and n-pentanol; methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, acetoacetic acid Esters such as methyl, ethyl acetoacetate and ethyl lactate; ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether Ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and dioxane; ketones such as acetone, acetylacetone and diacetone alcohol; halogenated hydrocarbons such as methylene chloride; hexane, heptane, cyclohexane, benzene, toluene, Hydrocarbons such as xylene; and the like. These organic solvents may be used alone, but it is preferable to use a mixture of two or more kinds for the purpose of controlling the physical properties of the coating composition.

  In addition, (B) the epoxy group-containing silicon compound and the solubility in an acid aqueous solution used for the purpose of hydrolyzing an organosilicon compound used as a binder component other than (B), easy formation of a cured product layer Among these organic solvents, it is preferable to use methanol, isopropanol, t-butanol, acetylacetone, diacetone alcohol, ethylene glycol monoisopropyl ether, etc., from the viewpoint of forming a hardened layer smoothly. It is.

  Although the usage-amount of an organic solvent is not specifically limited, Usually, it is preferable to use it so that the total amount may become the range of 100-2500 mass parts per 100 mass parts of said (B) component, especially 140-1500 mass parts. . (In the case where alcohol or the like is used as a dispersion medium for the composite metal oxide fine particles of the component (A) described above, the amount of such a dispersion medium is also included in the amount of the organic solvent.)

<(D) component>
The (D) component acetylacetonate complex is used as a curing catalyst for the epoxy group-containing silicon compound (B) described above, and is soluble in the coating composition and storage stability of the coating composition. A known material can be used without any limitation as long as it is appropriately selected in consideration of physical properties such as hardness of the formed cured product layer. Specific examples thereof include Li (I), Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III ), Mn (III), La (III), Cr (III), V (III), Co (III), Fe (III), Al (III), Ce (IV), Zr (IV), V (IV ) And the like as the central metal atom. Particularly preferred is an acetylacetonate complex having Al (III), Fe (III), or Li (I) as a central metal. These acetylacetonate complexes may be used alone or in combination of two or more without any problem.

  Although the addition amount of said acetylacetonate complex is not specifically limited, It is 0.1-15 mass parts per 100 mass parts of said (B) component, It is preferable that it is 0.2-10 mass parts especially. Moreover, it is more preferable that it is 0.01-5.0 mass parts with respect to 100 mass parts of hardened | cured material layers finally formed, especially the range of 0.1-3.0 mass parts.

<Other ingredients>
In the coating composition used in the present invention, various components can be blended in addition to the components (A) to (D) described above as long as excellent properties such as moisture sensitivity and weather resistance are not impaired. .
For example, an organosilicon compound or an epoxy compound other than the component (B) described above can be blended as the binder component.

  Such organosilicon compounds include tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxy. Silane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyl Triethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, 1,6-bistrimethoxysilane, 3-ureidopropyl Riethoxysilane, trifluoropropyltrimethoxysilane, perfluorooctylethyltriethoxysilane, γ-chloropropyltrimethoxysilane, vinyltri (β-methoxy-ethoxy) silane, allyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane Γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldimethoxymethylsilane, γ-mercaptopropyltrialkoxysilane, γ-aminopropyltri Methoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, p-styryl Examples include trimethoxysilane and 3-isocyanatopropyltriethoxysilane, which can be used alone or in combination of two or more. Further, such an organosilicon compound is preferably blended after hydrolysis. The blending amount of the organosilicon compound may be appropriately determined according to the desired physical properties depending on the purpose of the finally obtained cured product layer. Generally, the epoxy group-containing silicon compound (B) or a partially hydrolyzed component thereof is generally used. It is preferably 150 parts by mass or less, particularly 100 parts by mass or less per 100 parts by mass of the decomposed product. Moreover, it is preferable that it is 30 mass parts or less per 100 mass parts of hardened | cured material layers finally formed.

