JPH0551471A - Coated laminate - Google Patents

Abstract

PURPOSE:To obtain the title laminate useful for optical lens, transparent base material, etc., having excellent non-fogging properties, durable adhesivity, scratching resistance and durability by providing a substrate having at least a surface layer part composed of a polymer compound containing P=N skeleton with a curable coating film. CONSTITUTION:A curable phosphazene resin comprising a compound shown by formula I (R is group shown by formula II) as a monomer component is polymerized and cured by irradiation with ultraviolet rays by using a glass mold to give a transparent plate having at least a surface layer part composed of a polymer compound having-N=P-skeleton. Then, the transparent plate is used as a base material, the surface of the base material is coated with a coating compound prepared by blending a hydrolyzate of gamma- glycidoxypropyltrimethoxysilane with polyvinyl alcohol, 1,4-dioxane, methanol, aluminum acetylacetonate of a catalyst and a silicone-based surfactant, and a coating film is formed by heating and curing at 130 deg.C for 2 hours to give the objective coated laminate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating laminate, and more particularly to a transparent substrate such as an optical lens, a vehicle headlamp and a window, a display front plate and filter, a window glass, a washbasin, It is preferably used as a mirror material for compacts and the like, as well as goggles, dental mirrors, windshields, helmet shields, showcases, meter covers and the like.

[0002]

2. Description of the Related Art It is known that a polymer compound having a -P = N- skeleton has a high hardness surface (JP-A-63-63).
-241075, Japanese Patent Laid-Open No. 2-284925), for example, it has been attempted to be widely used for articles such as window glass, mirror surface, spectacle lens or goggles. However, as a drawback of the article using this, for example, when it is used in a hot and humid place, a boundary surface with a large temperature or humidity difference, or a place where there is an environmental change, dew condensation occurs on the surface of the article, which causes The surface of the can be clouded.

[0003]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the drawbacks of the prior art, and to provide a coating laminate having excellent scratch resistance, antifogging property and durability thereof. With the goal.

[0004]

In order to achieve the above object, the present invention has the following constitution.

"Coating laminate comprising a base material made of a polymer compound having at least a surface layer portion having a -P = N- skeleton and a curable coating film.""At least the surface layer" in the present invention The part "a base material made of a polymer compound having a -P = N- skeleton" may have a polymer compound having a -P = N- skeleton in at least the surface layer portion, and for example, -P = A base material in which a polymer compound having an N-skeleton is laminated only on the surface layer portion, or -P = N-
The base material may be composed only of a polymer compound having a skeleton.

As the polymer compound having a -P = N- skeleton in the present invention, any polymer compound having such a skeleton can be used without limitation.
The = N- skeleton may be chain-shaped or cyclic. In particular, in the case of coating applications, cast polymerization applications, etc., those having a cyclic structure are preferable because high viscosity is not preferable. As a method for synthesizing such a polymer having a -P = N- skeleton, a functional group is introduced into a monomer having a -P = N- skeleton, and a monomer such as polycondensation is allowed to react with it alone or with another compound. , And a method of using a cured resin. Examples of the monomer having a -P = N- skeleton include, for example, the general formula-[NP (X) _a (Y) _b ] _n- (X in the formula.
At least one of Y and Y is a polymerization-curable group, and a +
Examples thereof include compounds represented by b = 2 and n is an integer.

As the above-mentioned functional groups, vinyl-polymerizable functional groups such as acryl group, methacryl group, styryl group and allyl group, hydroxy group, amino group, carboxyl group, mercapto group, epoxy group, isocyanate group, etc. Various functional groups are mentioned, and an acrylic group or a methacrylic group is particularly preferable from the viewpoints of easy handling, easy availability, and transparency. Examples of compounds capable of reacting with these functional groups include a melamine functional group, a silanol group, and a urea group, in addition to the above functional groups, and it is preferable to use a compound having these functional groups as a copolymerization component. As the copolymerizable monofunctional or polyfunctional monomer or prepolymer, various compounds having a photopolymerizable acryloyl group, methacryloyl group, vinyl group or the like are used. Specifically, epoxy (meth) acrylate, Urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, epoxy di (meth) acrylate, urethane di (meth) acrylate, polyester di (meth) acrylate, hydroxyalkyl (meth)
Examples thereof include compounds having a reactive double bond such as acrylate, dialkylaminoalkyl (meth) acrylate, and di (meth) acrylate having a polyalkylene oxide chain, and it is also preferable to use a plurality of these in combination.

