JP2000290397A - Film for floor material surfacing and floor material prepared by using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film which has good processibility and surface hardness and, when laminated to the surface of a floor material, can give a surface- covered floor material easily in a simple way by forming a composition comprising an acrylic resin and a rubbery elastomer in a specified ratio into a film with a specified thickness. SOLUTION: A composition comprising 40-95 wt.% acrylic resin and 5-60 wt.% rubbery elastomer is formed into a film with a thickness of 500 μm or lower. A (co)polymer resin containing 50-100 wt.% methyl methacrylate units is preferable as the acrylic resin, though the resin may contain 50 wt.% or lower glutaric anhydride units. Preferably, the resin has a heat distortion temperature of 80 deg.C or higher. An acrylic rubbery elastomer is especially preferable as the elastomer. Preferably, the elastomer has a core-shell structure wherein a crosslinked rubber layer having a glass transition point (Tg) of 0 deg.C or lower is covered with at least one graft layer. Still preferably, the crosslinked rubber layer contains therein at least one inner polymer layer having a Tg of 20 deg.C or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a skin film for decorative flooring used in public facilities, commercial facilities and the like, and a decorative flooring obtained by laminating the film on the surface.

[0002]

2. Description of the Related Art For the purpose of improving the design of decorative flooring materials, for example, Japanese Patent Application Laid-Open No. H10-169173 describes a method of forming a decorative pattern on a base material by embossing printing or the like. A method of laminating a transparent thick coating or a resin layer on the surface of the handle of such a flooring material is widely used. In particular, lamination of an acrylic resin is widely used in these applications because of its excellent transparency.
As a method of laminating a transparent skin of an acrylic resin on these decorative flooring materials, a method of repeatedly applying an acrylic paint or a method of polymerizing a monomer or oligomer on the surface is used.

However, these methods have disadvantages in that a monomer or an organic solvent is used, and that the steps are complicated. In order to solve these problems, a method of laminating an acrylic resin film is known.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have conducted intensive studies on an acrylic resin film for the skin of a flooring material, and as a result, have found that a film for a skin composed of a predetermined ratio of an acrylic resin and a rubber elastic body has a workability, The inventors have found that the surface hardness is excellent, and have completed the present invention.

An object of the present invention is to provide a floor covering film having good workability and surface hardness, and a floor covering obtained by laminating the film on the surface.

[0006]

That is, the present invention provides an acrylic resin (A) of 40 to 95% by weight and a rubber elastic body (B) 5
It is a flooring material film composed of ６０60% by weight and having a thickness of 500 μm or less, and a flooring material characterized in that the flooring material film is laminated on the surface of a flooring material base material.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The acrylic resin (A) used in the present invention is not particularly limited as long as it is a polymer containing methyl methacrylate as a main component. ,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth)
Alkyl (meth) acrylate having an alkyl group of 1 to 8 carbon atoms such as octyl acrylate and 2-ethylhexyl (meth) acrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; N-phenylmaleimide; Maleimides such as cyclohexylmaleimide; maleic acid,
Acid group-containing unsaturated compounds such as maleic anhydride; copolymerizable monomers 0 to 50 such as nitriles such as acrylonitrile
What is obtained by copolymerizing the compound of the formula (1) and (2) is preferable. Alternatively, a glutaric anhydride (GAH) structure may be contained in a range of 50% by weight or less. Those having a heat distortion temperature of 80 ° C. or more measured according to ASTM D648 are more preferable for obtaining a practical film surface hardness. Also,
In order to improve transparency and appearance, which are important in film properties, it is more preferable that the content of methyl methacrylate is 70% by weight or more, and two or more copolymerizable monomers may be used depending on the purpose.

The content of the acrylic resin (A) in the floor covering film must be 40 to 95% by weight. If it is less than 40% by weight, the surface hardness of the film is insufficient. 95% by weight
When the value exceeds, the film becomes extremely brittle, resulting in poor film formation, and even if the film can be formed, the workability when processing the floor material is poor. The preferable addition amount of the acrylic resin (A) is 70 to 90% by weight.

