JP2002160320A - Decorative sheet and plastic molded object using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which has water resistance, and is free from deterioration of a plastic mother material or a base material and suitable for obtaining a plastic molded object with surface hydrophilicity, and also to provide the plastic molded object using this sheet. SOLUTION: In this decorative sheet, on its surface material, a base layer formed of an acrylic polyol resin having an alkoxysilyl group as a coating material, and a surface layer formed with a coating material for a surface layer including a chemical compounds represented by a formula : (R1)n-Si-(OR 2)4-n (in the formula, R1 is a 1-6C an alkyl group, an epoxy alkyl group, an aryl group, or an alkenyl group; R2 is a 1-6C alkyl group; n is 0-2) and at least one or more kind inorganic oxides as a surface coating material, are set up.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a decorative sheet suitable for imparting hydrophilicity to the surface of a plastic molded article by molding using a molding material such as a sheet molding compound or a bulk molding compound, and a plastic molded article using the same. About.

[0002]

2. Description of the Related Art Conventionally, for example, dressing shelves for bathrooms or toilets, wall panels and ceiling panels for bathrooms, washing places (waterproof pans) for bathrooms, top plates and sinks for wash basins, and places around water such as bathtubs. A plastic molding mainly made of fiber reinforced plastic is used for housing equipment members. However, sheet molding compound (SM
C) or a fiber-reinforced plastic molded article formed using only bulk molding compound (BMC) is inferior in design. Therefore, a non-woven fabric having a desired decorative layer provided on the surface by printing or the like during molding of the fiber-reinforced plastic molded article. Or, an appropriate decorative surface material such as a woven cloth is superposed on a molding material to be integrated (for example, JP-A-51-20951, JP-A-53-14).
6769, JP-B 1-32767, and JP-A-4-341809).

[0003] When housing equipment members made of plastic molded articles provided with these decorative layers are used in places where water is supplied such as bathrooms, washrooms, toilets, and kitchens, insoluble dirt such as water scale and soap scum is easily generated. In addition, it is strongly adhered to the surface with the passage of time, and the cleaning operation becomes difficult.

Therefore, recently, the surface of the plastic molded body is processed to be hydrophilic so that water scale, soap scum, and the like are hardly adhered to such insoluble dirt and the like in places around water. Means have been introduced to enable the removal of contaminants by only a simple cleaning operation such as washing with water.

Conventionally, as a method for making the surface of a plastic molded article hydrophilic, a film formed using a coating material containing a hydrophilic resin such as a nylon resin or an acrylic resin as a coating material, or a photocatalytically active material. The surface is made hydrophilic by a film containing a metal oxide having the following.

The above-mentioned metal oxide having photocatalytic activity includes titanium oxide, and a film containing this titanium oxide is, for example, a sol-gel method formed by hydrolysis using an alkoxide of titanium. Coatings are most commonly known.

As a film having photocatalytic activity formed by using an alkoxide of titanium, a film obtained by applying a composition obtained by adding an amide or a glycol to a titanium alkoxide and baking the same (Japanese Patent Application Laid-Open No. 4-83537). Patent Document), a coating obtained by applying a composition obtained by adding an alcoholamine to a titanium alkoxide and firing the composition.
(See Japanese Patent Application Laid-Open No. 7-100378). In addition, an inorganic binder such as water glass and colloidal silica, and some weather-resistant binders such as a fluororesin are mixed and applied to the crystalline titanium oxide particles, and a coating obtained without a firing step is formed. Known (Japanese Patent Laid-Open No. 7-1
No. 71408).

[0008]

However, a film formed by using a paint containing a hydrophilic resin as a coating material has poor water resistance, and swells with time to cause swelling and peeling. was there. In addition, since such a film has a hygroscopic property, in a humid environment where water is present, the surface of the film is always in a wet state, so that various germs and molds are easy to propagate, which causes a bad smell or a sanitary condition. There was a problem.

