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WO2006001354A1 - Produit en couches - Google Patents

Produit en couches Download PDF

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Publication number
WO2006001354A1
WO2006001354A1 PCT/JP2005/011575 JP2005011575W WO2006001354A1 WO 2006001354 A1 WO2006001354 A1 WO 2006001354A1 JP 2005011575 W JP2005011575 W JP 2005011575W WO 2006001354 A1 WO2006001354 A1 WO 2006001354A1
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WO
WIPO (PCT)
Prior art keywords
group
coating composition
carbon atoms
component
mass
Prior art date
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Ceased
Application number
PCT/JP2005/011575
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English (en)
Japanese (ja)
Inventor
Katsuhiro Mori
Noriaki Tahara
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Tokuyama Corp
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Tokuyama Corp
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Filing date
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Publication of WO2006001354A1 publication Critical patent/WO2006001354A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • the present invention relates to a laminate in which a cured product layer of a coating composition is formed on the surface of a resin substrate made of a specific synthetic resin, and the cured product layer has adhesion, scratch resistance, and chemical resistance.
  • the present invention relates to a laminate having excellent durability such as heat resistance, hot water resistance, heat resistance, and weather resistance, and in which interference fringes are hardly generated between a resin substrate and a cured product layer.
  • 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.
  • synthetic resin lenses those made of diethylene glycol bisvalyl carbonate resin have been widely used.
  • the refractive index is 1.50 or more, which is lower than that of glass, and the outer periphery of the lens is thick. There are drawbacks. For this reason, recently, the thickness of the lens has been reduced by increasing the refractive index of the synthetic resin lens.
  • a silicone-based coating film is applied to the surface of the synthetic resin lens.
  • This silicone-based coating film is obtained by, for example, 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.
  • a coating composition mainly composed of silica fine particles, a polymerizable organic silane compound, a polymerization catalyst, an acid aqueous solution, and a solvent
  • Coating composition in which fine particles of metal oxide or composite oxide containing at least one metal selected from Al, Sn, Sb, Ta or Ce are used in place of silli force fine particles (Japanese Patent Laid-Open No. 8-31 1 408)
  • a metal oxide or composite metal oxide fine particle containing at least one metal selected from Ti, Sb, Ce, Sn, W or Fe is used instead of silica fine particles. Iting composition (Patent No. 28821 8 1)
  • a coating composition using a metal oxide having a refractive index higher than that of silica fine particles alone is referred to as a high refractive index coating composition.
  • the present invention is a laminate in which a cured product layer of a coating composition is formed on the surface of a resin base material such as a synthetic resin lens, and the cured product layer (coat film) is whitened by the influence of moisture. Is effectively suppressed, and even when heat shock is applied, the cured product layer does not crack, and furthermore, it has excellent weather resistance, and even when kept under light irradiation for a long time, the cured product layer And the resin substrate are maintained at a high level as in the initial stage.
  • An object of the present invention is to provide a laminated body. The present inventors have intensively studied to solve the above problems.
  • an antimony pentoxide sol a silicon compound having a specific structure or a hydrolyzate thereof, an epoxy group-containing silicon compound or a hydrolyzate thereof, an organic solvent and a coating composition containing an acetylylacetonate complex are used.
  • the cured product layer of the coating composition is formed on the surface of the substrate made of a specific synthetic resin, whitening of the cured product layer due to the influence of moisture is effectively suppressed (sensitivity to moisture) is transparent.
  • the coating composition contains the following components (A) to (E):
  • R 1 is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms
  • R 2 is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group
  • R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • A is an integer from 0 to 2
  • R 5 is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group
  • R 6 is a hydrogen atom or an alkyl having 1 to 4 carbon atoms.
  • X is a divalent organic residue or oxygen atom
  • b is an integer from 0 to 2
  • the resin base material is made of (meth) acrylic resin, aryl resin or epoxy resin.
