JP3502279B2 - Coated article on which gradient composition cured coating layer is formed and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coated article having a cured coating formed on the surface of a substrate, which has excellent wear resistance, heat resistance, chemical resistance, durability, weather resistance and adhesion to the substrate. And a manufacturing method thereof.

[0002]

2. Description of the Related Art Generally, a coating material, a main component material such as a molded product, or an inorganic material used as a filler has features such as high hardness and high heat resistance, but it is rapidly and densely solidified from a liquid phase or a solution. Heating and firing are required to form the phases. In addition, these inorganic materials have poor affinity with organic solvents and organic phases. On the other hand, organic materials have characteristics such as flexibility and rapid film formation at room temperature, but have poor hardness and heat resistance.

For this reason, conventionally, an inorganic material which has the characteristics of both an inorganic material and an organic material and which has improved the above-mentioned drawbacks
Organic hybrid materials have been developed, and it has been desired to develop an effective manufacturing method capable of rapidly manufacturing at a temperature near room temperature.

For example, Japanese Patent Application Laid-Open No. 1-108272 discloses an inorganic-organic hybrid paint. This paint is an abrasion resistant coating material consisting of a partial hydrolyzate of epoxysilane, a reaction product of a carbonyl group-containing compound and a non-silane based aliphatic polyamine. However, the inorganic structure in the coating film is limited to a part introduced into the organic polymer, and further, the inorganic structure portion does not grow or form a film during the formation of the coating film due to the organic reaction near room temperature. Therefore, the characteristics of the inorganic material cannot be sufficiently expressed, and a dramatic improvement in physical properties and the like cannot be expected as compared with the organic polymer.

Therefore, the present applicant has proposed that a tetrahedral structure layer formed by hydrolysis / dehydration condensation of an alkoxy group of an organoalkoxysilane having at least an alkoxy group and an organic group, and Mg, Al, Ni, Co, Cu. , Mn, F
Crystalline laminated structure filler comprising an octahedral structure layer having at least one metal selected from the group consisting of e, Li, V and Zr as a central atom, and at least one (meth) acryloyloxy group in the molecule And a method for producing a wear-resistant article using the coating material composition comprising the compound having the above and an active energy ray-sensitive radical polymerization initiator (JP-A-8-12899). According to this coating material composition, the inorganic part and the organic part are firmly bonded to each other, and a polymer film having a robust and dense solid phase can be formed, and the ratio of the inorganic part and the organic part can be easily adjusted. An excellent abrasion resistant article can be provided because of its controllability.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a wear-resistant article whose surface is coated with the above-mentioned coating material composition, which enhances the wear resistance to the same level as an inorganic material, and has durability and weather resistance. It was made to further improve the sex.

That is, the object of the present invention is to have the same abrasion resistance as the inorganic material on the surface of the base material, scratch resistance, heat resistance, chemical resistance, durability, weather resistance and It is an object of the present invention to provide a coated article on which a cured coating having excellent adhesiveness is formed, and a method by which the ratio of an inorganic part to an organic part can be easily controlled and which can easily produce a coated article excellent in each of the above properties.

[0008]

The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, have achieved high wear resistance by using a specific hybrid layered polymeric material structure or the like on the surface of a base material. In forming a cured coating having properties, after coating the coating material composition, by heat treatment for a predetermined time, the composition ratio of the hybrid layered polymeric material structure and the organic material to the substrate surface side and the atmosphere side By forming a gradient composition cured coating layer that is continuously or layered between
It was found that a coated article excellent in abrasion resistance, heat resistance, chemical resistance, durability, weather resistance, etc. can be obtained, and the present invention has been completed.

That is, the coated article of the present invention is an organic compound formed on the surface of a substrate by hydrolysis / dehydration condensation of the alkoxy group of (A) an organoalkoxysilane having an alkoxy group and an organic group in the molecule. Structural layer, Mg, A
l, Ni, Co, Cu, Mn, Fe, Li, V, Zr,
Ca, Y, Ga, In, Tl, Sb, Rh, Ru, P
Hybrid layered polymeric material structure 5 to 95 parts by weight in which at least one metal selected from the group consisting of d, Sn, Zn, Pb and Ce and an inorganic crystal structure centered on a metal are covalently bonded to each other in layers Parts, and (B) a cured coating layer of a coating material composition comprising 95 to 5 parts by weight of a compound having at least one (meth) acryloyloxy group in the molecule, and the cured coating layer is It is a gradient composition cured coating layer in which the composition ratio of the component (A) and the component (B) in the layer changes continuously or in a layered manner between the substrate surface side and the atmosphere side. It is a coated article.

