JPH02300390A - Floor covering material - Google Patents

Abstract

PURPOSE:To obtain a floor covering material having excellent adhesivity, weather resistance and stain resistance by forming a coating film of coating material consisting essentially of a fluorine-contained polymer having crosslinked sites and an acrylic polymer having compatibility with the fluorine-contained polymer on a thermoplastic resin sheet. CONSTITUTION:A thermoplastic sheet such as vinyl chloride or polyethylene resin sheet is coated with a coating material comprising a fluorine-contained polymer having crosslinked sites and an acrylic polymer having compatibility with the fluorine-contained polymer, especially a polymer having crosslinked sites as main components and further a fluoroalkyl group-containing acrylic polymer and a curing agent (e.g. isocyanate base) to give floor covering material which is provided with a coating film having excellent adhesivity and has excellent stain resistance and weather resistance. A fluorine-contained copolymer having >=10wt.% fluorine content based on fluoroolefin base may be cited as the fluorine-contained polymer having the crosslinked sites (preferable example: hydroxyl group) and a (meth)acrylic acid 1-12C alcohol ester having crosslinked sites (hydroxyl group) as the acrylic polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to flooring materials. [Prior Art J] Conventionally, many flooring materials have been coated with a protective coating material having relatively good weather resistance, such as acrylic resin, for the purpose of improving weather resistance. [Problems to be Solved by the Invention] Conventionally, floor materials described as having excellent weather resistance had poor adhesion between the protective coat and the sheet, and could not be used satisfactorily. The object of the present invention is to solve the above-mentioned problems of the prior art, that is, to provide a flooring material with excellent weather resistance 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 includes fluorine-containing copolymers (a) and (a) having a crosslinking site on a thermoplastic resin sheet. The object of the present invention is to provide a flooring material formed by forming a coating film of a coating material whose main component is an acrylic polymer (b) that is compatible with the acrylic polymer (b). Examples of the thermoplastic resin as the base material of the flooring material of the present invention include vinyl chloride resin, polyethylene resin, and polyester resin. Among them, vinyl chloride resins, particularly soft vinyl chloride resins, are most commonly used. Such vinyl chloride resins include vinyl chloride and vinyl acetate, ethylene, propylene, in addition to vinyl chloride homopolymers.
40% by weight or less, preferably 30% by weight of at least one monomer such as acrylic ester or methacrylic ester
% by weight or less, and polymers that are compatible with these homopolymers or copolymers, such as ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, etc. May be blended. In addition, an appropriate amount of plasticizer is added to the vinyl chloride resin,
The blending amount of the plasticizer, which is often used as a soft vinyl chloride resin, 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. Moreover, usual additives such as a lubricant, an antioxidant, an antistatic agent, a heat stabilizer, a coloring agent, and a flame retardant may be added to the vinyl chloride resin. Furthermore, a surfactant may be added to the vinyl chloride resin for the purpose of antifogging. As such a surfactant, a nonionic surfactant is preferably employed. In the present invention, the paint for forming a film on the thermoplastic resin sheet includes a fluorine-containing copolymer (a) having a crosslinking site and an acrylic polymer (b) that is compatible with (a).
The main component is used. Here, as the fluorine-containing copolymer (a) having a crosslinking site, a solvent-soluble fluorine-containing copolymer having a fluorine content of 10% by weight or more based on fluoroolefin units is preferably employed. The fluorine-containing copolymer (a) above has a fluorine content based on fluoroolefin units of 10% by weight or more, preferably 10 to 70% by weight, more preferably 15 to 50% by weight, and is in an uncured state. Those having an intrinsic viscosity of 0.01 to 4.0 dl/g as measured in tetrahydrofuran are used. Therefore, if the fluorine content is less than 10% by weight, the intended effect of improving weather resistance will be reduced. Further, when the intrinsic viscosity is within the above range, the coating properties as a paint will be good, and the physical properties of the formed film will also be excellent. As such a fluorine-containing polymer, a copolymer with an ethylenically unsaturated compound as a fluoroolefin and a comonomer copolymerizable with the fluoroolefin is preferably employed. Such fluoroolefins include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, hexafluoropropylene,