The number of functional groups contained in the above -P = N- skeleton is preferably one or more per -P = N- skeleton, and has two or more, and further four or more functional groups. A method of polymerizing a polyfunctional monomer is also preferable.

As the polymer having a -P = N- skeleton, a phosphazene curing resin obtained by introducing a polymerizable functional group into a polymer such as polydichlorophosphazene and polymerizing the polymer is also preferably used.

Is preferably a cured phosphazene resin obtained by introducing a polymerization functional group from polydichlorophosphazene as a raw material and polymerizing it. For the preparation of the phosphazene resin, a method of polymerizing a polyfunctional monomer having an acrylic group or a methacrylic group as a polymerizable functional group and containing two or more, preferably four or more in one phosphazene skeleton is preferably adopted.

Examples of the curing accelerator include photopolymerization with ultraviolet rays and visible rays, and further polymerization with active rays such as X-rays, electron beams and α rays.

As the photopolymerization initiator, benzoins such as benzoin, benzoin ethyl ether, benzoin methyl ether and benzoin isobutyl ether, benzophenone, 4,4'-bismethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone,
Benzophenones such as 4,4′-dichlorobenzophenone, p-chlorobenzophenone and p-methoxybenzophenone, ketals such as benzylmethyl ketal, 9,
Anthraquinones such as 10-anthraquinone and 2-ethylanthraquinone, phenyl ketones such as 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2.
Propiophenones such as methylpropiophenone, p-
Examples thereof include acetophenones such as tert-butyl trichloroacetophenone and 2,2-diethoxyacetophenone, and thioxanthones such as 2-chlorothioxanthone. These photopolymerization initiators may be used alone, but 2
You may use it in combination of 2 or more types. These curing accelerators are added in an amount of 0.10 with respect to 100 parts by weight of the phosphazene resin.
It can be preferably used in an amount of up to 5.0 parts by weight.

In photopolymerization with ultraviolet rays, low-pressure, high-pressure, and ultra-high-pressure mercury lamps, chemical lamps, metal halide lamps and the like can be used as a light source for ultraviolet ray irradiation. Among them, the high pressure mercury lamp is most preferably used because of its good irradiation efficiency.

Further, as a curing accelerator in the case of heat curing or room temperature curing, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, p-chlorobenzoyl peroxide, t-butyl peroxyacetate, Organic peroxides such as t-butylperoxybenzoate, organic azo compounds such as azobisisobutyronitrile, and amine compounds such as methylethylamine, t-butylamine, dimethyl-p-toluidine, diphenylamine and o-nitroaniline. And amine-based compounds such as These can be used peroxide compounds, organic azo compounds, and amine compounds singly or in combination, and the amount thereof is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the phosphazene resin. It can be used suitably between.

Other curable resins, curable compounds, polymerizable diluents, fillers, stabilizers, solvents, leveling agents, defoamers, antistatic agents, etc. may be added to the polymer compound of the present invention. It is possible. Examples of the curable resin include thermosetting resins such as epoxy resin, melamine resin, and silicone resin.

As the filler in the present invention, silica,
Examples include metal compounds, glass, and ceramics,
For the purpose of transparency, fine particles of colloidal inorganic oxide are preferably used.

The inorganic oxide fine particles are preferably used for various improvements such as hardness and durability as well as antistatic property and conductivity. For example, silicon, titanium, magnesium, antimony, cerium, tin, aluminum, zirconium, tantalum, tungsten. , Fine particles of oxide such as indium. These substances can be used not only in one kind but also in a mixture of two or more kinds, and a colloidal dispersion prepared by dispersing in an organic solvent or water is preferable. Those having an average particle diameter of about 5 to 200 mμ are preferably used, but those having a diameter of about 7 to 50 mμ are particularly preferable.