Further, the method for producing a coated article of the present invention is formed by hydrolyzing / dehydrating and condensing an alkoxy group of (A) an organoalkoxysilane having an alkoxy group and an organic group in the molecule on the surface of a substrate. Organic structure layer, M
g, Al, Ni, Co, Cu, Mn, Fe, Li, V,
Zr, Ca, Y, Ga, In, Tl, Sb, Rh, R
Hybrid layered polymeric material structure 5 in which an inorganic crystal structure centered on at least one metal selected from the group consisting of u, Pd, Sn, Zn, Pb and Ce is covalently bonded to each other in a layered form 5 95 parts by weight, (B) a compound having at least one (meth) acryloyloxy group in the molecule 95 to 5 parts by weight [(A) component and (B)]
The total amount of the components is 100 parts by weight. ], And (C) active energy ray sensitive radical polymerization initiators 0.1 to 10
By applying a coating material composition comprising a part by weight, by subjecting the coating film of the coating material composition to heat treatment,
Active in the coating film after the heat treatment, a step of changing the composition ratio of the component (A) and the component (B) in the coating film continuously or in a layered manner between the substrate surface side and the atmosphere side. Gradient composition cured film in which the composition ratio of the component (A) and the component (B) in the layer changes continuously or in a layered form between the base material surface side and the atmosphere side by irradiation with energy rays And a step of forming a layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be described below.

[Component (A)] The component (A) comprises an organic structure layer formed by hydrolysis and dehydration condensation of an alkoxy group of an organoalkoxysilane having an alkoxy group and an organic group in the molecule, Mg, Al, Ni, Co, C
u, Mn, Fe, Li, V, Zr, Ca, Y, Ga, I
n, Tl, Sb, Rh, Ru, Pd, Sn, Zn, Pb
And an inorganic crystal structure having at least one metal selected from the group consisting of Ce and Ce as a center, which are bonded to each other in a layered form by a covalent bond.

The component (A) is an organoalkoxysilane (a-ii) M having (a-i) an alkoxy group in the molecule and an organic group containing a radically polymerizable functional group.
g, Al, Ni, Co, Cu, Mn, Fe, Li, V,
Zr, Ca, Y, Ga, In, Tl, Sb, Rh, R
u, Pd, Sn, Zn, Pb and at least one metal selected from the group consisting of Ce, an organic salt, or an alkoxide, optionally (a-iii) having an alkoxy group in the molecule, It is preferable that the structure is obtained by a reaction in the presence of an alkoxysilane having no radically polymerizable functional group and, if necessary, (a-iv) a polar solvent.

For example, the component (a-i), the component (a-ii), and if necessary, the component (a-iii),
The pH is adjusted to be weakly alkaline by dissolving or dispersing in a polar solvent as a component. Thereby, while the inorganic crystal structure layer having the metal as the central atom grows in advance, the silicon of the organoalkoxysilane as the component (a-i) follows the dehydration condensation after hydrolysis of the alkoxy group. Therefore, it is assumed that the organic structure layer is bonded to the inorganic crystal structure layer and the organic structure layer grows around this silicon.

The alkoxysilane which is the component (a-iii) is also incorporated in the hybrid layered polymer material structure in the same manner as the organoalkoxysilane which is the component (ai). Therefore, by using the radical-polymerizable alkoxysilane having no radical-polymerizable organic group, which is the component (a-iii), in combination with the component (a-i) in a desired ratio, the hybrid layered structure, which is the component (A), can be used. The proportion of functional groups capable of radical polymerization in the polymeric material structure can be adjusted.

The component (a-i) is an organoalkoxysilane having an alkoxy group in the molecule and an organic group containing a radically polymerizable functional group. This component (a-i) is used to supply an organic group to the hybrid layered polymer material structure, and the ratio of the number of alkoxy groups to the number of organic groups is from the ratio of alkoxy group / organic group = 3/1. , Alkoxy groups / organic groups = 1/3 can be used.

Specific examples of the component (a-i) include 3-
(Meth) acryloyloxypropyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth ) Acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyldimethylmethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,
4-vinylbutyltrimethoxysilane, 8-vinyloctyltrimethoxysilane, 3-vinyloxypropyltrimethoxysilane, styrylsilane and the like can be mentioned.
These monomers may be used alone or in combination of two or more.

The amount of the component (ai) used is from (ai) to
Of the total 100 parts by weight of the component (a-iii), 10 to 99 parts by weight are preferable. When the amount of the component (ai) used is 10 parts by weight or more, the amount of the organic part introduced into the component (A) together with silicon increases, and the swelling property and compatibility with other organic phases are improved. Further, when the amount is 99 parts by weight or less, the number of metal atoms forming the inorganic crystal part can be relatively increased, and the formation of the hybrid layered polymer material structure which is the component (A) becomes easy. The amount of the component (ai) used is 30 to 7
0 parts by weight is preferred.

Component (a-ii) is Mg, Al, Ni, C
o, Cu, Mn, Fe, Li, V, Zr, Ca, Y, G
a, In, Tl, Sb, Rh, Ru, Pd, Sn, Z
at least one selected from the group consisting of n, Pb and Ce
It is an inorganic salt, organic salt, or alkoxide of the seed metal.
The component (a-ii) is used to supply the central atom of the inorganic crystal layer of the hybrid layered polymeric material structure which is the component (A).

In the component (a-ii), the type of inorganic salt, organic salt or alkoxide that should form a salt with a metal is not particularly limited. In the reaction process of synthesizing the component (A), part of the metal in the component (a-ii) may be replaced with silicon, which is the central atom of the organic bonding layer.

