JP2808663B2 - Wall paper - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a wallpaper.

[Prior Art] Conventionally, for the purpose of improving durability and antifouling property, wallpaper that has been protectively coated with a coating material having relatively excellent weather resistance such as acrylic resin has been used in many cases.

[Problems to be Solved by the Invention] Conventionally, there was a wallpaper coated with an acrylic resin as an excellent antifouling property, but the durability was poor and it was not enough to withstand long-term use.

The present invention solves the above-mentioned problems of the prior art, that is,
It is an object of the present invention to provide a wallpaper having excellent weather resistance and long-term antifouling property and excellent adhesion of a protective coat.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and a fluorine-containing copolymer (a) and (a) each having a crosslinked site on a thermoplastic resin sheet. The present invention provides a wallpaper formed by forming a coating film of a paint containing, as a main component, an acrylic polymer (b) which is compatible with water.

As the thermoplastic resin as the base material of the wallpaper of the present invention,
Examples thereof include a vinyl chloride resin, a polyethylene resin, and a polyester resin. Among them, a vinyl chloride resin, particularly a soft vinyl chloride resin, is most generally used. As such a vinyl chloride resin, in addition to a vinyl chloride homopolymer, vinyl chloride and vinyl acetate, ethylene, propylene,
Copolymers of at least one of monomers such as acrylic acid esters and methacrylic acid esters with an amount of 40% by weight or less, preferably 30% by weight or less, and compatible with these homopolymers or copolymers Certain polymers, for example, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer and the like may be blended. In addition, an appropriate amount of a plasticizer is blended with the vinyl chloride resin, and is often used as a soft vinyl chloride resin. The amount of the plasticizer 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, ordinary additives such as a lubricant, an antioxidant, an antistatic agent, a heat stabilizer, a colorant, and a flame retardant may be added to the vinyl chloride resin.

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

In the present invention, as a coating material for forming a film on the thermoplastic resin sheet, a fluorinated copolymer (a) having a crosslinked site and an acrylic polymer (b) compatible with (a) are mainly used. Is adopted.

Here, as the fluorine-containing copolymer (a) having a cross-linking site, a solvent-soluble fluorine-containing copolymer having a fluorine content of 10% by weight or more based on a fluoroolefin unit is preferably employed.

The above fluorine-containing copolymer (a) has a fluorine content of 10% by weight or more, preferably 10 to 70% by weight, more preferably 15 to 50% by weight, based on the fluoroolenfin unit, and is in an uncured state. And an intrinsic viscosity measured in tetrahydrofuran of 0.01 to 4.0 dl / g. Thus, if the fluorine content is less than 10% by weight, the intended improvement in weather resistance will be reduced. Further, when the intrinsic viscosity is within the above range, the paintability as a coating material is good, and the physical properties of the formed film are also excellent. As such a fluorinated copolymer, a copolymer with an ethylenically unsaturated compound is preferably employed as a fluoroolefin and a comonomer copolymerizable with the fluoroolefin.

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

Among them, olefins having excellent copolymerizability with fluoroolefins, especially vinyl ethers, vinyl esters, allyl ethers having a linear, branched or alicyclic alkyl group having about 1 to 10 carbon atoms. Are preferred.

In the fluorinated copolymer (a), the unit based on the fluoroolefin preferably contains 30 to 70 mol%,
If it is less than 30 mol%, the effect of improving weather resistance is not sufficient,
If it exceeds 70 mol%, the solubility in a solvent tends to decrease, which may hinder the application operation as a paint. In the copolymer, the fluoroolefin and the ethylenically unsaturated compound may be used alone or in combination of two or more.

Among the main constituent components of the paint of the present invention, those having a crosslinked site in the fluorine-containing copolymer (a) form a three-dimensional network structure by reacting between other components, a curing agent, or the copolymer, A film having a cross-linking site is preferably employed because it gives a favorable result of improving the solvent resistance, acid resistance and alkali resistance of the coating.

Thus, as a crosslinking site, a hydroxyl group, a carboxylic acid group,
Examples thereof include active hydrogen-containing groups such as acid amide groups, amino groups, and mercapto groups, and active halogen groups such as epoxy groups, carbon-carbon unsaturated groups, bromine, and iodine. Of these, active hydrogen-containing groups are preferred in that they have excellent reactivity with isocyanate-based curing agents, aminoplast-based curing agents, and the like, which are usually used as curing agents, and hydroxyl groups are particularly preferred.

