JPS59161466A - Multi-layered coating film - Google Patents

Abstract

PURPOSE:To obtain a multi-layered coating film having improved antistaticity, by applying a cured coating film of a composition containing a specific metal alkoxide (hydrolyzate) (condensate) to the surface of a substrate as a base coating film, and applying a top-coating film to the film. CONSTITUTION:The objective multi-layered coating film is a film applied to the surface of a substrate and consisting of (A) a base coating film obtained by the curing of a composition containing the compound of formula I [M is Ti(IV), Si(IV) or ZR(IV); m+n is integer of 1-4; m and n are 0-4; R and R' are 1-10C (alkoxy)alkyl or acyl; X is ligand derived from the compound of formula II or formula III (M<1>, M<2>, M<3> and M<4> are <=6C alkyl)], its hydrolyzed product, and/or its oligomer or polymer obtained by the polycondensation thereof, and (B) a top coating film having a thickness of 0.01-10mu and composed of hydrolyzed silane, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to coatings formed on various substrates, and particularly to multilayer coatings with improved antistatic properties.

PRIOR TECHNOLOGY With regard to the preservation of various base materials and the improvement of their appearance quality, 22 methods have been widely used to solve the problems by coating the base materials with various coating materials. There are various proposals regarding coating methods.

On the other hand, such coating materials are charged with static electricity, which often causes problems. For example, the ease with which it gets dirty due to the adhesion of dust,
Disturbing electric sparks caused by contact with human bodies in low humidity conditions can cause malfunctions in instruments, electronic equipment, etc., especially due to electrostatic charge.

Various proposals have been made to solve these problems. For example, antistatic substances such as surfactants are added to the coating material or coated on the coating material.

These antistatic properties are temporary, and especially when added to a coating material, they have adverse effects such as lowering the water resistance of the coating material. There are other proposals for coating films with antistatic properties and high hardness (Japanese Patent Laid-Open No. 109084/1984), but these require the selection of a balance with other properties in order to primarily impart antistatic properties to the outermost layer. Have difficulty.

Purpose of the Invention The purpose of the present invention is to provide a multi-layered coating that allows a wide selection of coatings with various surface properties and improves the antistatic properties of these coatings, with particular emphasis on surface hardness and transparency. Our objective is to provide a multilayer coating with excellent durability, impact resistance, etc.

Structure of the Invention In the present invention, the lower layer film is obtained by curing a composition containing the following component A'f, and the upper layer film has a thickness of 000.
The structure is a multilayer coating characterized by a coating thickness of 1 μm to 10 μm.

A, a compound represented by the general formula % (), a hydrolyzate thereof, and/or a condensed oligomer or polymer thereof.

Here, M is Ti (Technical V), 5i (IV), Zr (I
IV), man is an integer from 1 to 4, m and n are 0 and 1, respectively.
, 2, 3 or 4, R and R' are alkyl groups having 1 to 10 carbon atoms.

Alkoxyalkyl group or acyl group, X is M'C0
A ligand derived from a compound selected from the group consisting of CH, COM' and M"cOCH, C00M', where Ml.

M', M'' and M4 are alkyl groups having 6 or less carbon atoms)
It is.

Here, titanium shown as component A in the present invention,
The silicon and zirconium compounds are alcoquine, carboxylate and/or chelate compounds of these compounds, and these compounds are present in the lower layer film forming composition in a film forming component in an amount of 10.0 or more by weight in terms of MO. It is necessary that the required amount is contained (here, M represents the tetravalent element defined above).

If these amounts are small, the desired antistatic properties will not be exhibited.

Specific examples of the compound represented by the above general formula include:
Titanium tetraethoxide, titanium tetra-1-propoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide, titanium tetra-5ec-butoxide, titanium tetra-tert-butoxide, aluminum triethoxide, aluminum tri-1 -10 phooxide, aluminum triptoxide, zirconium tetraethoxide, zirconium tetra-1-propoxide,
Zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-8ec
Alcoholate compounds such as -butoxide, zirconium tetra-tert-butoxide, methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, SθC-butyl silicate and t-butyl silicate, di-iso Propoxytitanium bisacetylacetonate, di-butoxytitanium bisacetylacetonate, di-ethoxytitanium bisacetylacetonate, tri-n-butoxyzirconium monoethylacetoacetate, zirconium monobutoxytrisacetylacetoacetate, zirconium dibutoxybisacetonate Examples include quiV-to compounds such as ditylacetonate, zirconium tributoxyacetylacetonate, zirconium monobutoxytrisethylacetoacetate, and zirconium butoxybisethylacetoacetate.

