JP2018167495A - Decorative sheet and decorative material using the same - Google Patents

Abstract

To provide a decorative sheet having excellent working characteristics, weather resistance and scratch resistance, and to provide a decorative material using the same.SOLUTION: There are provided a decorative sheet which has a base material, an intermediate resin layer and a surface protective layer in this order, where the surface protective layer is a cured product of a curable resin composition, the intermediate resin layer and the surface protective layer contain an ultraviolet absorber, and a content (M) of the ultraviolet absorber with respect to 100 pts.mass of a resin constituting the intermediate resin layer is larger than a content (M) of the ultraviolet absorber with respect to 100 pts.mass of a resin constituting the surface protective layer; and a decorative material using the same.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet and a decorative material using the decorative sheet.

  Interior materials or exterior members of buildings such as walls, ceilings, floors, entrance doors, window frames, doors, handrails, skirting boards, surrounding edges, malls and other fittings or construction materials, kitchens, furniture or light electrical appliances, Generally, a decorative sheet for a surface decorative plate of a cabinet such as OA equipment, a vehicle interior material or exterior member is a metal member such as a steel plate, a resin member, or a wooden member. The thing which stuck together is used. For the decorative sheets used for these members, weathering agents such as ultraviolet absorbers and light stabilizers are usually used in order to prevent deterioration due to use.

  As such a decorative sheet, it has a base sheet, a pattern layer, a transparent resin layer and a surface protective layer, the surface protective layer is formed from a composition containing an ionizing radiation curable resin, and the transparent resin layer has irregularities. A decorative sheet in which a colored resin layer using a predetermined resin is formed in the concave and convex portions has been proposed (for example, Patent Document 1).

JP 2006-095992 A

  However, the decorative sheet described in Patent Document 1 is used for a member used in a particularly severe environment such as an exterior member such as an entrance door, an environment exposed to direct sunlight such as a window frame and a door and other fittings. Then, with use, a change in color tone, floating between layers, cracks, and the like occurred, and the long-term weather resistance was poor. As a means for improving the weather resistance, each layer constituting the decorative sheet, preferably the surface layer, and the decorative sheet described in Patent Document 1, the surface protective layer is provided with a larger amount of a weathering agent such as an ultraviolet absorber. It can be included. By using a large amount of the ultraviolet absorber, excellent weather resistance can be obtained in the short term. However, as it is used, the ultraviolet absorber leaks from the surface protective layer, so-called bleed-out (also referred to as bleed-out transition) occurs, and the ultraviolet absorber in the decorative sheet decreases, thereby reducing the weather resistance. In addition, there is a negative effect such as stickiness on the surface of the decorative sheet.

  The present invention has been made under such circumstances, and an object of the present invention is to provide a decorative sheet having excellent weather resistance and a decorative material using the decorative sheet.

  As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by the invention relating to the decorative sheet having the following configuration and the decorative material using the same.

[1] A substrate, an intermediate resin layer, and a surface protective layer are provided in this order, the surface protective layer is a cured product of the curable resin composition, and the intermediate resin layer and the surface protective layer contain an ultraviolet absorber. And the content (M ₁ ) of the ultraviolet absorber with respect to 100 parts by mass of the resin constituting the intermediate resin layer is greater than the content (M ₂ ) of the ultraviolet absorber with respect to 100 parts by mass of the resin constituting the surface protective layer. Also a large, decorative sheet.
[2] A cosmetic material having an adherend and the decorative sheet according to [1].

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet which has the outstanding weather resistance, and a decorative material using the same can be provided.

It is a schematic diagram which shows the cross section of an example of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of an example of the decorative sheet of this invention. It is a cross-sectional schematic diagram which shows an example of the layer structure of the decorative material of this invention.