The amount of the component (a-ii) used is from (a-i) to
The total amount of component (a-iii) is preferably 1 to 80 parts by weight based on 100 parts by weight. When the amount of the component (a-ii) used is 1 part by weight or more, the structure-regulating regularity of the inorganic crystal part of the hybrid layered polymeric material structure which is the component (A) becomes good. Further, when the amount is 80 parts by weight or less, the amount of the organic portion introduced together with silicon is increased with respect to the metal atoms constituting the inorganic crystal portion, and thus the swelling property and the compatibility with other organic phases are improved and the coating It becomes easy to apply as a material. The amount of component (a-ii) used is preferably 10 to 60 parts by weight.

The component (a-iii) is an alkoxysilane having an alkoxy group in the molecule and not having a radically polymerizable functional group. The component (a-iii) is added as necessary (a-i) in order to adjust the content of the radically polymerizable functional group in the hybrid layered polymeric material structure.
Used in combination with the component organoalkoxysilane. As the component (a-iii), those having one alkoxy group to those having four alkoxy groups can be used.

When a component having four alkoxy groups such as tetramethylorthosilicate (tetramethoxysilane), that is, a component having no organic group, is used as the component (a-iii), it is (a-i). The ratio of the organic group in the hybrid layered polymeric material structure can also be adjusted by using the component in combination at a desired ratio. (A-
The amount of the component iii) used is preferably 0 to 70 parts by weight in the total 100 parts by weight of the components (ai) to (a-iii).

Specific examples of the component (a-iii) include tetramethyl orthosilicate, tetraethyl orthosilicate, methyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane and dodecyl. Trimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like.

The component (a-iv) is an inorganic or organic polar solvent, and is, for example, one kind of solvent such as water, alcohol, acetone, organic acid or inorganic acid, or a mixture of two or more kinds thereof. A solvent can be used. The amount of the component (a-iv) used is preferably 0 to 2,000 parts by weight based on 100 parts by weight of the total of the components (ai) to (a-iii).

As described above, the component (A) includes, for example, the component (a-i), the component (a-ii) and, if necessary, the component (a-iii) and the component (a-iv). It can be synthesized by dissolving or dispersing it in a polar solvent which is, and adjusting the pH to be weakly alkaline. That is, the (a-i) component,
The component (a-ii) and the component (a-iii) are (a-iv)
It does not necessarily have to be completely dissolved in the component solvent,
It is sufficient even if it is in a dispersed state to some extent.

Here, the weakly alkaline pH may be such that crystallization as the hybrid layered polymeric material structure, that is, gelation occurs at a rate higher than a desired rate and the organic group is not damaged, It may be appropriately determined according to the type of raw material components. Usually, the pH is about 8 to 10. This pH adjustment may be performed by adding an alkaline component to the solution or dispersion, and there is no limitation on the type of alkaline component.

Further, the reaction (gelation process) for synthesizing the component (A) sufficiently occurs even at a temperature of about room temperature, but even if it is gelled under a relatively high temperature condition at which the organic group is not damaged. Good. This gelling process may be completed immediately depending on the selection of raw material system and reaction conditions.
Aging to some extent (for example, about 1 to 2 days) may be required. The obtained crystalline hybrid layered polymeric material structure may be once removed of the solvent and recovered as a dry powder, or may be used in a gel state.

The amount of the hybrid layered polymeric material structure as the component (A) obtained as described above is
5 to 100 parts by weight of the total of the components (A) and (B)
95 parts by weight. If the amount of component (A) used is less than 5 parts by weight, a cured coating having sufficient abrasion resistance cannot be obtained, and
If it exceeds 5 parts by weight, cracks are likely to occur in the cured coating, resulting in insufficient heat resistance and durability. The amount of component (A) used is more preferably 5 to 70 parts by weight, and particularly preferably 10 to 60 parts by weight.

[About Component (B)] The component (B) is a compound having at least one (meth) acryloyloxy group in the molecule. The component (B) is used as a binder component of the hybrid layered polymeric material structure which is the component (A), and improves the durability and heat resistance of the coating layer.

Examples of the component (B) include mono- or poly (meth) acrylates of aliphatic, alicyclic or aromatic mono- or polyalcohols, and aliphatic, alicyclic or aromatic urethane poly (meth). ) Acrylate, epoxy poly (meth) acrylate, polyester poly (meth) acrylate and the like. In addition, in this invention, "(meth) acrylate" shows "acrylate and / or methacrylate." Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate. , Cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phthalic anhydride and 2 A mono (meth) acrylate compound such as an adduct with hydroxyethyl (meth) acrylate;
1,4-butanediol di (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, 1,9-
Nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (n = 2 to 15) di (meth) acrylate, polypropylene glycol (n = 2 to 15) di (Meth) acrylate, polybutylene glycol (n = 2 to 15) di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acrylate Acryloyloxydiethoxyphenyl) propane, trimethylolpropane di (meth) acrylate, di (meth) acrylate compounds such as bis (2- (meth) acryloyloxyethyl) -hydroxyethyl-isocyanurate; trimethylolpropane tri (meth) Acrylate Tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Polyfunctional (meth) acrylate compounds such as erythritol hexa (meth) acrylate; epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy with (meth) acrylic acid, isophorone diisocyanate and 2-
Urethane di (meth) acrylate reacted with hydroxypropyl (meth) acrylate, urethane di (meth) acrylate reacted with dicyclohexylmethane diisocyanate and 2-hydroxyethyl (meth) acrylate, trimethylolethane with succinic acid and (meth) Examples thereof include polyester (meth) acrylate reacted with acrylic acid, polyester (meth) acrylate reacted with trimethylolpropane and succinic acid, ethylene glycol, and (meth) acrylic acid.
These monomers may be used alone or in combination of two or more. As the component (B),
It is preferable to form a crosslinked cured coating layer by using a component capable of undergoing a crosslinking reaction, that is, a compound having two or more (meth) acryloyloxy groups in the molecule, at least in part.

