JPH0673330A - Coated thermoplastic sheet and coating composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic sheet excellent in weathering resistance and good in bondability by heat welding or the like, by coating a sheet with a composition obtained by mixing two specified copolymers as the principal components with a specified amount of an aluminum chelate compound. CONSTITUTION:Carboxylated fluorocopolymer (e.g. hexahydrophthalic-anhydride- modified tetrafluoroethylene/n-butyl vinyl ether copolymer) of an acid value of 10-150mgKOH/g is mixed with a carboxylated acrylic copolymer (e.g. methyl acrylate/acrylic acid copolymer) of an acid value of 10-150mgKOH/g and compatible therewith. 0.1-30 pts.wt. aluminum chelate compound (e.g. ethyl acetoacetate aluminum diisopropylate) is added to 100 pts.wt. mixed resin. A thermoplastic resin sheet (e.g. vinyl chloride resin sheet) is coated with the obtained coating composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a coated thermoplastic sheet.

[0002]

2. Description of the Related Art Conventionally coated thermoplastic sheets are often used for the purpose of improving weather resistance, which are protectively coated with a coating material having relatively excellent weather resistance such as acrylic resin.

Further, for the purpose of further improving the weather resistance, there has been proposed a protective coating of a covering material made of a fluororesin (Japanese Patent Laid-Open No. 60-101043). Further, many of these thermoplastic sheets are matte coated.

[0004]

Conventionally, examples of the coated thermoplastic sheet having excellent weather resistance include those described in JP-A-60-101043, which is known as an agricultural plastic sheet. The adhesion between the protective coat and the sheet was poor, and it was not sufficiently durable for use.

Further, in order to solve these problems, the present inventors have disclosed, as described in Japanese Patent Application No. 2-412091, a fluorine-containing copolymer having a cross-linking site having active hydrogen and a compatible copolymer. A coating composition has been devised which has a so-called temperature-sensitive amine catalyst as a main component, an acrylic copolymer as a main component, a polyisocyanate compound as a cross-linking agent, and an oxidizer in accordance with workability of line coating. This product has excellent weather resistance and adhesiveness, is excellent in removing stains, and has the property of effectively preventing the leaching of the plasticizer from the thermoplastic sheet.

However, as a demand for further processability, a one-pack type is desired rather than a two-pack type which requires mixing and control of pot life. In addition, the cross-linking by urethane bond,
Since it is sufficiently dense and has heat resistance, there are cases in which the advantage of using the thermoplastic sheet, such as the welder and the adhesion by heat fusion, is rather damaged. For example, there is a problem that the wide welder is hard to be applied even if the general welder property is sufficient. Further, as a matting formulation, a method using a matting agent such as fine silica or acrylic resin gel has been known so far, but fine silica has poor water resistance and acrylic resin gel has poor weather resistance.

The present invention solves the above-mentioned problems of the prior art, that is, it is a one-pack type and has good productivity, excellent weather resistance, adhesiveness, and stain removability. It is an object of the present invention to provide a coated thermoplastic sheet which does not impair the fusion property. Also,
It provides a composition having excellent weather resistance even in the case of matting.

[0008]

The present invention has been made to solve the above-mentioned problems, and has a carboxyl group having an acid value of 10 to 150 (mgKOH / g) on a thermoplastic resin sheet. An acid value compatible with the fluorine-containing copolymers (A) and (A) is 10 to 150 (mgKOH
/ G) an acrylic copolymer (B) having a carboxyl group as a main component, and a coating containing 0.1 to 30 parts by weight of an aluminum chelate compound per 100 parts by weight of the total of (A) and (B). It is intended to provide a thermoplastic sheet coated with the composition.

Examples of the thermoplastic resin as the base material of the coated thermoplastic sheet of the present invention include vinyl chloride resin, polyethylene resin, polyester resin and the like. Of these, vinyl chloride resins, especially soft vinyl chloride resins, are most commonly used. As such a vinyl chloride resin, in addition to a vinyl chloride homopolymer, 40% by weight or less of at least one kind of monomers such as vinyl chloride and vinyl acetate, ethylene, propylene, acrylic acid ester, and methacrylic acid ester, preferably Copolymers in an amount of 30% by weight or less, and polymers compatible with these homopolymers or copolymers, for example, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, etc. May be blended. Further, a vinyl chloride resin is often blended with an appropriate amount of a plasticizer and used as a soft vinyl chloride resin. The amount of the plasticizer blended is preferably in the range of about 30 to 70 parts by weight per 100 parts by weight of the vinyl chloride resin. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, diisodecyl adipate, tricresyl phosphate, epoxidized soybean oil, and epoxidized linseed oil. Further, the vinyl chloride resin may be added with usual additives such as a lubricant, an antioxidant, an antistatic agent, a heat stabilizer, a coloring agent and a flame retardant.