[Decorative sheet]
The decorative sheet of the present invention has a substrate, an intermediate resin layer, and a surface protective layer in this order, the surface protective layer is a cured product of the curable resin composition, and the intermediate resin layer and the surface protective layer are The content (M ₁ ) of the ultraviolet absorber with respect to 100 parts by mass of the resin that contains the ultraviolet absorber and constitutes the intermediate resin layer is the content of the ultraviolet absorber with respect to 100 parts by mass of the resin that constitutes the surface protective layer ( It is characterized by being larger than M ₂ ).
The structure of the decorative sheet of the present invention will be described with reference to FIGS. FIG. 1 is a schematic diagram showing a cross section of an example of the decorative sheet 10 of the present invention, which has a base material 11, an intermediate resin layer 14, and a surface protective layer 15. Shows that the ultraviolet absorber 17 is contained, and the content of the ultraviolet absorber 17 in the intermediate resin layer 14 is larger.
FIG. 2 is a schematic view showing a cross section of an example of a preferred embodiment of the decorative sheet 10 of the present invention. The decorative sheet 10 includes a base material 11, a decorative layer 12, an adhesive layer 13, an intermediate resin layer 14 (resin layer 14a). , Primer layer 14 b), and surface protective layer 15 in this order, and the back surface primer layer 16 is provided on the surface opposite to the surface of the base material 11 on the surface protective layer 15 side. Includes a white pigment 18. In FIG. 2, the intermediate resin layer 14 is composed of two layers, a resin layer 14a and a primer layer 14b. These layers contain the ultraviolet absorber 17 and the ultraviolet absorption contained in these layers. It is shown that the content of the agent 17 is higher than the content of the ultraviolet absorber 17 in the surface protective layer 15. In FIG. 2, the surface protective layer 15 has a concave portion 19 on the surface (outermost surface) opposite to the base material 11, and the concave portion 19 includes an intermediate resin that remains in the surface protective layer 15. It is shown that there are those that reach the layer 14 and those that reach the substrate 11.

(Content of UV absorber)
In the decorative sheet of the present invention, the content (M ₁ ) of the ultraviolet absorber (hereinafter sometimes simply referred to as “content (M ₁ )”) with respect to 100 parts by mass of the resin constituting the intermediate resin layer. It is larger than the content (M ₂ ) of the ultraviolet absorber with respect to 100 parts by mass of the resin constituting the surface protective layer (hereinafter sometimes simply referred to as “content (M ₂ )”), that is, by the following inequality. It has the relationship shown.
Content (M ₁ )> Content (M ₂ )
When using the decorative sheet in a harsh environment exposed to direct sunlight, in order to suppress the deterioration of the decorative sheet, from the viewpoint of reducing the amount of ultraviolet light passing through the decorative sheet, the outermost layer that is directly exposed to direct sunlight, It is preferable that the surface protective layer contains more ultraviolet absorber. However, if a large amount of the UV absorber is contained in the surface protective layer, the UV absorber will bleed out during long-term use, and the content of the UV absorber retained in the decorative sheet will decrease. The weather resistance will be reduced. In the present invention, the intermediate resin layer sandwiched between the surface protective layer and the base material contains more UV absorber, and the surface protective layer is a cured product of the curable resin composition. In addition, since the bleeding out of the ultraviolet absorbent in the intermediate resin layer can be suppressed and the content of the ultraviolet absorbent held in the decorative sheet can be maintained even after long-term use, excellent weather resistance can be obtained.

In the present invention, the content (M ₁₎ is meant that greater than the content (M ₂₎ can be classified into the following embodiments by the configuration of the intermediate resin layer. (I) When the intermediate resin layer has a _single layer structure, the content of the ultraviolet absorber in the intermediate resin layer is defined as “content (M ₁ )”, and the content (M ₁ ) is the content (M ₂ ). (Ii) when the intermediate resin layer has a multilayer structure having at least two layers, and the ultraviolet absorber is contained in one layer constituting the intermediate resin layer, the inclusion of the ultraviolet absorber in the one layer The amount is “content (M ₁ )”, the content (M ₁ ) is larger than the content (M ₂ ), and (iii) the intermediate resin layer has at least two layers, When the ultraviolet absorber is contained in two or more layers constituting the resin layer, it is sufficient that the content of the ultraviolet absorber in at least one layer is larger than the content (M ₂ ). The content of the UV absorber in the layer with the largest content of And Yuryou _{(M 1)} ", the content of _{(M 1)} is larger than the content _{(M 2),} which means that.

