JP6760459B2 - Decorative sheet - Google Patents

Description

The present invention relates to a decorative sheet.

Interior / exterior members of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, surrounding edges, fittings such as malls, kitchen, furniture or light electric, cabinet surface veneer for OA equipment, etc. As the interior / exterior member of a vehicle, a metal member such as a steel plate, a resin member, or a wood member is generally used as an adherend, and a decorative sheet is attached thereto (for example, Patent Document 1). Among them, members such as exterior members, doors, and window frames are used in an environment exposed to direct sunlight, so that there is a problem that warpage occurs due to an increase in temperature. There is also a problem that the heat of direct sunlight propagates to the inside of the building through these members, and the temperature inside the building rises. This problem occurs when carbon black, which easily absorbs heat, is used as a pigment generally used for any of the layers constituting the decorative member, for example, an adherend, a base material, and a decorative layer, particularly a black pigment. It is remarkable.

In order to solve various problems caused by direct sunlight, a heat-shielding decorative sheet characterized by using perelin black as a pigment used for a printing layer in a decorative sheet has been proposed (for example, Patent Document 2). Further, a heat-shielding decorative sheet characterized by using an azomethine-azo resin as a black pigment for the pattern layer has also been proposed (for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 59-178252 Japanese Unexamined Patent Publication No. 2013-237248 Japanese Unexamined Patent Publication No. 2014-43066

However, in Patent Documents 2 and 3, although heat shielding is studied depending on the type of pigment used for the printing layer, heat shielding is not studied depending on the mode of the layer constituting the decorative sheet. Further, since pererin black and azomethine azo resins are organic pigments and have weaker hiding power and coloring power than inorganic pigments, it is difficult to meet the strict needs of customers from the viewpoint of design.

The present invention has been made under such circumstances, and an object of the present invention is to provide a decorative sheet having excellent heat-shielding performance and designability.

As a result of intensive studies to solve the above problems, the present inventors have found that the following inventions can solve the problems. That is, the present invention provides a decorative sheet having the following constitution.

[1] A decorative sheet having a base sheet, a decorative layer, and a surface protective layer in this order, and carbon black or calcium element, titanium element, and carbon black or calcium element, titanium element, and one or both of the base sheet and the decorative layer are used. It contains a colorant composed of a composite oxide containing a manganese element, and the volume occupancy of the base sheet with respect to the decorative sheet is 75% or less, and the wavelength range of the decorative sheet calculated according to JIS K 5602: 2008. The solar reflectance at 780 to 2500 nm is 25% or more, and the solar reflectance of the decorative member in the wavelength range of 780 to 2500 nm calculated according to JIS K 5602: 2008 is 35% or more, and the above-mentioned decorative sheet. The brightness (CIE (International Commission on Illumination) L ^* a ^* b ^* L ^* value in the color system) specified in JIS Z 8729-1994 is 50 or less, and the decorative sheet does not contain carbon black. A decorative sheet that is a thing.
[2] The decorative sheet according to the above [1], which has a resin layer between the decorative layer and the surface protective layer.

According to the present invention, it is possible to provide a decorative member having excellent heat-shielding performance and designability.

It is sectional drawing which shows an example of the layer structure of the decorative member of this invention.

[Cosmetic material]
The decorative member of the present invention is a decorative member having an adherend, a base sheet, a decorative layer, and a decorative sheet having a surface protective layer in this order, and occupies the volume of the base sheet with respect to the decorative sheet. The rate is 75% or less, and the solar reflectance in the wavelength range of 780 to 2500 nm of the decorative sheet calculated according to JIS K 5602: 2008 is 25% or more, and is calculated according to JIS K 5602: 2008. It is characterized in that the solar reflectance in the wavelength range of 780 to 2500 nm of the decorative member is 35% or more.
Hereinafter, the configuration of the decorative member of the present invention will be described in detail with reference to FIG. FIG. 1 shows an example of a preferable layer structure of the decorative member 10 of the present invention, and the decorative member 10 shown in FIG. 1 is a base material sheet on an adherend 1 via an adhesive layer 2. It has a decorative sheet 3 including 31, a decorative layer 32, a surface protective layer 34, and a resin layer 33 preferably provided between the decorative layer 32 and the surface protective layer 34.

First, the volume occupancy of the base sheet of the present invention with respect to the decorative sheet and the solar reflectance of the decorative sheet and the decorative member will be described.
In the present invention, the volume occupancy of the base sheet with respect to the decorative sheet is required to be 75% or less. If the volume occupancy exceeds 75%, heat tends to be accumulated in the base sheet, so that excellent heat shielding performance cannot be obtained. From the viewpoint that excellent heat shielding performance can be obtained, it is easy to handle as a decorative sheet, and when the base sheet is colored, the adherend can be concealed and excellent designability can be obtained. The volume occupancy of the base sheet with respect to the decorative sheet is preferably 20 to 75%, more preferably 25 to 70%, still more preferably 25 to 55%.
In the present specification, the volume occupancy of the base sheet with respect to the decorative sheet is calculated from the cross-sectional area of the base sheet and the decorative sheet per unit length.