As the method for molding the substrate of the present invention, cast polymerization in which a monomer is injected between various plates to polymerize is most easily applied and a substrate having a good surface property can be obtained, which is preferably applied. .. When a glass plate is used as the plate, it is preferable that the surface of the glass plate be strengthened in terms of releasability. As the strengthening treatment, a treatment method such as chemical strengthening or heat strengthening can be applied. The molded base material may have various shapes, and may have a flat plate shape, a plate shape having a curvature, a lens shape, or a tube shape. When it is used in the form of a plate, its thickness should be selected and determined from the viewpoint of its impact resistance, specific gravity, etc., but it is 0.1 from the viewpoint of easiness of handling, shape retention characteristics, post-processing and the like. It is preferably 10 mm.

Further, a plastic substrate or a glass substrate,
By coating a ceramic substrate and curing it, it can be applied in various shapes and applications. For example, polycarbonate resin, polyethylene resin,
ABS resin, acrylic resin, polystyrene resin, polyamide resin, polypropylene resin, polyvinyl chloride resin,
Examples thereof include diethylene glycol bisallyl carbonate resin, float glass, and tempered glass. In addition, the substrate is for the purpose of improving the adhesion with the coating film,
An activated gas treatment, a physical treatment such as sandblasting, a chemical treatment such as an acid / base / oxidizing agent, or a coating with a primer may be used.

As a method for coating the substrate, various commonly known methods such as brush coating, dip coating, spin coating, flow coating, spray coating, roll coating and flow coating can be used.

As the solvent used for coating,
Examples thereof include water, alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, 1,4-dioxane, N, N-dimethylformamide, and dimethylimidazolidinone. Further, these solvents can be used as a mixed solvent of two or more kinds, if necessary.

When a polymer compound having a -P = N- skeleton is coated on the substrate, the thickness of the cured coating can be selected at any time depending on the purpose of the function, but is in the range of 0.1 to 100 μm. preferable. If it is less than 0.1 μm, the function of scratch resistance of the coated laminate cannot be obtained, and if it exceeds 100 μm, the difference in thermal dimensional change from the substrate becomes large, and sufficient adhesion cannot be obtained.

When a curable coating is provided on a substrate made of a polymer having a -P = N- skeleton, a chemical treatment or a physical treatment is used as a method for improving the adhesion between the substrate and the curable coating. Etc. Examples of the physical treatment include plasma treatment, ion beam treatment, and ultraviolet irradiation treatment. Examples of the chemical treatment include chemical treatment using acid or alkali and solvent treatment using organic solvent. In addition, there is no problem even if two or more methods are performed. From the viewpoint of workability and cost efficiency, for example, NaOH, KO
Solution immersion treatment using an alkali such as H, LiOH, or ammonia is preferable. Two or more kinds of alkalis may be mixed, or an organic solvent, a surfactant may be added, if necessary.

Immersion with an alkali or the like also has a function of cleaning the surface of the substrate, removing residual monomers, etc., and also improves scratch resistance.

The curable coating in the present invention is not particularly limited as long as it can be adhered to the base material of the present invention and exhibits the expected function, but it is a thermosetting coating or a photocurable coating. In particular, a thermosetting coating is preferably used because it can be coated with a hydrophilic coating or an inorganic material by a vapor deposition method and has good adhesion to a substrate.
Above all, it is particularly preferable to impart antifogging property to the curable coating, and in that case, it can be achieved by curing the composition containing the hydrophilic resin to form a coating. Hydrophilic resins include various water-soluble resins, for example, hydroxyalkyl-substituted derivatives of cellulose, polyacrylamide, poly (meth) acrylic acid and its metal salts, completely or partially saponified polyvinyl acetate, polyvinylpyrrolidone, polyhydroxyalkyl. Examples thereof include (meth) acrylate or a copolymer thereof, an alkyl polyalkylene oxide (meth) acrylate polymer or a copolymer thereof, and a hydrophilic urethane resin.

Among them, polyvinyl alcohol obtained by partial hydrolysis or complete hydrolysis of polyvinyl acetate is preferably used in the present invention. Particularly, polyvinyl alcohol having a hydroxyl group having an average degree of polymerization of 300 to 3000 and a degree of saponification of 70 mol% or more is preferably used in the present invention. If the average degree of polymerization is less than 300, the durability and water resistance tend to decrease,
If it is greater than 00, the viscosity increases when it is used as a paint, and it is difficult to obtain a smooth coating film.
Further, when the saponification degree is lower than 70 mol%, it may be difficult to exhibit sufficient performance in terms of antifogging property.

