JP2013099959A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which can present matte effect for a long time, has superior scratch resistance and can further present superior designability.SOLUTION: The decorative sheet is configured to laminate a substrate, a pattern layer, and a surface protective layer containing a matte agent and sodium calcium aluminosilicate particle in a curable resin composite in this order.

Description

  The present invention relates to a decorative sheet used for surface decoration such as house interiors and furniture, and a decorative plate using the decorative sheet. In particular, the present invention relates to a decorative sheet that can be used on a horizontal surface in furniture and the like and has excellent durability (friction resistance, scratch resistance, stain resistance) and a decorative board using the same.

  Conventionally, decorative sheets have been used in the fields of interiors, fittings, furniture, and the like of houses. In a layer located on the outermost surface of the decorative sheet (sometimes referred to as a “surface protective layer” or “topcoat layer”), so-called durability such as abrasion resistance, scratch resistance, and stain resistance is imparted. For this purpose, thermosetting resins (two-component curable resins) made of urethane resin and the like, and ionizing radiation curable resins that are cured by ionizing radiation such as ultraviolet rays and electron beams are used.

  Further, for the purpose of imparting a matte effect (matte feeling) to the decorative sheet, silica particles are also contained in the layer located on the outermost surface of the decorative sheet. Furthermore, in recent years, there is also a technique using silica particles having a specific oil supply amount as silica particles to be contained for the purpose of imparting antifouling properties (for example, Patent Document 1).

  However, when silica is included in the layer located on the outermost surface of the decorative sheet for the purpose of the matte effect, the surface of the layer is in a state where the silica is exposed. Although the matting effect can be exhibited by the exposed silica, the exposed silica is worn with time, and the original matting effect may not be exhibited.

JP 10-337997 A

  The present invention has been made in view of such circumstances, and can provide a decorative sheet and a makeup that can exhibit a matting effect for a long time, have good scratch resistance, and can exhibit excellent design properties. The main issue is to provide a board.

  The decorative sheet of the present invention for solving the above problems comprises a substrate, a pattern layer, and a surface protective layer containing a matting agent and sodium calcium aluminosilicate particles in a curable resin composition. It is characterized by being laminated in order.

  Moreover, in the said decorative sheet, it is preferable that the said sodium calcium aluminosilicate particle | grain is contained in the ratio of 5-20 weight part with respect to 100 weight part of said curable resin compositions.

  In the decorative sheet, the weight ratio of the matting agent and the sodium calcium aluminosilicate particles is preferably 1: 2 to 1: 6.

  Moreover, in the said decorative sheet, 3-7 micrometers may be sufficient as the average particle diameter of the said sodium calcium aluminosilicate particle | grains.

  In the decorative sheet, the matting agent may be silica.

  Moreover, in the said decorative sheet, the said curable resin composition may be a thermosetting resin composition.

  Moreover, in the said decorative sheet, the moisture-proof sheet which consists of a base material for moisture-proof sheets and a vapor deposition layer may be formed in the side in which the pattern layer of the said base material is not provided.

  Furthermore, the decorative board of the present invention for solving the above-mentioned problems is characterized in that the decorative sheet of the present invention is pasted on a decorative board substrate.

  The decorative sheet of the present invention is characterized in that the curable resin composition forming the surface protective layer contains sodium calcium aluminosilicate particles in addition to the conventional matting agent. The sodium calcium aluminosilicate particles are harder than the general silica particles used as a matting agent, and therefore hardly wear. Therefore, the sodium calcium aluminosilicate particles are used in the surface protective layer. By exposing from the surface, it is possible to effectively prevent the matting agent exposed from the surface of the surface protective layer from being worn. Moreover, even if the matting agent is not worn away, the sodium calcium aluminosilicate particles can exist in an exposed state, which can provide a matte effect over a long period of time and has good scratch resistance. It is.

  Furthermore, since the decorative sheet of the present invention contains two kinds of particles of “matting agent” and “sodium calcium aluminosilicate particles” in the curable resin composition forming the surface protective layer, these particles Are exposed from the surface protective layer, and the light is complicatedly scattered by each of these particles, which can provide a matte feeling (matte feeling) that has never been seen before.