  In addition, as the epoxy compound other than the component (B) (that is, an epoxy compound having no silyl group), those known per se can be used, and specific examples thereof include 1,6-hexane. Diol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neopentyl glycol Glycidyl ether, diglycidyl ether of neopentyl glycol hydroxypivalate, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, diglycerol triglycidyl ether , Diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate , Tris ( Aliphatic epoxy compounds such as triglycidyl ether of hydroxyethyl) isocyanurate; Alicyclic epoxy compounds such as isophoronediol diglycidyl ether and bis-2,2-hydroxycyclohexylpropane diglycidyl ether; Resorcin diglycidyl ether, bisphenol A Aromatic epoxy compounds such as diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, etc., and these epoxy compounds Can be used alone or in combination of two or more. Among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl ether are particularly preferable. The compounding amount of such an epoxy compound may be appropriately determined according to the desired physical properties according to the purpose of the finally obtained cured product layer, and the epoxy group-containing silicon compound of the component (B) or its partial hydrolysis It is preferably 150 parts by mass or less, particularly 100 parts by mass or less per 100 parts by mass of the product. Moreover, it is preferable that it is 30 mass parts or less per 100 mass parts of hardened | cured material layers finally formed.

  Moreover, an acid aqueous solution can be mix | blended in order to hydrolyze the organosilicon compound other than the epoxy group containing silicon compound of the (B) component mentioned above and (B) component. As the acid aqueous solution, any known acid can be used without any limitation as long as it has a function of hydrolyzing and condensing an alkoxysilyl group in the above compound. Examples of such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid and propionic acid. Among these, hydrochloric acid is preferably used from the viewpoints of storage stability and hydrolyzability of the coating composition. The concentration is preferably in the range of 0.01N to 5N. Such an acid aqueous solution is used in such an amount that hydrolysis of the above-described (B) epoxy group-containing silicon compound and the like is effectively promoted, for example, 100 parts by mass of the (B) epoxy group-containing silicon compound. It is good to mix | blend in the quantity used as 100 mass parts or less per hit, Preferably it is 5-80 mass parts, Most preferably, it is 10-50 mass parts.

  Furthermore, a curing catalyst other than the acetylacetonate complex can be blended if necessary. Examples of such a curing catalyst include perchloric acid, magnesium perchlorate, aluminum perchlorate, zinc perchlorate, and ammonium perchlorate. Perchloric acids such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, etc. Lewis such as stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, antimony chloride An acid etc. are mentioned.

  Further, the coating composition used in the present invention includes surfactants, antistatic agents, ultraviolet absorbers, antioxidants, disperse dyes, oil-soluble dyes, fluorescent dyes, pigments, photochromic compounds, hindered amines, hindered phenols, and the like. Additives can be blended alone or in combination of two or more, and by adding these additives, the coating properties of the coating composition and the film performance after curing can be improved.

[Resin substrate]
In the laminate of the present invention, it is important to select a thiourethane resin substrate or an allyl resin substrate as the resin substrate. That is, when other resin base materials are used, even if the above-described coating composition is used, a cured product layer excellent in water sensitivity and weather resistance cannot be formed. The reason for this is not clearly elucidated, but perhaps the coating composition described above forms a chemical or physical cross-link with the surface of the thiourethane resin or allyl resin substrate and thus cures. The adhesion between the physical layer and the resin base material surface is remarkably enhanced, and such cross-linking and the composite metal oxide in the coating composition are extremely stable against light, moisture, etc. Even when kept in the environment for a long time, the cross-linking bond is stably formed, so that it seems that excellent weather resistance is expressed. For example, when a cured product layer is formed on the surface of a polycarbonate resin substrate using the coating composition described above, the adhesion between the cured product layer and the resin substrate is insufficient from the beginning.

  Moreover, these resin base materials used in the present invention preferably have a refractive index of 1.55 or more in order to prevent generation of interference fringes due to a difference in refractive index from the coating composition.

  The thiourethane resin used as the resin substrate is obtained by reacting thiol and isocyanate. Examples of the thiol include 1,2-ethanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, propanetris (2-mercaptoacetate), 1,3-propanedithiol, tetrakis (mercaptomethyl). ) Methane, petaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptopropionate), tetrakis (2-mercaptoethylthiomethyl) propane, 2-mercaptoethanol, 2,3-dimercaptopropanol, 3 -Mercapto-1,2-propanediol, di (2-mercaptoethyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, tris (mercaptomethyl) Isocyanurate 1,4-dimercaptocyclohexane, 4-mercaptophenol, 1,2-benzenedithiol, 1,3,5-benzenetrithiol, 1,2-dimercaptomethylbenzene, 1,3-dimercaptomethylbenzene, , 4-dimercaptomethylbenzene, 1,3,5-trimercaptomethylbenzene, bismercaptoethyl sulfide, 1,2-bis {(2-mercaptoethyl) thio} -3-mercaptopropane, 1,2-bis ( Mercaptomethylthio) ethane, tetrakis (mercaptoethylthiomethyl) methane and the like.