Further, a surfactant may be added to the vinyl chloride resin for the purpose of antifogging. As such a surfactant, a nonionic surfactant is preferably adopted.

In the present invention, the coating composition for forming a film on the thermoplastic resin sheet has an acid value of 10 to 150 (mgKOH / mgKOH / mg on the thermoplastic resin sheet.
g) Fluorine-containing copolymer (A) having a carboxyl group
And an acid value compatible with (A) of 10 to 150 (mg
KOH / g) as a main component of an acrylic copolymer (B) having a carboxyl group, and a total of 100 of (A) and (B)
0.1 to 3 aluminum chelate compound per part by weight
Those containing 0 parts by weight are adopted. Here, the fluorine-containing copolymer (A) having a carboxyl group of 10 to 150 (mgKOH / g) as an acid value is a solvent-soluble fluorine-containing copolymer having a fluorine content based on a fluoroolefin unit of 10% by weight or more. Coalescence is preferably adopted.

The fluorine-containing copolymer (A) has a fluorine content based on the fluoroolefin unit of 10% by weight or more, preferably 10 to 70% by weight, more preferably 1%.
5 to 50% by weight and an intrinsic viscosity of 0.01 to 4.0 dl measured in tetrahydrofuran in the uncured state
/ G is used. However, the fluorine content is 10
If it is less than wt%, the desired effect of improving the weather resistance will decrease. Further, when the intrinsic viscosity is within the above range, the coating property as a coating material becomes good, and the physical properties of the formed film become excellent. As such a fluorine-containing polymer,
As the fluoroolefin and the comonomer copolymerizable with the fluoroolefin, a copolymer with an ethylenically unsaturated compound is preferably adopted.

Examples of such fluoroolefins include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene and pentafluoropropylene. Of these, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, and hexafluoropropylene are particularly preferably used. Further, as the ethylenically unsaturated compound as a monomer copolymerizable with a fluoroolefin, olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acryloyl group-containing compounds, methacryloyl group-containing And the like.

Of these, olefins, vinyl ethers, vinyl esters, and allyl ethers, which have excellent copolymerizability with fluoroolefins, have 1 to 10 carbon atoms.
Those having about 10 linear, branched or alicyclic alkyl groups are preferable.

In the fluorine-containing copolymer (A), the unit based on the fluoroolefin is preferably contained in an amount of 30 to 70 mol%, and when it is 30 mol% or less, the effect of improving the weather resistance is not sufficient, and 70 mol% If it exceeds the range, the solubility in a solvent tends to decrease, which may hinder the coating work as a paint. Moreover, in the copolymer, the fluoroolefin and the ethylenically unsaturated compound may be used alone or in combination of two or more kinds.

The carboxyl group in the fluorine-containing copolymer (A) having a carboxyl group of 10 to 150 (mgKOH / g) as an acid value in the main constituent components of the coating composition of the present invention is an aluminum chelate compound or other It is necessary to be able to form crosslinks with the components and functional groups of.

The carboxyl group forms a cross-link by a chemical bond at room temperature or after heating after coating with the aluminum chelate compound and evaporation of the solvent or stabilizer, and other functional groups such as a hydroxyl group, an acid amide group, an amino group and a mercapto group. Active hydrogen-containing groups such as, epoxy groups, carbon-carbon unsaturated groups, active halogen groups such as bromine and iodine, alkoxysilyl groups, acetylacetoxy groups, etc. among the types of aluminum chelate compounds and combinations with other components. It goes without saying that it can be used for the purpose of the original cross-linking, or as a thickener and for adjusting the solubility.