Examples include pentafluoropropylene. Among these, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, and hexafluoropropylene are particularly preferably employed. In addition, examples of ethylenically unsaturated compounds as monomers that can be copolymerized with fluoroolefins include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acryloyl group-containing compounds, and methacryloyl group-containing compounds. Examples include compounds such as Among these, olefins, vinyl ethers, vinyl esters, and allyl ethers have linear monobranched or alicyclic alkyl groups with about 1 to 10 carbon atoms, which have particularly excellent copolymerizability with fluoroolefins. Preferably. The fluorine-containing copolymer (a) preferably contains 30 to 70 mol% of units based on fluoroolefin; if it is less than 30 mol%, there is no sufficient effect of improving weather resistance, and if it exceeds 70 mol%, There is a tendency for the solubility in solvents to decrease, which may cause problems in coating work as a paint. Furthermore, in the copolymer, the fluoroolefins and ethylenically unsaturated compounds may be used alone, or two or more of them may be used in combination. Among the main components of the coating material of the present invention, the fluorine-containing copolymer (a) having a crosslinking site may be other components,
Curing agents or copolymers react with each other to form a three-dimensional network structure, giving favorable results such as improving the solvent resistance, acid resistance, and alkali resistance of the coating, so those having crosslinking sites are preferably employed. . Examples of crosslinking sites include active hydrogen-containing groups such as hydroxyl groups, carboxylic acid groups, acid amide groups, amino groups, and mercapto groups, as well as active halogen groups such as epoxy groups, carbon-carbon unsaturated groups, and bromine and iodine groups. Examples include. Among these, active hydrogen-containing groups are preferred in that they have excellent reactivity with isocyanate curing agents, aminoblast curing agents, etc. that are commonly used as curing agents, and hydroxyl groups are particularly preferred. Methods for introducing such crosslinking sites into the copolymer include, for example, hydroxyalkyl vinyl ether, hydroxyalkyl allyl ether, hydroxyaryl vinyl ether, hydroxyalkyl allyl ether, hydroxyalkyl vinyl ester, glycidyl vinyl ether, acrylic acid, methacrylic acid, aryl vinyl ether, The methods employed include copolymerizing a monomer having a crosslinking reaction site such as diaminoethyl vinyl ether, or reacting and adding an acid anhydride, incyanate, alkyl (meth)acrylate, etc. to a fluorine-containing copolymer. In addition, as a method for partially decomposing a copolymer, a monomer having a hydrolyzable ester group is copolymerized, and then the copolymer is hydrolyzed to produce carboxylic acid or hydroxyl groups in the copolymer. A method of generating the . Furthermore, a method of introducing a carboxylic acid group by reacting a divalent carboxylic acid anhydride such as succinic acid with a hydroxyl group-containing copolymer is also adopted. The acrylic polymer (b) that is compatible with the fluorine-containing 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 with a molecular weight of 500 to go, ooo. Such acrylic polymers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl methacrylate, 1so-butyl methacrylate, tert-
Examples include butyl methacrylate, n-butyl acrylate, tert-butyl acrylate, acrylonitrile, methacrylonitrile, and the like. Preferably, copolymers of two or more of these monomers, or copolymers of acrylic acid with alcohol esters other than those listed above, styrene, maleic acid, vinyl esters (vinyl acetate, etc.), vinyl silane, etc. coalescence is used. More preferably, in the acrylic polymer, the polymer having a crosslinking site is crosslinked by reaction with the crosslinking site of the fluorine-containing copolymer, so that the paint film has a three-dimensional network structure,
Shows excellent properties. Here, the crosslinking site in the acrylic polymer (b) is preferably a hydroxyl group, a glycidyl group, an amide group, a silanol group, etc. 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-hydroxy Butyl acrylate, 3-hydroxybutyl methacrylate,
4-Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate% 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, etc., and for the introduction of glycidyl groups, glycidyl acrylate, glycidyl methacrylate, (
β-methyl)glycidyl acrylate, (β-methyl)
Glycidyl methacrylate, etc., and the introduction of an amide group into acrylamide, methacrylamide, dimethyl acrylamide, dimethyl methacrylamide, N-tert
-butylacrylamide, N-tert-butylmethacrylamide, N-octylacrylamide, N-octylmethacrylamide, diacetone acrylamide, diacetone methacrylamide, etc. Silanol groups can be introduced using monomers such as vinylsilane and the above-mentioned acrylic It is carried out by copolymerizing a polymer or a comonomer to form a copolymer. Silanol groups can also be introduced by adding isocyanate silane or a silane coupling agent to a hydroxyl group-containing acrylic polymer. Here, the acrylic polymer (b) may be a mixture of a polymer having a crosslinking site and a polymer not having a crosslinking site. It does not include copolymers with monomers having hydroxyl groups, glycidyl groups, amide groups, etc. The proportion of the acrylic polymer without crosslinking sites is preferably up to 50% by weight based on the acrylic polymer having crosslinking sites. Furthermore, (a) and (b), which are the main constituent components of the paint,