  Examples of the isocyanate include methylene diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,2-diisocyanate benzene, 1,3-diisocyanate benzene, 1,4- Diisocyanate benzene, 1,2-diisocyanate methylbenzene, 1,3-diisocyanate methylbenzene, 1,4-diisocyanate methylbenzene, 4,4'-diphenylene diisocyanate, 3,3'-dimethyl -4,4'-diphenylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, Tetramethyl xylylene diisocyanate, 1,3,5-isocyanatomethyl cyclohexane and the like.

  The allyl resin used as the resin substrate is a polymer obtained by polymerization of a monomer containing an allyl group. Specific examples of the allyl group-containing monomer include allyl diglycol carbonate, diallyl isophthalate and its oligomer, diallyl terephthalate, and The oligomer etc. are mentioned.

[Manufacture of laminates]
The laminate of the present invention is obtained by applying the coating composition on the surface of the resin base material (thiourethane resin base material or allyl resin base material) described above, and curing the composition to form a cured product layer. Manufactured.

  When applying the coating composition, the surface of the substrate is previously subjected to alkali treatment, acid treatment, surfactant treatment, UV ozone treatment, polishing with inorganic or organic fine particles for the purpose of improving the adhesion between the substrate and the cured product layer. It is effective to perform treatment or plasma or corona discharge treatment. The coating composition can be applied by a dipping method, a spin coating method, a spray method, a flow method, or the like. Particularly for eyeglass lens applications, a dipping method is preferably used in order to efficiently coat both surfaces of a large number of substrates.

  Curing after coating is usually performed by heat treatment after drying in air or air. The heating temperature is generally 80 ° C. or higher, particularly 100 ° C. or higher, and a temperature at which the resin base material does not deform, generally 150 ° C. or lower is preferable. The curing time is about 2 hours at 130 ° C. and about 2 to 5 hours at 100 to 120 ° C. The cured product layer formed by curing can have a thickness of about 0.1 to 50 μm, but when this laminate is used for an eyeglass lens, the thickness of the cured product layer is 1 to 10 μm. The range of is particularly suitable.

In the laminated body thus obtained, if necessary, as a coating method for forming an antireflection film made of an inorganic material on the surface of the cured product layer, a vacuum deposition method, an ion plating method, a sputtering method, etc. Is mentioned. In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used. Moreover, such an antireflection film may be either a single layer or a multilayer structure. Examples of inorganic substances forming an antireflection _{film, SiO 2, SiO, ZrO 2} , TiO 2, TiO, Ti 2 O 3, Ti 2 O 5, Al 2 O 3, Ta 2 O 5, CeO 2, MgO, Examples thereof include oxides such as Y ₂ O ₃ , SnO ₂ , MgF ₂ and WO ₃ . These inorganic oxides may be used alone or in combination of two or more.

<Example>
EXAMPLES Hereinafter, although an Example and a comparative example are hung up and this invention is demonstrated, this invention is not limited to these Examples.

In the examples and comparative examples, the following were used as the sol of the composite metal oxide fine particles.
Composite metal oxide fine particle sol (a): used in Examples 1 to 10 and Comparative Example 3 Composite metal oxide fine particles obtained by coating a composite metal oxide composed of tin oxide and zirconium oxide with antimony pentoxide and silicon oxide. Dispersed in methanol (HX series manufactured by Nissan Chemical Industries, Ltd.).
Tin oxide-zirconium oxide-antimony pentoxide-silicon oxide (mass%
Ratio): 77.7 / 11.7 / 7.0 / 3.6
Solid content concentration: 30.1% by mass
pH: 7.3

Composite metal oxide fine particle sol (b): used in Comparative Examples 1 and 4 A composite metal oxide comprising titanium oxide, tin oxide and zirconium oxide,
Mixed metal oxide fine particles coated with antimony pentoxide dispersed in methanol (HIT series manufactured by Nissan Chemical Industries, Ltd.).
Titanium oxide-tin oxide-zirconium oxide-antimony pentoxide (mass%
Ratio): 5-15 / 15-25 / 1-5 / 1-5
Solid content concentration: 30.0% by mass
pH: 7.5

Composite metal oxide fine particle sol (c): used in Comparative Example 2 Composite metal oxide fine particles composed of titanium oxide, zirconium oxide and silicon oxide dispersed in methanol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “ Op-trake 1130Z ").
Solid content concentration: 30.0% by mass
pH: 4.8

  Moreover, the property evaluation method of the hardened | cured material layer of the lens (laminated body) in each Example and a comparative example is as follows.