In the present invention, the solar reflectance of the decorative sheet is required to be 25% or more. If it is less than 25%, excellent heat shielding performance cannot be obtained. The solar reflectance of the decorative sheet is preferably 25 to 60%, preferably 30 to 55, from the viewpoint of obtaining excellent heat shielding performance, selecting the material forming each layer, and selecting the pattern and color tone of the decorative layer. % Is more preferred, and 35-55% is even more preferred. Here, the solar reflectance of the decorative sheet is calculated according to JIS K 5602: 2008 (how to obtain the solar reflectance of the coating film, wavelength range: 780 to 2500 nm). Specifically, a spectrophotometer Measure the spectral reflectance of the decorative sheet at an incident angle of 10 °, and use the obtained data to JIS K 5602: 2008 (How to determine the solar reflectance of the coating film, wavelength range: 780 to 2500 nm). It is calculated according to.

Further, in the present invention, the solar reflectance of the decorative member in the wavelength range of 780 to 2500 nm is required to be 35% or more. If it is less than 35%, excellent heat shielding performance cannot be obtained. From the viewpoint of obtaining excellent heat-shielding performance, selecting the material forming each layer, and obtaining the degree of freedom in selecting the pattern and color tone of the decorative layer, 40 to 70% is preferable, and 45 to 65% is more preferable. Here, the solar reflectance of the decorative member is calculated according to JIS K 5602: 2008 (how to obtain the solar reflectance of the coating film, wavelength range: 780 to 2500 nm), but specifically, a spectrophotometer. Measure the spectral reflectance of the decorative sheet at an incident angle of 10 °, and use the obtained data to JIS K 5602: 2008 (How to determine the solar reflectance of the coating film, wavelength range: 780 to 2500 nm). It is calculated according to.

(Adhesion material)
Next, each layer constituting the decorative member of the present invention will be described.
Examples of the adherend include flat plates of various materials, plate materials such as curved plates, three-dimensional articles, sheets (or films), and the like. For example, wood members such as wood single board, wood plywood, particle board, MDF (medium density fiberboard) and other wood fiber boards, and wood members used as three-dimensional articles; plate materials such as iron and aluminum, steel plates, and three-dimensional articles. , Or metal members used as sheets, etc .; ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates, and three-dimensional articles. Ceramic members; acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber plate, etc. Examples thereof include a shaped article, a resin member used as a sheet, and the like. In addition, these members can be used alone or in combination of two or more.

In the present invention, it may be appropriately selected from the above according to the intended use, and fittings such as interior and exterior members of buildings such as walls, ceilings and floors, window frames, doors, handrails, skirting boards, peripheral edges and moldings. When the above is used, a wood member, a metal member, a resin member, and a member combining these are preferable.

The solar reflectance in the wavelength range of 780 to 2500 nm of the adherend is preferably 50% or more, more preferably 60% or more, further preferably 70% or more, and the upper limit is 100, from the viewpoint of obtaining excellent heat shielding performance. % Or less is preferable, and considering the degree of freedom in selecting the adherend, 95% or less is more preferable, and 90% or less is further preferable. Further, the solar reflectance of the adherend is preferably higher than that of the decorative sheet.
The thickness of the adherend may be appropriately selected depending on the application and the material, and is usually preferably 0.1 to 5 mm, more preferably 0.1 to 3 mm.
The solar reflectance in the wavelength range of 780 to 2500 nm of the adherend can be calculated in the same manner as the solar reflectance of the decorative sheet described above.

(Adhesive layer)
The adherend and the decorative sheet are preferably bonded together via an adhesive layer in order to obtain excellent adhesiveness. The adhesive used for the adhesive layer is not particularly limited, and a known adhesive can be used, and for example, an adhesive such as a heat-sensitive adhesive or a pressure-sensitive adhesive is preferable. Examples of the resin used for the adhesive constituting this adhesive layer include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, and styrene-acrylic resin. At least one resin selected from polymerized resin, polyester resin, polyamide resin and the like is used. Further, a two-component curable polyurethane-based adhesive or a polyester-based adhesive using isocyanate or the like as a curing agent can also be applied.
An adhesive may also be used for the adhesive layer. As the pressure-sensitive adhesive, acrylic-based, urethane-based, silicone-based, rubber-based and other pressure-sensitive adhesives can be appropriately selected and used.

The adhesive layer is a solution or emulsion of the above resin in a form that can be applied, and is applied to the adherend and cosmetics by means such as a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate. It can be applied to at least one of the sheets and dried to form.
The thickness of the adhesive layer is not particularly limited, but is usually in the range of 1 to 100 μm. Within this range, excellent adhesiveness can be obtained.

[Cosmetic sheet]
The decorative member of the present invention has an adherend and a decorative sheet having a base sheet, a decorative layer, and a surface protective layer in this order, that is, the adherend and the base sheet of the decorative sheet face each other. It is provided as such.

(Base sheet)
As the base sheet of the decorative sheet used in the present invention, those usually used as the base sheet of the decorative sheet can be adopted without limitation, and since it is easy to handle, it is composed of a polyester resin and a polyolefin resin. A base sheet is preferable.
Preferred examples of the polyester resin include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, ethylene terephthalate-isophthalate copolymer, and polyallylate. Of these, polyethylene terephthalate and polybutylene terephthalate are more preferable, and polyethylene terephthalate is more preferable.
Examples of the polyolefin resin include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer and the like, with polyethylene and polypropylene being more preferable. ..