The amount of the component (B) used is 95 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount of the component (B) used is less than 5 parts by weight, a cured coating having sufficient durability and heat resistance cannot be obtained, and if it exceeds 95 parts by weight, the wear resistance decreases. Further, 95 to 30 parts by weight is preferable, and 90 to 40 parts by weight is particularly preferable.

[About component (C)] The component (C) is an active energy ray-sensitive radical polymerization initiator, and is a component which is added to the coating material composition to polymerize and cure them. Generally, an active energy ray-sensitive radical polymerization initiator has a high radical generation rate and generates radicals even at a low temperature, so that various abrasion resistant articles can be produced with high productivity.

Specific examples of the component (C) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane. -1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone,
UV-sensitive carbonyl compounds such as methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, etc. Sulfur compounds; 2,4,
An acylphosphine oxide such as 6-trimethylbenzoyldiphenylphosphine oxide; a radical polymerization initiator sensitive to ultraviolet rays or visible rays such as camphorquinone.

The amount of the component (C) used is 0.1 to 10 relative to 100 parts by weight of the total of the components (A) and (B).
Parts by weight are preferred. When the amount of component (C) used is 0.1 parts by weight or more, the curability of the coating composition will be good.
Further, if the amount is 10 parts by weight or less, yellowing of the cured coating film is unlikely to occur, and it is preferable in terms of cost. The amount of component (C) used is more preferably 0.5 to 5 parts by weight.

In the present invention, the components (A) to (C) described above are used as the constituent components of the coating material composition. In addition to these, for example, when the coating material composition is applied, For the purpose of adjusting the liquid viscosity, an organic solvent and a thinner which is a mixture thereof may be used. In this case, the components (A) to (C) do not necessarily have to be completely dissolved in the organic solvent and may be in a dispersed state to some extent.

When the coating composition is applied, a brush coating method, a spray method, a dipping method, a spin method, a flow method or the like is used, and the liquid viscosity may be adjusted appropriately for each method. .

Specific examples of the organic solvent include methanol, ethanol, isopropanol, n-butanol,
Alcoholic solvents such as isobutanol, methoxybutanol, methoxypropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether; ester solvents such as ethyl acetate, butyl acetate, diethylene glycol acetate; Examples thereof include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; hydrocarbon solvents such as hexane, cyclohexane, and mineral spirits. These solvents may be used alone, but usually 2
It is preferable to use a mixture of two or more species.

The amount of the organic solvent used is from the components (A) to (C).
0 to 1000 parts by weight is preferable, and 10 to 800 parts by weight is more preferable, based on the total 100 parts by weight of the components.

In the present invention, the coating material composition includes
In addition to the components described above, if necessary, antioxidants, yellowing agents, ultraviolet absorbers, bluing agents, pigments, leveling agents, anti-settling agents, defoamers, thickeners, electrostatic agents Various additives such as an inhibitor and an antifogging agent may be used.

When the coated article having the gradient composition coating of the present invention is produced, for example, the components (A), (B) and (C) are formed on the surface of a substrate such as thermoplastics, wood, paper or metal. ) Component and, if necessary, a coating material composition comprising an organic solvent and the like, the coating film is subjected to a heat treatment, and then radically polymerized by irradiation with active energy rays to obtain a wear-resistant graded composition cured coating film. Form the layers.

Here, in order to change the composition ratio of the component (A) and the component (B) in the cured coating layer continuously or in a layered form between the substrate surface side and the atmosphere side, heating after coating is performed. Processing conditions are important. As this heat treatment method, it is preferable to use a heat source such as hot air or infrared rays or a combination thereof, and it is preferable to heat the substrate surface temperature to 30 ° C to 150 ° C. This heating time is usually 5
The time is from 1 second to 1 hour, preferably from 10 seconds to 30 minutes, and the atmosphere may be air or an inert gas such as nitrogen or argon. When the base material is a plastic base material or the like, it may be heated so that the surface temperature of the base material does not exceed the glass transition temperature so as not to cause the deformation.

By performing this heat treatment, the composition ratio of the component (A) and the component (B) in the applied coating material composition is continuous or layered between the substrate surface side and the atmosphere side. The gradient composition changes to. Specifically, the composition has a small proportion of the component (A) on the base material side of the layer and a large proportion of the component (A) on the atmosphere side.

The higher the heat treatment temperature or the longer the heating time, the more the component (A), which is a component exhibiting wear resistance, becomes a gradient composition on the atmosphere side surface side, and the wear resistance of the cured coating layer itself becomes higher. improves.