Methods for introducing such a cross-linking site into the copolymer include, for example, cross-linking of hydroxyalkyl vinyl ether, hydroxyalkyl aryl ether, hydroxyaryl vinyl ether, hydroxyalkyl allyl ether, glycidyl vinyl ether, acrylic acid, methacrylic acid, aryl vinyl ether, diaminoethyl vinyl ether, etc. A method in which a monomer having a reactive site is copolymerized, or a method in which an acid anhydride, an isocyanate, an alkyl (meth) acrylate, or the like is added to a fluorine-containing copolymer by reacting the same, is employed. As a method for decomposing a part of the copolymer, a monomer having a hydrolyzable ester group is copolymerized, and then the carboxylic acid or the hydroxyl group is contained in the copolymer by hydrolyzing the copolymer. Is also adopted. Furthermore, a method of introducing a carboxylic acid group by reacting a divalent carboxylic anhydride such as succinic acid with a hydroxyl group-containing copolymer is also employed.

The acrylic polymer (b) that is compatible with the fluorinated copolymer (a), which is a main component of the paint of the present invention, is an alcohol ester of acrylic acid or methacrylic acid having 1 to 12 carbon atoms, It is an acrylic polymer having a molecular weight of 500 to 80,000. As monomers for constituting such an acrylic polymer, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
Propyl acrylate, propyl methacrylate, n-
Butyl methacrylate, iso-butyl methacrylate, t
ert-butyl methacrylate, n-butyl acrylate,
Examples include tert-butyl acrylate, acrylonitrile, methacrylonitrile, and the like. Also, preferably,
Copolymers of two or more of these monomers or copolymers with alcoholic esters of acrylic acid other than those described above, styrene, maleic acid, vinyl esters (such as vinyl acetate), and vinylsilane are used. . More preferably, in the acrylic polymer, a polymer having a cross-linking site is cross-linked by a reaction with a cross-linking site of a fluorinated copolymer, and a coating film of the coating material has a three-dimensional network structure and exhibits excellent characteristics.

Here, in the acrylic polymer (b), the cross-linking site is preferably a hydroxyl group, a glycidyl group, an amide group, a silanol group, or the like. Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 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, For example, 3-chloro-2-hydroxypropyl methacrylate, etc., and glycidyl groups are introduced by glycidyl acrylate, glycidyl methacrylate, (β-methyl) glycidyl acrylate, (β-methyl) glycidyl methacrylate, etc. Further, amide groups are introduced by acrylamide, methacrylamide. , Dimethylacrylamide, dimethylmethacrylamide, N-tert-butylacrylamide, N-tert
-Butyl methacrylamide, N-octyl acrylamide, N-actyl methacrylamide, diacetone acrylamide, diacetone methacrylamide and the like, and silanol groups are introduced with monomers such as vinyl silane and the above-mentioned acrylic polymer or copolymer By copolymerizing with a comonomer giving

Further, 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 polymer (b) may be a mixture of a polymer having a cross-linking site and a polymer having no cross-linking site. Does not include a copolymer with a monomer having a hydroxyl group, a glycidyl group, an amide group, or the like. Thus, the proportion of the acrylic polymer having no crosslinked site is preferably up to 50% by weight based on the acrylic polymer having the crosslinked site.

Further, it is of course possible to mix a curing agent with the main components (a) and (b) of the paint,
Those which are compatible with the fluorinated copolymer of (a) and the acrylic polymer of (b) and cure them are used. As such a curing agent, polyisocyanates, for example, hexamethylene diisocyanate, non-yellowing diisocyanates such as isophorone diisocyanate, and adducts thereof, and blocked isocyanates in which isocyanate groups are blocked with a blocking agent such as phenol are preferable. Can be adopted. Also, various curing agents such as melamine, metal alkoxide, urea resin, polybasic acid, epoxy, and silanol can be used.
Here, when the crosslinking site of the fluorinated copolymer (a) is a hydroxyl group, a polyisocyanate-based or metal alkoxide-based is preferred. As the melamine-based curing agent, melamine partially etherified with one or more lower alcohols such as methanol, ethanol, propanol, and butanol is preferably used. Such a curing agent has a very useful effect on the formation of a tertiary network structure of a copolymer or a polymer having a cross-linking site. A catalyst may be used in combination with the curing agent for the purpose of accelerating curing together with the curing agent. For example, dibutyltin dilaurate is used as an isocyanate-based curing agent, and a catalyst such as paratoluenesulfonic acid is used as a melamine-based curing agent at a ratio of 0.001 to 2 parts by weight based on 100 parts by weight of a fluorine-containing copolymer.