In the case of (iii), from the viewpoint of improving the weather resistance, the content of the ultraviolet absorber in more layers is preferably larger than the content of the ultraviolet absorber (M ₂ ) in the surface protective layer, It is preferable that the content of the ultraviolet absorber in all the layers constituting the intermediate resin layer is larger than the content (M ₂ ) of the ultraviolet absorber in the surface protective layer. In addition, for each layer constituting the intermediate resin layer, the content of the ultraviolet absorber in the layer closest to the base material is maximized, and the ultraviolet absorption in each layer is sequentially performed from the base material side to the surface protective layer side. The content of the UV absorber in the layer closest to the surface protective layer is reduced (the layer constituting the intermediate resin layer, the layer having the minimum UV absorber content). More preferably, the content of the ultraviolet absorber) is still larger than the content (M ₂ ) of the surface protective layer. The layers constituting the intermediate resin layer will be described later.

The content of the ultraviolet absorber of the intermediate resin layer (M ₁₎ and the content of the ultraviolet absorber in the surface protective layer in the sum of _{(M 2) (M 1 +} M 2) is preferably not less than 0.5 part by weight 1 mass part or more is more preferable, 5 mass parts or more is still more preferable, and 10 mass parts or more is still more preferable. Moreover, as an upper limit, 40 mass parts or less are preferable, 30 mass parts or less are more preferable, and 25 mass parts or less are still more preferable. The content _{(M 1)} is intended to be determined according to the above (i) ~ (iii). When the total (M ₁ + M ₂ ) is within the above range, the functions of the intermediate resin layer and the surface protective layer are not inhibited, and excellent weather resistance is obtained. In the present specification, the numerical values related to “above” and “below” related to the description of the numerical range are numerical values that can be arbitrarily combined.

The ratio (M ₁ / M ₂ ) of the content (M ₁ ) of the ultraviolet absorber in the intermediate resin layer and the content (M ₂ ) of the ultraviolet absorber in the surface protective layer is preferably 1.1 or more, 3 or more is more preferable, 5 or more is further preferable, and 10 or more is particularly preferable. Moreover, as an upper limit, 35 or less are preferable, 30 or less are more preferable, 25 or less are still more preferable, and 20 or less are especially preferable. The content _{(M 1)} is intended to be determined according to the above (i) ~ (iii). When the ratio (M ₁ / M ₂ ) is within the above range, the functions of the intermediate resin layer and the surface protective layer are not inhibited, and excellent weather resistance is obtained.

It is known that the ultraviolet absorption performance is proportional to the thickness of the layer containing the ultraviolet absorber, according to the Lambert-Beer law expressed by the following relational expression.
−log (I / IO) = ε × c × d
(Where IO is the intensity of the incident light, I is the intensity of the transmitted light, -log (I / IO) is the absorbance, ε is the optical coefficient, c is the concentration of the UV absorber, and d is the layer containing the UV absorber. Indicates the thickness.)
As can be seen from the above relational expression showing the Lambert-Beer law, there is a certain relationship between the concentration and thickness of the UV absorber in the layer containing the UV absorber, so the UV absorber in the intermediate resin layer The product (M ₁ × T ₁ ) of the content (M ₁ ) of the intermediate resin layer and the thickness (T ₁ ) of the intermediate resin layer determines the content (M ₂ ) of the ultraviolet absorber in the surface protective layer and the surface protection the thickness of the layer (T ₂₎ and the product (M ₂ × T ₂₎ greater than, that it is preferable to have a relationship shown by the following inequality.
Product (M ₁ × T ₁ )> Product (M ₂ × T ₂ )
When the product (M ₁ × T ₁ ) is larger than the product (M ₂ × T ₂ ), excellent weather resistance and scratch resistance are obtained. The content (M ₁ ) is determined according to the above (i) to (iii), and the thickness (T ₁ ) is the thickness of the layer having the content (M ₁ ). In addition, when the intermediate resin layer has a multilayer structure having two or more layers, it is sufficient that at least one layer has the above relationship, and from the viewpoint of obtaining excellent weather resistance, a plurality of layers have the above relationship. It is preferable that all the layers constituting the intermediate resin layer have the above relationship. In the present invention, the intermediate resin layer has a multilayer structure and is thicker than the thickness (T ₁ ) of the layer even though the content is smaller than the layer having the content (M ₁ ). The product of the content and the thickness may be larger than the product (M ₁ × T ₁ ), but even in such a case, the product (M ₁ × T ₁ ) is merely the content (M _The product corresponding to the layer having ₁ ).
From the same viewpoint, the ratio of the product (M ₁ × T ₁ ) to the product (M ₂ × T ₂ ) ((M ₁ × T ₁ ) / (M ₂ × T ₂ )) is 1 It is preferably large, more preferably 1.1 or more, more preferably 1.5 or more, further preferably 3 or more, and particularly preferably 5 or more. The upper limit is not particularly limited, but may be 30 or less.
Hereinafter, each layer which comprises the decorative sheet of this invention is demonstrated.