In the case of a film requiring a firing step, 3
The photocatalyst cannot be applied unless fired at a temperature of from 00 to 500 ° C., and thus can be applied to inorganic substances such as glass, ceramics, and metal materials. It could not be applied at all.

Further, an inorganic binder such as water glass or colloidal silica or a part of a weather-resistant binder such as a fluororesin is mixed and applied to the crystalline titanium oxide particles, and the mixture is obtained without a firing step. In the coating to be used, even if an inorganic binder or a fluororesin is used as the binder, the strong oxidative decomposition action of titanium oxide has
There has been a problem that the resin itself of the base material gradually decomposes with the passage of time, causing deterioration and detachment of the film.

On the other hand, if the content of titanium oxide in the coating film or the coating film is reduced, resin deterioration on the surface of the base material can be prevented to some extent, but there is a problem that the hydrophilicity of the surface becomes insufficient.

Further, since the photocatalytic activity of titanium oxide uses ultraviolet light having a wavelength shorter than that of visible light as excitation energy, there is also a problem that a sufficient hydrophilic surface cannot be maintained indoors where sunlight does not reach much.

The present invention has been made in view of the above-mentioned problems of the prior art, and is intended to provide a plastic molded article having water resistance, having no risk of deteriorating a plastic base material or a base material, and having a hydrophilic surface. It is an object of the present invention to provide a decorative sheet suitable for obtaining and a plastic molded body using the same.

[0014]

SUMMARY OF THE INVENTION The present invention relates to the following. (1) On a surface material, a base layer formed by using an acrylic polyol resin having an alkoxysilyl group as a coating material, and at least a compound represented by the formula (1) and at least one or more inorganic oxides are coated. A decorative sheet provided with a surface layer formed using a surface layer paint contained as a film material.

(R1) n-Si- (OR2) 4-n (1) (wherein, R1 is an alkyl group having 1 to 6 carbon atoms, an epoxyalkyl group, an aryl group, or an alkenyl group;
R2 is an alkyl group having 1 to 6 carbon atoms;
Or 2. (2) The compound represented by formula (1) is an alkoxysilane compound wherein n = 0 or 1 in formula (1).
The decorative sheet according to (1). (3) The decorative sheet according to (1) or (2), wherein one of the inorganic oxides is alumina. (4) A plastic molded article in which the decorative sheet according to any one of (1) to (3) is integrated with a surface of a plastic substrate. (5) The plastic molded article according to (4), wherein the plastic substrate is a sheet molding compound or a bulk molding compound.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the decorative sheet of the present invention, as a nonwoven fabric or a woven fabric used as a decorative surface material having a hydrophilic surface, those using cellulose fibers can be used. When the moldability of plastic molded products such as reinforced plastics (FRP) into three-dimensional shape, dimensional stability and strength are insufficient, and therefore thermoformability is required when molding fiber-reinforced plastic molded products It is preferable to use a thermoplastic resin whose temperature at the time of molding the fiber-reinforced plastic molded product is between the Vicat softening temperature and the melting point, such as vinylon or polyester, as a material. Also, a prepreg sheet for decoration obtained by semi-curing a thermosetting resin can be used.

When the surface of the above-mentioned nonwoven fabric or woven fabric is subjected to a decoration process for decorating, a pattern such as a wood grain pattern, a stone grain pattern, or a geometric pattern is mainly formed by printing. As a printing method of the picture pattern, any method such as letterpress printing, intaglio (gravure) printing, offset printing, silk printing and the like may be used.

When a surface protective layer is provided on the decorative surface material, a transparent or translucent plastic film is laminated or a protective layer is formed by coating.

In order to make these decorative surface material surfaces hydrophilic, first, an acrylic polyol resin having an alkoxysilyl group is applied to the first surface layer. Acrylic polyol resin having an alkoxysilyl group is generally produced by copolymerization of an acrylic monomer having a hydroxyl group and an acrylate ester, in which case, an unsaturated monomer having an alkoxysilyl group can be copolymerized, Various silicone-modified acrylic polyol resins can be synthesized.