The method of introducing such a crosslinking site into the copolymer is, for example, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyaryl vinyl ether, hydroxyalkyl allyl ester, hydroxyalkyl vinyl ester, glycidyl vinyl ether, acrylic acid, methacrylic acid, aryl. For example, a method of copolymerizing a monomer having a cross-linking reaction site such as vinyl ether or diaminoethyl vinyl ether, or a method of adding an acid anhydride, an isocyanate, an alkyl (meth) acrylate or the like to a fluorine-containing copolymer, and the like. Adopted. Further, as a method of decomposing a part of the copolymer, after copolymerizing a monomer having a hydrolyzable ester group, the copolymer is hydrolyzed to give a carboxylic acid or a hydroxyl group in the copolymer. Is also used. Further, a method of introducing a carboxylic acid group by reacting a hydroxyl group-containing copolymer with a divalent carboxylic acid anhydride such as succinic acid, hexahydrophthalic anhydride, or methyl-hexahydrophthalic anhydride is also adopted.

The acrylic copolymer (B) having a carboxyl group of 10 to 150 (mgKOH / g) as an acid value compatible with the fluorine-containing copolymer (A) in the present invention is
An alcohol ester of acrylic acid or methacrylic acid having 1 to 12 carbon atoms, having a molecular weight of 1,000 to 150,
000 acrylic copolymer. Such acrylic copolymers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Examples thereof include n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-butyl acrylate and tert-butyl acrylate acrylonitrile, methacrylonitrile.
Further, preferably, a copolymer composed of two or more of these monomers, or a copolymerization with an alcohol ester of acrylic acid other than the above examples, styrene, maleic acid, vinyl esters (vinyl acetate, etc.), vinyl silane, etc. Coalescence is used.

More preferably, in the acrylic copolymer, the polymer having a cross-linking site is cross-linked by the reaction between the cross-linking site of the fluorinated copolymer and the aluminum chelate compound, and the coating film of the paint has a three-dimensional network structure, It exhibits excellent properties.

The carboxyl group of the acrylic copolymer (B) can be introduced by copolymerizing an acrylic acid or methacrylic acid monomer. Further, as the other cross-linking site of the copolymer, it is preferable to use a hydroxyl group, a glycidyl group, an amide group, a silanol group, or the like. For example, the introduction of a hydroxyl group is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate. , 2-
Hydroxypropyl acrylate, 2-hydroxymethacrylate, 3-hydroxypropyl acrylate, 3
-Hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 3-
Chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, etc., and the introduction of glycidyl groups, such as glycidyl acrylate, glycidyl methacrylate, (β-methyl) glycidyl acrylate, (β-methyl) glycidyl methacrylate, etc. The introduction of the group is acrylamide, methacrylamide, dimethylacrylamide, dimethylmethacrylamide, N-tert-butylacrylamide, N-
tert-butyl methacrylamide, N-octyl acrylamide, N-octyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, etc.,
The introduction of silanol groups is carried out by copolymerizing a monomer such as vinylsilane with the above-mentioned acrylic copolymer or a comonomer which gives a copolymer.

The silanol group can also be introduced by a method of adding an isocyanate silane or a silane coupling agent to the hydroxyl group-containing acrylic polymer.

Here, the acrylic copolymer (B) is
It may be a mixture of a polymer having a crosslinking site and a polymer having no crosslinking site, and the polymer having no crosslinking site is a carboxyl group, a hydroxyl group, a glycidyl group, an amide group or the like as exemplified above. It does not include a copolymer with the monomer. Thus, the proportion of the acrylic copolymer having no crosslinking site is preferably up to 50% by weight based on the acrylic copolymer having a crosslinking site.

The acid value is 10 to 150 (mgKOH /
g) Fluorine-containing copolymer (A) having a carboxyl group
And an acid value compatible with (A) of 10 to 150 (mg
KOH / g) as a main component of an acrylic copolymer (B) having a carboxyl group, and a total of 100 of (A) and (B)
0.1 to 3 aluminum chelate compound per part by weight
Add 0 parts by weight to use.

If it is less than 0.1 part by weight, the crosslinking density is low and a sufficient effect cannot be obtained, and if it is more than 30 parts by weight, it is difficult to obtain storage stability as a solution, and the weather resistance and the thermoplastic sheet after coating are obtained. There is a problem in the welder workability and heat-sealing property.