However, since the heat resistance, the weather resistance and the durability are deteriorated while the abrasion resistance is improved, the heat treatment conditions that the substrate surface temperature is in the range of 50 ° C. to 130 ° C. are taken into consideration in consideration of the characteristics of both. Is particularly preferable, and more preferably in the range of 60 ° C to 120 ° C.

The gradient composition of this cured coating layer can be analyzed by measuring the silicon concentration [silicon is a constituent element of the component (A)] using, for example, an X-ray photoelectron spectrometer.

At the same time, this heat treatment can also serve to remove the organic solvent in the applied coating composition and improve the adhesion to the substrate.

The thickness of this cured coating layer is 1 to 500 μm.
Is preferable, and 3-100 micrometers is more preferable. For the irradiation of the active energy ray after the heat treatment, a light source such as a chemical reaction chemical lamp, a high-pressure mercury lamp, a metal halide lamp, a fusion lamp, and sunlight can be used. The wavelength from these light sources is 200-600
nm to 100-5000 mJ /
Irradiate to be cm ² . The atmosphere for irradiation may be air or an inert gas such as nitrogen or argon.

The substrate to which the gradient composition coating film of the present invention can be applied is not particularly limited. Specific examples thereof include plastic substrates such as methacrylic resin, polycarbonate resin, polyester resin polystyrene resin, ABS resin, AS resin, polyamide resin, polyethylene resin, polypropylene resin; various wooden substrates such as solid wood, plywood, and lauan boards. A metal substrate such as an iron plate, a stainless plate, an aluminum plate and a copper plate; an inorganic substrate such as a glass plate, pottery, ceramics; or a paper substrate.

[0050]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, "part" in an example shows a "weight part."

<Synthesis of Hybrid Layered Polymer (A-1)> 200 ml of 1N sodium hydroxide aqueous solution and 38 parts of water.
Dilute by adding 00 ml, and add sodium hydroxide aqueous solution (x
Liquid) was prepared. Apart from this, 1000m of methanol
1), 49.6 parts of 3-methacryloyloxypropyltrimethoxysilane as the component (ai), and (ai)
20.3 parts of magnesium chloride hexahydrate was added as a component i) and well stirred to prepare a liquid y. The pH of the solution y was adjusted to be weakly alkaline by adding and mixing the solution x with stirring, and a gel-like hybrid layered polymer was synthesized. The gelled product was filtered, washed with water, and vacuum dried to obtain a white powdery hybrid layered polymer (A-1).

<Synthesis of Hybrid Layered Polymer (A-2)> 200 ml of 1N sodium hydroxide aqueous solution and 38 parts of water.
Dilute by adding 00 ml, and add sodium hydroxide aqueous solution (x
Liquid) was prepared. Apart from this, 1000m of methanol
1), 33.0 parts of 3-methacryloyloxypropyltrimethoxysilane as the component (ai), and (ai)
Add 23.8 parts of nickel chloride hexahydrate as component i),
The solution y was prepared by thoroughly stirring. The pH of the solution y was adjusted to be weakly alkaline by adding and mixing the solution x while stirring the solution y to synthesize a gel-like hybrid layered polymer. The gelled product was filtered, washed with water, and vacuum dried to obtain a green powdery hybrid layered polymer (A-2).

<Synthesis of Hybrid Layered Polymer (A-3)> 300 ml of 1N sodium hydroxide aqueous solution and 37 parts of water.
Dilute by adding 00 ml, and add sodium hydroxide aqueous solution (x
Liquid) was prepared. Apart from this, 1000m of methanol
1), 49.6 parts of 3-methacryloyloxypropyltrimethoxysilane as the component (ai), and (ai)
i) Add 37.3 parts of cerium chloride heptahydrate as a component,
The solution y was prepared by thoroughly stirring. The pH of the solution y was adjusted to be weakly alkaline by adding and mixing the solution x with stirring, and a gel-like hybrid layered polymer was synthesized. The gelled product was filtered, washed with water, and vacuum dried to obtain a yellow powdery hybrid layered polymer (A-3).

<Synthesis of Hybrid Layered Polymer (A-4)> 400 ml of 1N aqueous sodium hydroxide solution and 36 parts of water.
Dilute by adding 00 ml, and add sodium hydroxide aqueous solution (x
Liquid) was prepared. Apart from this, 1000m of methanol
l, 49.6 parts of 3-acryloyloxypropyltrimethoxysilane as the component (ai), and (a-ii)
46.7 parts of tin chloride hydrate was added as a component and well stirred to prepare a liquid y. The pH of the solution y was adjusted to be weakly alkaline by adding and mixing the solution x with stirring, and a gel-like hybrid layered polymer was synthesized. The gelled product was filtered, washed with water, and vacuum dried to obtain a white powdery hybrid layered polymer (A-4).