  Needless to say, the decorative board of the present invention has the same effects as described above.

It is a schematic sectional drawing for demonstrating the structure of the decorative sheet of this invention. It is a schematic sectional drawing for demonstrating another structure of the decorative sheet of this invention.

  Below, the decorative sheet of this invention and the decorative board using the same are demonstrated concretely using drawing.

<Coating sheet>
FIG. 1 is a schematic cross-sectional view for explaining the configuration of the decorative sheet of the present invention.

  As shown in FIG. 1, the decorative sheet 100 of this invention is comprised by laminating | stacking the base material 1, the pattern layer 2, and the surface protective layer 3 in this order.

  Hereinafter, each layer will be described in detail.

(Base material)
The base 1 is not particularly limited in shape, material, and other characteristics. For example, the shape may be a so-called sheet shape, and the size and thickness are not particularly limited. The material is paper, wood, metal, inorganic non-metal (ceramic, non-ceramic ceramics, etc.), resin, or the like. Moreover, any of those having ink permeability (paper, nonwoven fabric, etc.) and those having no ink permeability (resin sheet etc.) may be used. Of these, paper and resin sheets (films) are typical.

  In addition, as the fibrous base material other than paper, non-woven fabric made of fibers such as polyester resin, acrylic resin, nylon, vinylon, glass and the like are also used. The non-woven fabric may be added with a resin such as an acrylic resin, a styrene butadiene rubber, a melamine resin, or a urethane resin (impregnated with a resin after paper making, or embedded during paper making), as in the case of the paper type.

  In the resin system, for example, polyolefin resins such as polyethylene, polypropylene, and olefin thermoplastic elastomer, vinyl resins such as vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer, polyethylene terephthalate, and polybutylene. Polyester resin such as terephthalate, acrylic resin such as polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), resin such as cellulose triacetate, cellophane, polycarbonate There are resin materials such as. These resins are used as sheets, plates, and three-dimensional objects. In the resin system, a thermosetting resin plate made of a thermosetting resin such as phenol resin, urea resin, unsaturated polyester resin, urethane resin, epoxy resin, melamine resin, phenol resin, urea resin, unsaturated polyester resin, Resins such as so-called FRP (fiber reinforced plastic) plates made by impregnating and curing resin such as urethane resin, epoxy resin, melamine resin and diallyl phthalate resin on glass fiber nonwoven fabric, fabric, paper and other various fibrous substrates There is also a sheet.

The thickness of the base material depends on the shape, material, application, etc., but when using a fibrous base material such as paper, for example, the basis weight is about 23 to 150 g / m ² and the thickness is 30 to 300 μm. Degree is desirable.

(Cosmetic base material)
Examples of the base material for makeup include wood materials such as veneer, plywood, particle board, fiberboard, and laminated wood made of cedar, straw, straw, lawan, teak and the like. Moreover, in a metal system, there exist metal materials, such as iron, aluminum, stainless steel, copper, for example. Metal systems are used as sheets (foil), plates, and three-dimensional objects. In inorganic non-metallic systems, for example, extruded cement, slag cement, ALC (lightweight cellular concrete), GRC (glass fiber reinforced concrete), pulp cement, wood chip cement, asbestos cement, calcium silicate, gypsum, gypsum slag, etc. There are non-ceramic ceramic materials, ceramic materials such as earthenware, ceramics, porcelain, setware, glass and glazing.

(Picture layer)
The pattern layer 2 is a layer formed to give a desired pattern to the decorative sheet 100, and is formed by a conventionally known forming method / material for the decorative sheet according to the desired design expression or required physical properties. There is no particular limitation.