The aluminum chelate compound used here mainly causes a chelate reaction with a carboxyl group after evaporation of the solvent, but may have an alcoholate which forms a chemical bond with a hydroxyl group or the like in a solution in a part of the structure. Of course, specifically, ethylacetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetonate), alkylacetoacetate aluminum. Examples include diisopropylate and the like, which give good effects.

Such an aluminum chelate compound has an acid value of 10 to 150 upon evaporation of the solvent at room temperature or by heat drying.
An acid value compatible with the fluorine-containing copolymers (A) and (A) having a carboxyl group of (mgKOH / g) is 10
Crosslinking and curing are carried out by reacting with a functional group such as a carboxyl group of the acrylic copolymer (B) having a carboxyl group of up to 150 (mgKOH / g).

In addition to the aluminum chelate compound, a stabilizer may be used if necessary, and mainly acetylacetone ethylacetoacetate, methylacetoacetate and the like are added. Similarly, the solvent is xylene, toluene,
In addition to general solvents such as ethyl acetate, methyl acetate, and methyl ethyl ketone, alcohols such as n-butanol and isopropanol are used in combination to serve as a stabilizer.

The proportion of each of the main constituents in the coating composition of the present invention is such that the fluorine-containing copolymer 30 of (A) is used.
~ 90% by weight, (B) acrylic copolymer 10-70
It is preferably in weight%. When the amount of the fluorine-containing copolymer is small, the fluorine content is reduced, and the desired effect of improving the weather resistance is not achieved. On the other hand, when the amount of the acrylic copolymer is small, the adhesion to the substrate is deteriorated. Thus, it is needless to say that each of the fluorine-containing copolymer and the acrylic copolymer is not limited to one type within the above range and two or more types may be used in combination. Next, the aluminum chelate compound is added in an amount of 0.1 to 30 per 100 parts by weight of the total amount of the fluorine-containing copolymer and the acrylic copolymer for the above-mentioned reason.
Used in proportions by weight.

When the coating composition of the present invention is used for matting, it can be prepared by adding and mixing an aluminum chelate compound to the mixture of the copolymers (A) and (B). In order to achieve a good matting effect, use a highly reactive aluminum chelate compound such as ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate, aluminum tris acetyl acetate), or with a fluorine-containing copolymer. It is preferable to use a relatively large amount such as 20 parts by weight or more per 100 parts by weight of the total amount of the acrylic copolymer.

In addition to the aluminum chelate compound, other metal chelate compounds or alkoxides may be added. Examples of such metals include titanium and zirconium, and specifically, diisopropoxybis (acetylacetonate) titanium and the like.

For matte coating, a composition prepared by simply adding and mixing an aluminum chelate compound to a mixture of the copolymers (A) and (B) may be used to form a film by a conventional method. It is also possible to age this composition for a while and then add and mix it with other paints before use. That is, after the copolymers of (A) and (B) and the aluminum chelate compound are mixed, the co-weight of (A) and (B) having a high matte degree, a non-matte degree or a low matte degree, which has been previously mixed. A matte coating composition can be synthesized by mixing the coalescent and aluminum chelate compound into the mixed coating composition. The coating film formed through the stepwise process in this case has a higher glass transition temperature than the coating film formed in one step and becomes a hard coating film.

The matting composition can be applied to other solvent-based coating compositions as well as water-based coating compositions such as water-soluble paints, emulsion paints and electrodeposition paints. In particular, since the electrodeposition coating composition uses a copolymer having a large amount of carboxyl groups, it is easy to apply a matte formulation using this aluminum chelate compound. When applied to a water-based coating composition, it is preferable to employ an isopropanol / water system as a solvent.

The coating composition of the present invention contains an antistatic agent, a pigment, a dispersion stabilizer, a leveling agent, an antifoaming agent, a viscosity modifier, an antiblocking agent, which are generally used for paints.
Slip agents and other paint additives may be added.

The coating composition contains, in addition to the above-mentioned components,
By containing 0.5 to 20% by weight of the ultraviolet absorber with respect to the total amount of the fluorinated copolymer (A) and the acrylic copolymer, the weather resistance can be further improved. As such an ultraviolet absorber, conventionally known or well-known 2-hydroxybenzophenone, 2,4-hydroxybenzophenone, 2-hydroxide 4-n-octoxybenzophenone, 2-hydroxy-4- (1-methyl-2-hydroxy). ) Ethoxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy)
Benzophenone series such as propoxybenzophenone or 2- (2'-hydroxy-5'-methylphenyl)
Benzotriazole, 2- (2'-hydroxy-3 ',
A benzotriazole-based compound such as 5′-di-tert-butylphenyl) benzotriazole is used alone or in combination.

