JP2015221519A - Decorative sheet with high luminance ornamental design - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet to which a design with high brightness feeling is given without damaging its profound feeling and dark feeling even when the colored substrate film has a dark color such as black, brown and condensed gray.SOLUTION: There is provided a decorative sheet which has (A) a transparent resin film layer, (B) an adhesive layer containing a high luminance pigment, (C) a colored substrate film layer in this order from a surface side, the (B) adhesive layer containing the high luminance pigment contains 100 pts.mass of (b1) a transparent adhesive agent and 0.01 to 5 pts.mass of (b2) glass particle coating treated by one or more selected from a group consisting of titanium oxide, indium oxide, zinc oxide and tin oxide on a surface having an average particle diameter of 10 to 250 μm and the (C) colored resin film layer has a dark color.

Description

The present invention relates to a decorative sheet provided with a high-luminance design. More specifically, the present invention relates to a decorative sheet to which a design having a high luminance feeling is imparted without impairing the darkness or darkness of dark colors such as black, brown and dark ash of the colored base film.

Traditionally, furniture such as display cabinets, storage cabinets, cupboards, and desks; household appliances such as refrigerators, washing machines, air conditioners, mobile phones, and PCs; or wood, plywood as building components such as floors, walls, and bathrooms On the surface of base materials made of wood-based materials such as laminated wood, particle board, and hard board; or on the surface of base materials made of metal-based materials such as iron and aluminum; As such a decorative sheet, a high-luminance design using a high-luminance pigment such as aluminum, brass, mica, and pearls has been proposed (for example, Patent Document 1). ).

However, when high-luminance pigments such as aluminum, brass, mica, and pearls are applied to dark colored substrate films such as black, brown, and dark ash, high luminance can be obtained, but the dark color of the colored substrate film There was a problem that the sense of depth and darkness of the image was lost, and it became whitish.

In addition, when high brightness pigments such as aluminum, brass, mica, and pearls are applied to dark colored substrate films such as black, brown, and dark ash, even a slight dispersion unevenness may stand out as a design unevenness. there were.

JP-A-8-156215

An object of the present invention is to provide a decorative sheet having a design with a high brightness feeling without impairing the sense of depth or darkness even if the colored base film is a dark color such as black, brown and dark ash. Is to provide.

As a result of diligent research, the present inventors have found that the decorative sheet having a specific layer structure having a transparent adhesive layer containing a specific amount of glass particles having a specific particle diameter whose surface is coated with a metal oxide having light transmittance, I found that I can achieve the task.

That is, the present invention includes (A) a transparent resin film layer, (B) an adhesive layer containing a high-brightness pigment, and (C) a colored base film layer in order from the surface side. The adhesive layer containing
(B1) 100 parts by mass of a transparent adhesive; and (b2) an average particle diameter of 10 to 250 μm, and the surface was coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide. 0.01 to 5 parts by mass of glass particles;
The (C) colored resin film layer is dark.
It is a decorative sheet.

A second invention of the present invention is an article using the decorative sheet according to the first invention.

The third invention of the present invention is the use of the decorative sheet according to the first invention for decorative decoration of articles.

The decorative sheet of the present invention is provided with a design having a high luminance feeling without impairing the darkness of the dark color such as black, brown and dark ash of the colored base film. Therefore, it is suitable for furniture such as display racks, storage cabinets, cupboards, and desks; household appliances such as refrigerators, washing machines, air conditioners, mobile phones, and personal computers; Can be used.

The decorative sheet of the present invention has (A) a transparent resin film layer, (B) an adhesive layer containing a high-luminance pigment, and (C) a colored base film layer in order from the surface side. By having such a layer structure, a high brightness feeling due to the high brightness pigment of the layer B emerges in the dark color of the innermost layer C, and the presence of the transparent layer A gives a high depth feeling and transparency. .

The layer A is a layer made of a transparent resin film, and effectively exerts the design effect of the high-brightness pigment in the layer B and the dark color of the layer C, and also has a function of imparting a high depth and transparency. To do.

The transparent resin film preferably exhibits a total light transmittance in order to effectively exhibit the design effect of the high-brightness pigment in the layer B and the dark color of the layer C, and to impart a high depth and transparency. 80% or more, more preferably 85% or more, and still more preferably 90% or more. A higher total light transmittance is preferable. In this specification, the total light transmittance is a value measured according to JIS K 7361-1: 1997.

The thickness of the transparent resin film is preferably 25 μm or more, more preferably 50 μm or more, and further preferably 80 μm or more. The depth and transparency of the decorative sheet can be enhanced. The upper limit of the thickness is not particularly from the viewpoint of enhancing the depth and transparency of the decorative sheet, but preferably from the viewpoint of being able to produce the decorative sheet of the present invention using a known web device. It may be 1000 μm or less, more preferably 300 μm or less.

