JP2000025168A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet usable as a surface material of a mirror surface wall panel for a bathroom. SOLUTION: A transparent hard acrylic resin sheet 1 with a thickness of 0.1-0.6 mm and pencil hardness of H or more consists of 60-75 wt.% of a polymer (A) with reduction viscosity of 0.1 (l/g) or less obtained by polymerizing a monomer containing 50 wt.% or more of alkyl ester methycrylate and 25-40 wt.% of a rubber-containing polymer (B) with a particle size of 0.1-0.4 μm obtained by bonding a polymer (B2) comprising 10-400 pts.wt. of a monomer or monomer mixture containing 50 wt.% or more of methacrylic acid ester to 100 pts.wt. of an elastic copolymer (B1) consisting of 50-99.9 wt.% of acrylic acid ester and 0.1-10 wt.% of a copolymerizable crosslinkable monomer and this sheet 1 is laminated to a polyolefinic resin base material sheet 2 through an adhesive layer 4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a decorative sheet,
More particularly, the present invention relates to a decorative sheet having excellent properties which can be used without surface coating, particularly as a surface material for a bathroom wall panel such as a unit bath.

[0002]

2. Description of the Related Art Conventionally, as a wall panel for a bathroom such as a unit bath, a vinyl chloride steel plate, a ceramic tile panel, a molded panel made of FRP, and the like are generally used.

On the other hand, with the recent spread of system buses for detached houses (unit buses for detached houses are referred to as system buses for apartment houses), they have a higher quality than bathroom wall panels, and maintenance is required. There is a growing need for mirror wall panels for bathrooms that are easier to use.

[0004] The mirror wall panel for bathrooms currently used in the market is made of a thermosetting resin such as a diallyl phthalate resin (DAP resin) or a polyester resin, which is gel-coated on the surface of a base material sheet and thermally cured to form a mirror-finished mirror. It is common that a transparent layer is formed. In addition, acrylic resin,
UV curable resin such as acrylic / urethane resin (U
V paint) is applied to the surface of a base material sheet to form a layer cured by ultraviolet rays.

[0005]

However, the above-mentioned bathroom mirror wall panel has the following problems. In order to form a transparent layer by gel coating, the thickness of the transparent layer is 0.1 to 0.2.
mm, the transparent layer is thicker, and a deep mirror surface cannot be formed. In addition, DAP resins and polyester resins do not always have high transparency, and also have a problem with respect to solvent resistance when used for bathroom wall panels. That is, soap and various detergents are frequently used in the bathroom, so that a high degree of alkali resistance is required. In addition, performance such as stain resistance to hair dye solution and the like, and chemical resistance to disinfectant and the like is required, but DAP resin and polyester resin cannot satisfy all of these properties.

Next, the above-mentioned prescription by painting has the following problems. That is, the first problem is that the thickness of the coating is 0.1 mm at the maximum. In the case of UV coating, when thick coating is applied, cracks occur due to changes in temperature and humidity. For this reason, in order to form a deep mirror surface, a method of previously laminating a transparent sheet of a predetermined thickness on a printing layer and coating on the printing layer is used, but it is said that the number of steps increases and the cost increases. There are drawbacks. The second problem is stain resistance to hair dyes and the like. UV paints are generally excellent in stain resistance, chemical resistance and the like, but have the disadvantage that they are easily stained by hair dyes.

In recent years, with the sophistication of consumer needs, bathrooms such as system baths have become more demanding in terms of design and quality, and have a sense of quality and a mirror surface which is less likely to be stained. The need for wall panels is growing rapidly. However, as described above, the current product has a number of problems, and in fact, an appropriate bathroom mirror wall panel has not yet emerged.

Further, the base material of the decorative sheet used for such a mirror wall panel for a bathroom is generally a vinyl chloride resin sheet from the viewpoint of workability and the like. There is a problem that chlorine, dioxin, etc. are generated at the time of disposal, and an environmental pollution problem has been pointed out. It is also known to use a polyolefin-based resin sheet laminated with a soft acrylic film, but the soft acrylic film layer on the surface of the polyolefin-based resin sheet has insufficient hardness and is easily damaged and is not suitable as a decorative sheet. It is.