The rubber elastic body (B) used in the present invention may be an acrylic, butadiene, polyolefin, silicone or fluorine rubber elastic body.
Considering transparency and the like, an acrylic rubber elastic body is particularly preferable. Examples of the acrylic rubber elastic body include alkyl acrylates having alkyl groups having 1 to 8 carbon atoms, such as 80 to 9 alkyl acrylates.
9.9% by weight, 15% by weight or less of a monomer having one copolymerizable double bond and 0.1 to 5% by weight of a polyfunctional monomer having two or more copolymerizable double bonds A crosslinked elastic rubber having a glass transition temperature (hereinafter, abbreviated as Tg) of 0 ° C. or lower is preferred from the viewpoint of physical properties such as transparency and elongation of the film. Further, the crosslinked elastic rubber is used as a rubber layer (b-1).
At least one graft layer (b) composed of 20 to 80% by weight of a monomer having a double bond copolymerizable with 20 to 80% by weight of an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms. Rubber elastic bodies having a core-shell structure having -2) are particularly preferable because they reduce stress whitening of the film.

Further, in order to improve the transparency and the impact strength, it is necessary to use at least 50% by weight of methyl methacrylate, for example, methyl acrylate, ethyl (meth) acrylate, (meth)
Alkyl groups such as propyl acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate have 1 to 1 carbon atoms.
8 alkyl (meth) acrylates; aromatic vinyl compounds such as styrene and α-methylstyrene; maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; and unsaturated compounds containing acid groups such as maleic acid and maleic anhydride. And Tg obtained by copolymerizing less than 50% by weight of a copolymerizable monomer such as nitronyl such as acrylonitrile.
Is an inner layer polymer (b-
More preferably, it has a structure having 3) in the rubber layer (b-1).

The rubber elastic body (B) needs to be 5 to 60% by weight in the floor covering film. If the content is less than 5% by weight, the film becomes extremely brittle, resulting in poor film formation. Even if the film can be formed, the workability when processing it into a flooring material is unfavorable. If it exceeds 60% by weight, the surface hardness of the film becomes insufficient. The preferred addition amount is 15 to 35% by weight.

The floor covering film of the present invention contains 40% acrylic resin (A) in terms of surface hardness, film-forming properties and workability.
It is necessary that the rubber elastic body (B) is composed of 5 to 60% by weight.
A 4% by weight acetone solution was prepared, left at room temperature for 24 hours at 25 ° C., refluxed for 4 hours, and then centrifuged at 14,000.
The ratio of the acrylic resin (A), which is the matrix resin, to the rubber elastic body (B) is determined within the range where the acetone-insoluble content obtained by centrifuging at 60 rpm for 60 minutes is 5 to 30%. It is more preferable from the viewpoint of physical properties, film forming properties, and workability.

As the acrylic resin (A) used in the present invention, those produced by various production methods such as suspension polymerization, bulk polymerization and emulsion polymerization can be used. As the rubber elastic body (B), a rubber elastic body (B) manufactured by the same manufacturing method as that of the acrylic resin can be used, but in order to obtain a multilayer structure, it is preferable to manufacture the rubber elastic body by emulsion polymerization. In addition, the acrylic resin (A) and the rubber elastic body (B) used in the present invention can be manufactured continuously from both components. For example, the acrylic resin (A) and the rubber elastic body (B) can be produced in the presence of a latex of the rubber elastic body (B). )) And a method of polymerizing by adding the monomer constituting the above.

[0014] The floor covering film of the present invention is made of JIS
It preferably has a surface hardness of F or more in a pencil hardness test based on K-5401. If the surface hardness is insufficient, the wear resistance is poor.

[0015] The floor covering film of the present invention may contain known additives such as stabilizers, lubricants, processing aids, etc.
Plasticizer, impact aid, colorant, UV absorber, antibacterial,
Matting agents and the like can be added.