Although these compounds alone can cure to form a film, coating film modifiers such as various resins can also be added.

In particular, for the purpose of improving adhesion with the upper layer, hardness, or durability, colloidal bath liquids in which high molecular weight silicic acid anhydride, generally called ``silica sol'', is dispersed in a hydrophilic solvent of water or alcohol, as well as various polymerizable Organosilicon compounds can preferably be blended.

The former is manufactured by a well-known method and is commercially available, and has an average particle size of 1
~200 mμ, particularly 5~80 mμ is preferably used. As the latter polymerizable organosilicon compound, an organosilicon compound represented by the general formula % and/or a hydrolyzate thereof can be used.

Here, R' and R' are an alkyl group and an alkenyl group, respectively.

Allyl group, ti is halogen group, epoxy group, amino group,
a hydrocarbon group having a mercapto group, a methacryloxy group or an ano group;
is 0 or 1, and a is 1 or 2.

Examples of such compounds include methyltrimethoxysila/
, methyltrimethoxysilane, methyltriliethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane.

Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane.

γ-chloropropyltriethoxy/silane, γ-chloropropyltriacetoxysilane, 6. 3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane Ethoxysilane, N-β('aminoethyl)-γ-aminopropyltrimethhinesilane, β-anoethyltriethquinsilane, methyltriphenoquinesilane, chloromethyltrimethoxysilane, chloromethyltriethoxynolan, glycidoxy Methyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, α
-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, a-glycidoxypropyltrimethoxysilane ethoxysilane, β-glycidoxypropyltrimethoxysilane , β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxinelan, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltrif Enoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ
-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3.4-epoxycyclohexyl)
Methyltritoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β-(3.4-
epoxycyclohexyl)ethyltrimethoxysilane,
β-(3.4-epoxycyclohexyl)ethyltriethoxysilane, β-(3.4-epoxycyclohexyl)ethyltriethoxysilane, β-(3.4-epoxycyclohexyl/l/)ethyltributoxysilane, β
-(3.4-epoxycyclohexyl)ethyltrimethyneethokylesilane, β-(3.4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3.4-
ζxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxy/chlorohexyl)propyltriethquinsilane, β-(6,4-epoxycyclohexyl)butyltrimethoxysilane, δ(3,4-epoxycyclohexyl) Trialkoxy, triacyloxymatatriphenoxysilane such as butyltriethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyljetoxysilane, etc. Lanlan, γ-methacryloxypropylmethylsimethoxysilane, γ-methacryloxyglopylmethyldimethoxysilane, γ-methacryloxypropylmethyljethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyljethoxysilane , ′γ-aminopropylmethyldimethoxysilane, γ
-Aminopro, vilmethyljethoxysilane, methylvinyldimethoxysilane, methylvinylshedkinsilane.

Glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyljethoxysilane, α-glycidoxyethylmethyldimethoxysilane, a-glycidoxyethylmethyljethoxysilane.

β-glycidoxyethylmethyljethoxysilane.

β-Glycidoxyethylmethyldiethoxy/Nran.

α-glycidoxypropyl methyldimethoxine run, α
-glycidoxypropyl methyljethoxy 7-lane, β-
Glycidoxypropylmethyljethoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypyrobylmethyljethoxysilane, γ-crisitoxypropylmethyl Dipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane.

γ-glycidoxypropylmethyldiphenoxysilane,
γ-Glycidoxypropylethylcimethoxysilane, γ
-Glyndoxypropylethyldimethquine silane, γ-
Glycidoxyprobyl ethyljethoxysilane, γ-glycidoxypropylbinyldimethoxysilane, γ-glycidoxyderobylvinylinethoxysilane, γ-glycidoxypropylphenylcimethoxysilane, γ-glycid Sialcoquine silanes or diacyloxysilanes such as xypropylphenyl ethoxysilane are examples.

Such an underlayer film-forming composition is applied to a substrate.

Cured by heating. The film thickness is preferably between 10 mμ and 2 μm; if it is thicker than this, problems such as cracks will occur in the film, and if it is thinner, the antistatic properties will be insufficient. Furthermore, if only the lower layer coating is used, there is a problem that scratches easily occur due to friction caused by fingernails, etc., and the durability is extremely poor.