<Synthesis of hybrid layered polymer (A-5)> 300 ml of 1N sodium hydroxide aqueous solution and 37 parts of water.
Dilute by adding 00 ml, and add sodium hydroxide aqueous solution (x
Liquid) was prepared. Separately, methanol 1500m
in a mixed solvent of 1 and 500 ml of acetone, 37.2 parts of 3-methacryloyloxypropyltrimethoxysilane as the component (a-i), 12.4 parts of decyltrimethoxysilane as the component (a-iii), and (a-ii). 24.1 parts of aluminum chloride hexahydrate as a component) and well stirred to prepare liquid y. The pH is adjusted to be weakly alkaline by adding and mixing the solution x while stirring the solution y.
A gel-like hybrid layered polymer was synthesized. The gelled product was filtered, washed with water, and vacuum dried to obtain a blue powdery hybrid layered polymer (A-5).

Example 1 <1. Preparation of coating material composition> 45 parts of the hybrid layered polymer (A-1) as the component (A), and the component (B):
15 parts of urethane diacrylate consisting of 1 mol of isophorone diisocyanate and 2.1 mol of 2-hydroxypropyl acrylate and 55 parts of 1,6-hexanediol diacrylate, 1-hydroxycyclohexyl phenyl ketone as the component (C) [trade name: Irgacure 18
4, Ciba-Geigy] 3 parts, and 2- (2-hydroxy-5-methylphenyl) -benzotriazole [trade name: Tinuvin P, Ciba-Geigy] 8 parts as an ultraviolet absorber, n-as a diluting organic solvent 130 parts of butanol and 60 parts of 2-methoxypropanol were stirred and mixed to obtain a coating material composition.

<2. Formation of Crosslinked Cured Coating Layer> This coating material composition was used as a base material for a polycarbonate resin plate [PC, GE
100mm x 100mm x 3mm (thickness) of Lexan LS-2 (color tone clear) manufactured by the company by injection molding
The plate formed into the size of [1]] was applied by the dip method. Specifically, after immersing the base material in the liquid of the coating material composition for 1 minute, 0.5 cm / sec. I pulled it up at a constant speed. This coated plate was left in a hot air dryer at 120 ° C for 5 minutes to bring the surface temperature of the base material to 95 ° C, and then the high pressure mercury lamp (80
W / cm, 2 kW), and a conveyor speed of 2 m / min. 2500ml / c under the condition of
It was irradiated with m ² of ultraviolet energy.

<3. Evaluation of Wear-Resistant Article> The film thickness of the coating of this wear-resistant polycarbonate resin plate was about 5 μm. About this abrasion-resistant polycarbonate resin plate,
The performances (1) to (6) were evaluated by the following methods.

(1) Transparency The haze value was measured according to ASTM D-1033.

(2) Abrasion resistance (Taber abrasion resistance) Evaluation was performed according to ASTM D-1044. Specifically, CS-10F was used as a Taber wear wheel, a load of 500 g was applied to each wheel, and the wheel was worn for 500 rotations, and then the haze value of the worn portion was measured. Abrasion resistance was shown by the value obtained by subtracting the haze before abrasion from the haze after abrasion.

(3) Adhesive coating The surface of the coated film is cut with a razor to reach 11 lengthwise and 11 widthwise sides at intervals of 1.5 mm to make 100 squares, and cellophane tape (25 mm wide, made by Nichiban) Was closely adhered to the above and rapidly peeled off, and then the number of unpeeled eyes was counted.

(4) Heat-resistant water Abrasion-resistant polycarbonate resin plate was immersed in hot water at 80 ° C for 2 hours.
After soaking for 1 hour and standing at room temperature for 1 hour, appearance change and adhesion were evaluated. The evaluation of the adhesiveness was performed by the method (3).

(5) Chemical resistance Abrasion resistance Polycarbonate resin plate was spotted with acetone, toluene, 5% NaOH aqueous solution, 5% sulfuric acid aqueous solution (diameter 8-10 mm), and the change was visually observed after standing at room temperature for 24 hours. I observed.

(6) A weather resistant and abrasion resistant polycarbonate resin plate was applied to a carbon arc weather meter [WEL-SUN manufactured by Suga Test Instruments Co., Ltd., test conditions: black panel temperature 63 ° C., irradiation rain for 12 minutes, 4
It was exposed for 2000 hours in a repeated cycle of irradiation for 8 minutes, and the appearance change and the adhesiveness were evaluated.

Table 2 shows the evaluation results of these performances (1) to (6).

Further, the silicon (Si) concentration near the film surface (air interface side) of the abrasion-resistant polycarbonate resin plate obtained in Example 1 was analyzed by XPS (X-ray photoelectron spectrometer). The results are shown in Table 3. As shown in Table 3, it was confirmed that the concentration of Si in the vicinity of the surface was high and that the gradient composition cured coating layer having a large proportion of the component (A) on the surface (air interface side) of the film was obtained.

[Examples 2 to 4] Abrasion resistant polycarbonate resin plates were obtained in the same manner as in Example 1 except that the heat treatment temperature after coating and the substrate surface temperature were changed as follows. , And evaluated in the same manner.

Example 2: Heat treatment temperature 100 after coating
C, substrate surface temperature 86 ° C., Example 3: heat treatment temperature after coating 80 ° C., substrate surface temperature 71 ° C., Example 4: heat treatment temperature after coating 60 ° C., substrate surface temperature 55 ° C.