The cross-linking agent for achieving three-dimensionalization of polyvinyl alcohol is not particularly limited as long as it can insolubilize polyvinyl alcohol, and many known cross-linking agents can be used. Specific cross-linking agents include epoxy resins, melamine resins, silane coupling agents, various metal compounds, urea resins, and silica fine particles. Among the above crosslinking agents, transparency, ease of crosslinking, hardness improvement,
A silane coupling agent is preferable from the viewpoint of many properties such as water resistance, and a compound represented by the following general formula (I) or (II) and a hydrolyzate thereof are particularly preferable.

R ¹ _a R ² _b SiX _{4- (a + b)} (I)

[0029]

[Chemical 1]

(Here, R ¹ , R ³ and R ⁵ are epoxy group-containing organic groups having ^{4 to} 14 carbon atoms, R ² , R ⁴ and R ⁶ are hydrocarbon groups having 1 to 14 carbon atoms, or A hydrocarbon group having 1 to 14 carbon atoms having a substituent selected from a halogen group, a mercapto group, a cyano group, a (meth) acryloxy group and an amino group, X and Q represent a hydrolyzable group.
c and e are 0 or 1 respectively, and b, d and f are 0, 1 or 2 respectively. Further (a + b),
(C + d) and (e + f) are 0, 1 or 2, respectively. Y is an organic group having 2 to 40 carbon atoms. ) In the general formula (I), aliphatic epoxy group such as glycidoxy group and examples of the epoxy group contained in R ^1, and alicyclic epoxy group such as 3,4-epoxycyclohexyl group and the like, R ¹ Is an organic group having 4 to 14 carbon atoms including these epoxy groups, and S is a monovalent organic group.
It is contained in the silane compound by the i-C bond. Further, R ² includes a hydrocarbon group having 1 to 14 carbon atoms such as a methyl group, an ethyl group, a vinyl group, a propyl group, an octyl group and a phenyl group, and a substituent derivative of these hydrocarbon groups. Examples of such a substituent include a halogeno group such as a chloro group and a fluoro group, a mercapto group, a cyano group, a (meth) acryloxy group, and an amino group.
Like R ¹ , R ^{2 is} also a monovalent organic group, and is contained in the silane compound through a Si—C bond. Further, X is a hydrolyzable group, such as an alkoxy group such as a methoxy group, an ethoxy group and a butoxy group, a carboxy group such as an acetoxy group, a halogeno group such as a chloro group and a bromo group, a methoxyethoxy group and an ethoxyethoxy group. Examples thereof include an alkoxyalkoxy group, a ketoxime group and a propenyl group. Further, a is 0 or 1 and b
Is 0, 1 or 2. Furthermore, (a + b) is 0,
1 or 2. When b is 2, R ² may be the same or different.

Specific examples of the organosilicon compound represented by the general formula (I) include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ
-Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrisilane Methoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxyethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrisilane Methoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane Orchid, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane,
α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane , Α-glycidoxybutyltrimethoxysilane, α-
Glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ- Glycidoxybutyltrimethoxysilane, δ
-Glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4
-Epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4 -Epoxycyclohexyl) propyltriethoxysilane,
Trialkoxysilanes such as δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilanes or triphenoxysilanes or their hydrolysates and dimethyl Dimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane,
γ-methacryloxypropylmethyldimethoxysilane,
γ-methacryloxypropylmethyldiethoxysilane,
γ-mercaptopropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane Silane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxymethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropyl Methyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyl Ludimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ- Glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane , Γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc. dialkoxysilane, diphenoxysilane or diacyloxy Orchids or a hydrolyzate thereof are examples.

On the other hand, in the compound represented by the general formula (II) which is another preferred silane coupling agent, R ³ and R ⁵ are R ¹ of the above general formula (I).
An example similar to can be given. Examples of R ⁴ and R ⁶ are the same as those of R ^{2 in the} general formula (I). Further, as the hydrolyzable group for Q, the same examples as for X in the general formula (I) can be given. Also,
c and e are 0 or 1 respectively, and d and f are 0, 1 or 2 respectively. Furthermore, (c + d), (e +
f) is 0, 1 or 2, respectively. d or f
When is 2, R ⁴ and R ⁶ may be the same or different.