(Base material)
As the base material, those usually used as a base material for decorative sheets can be employed without limitation, and a resin base material made of a thermoplastic resin is typically used. Examples of the thermoplastic resin include polyolefin resins such as polypropylene and polyethylene, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as “ABS resins”), acrylic resins, and vinyl chloride resins. The Among these, considering processing characteristics, polyolefin resin, polyester resin, polycarbonate resin and ABS resin are preferable, and polyolefin resin is particularly preferable. In this invention, these resin can be used individually or in combination of multiple types.

  The polyolefin resin is not particularly limited. For example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate. Examples thereof include a copolymer, an ethylene-acrylic acid copolymer, an ethylene-propylene-butene copolymer, and a polyolefin-based thermoplastic elastomer. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferable.

In the decorative sheet of the present invention, it is preferable that at least one of the base material and the surface protective layer contains a white pigment. In this case, the white pigment may be included only in the base material, may be included only in the surface protective layer, or may be included in the base material and the surface protective layer.
In the present invention, the base material is preferably a colored resin base material containing a white pigment. By using a resin base material colored with a white pigment, when the surface hue of the adherend to which the decorative sheet is stuck varies, the surface hue is easily concealed and a better design can be obtained. The stability of the color tone of the decorative layer provided as desired can be improved.

Examples of the white pigment include titanium oxide (titanium white), lead white, antimony white, titanium dioxide-coated mica, and the like, and these can be used alone or in combination. In the present invention, titanium oxide (titanium white) is preferable in consideration of concealability (color development), ease of handling, and the like.
Titanium oxide includes anatase type, brookite type, and rutile type, and any of them can be used. However, in view of weather resistance, the rutile type is preferable. Since rutile type titanium oxide has low photocatalytic activity, even if it is used in an environment exposed to direct sunlight, the photocatalytic reaction is unlikely to occur, and the base material and surface protective layer formed by the photocatalytic reaction and other optional layers are not provided. Deterioration hardly occurs, and as a result, the weather resistance is improved.

The white pigment is preferably surface-treated in consideration of the influence on weather resistance. Preferred examples of the surface-treated white pigment include those that have been surface-treated with an inorganic metal hydroxide and the surface is covered with inorganic hydroxide oxide fine particles. Preferred examples of the inorganic metal hydrous oxide include alumina, silica, titania, zirconia, tin oxide, antimony oxide, zinc oxide and the like. In addition, a titanium oxide whose surface is not treated, or a titanium oxide surface-treated with the above inorganic metal hydrous oxide, a coupling agent such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or a silicone oil A surface treatment with a fluorine-based oil or the like to make the surface hydrophobic or lipophilic is also preferable. In the present invention, a white pigment that has been subjected to the above surface treatment alone or a combination of a plurality of surface treatments can be used.
In the present invention, from the viewpoint of obtaining excellent concealability, surface treatment with alumina, silica and zinc oxide is preferred, surface treatment with alumina and silica is more preferred, and surface treatment with alumina and silica is particularly preferred.

  The average particle size of the primary particles of the white pigment is preferably 0.02 μm or more and 1.5 μm or less, more preferably 0.15 μm or more and 0.5 μm or less, and further preferably 0.1 μm or more and 0.3 μm or less. When the average particle diameter of the white pigment is within the above range, excellent color development can be obtained, and design properties can be obtained with high concealability. Here, an average particle diameter is a value which can be calculated | required as the mass average value D50 in the particle size distribution measurement by a laser beam diffraction method.

