JP3363385B2 - Decorative sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a decorative sheet,
More specifically, the present invention relates to a decorative sheet having excellent properties that can be used as a surface material for bathroom wall panels such as unit baths without surface coating.

[0002]

2. Description of the Related Art Conventionally, vinyl chloride steel plates, ceramic tile panels, FRP molded panels, etc. have been generally used as wall panels for bathrooms such as unit baths.

On the other hand, in recent years, with the spread of system buses for detached houses (unit buses for detached houses are referred to as system buses for collective houses), there is a feeling of higher quality than wall panels for bathrooms and maintenance. There is an increasing need for bathroom mirror wall panels that are easy to install.

Currently, bathroom mirror surface wall panels used in the market are mirror-coated by thermosetting a thermosetting resin such as diallyl phthalate resin (DAP resin) or polyester resin on the surface of a base material sheet and thermally curing it. A transparent layer is generally formed. In addition, acrylic resin type,
UV curable resin such as acrylic / urethane resin (U
A method is also known in which 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 surface panel has the following problems. For the thermosetting type decorative sheet, the transparent layer is formed by gel coating, so the thickness of the transparent layer is 0.1 to 0.2.
Since there is no choice but to limit the thickness to about mm, there is a problem in that the transparent layer is thicker and a deep mirror surface cannot be formed. Further, the DAP resin and the polyester resin do not necessarily have high transparency, and also have a problem regarding solvent resistance when they are used for bathroom wall panels. In other words, soap and various detergents are often used in the bathroom, and therefore high alkali resistance is required. Further, performance such as stain resistance against hair dyeing liquid and chemical resistance against disinfectant and the like is required, but DAP resin and polyester resin cannot satisfy all of these performances.

[0006] Next, the above-mentioned coating formulation has the following problems. That is, the first problem is that the maximum coating thickness is 0.1 mm. In the case of UV coating, a thick coating causes cracks 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 the printing layer and coating it on it is taken, but the number of steps increases and the cost becomes high. There are drawbacks. The second problem is stain resistance to hair dye and the like. UV paints are generally excellent in stain resistance, chemical resistance, etc., but have the drawback that they are easily contaminated by hair dye.

In recent years, with the sophistication of consumer needs, bathrooms such as system baths are required to have better design and quality, and the mirror surface has a high-class feeling and is hard to be stained. The need for wall panels is growing rapidly. However, as described above, the current products have many problems, and the reality is that proper bathroom mirror wall panels have not yet appeared.

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

[0009]

Provided is a decorative sheet which can be suitably used as a mirror wall panel for a bathroom, has a good quality, is highly transparent, and has a deep depth, and has little environmental pollution at the time of disposal. It is a thing.

[0010]

As a result of intensive 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 base sheet through an adhesive layer. As a result, they have found that the above-mentioned object can be achieved and completed the present invention.

That is, the gist of the present invention consists of 60 to 75% by weight of the thermoplastic polymer (A) shown below and 25 to 40% by weight of the rubber-containing polymer (B) shown below, and has a thickness of 0. A transparent hard acrylic resin sheet having a pencil hardness of H or more and having a pencil hardness of 1 to 0.6 mm is a decorative sheet for a surface material of a bathroom wall panel, which is laminated on a polyolefin resin base sheet via an adhesive layer. Thermoplastic polymer (A): carbon number 1
Methacrylic acid ester unit 5 having 4 to 4 alkyl groups
A polymer comprising 0 to 100% by weight, 0 to 50% by weight of an acrylic acid ester unit, and 0 to 49% by weight of at least one other copolymerizable vinyl monomer unit, and the reduced viscosity of the polymer ( 0.1 g of polymer to 100 ml of chloroform
A thermoplastic polymer which is dissolved in and is 0.1 (l / g) or less at 25 ° C.). Rubber-containing polymer (B): 50 to 99.9% by weight of acrylic acid ester unit, 0 to 49.9% by weight of other copolymerizable vinyl monomer unit, and other copolymerizable crosslinkable monomer. 100 parts by weight of an elastic copolymer (B1) consisting of 0.1 to 10% by weight of a unit, 50 to 100% by weight of a methacrylic acid ester unit and 0 to 50% by weight of another copolymerizable vinyl monomer unit. A rubber-containing polymer to which a polymer (B2) consisting of 10 to 400 parts by weight of a monomer or a mixture of monomers is bound and which has 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]