Y is an organic group having 2 to 40 carbon atoms. That is, Y is a functional group contained in the molecule through two Si atoms and a Si—C bond, and the functional group contains a heteroatom other than carbon and hydrogen such as an oxygen atom and a nitrogen atom. There is no problem. Furthermore, within the range of 2 to 40 carbon atoms, the organic group may be chain-like or cyclic, and there is no problem even if an oxygen atom or the like is present as an epoxy ring or the like. In particular, when an oxygen atom or the like is present as an epoxy ring or the like, it is preferable because it contributes as a functional group during curing.

As a specific example of Y,

[0035]

[Chemical 2]

And the like.

Among the organosilicon compounds represented by the above general formula (I) or (II), it is preferable to use an organosilicon compound containing an epoxy group or a glycidoxy group especially for the purpose of improving low temperature curability and hardness. is there. Also, from the viewpoints of curing speed and ease of hydrolysis, X and Q have 1 to 4 carbon atoms.
The alkoxy group or the alkoxyalkoxy group is preferably used.

Among these organosilicon compounds and / or their hydrolysates, hydrolysates are preferred in order to lower the curing temperature and promote crosslinking.

Hydrolysis is produced by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid and stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution added. At the time of hydrolysis, it is particularly preferable to add pure water or an acidic aqueous solution in an equimolar or more and 3 times or less molar amount with respect to the X group or Q group of the general formula (I) or (II) from the viewpoint of promoting the curing.

Since alcohol and the like are produced during the hydrolysis, it is possible to perform the hydrolysis without a solvent. However, for the purpose of performing the hydrolysis more uniformly, after mixing the organic silicon compound and the solvent, the hydrolysis is performed. It is also possible to disassemble. It is also possible to remove an appropriate amount of alcohol after hydrolysis under heating and / or reduced pressure for use depending on the purpose, and to add an appropriate solvent after that.

Examples of these solvents include alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic hydrocarbons such as toluene and xylene, and solvents such as N, N-dimethylformamide and dimethylimidazolidinone. Further, these solvents can be used as a mixed solvent of two or more kinds, if necessary. Further, depending on the purpose, it is possible to accelerate the hydrolysis reaction and further heat it to room temperature or higher in order to proceed the reaction such as precondensation, or to lower the hydrolysis temperature to room temperature or lower in order to suppress precondensation. It goes without saying that it is possible to do it.

As a preferable crosslinking agent, silica sol using fine particle silica having an average particle diameter of 5 to 200 mμ is effective. The silica sol is preferably a colloidal dispersion of high molecular weight silicic acid anhydride in a solvent such as water and / or alcohol. For purposes of this invention, an average particle size of about 5 to 200
Those having a diameter of mμ are preferably used, but those having a diameter of about 7 to 50 mμ are particularly preferable. If the average particle size is less than 5 mμ, the stability of the dispersed state is insufficient, and it tends to be difficult to obtain a product of uniform quality.
If it exceeds mμ, the resulting coating film may have poor transparency.

The addition ratio of the polyvinyl alcohol and the crosslinking agent should be appropriately optimized depending on the desired antifogging property and the substrate to which it is applied. When the heat resistance of the material is 100 ° C. or higher, or when the heat resistance is higher than 5 ° C., polyvinyl alcohol is 5 to 5 parts by weight with respect to 10 parts by weight of the crosslinking agent component.
It is preferably 300 parts by weight. Particularly when both functions of high surface hardness and antifogging property are satisfied at the same time, polyvinyl alcohol is added to 10 parts by weight of the crosslinking agent component.
A range of 5 to 150 parts by weight is preferable.

The performance of the cured film of the present invention can be improved or modified by adding components other than the above components.

For example, it is also preferable to add a dye or pigment to the extent that transparency is not impaired, and it is also possible to dye the cured film.

Further, in order to improve weather resistance and adhesion, it is preferable to use various epoxy resins, urethane resins and acrylic resins. Among them, the aliphatic type epoxy resin is particularly preferable because the improvement effect can be greatly enhanced.