[0009]

SUMMARY OF THE INVENTION A decorative sheet which can be suitably used as a mirror wall panel for a bathroom, has good quality, has high transparency and has a high depth, and has little environmental pollution at the time of disposal. Things.

[0010]

Means for Solving the Problems As a result of diligent studies, the present inventor has found that a transparent hard acrylic resin having a specific composition and physical properties is laminated on a polyolefin resin substrate sheet via an adhesive layer. As a result, the above-mentioned object can be achieved, and the present invention has been completed.

That is, the gist of the present invention is that a thermoplastic polymer (A) shown below is 60 to 75% by weight and a rubber-containing polymer (B) shown below is 25 to 40% by weight and has a thickness of 0.1 to 0.4%. A decorative sheet in which a transparent hard acrylic resin sheet having a pencil hardness of 1 mm or more and a pencil hardness of H or more is laminated on a polyolefin-based resin base material sheet via an adhesive layer. Thermoplastic polymer (A): 50 to 100% by weight of a methacrylate unit having an alkyl group having 1 to 4 carbon atoms, 0 to 50% by weight of an acrylate unit and another copolymerizable vinyl monomer unit A polymer comprising at least one kind of 0 to 49% by weight, and a reduced viscosity of the polymer (polymer 0.1
g in 100 ml of chloroform and measured at 25 ° C.)
Is 0.1 (l / g) or less. Rubber-containing polymer (B): 50-99.
9% by weight, other copolymerizable vinyl monomer units 0 to 4
Elastic copolymer (B1) 10 comprising 9.9% by weight and 0.1 to 10% by weight of other copolymerizable crosslinkable monomer units
A polymer consisting of 50 to 100% by weight of a methacrylate unit and 0 to 50% by weight of another copolymerizable vinyl monomer unit or 10 to 400 parts by weight of a monomer mixture in 0 part by weight. (B2) is combined, and
A rubber-containing polymer having a particle size of 0.1 to 0.4 μm.

Further, the gist of the present invention resides in the above decorative sheet, wherein the polyolefin resin base sheet is a resin mainly composed of polyethylene.

[0013]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a decorative sheet according to the present invention will be described with reference to the drawings. FIG. 1 shows an enlarged cross section of a decorative sheet according to the present invention, wherein reference numeral 1 denotes a transparent hard acrylic resin sheet, and reference numeral 2 denotes a polyolefin-based resin base sheet. The decorative sheet of the present invention is formed by laminating a transparent hard acrylic resin sheet 1 on the surface of a polyolefin-based resin base sheet 2 via an adhesive layer 4 as shown in the figure.
In the decorative sheet of the present invention, the pattern 3 can be provided between the adhesive layer 4 and the transparent hard acrylic resin sheet 1.

FIG. 2 is an enlarged sectional view showing an example of a bathroom mirror wall panel in which the decorative sheet 5 shown in FIG. 1 is laminated on a base material 6 via an adhesive layer 7.

The transparent hard acrylic resin sheet 1 used in the present invention comprises a thermoplastic polymer (A) and a rubber-containing polymer (B).
Obtained by molding a resin consisting of

The thermoplastic polymer (A) contains 50 to 1 methacrylate units having an alkyl group having 1 to 4 carbon atoms.
It is a polymer comprising 00% by weight, 0 to 50% by weight of an acrylate unit and 0 to 49% by weight of at least one kind of other copolymerizable vinyl monomer units.

The carbon number 1 constituting the thermoplastic polymer (A)
Examples of the methacrylate having an alkyl group of from 4 to 4 include methyl methacrylate, ethyl methacrylate,
Butyl methacrylate and the like. Of these, the use of methyl methacrylate is preferred. As the acrylate, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate,
2-ethylhexyl acrylate and the like can be mentioned. Further, as other vinyl monomers copolymerizable with these,
Examples thereof include aromatic vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, and vinyl toluene, and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. These can be used alone or in combination with one or more other types. If the content of the methacrylate unit in the thermoplastic polymer (A) is less than 50% by weight, the inherent properties of the acrylic resin will be lost, and the heat resistance, weather resistance and transparency of the obtained resin material will be reduced.