When the substrate is a colored resin substrate containing a white pigment, there is no particular limitation on the coloring mode, and it may be transparent coloring or opaque coloring (hiding coloring). Can be arbitrarily selected. For example, when the ground color of an adherend such as a steel plate to which a decorative sheet is attached is colored and concealed, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend used for the decorative material visible, it is sufficient to select transparent coloring.
The content of the white pigment may be appropriately adjusted depending on whether it is transparent coloring or opaque coloring (concealing coloring). For example, it is 1 part by mass or more and 50 parts by mass with respect to 100 parts by mass of the resin constituting the substrate. The mass is preferably 3 parts by mass or more, more preferably 3 parts by mass or more and 40 parts by mass or less, still more preferably 5 parts by mass or more and 30 parts by mass or less, and particularly preferably 5 parts by mass or more and 20 parts by mass or less.

  The base material may contain a colorant other than the white pigment. For example, inorganic pigments such as iron black, yellow lead, titanium yellow, petal, cadmium red, ultramarine, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; scaly forms such as aluminum and brass Examples thereof include metal pigments composed of foil pieces; colorants such as pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate.

  An additive may be blended in the base material as necessary. Examples of the additive include inorganic fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive is not particularly limited as long as it does not impair the processing characteristics, and can be appropriately set according to the required characteristics.

From the viewpoint of improving the weather resistance of the decorative sheet of the present invention, among the additives, weathering agents such as an ultraviolet absorber and a light stabilizer are preferably used, and a light stabilizer is preferably used.
Since the base material is a layer located between the surface protective layer and the adherend when it is used as a decorative material, it affects the deterioration of weather resistance due to bleeding out of weathering agents such as UV absorbers and light stabilizers. Can be said to be smaller than other layers. There is no restriction | limiting in particular as an ultraviolet absorber used for a base material, For example, a benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, a triazine type ultraviolet absorber, etc. are mentioned. Further, for example, hydroxyphenyl triazine-based ultraviolet absorbers exemplified as those particularly preferably used for the intermediate resin layer described later, and further, a hydroxyphenyl triazine-based ultraviolet absorber represented by a specific general formula (1) are also preferably used. it can.

  As the light stabilizer, a hindered amine light stabilizer is preferable. For example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl (meta ) Acrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4) -Piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl) ami No] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxylate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxy-benzyl) -2-n-butylmalonate Etc. Among these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2) , 2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl- A hindered amine light stabilizer derived from decanedioic acid (sebacic acid) such as 4-piperidinyl) sebacate is preferred.

  These ultraviolet absorbers and light stabilizers can be used alone or in combination. Further, as exemplified above as one of the light stabilizers, the ultraviolet absorber and the light stabilizer are, for example, reactive functional groups having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. It may have a group.

  The content of the ultraviolet absorber in the substrate is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.2 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the resin constituting the substrate. More preferably, it is 0.3 parts by mass or more and 2 parts by mass or less. The content of the light stabilizer in the base material is preferably 0.5 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the resin constituting the base material. More preferably, 3 parts by mass or more and 6 parts by mass or less. When the contents of the ultraviolet absorber and the light stabilizer in the substrate are within the above ranges, an excellent additive effect can be obtained without bleeding out.

The base material may have any structure of a single layer of the above resin or a multilayer of the same kind or different kind of resin.
The thickness of the substrate is preferably 20 μm or more and 150 μm or less, more preferably 25 μm or more and 120 μm or less, further preferably 30 μm or more and 100 μm or less, and particularly preferably 40 μm or more and 80 μm or less, particularly considering processing characteristics.

In addition, for improving the interlaminar adhesion between the substrate and other layers, and for enhancing the adhesion with various adherends, the base material has an oxidation method, an unevenness method, etc. on one side or both sides. Surface treatment such as physical surface treatment or chemical surface treatment can be performed.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method, and the like. Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the substrate, but generally, a corona discharge treatment method is preferably used from the viewpoint of the effect of surface treatment and operability.
In addition, in order to improve the interlayer adhesion between the substrate and other layers, to enhance the adhesion to various adherends, and to suppress deterioration due to white pigment, etc., a primer layer on the substrate and a back primer layer You may perform the process of forming. These primer layers will be described later.

(Intermediate resin layer)
The intermediate resin layer is a layer provided between the base material and the surface protective layer, contains an ultraviolet absorber, and the content (M ₁ ) is the content of the ultraviolet absorber in the surface protective layer ( It is a layer that needs to be larger than M ₂ ).
The intermediate resin layer may have a single layer structure or a multilayer structure having at least two layers. For example, it is preferable to have a resin layer and a primer layer from the viewpoint of improving performance as a decorative sheet.