A nitrogen-containing organic solvent is preferably used as a solvent in the coating composition for forming a cured film having antifogging property. Above all, a nitrogen-containing organic solvent having a boiling point of 105 ° C. or higher and 300 ° C. or lower is preferable. When the boiling point is 105 ° C. or higher, particularly good smoothness can be obtained in the resulting coating film,
When the temperature is 300 ° C or lower, the formed coating film is particularly easily cured. In addition to the nitrogen-containing organic solvent, it is also preferable to use an organic solvent having a boiling point of 105 ° C or higher and 300 ° C or lower in combination.

As the nitrogen-containing organic solvent,
It is preferable that polyvinyl alcohol can be dissolved at a concentration of 1 wt% or more. Here, the term "dissolve" means that the polyvinyl alcohol is made transparent, and includes those having thixotropy.

Specific examples of the nitrogen-containing organic solvent include dimethylformamide, dimethylacetoxyamide, pyridine and dialkylimidazolidinone. Among them, dimethylformamide and dialkylimidazolidinone having an alkyl group having 1 to 4 carbon atoms are preferable because they have a boiling point of 105 ° C or more and 300 ° C or less and are soluble solvents of polyvinyl alcohol, and among them, dimethylimidazo Lidinone is preferably used because it is easily available. Further, there is no problem if these nitrogen-containing organic solvents remain in a state of reacting or unreacting in the coating film after forming the coating film, for example, a glass substrate or a group having a polysiloxane coating. When the antifogging coating of the present invention is provided on the material, from the viewpoint of improving adhesion and water resistance, at least a part of the nitrogen-containing organic solvent remains in the cured coating in a state of reacting with other components. Preferably.

The coating composition may contain solvents other than the above-mentioned components, additives, various improving agents and the like.

As the solvent, for example, water, various alcohols, ketones, esters, ethers, cyclic ethers, dimethylsulfoxide and the like can be appropriately used.

As the additive, various surfactants can be used for the purpose of improving the surface smoothness, and silicone compounds, fluorine-based surfactants, organic surfactants and the like can be used as examples.

Further, as an improving agent, an organic polymer having good compatibility with the composition for forming a cured film having antifogging property, such as hydroxyethyl cellulose, polyhydroxyethyl methacrylate, or a copolymer thereof, alcohol-soluble nylon, poly Examples thereof include acrylamide, polyvinylpyrrolidone, and copolymers thereof. Further, tetrafunctional silane compounds such as ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, i-butyl silicate, t-butyl silicate, and amide resin can be added.

If necessary, various catalysts known as catalysts for condensation of silanol and / or reaction of silanol and hydroxyl group are used for the purpose of promoting curing.
An aluminum chelate compound represented by 1 · X _a · Y _3-a can be particularly preferably used (where X is a lower alkoxy group and Y is M ¹ COCH ₂ COM ² and M ^3).
A ligand derived from a compound selected from the group consisting of COCH ₂ COOM ⁴ (M ¹ , M ² , M ³ and M ⁴ are lower alkyl groups), a is 0, 1 or 2. Various compounds can be used as the aluminum chelate compound, but as a particularly preferable example from the viewpoint of catalytic activity, solubility in the composition, and stability, aluminum acetylacetonate, aluminum ethylacetoacetate bisacetylacetonate, Aluminum bisethylacetoacetate monoacetylacetonate, aluminum di-n-butoxide monoethylacetoacetate, aluminum di-i-propoxide monomethylacetoacetate, and the like, and a mixture of these compounds can also be used.

Such an additive component may be heat resistant, weather resistant, water resistant, adhesive or chemical resistant to the cured film formed from the antifogging coating composition, depending on the application to which the present invention is applied. Therefore, various practical characteristics can be improved.

In order to obtain the above-mentioned coating composition, for example, there may be mentioned a method of simply mixing the respective components, or a method of mixing the other components with a component which has been previously subjected to treatment such as hydrolysis. , These are all useful methods. In the coated laminate of the present invention, the curable coating may be a single layer or a multi-layered film, and by coating it on a substrate, heat resistance, scratch resistance, moisture resistance, durability, etc. are improved. Can be a coated laminate. When a substrate obtained by providing a coating having a polymer compound having a -P = N- skeleton on a substrate is used, such a coating can also serve as a primer layer.