Of course, it is possible to add a curing agent to (a)
A material that is compatible with the fluorine-containing copolymer (b) and the acrylic polymer (b) and hardens them is used. Examples of such curing agents include polyisocyanates, such as non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and adducts thereof, and blocked isocyanates in which isocyanate groups are blocked with a blocking agent such as phenol. etc. can be suitably adopted. Furthermore, various curing agents such as melamine type, metal alkoxide type, urea resin type, polybasic acid type, epoxy type, and silanol type can also be used. Here, when the crosslinking site of the fluorine-containing copolymer (a) is a hydroxyl group,
Polyisocyanate-based and metal alkoxide-based materials are preferred. As the melamine curing agent, melamine partially etherified with one or more lower alcohols such as methanol, ethanol, propatool, and butanol is particularly suitable. Such a curing agent has an extremely useful effect on the formation of a tertiary network structure of a copolymer or polymer having crosslinking sites. For the purpose of accelerating curing together with the curing agent, a catalyst may be used in combination, and such curing aids include, for example, dibutyltin laurate for isocyanate curing agents, and p-toluenesulfonic acid catalysts for melamine curing agents. It is used in an amount of 0.001 to 2 parts by weight per 100 parts by weight of the fluorine-containing copolymer. The respective proportions of the main components in the paint of the present invention are (a) 30 to 90% by weight of the fluorine-containing copolymer; (b)
It is preferable that the amount of the acrylic polymer is 10 to 70% by weight. If the amount of the fluorine-containing copolymer is small, the fluorine content will be reduced and the desired effect of improving weather resistance will not be achieved, while if the amount of the acrylic polymer is too small, the adhesion to the substrate will be reduced. Therefore, it goes without saying that the fluorine-containing copolymer and the acrylic polymer are not limited to one type within the above ratio range, and two or more types may be used in combination. is used in an amount of 0 to 20% by weight based on the total amount of the fluorine-containing copolymer and the acrylic polymer. In addition to the main components, the paint contains 0.5 to 20% of an ultraviolet absorber based on the total amount of fluorine-containing copolymer and acrylic polymer, which can further improve weather resistance. It is. Examples of such ultraviolet absorbers include conventionally known or well-known 2-hydroxybenzophenone, 2,4-hydroxybenzophenone, 2-hydroxide 4-n-octoxybenzophenone, and 2-hydroxy-4-(1-methyl-2-hydroxy ) Ethoxybenzophenone, 2-hydroxy-4-(2-hydroxy-3
-Methacryloxy)propoxybenzophenone and other benzophenones, 2-(2°-hydroxy-5′-methylphenyl)benzotriazole, 2-(2′
-hydroxy-3°,5°-di-t-butylphenyl)
Benzotriazole compounds such as benzotriazole are used alone or in combination. Furthermore, 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, the fluorine-containing copolymer (a) or the acrylic polymer (b)
It is preferable to use a material having a crosslinking site similar to that of the above, since water repellency and the like are maintained over a long period of time. The amount of the acrylic polymer (c) having such a fluoroalkyl group is 0.000 parts per 100 parts by weight of the fluorine-containing copolymer (a) and the acrylic polymer (b).
It is preferable to use 1 to 30 parts by weight. In addition, additives such as antifoaming agents, antistatic agents, pigments, dispersion stabilizers, viscosity modifiers, leveling agents, and antigelation agents may be added to the paint for the purpose of improving properties. The pigment formulation has the effect of masking the coating. Furthermore, it is of course possible to use a brimer for the purpose of obtaining the necessary bending adhesion. The coating material of the present invention has main components such as the fluorine-containing copolymer (a) and the acrylic polymer (b) as described above, and if necessary, a curing agent, an ultraviolet absorber, and an acrylic polymer having a fluoroalkyl group. (C) Obtained by dissolving other additives in an organic solvent, examples of solvents used include aromatic hydrocarbons such as toluene and xylene, alcohols such as propatool and butanol, ethyl acetate, and butyl acetate. esters such as methyl ethyl ketone, ketones such as methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, and various commercially available dinals. The concentration of the coating components is preferably adjusted to 1 to 60% by