The thickness of the base sheet is not limited as long as the volume occupancy of the base sheet with respect to the decorative sheet is 75% or less, and is preferably, for example, 20 to 130 μm, more preferably 30 to 100 μm, and 40 to 40. 90 μm is more preferable.

The base material sheet is preferably a colored resin sheet composed of a colored resin. By using the colored resin, when the surface hue of the adherend to which the decorative sheet is attached varies, the surface hue can be well concealed, so that excellent designability can be obtained, and if desired. It is possible to ensure the stability of the hue of the decorative layer provided accordingly. Further, from the viewpoint of obtaining excellent heat shielding performance, it is preferably white.

The colorant used for the above-mentioned purpose may be appropriately selected depending on the intended use. For example, the base material sheet can be colored transparent or colored opaque. Since it is generally necessary to conceal the surface of the adherend, it is preferable to make it colored and opaque.
Colorants include inorganic pigments such as iron black, titanium white, antimony white, yellow lead, titanium yellow, petals, cadmium red, ultramarine blue, and cobalt blue; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue. Dyes: Metal pigments made of scaly foil pieces such as aluminum and brass; Titanium dioxide-coated mica, pearl pigments made of scaly foil pieces such as basic lead carbonate, and the like are preferably used. In the present invention, from the viewpoint of obtaining excellent heat shielding performance, the amount of carbon black (black) added as a colorant is preferably 5.0 parts by mass or less with respect to 100 parts by mass of the resin forming the base sheet. It is more preferably 1.0 part by mass or less, and further preferably not added. Since carbon black (ink) has the property of easily absorbing heat, the use of carbon black (ink) in the decorative sheet makes it easier for the decorative sheet to absorb heat, and the heat shielding performance deteriorates. is there. When titanium oxide is used as the white pigment, the crystal type is known as a rutile type, an anatase type, brookite type, etc., although it is not particularly limited, and has excellent whiteness, weather resistance and heat shielding. The rutile type is preferable because of its performance and other characteristics. Further, since titanium oxide may deteriorate the resin by the photocatalytic action, it is preferable that the surface is treated with a surface coating agent for the purpose of stabilizing the photocatalytic action, and the composition of the surface coating agent is limited. Although not intended, examples thereof include inorganic oxides such as silicon oxide, alumina, and zinc oxide. The coating method of the surface coating agent is not particularly limited, and titanium oxide obtained by a known method can be used.
The amount of the colorant added is preferably 1 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin forming the above-mentioned base material sheet so that the resin content is not extremely reduced in consideration of weather resistance. More preferred.

In addition, the base material sheet has physical properties such as an oxidation method or an unevenness method on one side or both sides in order to strengthen the interlayer adhesion between the base material sheet and other layers and the adhesiveness with various adherends. Physical or chemical surface treatments can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method and the like, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments are appropriately selected depending on the type of the base material, but in general, the corona discharge treatment method is preferably used from the viewpoints of effectiveness and operability.
Further, a treatment such as forming a primer layer or a back surface primer layer may be performed for the purpose of strengthening the interlayer adhesion between the base sheet and each layer.

Further, an inorganic filler may be added to the base sheet as needed, and the inorganic filler includes calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), alumina (aluminum oxide) and the like. Powder and the like. The amount of the inorganic filler added is usually 1 to 50 parts by mass with respect to 100 parts by mass of the resin forming the base sheet.
Further, the base material sheet may contain various other additives such as a foaming agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer, if necessary.

(Decorative layer)
The decorative layer of the decorative sheet used in the present invention imparts decorativeness to the decorative member of the present invention, and may be a colored layer (so-called solid colored layer) that covers the entire surface, or inks various patterns. It may be a pattern layer formed by printing using a printing machine, or it may be a combination of these.

As the ink used for the decorative layer, an ink in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is appropriately mixed is used.
The binder is not particularly limited, and curable resins such as thermoplastic resins, one-component curable resins and two-component curable resins can be used. For example, urethane resin, acrylic urethane resin, vinyl chloride / vinyl acetate co-weight. From coalescence resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin (nitrified cotton), cellulose acetate resin, etc. Any one may be used alone or in admixture of two or more.

As the colorant, the same colorants as those exemplified as the colorants used for the above-mentioned base material sheet can be preferably mentioned. It is also preferable not to use carbon black (black).

When the decorative layer has a pattern, the pattern includes a stone pattern that imitates the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), a fabric pattern that imitates a texture or a cloth-like pattern, and tiles. There are patterns, brickwork patterns, etc., and there are also patterns such as parquet, patchwork, etc. that combine these. These patterns are formed by multicolor printing with ordinary yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing plates of the individual colors that make up the pattern. Will be done.
In the present invention, excellent designability can be obtained even in the case of dark colors, and the texture (tactile sensation) can be expressed by the concave shape described later, so that the wood grain pattern can be obtained from the viewpoint of obtaining realistic designability and texture. Are suitable. Further, as described above, it is preferable not to use carbon black (black) from the viewpoint of heat shielding performance, but in the present invention, even if carbon black is not used, the volume occupancy of the base sheet, the decorative sheet and the decorative member The configuration with the solar reflectance in a specific range makes it possible to obtain excellent design even in the case of dark colors, and achieves both excellent heat shielding performance and design.