The respective proportions of the main constituent components in the coating material of the present invention are preferably 30 to 90% by weight of the fluorine-containing copolymer (a) and 10 to 70% by weight of the acrylic polymer (b).
If the fluorine-containing copolymer is small, the fluorine content decreases,
The desired effect of improving the weather resistance is not achieved. On the other hand, when the amount of the acrylic polymer is small, the adhesiveness to the substrate is reduced. Thus, each of the fluorine-containing copolymer and the acrylic polymer is not limited to one type within the above-mentioned ratio, and two or more types may be used in combination. Next, a curing agent is used at a ratio of 0 to 20% by weight based on the total amount of the fluorine-containing copolymer and the acrylic polymer.

It is possible to further improve the weather resistance by including 0.5 to 3% of an ultraviolet absorber with respect to the total amount of the fluorinated copolymer and the acrylic polymer, in addition to the main constituent components. . Such UV absorbers include:
Conventionally known or well-known 2-hydroxybenzophenone,
2,4-dihydroxybenzophenone, 2-hydroxy-
4-n-octoxybenzophenone, 2-hydroxy-
4- (1-methyl-2-hydrooxy) ethoxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-
Benzophenones such as methacryloxy) propoxybenzophenone or 2- (2'-hydroxy-5'-
Benzotriazoles such as methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole are used alone or in combination.

Further, an acrylic polymer (c) having a fluoroalkyl group may be added to such a paint to improve the water repellency of the plastic sheet. As the acrylic polymer (c) having such a fluoroalkyl group, a polymer having a cross-linking site similar to that of the fluorine-containing copolymer (a) or the acrylic polymer (b) is adopted.
It is preferable because water repellency and the like are maintained for a long time.
The addition amount of the acrylic polymer (c) having a fluoroalkyl group is 0.1 to 30 per 100 parts by weight of the total of the fluorine-containing copolymer (a) and the acrylic polymer (b).
It is preferable to employ it in the range of about parts by weight.

In addition, for the purpose of improving the properties, paints include, for example, an antifoaming agent, an antistatic agent, a pigment, a dispersion stabilizer, a viscosity modifier,
Additives such as a leveling agent and an anti-gelling agent may be added. The compounding of the pigment has the effect of shading the coating.

In addition, it is of course possible to use a primer for the purpose of obtaining the required bending adhesion.

The coating material of the present invention is, as described above, a fluorine-containing copolymer (a)
And a main component such as an acrylic polymer (b) and, if necessary, a curing agent, an ultraviolet absorber, an acrylic polymer having a fluoroalkyl group (c) and other additives dissolved in an organic solvent. However, examples of the solvent used include toluene, aromatic hydrocarbons such as 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. Glycol ethers such as
Further, various general organic solvents such as various commercially available thinners. The concentration of the coating component is adjusted to 1 to 60% by weight, preferably 5 to 50% by weight, which is suitable in terms of workability of forming a coating.

In preparing the paint, for example, ball mill, paint shaker, sand mill, jet mill, three rolls,
It is carried out by using various devices used for ordinary coating, such as a kneader, and is not particularly limited. At this time, additives such as those described above can be added.

In the present invention, a method of forming a coating film of a paint on a thermoplastic resin sheet is performed by brushing a paint on a molded article, spraying, applying by a flow coater, or by applying the sheet by immersing the sheet in the paint, The coating is 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 formed coating film is 2 to 100 μm. The adjustment of the thickness of the film is determined by the component concentration of the paint and the application conditions, but there is no problem even if it is formed into a multilayer film. The shape of the molded body is not limited at all.