[Examples 5 to 6] Abrasion resistant polycarbonate resin plates were obtained in the same manner as in Example 1 except that the amounts of the components (A) to (C) were changed as shown in Table 1. It evaluated similarly.

[Example 7] As a base material, a methacrylic resin plate [PMMA, a trade name of Acrypet (registered trademark) VH001 (color tone clear) manufactured by Mitsubishi Rayon Co., Ltd., 100 mm x 100 mm x 3 mm (thickness) A plate formed into a size of 4) was used, and the coating material composition was applied by the dipping method in the same manner as in Example 1. This coated plate was left in a hot air dryer at 80 ° C. for 5 minutes and then, using three high pressure mercury lamps (80 W / cm, 2 kW), a irradiation speed of 20 cm and a conveyor speed of 2 m / min. 700 on condition
It was irradiated with ultraviolet energy of mJ / cm ² . The resulting abrasion-resistant methacrylic resin plate was evaluated in the same manner as in Example 1.

Example 8 A coating material composition was obtained in the same manner as in Example 1 except that 200 parts of n-butanol and 100 parts of 2-methoxypropanol were used as the diluting organic solvent. This is applied to a veneer-coated decorative board [100 mm x 100 mm x 1 mm (thickness)] as a base material by a spray method, and left in a hot air dryer at 60 ° C for 15 minutes, and then a high pressure mercury lamp (80 W / cm, 2 kW) ), The irradiation speed is 20 cm and the conveyor speed is 2 m / min. 700 on condition
It was irradiated with ultraviolet energy of mJ / cm ² . The obtained abrasion resistant decorative plate was evaluated in the same manner as in Example 1. However, regarding the transparency and the abrasion resistance (taper) among the evaluation items, the haze cannot be measured, and thus the visual inspection was performed.

[Example 9] Except that the coating plate was left in a hot air dryer at 40 ° C for 3 minutes under the conditions for forming the crosslinked cured coating layer of Example 1, and the substrate surface temperature was 34 ° C. In the same manner as in Example 1, a wear-resistant polycarbonate resin plate was obtained and evaluated in the same manner. Further, in the same manner as in Example 1, silicon (Si) concentration analysis was also performed.

[Comparative Example 1] The same as Example 1 except that the coating composition was not heat-treated after application, was kept at room temperature (25 ° C) for 15 minutes, and was then irradiated with ultraviolet rays to be cured. An abrasion resistant polycarbonate resin plate was obtained and evaluated in the same manner.

Further, Table 3 shows the results of analysis of the silicon concentration near the film surface of this abrasion-resistant polycarbonate resin plate in the same manner as in Example 1. As shown in Table 3, no gradient composition was observed in this comparative example in which the heat treatment was not performed.

[Comparative Examples 2 to 3] Abrasion resistant polycarbonate resin plates were obtained in the same manner as in Example 1 except that the amounts of the components (A) to (C) were changed as shown in Table 1. It evaluated similarly.

Comparative Example 4 Only the polycarbonate resin plate base material used in Example 1 was evaluated in the same manner as in Example 1.

[Comparative Example 5] Only the methacrylic resin plate base material used in Example 7 was evaluated in the same manner as in Example 7.

[Comparative Example 6] Only the veneer-coated decorative board substrate used in Example 8 was evaluated in the same manner as in Example 8.

The composition, film thickness, etc. of each of the above Examples and Comparative Examples are summarized in Table 1 below, and the evaluation results are summarized in Tables 2 and 3 below.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

As described above, since the coated article of the present invention has the graded composition cured coating layer formed on the surface of the base material, it has a high abrasion resistance which has never been possible before. It has excellent scratch resistance, heat resistance, chemical resistance, durability, weather resistance and adhesion to the substrate.

Further, according to the production method of the present invention, the gradient composition cured coating layer can be easily formed, the ratio of the inorganic part to the organic part can be easily controlled, and the abrasion-resistant coated article excellent in the above-mentioned respective properties can be obtained. This is an easily obtained method.

Since the present invention has such an effect, the present invention
It is extremely useful as a coating technique for improving the surface characteristics of various base materials such as plastic, metal, wood and paper.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08F 283/12 C08F 283/12 C08J 7/04 C08J 7/04 M C09D 4/02 C09D 4/02 (73) Patent holder 000003207 Toyota Motor Corporation, Toyota City, Aichi Prefecture, 1-chome (74) 1 agent above 100088328 Attorney Nobuyuki Kaneda (2 outside) (72) Inventor Hiroshi Fukushima 4-chome Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Mitsubishi Rayon Co., Ltd. Product Development Research Center (72) Inventor Misao Tamura 4-60 Sunadabashi, Higashi-ku, Aichi Prefecture 1 of 41 Yorokomichi, Toyota Central Research Institute Co., Ltd. (72) Inventor Kazuo Okamoto Nagakute-cho, Aichi-gun, Aichi 41 Address 1 Toyota Central Research Institute Co., Ltd. (72) Inventor Kisho Fukushima Nagachite, Aichi-gun, Aichi Prefecture 1 in 41 Yokomichi Yokomichi Yokosuka Central Research Institute Co., Ltd. (72) Inventor Osamu Kito 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Takayuki Nagai 1 Town, Toyota Town, Aichi Prefecture Toyota Motor Corporation (72) Inventor Katsuya Mizutani 4-7-23 Naka Station, Nakamura-ku, Aichi Prefecture Toyota Building Toyota Tsusho Corporation (56) Reference JP-A-11-268202 (JP, A) JP-A-2000-336281 (JP, A) JP-A-8-12899 (JP, A) JP-A-10-180933 (JP, A) JP-A-10-264291 (JP, A) JP-A-6-25555 ( (58) Fields surveyed (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 B05D 5/00-7/24 C08J 7/04-7/06 C09D 1/00-201 /Ten