The thickness of the decorative layer may be appropriately selected according to the desired pattern, but is usually 1 to 20 μm, preferably 1 to 10 μm.

(Surface protective layer)
The surface protective layer of the decorative sheet used in the present invention is provided directly on the decorative layer or on another layer, for example, a resin layer described later provided on the decorative layer, if necessary. It is a layer located on the outermost surface of the decorative member, and is a layer that imparts surface characteristics such as scratch resistance, abrasion resistance, and chemical resistance to the decorative member of the present invention. The surface protective layer is preferably composed of a cured product of a resin composition containing a curable resin. By being composed of a cured product of the curable resin composition, the surface characteristics of the decorative member can be improved.

As the curable resin used for forming the surface protective layer, a thermosetting resin such as a two-component curable resin and an ionizing radiation curable resin are preferably used, and a plurality of these are used, for example, ionizing radiation curing. It may be a so-called hybrid type in which a sex resin and a thermosetting resin are used in combination, or a curable resin and a thermoplastic resin are used in combination.
From the viewpoint of increasing the crosslink density of the resin forming the surface protective layer and improving the scratch resistance and abrasion resistance of the surface, an ionizing radiation curable resin is preferable, and it can be applied without a solvent and can be handled. An electron beam curable resin is more preferable from the viewpoint of ease of use.

(Ionizing radiation curable resin)
The ionizing radiation curable resin is a resin having an energy quantum capable of cross-linking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, a resin that is cross-linked and cured by irradiating with ultraviolet rays or electron beams. is there. Specifically, it can be appropriately selected and used from the polymerizable monomer and the polymerizable oligomer or prepolymer conventionally used as an ionizing radiation curable resin.

Typically, as the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate is preferable. Here, "(meth) acrylate" means "acrylate or methacrylate". The polyfunctional (meth) acrylate may be any (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule, and is not particularly limited. One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

Next, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate-based, urethane (meth) acrylate-based, polyester (meth) acrylate-based, or polyether (meth) acrylate. The system etc. can be mentioned.
Further, as the polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group on the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond on the main chain. In molecules such as aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resins having many reactive groups in small molecules, novolak type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers and the like having cationically polymerizable functional groups.

In the present invention, a monofunctional (meth) acrylate may be appropriately used in combination with the polyfunctional (meth) acrylate or the like for the purpose of reducing the viscosity thereof, as long as the object of the present invention is not impaired. .. One of these monofunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

The thickness of the surface protective layer is preferably 2 to 25 μm, more preferably 2 to 15 μm, and 2 to 15 μm from the viewpoint of obtaining excellent scratch resistance and its durability, as well as surface characteristics such as abrasion resistance and chemical resistance. 10 μm is more preferable.

The resin composition forming the surface protective layer may contain various additives other than the above as long as the performance is not impaired. Examples of various additives include polymerization inhibitors, cross-linking agents, antistatic agents, adhesive improvers, antioxidants, leveling agents, thixophilic imparting agents, coupling agents, plasticizers, defoaming agents, fillers, and solvents. And so on.

(Resin layer)
The decorative sheet used in the present invention preferably has a resin layer between the base material sheet and the surface protective layer from the viewpoint of protecting the decorative layer and improving scratch resistance.
As the resin constituting the resin layer, in addition to the polyester resin and polyolefin resin used as the base material sheet, acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, vinyl chloride resin, vinyl acetate resin and the like are preferably mentioned. From the viewpoint of improving moldability and scratch resistance, polyester resin and polyolefin resin are preferable, and polyolefin resin is more preferable. From the same viewpoint as this, it is preferable that both the base material sheet and the resin constituting the resin layer are polyolefin resins.

The resin layer may be provided between the base sheet and the surface protective layer, and is preferably provided between the decorative layer and the surface protective layer from the viewpoint of protecting the decorative layer.
The resin layer may be transparent or opaque, and when it is provided between the decorative layer and the surface protective layer, it is preferably transparent from the viewpoint of making the decorative layer more clearly visible. Here, the term "transparent" includes not only colorless and transparent but also colored transparent and translucent. In the case of being colored, as the colorant used, those exemplified as the colorant used for the above-mentioned base sheet can be preferably mentioned. It is also preferable not to use carbon black (black).

The thickness of the resin layer is preferably 20 to 130 μm, more preferably 30 to 100 μm, and even more preferably 40 to 90 μm. When the thickness of the resin layer is within the above range, the protective function of the decorative layer and the improvement of scratch resistance can be expected.

From the viewpoint of improving the adhesiveness with each layer, the resin layer can be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides. As these physical or chemical surface treatments, the same method as the above-mentioned surface treatment of the base sheet is preferably exemplified. Further, the resin layer may be subjected to a treatment such as forming a primer layer or a back surface primer layer from the viewpoint of improving the adhesiveness with each layer.