Examples Examples 1 to 11 and Comparative Examples 1 to 3 Paint Nos. 1 to 13 having the compositions shown in Table 1 were prepared.
Paint No. 1 to 13 is applied to the surface of the wallpaper by adjusting the thickness of the coating formed by the gravure coater to 5 μm, dried at room temperature, and then heated at 60 ° C. for 10 minutes to form a cured coating. Was formed.

Table 2 shows the results of the following evaluation tests performed on the sheet on which the coating was formed.

Contact angle: The contact angle between water and n-hexadecane was measured.

Adhesion: The adhesion of the coating is measured according to the method of ASTM-3359 initially, after immersion in warm water (60 ° C. × 30 days), and after treatment with a sunshine weather meter for 1000 hours, and evaluated by the number of remaining cells.

Weather resistance: Measured with a color measuring instrument (SM-3, manufactured by Suga Test Instruments Co., Ltd.) before and after the treatment for 1000 hours with the Sun Shan In Weather Meter, and its yellowing deterioration is determined as the difference (ΔE) between before and after the treatment.

In Table 1, FA of the fluorine-containing copolymer is a copolymer having a ratio of TFE / HBVE / n-BVE = 48.1 / 12.5 / 39.4 (% by weight), and 30% in tetrahydrofuran.
The intrinsic viscosity (referred to as [η]) measured at 0.1 ° C is 0.15 (dl /
g) is a copolymer. FB is CTFE / HBVE / CHVE / EVE = 56.4 / 5.7 / 12.4 / 25.5,
[Η] = 0.21 dl / g.

FC is HFP / HBVE / n-BVE = 66.7 / 8.0 / 25.3, [η] =
0.08dl / g.

F-D _{is, TFE / CH 3 COOCH = CH} 2 / CH 2 = CHCH 2 OCH 2 CH 2 OH = 5
3.7 / 23.1 / 23.2, [η] = 0.18 dl / g.

FE is CTFE / EVE / HBVE / Veova 9 = 39.4 / 17.2 / 9.5 / 3
3.9, [η] = 0.40 dl / g.

FF is TFE / EVE / HBVE / CH ₂ = CHOCH ₂ CF ₂ CF ₂ H = 57.0 / 2
2.4 / 10.8 / 9.8, [η] = 0.10dl / 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 It is a vinyl ether having a branched alkyl group having 9 carbon atoms manufactured by Shell Chemical Co., Ltd.).

M-1 is iso-butyl methacrylate / n-butyl acrylate / 2-hydroxyethyl methacrylate = 7/2 /
A copolymer copolymerized at a ratio of 1 (molar ratio) (the same applies hereinafter).

M-2 is methyl acrylate / n-butyl acrylate / glycidyl acrylate = 8/1/1.

M-3 is n-butyl methacrylate / iso-butyl methacrylate / acrylonitrile / 2-hydroxyethyl methacrylate = 1/7/1/1.

M-4 is methyl methacrylate / n-butyl methacrylate = 5/5.

Represents

Acrylic polymer containing fluoroalkyl group is CH ₂ ＝ CHC
OOCH ₂ CH ₂ (CF ₂ ) ₁₀ F / iso-butyl methacrylate / n-butyl acrylate / 2-hydroxyethyl methacrylate = 20/60/10/10% by weight copolymer.

The isocyanate curing agent is Coronate EH (manufactured by Nippon Polyurethane).

The ultraviolet absorber is Biosorb 130 (manufactured by Kyodo Chemical).

Example 12 The same procedure as in Example 1 was carried out except that the drying conditions were changed to 120 ° C. for 1 minute, and almost the same effects as in Example 1 were obtained.

[Effects of the Invention] The wallpaper of the present invention is extremely excellent in durability and antifouling property because a coating of a specific paint is formed while maintaining good adhesion.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D06N 7/04 B32B 27/30 D B32B 27/30 A D06N 3/08 C08J 7/04 CEV Z

Claims (4)

(57) [Claims] 1. A coating film mainly composed of a fluorine-containing copolymer (a) having a cross-linking site and an acrylic polymer (b) compatible with (a) is formed on a thermoplastic resin sheet. Wallpaper. 2. The wallpaper according to claim 1, wherein the acrylic polymer (b) has a crosslinked site. 3. The wallpaper according to claim 1, wherein the paint further contains an acrylic polymer (c) having a fluoroalkyl group. 4. The wallpaper according to claim 1, wherein the paint further comprises a curing agent.