BEST MODE FOR CARRYING OUT THE INVENTION The decorative sheet of the present invention will be described below 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 is a transparent hard acrylic resin sheet, and 2 is a polyolefin resin base sheet. The decorative sheet of the present invention is configured by laminating a transparent hard acrylic resin sheet 1 on the surface of a polyolefin-based resin base sheet 2 with 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 cross-sectional view showing an example of a bathroom mirror surface 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).
It is obtained by molding a resin composed of

The thermoplastic polymer (A) comprises 50 to 1 methacrylic acid ester 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 acrylic acid ester unit, and 0 to 49% by weight of at least one other copolymerizable vinyl monomer unit.

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

The thermoplastic polymer (A) is 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 of the thermoplastic polymer (A) used in the present invention (measured at 25 ° C. by dissolving 0.1 g of the polymer in 100 ml of chloroform) is 0.1.
It is not more than (l / g), and if the reduced viscosity is large, the workability is deteriorated, which is not preferable.

On the other hand, the rubber-containing polymer (B) used in the present invention is a component that imparts elasticity to the transparent hard acrylic resin sheet. The rubber-containing polymer (B) is composed of 50 to 99.9% by weight of an acrylic acid ester unit, 0 to 49.9% by weight of another copolymerizable vinyl monomer unit and a copolymerizable crosslinkable monomer unit. 100 parts by weight of an elastic copolymer (B1) consisting of 0.1 to 10% by weight, 50 to 100 parts by weight of a methacrylic acid ester unit and 0 to 50% by weight of another copolymerizable vinyl monomer unit. It is obtained by binding a polymer (B2) consisting of 10 to 400 parts by weight of a monomer or a monomer mixture.

As the acrylic acid ester constituting the elastic copolymer (B1), for example, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like 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, methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, vinyltoluene, and α-.
Aromatic vinyl monomers such as methylstyrene can be used.
Examples of the copolymerizable crosslinkable monomer include ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, polyfunctional methacrylic acid ester monomers such as allyl methacrylate, and 1,4-butanediol. Diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyfunctional acrylic ester monomers such as allyl acrylate, diallyl maleate, diallyl phthalate, triallyl cyanurate, Examples thereof include triallyl isocyanurate, diallyl fumarate, triallyl trimellitate, and divinylbenzene.

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

The rubber-containing polymer (B) can be obtained by a known polymerization method such as emulsion polymerization. The particle size of the rubber-containing polymer (B) used in the present invention is 0.1 to 0.4.
Those in the μm range are used. If it is out of this range, impact resistance, gloss and transparency are deteriorated, which is not preferable.

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 in view of the balance between heat processability and surface hardness.
It is important that the range is 25% by weight and (B) 25 to 40% by weight. If the proportion of the rubber-containing polymer is higher than this range, the hardness of the surface will decrease. On the other hand, when the proportion of the rubber-containing polymer is low, the rubber-containing polymer is easily broken during the production of the sheet, and it is also difficult to bond it to the polyolefin resin sheet when producing the decorative sheet.

The method for molding the transparent hard acrylic resin sheet 1 is not particularly limited, but from the viewpoint of improving production efficiency and forming a sheet having a thickness of 0.1 to 0.6 mm, a T die extrusion method and a belt pressing method are used. 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 thin, the hardness of the base material affects the surface hardness, and if it is too thick, it becomes difficult to wind it into a roll or continuously laminate it. Further, if the pencil hardness is lower than H, the surface is likely to be scratched and is 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, the thinnest one has a thickness of 1.0 mm, and the shape is cut into a certain size. Therefore, it is not suitable for the transparent hard acrylic resin sheet of the present invention because it cannot be continuously laminated and is expensive.
In addition, a soft acrylic film is also commercially available. In this case, there is an advantage such as continuous thermal lamination with the polyolefin resin base sheet 2, but the thickness is 0.2 mm or less. The transparent layer lacks in texture and is soft, so the surface hardness is low (pencil hardness is B or less). Therefore, it is not appropriate to use it as a wall panel as it is without coating.