Typical examples of the alkoxysilyl group-containing monomer described above include the following. Vinylmethyldimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane, vinyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-
[(2-propen-2-yloxycarbonyl) benzoyloxy] propylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane,
And γ-methacryloyloxypropyltriethoxysilane. These compounds are compounds in which one group having a polymerizable unsaturated bond, 0 to 2 hydrocarbon groups and 1 to 3 alkoxy groups are bonded to silicon, and are copolymerized with a hydroxyl group-containing acrylic monomer. Thereby, a silicone-modified acrylic polyol resin having an alkoxysilyl group as a pendant group is obtained.

The monomers copolymerizable with the hydroxyl group-containing acrylate and the alkoxysilyl group-containing monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i- Alkyl (meth) acrylates such as butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and lauryl (meth) acrylate: styrene;
Aromatic vinyl compounds such as vinyltoluene: acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid and the like. Glycidyl (meth) acrylate having an epoxy group can also be used. In addition, if necessary,
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-
There are amino group-containing monomers such as butoxymethyl (meth) acrylamide and N-methylacrylamide, and acrylamides.

The acrylic polyol resin having an alkoxysilyl group has a hydroxyl value of 5 to 300 mg KOH.
/ G, and a hydroxyl value of 50 to 200 mg
More preferably, it is KOH / g. Hydroxyl value is 5mg
If it is less than KOH, it tends to cause poor curing and lower hydrophilicity.
If it exceeds H / g, the durability, acid resistance, alkali resistance and the like of the film tend to decrease.

The hydroxyl group-containing acrylic monomer, the alkoxysilyl group-containing monomer and the other ethylenically unsaturated monomers are contained in a total of 100 (weight ratio), and the hydroxyl group-containing acrylic monomer 5 to 40, the alkoxysilyl group-containing monomer 10 to 70, It is preferable to use other ethylenically unsaturated monomer residues. When the ratio of the alkoxysilyl group-containing monomer is less than 10, the adhesion to the components of the surface layer coating material tends to decrease, and when the ratio of the alkoxysilyl group-containing monomer exceeds 70, the pot life becomes short, so that handling is performed. It tends to worsen.

The resin composition for forming a first layer (base layer) into which an alkoxysilyl group is introduced as a pendant group is used to promote a curing reaction of the resin and a condensation reaction of a silanol group generated by the alkoxysilyl group. A catalyst such as an inorganic acid, an organic acid, an inorganic base, an organic base, an organic metal, or a metal alkoxide is added.

As the catalyst, for example, hydrochloric acid, acetic acid, sulfuric acid,
Inorganic acids such as phosphoric acid, organic acids such as formic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid, potassium hydroxide, sodium hydroxide,
Inorganic bases such as calcium hydroxide, triethylamine, ethylamine, diethylamine, dibutylamine, tributylamine, tetrabutylguanidine, aniline, pyridine, ammonia, inorganic bases such as piperidine, dibutyltin dilaurate, dibutyltin dioctylate,
Organic tin compounds such as dibutyltin diacetate, aluminum tris (acetylacetonate), titanium tetrakis (acetylacetate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (isopropoxy) bis (acetylacetonate),
Metal chelate compounds such as zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bisacetylacetonate, and zirconium bis (isopropoxy) bis (acetylacetonate).

The solvent for the coating solution for forming the first layer (base layer) is not particularly limited. For example, benzene, toluene, xylene, styrene, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichloromethane, dichloroethylene, trichlene, perchloroethylene, ethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, diglyme, anisole,
Methanol, ethanol, propanol, 2-propanol, t-butanol, ethyl cellosolve, methyl cellosolve, butyl cellosolve, phenol, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone,
-Pentanone, ethyl acetate, butyl acetate, triethylamine, piperidine, pyridine, acetonitrile, N, N
-Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, N-methylpyrrolidone, methyl methacrylate,
Dioctyl phthalate, water and the like are used, and they may be used as a mixed solvent thereof.