  If the pattern layer 2 is divided into partial formation and full surface formation, as shown in FIG. 1, the pattern layer 2 is formed on the entire surface with a pattern pattern layer 2B formed partially to express an arbitrary pattern shape. It can be classified into all solid layers 2A. Although the whole solid layer 2A and the pattern pattern layer 2B may be used independently, normally, the whole solid layer 2A as a base and the pattern pattern layer 2B for forming a pattern pattern on the whole solid layer 2A. Are often used in combination.

  The pattern layer 2 may be formed by a conventionally known printing method such as gravure printing, silk screen printing, offset printing, electrophotographic copying, and hand drawing (for example, handwriting), and the like. The pattern layer is usually a layer colored by adding a pigment. The pattern represented by the pattern layer is arbitrary, and may be, for example, a wood grain pattern, a stone pattern, a cloth pattern, a tile tone pattern, a brick tone pattern, a leather pattern, a character, a geometric pattern, and the like. In addition, all the solid layers which become a whole surface solid among pattern layers can also be formed with a coating material by well-known coating methods, such as a gravure coat and a roll coat.

  The ink (or paint) for forming the pattern layer is composed of a vehicle comprising a binder, a colorant such as a pigment or a dye, and various additives appropriately added thereto, as in the case of general ink (or paint). As the binder resin, for example, a general-purpose resin such as a chlorinated polyolefin resin, a polyester resin, an acrylic resin, a cellulose resin, a vinyl chloride-vinyl acetate copolymer, and a polyurethane resin can be selected. use. However, from the viewpoint of adhesion to the recoatable ionizing radiation curable resin layer, nitrocellulose and acrylic resins are desirable resins as the binder resin.

  Examples of the colorant include inorganic pigments such as titanium white, zinc white, dial, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, and carbon black, isoindolinone, Hansa Yellow A, quinacridone, and permanent red. Pearl luster made of organic pigments (including dyes) such as 4R, phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments such as aluminum and brass, titanium dioxide-coated mica, and foil powder such as basic lead carbonate ( Pearl) pigments may be used.

  The pattern layer 2 may be a metal thin film layer or the like. The metal thin film layer is formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. Alternatively, a combination thereof may be used. The metal thin film layer may be provided on the entire surface (becomes the entire solid layer 2A), or may be partially provided in a pattern (becomes the pattern pattern layer 2B).

(Surface protective layer)
Next, the surface protective layer 3 will be described.

  The surface protective layer in the decorative sheet 100 of the present invention is configured by containing the matting agent 3B and the sodium calcium aluminosilicate particles 3C in the curable resin composition 3A.

  Since the sodium calcium aluminosilicate particle 3C has a hard property as compared with the general matting agent 3B, the sodium calcium aluminosilicate particle 3C hardly wears. By exposing from the surface, it is possible to effectively prevent the matting agent 3B exposed from the surface of the surface protective layer 3 from being worn. Further, even if the matting agent 3B is no longer worn, the sodium calcium aluminosilicate particles 3C can be present in an exposed state, thereby being able to exhibit a matte effect over a long period of time and being scratch resistant. Is also good.

  Further, by containing two kinds of particles, matting agent 3B and sodium calcium aluminosilicate particles 3C, in the curable resin composition 3A forming the surface protective layer 3, as described above, each of these particles can protect the surface. It is in the state exposed from the layer 3, and the light is complicatedly scattered by each of these particles, and an unprecedented matte feeling (mat feeling) can be provided.

<Curable resin composition>
As the curable resin composition 3A for forming the surface protective layer 3, the properties required for the outermost surface layer of a normal decorative sheet such as scratch resistance, abrasion resistance, stain resistance, water resistance, weather resistance, etc. are appropriately selected. It can be formed by using a known thermosetting resin or a known ionizing radiation curable resin.

  The thermosetting resin is preferable because it is easy to handle and has the above-mentioned various properties. Specifically, it is preferable to use a two-component curable resin such as a two-component curable urethane resin. As a two-component curable urethane resin, a polyol such as acrylic polyol, polyester polyol, or polyether polyol is used as a main agent, and 2,4-tolylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone is used as a crosslinking agent (curing agent). What is necessary is just to select suitably from well-known urethane resins using polyisocyanate, such as diisocyanate.