Further, a fluoroalkyl group-containing acrylic copolymer (C) may be added to the coating composition to improve the water repellency of the plastic sheet. As the acrylic copolymer (C) having such a fluoroalkyl group, if one having the same cross-linking site as the fluorine-containing copolymer (A) or the acrylic copolymer (B) is adopted, water repellency, etc. Are retained for a long period of time, which is preferable. Further, the addition amount of the acrylic copolymer (C) having the fluoroalkyl group is 0.1 to 30 parts by weight per 100 parts by weight of the total of the fluorine-containing copolymer (A) and the acrylic copolymer (B). It is preferable to adopt it in the range of about a part.

In addition, for the purpose of improving the properties, the coating composition contains additives such as an antifoaming agent, an antistatic agent, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent and an antigelling agent. It can also be blended. The combination of pigments has the effect of hiding the coating.

The coating composition of the present invention comprises the fluorine-containing copolymer (A) and the acrylic copolymer (B) as described above.
It can be obtained by dissolving a main constituent component such as an aluminum chelate compound, and if necessary, an ultraviolet absorber, an acrylic copolymer (C) having a fluoroalkyl group and other additives in an organic or aqueous solvent. Examples of the organic solvent used include aromatic hydrocarbons such as toluene and xylene, alcohols such as propanol and butanol, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ethyl cellosolve. Various general organic solvents such as glycol ethers and various commercially available cinnals are exemplified. The concentration of the film-forming component is adjusted to 1 to 60% by weight, preferably 5 to 50% by weight, which is suitable for workability in forming a film.

The preparation of the coating composition is carried out by using various equipment normally used for coating, such as a ball mill, a paint shaker, a sand mill, a jet mill, a triple roll, a kneader, etc., and is not particularly limited. . At this time, the additives as exemplified above can be added.

In the present invention, the method of forming a coating film of the coating composition on the thermoplastic resin sheet is carried out by applying the coating composition onto the molded product by brushing, spraying, flow coater, or the like, or coating composition. The sheet is applied by immersing the sheet in the material, dried sufficiently to evaporate the solvent, and then heated or left at room temperature to form a film. The heat treatment at this time is performed at a temperature not higher than the temperature at which the molded body is not deformed, and for example, treatment at 60 ° C. for 10 minutes is sufficient.

A sufficient effect is recognized when the thickness of the coating film formed is 2 to 100 μm. The thickness of the coating is adjusted depending on the component concentration of the coating composition and the coating conditions, but there is no problem even if it is formed into a multilayer coating. The shape of the molded body is not limited at all.

[0042]

【Example】

[Examples 1 to 9 and Comparative Examples 1 to 4] Coating composition No. 1 having the composition shown in Table 1. 1 to 13 were adjusted. Paint No. on the surface of the soft vinyl chloride resin sheet. 1 to 13 were adjusted and applied so that the film thickness of the film formed by the gravure coater would be 15 μm, dried at 80 ° C. for 3 minutes, and the curing period until performance evaluation was 7 days at room temperature.

Table 2 shows the results of the following evaluation tests performed on the sheet thus formed with the coating film. Adhesion: Adhesion of the coating film was determined according to the method of ASTM-3359: (1) initial stage, (2) after hot water immersion (60 ° C. × 30 days),
(3) Sunshine weather meter: Measured after 1000 hours of treatment and evaluated by the number of squares remaining. Weather resistance: Color measuring machine (Suga Test Instruments Co., Ltd. = SM- before and after 1000 hours of sunshine weather meter treatment)
3), and the yellowing deterioration was measured by the difference (ΔY.I.
) As. Blocking resistance: 2 seconds at 80 ° C after curing at 80 ° C for 20 seconds
When laminated with a load of 1 kg / cm ² for 4 hours, no blocking was evaluated as ◯, blocking was evaluated as x, and some blocking was evaluated as Δ. Storage stability: good for good, bad for bad after left at room temperature for 1 month
And Welder property: Adhesiveness at 40 Hz, 2 KW, and 7 seconds was evaluated. Good was rated as ◯, almost good (within a practical range) was rated as Δ, and no bonding was rated as x.