The coated laminate formed as described above is particularly preferably used for window glasses, lenses, goggles, front plates of displays and the like.

[0058]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of Substrate As a plastic substrate,

[0060]

[Chemical 3]

A cured phosphazene resin (manufactured by Idemitsu Petrochemical Co., Ltd.) containing the compound represented by the formula (1) as a monomer component was polymerized and cured by UV irradiation using a glass mold to obtain a transparent plate having a thickness of 2 mm.

(2) Preparation of curable coating material Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate 236 g of γ-glycidoxypropyltrimethoxysilane was charged into a reactor equipped with a rotor, and a liquid was prepared. Keep the temperature at 10 ℃ and stir with a magnetic stirrer to 0.01
54 g of a normal hydrochloric acid aqueous solution was gradually added dropwise. After completion of the dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

Preparation of paint Polyvinyl alcohol (product of Nippon Synthetic Chemical Industry Co., Ltd.,
AL-06, saponification degree 91.0-94.0 mol%) 2
After weighing 532 g of a 7.1 wt% aqueous solution in a beaker, 62.4 g of the hydrolyzate of γ-glycidoxypropyltrimethoxysilane, and 107.6 g of 1,4-dioxane, and 52. 4 g, dimethyl imidazolidinone 66.63 g, aluminum acetylacetonate as a catalyst 3.6 g, and a silicone-based surfactant 0.6 g were mixed and dissolved to obtain a paint.

(3) Preparation of Coated Laminate The substrate was immersed in a 20% aqueous NaOH solution (25 ° C.) for 10 minutes for alkali treatment, washed with water and dried. Next, the coating material prepared in (2) was coated using a Rhone coater and cured at 130 ° C. for 2 hours. Then 0.1% N
It was dipped in an aOH aqueous solution (60 ° C.) for 5 minutes to obtain a coated laminate.

(4) Evaluation (a) Adhesiveness The edge of the coating film surface reaching 1 mm substrate was cut with a steel knife for 10
0 pieces were put and cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) was strongly adhered and rapidly peeled in the direction of 90 degrees, but no peeling of the coating film was observed and good adhesiveness was obtained. Was.

(B) Surface hardness When the pencil hardness was measured according to JIS K5400, it was 2
It was H.

(C) Anti-fog property When exhaled breath was observed and a cloudy condition was observed, no cloudiness occurred at all.

Example 2 A coated laminate was prepared in the same manner as in Example 1 except that the substrate was changed to the following method, and evaluated in the same manner. As a result, the adhesion was good, the surface hardness was 2H, and no clouding occurred in the antifogging property.

A substrate was prepared by the following method.

On a polycarbonate transparent substrate having a thickness of 2 mm,
The phosphazene monomer used in Example 1 was coated and cured by UV irradiation to form a phosphazene resin layer 3 μm
A polycarbonate plate having

Comparative Example 1 In Example 2, the substrate was a polycarbonate resin plate (2 mm
A coated laminated body was prepared in the same manner as in Example 2 except that the thickness was changed, and evaluated in the same manner as in Example 1. As a result, it did not have adhesiveness.

Example 3 A coating laminate was prepared in the same manner as in Example 1 except that the curing temperature of the paint was changed to 170 ° C., and the same evaluation was performed. As a result, adhesion, goodness, surface hardness, 5H,
In the antifogging property, no fogging occurred.

[0073]

The coated laminate obtained according to the present invention can be imparted with excellent antifogging property, excellent durability of antifogging property and excellent durable adhesion.

Claims (4)

[Claims] 1. A coated laminate comprising a base material made of a polymer compound having a -P = N- skeleton at least in a surface layer portion, and a curable coating provided on the base material. 2. The coated laminate according to claim 1, wherein the curable coating is an antifogging coating. 3. The coating laminate according to claim 2, wherein the antifogging coating contains the following components A and B as main components. A Polyvinyl alcohol having a saponification degree of 70 mol% or more and an average polymerization degree of 300 or more B Crosslinking agent 4. A polymer compound having a -P = N- skeleton,
The coating laminate according to claim 1, which is a cured phosphazene resin obtained by introducing a polymerizable functional group into polydichlorophosphazene and polymerizing the same.