The upper layer coating applied on the lower layer coating is 001 μ~
Any material that can achieve the desired coating performance with a film thickness of 10 μm will suffice, but various acrylic resins, urethane resins, epoxy resins, etc. are durable.

Aesthetics 9 Preferably from the viewpoint of coloring properties 1 For the purpose of imparting surface hardness, the general formula (where l is 1 to 5. R5 is an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group, or an aryl group) , R' is an atom group having 1'0 or less carbon atoms having an Epoquine group, and R' is an alkyl group having 1 to 2 carbon atoms, a vinyl group, or an aryl group). Decomposition products are preferred. Specific representative examples of these organosilicon compounds include glycidoxymethyltrimethoxysilane,
Glycidoxymethyltriethoxysilane, a-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltriethoxysilane, β-glycidoxyethyltriethoxysilane, a-glycidoxyethyltriethoxysilane Sidoxyethyltrimethoxysilane, alpha
-Glycidoxypropyltriethoxysilane, β-glycidoxypropyltriethoxysilane, β-glycidoxy/propyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , γ-glycidoxypropyltribroboxysilane, γ-glycidoxypropyltributquinsilane, γ-glycidoxypropyltrimethoxyethoxinelan, γ-glycidoxypropyltriphenoxysilane, a-glycid xybutyltrimethoxysilane, α
-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltriethoxysilane, Sidoxybutyltrimethoxysilane
δ-glycidoxybutyltriethoxysilane, (3,4
-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane.

β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(6°4-epoxycyclohexyl)ethyltripropoxysilane, 6.4-Epoxycyclohexyl)ethyldriftoxysilane, β-(3,4-epoxycyclohexyl)ethyltritoxyethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-
(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)
Propyltriethoxysilane, β-(3,4-epoxycyclohexyl)butyltrimethquine silane.

β-(ro,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyljethoxysilane, a
-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyljethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyljethoxysilane, a-glycidoxyethylmethyldimethoxysilane Silane, a-glycidoxypropylmethyljethoxysilane, β-glycidoxypropylmethylcimethoxysilane, β-glycidoxypropylmethyljethoxysilane, γ-glycidoxypropylmethylcimethoxysilane, γ- Glycidoxypropylmethyldiethquine silane.

γ-glycidoxypropylmethylsideroboxysilane,
γ-glycidoxyproylmethylsibutquin silane, γ
- Glycidoxypropylmethylsimethoxyethoxysilane, γ-glycidoxypropylmethylsiphenoxysilane, γ-glycidoxypropylethyldimethoxy 7rane, γ-glycidoxypropylethyldiethoxysilane,
γ-crisitoxypropylvinylcimethoxysilane, γ
- Chrysitoxypropylvinyljethoxysilane.

T-glycidoxypropylphenyldimethoxysilane,
γ-glycidquinpropylphenyldiethquinsilane,
Examples include γ-glycidoxypropyldimethylmonomethoxysilane and γ-glycidoxypropyldimethylmonoethoxysilane.

Among these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxyprobyl triproboquine silane, γ-
Glycidoxypropyltri, butoxysilane, γ
- glycidoxypropyltrimethoxyethoxysilane,
γ-glycidoxypropyl methyldimethoxysilane, r-glycidoxypropyl methyljethoxysilane, γ
-Glycidoxyglobylmethyldiproboxysilane, γ
-g, lysidoxypropylmethyldibutoxysilane, γ
Disilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(6,4-epoxycyclohexyl)ethyltriethoxysilane.

Epoxy group-containing organic compounds such as β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, and β-(3,4-epoxycyclohexyl)ethyltritoxyethoxycin. Hydrolysates of silicon compounds are particularly effective in the present invention.

These organosilicon compounds lower the curing temperature.

It is used after being hydrolyzed to advance the hardening process. 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. When hydrolyzed, the amount is equal to or more than the alkoxy group.

Addition of pure water or acidic aqueous solution in an amount of 6 times the mole or less is particularly preferred from the viewpoint of accelerating curing.

During hydrolysis, alcohol and other substances are produced, so it is possible to hydrolyze without a solvent, but in order to make the hydrolysis more even, it is possible to mix the organosilicon compound and a solvent before hydrolysis. is also possible. Depending on the purpose, it is also possible to remove an appropriate amount of the hydrolyzed alcohol etc. under heating and/or reduced pressure before use, and it is also possible to add an appropriate solvent afterwards. These solvents include alcohols, esters, ethers,
Examples include solvents such as ketones, halogenated hydrocarbons, and aromatic hydrocarbons such as toluene and xylene. Moreover, these solvents can also be used as a mixed solvent of two or more types as required. It can also promote hydrolysis reactions depending on the purpose.