[0044]

[Table 1]

In Table 1, FA of the fluorine-containing copolymer is TFE
/ HBVE / n-BVE = 48.1 / 12.5 / 39.4 (wt%), and the intrinsic viscosity (referred to as [η]) measured at 30 ° C in tetrahydrofuran is 0.15 (dl / g). A copolymer in which all of the hydroxyl groups have been modified with hexahydrophthalic anhydride to introduce carboxyl groups. (Less than,
Same) FB is CTFE / HBVE / CHVE / EVE = 56.4 / 5.7 / 1
2.4 / 25.5, [η] = 0.21 / dl / g. FC is HFP / HBVE / n-
BVE = 66.7 / 8.0 / 25.3, [η] = 0.08 / dl / g. FD is TF
E / CH ₃ COOCH = CH ₂ / CH ₂ = CHCH ₂ OCH ₂ CH ₂ OH = 53.7 / 23.1 / 23.
2, [η] = 0.18 dl / g. FE is CTFE / EVE / HBVE / Beoba 9 = 39.4 / 17.2 / 9.5 / 33.9, [η] = 0.40dl / g. FF
Is TFE / EVE / HBVE / CH ₂ = CHOCH ₂ CF ₂ CF ₂ H = 57.0 / 22.4 /
10.8 / 9.8, [η] = 0.10 dl / g. (TFE is tetrafluoroethylene, HBVE is ω-hydroxybutyl vinyl ether, n-BVE is n-butyl vinyl ether, CTFE is chlorotrifluoroethylene, CHVE is cyclohexyl vinyl ether, EVE is ethyl vinyl ether, HFP is hexafluoropropylene, and Veova 9 is This is a vinyl ether having a branched alkyl group having 9 carbon atoms, manufactured by Shell Chemical Co., Ltd.) FG is a copolymer before modification of FA.

In the acrylic copolymer, M-1 is i
Copolymer copolymerized at a ratio of so-butyl methacrylate / n-butyl methacrylate / methacrylic acid = 6/2/2 (molar ratio) (hereinafter the same), M-2 is methyl acrylate / n-butyl acrylate / acryl Acid = 7/1/2, M-3
Is n-butyl methacrylate / iso-butyl methacrylate / acrylonitrile / methacrylic acid = 1/6/1/2
, M-4 represents methyl methacrylate / n-butyl methacrylate = 5/5, and M-5 represents iso-butyl methacrylate / n-butyl acrylate / 2-hydroxyethyl methacrylate = 7/2/1.

The fluoroalkyl group-containing acrylic polymer is
CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₁₀ F / iso-butyl methacrylate / n-butyl acrylate / acrylic acid = 20/50/10/2
0% by weight of copolymer.

Chelate D with an aluminum chelate compound
Is aluminum monoacetylacetonate bis (ethylacetoacetonate) / isopropanol 70% liquid (manufactured by Kawaken Fine Chemicals Co., Ltd.), and ALCH-TR is aluminum tris (ethylacetoacetate) (manufactured by Kawaken Fine Chemicals Co., Ltd.). The isocyanate curing agent in Comparative Example was Coronate HX (manufactured by Nippon Polyurethane Co., Ltd.), and 350 ppm of dibutyltin dilaurate was added. The ultraviolet absorber is Biosorb 130 (manufactured by Kyodo Chemical Co., Ltd.), and the solvent is a mixture of a solvent and a stabilizer (toluene / n-butanol / acetylacetone = 49/50/1). In the comparative examples, some of the solvents were toluene only.

The numbers in Table 1 are parts by weight.

[0050]

[Table 2]

[Example 10] The same effect as in Example 1 was obtained except that the drying condition was room temperature for 3 minutes and the curing condition until performance evaluation was room temperature for 7 days. was gotten.

[Example 11] A coating film formed in the same manner as in Example 1 except that ethyl acetoacetate aluminum diisopropylate was used as the aluminum chelate compound was in a matte state, and JIS K5 was used.
The gloss was measured according to 400 and was 25. Further, this coating composition was suitable for a coating system requiring high viscosity such as screen printing coating.