  • the laminate of the present invention is a substrate in which the hardened layer of the coating composition containing the above components (A) to (E) is made of a specific resin (that is, (meth) acrylic resin, aryl resin or epoxy resin). Since it is formed on the surface, it has the characteristics of low sensitivity to moisture and excellent weather resistance. For example, even when the coating composition is applied under high humidity or when the coating composition is applied to the surface of the resin substrate in a water-absorbed state, a transparent cured product layer without cloudiness can be obtained. In addition, as shown in the examples described later, even after a long time (20 hours) deterioration promotion test, the adhesion between the cured product layer and the resin base material does not decrease, and is high. Adhesion is maintained. Thus, the laminate of the present invention is extremely excellent in terms of both moisture sensitivity and weather resistance.
  • a specific resin that is, (meth) acrylic resin, aryl resin or epoxy resin
  • the presence or absence of cloudiness (or whitening) of the laminate is visually observed by irradiating the laminate with light along the layer direction of the cured product layer.
  • the cloudy layer is very thin. This is because the light path of the light passing through the cloudy layer is extremely short, and the cloudiness is hardly observable with the sun.
  • the laminate of the present invention is excellent in both moisture sensitivity and weather resistance, and excellent properties such as transparency, adhesion, and scratch resistance are maintained over a long period of time.
  • As a lens its industrial value is high.
  • the coating composition used for producing the laminate of the present invention contains the following components (A) to (E).
  • the component (A) in the coating composition used in the present invention is an antimony pentoxide sol. This component is usually used in a colloidal dispersion with water, alcohol or other organic solvent as a dispersion medium.
  • 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.
  • the ratio of the antimony pentoxide sol in the dispersion medium at this time increases the refractive index of the cured layer (coat film) of the coating composition, so that the antimony pentoxide sol is not contained in the dispersion medium.
  • 10 to 50% by mass is preferable.
  • the surface of the antimony pentoxide sol is made of an amine compound and a phosphonic acid or carboxylic acid. It is also possible to use the processed one.
  • amine compounds examples include ethylamine, ⁇ ethylamine, isopropylamine, n-propylamine, dimethylamine, jetylamine, dipropylamine, alkylpropylamine such as dipropylamine, and alkylammonium; aralkylamine such as benzylamine; morpholine, piperidine Alicyclic amines such as monoethanolamine, diethanolamine, trietanoh Alkanolamines such as luamine and isopropanolamine;
  • carboxylic acid examples include acetic acid, oxalic acid, lactic acid, malic acid, citrate, tartaric acid, salicylic acid, glycolic acid, benzoic acid, phthalic acid, malonic acid, and mandelic acid. These amine compounds and carboxylic acids can be added in an amount of about 0.01 to 5% by mass relative to the antimony pentoxide sol.
  • the particle diameter of the antimony pentoxide sol to be used is not particularly limited, but the average particle diameter is preferably 1 to 300 nm in order not to impair the transparency of the resulting cured product layer.
  • the pH of the dispersion is preferably 4.0 to 9.5.
  • the blending amount of the antimony pentoxide sol in the coating composition used in the present invention may be appropriately determined according to the desired physical properties depending on the purpose of the finally obtained cured product layer (coat film), which will be described later (B).
  • the total amount of the component and the (C) component is preferably 25 to 2500 parts by mass, more preferably 40 to 200 parts by mass, with respect to 100 parts by mass.
  • the blending amount of the antimony pentoxide sol based on the above standard is less than 25 parts by mass, the cured product layer is scratch-resistant, or adheres to the inorganic vapor deposition film formed on the cured product layer as necessary, and is cured.
  • the refractive index of the physical layer becomes insufficient, and if it exceeds 250 parts by mass, the cured product layer tends to crack.
  • R 1 is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms
  • R 2 is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group,
  • R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a is an integer from 0 to 2,
  • R 5 is an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, or an aryl group,
  • R 6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • X is a divalent organic residue or oxygen atom
  • b is an integer from 0 to 2
  • At least one kind of silicon compound selected from the group consisting of hydrolysates thereof and the following compounds:
  • the group R 1 in the general formula (′ 1) is an alkyl group having 6 to 30 carbon atoms or an alkenyl group having 6 to 30 carbon atoms.
  • the alkyl group a hexyl group, heptyl Group, octyl group, decyl group, dodecyl group, octadecyl group and the like
  • examples of the alkenyl group include octenyl group, docosenyl group and the like.