(Adhesive layer)
The decorative sheet used in the present invention may have an adhesive layer, if necessary. In particular, when the resin layer is provided, it is effective to provide the adhesive layer when improving the adhesiveness between the resin layer and the decorative layer. As the adhesive constituting the adhesive layer, an adhesive usually used in a decorative sheet can be used, and the thickness thereof is about 0.1 to 50 μm, which is 1 to 30 μm from the viewpoint of obtaining sufficient adhesiveness. The range is preferred.

The adhesive is not particularly limited, and examples thereof include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, and rubber-based adhesives. Among them, urethane-based adhesives are preferable in terms of adhesive strength. .. As such a urethane-based adhesive, for example, a two-component curable type containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate. An adhesive using a urethane resin can be mentioned. Acrylic-polyester-vinyl acetate resin and the like are also suitable adhesives that easily develop adhesiveness by heating and can maintain adhesive strength even when used at high temperatures.
The adhesive layer can be formed by a known layer forming method such as a coating method using an adhesive composition made of these resins or the like.

(Primer layer)
As described above, the decorative sheet used in the present invention may have a primer layer and a back surface primer layer in either of the layers in order to improve the adhesion between the layers, if necessary. For example, by providing a primer layer as a back surface primer layer on the base sheet side between the adherend and the base sheet, a decorative member having excellent interlayer adhesion can be obtained. Further, it is effective to provide a primer layer between the surface protective layer and another layer, for example, when a resin layer is provided, from the viewpoint of obtaining excellent scratch resistance of the decorative member of the present invention.

The primer layer is a transparent or translucent layer, and can be formed by using, for example, a resin exemplified as the binder resin used for the above-mentioned decorative layer. The thickness of the primer layer is usually about 0.5 to 20 μm, preferably 0.5 to 5 μm, and more preferably 0.5 to 3 μm.

(Concave shape)
The decorative member of the present invention preferably has a concave shape at least on the surface protective layer. Since the decorative member of the present invention has a concave shape, the texture (tactile sensation) is particularly excellent. This concave shape may be present at least in the surface protective layer, and may reach the base sheet. From the viewpoint of obtaining an excellent texture (tactile sensation), it is preferable that not only the material that stays in the surface protective layer but also the material that extends to the resin layer, the decorative layer, and the base material sheet are combined.
In the present specification, when the surface protective layer or the like has the concave shape, the thickness of the surface protective layer or the like means the thickness measured at a place having no concave shape.

The maximum depth of the concave shape is preferably 15% or more and less than 100%, more preferably 15 to 80%, still more preferably 25 to 80% with respect to the total thickness of the decorative sheet. The maximum depth of the concave shape is preferably 15 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more. By having such a maximum depth, the decorative sheet is not broken during concave shape processing, for example, embossing, and the concave shape is not finished as if it is crushed, which is excellent. A texture (tactile sensation) is obtained, and as a result, excellent designability is obtained.

Here, the maximum depth of the concave shape is measured by using a surface roughness shape measuring machine to measure the height from the lowest point of the concave shape to the surface of the surface protective layer for any 30 concave shapes. , Cutoff value: 2.50 mm, Cutoff filter type: 2RC, Tilt correction method: Measured under straight line measurement conditions, and the deepest one was taken as the maximum depth.

The method of forming the concave shape on the surface protective layer is not particularly limited, and for example, considering the ease of work, it is preferable to adopt embossing. The embossing may be performed by a usual method using a known single-wafer or rotary embossing machine.

The decorative sheet used in the present invention has a brightness (CIE (International Commission on Illumination) L ^* a ^* b ^* L ^* value in the color system specified in JIS Z 8730: 2009) depending on the desired design. However, for example, when a dark-colored design is desired, 50 or less is preferable, 45 or less is more preferable, and 35 or less is further preferable. When the lightness is within the above range, excellent designability can be obtained even in the case of a dark color, and particularly when a wood grain pattern is adopted as the pattern, excellent designability can be obtained. When the brightness of the conventional decorative sheet is as low as 50 or less, the solar reflectance becomes a low value of less than 25% and sufficient heat shielding performance cannot be obtained. However, the decorative sheet used in the present invention has a brightness. Even when the value is as low as 50 or less, the solar reflectance is controlled to be 25% or more as described above, so that it has sufficient heat shielding performance.

(Manufacturing method of decorative parts)
Regarding the method for producing a decorative member of the present invention, an adherend, which is one of the preferred embodiments of the decorative member of the present invention, and a decorative sheet having a base sheet, a decorative layer, a resin layer, and a surface protective layer in this order are provided. The manufacturing method will be described by taking the provided decorative member as an example. The decorative member of the present invention is, for example, a step of providing a decorative layer on a base material sheet (1), a step of providing a resin layer on the decorative layer (2), and a curable resin composition applied on the resin layer. It can be produced by sequentially going through a step (3) of curing to form a surface protective layer to produce a decorative sheet and a step (4) of laminating the decorative sheet and an adherend.