<Matting agent>
The matting agent 3B contained in the curable resin composition 3A is not particularly limited as long as it is a matting agent used in conventional decorative sheets, and can be arbitrarily selected. Specifically, inorganic fine powder made of silica, alumina, calcium carbide, barium sulfate, magnesium carbonate, glass balloon, etc., organic fine powder made of polyethylene, polyurethane, polycarbonate, silicone, phenolic resin, melamine resin, etc. Can do.

  Among these, silica is particularly preferable since it has a high matting effect and has almost the same refractive index as that of the curable resin composition 3A, so that the transparency of the surface protective layer is hardly impaired.

<Sodium calcium aluminosilicate particles>
In combination with the matting agent 3B, the sodium calcium aluminosilicate particles 3C contained in the curable resin composition 3A are composite oxide particles mainly composed of calcium, sodium, aluminum, and silicon. The proportions of the constituent elements are as follows: Ca element is 3 to 10 wt% in terms of CaO, Na element is 5 to 12 wt% in terms of Na ₂ O, and Al element is 20 to 30 wt in terms of Al ₂ O _3. %, Si element is 50 to 60% by weight in terms of SiO ₂ .

  The shape of the sodium calcium aluminosilicate particles 3C is granular (spherical), and the average particle size is preferably about 3 to 7 μm. If it is smaller than 3 μm, the effect of the sodium calcium aluminosilicate particles described above may not be sufficiently exhibited. On the other hand, if it is larger than 7 μm, the effect of the matting agent may be hindered.

  Further, the content of the sodium calcium aluminosilicate particles 3C is not particularly limited as long as the above effect is achieved. Specifically, for example, the content of the curable resin composition is 100 parts by weight. It is preferable to contain in the ratio of 5-20 weight part with respect to. If the content is less than 5 parts by weight, the above-mentioned effects of the sodium calcium aluminosilicate particles may not be fully exhibited. This is because there is a possibility of inhibiting.

  Further, the weight ratio (mixing ratio) between the matting agent 3B and the sodium calcium aluminosilicate particles 3C is not particularly limited as long as the above effect is achieved. Specifically, for example, the mat The weight ratio of the agent to the sodium calcium aluminosilicate particles is preferably 1: 2 to 1: 6. In order to fully exhibit the above effect of the sodium calcium aluminosilicate particles, the amount of the matting agent is required to be twice or more that of the matting agent. Because.

  FIG. 2 is a schematic cross-sectional view for explaining another embodiment of the decorative sheet of the present invention.

  As shown in FIG. 2, in the decorative sheet 300 of the present invention, the moisture-proof sheet 200 composed of the moisture-proof sheet substrate 20 and the vapor deposition layer 21 is formed on the back side of the decorative sheet (100) described in FIG. It has a form.

  The moisture-proof sheet substrate 20 and the vapor deposition layer 21 constituting the moisture-proof sheet 200 will be described below.

(Base material for moisture-proof sheet)
The material of the moisture-proof sheet substrate 20 is not particularly limited, and any material can be used as long as it can be bonded to the decorative sheet substrate 1 with an adhesive or the like. Specifically, various synthetic synthetic resins are preferably used, for example, olefinic thermoplastic resins such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl alcohol copolymer, or a mixture thereof, polyethylene Ester thermoplastic resins such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, methyl polymethacrylate, ethyl polymethacrylate, polybutyl acrylate, etc. Acrylic thermoplastic resins or non-halogen thermoplastic resins such as polyimide, polyurethane, polystyrene, and acrylonitrile-butadiene-styrene resin can be used. These may be uniaxially or biaxially stretched sheets or unstretched, but the mechanical strength is high due to the fact that a vapor deposition layer 21 to be described later is formed on at least one surface. A sheet stretched in the biaxial direction is preferable for reasons such as excellent stability. The thickness of the moisture-proof sheet substrate 20 is generally 9 to 25 μm.

(Deposition layer)
Next, the vapor deposition layer 21 will be described.