  • These alkyl groups and alkenyl groups may have a substituent.
  • substituents include halogen atoms such as chlorine, bromine and fluorine; acryloyloxy group, methacryloyloxy group , Aryl group, aryloxy group, aldehyde group, amino group and the like.
  • halogen atoms such as chlorine, bromine and fluorine
  • acryloyloxy group methacryloyloxy group
  • Aryl group aryloxy group
  • aldehyde group amino group and the like.
  • the number of carbon atoms must be within the range (6 to 30) including the substituent (illustrated below). The same applies to the groups that do).
  • the group R 2 in the general formula (1) is an alkyl group having 5 or less carbon atoms, a cycloalkyl group having 5 or less carbon atoms, an alkenyl group having 5 or less carbon atoms, or an aryl group.
  • alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a heptyl group; a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group; a propenyl group, 1
  • An alkenyl group such as a butenyl group; an aryl group such as a benzyl group or a naphthyl group;
  • these groups may have a substituent, and examples thereof include halogenated alkyl groups such as chloromethyl group, bromoethyl group, and dichloropropyl group.
  • the group R 3 in the general formula (1) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isop A mouth pill group, a butyl group, etc. can be mentioned, These alkyl groups may also have the substituent mentioned above.
  • a in the general formula (1) is an integer of 0 to 2, and is preferably 0 or 1 from the viewpoint of obtaining a highly hard film (cured product layer).
  • silicon compound represented by the above general formula (1) examples include n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexylmethyl dimethoxysilane, n-octyltrimethoxysilane, n-octyl.
  • the group R 5 in the general formula (2) is an alkyl group, a cycloalkyl group, an alkenyl group (all having 5 or less carbon atoms), or an aryl group, and the group R 2 in the general formula (1) It is synonymous.
  • the group R 6 in the general formula (2) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and has the same meaning as the group R 3 in the general formula (1).
  • X in the general formula (2) is a divalent organic residue or an oxygen atom.
  • the structure of the organic residue is not particularly limited as long as it is a group capable of bonding two Ge atoms having one or more alkoxy groups.
  • the structure includes an ether bond, Steal bond, amide bond, amino bond, urethane bond, thioether bond, It may have a bond other than a carbon-carbon bond such as a phonyl bond, and may further contain an oxa group (ketone carbon).
  • a divalent organic residue X include an alkylene group having 1 to 15 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group; or a group represented by the following formula: And a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkyl group such as a methyl group or an ethyl group; an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group; a hydroxyl group And groups in which an amino group, a mercapto group or the like is bonded as a substituent.
  • m, n and I in the following formula are each an integer of 0 to 10)
  • the compound represented by the above general formula (1) or (2) is used as the component (B) in the form of a hydrolyzate or a combination of two or more, respectively.
  • the hydrolyzate is partially hydrolyzed, or The whole may be hydrolyzed, or may have progressed from hydrolysis to partial condensation.
  • the blending amount of the component (B) in the coating composition used in the present invention may be appropriately determined according to the desired physical properties depending on the purpose of the finally obtained cured product layer (coat film), and finally formed.
  • Cured product layer (coat film) 1 to 30 parts by mass, preferably 5 to 20 parts by mass, relative to 100 parts by mass.
  • the mass of the cured product layer (coat film) to be finally formed is (A) component, (B) component, (C) component described later, and further blended as necessary (A),
  • (B) and a solid component other than (C) for example, a polymer and a condensate of an organic silicon compound or an epoxy compound other than (B) and (C)
  • a coating Organic solvent such as methanol added to the composition (described later)
  • (D) component is volatilized during the formation of the cured product layer, and is not left in the finally obtained cured product layer, so it is not included in the mass of the cured product layer (coat film).
  • the component (C) in the present invention in the coating composition is an epoxy group-containing silicon compound, and any known silicon compound or hydrolyzate thereof may be used without any limitation as long as it contains an epoxy group. be able to. Specific examples thereof include: r-glycidoxypropyl trimethoxysilane, r-glycidoxypropylmethyldimethoxysilane, r-glycidoxypropylmethyljetoxysilane, r-glycidoxypropyl triethoxysilane, (3,4-epoxycyclohexyl) etyltrimethoxysilane and hydrolysates thereof.