In the step of forming the first layer (base layer), a good result can be obtained by a roll coating method, a die coating method, or the like when the coating method is applied to a film-like substrate (surface material). . Further, a spin coating method, a dip coating method, a flow coating method, a spray coating method, or the like can also be used.

The thickness of the film of the first layer (base layer) is 0.1
The thickness is preferably from 100 to 100 μm, and more preferably from 0.2 to 50 μm. If the thickness is less than 0.1 μm, it may not be possible to sufficiently ensure the adhesion between the base material and the second layer. In order to obtain a film thickness of 100 μm or more, several recoatings may be required, and the workability may deteriorate or the hardness of the coating film may be reduced due to the thick coating film.

It is necessary to dry the coating solution layer formed from the solution for forming the first layer (base layer). The drying temperature is not particularly limited, but it is generally 20 to 140 ° C. preferable. For this temperature range, it is necessary to select a temperature at which the coating material base material or the base material does not deform, discolor, or the like.

After the formation of the first layer (base layer) is completed, an inorganic oxide layer is formed thereon as a second layer (surface layer).

In the present invention, in order to form the second layer (surface layer), a mixed solution of alumina and an alkoxysilane compound as an inorganic oxide is applied on the surface of the first layer and dried. Alumina used for forming the second layer (surface layer) has various crystalline states, but is not particularly limited. Preferably, boehmite-type alumina having a large number of hydroxyl groups on the crystal surface, γ-type alumina and α-type alumina having high wet heat and high sinterability are preferably used.
These aluminas are used as a colloid solution or a slurry solution.

The compound mixed with the inorganic oxide alumina to form the second layer (surface layer) is represented by the following chemical formula (1)
And at least one kind of partially hydrolyzed condensate of the alkoxysilane represented by

In the alkoxysilane compound represented by formula (1) (hereinafter referred to as alkoxysilane compound), R
1 is C1-6 alkyl, epoxyalkyl, aryl or alkenyl, R2 is C1-6 alkyl,
n is 0, 1 or 2. R1 is a C1-6 alkyl group such as an ethyl group, a methyl group and a propyl group; an epoxyalkyl group such as a glycidoxypropyl group and an epoxycyclohexylethyl group; an aryl group such as a phenyl group and a benzyl group; a vinyl group and an allyl And alkenyl groups such as an acryloyloxypropyl group and a methacryloyloxypropyl group. R2 is a C1-6 alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group.

Specific examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane,
(Tetrafunctional) tetraalkoxysilanes such as tetrapropoxysilane and tetrabutoxysilane; and others, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and benzyl Examples include trifunctional alkoxysilane compounds such as trimethoxysilane, benzyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane. Further, in (1) of Chemical formula 2, a preferable number of n is n = 0 (tetrafunctional) or n = 1 (trifunctional). When n> 2, the curing reaction by hydrolysis and condensation of the alkoxysilane compound is reduced, and the immobilization of alumina and the surface hardness are not improved. That is, tetraalkoxysilane when n = 0 is particularly desirable.

Further, in the chemical formula (1), the carbon number of the substituent R2 is preferably C1 to C3. That is, the alkyl group is a methyl group, an ethyl group, or a propyl group. If the number of carbon atoms is too large, the hydrolysis and condensation reactions become slow, and it becomes difficult to easily produce a partially hydrolyzed condensate of the alkoxysilane compound.

Examples of preferred alkoxysilane compounds are:
Examples include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, and ethyltrimethoxysilane.

The concentration of alumina and the alkoxysilane compound forming the second layer (surface layer) is preferably adjusted to 5 to 50% by weight of the alkoxysilane compound. If the amount of the alkoxysilane compound is less than 5% by weight, the binding of alumina may not be sufficient, and the coating film may have a low surface hardness. On the other hand, if it exceeds 50% by weight, the hydrophilicity of the surface is reduced, and the acid resistance, alkali resistance, water resistance and the like tend to be weak.