  The vapor deposition layer 21 is an inorganic vapor deposition layer made of a metal thin film typified by aluminum, or an inorganic oxide vapor deposition layer made of an inorganic oxide thin film typified by silicon oxide, magnesium oxide, or aluminum oxide. The vapor deposition layer 11 is formed into a thin film on at least one surface of the moistureproof sheet substrate 20 by a known vapor deposition method such as a vacuum vapor deposition method or a plasma activated chemical reaction vapor deposition method. In addition, since the vapor deposition layer which consists of a metal thin film represented by aluminum has a metallic luster, when using it for a decorative sheet, it may be necessary to conceal the metallic luster from the viewpoint of the design property. From this, it is preferable that a vapor deposition layer is a transparent inorganic oxide vapor deposition layer. Further, for the purpose of further improving the gas barrier property of the vapor deposition layer 21, a composition in which an inorganic oxide typified by silicon oxide, magnesium oxide, and aluminum oxide is added to the vapor deposition layer 21 to polyvinyl alcohol or polyvinyl alcohol. You may form well-known coating methods, such as a roll coat method and a gravure coat method (not shown).

  Regarding the adhesion between the decorative sheet (100) and the moisture-proof sheet 200 described above, as shown in FIG. 2, it is common to use an adhesive layer 22, but the material and the like of the adhesive layer 22 are particularly important. It does not limit, What is necessary is just to select and use conventionally well-known various adhesive agents arbitrarily.

  Further, the decorative board of the present invention can be formed by sticking the decorative sheet 100 shown in FIG. 1 and the decorative sheet 300 shown in FIG. 2 to a decorative board substrate.

  The decorative board substrate used here, and the method for attaching the decorative board substrate and the decorative sheet are not particularly limited, and a conventionally known sticking method is used using a conventionally known decorative board substrate. Adopt it.

Example 1
Using a thin paper of 30 g / m ^{2 as} a base material, a pattern layer composed of a solid layer and a pattern pattern layer exhibiting a wood grain pattern on one side of the base material using a printing ink having a nitrified cotton-based resin as a vehicle. It formed by the gravure printing method.

  Next, a two-component curable resin containing silica as a matting agent and sodium calcium aluminosilicate particles is prepared, and this is applied onto the pattern layer by a gravure printing method to form a surface protective layer. The decorative sheet of Example 1 was obtained.

The composition of the two-component curable resin is as follows.
・ Addition of isocyanate as curing agent to acrylic polyol resin ・ Silica (7% by weight based on the resin)
・ Sodium calcium aluminosilicate particles (16% by weight based on the resin)

(Comparative Example 1)
A decorative sheet of Comparative Example 1 was produced under the same conditions except that the surface protective layer did not contain sodium calcium aluminosilicate particles.

(Contrast experiment)
The surface protective layer side of the decorative sheets of the above examples and comparative examples was rubbed for 40 reciprocations with a load of 250 g / cm ² using steel wool (manufactured by Nippon Steel Wool Co., Ltd .: Bonstar # 00). Compared.

  As a result, the decorative sheet of Example 1 had no change in mat feeling before and after the steel wool test, whereas the decorative sheet of Comparative Example 1 had a significant change in mat feeling.

  Also from this fact, it was found that the decorative sheet of the present invention can exhibit a matting effect for a long time and has good scratch resistance.

DESCRIPTION OF SYMBOLS 100, 300 ... Cosmetic sheet 200 ... Moisture-proof sheet 1 ... Base material 2 ... Pattern layer 2A ... All solid layer 2B ... Pattern pattern layer 3 ... Surface protective layer 3A ... Curable resin composition 3B ... Matting agent 3C ... Sodium calcium alumino Silicate particle 20 ... moisture-proof sheet 21 ... moisture-proof sheet substrate 22 ... vapor deposition layer

Claims (1)

A substrate;
The pattern layer,
A surface protective layer comprising a matting agent and sodium calcium aluminosilicate particles in a curable resin composition;
A decorative sheet characterized by being laminated in this order.

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