  • the hydrolyzate may be partially hydrolyzed or fully hydrolyzed, or may be one that has progressed from hydrolysis to partial condensation.
  • r-glycidoxypropyl trimethoxysilane,: -glycidoxypropylmethyldimethoxysilane, and a hydrolyzate thereof are preferable.
  • the epoxy group-containing silicon compound may be used alone or in combination of two or more.
  • the blending amount of the component (C) in the coating composition is appropriately determined according to the desired physical properties depending on the purpose of the finally obtained cured product layer (coat film).
  • the component (B) it is preferably 29 to 79 parts by mass, more preferably 30 to 65 parts by mass with respect to 100 parts by mass of the finally formed cured product layer. .
  • the blending amount of the component (C) is less than 29 parts by mass, cracks tend to occur in the cured product layer (coat film) when the heat shock test is carried out, and when it exceeds 79 parts by mass, scratch resistance and curing are achieved. There is a tendency that the adhesion between the physical layer and, if necessary, the inorganic vapor-deposited film formed on the cured product layer, the refractive index of the cured product layer, and the like are insufficient.
  • the component (B) described above is used.
  • the component (C) in such an amount that the mass ratio (B Z C) is in the range of 0.01 to 1, particularly 0.02 to 0.5.
  • the component (D) is an organic solvent, and the organic components other than the components (B) and (C) and the components (B) and (C) which are blended as necessary
  • organic solvents examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and n-pentanol; methyl acetate, ethyl acetate, propyl acetate, propionate Esters such as ethylene, methyl acetoacetate, ethyl acetoacetate, and ethyl acetate; 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 Ethers such as butyl ether, propylene glycol monomethyl ether
  • the component (B), the component (C), and the acid used for the purpose of hydrolyzing the organic silicon compound other than the component (B) and the component (C) Methanol isopropanol, t-butanol, acetylacetone, diacetone from the viewpoints of solubility in aqueous solution, easy volatility when forming a cured product layer (coat film), and smoothness when forming a cured product layer
  • alcohol ethylene glycol monoisopropyl ether, or the like.
  • the amount of such an organic solvent used is not particularly limited, but is usually 100-2500 parts by mass, particularly 140-1500 parts by mass with respect to 100 parts by mass of the total amount of the component (B) and the component (C). A range of parts is preferably used.
  • alcohol or the like is used as a dispersion medium for the antimony pentoxide sol as the component (A) described above, the amount of such a dispersion medium is also included in the amount of the organic solvent.
  • the component (E) in the coating composition is an acetylylacetonate complex and is used as a curing catalyst for the coating composition.
  • Such an acetylenic toner complex is known if it is appropriately selected in consideration of physical properties such as solubility in other components, storage stability of the coating composition, and hardness of the resulting cured product layer (coat film).
  • the compound can be used without any limitation. Specific examples include Li (I), Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III) , T i (III), Mr. (Ill), L a (III), C r (III),
  • An acetylethylacetonate complex having V (IV) or the like as a central metal atom can be mentioned.
  • Particularly preferable examples include acetyl acetyltonate complexes having A I (III), Fe (III), and Li (I) as a central metal. Also, these acetyl acetyltonate complexes have no problem whether used alone or in combination of two or more.
  • the addition amount of the above acetyl acetyltonate complex is not particularly limited.
  • the total amount of the component and the component (C) is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass.
  • an organic silicon compound not corresponding to any of the component (B) and the component (C) can be added.
  • organic silicon compounds include tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethyloxysilane, n-propyl trimethoxysilane, n-propyltrimethoxysilane, isoptyltrimethoxysilane, isoptyltrioxysilane, isoptyltrioxysilane,
  • organic silicon compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and the like from the viewpoint of improving the scratch resistance of the resulting cured layer.
  • the blending amount of such other organic silicon compound is preferably 100 parts by mass or less with respect to 100 parts by mass of the total amount of the component (B) and the component (C).
  • the coating composition used in the present invention contains an aqueous acid solution for the purpose of hydrolyzing the above-mentioned (B) component and (C) component, and the above-mentioned other organic silicon compounds.