Example 12 A composition was prepared by using 30 parts by weight of aluminum tris (ethylacetoacetate) as the aluminum chelate compound in Example 1. When this composition was mixed with the coating composition of Example 1 to form a film, a matte coating having a gloss of 35 was formed.

[Example 13] 10 parts by weight of triethanolamine was added to the mixture of the fluorine-containing copolymer and the acrylic copolymer of Example 1 and the solvent was added, followed by isopropanol / water mixed solvent (85/15). (Weight ratio) 100 parts by weight is added to form a varnish for water-based paint, aluminum diisopropoxide monoacetylacetate is added thereto and mixed, and further 30 parts by weight of methylolated melamine are mixed to prepare a coating composition for electrodeposition. Prepared. Aluminum was subjected to electrodeposition coating using this coating composition for electrodeposition and baked at 180 ° C. for 30 minutes. The gloss of this coating film was 25. The electrodeposition coating conditions are as follows: an aluminum plate having a thickness of 9 μm and an anodized film formed on it, the distance between electrodes is 10 mm, and the electrode ratio is +
/-= 2/1, the liquid temperature was 20 ° C, and the voltage was 160 V for 3 minutes for DC energization.

Example 14 The same amount of the electrodeposition coating composition prepared in Example 13 was mixed with any of the electrodeposition coating compositions, and electrodeposition coating was performed under the above conditions to obtain a coating film. Was 27.

Chlorotrifluoroethylene 3 was added to a stainless steel autoclave with a stirrer (pressure resistance 50 kg / cm ² ).
5 parts, cyclohexyl vinyl ether 11 parts, ethyl vinyl ether 4.3 parts, ω-hydroxybutyl vinyl ether 15 parts, xylene 98 parts, ethanol 28 parts,
0.5 parts of azobisisobutyronitrile and 1.5 parts of anhydrous potassium carbonate were charged, and after cooling with liquid nitrogen to remove dissolved air by solidification deaeration, reaction was carried out at 65 ° C. for 16 hours to contain a hydroxyl group. A fluoropolymer was obtained.

A 60% xylene solution of the obtained fluorine-containing polymer having a hydroxyl group (having a hydroxyl value of about 120 mgKOH / g) was heated to 90 ° C., and 3.6 parts of succinic anhydride was added to 100 parts of the polymer. In addition, a further 0.2 part of triethylamine was added and the reaction was carried out for 2 hours. The acid value of this fluoropolymer is 20 mgKOH / g, and the hydroxyl value is 100 mgK.
It was OH / g. The obtained fluoropolymer is
After the solvent was once evaporated and the polymer solid was isolated, it was newly dissolved in isopropyl alcohol to give an isopropyl alcohol solution of about 60%.

Fluorine-containing polymer solution 2 prepared as described above
00 parts, 21 parts of methyl ethyl mixed etherified methylol melamine (trade name, Cymel 1116, manufactured by Mitsui Toatsu Co., Ltd.) were added, 3.3 parts of triethylamine was added while continuing stirring, and then 19 parts of butyl cellosolve was added, followed by further removal. A coating for electrodeposition was prepared by adding 214 parts of ionized water.

[0059]

The coated thermoplastic sheet of the present invention comprises:
The coating of the specific coating composition retains good adhesion,
Since it is formed, it has extremely excellent weather resistance, and since it does not impair the adhesiveness due to the welder and heat fusion, which are the original characteristics of the thermoplastic sheet, industrial production is easy. Further, the composition of the present invention has excellent storage stability,
It is a one-component type and the painting work is easy.

Claims (2)

[Claims] 1. An acid value of 10 on a thermoplastic resin sheet.
To 150 (mgKOH / g) carboxyl group-containing fluoropolymer (A) and an acrylic copolymer (10) having an acid value compatible with (A) of 10 to 150 (mgKOH / g) carboxyl group ( B) as the main component,
A thermoplastic sheet coated with a coating composition containing 0.1 to 30 parts by weight of an aluminum chelate compound per 100 parts by weight of (A) and (B) in total. 2. An acid value of 10 to 150 (mgKOH /
g) Fluorine-containing copolymer (A) having a carboxyl group
And an acid value compatible with (A) of 10 to 150 (mg
KOH / g) as a main component of an acrylic copolymer (B) having a carboxyl group, and a total of 100 of (A) and (B)
0.1 to 3 aluminum chelate compound per part by weight
A coating composition containing 0 part by weight.