Moreover, it is preferable to use the said transparent resin film with a 60 degree gloss high at least on the surface which becomes the surface layer side of a decorative sheet. The 60 ° gloss is preferably 80% or more, more preferably 90% or more, and still more preferably 100% or more. A higher 60 ° gloss is preferred. The deep feeling and darkness of dark colors such as black, brown, and dark ash of the colored base film can be enhanced, and a high depth and transparency can be obtained. In this specification, 60 ° gloss is a value measured according to JIS-K 7105: 1981.

Examples of such transparent resin films include polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polyvinyl chloride resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene. Cellulosic resins such as cellophane, triacetyl cellulose, diacetyl cellulose, acetyl cellulose butyrate; polystyrene, acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / Styrene resins such as butadiene / styrene copolymers; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; Can be mentioned transparent resin film such as; call, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated | stacked 1 type (s) or 2 or more types of these films may be sufficient.

Among these, from the viewpoint of design properties, films of polyester resins, acrylic resins, and polyvinyl chloride resins are preferable.

The adhesive layer containing the (B) high-brightness pigment comprises: (b1) 100 parts by mass of a transparent adhesive; and (b2) an average particle size of 10 to 250 μm on the surface of titanium oxide, indium oxide, zinc oxide, and tin oxide. Glass particles coated with one or more selected from the group consisting of 0.01 to 5 parts by mass.

The component b1 includes a high-intensity pigment and functions to bond the layer A and the layer C together. The component b1 is transparent in order to effectively exhibit the design effect due to the dark color of the high-luminance pigment or layer C.

In the present specification, the “transparent adhesive” means an adhesive having a visible light transmittance of 30% or more, preferably 50% or more, more preferably 80% or more. Here, the visible light transmittance is a transmission spectrum at a wavelength of 380 to 780 nanometers of an adhesive using a spectrophotometer “SolidSpec-3700 (trade name)” manufactured by Shimadzu Corporation and a quartz cell having an optical path length of 10 mm. This is a value calculated as a ratio of the integral area of the transmission spectrum of the adhesive to the integral area of the transmission spectrum when it is assumed that the transmittance in the entire range of wavelengths from 380 to 780 nanometers is 100%.

In this specification, the term “adhesive” is used as a term including an adhesive.

The component b1 is transparent not only when producing decorative sheets, but also when decorating and decorating articles using a decorative sheet, and when decoratively decorated articles are used. Is preferred.

As said component b1, it is not restrict | limited except having sufficient adhesive force and being transparent, Arbitrary adhesives can be used. For example, polyester, polyurethane, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, epoxy, polychloroprene, polyacryl, polymethacryl, polystyrene, polyamide, cellulose, And an adhesive comprising one or a mixture of two or more adhesives such as styrene-butadiene copolymer.

Among these, from the viewpoint of adhesive strength and transparency, polyester-based, polyurethane-based, polyvinyl chloride-based, polyacryl-based, polymethacryl-based, and polyvinyl acetate-based adhesives are preferable.

The component b2 functions to impart a high-luminance design to the decorative sheet as a high-luminance pigment and to effectively exhibit the design effect of the layer C due to the dark color.

The component b2 is a glass particle whose surface is coated with one or more metal oxides selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide. The glass and the metal oxide are transparent substances, and the light reflected by the component b2, that is, the light reflected on the surface of the glass particles or the surface of the metal oxide coating layer is small, but the surface of the glass particles. Since a large path difference occurs depending on whether the light is reflected by the metal oxide coating layer or the metal oxide coating layer, even a small amount makes the human eye feel a high luminance feeling. In addition, since a lot of light passes through the component b2, the design effect by dark colors such as black, brown, and dark ash of the layer C is effectively exhibited, and the sense of depth or darkness is not impaired.

Among the metal oxides, titanium oxide is preferable from the viewpoint of design.

The component b2 has an average particle size of 10 to 250 μm. When the average particle diameter is 10 μm or more, preferably 20 μm or more, more preferably 40 μm or more, both high brightness and the design effect by the dark color of the layer C can be achieved. Further, when the thickness is 250 μm or less, preferably 200 μm or less, more preferably 120 μm or less, the design effect due to the dark color of the layer C and the effect of making the dispersion unevenness of the component b2 inconspicuous can be obtained.

In this specification, the average particle size is the cumulative particle size from the smaller particle in the particle size distribution curve measured using a laser diffraction / scattering particle size analyzer “MT3200II (trade name)” manufactured by Nikkiso Co., Ltd. The particle diameter is 50% by mass.