(A) Appearance The transparency of the cured product layer was observed by visual inspection. That is, a light source (color CABIN manufactured by Cabin Industry Co., Ltd.)
III) The sample lens is arranged in the light beam so that the optical axis of the sample lens is perpendicular to the direction of the light beam from III), and is visually observed from the optical axis direction of the lens, thereby causing a cured product with a degree of white turbidity. The transparency of the layer was evaluated. The evaluation criteria are as follows.
(Double-circle): The lens which has a hardened | cured material layer is substantially transparent, and cloudiness is not observed.
○: Some cloudiness is observed.
Δ: A considerable degree of cloudiness is observed.
X: It is completely cloudy.

(B) Solvent resistance Each sample lens was impregnated with methanol, isopropyl alcohol, toluene, acetone or a 0.4 mass% NaOH aqueous solution for 24 hours, and the solvent resistance was evaluated by the change in surface condition. The evaluation criteria are as follows.
○: No change from before impregnation.
X: Change is recognized compared with before impregnation.

(C) Scratch resistance Using steel wool (Bonster # 0000 manufactured by Nippon Steel Wool Co., Ltd.), the surface of the sample lens (cured material layer surface) was rubbed 10 times with a load of 1 kg, and the degree of damage was visually 3 Graded. The evaluation criteria are as follows.
A: Almost no damage.
B: Slightly scratched.
C: The coating film is peeled off.

(D) Adhesiveness Adhesiveness between the cured product layer and the lens base material (resin base material) was evaluated by a cross-cut tape test according to JISD-0202.
That is, using a cutter knife, cuts are made at intervals of about 1 mm on the lens surface (cured material surface) to form 100 squares. A cellophane adhesive tape (cello tape manufactured by Nichiban Co., Ltd.) was strongly pasted thereon, and then pulled and peeled from the surface in a 90 ° direction at a stretch, and then the squares remaining in the cured product layer were measured. The evaluation result was expressed as (number of remaining cells) / 100.

(E) Weather resistance In order to evaluate the weather resistance (corresponding to durability) of the cured product layer by light irradiation, a deterioration acceleration test is performed, and after the deterioration acceleration test, the adhesion is measured by the same method as described above. The weather resistance was evaluated by adhesion.
The deterioration acceleration test was performed by accelerating and aging the sample lens for 200 hours with a Xenon Weather Meter X25 manufactured by Suga Test Instruments Co., Ltd.

(F) Storage stability After preparation of the coating composition, after storage for 3 weeks and 5 weeks at a temperature of 20 ° C., a cured product layer is formed using each coating composition, and the appearance of the obtained cured product layer The storage stability was evaluated by evaluating solvent resistance, scratch resistance, adhesion, and weather resistance.

Example 1
(1) Preparation of coating composition 530.1 parts by mass of γ-glycidoxypropyltrimethoxysilane and 700 parts by mass of methanol were mixed. While sufficiently stirring this liquid, 121.3 parts by mass of 0.05N hydrochloric acid aqueous solution was added and stirred continuously for 3 hours. Then, to this mixture,
Silicone surfactant (Nippon Unicar Co., Ltd., trade name “L-7001”)
2.0 parts by mass,
7.3 parts by mass of Al (III) acetylacetonate,
400 parts by mass of t-butyl alcohol,
1250 parts by mass of composite metal oxide fine particle sol (a),
Were added and mixed, stirred for 5 hours, and then aged for a whole day and night to obtain a coating composition (A).
Further, a part of the coating composition (A) was subdivided, distilled water was added thereto so that the content was 10% by mass, and the mixture was stirred for about 1 hour to prepare a water-added coating composition (A ′). .