Claims (7)

(57) [Claims] 1. An organic structure layer formed by hydrolysis / dehydration condensation of an alkoxy group of an organoalkoxysilane having an alkoxy group and an organic group in the molecule (A) on the surface of a substrate, and Mg, Al. , Ni, Co, Cu, Mn, F
e, Li, V, Zr, Ca, Y, Ga, In, Tl, S
Hybrid layered polymeric material in which an inorganic crystal structure centered on at least one metal selected from the group consisting of b, Rh, Ru, Pd, Sn, Zn, Pb and Ce is covalently bonded to each other in a layered manner. A cured coating layer comprising a structure 5 to 95 parts by weight and (B) 95 to 5 parts by weight of a compound having at least one (meth) acryloyloxy group in the molecule; The cured coating layer is a gradient composition cured coating layer in which the composition ratio of the component (A) and the component (B) in the layer changes continuously or in a layered manner between the substrate surface side and the atmosphere side. A coated article characterized by being. 2. The hybrid layered polymer material structure (A) has 10 to 99 parts by weight of an organoalkoxysilane (a-i) having an alkoxy group in the molecule and an organic group containing a radically polymerizable functional group. , (A-ii) Mg, A
l, Ni, Co, Cu, Mn, Fe, Li, V, Zr,
Ca, Y, Ga, In, Tl, Sb, Rh, Ru, P
1 to 80 parts by weight of an inorganic salt or organic salt of at least one metal selected from the group consisting of d, Sn, Zn, Pb and Ce, and (a-iii) having an alkoxy group in the molecule, a radical Alkoxysilane having no polymerizable functional group 0 to 70 parts by weight [(a-i) to (a-iii)]
The total amount of the components is 100 parts by weight. ], And (a-
iv) The coated article according to claim 1, which is a structure obtained by a reaction in the presence of 0 to 2000 parts by weight of a polar solvent. 3. The coated article according to claim 1, wherein the cured coating layer is a layer formed by heating the coating material composition so that the substrate surface temperature is 30 to 150 ° C. 4. The coated article according to claim 1, wherein the cured coating layer is a layer formed by heating the coating material composition so that the surface temperature of the substrate becomes 50 to 150 ° C. 5. An organic structure layer formed by hydrolysis / dehydration condensation of an alkoxy group of an organoalkoxysilane (A) having an alkoxy group and an organic group in the molecule on the surface of a substrate, and Mg, Al. , Ni, Co, Cu, Mn, F
e, Li, V, Zr, Ca, Y, Ga, In, Tl, S
Hybrid layered polymeric material in which an inorganic crystal structure centered on at least one metal selected from the group consisting of b, Rh, Ru, Pd, Sn, Zn, Pb and Ce is covalently bonded to each other in a layered manner. Structure 5 to 95 parts by weight, (B) compound having at least one (meth) acryloyloxy group in the molecule 95 to 5 parts by weight [the total amount of the components (A) and (B) is 100 parts by weight] To do. ],
And (C) a step of applying a coating material composition containing 0.1 to 10 parts by weight of an active energy ray-sensitive radical polymerization initiator, and a heat treatment to a coating film of the coating material composition, A step of continuously or layer-wise changing the composition ratio of the component (A) and the component (B) in the coating film between the substrate surface side and the atmosphere side, and active in the coating film after the heat treatment Gradient composition cured film in which the composition ratio of the component (A) and the component (B) in the layer changes continuously or in a layered form between the base material surface side and the atmosphere side by irradiation with energy rays And a step of forming a layer. 6. The hybrid layered polymer material structure (A) has 10 to 99 parts by weight of organoalkoxysilane (a-i) having an alkoxy group in the molecule and an organic group containing a radically polymerizable functional group. , (A-ii) Mg, A
l, Ni, Co, Cu, Mn, Fe, Li, V, Zr,
Ca, Y, Ga, In, Tl, Sb, Rh, Ru, P
Inorganic salt or organic salt of at least one metal selected from the group consisting of d, Sn, Zn, Pb and Ce, or 0 to 70 parts by weight of alkoxide, (a-iii) having an alkoxy group in the molecule, radical Alkoxysilane having no polymerizable functional group 0 to 70 parts by weight [(a-i) to (a-iii)]
The total amount of the components is 100 parts by weight. ], And (a-
iv) The method for producing a coated article according to claim 5, which is a structure obtained by a reaction in the presence of 0 to 2000 parts by weight of a polar solvent. 7. The heat treatment of the coating film of the coating material composition is performed by 3
The method for producing a coated article according to claim 5, which is performed in the range of 0 to 150 ° C.