The compounding amount of the component b2 is 0.01 to 5 parts by mass with respect to 100 parts by mass of the component b1. When the blending amount is 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, a high luminance feeling can be obtained. Moreover, the design effect by the dark color of the layer C can be acquired by being 9 mass parts or less, Preferably it is 5 mass parts or less, More preferably, it is 1 mass part or less.

As a commercial example of the said component b2, "Metashine (brand name)" of Nippon Sheet Glass Co., Ltd. can be mention | raise | lifted.

The adhesive containing the high-intensity pigment can further contain an optional component other than the component b1 and the component b2 as desired, as long as the object of the present invention is not adversely affected. Examples of the optional component include a photopolymerization initiator, a compound having two or more isocyanate groups in a molecule, an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, an antifouling agent, and a printability improving agent. And additives such as antioxidants, weather resistance stabilizers, light resistance stabilizers, ultraviolet absorbers, heat stabilizers, pigments other than component b2, and fillers. The compounding quantity of the said arbitrary component is about 0.01-10 mass parts with respect to 100 mass parts of component b1.

The method in particular of providing an adhesive bond layer is not restrict | limited, A well-known web application | coating method can be used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating. At this time, any dilution solvent such as 1-methoxy-2-propanol, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary.

The (C) colored resin film layer is a layer composed of a colored resin film, which gives the decorative sheet a design effect with dark colors such as black, brown, and dark ash, and absorbs unevenness of the article as a base film. The decorative decorative surface is made smooth, or the color or pattern unfavorable to the design of the article is concealed.

Since the colored film is a dark color, the brightness feeling due to the adhesive layer containing the (B) high-luminance pigment can be increased. In this specification, “dark color” means that the brightness measured using a spectrocolorimeter “CM-600d (trade name)” manufactured by Konica Minolta Co., Ltd. is 0 or more and less than 5 according to JIS Z8721: 1993. Means color. Preferably, it means 0 or more and 3 or less colors.

The colored film is not limited except that it is dark, and any colored film can be used. For example, polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polyvinyl chloride resins; polycarbonate resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellophane, triacetyl cellulose, diacetyl cellulose Cellulose resins such as acetylcellulose butyrate; polystyrene, styrene such as acrylonitrile / butadiene / styrene copolymer resin (ABS resin), styrene / ethylene / butadiene / styrene copolymer, styrene / ethylene / butadiene / styrene copolymer -Based resins; polyvinylidene chloride resins; fluorine-containing resins such as polyvinylidene fluoride; others, polyvinyl alcohol, ethylene vinyl alcohol, polyether ether ketone It can be mentioned colored film and the like; nylon, polyamide, polyimide, polyurethane, polyether imide, polysulfone, polyether sulfone. These films include unstretched films, uniaxially stretched films, and biaxially stretched films. Moreover, the laminated film which laminated | stacked 1 type (s) or 2 or more types of these films may be sufficient.

Among these, from the viewpoint of secondary processability of the decorative sheet, films of polyester resins, acrylic resins, and polyvinyl chloride resins are preferable.

The thickness of the colored film may be 50 μm or more, preferably 80 μm or more from the viewpoint of absorbing the unevenness of the article as a base film and smoothing the decorative decorative surface. The upper limit of the thickness is not particularly limited from the viewpoint of absorbing unevenness, but is preferably 1000 μm or less, more preferably 300 μm or less, from the viewpoint that the decorative sheet of the present invention can be produced using a known web device. It may be.

The decorative sheet of the present invention may further be provided with a hard coat layer on the surface layer side of the (A) transparent resin film layer as desired. The scratch resistance of the decorative sheet can be increased. The hard coat layer contains, for example, an active energy ray curable resin together with a compound having two or more isocyanate groups (—N═C═O) and / or a photopolymerization initiator in one molecule. Using a resin composition, it can be formed using a known web coating method.

You may give an embossing pattern to the decorative sheet of this invention using well-known apparatuses, such as an embossing roll, as needed. Usually, if the portion that is matted by embossing is 80% or less of the whole, preferably 60% or less, the glossiness, darkness, high brightness, depth, and transparency from other glossy parts And the effects of the present invention can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Measuring method (b) Luster (luminance):
In a dark place, light from a 40W white fluorescent lamp (300 lux) is perpendicularly incident from a position separated by a distance of 50 cm from the surface of the decorative sheet, forms an angle of 45 ° with the surface of the decorative sheet, and has a distance of 50 cm. The decorative sheet was visually observed from the separated position and evaluated according to the following criteria.
A: The glitter is very high.
○: High brightness.
Δ: Low glitter.
X: There is almost no glitter.