The step (1) is a step of providing a decorative layer on the base material sheet. The decorative layer is formed by applying an ink used for the decorative layer on a base sheet to provide a desired colored layer and a pattern layer. The ink is applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method, preferably a gravure printing method.

When the base sheet is surface-treated, the surface treatment may be performed before applying the ink used for the decorative layer. When the primer layer is provided between the base sheet and the decorative layer, it may be provided before applying the ink used for the decorative layer, and the surface of the base sheet opposite to the surface on which the decorative layer is provided ( When the back surface primer layer is provided on the back surface), it may be provided when applying the ink used for the decorative layer. The primer layer is formed by applying a resin composition for forming a primer layer by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. Can be done.

The step (2) is a step of providing a resin layer on the decorative layer. For the resin layer, an adhesive is applied to the base sheet having the decorative layer as needed to form the adhesive layer, and then the resin layer is extruded and laminated using a resin composition for forming the resin layer. It can be formed by laminating and laminating by adhering and crimping by a method such as lamination, wet lamination, thermal lamination and the like.

The step (3) is a step of applying a curable resin composition on the resin layer and curing the resin layer to form a surface protective layer to prepare a decorative sheet. The surface protective layer is obtained by applying an ionizing radiation curable resin composition containing the above-mentioned ionizing radiation curable resin onto a resin layer or a primer layer provided on the resin layer as desired and curing the surface protective layer. Be done. When the resin layer is not provided, the decorative layer may be provided on the base sheet, and then the curable resin composition may be applied and cured to form the surface protective layer.

The resin composition for forming the surface protective layer is preferably applied with a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat or the like so that the thickness after curing is usually about 1 to 20 μm. It is carried out by a known method, more preferably by a gravure coat.

When an ionizing radiation resin composition is used to form the surface protective layer, the uncured resin layer formed by applying the resin composition is subjected to ionizing radiation such as an electron beam or ultraviolet rays to form a cured product on the surface. It becomes a protective layer. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but the uncured resin layer can usually be cured at an accelerating voltage of about 70 to 300 kV. preferable.

The irradiation dose is preferably an amount at which the crosslink density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and for example, a cockloft Walton type, a bandegraft type, a resonance transformer type, an insulated core transformer type, or various electron beam accelerators such as a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. The ultraviolet source is not particularly limited, and for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like is used.

When a thermosetting resin composition is used for forming the surface protective layer, the surface protective layer may be formed by performing a heat treatment according to the resin composition to be used and curing the surface protective layer.

The step (4) is a step of laminating the adherend and the decorative sheet produced by the above steps (1) to (3), and the base sheet of the decorative sheet and the adherend are opposed to each other. Laminate. Examples of the method of laminating the adherend and the decorative sheet include a laminating method of laminating the decorative sheet on a plate-shaped adherend by pressing with a pressure roller with an adhesive in between, and an adhesive in between. While supplying the decorative sheet through, the decorative sheet is sequentially pressure-bonded and laminated on a plurality of side surfaces constituting the adherend by a plurality of rollers having different orientations, and is fixed to a fixed frame. The decorative sheet is heated by a heater through a silicone rubber sheet until it reaches a predetermined temperature at which it softens, and the vacuum forming mold is pressed against the heated and softened decorative sheet, and at the same time, air is sucked from the vacuum forming mold with a vacuum pump or the like. A vacuum forming process or the like in which the decorative sheet is firmly adhered to the vacuum forming die is preferable.

When a hot melt adhesive (heat sensitive adhesive) is used in the laminating process or wrapping process, the heating temperature is usually 160 to 200 ° C, although it depends on the type of resin constituting the adhesive, and the reactive hot melt adhesive is used. It is usually about 100 to 130 ° C. Further, in the case of vacuum forming, it is generally performed while heating, and it is usually performed at about 80 to 130 ° C., preferably about 90 to 120 ° C.