weight, preferably 5 to 50% by weight in terms of workability in forming a film. The preparation of the paint is carried out by using various equipment commonly used for forming paints, such as a ball mill, paint shaker, sand mill, jet mill, triple roll, kneader, etc., and is not particularly limited. Additives such as those exemplified above can be added. In the present invention, the method of forming a paint film on a thermoplastic resin sheet is to apply the paint onto the molded body by smearing, spraying, flow coater, etc., or by dipping the sheet in the paint. The film is dried sufficiently to volatilize the solvent, and then heated or left at room temperature to form a film. The heat treatment at this time is carried out at a temperature below which the molded body does not deform, and for example, treatment at 60° C. for 10 minutes is sufficient. A sufficient effect is observed when the thickness of the paint film formed is 2 to 100 μI. The thickness of the coating is determined by the component concentration of the coating material and the coating conditions, but there is no problem even if the coating is formed into a multilayer coating, and the shape of the molded product is not limited in any way. [Example 1 Example 1-11. Comparative Examples 1-3 Paint No. 1-13 having the composition shown in Table 1 was prepared. Coating No. 1-13 was applied to the surface of the flooring material using a flow coater so that the thickness of the film formed was adjusted to 15 μm, and after drying at room temperature, it was cured by heating at 60°C for 10 minutes. A film was formed. Table 2 shows the results of the following evaluation tests performed on the sheets on which the coatings were formed in this way. Contact angle: The contact angle of water and n-hexadencane was measured. Adhesion: The adhesion of the film was measured according to the method of ASTM-3359 at (1) initial stage, (2) after immersion in warm water (60°C x 30 days), and (2) after 1000 hours of treatment with a sunshine weather meter, and evaluated by the number of remaining squares. Weather resistance: Measured with a color measuring machine (manufactured by Suga Test Instruments Co., Ltd. = 5M-3) before and after processing for 1000 hours with a Sunshine Weather Meter, and the yellowing deterioration is determined as the difference (ΔE) before and after processing. In Table 1, F-A of the fluorine-containing copolymer, TFE/HOVE/n-BYE = 411
It is copolymerized at a ratio of 1.1/12.5/39.4 (wt%), and the intrinsic viscosity (referred to as [η]) measured at 30°C in tetrahydrofuran is 0.15 (di/g). Copolymer (hereinafter the same) F-8 is C-FE/HBVE/CHVE/EVE
:5G, 415.7/12.4/25.5. [η]
=0.21/dl/g. F-C,)IFP/HBVE/n-BYE=
66, 7/8.0/25.3° [η] =+0.08
/di/g. FD is TFE/CHsCQOCH:, CHm/
CHmlIC)lcHgOcH*CH,0H=53.7
/23.1/23.2. [η] = 0.18dl
/g. FE is CTFE/EVE/HBVE/Heova9 = 39.4/17.2/9.5/33.9.
[η]: 0.40 dl/g. F-F is TFE/EVE/HOVE/CH
m: CHOCH*CFsCF*H depth 57.0/22.4
/10.8/9.8. [η] =O, 1Odl/g
. (TFE is tetrafluoroethylene, HBVE is ω-hydroxybutyl vinyl ether, n4VE is n-butyl vinyl ether, CTFE is chlorotrifluoroethylene, CHVE is cyclohexyl vinyl ether, EV
E is ethyl vinyl ether, HFP is hexafluoropropylene, and Beoba 9 is a vinyl ether manufactured by Shell Chemical Co., Ltd. and having an alkyl group on a branch with 9 carbon atoms. ) M-1 is Lso-butyl methacrylate/n-butyl acrylate/2-hydroxyethyl methacrylate=
A copolymer copolymerized at a ratio of 7/2/1 (mole ratio) (the same applies hereinafter). M-2 is methyl acrylate/n-butyl acrylate/glycidyl acrylate=8/l/l. 3 is n-butyl methacrylate/1so-butyl methacrylate/acrylonitrile/2-hydroxyethyl methacrylate=1/7/l/1. 4 represents methyl methacrylate/n-butyl methacrylate=515°. Fluoroalkyl group-containing acrylic polymer is CHm”CH
COOCHxC)Is (CFg) + oF/ 1s
o-butyl methacrylate/n-butyl acrylate/
2-hydroxyethyl methacrylate = 20/60/1
0/10% by weight copolymer. The incyanate curing agent is Coronate EH (manufactured by Nippon Polyurethane Co., Ltd.). The ultraviolet absorber is Biosorb 130 (manufactured by Kyodo Yakuhin). Comparative Example 2 in Table 2 is a flooring material on which a paint film is not formed. Example 12 When Example 1° was carried out in the same manner as in Example 1 except that the drying conditions were changed to 120° C. for 1 minute, the same effects as in Example 1 were obtained. [Effects of the Invention] The flooring material of the present invention has excellent weather resistance and antifouling properties because the specific coating film is formed with good adhesion.

Claims (1)

[Scope of Claims] 1. A coating film of a paint on a thermoplastic resin sheet, the main component of which is a fluorine-containing copolymer (a) having a crosslinking site and an acrylic polymer (b) that is compatible with (a). A flooring material made of 2. The flooring material according to claim 1, wherein the paint further comprises (c) an acrylic polymer having a fluoroalkyl group. 3. The flooring material according to claim 1, wherein the acrylic polymer (b) has a crosslinking site. 4. The flooring material according to claim 1, wherein the paint further contains a curing agent.