  • an acid aqueous solution a known acid aqueous solution can be used without any limitation as long as it is an acid aqueous solution having 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.
  • hydrochloric acid is preferably used from the viewpoints of hydrolyzability and storage stability of the coating composition.
  • the concentration of the acid aqueous solution is preferably from 0.01 N to 5 N.
  • Such an acid aqueous solution has a coating composition so that the amount of water is 0.1 to 3 times the total number of moles corresponding to the alkoxy group to be hydrolyzed contained in the polymerizable silicon compound. It is suitable to mix in the product.
  • an epoxy compound that does not correspond to the component (C) described above may be added to the coating composition in order to adjust the physical properties of the cured layer of the coating composition.
  • Such an epoxy compound (hereinafter referred to as another epoxy compound) has an epoxy group, but unlike the component (C), it does not have a silyl group.
  • 1,6-hexanediol diglycidyl ether 1,6-hexanediol 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 diglycidyl ether, neopentyl glycol hydroxyhybalate diglycidyl ether, trimethyl Roll propane diglycidyl ether, trimethylol propane triglycidyl ether, glycerol diglycidyl ether, g
  • Alicyclic epoxy compounds resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ol Phthalic acid diglycidyl ester, phenol novolak polyglycidyl ether, aromatic epoxy compounds such as cresol Pollack polyglycidyl ether; and the like.
  • epoxy compounds examples include 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether Particularly preferred is glycerol triglycidyl ether.
  • These other epoxy compounds may be used in combination of two or more.
  • the blending amount of the other epoxy compound in the coating composition used in the present invention is 100 parts by mass or less with respect to 100 parts by mass of the total amount of the component (B) and the component (C) (B). Is preferred.
  • a curing catalyst other than the aforementioned acetylylacetonate complex (hereinafter referred to as other curing catalyst) can be used in combination.
  • other curing catalysts include perchloric acids such as perchloric acid, magnesium perchlorate, aluminum perchlorate, zinc perchlorate, and ammonium perchlorate: sodium acetate, zinc naphthenate, and naphthenic acid.
  • Organic metal salts such as balt and zinc octylate; stannic chloride, aluminum chloride, chloride Lewis acids such as ferric iron, titanium chloride, zinc chloride, and antimony chloride;
  • stannic chloride aluminum chloride
  • chloride Lewis acids such as ferric iron, titanium chloride, zinc chloride, and antimony chloride
  • These other curing catalysts can be generally used in an amount of 100 parts by mass or less per 100 parts by mass of the acetylyl senanate complex ((E) component).
  • additives can be blended as necessary.
  • additives include surfactants, antistatic agents, ultraviolet absorbers, antioxidants, disperse dyes, oil-soluble dyes, fluorescent dyes, materials, photochromic compounds, hindered amines, hindered phenols, and the like. These additives can be used alone or in admixture of two or more.
  • a resin base material composed of these resins is selectively used, and a cured product layer is formed on the surface of the resin base material using the coating composition containing the components (A) to (E) described above.
  • a laminate having low transparency effectively suppressing white turbidity due to the influence of moisture, and having excellent transparency, and the laminate.
  • the reason why the laminate having the excellent characteristics as described above can be obtained by selecting the above-mentioned specific resin base material has not been clearly elucidated, but is probably the coating composition described above. However, it forms a chemical or physical cross-linking bond with the surface of the (meth) acrylic resin base material, the aryl resin base material or the epoxy resin base material, and thus the adhesion between the cured product layer and the resin base material surface.
  • the cross-linking bond and the composite metal oxide in the coating composition are improved by light and water. This is probably because the cross-linking bond is stably formed even when kept in a poor environment for a long time.
  • these resin substrates 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 (meth) acrylic resin used as a resin base material is a polymer obtained by polymerization of a monomer having a (meth) acrylic group such as (meth) acrylic acid or (meth) acrylic acid ester
  • the aryl resin is a polymer obtained by polymerization of a monomer containing an aryl group such as aryl diglycol power, ponate, diaryl isophthalate and its oligomer, diaryl terephthalate and its oligomer.
  • the epoxy resin is a polymer obtained by polymerization of a monomer containing an epoxy group such as 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether or the like.