(2) Formation of cured product layer A thiourethane resin lens (resin made by Mitsui Toatsu: MR8) having a refractive index of 1.60 is prepared, and this thiourethane resin lens is immersed in a 10% NaOH aqueous solution at 40 ° C. for 5 minutes. The alkali treatment was performed.
The coating composition (A) or (A ′) obtained above is dipped with the alkali-treated thiourethane resin lens and pulled up at a rate of 30 cm / min to form a coating composition on the surface of the thiourethane resin lens. The object was applied. The dipping was performed under three conditions of a relative humidity of 30% RH, 50% RH, and 70% RH (all temperatures are about 23 ° C.). After coating, the film was dried at 70 ° C. for 20 minutes, and then cured at 120 ° C. for 4 hours to obtain a lens having a cured product layer on the surface.
The formed cured product layer was a colorless and transparent film having a thickness of about 2 microns and a refractive index of 1.60.
For the lens (cured product layer) formed by dipping the coating compositions (A) and (A ′) under 30% RH conditions, the aforementioned (a) appearance, (b) solvent resistance, Evaluate all of scratch resistance, (d) adhesion, (e) weather resistance, and for lenses formed by dipping under 50% RH and 70% RH conditions, (a) evaluate only the appearance, The results are shown in Table 1.
Furthermore, the same applies to the lens in which the coating composition (A) and (A ′) was held at a temperature of 20 ° C. for 3 weeks and 5 weeks and then a cured product layer was formed in the same manner as described above. The storage stability was evaluated by evaluating each characteristic. The results are shown in Tables 2 and 3.

-Example 2-
Except for using a thiourethane resin lens having a refractive index of 1.67 (resin made by Mitsui Toatsu Co., Ltd .: MR7) instead of a 1.60 thiourethane resin lens as the resin base material, it is exactly the same as in Example 1. Then, a lens having a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.60 was prepared, and various characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 1. To Table 3.

-Example 3-
Except for using an allyl resin lens with a refractive index of 1.60 instead of a 1.60 thiourethane resin lens as the resin base material, the thickness is about 2 microns and the refractive index is the same as in Example 1. A lens having a 1.60 colorless and transparent cured product layer on its surface was prepared, and various properties were evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

Example 4
530.1 parts by mass of γ-glycidoxypropyltrimethoxysilane, 125 parts by mass of methanol, 200 parts by mass of acetylacetone, and 375 parts by mass of isopropyl alcohol were mixed. In this liquid, a 0.05N hydrochloric acid aqueous solution, a silicon surfactant, Al (III) acetylacetonate, t-butyl alcohol, and a composite metal oxide fine particle sol (a) were mixed in the same manner as in Example 1. Thus, a coating composition (B) was obtained. Furthermore, a water-added coating composition (B ′) was prepared in exactly the same manner as in Example 1.
Except for using the coating compositions (B) and (B ′), a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.60 was provided on the surface in the same manner as in Example 1. Further, various characteristics were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 to 3.

-Example 5
530.1 parts by mass of γ-glycidoxypropyltrimethoxysilane, 400 parts by mass of methanol and 300 parts by mass of isopropyl alcohol were mixed. While sufficiently stirring this liquid, 121.3 parts by mass of 0.05N hydrochloric acid aqueous solution was added and stirred continuously for 3 hours. Then, to this mixture,
Silicone surfactant (Nippon Unicar Co., Ltd., trade name “L-7001”)
2.0 parts by mass,
7.3 parts by mass of Al (III) acetylacetonate,
400 parts by mass of ethylene glycol monoisopropyl ether,
1250 parts by mass of composite metal oxide fine particle sol (a),
Were added and mixed, stirred for 5 hours, and then aged for a whole day and night to obtain a coating composition (C). Further, a water-added coating composition (C ′) was prepared in exactly the same manner as in Example 1.
A thiourethane resin lens having a refractive index of 1.67 (manufactured by Mitsui Toatsu) is used as the resin substrate, using the above coating composition (C) or (C ′), instead of a 1.60 thiourethane resin lens. Resin: Except that MR7) was used, a lens having a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.60 was prepared in the same manner as in Example 1, and Example Various characteristics were evaluated in exactly the same manner as in Example 1, and the results are shown in Tables 1 to 3.