Examples of the polyolefin resin used for the base sheet 2 used in the present invention include polyethylene, ethylene / propylene copolymer, ethylene / butene copolymer, polypropylene, propylene / butene copolymer, polybutene, butene / Examples include propylene / ethylene terpolymer, polymethylpentene, and the like. The decorative sheet is often used in the form of a flat sheet, but it may be further thermoformed, and the polyethylene resin is most excellent in such applications. Generally known inorganic fillers such as calcium carbonate, barium sulfate, titanium oxide, and alumina oxide may be added to the base resin, or an appropriate dye or pigment may be added for coloring. Is also possible. The thickness of the polyolefin resin base sheet is not particularly limited, but a range of 0.1 to 0.5 mm is preferable.

Further, the polyolefin resin base sheet 2
Since the transparent hard acrylic resin sheet 1 and the transparent hard acrylic resin sheet 1 have poor adhesion and cannot be directly laminated, they are laminated via the adhesive layer 4. In laminating, the surface of the base material sheet 2 is preferably treated for easy adhesion in order to improve adhesion. As the adhesive constituting the adhesive layer 4, acrylic, vinyl acetate, polyester, urethane or the like is used. Corona discharge treatment, plasma treatment, and the like are known for the easy adhesion treatment of the surface of the base material sheet 2, and these treatments can be combined.

A pattern 3 is provided between the adhesive layer 4 and the transparent hard acrylic resin sheet 1 if necessary. The pattern 3 is provided for the purpose of imparting a design property to the decorative sheet of the present invention, and in addition to patterns of natural materials such as wood grain and stone tone, free designs such as geometric patterns and random patterns. The pattern is illustrated. The pattern is printed on the adhesive layer 4 or the transparent hard acrylic resin sheet 1 by a gravure coat 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 the polyolefin-based resin base sheet 2 are laminated and integrated with an adhesive layer 4 as shown in FIG. At that time, the aforementioned pattern 3 can be provided. The method for laminating the transparent hard acrylic resin sheet 1 on the polyolefin-based resin base sheet 2 is not particularly limited, and for example, a mirror surface thermal laminating machine is used to heat the transparent hard acrylic resin sheet on the mirror surface of the mirror surface while applying heat. It is preferable to use a technique such as fusion-lamination.

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

[0032]

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

Example 1 An example of producing the decorative sheet of the present invention and an example of producing a wall panel made of the sheet are described in the following (1).
It was performed according to the procedure (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) 0.3 mm thick x 1000 mm wide continuously extruded and cooled through a mirror belt press, about 50 at both ends
It is rolled up to a thickness of 0.
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 composed of 99% by weight of a methyl methacrylate unit and 1% by weight of a methyl acrylate unit, and having a reduced viscosity of 0.06 (l / g).
Is an acrylic thermoplastic polymer.

Rubber-containing polymer (B): an elastic copolymer consisting 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 100 parts by weight of a polymer and 60 parts by weight of a monomer mixture containing 95% by weight of a methyl methacrylate unit and 5% by weight of a methyl acrylate unit was bonded to obtain a particle size of 0.25 μm.
Is a rubber-containing polymer.

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

(3) Production of decorative sheet A polyethylene resin substrate sheet having the transparent hard acrylic resin sheet of (1) above as a surface layer, the treatment of (2) above, the formation of an adhesive layer, and a pattern printed on the back surface, Laminate the transparent hard acrylic resin sheet so that the pattern is in contact with the back surface, and use a mirror heat laminating machine to press the transparent hard acrylic resin sheet onto the mirror surface roll surface at 165 ° C x 5
A heat-fusing laminate was performed under the condition of m / min to prepare a decorative sheet.

(4) Manufacture of mirror surface wall panel for bathroom The decorative sheet obtained in (3) above is 800 mm × 200
Cut to a size of 0 mm and sanded for the purpose of improving the surface level of the substrate, improving water resistance, improving adhesiveness with the surface material, etc. Thickness 6 mm × width 800
An epoxy water-resistant adhesive is applied to the treated surface of a calcium silicate plate having a length of mm × 2000 mm by a knife coater to form an adhesive layer, and a polyethylene resin substrate sheet surface is formed on the surface of the adhesive layer. Surface-pressed and joined to create a mirror-finished wall panel for bathroom.

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

(5) Contamination resistance A character 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 of it was left. A hair dye "Vigen Cream Tone" (trade name) manufactured by Hoyu Co., Ltd. was applied to the same acrylic resin sheet surface and left at 23 ° C for 7 days, but there was no contamination after washing with water.