The thermoplastic polymer (A) can be prepared by a known polymerization method,
For example, it can be obtained by a suspension polymerization method, a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, or the like. The reduced viscosity (0.1 g of the polymer dissolved in 100 ml of chloroform and measured at 25 ° C.) of the thermoplastic polymer (A) used in the present invention is 0.1.
(L / g) or less, and when the reduced viscosity is large, the processability is deteriorated, which is not preferable.

On the other hand, the rubber-containing polymer (B) used in the present invention is a component for imparting elasticity to the transparent hard acrylic resin sheet. The rubber-containing polymer (B) comprises 50 to 99.9% by weight of an acrylate unit, 0 to 49.9% by weight of another copolymerizable vinyl monomer unit, and a copolymerizable crosslinkable monomer unit. In 100 parts by weight of the elastic copolymer (B1) consisting of 0.1 to 10% by weight, 50 to 100 parts by weight of a methacrylate unit unit and 0 to 50% by weight of another copolymerizable vinyl monomer unit are added. It is obtained by bonding a polymer (B2) comprising 10 to 400 parts by weight of a monomer or monomer mixture.

As the acrylate constituting the elastic copolymer (B1), for example, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate having an alkyl group having 8 or less carbon atoms are preferable, and particularly preferable. Is n-butyl acrylate. Other copolymerizable vinyl monomers include, for example, methacrylate monomers such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate, and styrene, vinyl toluene, α-
An aromatic vinyl monomer such as methylstyrene is exemplified.
Examples of the copolymerizable crosslinking monomer include polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and allyl methacrylate; and 1,4-butanediol. Diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyfunctional acrylate monomers such as allyl acrylate, diallyl maleate, diallyl phthalate, triallyl cyanurate, Triallyl isocyanurate, diallyl fumarate, triallyl trimellitate, divinylbenzene and the like can be mentioned.

Examples of the methacrylic acid ester constituting the polymer (B2) include those exemplified for the structure of the thermoplastic polymer (A). Similarly, examples of other copolymerizable vinyl monomers include acrylates and vinyl monomers exemplified in the constitution of the thermoplastic polymer (A).

The rubber-containing polymer (B) can be obtained by a known polymerization method, for example, emulsion polymerization. The rubber-containing polymer (B) used in the present invention has a particle size of 0.1 to 0.4.
Those having a range of μm are used. Outside of this range, impact resistance, gloss and transparency are undesirably reduced.

The transparent hard acrylic resin sheet 1 used in the present invention is composed of a resin composed of the thermoplastic polymer (A) and the rubber-containing polymer (B) obtained by the above-mentioned method. The composition ratio of (A) and the rubber-containing polymer (B) is (A) 60 to 75 from the balance between heat workability and surface hardness.
It is important that the content be in the range of 25% by weight to 25% by weight (B). If the proportion of the rubber-containing polymer is larger than this range, the hardness of the surface decreases. On the other hand, if the proportion of the rubber-containing polymer is small, the sheet is liable to be broken at the time of manufacturing the sheet, and it is difficult to bond the polyolefin resin sheet at the time of manufacturing the decorative sheet.

The method of forming the transparent hard acrylic resin sheet 1 is not particularly limited, but T-die extrusion and a belt press method are used from the viewpoint of improving production efficiency and forming a sheet having a thickness of 0.1 to 0.6 mm. It is preferable to adopt and manufacture.

It is important that the transparent hard acrylic resin sheet 1 used in the present invention has a thickness of 0.1 to 0.6 mm and a pencil hardness of H or more. This is because if the thickness is too small, the surface hardness is reduced due to the influence of the hardness of the base material, while if it is too thick, it becomes difficult to wind it into a roll or to laminate continuously. Furthermore, if the pencil hardness is lower than H, the surface is easily scratched and becomes unsuitable as a decorative sheet.