The method for producing the floor covering film of the present invention is not particularly limited, and various methods can be used.
A method of forming an acrylic resin into a film using a melt extrusion method such as a die method or an inflation method, a calendar method, or the like.

The thickness of the floor covering film of the present invention is 5
It is necessary that the thickness be not more than 00 μm. If it exceeds 500 μm, workability will deteriorate. Considering the surface design, the thickness of the floor material surface film is more preferably 50 to 300 μm.

The floor material base material used for the floor material of the present invention may be any material which has been conventionally used as a floor material. For example, a synthetic resin sheet made of an ABS resin, a polyvinyl chloride resin, an acrylic resin, or the like, a glass fiber reinforced resin sheet thereof, a fiber sheet made of glass fiber, pulp, rock wool, or the like, a fiber sheet of a nonwoven fabric, or the like can be given. In addition, the floor material base material in the present invention refers to a plate material used for forming a floor surface.

Although any method may be used to laminate the floor covering film of the present invention on these flooring substrates, the method of heat laminating is economically advantageous. For a substrate that cannot be thermally laminated, it is possible to bond the substrate using an adhesive. Further, a method of providing a printed layer also serving as an adhesive layer on the surface of the floor covering film and laminating and integrating them is advantageous from the viewpoint of design.

[0020]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means “parts by weight”. Acrylic resin (A) Acrylic resin A-1 to A-
As for 4, the one shown in Table 1 was used.

[0021]

[Table 1] MMA: Methyl methacrylate MA: Methyl acrylate St: Styrene GAH: Glutaric anhydride ・ Preparation of rubber elastic body (B-1) The following raw materials are charged into a reaction vessel and stirred at 50 ° C. for 4 hours in a nitrogen atmosphere. The polymerization was completed while the reaction was carried out to obtain an elastic latex.

Butyl acrylate 77.0 parts Styrene 22.7 parts Allyl methacrylate 0.3 parts Sodium dioctyl sulfosuccinate 2.0 parts Deionized water 300.0 parts Potassium persulfate 0.3 parts Disodium phosphate 12 0.5 part of water salt 0.3 part of sodium hydrogen phosphate dihydrate 0.3 part 100 parts of this elastic latex (as solid content) is placed in a reaction vessel, and sufficiently purged with nitrogen while stirring.
After adding an aqueous solution consisting of 0.125 part of sodium formaldehyde sulfoxylate, 5 ppm of ferric sulfate, 15 ppm of disodium ethylenediaminetetraacetate and 2 parts of pure water, methacrylic acid was maintained at 80 ° C. 60 parts of methyl, n-octyl mercaptan 0.
05 parts and t-butyl hydroperoxide 0.1
The mixture consisting of 25 parts was dropped over 2 hours and then kept for 2 hours to obtain a rubber elastic body (B-1) having a particle diameter of 0.15 μm. Preparation of Rubber Elastic Body (B-2) The following materials were charged into a reaction vessel, and polymerization was completed while stirring at 50 ° C. for 4 hours under a nitrogen atmosphere to obtain an elastic latex.

Methyl methacrylate 39.0 parts Styrene 1.0 part Allyl methacrylate 0.1 part Sodium dioctyl sulfosuccinate 2.0 parts Deionized water 300.0 parts Potassium persulfate 0.3 parts Disodium phosphate 12 Water salt 0.5 part sodium hydrogen phosphate dihydrate 0.3 part
After adding an aqueous solution consisting of 0.125 part of sodium formaldehyde sulfoxylate, 5 ppm of ferric sulfate, 15 ppm of disodium ethylenediaminetetraacetate and 2 parts of pure water, acrylic acid was added while maintaining the temperature at 80 ° C. 55 parts of n-butyl, 3 parts of methyl methacrylate, 2 parts of styrene, 0.3 part of allyl methacrylate, and 0.05 part of t-butyl hydroperoxide were added dropwise over 3 hours and maintained for 1 hour. Thereafter, 59 parts of methyl methacrylate, 1 part of methyl acrylate, 0.05 parts of n-octyl mercaptan
Parts, a mixture consisting of 0.125 parts of t-butyl hydroperoxide was added dropwise over 2 hours, and then kept for 2 hours.
A rubber elastic body (B-2) having a particle diameter of 0.25 μm was obtained.