The decorative member obtained as described above can be arbitrarily cut, and the surface and the end of the wood can be arbitrarily decorated by using a cutting machine such as a router or a cutter to perform groove processing, chamfering, or the like. And various uses, for example, interior and exterior members of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, surrounding edges, fittings such as malls, kitchens, furniture or light electric appliances, OA equipment, etc. It can be used for the surface veneer of the cabinet, the interior of the vehicle, the exterior, etc.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.
(Evaluation method)
(1) Calculation of solar reflectance For the decorative sheets and decorative members obtained in each Example and Comparative Example, a spectrophotometer (“UV-3100PC (model number)”, manufactured by Shimadzu Corporation) was used to protect the surface. The spectral reflectance was measured from the layer side at an incident angle of 10 °, and the obtained data was used to calculate the solar reflectance in the wavelength range of 780 to 2500 nm in accordance with JIS K 5602: 2008.
(2) Measurement of brightness (L ^* value) For the decorative sheets obtained in each Example and Comparative Example, a spectrocolorimeter (“CM-3700d (model number)”, manufactured by Konica Minolta Holdings Co., Ltd.) was used. From the surface protective layer side, the L ^* value in the CIE (International Commission on Illumination) L ^* a ^* b ^* color system specified in JIS Z 8730: 2009 was measured.
(3) Evaluation of Designability The appearance of the decorative sheets and decorative members obtained in each Example and Comparative Example was visually observed and evaluated according to the following criteria.
A: The design of the decorative member did not change significantly from the design of the decorative sheet.
B: Although the design of the decorative member changed from the design of the decorative sheet, there was no problem in practical use.
C: The design of the decorative member has changed significantly from the design of the decorative sheet, causing a practical problem.
(4) Evaluation of heat shielding performance A 200 W type lamp (incandescent lamp, manufactured by Iwasaki Electric Co., Ltd.) was used for the decorative members obtained in each Example and Comparative Example at room temperature (23 ° C.) and relative humidity of 50%. Under the above conditions, irradiation was performed from a height of 30 cm, and the temperature of the decorative member after 10 minutes was measured and evaluated according to the following criteria.
A: The temperature rise was less than 75 ° C.
B: The temperature rise was 75 ° C. or higher and lower than 85 ° C.
C: The temperature rise was 85 ° C. or higher and lower than 95 ° C.
D: The temperature rise was 95 ° C. or higher.
(5) Appearance evaluation of weather resistance For the decorative members obtained in each Example and Comparative Example, a sunshine weather meter WEL-300 (manufactured by Suga Test Instruments Co., Ltd.) was used at a black panel temperature of 63 ° C. for 120 minutes. A weather resistance test was conducted under the condition of rainfall for 18 minutes, and after 4000 hours, it was visually observed, and the presence or absence of appearance abnormalities such as floating and falling off of each layer such as the surface protective layer was inspected and evaluated according to the following criteria. ..
A: No significant change in appearance was observed. That is, there was almost no change in appearance.
B: A slight change in appearance was observed.
C: A large change in appearance was observed, which was a problematic level.

Reference example 1
Polypropylene resin sheet subjected to double-sided corona discharge treatment (white colored resin sheet, thickness: 80 μm, containing 0.01 part by mass of carbon black as a pigment with respect to 100 parts by mass of polypropylene resin, 10 mass including titanium oxide Part) is used as a base sheet, a two-component curable acrylic-urethane resin is used as a binder, and a printing ink containing 1.0 part by mass of carbon black as a colorant is applied to one surface of the base sheet by a gravure printing method. A wood grain decorative layer (thickness: 2 μm) was provided, and a two-component curable urethane-nitrated cotton mixed resin composition was applied to the other surface to form a back surface primer layer (thickness: 2 μm). A transparent polyurethane resin-based adhesive is applied onto the decorative layer to form an adhesive layer (thickness after drying: 3 μm), and the transparent polypropylene resin is heated, melted and extruded by a T-die extruder to make it transparent. A resin layer was formed.
Next, after corona discharge treatment is applied to the surface of the resin layer, a two-component curable acrylic-urethane resin composition is applied by a gravure printing method to form a primer layer (thickness after drying: 1 μm), which is further transparent. The electron beam curable resin composition (electron beam curable resin: trifunctional urethane acrylate) was applied by a roll coating method (solid content: 3 g / m ² ) and dried to form an uncured resin layer, and the oxygen concentration was increased. The uncured resin layer was cured by irradiating an electron beam (pressurized voltage: 125 KeV, 5Mrad) in an environment of 200 ppm to obtain a surface protective layer (thickness: 3 μm). Then, embossing was performed from the surface protective layer side to form an uneven pattern of a wood grain conduit pattern having a concave shape with a maximum depth of 30 μm, and a decorative sheet (total thickness: 160 μm) of Reference Example 1 was obtained. The volume occupancy of the base sheet in this decorative sheet is 50%.
A coated steel sheet (thickness: 0.4 mm) coated with an adhesive made of a two-component curable urethane resin is placed in an oven and cured at 150 ° C. for 1 minute, and then immediately using a roll laminator to apply the above decorative sheet. It was attached to prepare a decorative member. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

Reference Examples 2 and 6, Comparative Example 4
In Reference Example 1, Reference Examples 2 and 6 are the same as in Reference Example 1 except that the volume occupancy of the base sheet is changed to the occupancy as shown in Table 1 by changing the thickness of the base sheet. , The decorative sheet and the decorative member of Comparative Example 4 were prepared. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

Reference example 3
In Reference Example 1, a decorative sheet and a decorative member were produced in the same manner as in Reference Example 1 except that the carbon black content of the printing ink used for the decorative layer was changed to 3.0 parts by mass. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

Reference example 4
In Reference Example 1, a decorative sheet and a decorative member were produced in the same manner as in Reference Example 1 except that the carbon black content of the printing ink used for the decorative layer was changed to 0.1 parts by mass. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

Example 5
In Reference Example 1, the base sheet is replaced with a base sheet containing no carbon black and titanium oxide (polypropylene resin sheet, transparent colorless, thickness: 80 μm), and the ink used for the decorative layer is an ink containing no carbon black (ink using carbon black). The decorative sheet and the decorative sheet and the decorative member are in the same manner as in Reference Example 1 except that the solar reflectance of the decorative sheet and the decorative member is as shown in Table 1 instead of the composite oxide containing calcium element, titanium element, and manganese element. A decorative member was produced. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