  • the above resin base material is a blend or co-polymer of the above-mentioned various resins and other resins (for example, vinyl resins) as long as the excellent characteristics due to the formation of the cured product layer of the coating composition described above are not impaired. It may be made of a polymer. For example, in the range of 30% by mass or less, other resin components or polymerized units that become other resin components can be contained.
  • the laminate of the present invention is produced by applying the coating composition to the surface of the resin substrate described above and curing the composition to form a cured product layer.
  • the substrate surface is treated beforehand with alkali treatment, acid treatment, surfactant treatment, UV ozone treatment, inorganic or organic fine particles. It is effective to perform polishing 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, the dating method is preferably used in order to efficiently coat both surfaces of many substrates.
  • Curing after application is usually performed by heat treatment after drying in dry air or air. Is done by doing.
  • 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 1300C 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 / m. However, when this laminate is used for an eyeglass lens, the thickness of the cured product layer is 1 A range of ⁇ 10 m is particularly suitable.
  • an antireflection film made of an inorganic material can be formed on the surface of the cured product layer.
  • film forming means include vacuum vapor deposition, ion Examples thereof include a plating method and a sputtering method. In the vacuum deposition method, an ion beam assisted method of simultaneously irradiating an ion beam during deposition may be used.
  • Such an antireflection film may be either a single layer or a multilayer structure.
  • the inorganic material forming the antireflection film include S i O, S i O, Z r 0 2 , T i 0 2 , T i O, and T i. 0. , T i. 0 5 ,
  • Oxides such as W0 3 and the like. These inorganic oxides may be used alone or in combination of two or more.
  • T i — Z r — S i sol (comparative example): Methanol-dispersed titanium oxide Zirconium monoxide Ge monoxide composite metal oxide sol
  • ODS n-year-old octylmethyldimethoxysilane
  • ODT ES n-year-old kutadecyltriethoxysilane
  • UDTS 1 0—Undecenyl trimethoxysilane
  • EGEE Ethylene glycol monoethyl ether
  • BTMS n-butyltrimethoxysilane
  • AP TES T-acryloxyprovir triethoxysilane
  • P C Polycarbonate (refractive index 1.59)
  • the characteristics of the lenses (laminates) obtained in the examples and comparative examples were evaluated by the following methods.
  • the transparency of the coat film (cured product layer) was observed by visual inspection. That is, 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 the light source (Cabin Industry Co., Ltd. colorCABIN 111), and is visually observed from the optical axis direction of the lens. By observing, the transparency of the cured product layer was evaluated based on the degree of cloudiness. The evaluation criteria are as follows.
  • Each sample lens (laminated body) was impregnated with methanol, isopropyl alcohol, toluene, acetone, or 0.4 mass% aqueous NaOH solution for 24 hours, and the surface state change was examined.
  • the evaluation criteria are as follows.
  • the adhesion between the coating film and the lens was determined by a cross-cut tape test according to JISD-02020.
  • a cellophane adhesive tape manufactured by Nichiban Co., Ltd. was affixed strongly on it, and was then pulled away from the surface in a 90 ° direction at once, and then the cells with the remaining coating film were measured.
  • the evaluation results are expressed as (number of remaining cells) Z 1 0 0.
  • the following deterioration acceleration test was conducted. That is, the lens having the obtained coating film was accelerated and deteriorated for 20 hours using a Xenon Weather Meter X 2 5 manufactured by Suga Test Instruments Co., Ltd. Thereafter, adhesion was evaluated by the same method as in (4) above.
  • the sample lens (laminated body) was immersed in boiling water for 1 hour, and then immersed in cold water adjusted to 5 ° C or lower for 1 minute, and the degree of occurrence of cracks in the coating film was visually evaluated in three stages.
  • the evaluation criteria are as follows.
  • Example 1 After preparing the coating composition, after storing it at 20 ° C for 3 weeks and 5 weeks, use each coating composition to form a coating film on the surface of the plastic lens substrate by the method shown in each example and comparative example. The appearance, solvent resistance, and abrasion resistance of the resulting coating film Scratch, adhesion, weather resistance and heat shock resistance were evaluated by the methods described above.