(B) Transparency (design effect due to the dark color of layer C):
In a dark place, the light of a 40 W white fluorescent lamp (300 lux) is irradiated in parallel so that the surface of the decorative sheet and the light beam of the fluorescent lamp are separated from each other by a distance of 50 cm. The decorative sheet was visually observed from positions separated by a distance of 50 cm and evaluated according to the following criteria.
A: The dark color of the layer C is not impaired at all.
○: The dark color of the layer C is hardly impaired.
Δ: The dark color of the layer C is slightly damaged.
X: The dark color of the layer C is greatly impaired.

(C) Darkness:
In a dark place, the light of a 40 W white fluorescent lamp (300 lux) is irradiated in parallel so that the surface of the decorative sheet and the light beam of the fluorescent lamp are separated from each other by a distance of 50 cm. The decorative sheet was visually observed from positions separated by a distance of 50 cm and evaluated according to the following criteria.
A: Darkness is very high.
○: Darkness is high.
Δ: Low darkness.
X: There is no darkness.

Raw materials used (A) Transparent resin film:
(A-1) A transparent polyvinyl chloride resin film having a thickness of 80 μm, a total light transmittance of 85%, and a 60 ° gloss of 90%.

(B1) Transparent adhesive:
(B1-1) Vinyl chloride / vinyl acetate / acrylic copolymer adhesive “VTP-NT (trade name)” from DIC Graphics, Inc., total light transmittance 92%.

(B2) Glass particles:
(B2-1) Titanium oxide coated glass particles “Metashine 1080RS (trade name)” manufactured by Nippon Sheet Glass Co., Ltd., particle size of 80 μm.
(B2-2) Titanium oxide-coated glass particles having a particle diameter of 20 μm.
(B2-3) Titanium oxide-coated glass particles having a particle diameter of 40 μm.
(B2-4) Titanium oxide-coated glass particles having a particle diameter of 120 μm.
(B2-5) Titanium oxide-coated glass particles having a particle diameter of 200 μm.

(B′2) Comparative component:
(B′2-1) Titanium oxide-coated glass particles having a particle diameter of 5 μm.
(B′2-2) Titanium oxide-coated glass particles having a particle diameter of 300 μm.
(B′2-3) Nippon Sheet Glass Co., Ltd. silver-coated glass particles “Metashine 1080PS (trade name)”, particle size 80 μm.

(C) Colored substrate film:
(C-1) A colored polyvinyl chloride resin film having a thickness of 80 μm and a black color (lightness 2.3).
(C-2) A colored polyvinyl chloride resin film having a thickness of 80 μm and a dark gray color (lightness: 4.5).

(C ′) Comparative colored base film:
(C′-1) A colored polyvinyl chloride resin film having a thickness of 80 μm and a white color (lightness of 9.4).

Example 1
A knife containing 100 parts by mass of the component (b1-1) and 0.5 parts by mass of the component (b2-1) is added to the transparent resin film (A-1) so as to have a dry film thickness of 15 μm. After coating using a coater and drying, the colored base film (C-1) was heat-laminated on the coated surface under the condition of a surface temperature of a laminating roll of 150 ° C. to obtain a decorative sheet. The above (i) to (c) were evaluated. The results are shown in Table 1.

Examples 2-10, Comparative Examples 1-6
It carried out similarly to Example 1 except having changed the raw material to be used and a compounding ratio as shown in any one of Tables 1-3. The results are shown in any one of Tables 1-3.

The decorative sheet of the present invention has good gloss, transparency, and dark color. On the other hand, Comparative Example 1 is inferior in glitter because the particle diameter of component b2 is smaller than the specified range. Comparative Example 2 is inferior in transparency and darkness because the particle diameter of component b2 is larger than the specified range. In Comparative Example 3, the amount of component b2 is less than the specified range, so that the glitter is inferior. In Comparative Example 4, the blending amount of the component b2 is larger than the specified range, so that the transparency and dark color are inferior. Comparative Example 5 is inferior in transparency and darkness because the metal covering the glass particles is nonstandard silver. Comparative Example 6 is inferior in dark color because the colored base film has a bright color outside the specified range.

It is a conceptual diagram which shows the cross section of an example of the decorative sheet of this invention.

1: Transparent resin film layer 2: Adhesive layer containing high brightness pigment 3: Colored substrate film layer 4: High brightness pigment

Claims (3)

In order from the surface side, (A) a transparent resin film layer, (B) an adhesive layer containing a high-intensity pigment, (C) a colored substrate film layer,
The adhesive layer containing the (B) high brightness pigment is
(B1) 100 parts by mass of a transparent adhesive; and (b2) an average particle diameter of 10 to 250 μm, and the surface was coated with one or more selected from the group consisting of titanium oxide, indium oxide, zinc oxide, and tin oxide. 0.01 to 5 parts by mass of glass particles;
The (C) colored resin film layer is dark.
Makeup sheet.
An article using the decorative sheet according to claim 1.
Use of the decorative sheet according to claim 1 for decorative makeup of articles.

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