(6) Chemical resistance NaOH 5% aqueous solution, Ca (OH) ₂ 5% aqueous solution, sterilizing agent "Kabikiller" manufactured by Johnson & Johnson Co., Ltd.
When immersed in each of the liquids (trade name) at 23 ° C. for 7 days and the color difference was measured according to JIS K 6902, ΔE was 0.5 or less, which was good.

(7) Hot water resistance After being immersed in hot water of 85 ° C. for 240 hours, no abnormality was found in the appearance.

(8) The weather resistance sunshine weatherometer (sprayed pure water for 18 minutes during irradiation at 63 ° C. for 120 minutes) was used to expose the surface of the transparent hard acrylic resin sheet for 1000 hours. ΔE was 2. 0 was good.

(9) Surface hardness The pencil hardness of the surface of the transparent hard acrylic resin sheet was measured according to JIS D 0202, and the result was 2H.

[Examples 2 and 3] Instead of the calcium silicate plate used as the substrate in Example 1, a water resistant veneer (Example 2) and a board made of expanded polyethylene (Example 3) were used for sanding treatment. After that, a mirror surface wall panel for bathroom was prepared in the same manner, and the same evaluation as in Example 1 was performed. In all cases, good evaluation results were obtained.

A mirror surface wall panel for a bathroom prepared by 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 adhesiveness because the transparent hard acrylic resin sheet and the polyolefin resin base sheet are adhered via the adhesive layer.
Also, because 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 can be used as a decorative sheet for mirror surface 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, furniture, a cabinet face plate and the like. Further, the decorative sheet of the present invention can be produced at a low cost because it can be produced with high productivity by the heat fusion laminating method. Further, since the polyolefin resin is used as the base sheet, it is environmentally friendly even if it is discarded and incinerated. There is no adverse effect.

[Brief description of 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 bathroom mirror surface wall panel made of a decorative sheet according to the present invention.

[Explanation of symbols]

1 Transparent hard acrylic resin sheet 2 Polyolefin resin base sheet 3 patterns 4 Adhesive layer 5 makeup sheets 6 Substrate (calcium silicate plate) 7 Adhesive layer 8 Bathroom mirror panel

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayasu Inoue 3816 Noborito, Tama-ku, Kawasaki City, Kanagawa Sanryu Rayon Co., Ltd., Tokyo Technology & Information Center (56) Reference JP-A-8-323934 (JP, A) ) JP-A 1-252653 (JP, A) JP-A 6-262729 (JP, A) JP-A 8-118565 (JP, A) JP-A 10-109387 (JP, A) JP-A 9- 234836 (JP, A) JP-A-10-279766 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 5/18

Claims (2)

(57) [Claims] 1. A thermoplastic polymer (A) 6 shown below.
0 to 75% by weight and 25 to 40% by weight of the rubber-containing polymer (B) shown below, and the thickness is 0.1 to 0.6 m.
A decorative sheet for a surface material of a wall panel for a bathroom, which is obtained by laminating a transparent hard acrylic resin sheet having a pencil hardness of H or more and having a pencil hardness of H on a polyolefin-based resin substrate sheet via an adhesive layer. Thermoplastic polymer (A): 50 to 100% by weight of a methacrylic acid ester unit having an alkyl group having 1 to 4 carbon atoms, 0 to 50% by weight of an acrylate ester unit, and other copolymerizable vinyl monomer units. A polymer comprising at least one kind of 0 to 49% by weight, and having a reduced viscosity (polymer 0.
A thermoplastic polymer in which 1 g is dissolved in 100 ml of chloroform and measured at 25 ° C.) is 0.1 (l / g) or less. Rubber-containing polymer (B): acrylic acid ester unit 50 to 9
9.9% by weight, other copolymerizable vinyl monomer units 0 to
49.9% by weight and a copolymerizable crosslinkable monomer unit of 0.
100 to 100 parts by weight of an elastic copolymer (B1) consisting of 1 to 10% by weight, and 50 to 100% by weight of a methacrylic acid ester unit.
And 0 to 50% by weight of other copolymerizable vinyl monomer units
A rubber-containing polymer to which a polymer (B2) consisting of 10 to 400 parts by weight of the monomer or monomer mixture is bound, and the particle size thereof is 0.1 to 0.4 μm. 2. The decorative sheet according to claim 1, wherein the polyolefin-based resin base sheet is a resin mainly containing polyethylene.