It goes without saying that it is also possible to heat the mixture above room temperature in order to advance reactions such as precondensation, and it is also possible to lower the hydrolysis temperature to below room temperature in order to suppress precondensation.

It is also possible to add curing catalysts, curing accelerators, crosslinking agents, etc. for the same purpose. Examples of these include aluminum compounds such as aluminum alkoxides and aluminum acetylacetoites, other metal complex compounds, imidazole, Organic acid anhydride.

Epoxy resin curing agents such as various amine compounds can be used.

Furthermore, examples suitable for further enhancing the antistatic properties of the present invention include hydrolysates of various silicon tetraalkoxides and condensation products thereof. A specific example is methyl sulfate.

Ethyl silicate, n-propyl silicate, l-propyl silicate, n-butyl silicate.

Examples include t-butyl silicate and S-butyl silicate.

Furthermore, two or more types of coating compositions for forming these upper layer films can be used in combination depending on the purpose.

The present invention is used by dissolving or dispersing the upper layer film-forming composition as in the above example in a suitable solvent and applying it as a coating composition onto the lower layer film consisting of component A. The thickness of the coating is 0.001μ to 10μ, preferably 0.02μ to
It is appropriate to set it to 5μ. That is, if it becomes thicker than this, the improvement in antistatic properties, which is the objective of the present invention, will not be observed.

Furthermore, if the thickness is too thin, problems arise such as insufficient surface hardness. The upper coating may be composed of two or more layers if the above conditions are met.

Further, in the method of the present invention, by appropriately selecting the thickness and material of the lower layer containing component A and the upper layer coated thereon.

In addition to improving antistatic properties, it is also possible to provide the base material with a function of preventing reflection or increasing reflection.

The applied coating composition for each layer can be heat-cured and/or dried in stages.

After pre-curing and/or drying the bottom coating.

It is also possible to coat the top layer and heat cure and/or dry it. As a heating method, hot air, infrared rays, etc. can be used. The heating temperature of the kneading should be determined by the substrate to which it is applied and the coating composition used.

Usually 50-250℃, more preferably 60-200℃
is used. In the case of the lower layer coating, if the temperature is lower than this, curing or drying will be insufficient, and if the temperature is higher than this, thermal decomposition will occur, causing problems such as yellowing.

The upper coating can also be cured using radiation g' such as ultraviolet rays, electron beams, and gamma rays by utilizing the curable functional groups 1, such as double bonds in the polymer or prepolymer.

As the base material of the present invention, any material may be used as long as it does not itself require a coating material and has good antistatic properties, but from the viewpoint of liquid coating.

Glass and plastic materials give particularly effective results. The above plastic materials include polymethyl methacrylate and its copolymers, polycarbonate, thiethylene glycol bisallyl carbonate (CR-'5
9), polyesters, especially polyethylene terephthalate, and unsaturated poly(L), 1.7L, 7crylonitrile-styrene copolymers.

Vinyl chloride, polyurethane, epoxy resin, etc. are preferred.

Moreover, it can also be preferably used for glass.

The above plastic further coated with a coating material.

It can also be preferably applied to base materials such as crow.

In particular, the coating material further below the lower layer coating of the present invention improves adhesion, hardness, chemical resistance, and durability.

Physical properties such as dyeability can be improved.

Furthermore, these coating compositions contain smoothing agents, defoamers, ultraviolet absorbers as film modifiers, antioxidants, and other agents to improve coating workability.

Additives such as various surfactants can be used to impart antifogging properties. Furthermore, during coating operations, these compositions are usually diluted with a volatile solvent before being applied. What is used as a solvent?

Although there is no particular limitation, the use should be determined in consideration of the stability of the composition, wettability to the substrate, volatility, etc. Moreover, it is also possible to use not only one type of solvent but also a mixture of two or more types.

Among these solvents, some are useful for stabilizing the above-mentioned coating compositions, especially those that form a lower layer.9 For example, alcohols having 8 or less carbon atoms, ethylene glycol, monoalkyl ethers of diethylene glycol, and diketones such as acetylacetone. and ketoesters such as ethyl acetoacetate are particularly effective against alkoxides and chelate compounds such as titanium and zirconium.