Although a hard acrylic plate similar to the transparent hard acrylic resin sheet 1 used in the present invention is commercially available, it has a minimum thickness of 1.0 mm and is cut into a fixed size. Therefore, it is not suitable as the transparent hard acrylic resin sheet of the present invention because continuous lamination cannot be performed, and it is expensive.
A soft acrylic film is also commercially available. In this case, there is an advantage that continuous thermal lamination with the polyolefin resin base sheet 2 is possible, but the thickness is 0.2 mm or less. The texture as the transparent layer is insufficient, and the surface hardness is low due to the softness (the pencil hardness is B or less). Therefore, it is not appropriate to use it as a surface material without painting as a wall panel.

Examples of the polyolefin resin used for the base sheet 2 used in the present invention include, for example, polyethylene, ethylene-propylene copolymer, ethylene-butene copolymer, polypropylene, propylene-butene copolymer, polybutene, butene. Propylene / ethylene terpolymer, polymethylpentene, and the like. The decorative sheet is often used in the form of a flat sheet, but may also be used after being thermoformed. In such an application, a polyethylene resin is most excellent. The base resin may be added with generally known inorganic fillers such as calcium carbonate, barium sulfate, titanium oxide, and alumina oxide, or may be colored by adding an appropriate dye or pigment. Is also possible. The thickness of the polyolefin resin substrate sheet is not particularly limited, but is preferably in the range of 0.1 to 0.5 mm.

Further, the polyolefin resin base sheet 2
And the transparent hard acrylic resin sheet 1 are inferior in adhesion and cannot be directly laminated. In laminating, the surface of the base sheet 2 is preferably subjected to an easy-adhesion treatment in order to improve the adhesion. Acrylic, vinyl acetate, polyester, urethane and the like are used as the adhesive constituting the adhesive layer 4. Corona discharge treatment, plasma treatment, and the like are known as the easy adhesion treatment of the surface of the base sheet 2, and these treatments can be combined.

A picture 3 is provided between the adhesive layer 4 and the transparent hard acrylic resin sheet 1 as required. The pattern 3 is provided for the purpose of imparting a design property to the decorative sheet of the present invention. In addition to a pattern of a natural material such as a woodgrain or a stone, a free design such as a geometric pattern or a random pattern is provided. Is exemplified. The pattern is printed on the adhesive layer 4 or the transparent hard acrylic resin sheet 1 by a gravure coating method, a roll coater method, a knife coater method or the like.

In the decorative sheet of the present invention, the above-mentioned transparent hard acrylic resin sheet 1 and polyolefin resin base sheet 2 are laminated and integrated via an adhesive layer 4 as shown in FIG. At this time, the above-described pattern 3 can be provided. The method of laminating the transparent hard acrylic resin sheet 1 on the polyolefin-based resin base material sheet 2 is not particularly limited. For example, the transparent hard acrylic resin sheet is heat-bonded to the mirror roll surface by using a mirror heat laminating machine. It is preferable to use a technique such as fusion lamination.

The decorative sheet 5 of the present invention obtained as described above is obtained by laminating a polyolefin resin base material sheet 2 on a substrate 6 via an adhesive layer 7 as shown in FIG. Used as a surface material of the panel 8. Adhesive layer 7
For this, an adhesive such as an epoxy-based, urethane-based, vinyl acetate-based, silicon-based, or chloroprene rubber-based adhesive can be used.

[0032]

The present invention will be specifically described below with reference to examples.

Example 1 An example of manufacturing a decorative sheet of the present invention and an example of manufacturing a wall panel made of the sheet are described in the following (1).
To (4). (1) Production of transparent hard acrylic resin sheet 68 parts by weight of a thermoplastic polymer (A) shown below and 32 parts by weight of a rubber-containing polymer (B) shown below are mixed and melted.
T-die extruder (cylinder temperature 220 ° C, T-die temperature 2
(40 ° C.) and continuously extruded at a thickness of 0.3 mm × a width of 1000 mm, cooled through a mirror belt press, and cooled to about 50
mm, and rolled up into a roll while cutting to a thickness of 0.1 mm.
A transparent hard acrylic resin sheet having a size of 3 mm × width 900 mm × length 500 m was obtained.