The thickness of the second layer (surface layer) is not particularly limited, but is preferably 0.05 to 20 μm. If the thickness is less than 0.05 μm, the resulting second layer (surface layer) may not show a sufficient hydrophilic effect,
When the thickness exceeds m, cracks and peeling of the second layer (surface layer) are likely to occur due to heat shrinkage of the oxide.

The drying step after applying the coating material for the surface layer to form the second layer (surface layer) is not particularly limited to a drying temperature, but is preferably from 20 to 140 ° C. For this temperature range, it is necessary to select a temperature at which the coating material base material or the base material does not deform, discolor, or the like.

Next, when the molding material of the plastic molded article molded using the decorative sheet according to the present invention is a fiber-reinforced plastic, the thermosetting resin molding material includes glass fiber, carbon fiber, potassium titanate fiber and the like. And an unsaturated polyester resin or a vinyl ester resin obtained by kneading fibers, a catalyst, a filler, a release agent, and the like. Others
Thermosetting resins such as diallyl phthalate, acrylic, melamine, epoxy and the like are sometimes used. These resins are usually used in a prepolymer state. Fibers such as glass usually contain 10 to 70% by weight. As the filler, calcium carbonate, barium sulfate, aluminum hydroxide or the like is used. As the release agent, a metal fatty acid such as zinc stearate is used. In addition, if necessary, styrene monomer, reactive diluent such as tributylstyrene monomer, isocyanate,
Crosslinking agents such as amines, benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl perbenzoate,
A curing catalyst such as an organic sulfonate and a thermoplastic resin such as polymethyl methacrylate are added. The thermosetting resin composition is made of a sheet molding compound (SM
C) and bulk molding compound (BMC). The molding condition of the thermosetting resin molded body sets the temperature and time at which the thermosetting resin can be cured. Although this varies depending on the resin used, for example, the temperature is 60 to 180 ° C., the pressure is 30 to 200 kPa, and the molding time is about 1 to 30 minutes.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

(Preparation of Base Layer Coating Material 1) Synthesis of Silicone-Modified Acrylic Polyol Resin 1 In a flask equipped with a stirrer, a reflux condenser and a thermometer,
40 parts of isopropyl alcohol was charged and heated to 80 ° C. under a nitrogen stream, and 30 parts of γ-methacryloxypropyltrimethoxysilane, 30 parts of 2-hydroxyethyl acrylate, 30 parts of methyl methacrylate, 10 parts of butyl acrylate, 2,2 A mixed solution composed of 0.5 parts of -azobis-isobutyronitrile was added dropwise over 2 hours. Subsequently, a mixed solution of 2 parts of t-butylperoxy-2-ethylhexanoate and 20 parts of isopropyl alcohol was added dropwise over 30 minutes, and the temperature was further maintained for 3 hours. Thereafter, the mixture was cooled, and isopropyl alcohol was added so that the heating residue was about 50%, to obtain an alkoxysilyl group-containing copolymer solution. The heating residue of the obtained polymer solution was 50.0%, Gardner viscosity Z4, weight average molecular weight (measured by gel permeation chromatography (GPC), and converted by a calibration curve prepared using standard polystyrene. ) Is 8
It was 1,000. Further, the hydroxyl value of the obtained silicone-modified acrylic polyol resin 1 was 145 mg KO
H / g. By mixing 10 parts of this silicone-modified acrylic polyol resin 1, 90 parts of a mixed solvent of isopropanol and methyl cellosolve (isopropanol 7 vs. methyl cellosolve 3), and 0.3 part of oxalic acid,
Base layer paint 1 was prepared.