  • Example 1 After preparing the coating composition, after storing it at 20 ° C for 3 weeks and 5 weeks, use each coating composition to form a coating film on the surface of the plastic lens substrate by the method shown in each example and comparative example. The appearance, solvent resistance, and abrasion resistance of the resulting coating film Scratch, adhesion, weather resistance and heat shock resistance were evaluated by the methods described above.
  • Example 1 Example 1
  • GTS r-Glycidoxypropyl trimethysilane
  • B 1 gay compound
  • TES tetraethoxysilane
  • Silicone surfactant (made by Nippon Tunica Co., Ltd., trade name “Shiichi 7001”)
  • a coating composition (a ′) The mixture was stirred for 5 hours and then aged overnight to obtain a coating composition (a). Further, a part of the coating composition (a) was subdivided, and distilled water was added thereto so that the content was 10% by mass, followed by stirring for about 1 hour. This coating composition to which water was added was designated as a coating composition (a ′).
  • the coating composition (a) and (a ′) obtained above were dipped on a plastic lens substrate (T KA) that had been immersed in a 10% aqueous solution of 10% NaOH at 40 ° C for 5 minutes.
  • the coating composition was applied to the surface of the lens substrate (TKA) with a pulling speed of 30 cmZ. Datebing was performed under three conditions: relative humidity 30% RH, 50% RH, and 70% RH (all at a temperature of about 23 ° C).
  • the film was dried at 70 ° C. for 20 minutes, and then cured by holding at 120 ° C. for 4 hours to form a coating film to obtain a laminate (sample lens).
  • the coating film of the obtained laminate was a colorless and transparent film having a thickness of about 2 microns and a refractive index of 1.58.
  • Table 1 shows the composition of the coating composition used to form the coating film and the type of plastic lens substrate (resin substrate).
  • the coating compositions (a) and (a ′) devised under 3 Oo / oRH conditions are as described in (1) Appearance, (2) Solvent resistance, (3 ) Scratch resistance, (4) Adhesion, (5) Weather resistance, and (6) Heat resistance Shock resistance is evaluated.
  • Table 2 shows the composition of the coating composition used to form the coating film and the type of plastic lens substrate (resin substrate).
  • Coating compositions (b) to (o) were obtained in the same manner as in Example 1 except that the components shown in Table 1 were used. Further, a part of each coating composition was subdivided, and distilled water was added thereto so that the content became 10% by mass, followed by stirring for about 1 hour. The coating compositions to which water was added were designated as coating compositions (b ′;) to ( ⁇ ′). Using the above coating composition, a coat film was formed on the surface of the plastic lens substrate (resin substrate) shown in Table 1 in the same manner as in Example 1 to obtain a laminate (sample lens). It was.
  • Coating compositions ( ⁇ ), ( ⁇ ′), (q) and (q ′) were obtained in the same manner as in Examples 1 to 15 except that the components shown in Table 1 were used.
  • Example lens Using the above coating composition, a coat film was formed on the surface of the plastic lens substrate (resin substrate) shown in Table 1 in the same manner as in Example 1 to obtain a laminate (sample lens). It was.
  • Example lens in the same manner as in Example 1 except that TKA (aryl resin plastic lens) with a refractive index of 1.60 used in Example 1 was replaced with PC (polycarbonate resin lens) with a refractive index of 1.59. ) And the physical properties were evaluated. These results are shown in Table 2, Table 3 and Table 4.
  • Example 1 ⁇ ⁇ ⁇ o A 100/100 100/100 A a TKA ⁇ ⁇ ⁇ o A 100/100 100/100 A
  • Example 1 1 ⁇ ⁇ ⁇ o A 100/100 100/100 A
  • Example 1 7 ⁇ ⁇ ⁇ ⁇ A 100/100 100/100 A
  • Example 1 ⁇ ⁇ ⁇ o A 100/100 100/100 A a, TKA ⁇ ⁇ ⁇ o A 100/100 100/100 A
  • Example 2 a SE ⁇ ⁇ ⁇ o A 100/100 100/100 A a, SE ⁇ ⁇ O o A 100/100 100/100 A
  • Example 1 7 ⁇ ⁇ ⁇ ⁇ A 100/100 100/100 A
  • Comparative Example 1 As shown in Tables 2 to 4, the initial appearance, solvent resistance, scratch resistance, adhesion, and weather resistance are good, but the heat shock resistance is poor. It turns out that it is enough.