Here, the coating composition is a composition having a viscosity within a range that can be applied in normal coating operations, and which has a viscosity of 10% at the application temperature.
A poise or less, preferably 1 poise or less is used. That is, it is difficult to obtain a uniform coating with a coating composition having a viscosity higher than this. As a coating method, methods used in ordinary coating operations are possible, but from the viewpoint of controlling the thickness of the thin film, curtain flow coating, dip coating, spin coating, etc. are preferable.

These antistatic materials are used for optical lenses such as glasses and cameras, and for various display devices, especially CRTs.
It is effective for front panel iron plates, etc.

Various chemical treatments are used to apply each layer.

For example, hot water infiltration, solvent immersion, redox agent treatment.

Adhesion and wettability can also be improved by applying physical treatments such as acid and alkali treatments, such as low-temperature plasma treatment, corona discharge treatment, and ultraviolet irradiation, to layers in contact with each other.

The present invention will be explained in detail with reference to Examples below.

The present invention is not limited to this.

Example 1. Comparative Example 1 (11) Preparation of Lower Coating Composition 386.7 g of acetylacetone was mixed with tetra-n under stirring.
17.9 g of methanol-dispersed colloidal silica (average particle size 12±1 millimicrons, solid content 60%) were added, and 5% of silicone surfactant acetylacetate/ 17'g of solution
was added to prepare a coating composition.

(2) Preparation of upper layer coating composition (a) Preparation of silane hydrolyzate° 256 g of γ-gly7doki/propyltrimethoxysilane
Add 54g of 001N hydrochloric acid aqueous solution dropwise at 10°C and mix 1
-ta. After the dropwise addition was completed, stirring was further performed at room temperature for 1 hour to obtain a silane hydrolyzate.

(b) Preparation of coating composition 56.1 g of a 5% methanol solution of a silicone surfactant was added to 243.3 g of the silane hydrolyzate.

Aluminum acetylacetate plus water/methanol/ethylene glycol - 1/7
A coating composition was prepared by mixing 4,693.6 g of a 4/25 (weight ratio) mixed solvent.

(3) Coating and curing First, using the coating composition prepared in the previous section (1), a thiethylene glycol bisallyl carbonate polymer lens (straight g7
5 mm, thickness 2. 1 mm, CR-5
9 Praruns) by dipping method. The coating conditions were a pulling rate of 10 cmZ, and the coated lens was heated to 80°C.
It was heated and cured in a hot air dryer for 1 hour.

Thereafter, coating composition 9 was prepared in the previous section (2) and coated on the lower layer in the same manner as the lower layer.

The coated lenses were thermally cured at 80°C for 2 hours.

(4) The antistatic performance of the lens obtained from the test results was measured at 20°C. 65%R
After leaving it on H for one day and night. 10 on the static quota meter
The antistatic property was evaluated by measuring the half-life of the charging voltage under the conditions of kV and 10 DO rpm.

The results are shown in Table 1 along with comparative examples.

As a comparative example, the upper layer was directly coated on the lens without coating the lower layer.

In addition, the film thickness is 1flll on the high micron surface (Mod
e1HM'-90, newly manufactured by Nissho Precision Optical Manufacturing Co., Ltd.).

Example 2 The same procedure as in Example 1 was carried out except that the lower layer coating composition described below was used. The results are shown in Table 1.

[11 Preparation of lower layer coating composition Acetylacetone 382.6+gvC tetra-
A coating composition was prepared by adding 35.9 g of n-butyl titanate and 17 g of an acetylacetate/solution of a silicone surfactant of type 5.

Example 6 Everything was the same as in Example 1 except that the underlayer coating composition described below was used. Results (1) Preparation of lower layer coating composition (a) Preparation of silicate hydrolyzate 40 g of ethyl alcohol and 40 g of ethyl alcohol were mixed, heated to 10"C with stirring, and 13.85 g of 01N hydrochloric acid was added dropwise to the mixture. After finishing dropping, add 1 more
Stirring was continued for hours to obtain a hydrolyzate. , (b) Preparation of coating composition: 33.9 g of the hydrolyzate prepared in (a) above, 370.8 g of n-propyl alcohol, 169 g of methanol-dispersed colloidal silica as used in Example 1, 5% Noricone. n-propyl alcohol solution of surfactant 1
7 gf were added and mixed to prepare a coating composition.