(Preparation of Base Layer Coating Material 2) Synthesis of Silicone-Modified Acrylic Polyol Resin 2 In a flask equipped with a stirrer, a reflux condenser and a thermometer,
A mixture of 40 parts of isopropyl alcohol, heated to 80 ° C. under a nitrogen stream, and 70 parts of γ-methacryloxypropyltrimethoxysilane, 20 parts of 2-hydroxyethyl acrylate, 10 parts of methyl methacrylate and 10 parts of butyl acrylate Was added dropwise over 2 hours.
Subsequently, a mixed solution of 2 parts of t-butyl peroxy-2-ethylhexanoate and 20 parts of isopropyl alcohol was added to 3 parts.
The solution was added dropwise over 0 minutes, and the temperature was kept over 3 hours. Thereafter, the mixture was cooled, and isopropyl alcohol was added so that the heating residue was about 50%, to obtain an alkoxysilyl group-containing copolymer solution. The heating residue of the obtained polymer solution was 50.0%.
%, Gardner viscosity U +, and weight average molecular weight (measured by gel permeation chromatography (GPC) and converted by a calibration curve prepared using standard polystyrene) were 94,400. Further, the hydroxyl value of the obtained silicone-modified acrylic polyol resin 1 is 97 m
gKOH / g. The base layer coating material 2 was prepared by mixing 10 parts of this silicone-modified acrylic polyol resin 1, 90 parts of a mixed solvent of isopropanol and methyl cellosolve (isopropanol 7 vs. methyl cellosolve 3), and 0.15 part of oxalic acid.

(Preparation of Surface Layer Coating Material 1) Colloidal Alumina (Alumina Sol 520 manufactured by Nissan Chemical Industries, Ltd.)
By mixing 17 parts (using trade name), 17 parts of silica liquid (using ASR (trade name) manufactured by Sumitomo Osaka Cement Co., Ltd.), and 66 parts of methanol, coating material 1 for surface layer was prepared.

(Preparation of Surface Layer Paint 2) Colloidal Alumina (Alumina Sol 520, manufactured by Nissan Chemical Industries, Ltd.)
17 parts of a silica liquid (10 parts of tetraethoxysilane, 40 parts of water, 50 parts of methanol, and 1 part of nitric acid) were mixed in a flask equipped with a stirrer and a reflux condenser.
17 parts of a mixture heated at 0 ° C. for 3 hours) and 66 parts of methanol were mixed to prepare a surface layer coating material 2.

Example 1 A coating material for a base layer 1 was applied by a die coating method to a decorative printing side surface of a surface material of a decorative sheet (M film (trade name) manufactured by Dai Nippon Printing Co., Ltd.). Then 1
The solvent was evaporated in a warm air drying step at 20 ° C. for 5 minutes. After that, paint 1 for the surface layer is also formed by the die coating method.
Was applied, and the solvent was evaporated in a drying step at 100 ° C. for 5 minutes. Next, a thermosetting resin material SMC (WLP (trade name) manufactured by Hitachi Chemical Co., Ltd.) is cut into a predetermined size, set in a molding die, and then subjected to the surface hydrophilicity treatment prepared above. The decorative sheet was overlaid on the SMC, and was integrally formed with the SMC. The molding conditions are upper and lower mold temperatures of 146 to 150.
The heating and pressurizing were performed for 5 minutes at 100 ° C. and 100 ° C.

Example 2 A base layer coating material 2 was applied to the surface of a decorative sheet (decorative printing side surface of M film (trade name) manufactured by Dai Nippon Printing Co., Ltd.) by a die coating method. Then 1
The solvent was evaporated in a warm air drying step at 20 ° C. for 5 minutes. Then, paint 2 for the surface layer is also formed by the die coating method.
Was applied, and the solvent was evaporated in a drying step at 100 ° C. for 5 minutes. Next, a thermosetting resin material SMC (WLP (trade name) manufactured by Hitachi Chemical Co., Ltd.) is cut into a predetermined size, set in a molding die, and then subjected to the surface hydrophilicity treatment prepared above. The decorative sheet was overlaid on the SMC, and was integrally formed with the SMC. The molding conditions are upper and lower mold temperatures of 146 to 150.
The heating and pressurizing were performed for 5 minutes at 100 ° C. and 100 ° C.