-Example 6
471.0 parts by mass of γ-glycidoxypropyltrimethoxysilane, 69.0 parts by mass of tetraethoxysilane, and 400 parts by mass of methanol were mixed. While sufficiently stirring this liquid, 131.66 parts by mass of 0.05N hydrochloric acid aqueous solution was added and stirred continuously for 3 hours. Then, to this mixture,
Silicone surfactant (Nippon Unicar Co., Ltd., trade name “L-7001”)
2.0 parts by mass,
7.3 parts by mass of Al (III) acetylacetonate,
380 parts by mass of t-butyl alcohol,
1250 parts by mass of composite metal oxide fine particle sol (a),
Were added and mixed, stirred for 5 hours, and then aged overnight to obtain a coating composition (D). Further, a water-added coating composition (D ′) was prepared in exactly the same manner as in Example 1.
Except for using the coating composition (D) or (D ′), a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.60 is provided on the surface in the same manner as in Example 1. Further, various characteristics were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 to 3.

-Example 7-
375.0 parts by mass of γ-glycidoxypropyltrimethoxysilane, 150.0 parts by mass of γ-glycidoxypropylmethyldimethoxysilane, 400 parts by mass of methanol, and 300 parts by mass of isopropyl alcohol were mixed. While sufficiently stirring this liquid, 110.4 parts by mass of 0.05N hydrochloric acid aqueous solution was added and stirred continuously for 3 hours. Then, to this mixture,
Silicone surfactant (Nippon Unicar Co., Ltd., trade name “L-7001”)
2.0 parts by mass,
7.3 parts by mass of Al (III) acetylacetonate,
410 parts by weight of diacetone alcohol,
1250 parts by mass of composite metal oxide fine particle sol (a),
Were added and mixed, stirred for 5 hours, and then aged overnight to obtain a coating composition (E). Further, a water-added coating composition (E ′) was prepared in exactly the same manner as in Example 1.
Except for using the above coating composition (E) or (E ′), a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.60 was provided on the surface in the same manner as in Example 1. Further, various characteristics were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 to 3.

-Example 8-
A coating composition (F) was obtained in the same manner as in Example 1, except that Al (III) acetylacetonate was replaced with Fe (III) acetylacetonate. Further, a water-added coating composition (F ′) was prepared in exactly the same manner as in Example 1.
Except for using the coating composition (F) or (F ′) described above, a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.60 was provided on the surface in the same manner as in Example 1. Further, various characteristics were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 to 3.

-Comparative Example 1-
A coating composition (G) was obtained in the same manner as in Example 1 except that the composite metal oxide fine particle sol (b) was used instead of the composite metal oxide fine particle sol (a). Further, a water-added coating composition (G ′) was prepared in exactly the same manner as in Example 1.
Except for using the coating composition (G) or (G ′), a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.62 is provided on the surface in the same manner as in Example 1. Further, various characteristics were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 to 3.

-Comparative Example 2-
A coating composition (H) was obtained in the same manner as in Example 1 except that the composite metal oxide fine particle sol (c) was used instead of the composite metal oxide fine particle sol (a). Further, a water-added coating composition (H ′) was prepared in exactly the same manner as in Example 1.
Except that the above coating composition (H) or (H ′) was used, a colorless and transparent cured product layer having a thickness of about 2 microns and a refractive index of 1.62 was provided on the surface in the same manner as in Example 1. Further, various characteristics were evaluated in the same manner as in Example 1, and the results are shown in Tables 1 to 3.

-Comparative Example 3-
Curing with a thickness of about 2 microns and a refractive index of 1.60, as in Example 1, except that a polycarbonate resin lens with a refractive index of 1.59 was used instead of a thiourethane resin lens with a refractive index of 1.60. A lens having a physical layer on the surface was prepared, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3.

  As apparent from Tables 1 to 3, when the cured product layer was laminated on the surface of the thiourethane resin substrate or the allyl resin substrate using the coating compositions in Examples 1 to 8, the initial appearance (white turbidity) Degree), solvent resistance, scratch resistance, adhesion, and weather resistance were also good. In addition, the storage stability is also good. Even when a cured product layer is formed using a coating composition after 3 weeks and 5 weeks after storage, appearance, solvent resistance, scratch resistance, adhesion, weather resistance The physical properties such as properties were the same as the physical properties (initial physical properties) when a cured product layer was formed immediately after preparing the coating composition. Furthermore, even when the water-added coating composition was used, the appearance of the laminate was very good.