Examples 1-3, 5-6 and Comparative Examples 1-2 Adekastab LA- was added to the acrylic resin having the composition shown in Table 2.
32 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., ultraviolet absorber) 2
And 0.5 part of Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals, antioxidant), and a 40 mmφ screw type extruder (L / D = 2)
Using 6), the mixture was melt-kneaded at a cylinder temperature of 200 to 260 ° C. and a die temperature of 250 ° C. to form pellets. The obtained pellets were dried at 80 ° C. all day and night, and T
-A film having a thickness of 100 µm was obtained using a die.

Example 4 Adecastab LA was added to an acrylic resin having the composition shown in Table 2.
-31 (see above) 2 copies, Irganox 1076 (see above)
0.5 part and 5 parts of mica M400H (trade name, manufactured by Repco, inorganic matting agent) were added, and the cylinder temperature was 200 to 260 ° C. using a 40 mmφ screw type extruder (L / D = 26). The mixture was melt-kneaded at a die temperature of 250 ° C. and pelletized. The obtained pellets were dried at 80 ° C. for 24 hours, and the thickness was 75 μm using a T-die with a 40 mmφ extruder.
m matte film was obtained.

Example 7 The film obtained in Example 3 was adhered to a floor substrate using an adhesive to obtain a floor material. The workability was satisfactory and the surface hardness was sufficient.

Comparative Example 3 The film obtained in Comparative Example 2 was bonded to a flooring substrate using an adhesive, but the film often cracked and the workability was poor.

[0028]

[Table 2] The evaluation was based on the following. 1) Fragility was evaluated by the easiness of cracking when the film was handled by hand.

A: No cracking even when bent 180 ° B: No cracking even when bent 90 ° B: Partially cracked when bent 90 ° C: Cracked even when slightly bent 2) Each film was Diapet ABS 3001 (product) The pencil hardness of a sample obtained by heat laminating a floor material base material (30 × 30 × 3 mm) made of an injection-molded product of name (Mitsubishi Rayon Co., Ltd., ABS resin) was measured according to JIS K-54.
01 was measured.

[0030]

The film for floor covering of the present invention has good workability and surface hardness. By laminating the film on the surface of the floor, a surface covering floor can be easily obtained.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yukio Kitaike 20-1 Miyukicho, Otake City, Hiroshima Prefecture Mitsubishi Rayon Co., Ltd. Otake Works F-term (reference) 4F071 AA10 AA33 AA86 AF25 AH03 BB06 BC01 BC12 4J002 BG06W BN03X BN12X BN14X BN17X BN20X GL00

Claims (5)

[Claims] 1. An acrylic resin (A) of 40 to 95% by weight and a rubber elastic body (B) of 5 to 60% by weight having a thickness of 50%.
A floor covering film having a thickness of 0 μm or less. 2. The floor covering film according to claim 1, which has a surface hardness of F or more in a pencil hardness test according to JIS K-5401. 3. The rubber elastic body (B) has a core-shell structure comprising at least one rubber layer (b-1) having a glass transition temperature of 0 ° C. or lower and one or more graft layers (b-2). The floor covering film according to claim 1, which has 4. An inner layer polymer (b-3) comprising one or more rubber elastic bodies (B) and having a glass transition temperature of 20 ° C. or higher.
And one or more rubber layers (b-1) having a glass transition temperature of 0 ° C. or lower on the outer side of the inner layer polymer, and one or more graft layers (b-2) on the outermost layer. 2. The floor covering film according to 1 above. 5. A floor material comprising the floor material skin film according to claim 1 laminated on a surface of a floor material base material.