Example 4 All operations were carried out simultaneously with Example 1 except that the underlayer coating composition described below was used. The results are shown in Table 1.

(11 Preparation of Lower Coating Composition 375.1 g of n-propyl alcohol was mixed with zirconium tributoxyacetylacetate 29.5 g with stirring.
, g, 13.9 g of the same methanol-dispersed colloidal silica used in Example 1, n of 5% silico-silica surfactant.
- 17 g of propyl alcohol solution was added and mixed to form a coating composition.

Example 5. Comparative Example 2 The same procedure as in Example 1 was carried out except that the upper layer coating composition described below was used. The results are shown in Table 1. Note that the comparative example excludes the lower layer.

fl) Preparation of upper layer coating composition (a) Preparation of vinyltriethoxysilane hydrolyzate 20g of acetic acid was added to 260g of vinyltriethoxysilane, and while controlling the temperature at 20°C, 74g of 005N hydrochloric acid aqueous solution was added dropwise and mixed with stirring. do.

A hydrolyzate was obtained.

(b) Preparation of methyltrimethoxysilane hydrolyzate Add 37.2 g of methyltrimethoxysilane and 2.8 g of K acetic acid, and while controlling the temperature at 20°C, add 147 g of 001N hydrochloric acid solution dropwise with stirring in 1-. A hydrolyzate was obtained.

(cl) Preparation of coating composition The silane hydrolysates prepared in (a) and (b) above were mixed, and 8 g of xylene and 2 g of butyl acetate were added.
g, silicone surfactant 0.15g, sodium acetate 0
．． 2 g was uniformly dissolved in Disposal 1-1. This solution 42
．． 9g, methanol 179.7g, ethyl alcohol 129.0g, butyl acetate 137g, xylene 54g
It was diluted and dissolved with 7 g to prepare an upper layer coating composition.

Example 6. Comparative Example 5 Everything was the same as Example 1 except that a single layer coating composition was used as described below. The results are shown in Table 1.

Note that the comparative example excludes the lower layer.

fi+ Preparation of upper layer coating composition (a) Preparation of silane hydrolyzate γ-glycidoxypropylmethyldiethoxysilane IO
6.8 g was cooled to 10'C, and 155 g of 0.05N hydrochloric acid aqueous solution was gradually added dropwise while stirring.

After leaving the dropping path, stirring was continued for another 1 hour at room temperature to obtain a silane hydrolyzate.

(b) The day before preparation of the coating composition, 96 g of bisilane hydrolyzate, 48.0 g of ethyl silicate hydrolyzate used in Example 6, 66 g of water,
256.9 g of methanol, 85.9 g of ethylene glycol.
6g, 47g of 5% silicone surfactant in methanol and 0.6g of aluminum acetylacetonate.
g was added thereto and sufficiently stirred and mixed to obtain a coating composition.

Example 7. Comparative Example 4 The same procedure as in Example 1 was carried out except that the following upper layer coating composition 'f was used. The results are shown in Table 1. Note that the comparative example excludes the lower layer.

+l) Preparation of upper layer coating composition 15 g of polymethyl methacrylate (manufactured by Fujikura Kasei ■, trade name: "Acrybase") was dissolved in 7485 g of methyl ethyl keto to obtain a coating composition.

Comparative Example 5 In Example 7, the concentration of the upper layer coating composition was changed to 10 weight percent, and the upper layer coating composition was coated twice. The results are shown in Table 1.

Comparative Example 6 The coating of Example 1 except that the upper layer coating was removed, that is, the coating consisting only of the lower layer coating, was easily scratched even by friction with fingernails and had extremely poor durability.

Claims (1)

[Scope of Claims] A multilayer coating applied to the surface of a substrate, wherein the lower layer coating is obtained by curing a composition containing the following component A (y7), and the upper layer coating has a thickness of 001μ to 10μ. A, a compound represented by the general formula % (%), a hydrolyzate thereof, and/or a condensed oligomer or polymer thereof. V) + S]-(E'V)
+ Zr (engineering V), m+n is an integer from 1 to 4, m,
n is 0, 1, 2.3 or 4, respectively. R and R' are alkyl groups having 1 to 10 carbon atoms. Alkoxyalkyl group, or acyl group, or M'C0
CH, COM,” and M' C0CH, C00M'
(here, Ml; M', M' and M4 are alkyl groups having 6 or less carbon atoms).