Comparative Example As a comparative example of the present invention, a decorative sheet (with M film (trade name) manufactured by Dai Nippon Printing Co., Ltd.) not coated with a hydrophilic paint was integrally molded with SMC.

Evaluation of Film Performance The following evaluations were made on the plastic molded bodies produced in the above Examples and Comparative Examples. Table 1 shows the results.

Adhesion of coating film I A cellophane tape was stuck on the surface of the coating film and peeled off to examine the presence or absence of peeling of the coating film. The meanings of the symbols in the section of adhesion (I) in Table 1 are as follows. ：: No peeling of the coating film was observed and there was no change in appearance

Adhesion of Coating Film II A plastic molded body of a test piece was immersed in hot water at 90 ° C. for a long time, and then the coating film was visually inspected for peeling or swelling. The meanings of the symbols in the section of adhesion (II) in Table 1 are as follows. ：: No peeling / swelling was observed and no change in appearance

The wettability of the coating film The entire plastic molded body of the test piece was wetted with water, and the degree of spreading of the water film was examined. The meanings of the symbols in the section of wettability in Table 1 are as follows. ：: Water film spreads all over △: Water film spreads but gradually repels ×: Water film does not form and repels water

Hydrophilicity of Coating Film The static contact angle of water on the surface of the plastic molded body of the test piece was measured.

The weather resistance of the coating film A 240-hour test was conducted using a sunshine weather meter to examine the degree of deterioration of the coating film and the surface of the plastic substrate. The meanings of the symbols in Table 1 are as follows. ：: no change in the coating film △: clouding of the coating film ×: peeling or discoloration of the coating film, or deterioration of the plastic substrate observed

[0054]

[Table 1]

Table 1 shows that each of the plastic molded articles of the examples has a hydrophilic surface having a wettability and a water contact angle, and all have good adhesion and weather resistance. On the other hand, since the plastic substrate of the comparative example was not coated with a hydrophilic paint, it did not have wettability, had a high contact angle, and did not have hydrophilicity.

[0056]

The decorative sheet according to the present invention and the plastic molded article using the same have excellent surface hydrophilicity and durability, as well as good production efficiency as a plastic molded article.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int. Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 163/00 C09D 163/00 183/04 183/04 // B29K 105: 06 B29K 105: 06 B29L 9: 00 B29L 9:00 F term (reference) 4F100 AA17B AA19B AK01C AK01D AK25A AK52A AK52B AK52K AL06A AS00B BA03 BA04 BA07 BA10B BA10C BA10D GB08 GB81 JB05 JK07 JL09 4F204 AD09 AD20 AD34 FA01 FB13 NA03 FB13 PB03 PB05 PC08

Claims (5)

[Claims] 1. A base layer formed on a surface material of an acrylic polyol resin having an alkoxysilyl group as a coating material, at least a compound represented by formula (1) and at least one or more inorganic oxides Sheet provided with a surface layer formed by using a surface layer coating material containing as a coating material. (R1) n-Si- (OR2) 4-n (1) (wherein, R1 is an alkyl group having 1 to 6 carbon atoms, an epoxyalkyl group, an aryl group, or an alkenyl group;
R2 is an alkyl group having 1 to 6 carbon atoms;
Or 2. ) 2. The decorative sheet according to claim 1, wherein the compound represented by the formula (1) is an alkoxysilane compound wherein n = 0 or 1 in the formula (1). 3. The decorative sheet according to claim 1, wherein one of the inorganic oxides is alumina. 4. A plastic molded article in which the decorative sheet according to claim 1 is integrated with a surface of a plastic substrate. 5. The plastic molding according to claim 4, wherein the plastic substrate is a sheet molding compound or a bulk molding compound.