Thermoplastic polymer (A): a polymer comprising 99% by weight of methyl methacrylate units and 1% by weight of methyl acrylate units, having a reduced viscosity of 0.06 (l / g)
Acrylic thermoplastic polymer.

Rubber-containing polymer (B): An elastic copolymer composed of 65% by weight of n-butyl acrylate unit, 12% by weight of styrene unit, 22.9% by weight of methyl methacrylate unit and 0.1% by weight of allyl methacrylate unit. A polymer having a particle size of 0.25 μm obtained by bonding a polymer comprising 60 parts by weight of a monomer mixture comprising 95% by weight of methyl methacrylate units and 5% by weight of methyl acrylate units to 100 parts by weight of a polymer.
A rubber-containing polymer which is

(2) Easy adhesion treatment and pattern printing of polyethylene resin base sheet One side of a polyethylene resin sheet having a thickness of 0.1 mm, a width of 850 mm and a length of 500 m containing 35% by weight of calcium carbonate as an inorganic filler is coated with a corona. After the discharge treatment, a vinyl acetate adhesive was gravure coated to a thickness of 3 μm to form an adhesive layer. Further, a stone-tone pattern was printed thereon with an acrylic urethane-based printing ink.

(3) Production of decorative sheet A polyethylene resin base sheet having the transparent hard acrylic resin sheet of the above (1) as a surface layer, the treatment of the above (2), formation of an adhesive layer and printing of a pattern on the back surface, The pattern is laminated so that the pattern is in contact with the back surface of the transparent hard acrylic resin sheet, and the transparent hard acrylic resin sheet is 165 ° C. × 5 while being pressed against the mirror roll surface using a mirror heat laminating machine.
The decorative sheet was prepared by heat-sealing and laminating under a condition of m / min.

(4) Production of mirror wall panel for bathroom The decorative sheet obtained in the above (3) is 800 mm × 200
Cut to a size of 0 mm and sanded in advance for the purpose of improving the surface level of the substrate, improving the water resistance, improving the adhesion to the surface material, etc.
An epoxy-based water-resistant adhesive is applied with a knife coater on a treated surface of a calcium silicate plate having a size of 2,000 mm × length 2000 mm to form an adhesive layer, and a polyethylene resin substrate sheet surface is formed on the surface of the adhesive layer. Surface bonding was performed to form a mirror wall panel for a bathroom.

The obtained mirror wall panels for bathrooms were evaluated according to the following (5) to (9), and good results were obtained.

(5) Stain resistance A letter was written on the surface of the transparent hard acrylic resin sheet with a felt tip pen manufactured by Pentel Co., Ltd., and wiped off with ethanol, but no trace was left. The same acrylic resin sheet surface was coated with Hoyu Co., Ltd. hair dye "Vigen Cream Tone" (trade name) and left at 23 ° C. for 7 days, but after washing with water, there was no contamination at all.

(6) Chemical resistance NaOH 5% aqueous solution, Ca (OH) ₂ 5% aqueous solution, fungicide “Kabikiller” manufactured by Johnson & Johnson Co., Ltd.
It was immersed in each liquid (trade name) at 23 ° C. for 7 days, and the color difference was measured based on JIS K6902.

(7) Warm-resistant water When immersed in hot water of 85 ° C. for 240 hours, no abnormality was observed in appearance.

(8) Weather Resistance The transparent hard acrylic resin sheet surface was exposed for 1000 hours using a sunshine weatherometer (spraying pure water for 18 minutes during irradiation at 63 ° C. for 120 minutes). 0 was good.

(9) Surface Hardness The pencil hardness of the transparent hard acrylic resin sheet surface measured according to JIS D0202 was 2H.