  On the other hand, in Comparative Examples 1 and 2, the initial appearance, solvent resistance, scratch resistance, and adhesion were good, but the weather resistance was insufficient. The point that the weather resistance is inferior was also the same in the storage stability test (see Tables 2 and 3). In addition, in the case of using a water-added coating composition, it can be understood that the appearance of the coating composition is remarkably poor and the coating composition is sensitive to moisture and can be used only under limited conditions.

  Moreover, in Comparative Example 3 in which the cured product layer was formed using the coating composition of Example 1 on the surface of the polycarbonate resin lens, physical properties such as solvent resistance, adhesion, and scratch resistance were insufficient. As for the appearance, the surface of the polycarbonate resin lens is slightly clouded due to contact with the epoxy group-containing silicon compound.

-Example 9-
The thiourethane resin lens having a refractive index of 1.60 used in Example 1 was dyed with a dye (trade name BPI SunGray, manufactured by BPI) to obtain a pigment-containing lens. A cured product layer was formed on the surface of the dye-containing lens in the same manner as in Example 1 using the coating composition (A) prepared in Example 1.
For such a dye-containing lens, the color computer (Suga test) was used to determine the adhesiveness before and after the 200-hour acceleration test (before and after the weather resistance test) with the Xenon Weather Meter X25 manufactured by Suga Test Instruments Co., Ltd. The a * and b * values were determined using a machine). The results are shown in Table 4.

-Example 10-
The thiourethane resin lens having a refractive index of 1.67 used in Example 5 was dyed with a dye in the same manner as in Example 9 to obtain a pigment-containing lens. A cured product layer was formed on the surface of the dye-containing lens in the same manner as in Example 5. A cured product layer was formed on the surface of the dye-containing lens in the same manner as in Example 1 using the coating composition (C) prepared in the example.
For such a dye-containing lens, the adhesion and the color tone change were evaluated in the same manner as in Example 9, and the results are shown in Table 4.

-Comparative Example 4-
The thiourethane resin lens having a refractive index of 1.60 used in Example 1 (or Comparative Example 1) was dyed with a dye in the same manner as in Example 9 to obtain a pigment-containing lens. A cured product layer was formed on the surface of the dye-containing lens in the same manner as in Example 1 using the coating composition (G) prepared in Comparative Example 1.
For such a dye-containing lens, the adhesion and the color tone change were evaluated in the same manner as in Example 9, and the results are shown in Table 4.

  As understood from the results in Table 4, the laminates (Examples 9 and 10) of the present invention have good adhesion before and after the weather resistance test, and have little change in color tone. On the other hand, in the laminate of Comparative Example 4, when the weather resistance test is performed, the adhesion decreases and the color tone changes before and after the test.

Claims (7)

In the laminate in which the cured product layer of the coating composition is formed on the surface of the resin substrate, the coating composition includes the following components (A) to (D):
(A) Composite metal oxide fine particles not containing titanium oxide , coated with a composite metal oxide composed of tin oxide and zirconium oxide with antimony pentoxide and silicon oxide ;
(B) an epoxy group-containing silicon compound or a partial hydrolyzate thereof;
(C) an organic solvent;
(D) an acetylacetonate complex;
And the resin base material is a thiourethane resin base material or an allyl resin base material.   The coating composition comprises 25 to 250 parts by mass of the composite metal oxide fine particles of the component (A), 100 to 2500 parts by mass of the organic solvent of the component (C), per 100 parts by mass of the component (B). (D) The laminated body of Claim 1 which contains the acetylacetonate complex of a component in the quantity of 0.1-15 mass parts.   The laminate according to claim 1, wherein the refractive index of the thiourethane resin substrate or the allyl resin substrate is 1.55 or more.   The laminate according to claim 3, wherein the thiourethane resin substrate or the allyl resin substrate contains a pigment.   A plastic lens comprising the laminate according to claim 3.   A plastic lens comprising the laminate according to claim 4. On the surface of the thiourethane resin substrate or the allyl resin substrate, the following components (A) to (D):
(A) Composite metal oxide fine particles not containing titanium oxide , coated with a composite metal oxide composed of tin oxide and zirconium oxide with antimony pentoxide and silicon oxide ;
(B) an epoxy group-containing silicon compound or a partial hydrolyzate thereof;
(C) an organic solvent;
(D) an acetylacetonate complex;
The manufacturing method of the laminated body characterized by apply | coating the coating composition containing this, heating to the temperature of 80 degreeC or more, hardening this coating composition, and forming a hardened | cured material layer.