Reference example 7
In Reference Example 1, a decorative sheet and a decorative member were produced in the same manner as in Reference Example 1 except that the amount of titanium oxide in the polypropylene resin sheet subjected to the double-sided corona discharge treatment was increased to 30 parts by weight of the pigment. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

Comparative Example 1
A colorless and transparent polypropylene resin sheet subjected to double-sided corona discharge treatment is used as a resin layer, and one surface of the resin layer contains 1.0 part by mass of a two-component curable acrylic-urethane resin as a binder and carbon black as a colorant. A wood grain decorative layer (thickness: 2 μm) is provided by applying the printing ink to be used by the gravure printing method, and a two-component curable acrylic-urethane resin composition is applied to the other surface by the gravure printing method to provide a primer layer (thickness: 2 μm). The thickness after drying: 1 μm) is formed, and a transparent electron beam curable resin composition (electron beam curable resin: trifunctional urethane acrylate) is further applied by a roll coating method (solid content: 3 g / m ² ). , Dry to form an uncured resin layer, and irradiate an electron beam (pressurized voltage: 125 KeV, 5Mrad) in an environment with an oxygen concentration of 200 ppm to cure the uncured resin layer to cure the surface protective layer (thickness). : 3 μm) was obtained. Then, embossing was performed from the surface protective layer side to form an uneven pattern of a wood grain conduit pattern having a concave shape with a maximum depth of 30 μm, and a decorative sheet (total thickness: 120 μm) was obtained. Using the obtained decorative sheet, a decorative member was produced in the same manner as in Reference Example 1. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

Comparative Examples 2 and 3
In Reference Example 1, a base sheet (polypropylene resin sheet, brown color, thickness: 80 μm) containing 0.1 parts by mass of carbon black and an ink used for a decorative layer (Comparative Example 2: carbon black 8.0). Same as Reference Example 1 except that the mass content, Comparative Example 3: carbon black (15.0 parts by mass) was changed to make the solar reflectance of the decorative sheet and the decorative member as shown in Table 1. The decorative sheets and decorative members of Comparative Examples 2 and 3 were prepared. The above-mentioned evaluation was performed on the obtained decorative sheet and decorative member, and the evaluation results are shown in Table 1.

The decorative member of the present invention has an excellent heat-shielding performance with a B rating or higher (temperature rise is less than 85 ° C.) as an evaluation of the heat-shielding performance, conceals the adherend, and has excellent designability. It was confirmed that. Even in Example 5 in which carbon black was not used, the brightness (L * value) could be suppressed to 30, the subject was concealed, and the dark wood grain pattern was obtained, and excellent design was obtained. Further, even with the decorative member of Reference Example 4 having a bright color tone, it was possible to obtain designability as well as excellent heat shielding performance. Further, the decorative member of Reference Example 7 having a high content of titanium oxide in the base sheet has a smaller amount of resin component than the decorative member of Reference Example 1 and the like, and therefore has better weather resistance than Reference Example 1 and the like. It has become a little inferior.
On the other hand, the decorative member of Comparative Example 1 having a small volume occupancy of the base sheet was inferior in terms of design, while the decorative member of Comparative Example 4 having a large volume occupancy had a good design. , The heat shield performance has become inferior. Further, the decorative members of Comparative Examples 2 and 3 having low solar reflectance are inferior in heat shielding performance.

The decorative member of the present invention has excellent heat-shielding performance and also has designability, and is used for interior / exterior members of buildings such as walls, ceilings, and floors, window frames, doors, handrails, skirting boards, etc. In addition to fittings such as skirting boards and moldings, it is suitably used for kitchens, furniture or light electric appliances, surface decorative boards of cabinets such as OA equipment, and interior / exterior members of vehicles. In particular, by utilizing its heat shielding performance, it is suitably used for members used in an environment exposed to direct sunlight, such as exterior members, doors, and window frames.

1. 1. Adhesive material 2. Adhesive layer 3. Decorative sheet 31. Base sheet 32. Decorative layer 33. Resin layer 34. Surface protective layer 10. Cosmetic material

Claims (4)

A decorative sheet having a base sheet, a decorative layer, and a surface protective layer in this order.
One or both of the base sheet and the decorative layer contains a colorant composed of a composite oxide containing carbon black or a calcium element, a titanium element, and a manganese element.
The volume occupancy of the base sheet with respect to the decorative sheet is 75% or less, and the solar reflectance of the decorative sheet in the wavelength range of 780 to 2500 nm calculated according to JIS K 5602: 2008 is 25% or more. , JIS K 5602: 2008, the solar reflectance of the decorative sheet in the wavelength range of 780 to 2500 nm is 35% or more.
The brightness of the decorative sheet (CIE (International Commission on Illumination) L ^* a ^* b ^* L ^* value in the color system specified in JIS Z 8729-1994) is 50 or less.
A decorative sheet in which the decorative sheet does not contain carbon black. The decorative sheet according to claim 1, wherein the surface protective layer is a cured product of an ionizing radiation curable resin composition. The decorative sheet according to claim 1 or 2, wherein the base sheet is a colored resin sheet. The decorative sheet according to any one of claims 1 to 3, which has a resin layer between the decorative layer and the surface protective layer.

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