[Examples 2 and 3] Sanding treatment using a waterproof veneer (Example 2) and a foamed polyethylene board (Example 3) instead of the calcium silicate plate used as the substrate in Example 1 Thereafter, a mirror wall panel for a bathroom was prepared in the same manner, and the same evaluation as in Example 1 was performed. In each case, good evaluation results were obtained.

The bathroom mirror wall panel made using the decorative sheet of the present invention has a high quality mirror surface texture,
In terms of quality and performance, it has excellent suitability as described above.

[0047]

The decorative sheet of the present invention has excellent adhesion since the transparent hard acrylic resin sheet and the polyolefin resin base sheet are adhered through the adhesive layer.
In addition, since it has high transparency and deep texture, and excellent stain resistance, chemical resistance, weather resistance, and hot water resistance, it does not require surface painting work, and as a decorative sheet for mirror wall panels for bathrooms. Can be used. Further, since the decorative sheet of the present invention can be thermoformed, it can be suitably used for a system kitchen cabinet, a vanity table, furniture, a cabinet face plate and the like. Furthermore, the decorative sheet of the present invention can be produced at a low price because it can be manufactured with high productivity by a heat-sealing lamination method, and because the polyolefin-based resin is used as the base sheet, it is environmentally friendly even if it is incinerated and disposed No adverse effects.

[Brief description of the drawings]

FIG. 1 is an enlarged sectional view showing an example of a decorative sheet according to the present invention.

FIG. 2 is an enlarged sectional view showing an example of a mirror wall panel for bathroom made of a decorative sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent hard acrylic resin sheet 2 Polyolefin resin base material sheet 3 Picture 4 Adhesive layer 5 Decorative sheet 6 Substrate (calcium silicate board) 7 Adhesive layer 8 Bathroom mirror wall panel

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masayasu Inoue 3816 Noto, Noto, Tama-ku, Kawasaki-shi, Kanagawa F-term in the Tokyo Technology and Information Center, Mitsubishi Rayon Co., Ltd. 4F100 AA08H AA25J AK03B AK04B AK12B AK12 AK12A AK12J AK22G AK25A AK51AK80 AL01A AL05A AN00A AN02 BA02 BA23 CA23 CB00 DE01A EJ05A EJ55 GB08 GB81 HB00 HB11 JA06A JB01 JB07 JB16A JJ03 JK06 JL00 JL06 JL09 JN01 JN01A YY00A

Claims (2)

[Claims] 1. A thermoplastic polymer (A) 6 shown below
0 to 75% by weight and 25 to 40% by weight of a rubber-containing polymer (B) shown below, having a thickness of 0.1 to 0.6 m
m, a decorative sheet formed by laminating a transparent hard acrylic resin sheet having a pencil hardness of H or higher on a polyolefin resin base material sheet via an adhesive layer. Thermoplastic polymer (A): 50 to 100% by weight of a methacrylate unit having an alkyl group having 1 to 4 carbon atoms, 0 to 50% by weight of an acrylate unit and another copolymerizable vinyl monomer unit At least one 0-49% by weight
And a reduced viscosity of the polymer (measured at 25 ° C. by dissolving 0.1 g of the polymer in 100 ml of chloroform) of 0.1 (l / g) or less. Rubber-containing polymer (B): acrylic acid ester unit 50 to
99.9% by weight, other copolymerizable vinyl monomer units 0
Elastic copolymer (B1) 10 comprising -49.9% by weight and 0.1-10% by weight of copolymerizable crosslinkable monomer units
A polymer consisting of 50 to 100% by weight of a methacrylate unit and 0 to 50% by weight of another copolymerizable vinyl monomer unit or 10 to 400 parts by weight of a monomer mixture in 0 part by weight. (B2) is combined, and
A rubber-containing polymer having a particle size of 0.1 to 0.4 μm. 2. The decorative sheet according to claim 1, wherein the polyolefin resin base sheet is a resin mainly composed of polyethylene.