  • the storage stability is the same as the initial preparation of the coating composition after 3 weeks and 5 weeks of storage, and the physical properties such as appearance, solvent resistance, scratch resistance, adhesion, and weather resistance are good.
  • the heat shock resistance was insufficient.
  • Comparative Example 2 the initial appearance, solvent resistance, scratch resistance, adhesion, heat shock resistance and the like were good, but the weather resistance was insufficient.
  • Comparative Example 3 physical properties such as solvent resistance, scratch resistance, and adhesion were insufficient even when the initial and storage stability tests were performed, because a poly force-ponate was used for the base material. .
  • Comparative Example 3 since the physical properties were insufficient from the beginning, weather resistance and heat shock resistance were not evaluated. Further, as for the appearance, the polycarbonate resin lens surface was clouded by contact with the epoxy group-containing silicon compound. '

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Abstract

Produit en couches comprenant une base de résine et formée sur la surface de celle-ci une couche durcie obtenue à partir d'une composition de revêtement, caractérisé en ce que la composition de revêtement comprend (A) un sol de pentoxyde d'antimoine, (B) un composé du silicium représenté par la formule générale (1) suivante : R1R2aSi(OR3)3-a (1) (dans laquelle R1 est un alkyle en C6-30 ou un alcényle en C6-30 ; R2 est un alkyle en C1-5, un cycloalkyle en C1-5, un alcényle en C1-5 ou un aryle ; R3 est un hydrogène ou un alkyle en C1-4 ; et a est un nombre entier valant 0-2), (C) un composé du silicium époxydé, (D) un solvant organique et (E) un complexe d'acétylacétonato et en ce que la base de résine est sélectionnée parmi celles faites de résines (méth)acryliques, de résines allyliques et de résines époxydes. Ce produit en couches est extrêmement utile comme lentille en plastique. La composition de revêtement est moins affectée par l'eau. Même lorsque la composition de revêtement est appliquée dans une atmosphère à humidité élevée ou après avoir absorbé de l'eau, elle donne un film de revêtement (couche durcie) qui ne souffre d'aucune formation de voile et a une excellente résistance aux chocs thermiques. Le produit en couches peut conserver la couche durcie de façon satisfaisante.
PCT/JP2005/011575 2004-06-25 2005-06-17 Produit en couches Ceased WO2006001354A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2014119736A1 (fr) * 2013-01-31 2014-08-07 ホーヤ レンズ マニュファクチャリング フィリピン インク Composition de revêtement et procédé de production d'un objet optique
CN112094546A (zh) * 2020-09-15 2020-12-18 河南省阳光防腐涂装有限公司 一种快干道路标线漆及其制备方法

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US7778465B2 (en) 2007-02-14 2010-08-17 Kabushiki Kaisha Toshiba Image forming apparatus with a plurality of functions
JP2010270191A (ja) * 2009-05-20 2010-12-02 Tokuyama Corp コーティング組成物および光学物品
JP5678901B2 (ja) * 2012-01-25 2015-03-04 信越化学工業株式会社 硬化性樹脂組成物並びにその硬化成形品及び硬化皮膜を有する物品
JP6263154B2 (ja) * 2015-07-29 2018-01-17 株式会社Kri 可溶性塗膜用塗布液
JP2021080396A (ja) * 2019-11-21 2021-05-27 東洋インキＳｃホールディングス株式会社 高い透明性を有する無機酸化物分散体

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JPH02289801A (ja) * 1989-02-17 1990-11-29 Shin Etsu Chem Co Ltd ハードコーティング剤及びプラスチック製光学製品
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JPWO2014119736A1 (ja) * 2013-01-31 2017-01-26 イーエイチエス レンズ フィリピン インク コーティング組成物および光学物品の製造方法
CN112094546A (zh) * 2020-09-15 2020-12-18 河南省阳光防腐涂装有限公司 一种快干道路标线漆及其制备方法

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