(Resin layer)
The resin layer is a layer that is preferably provided from the viewpoint of protection of a decoration layer, which will be described later, processing characteristics, and scratch resistance. The resin layer preferably contains an ultraviolet absorber. When the intermediate resin layer has a single layer structure, the resin layer needs to contain an ultraviolet absorber. When the resin layer contains an ultraviolet absorber, more excellent weather resistance can be obtained.
Preferred examples of the resin constituting the resin layer include polyolefin resins, polyester resins, acrylic resins, polycarbonate resins, polyurethane resins, polystyrene resins, vinyl chloride resins, vinyl acetate resins, and the like. Among these, from the viewpoint of improving processing characteristics and scratch resistance and weather resistance, polyolefin resins and polyester resins are preferable, and polyolefin resins are more preferable. Examples of the polyolefin resin include resins exemplified as those capable of constituting a substrate, and among them, a polypropylene resin is preferable.

When the decorative sheet of the present invention has a decorative layer, the resin layer is provided between the decorative layer and the surface protective layer from the viewpoint of protecting the decorative layer, that is, the intermediate resin layer includes the decorative layer and the surface protective layer. It is preferable to be provided between.
The resin layer may be transparent or opaque, and when provided between the decorative layer and the surface protective layer, the resin layer is preferably transparent from the viewpoint of making the decorative layer visible more clearly. Here, the term “transparent” includes colorless and transparent as well as colored and translucent. Moreover, when it is colored, as the colorant used, the same colorants as those used for the above-mentioned substrate are preferably mentioned, and a white pigment can be preferably used.

  Examples of the ultraviolet absorber used for the resin layer include the ultraviolet absorbers exemplified as those that can be used for the substrate, such as benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Among the ultraviolet absorbers, a hydroxyphenyl triazine ultraviolet absorber in which at least one organic group selected from a hydroxyphenyl group, an alkoxyphenyl group and an organic group containing these groups is connected to the triazine ring is more preferable. A hydroxyphenyltriazine-based ultraviolet absorber represented by the following general formula (1) is more preferred. Since the hydroxyphenyltriazine-based ultraviolet absorber has a branched structure, it is expected to be difficult to bleed out from the intermediate resin layer, and excellent weather resistance can be obtained in the long term.

In General Formula (1), R ¹¹ is a divalent organic group, R ¹² is an ester group represented by —C (═O) OR ¹⁵ , and R ¹³ , R ^14, and R ¹⁵ are each independently It is a monovalent organic group, and n ₁₁ and n ₁₂ are each independently an integer of 1 to 5.

Examples of the divalent organic group represented by R ¹¹ include an aliphatic hydrocarbon group such as an alkylene group and an alkenylene group. From the viewpoint of weather resistance, an alkylene group is preferable, and the number of carbon atoms is preferably 1 or more and 20 or less. 1 or more and 12 or less are more preferable, 1 or more and 8 or less are still more preferable, and 1 or more and 4 or less are especially preferable. The alkylene group and alkenylene group may be linear, branched or cyclic, but are preferably linear or branched.
Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,3-propylene, 1,2-propylene, and 2,2-propylene. Various propylene groups (hereinafter, “various” indicates linear, branched, and isomers thereof), various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, Various octylene groups, various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecylene groups, various icosylene groups Groups.

Examples of the monovalent organic group for R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group, and an aromatic hydrocarbon group such as an aryl group and an arylalkyl group includes An aryl group is preferable. Among these, as the monovalent organic group for R ¹³ and R ¹⁴ , a phenyl group is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms, such as a phenyl group, various methylphenyl groups, and various ethylphenyl groups. Groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, and the like. The arylalkyl group is preferably an arylalkyl group having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and still more preferably 7 to 10 carbon atoms, such as a benzyl group, a phenethyl group, and various phenylpropyl groups. Groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, various hexylbenzyl groups, and the like.

Examples of the monovalent organic group for R ¹⁵ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group, and the like, and an aliphatic hydrocarbon group such as an alkyl group and an alkenyl group is preferable. Is more preferable. That is, R ¹² is preferably an alkyl ester group or an alkenyl ester group, and more preferably an alkyl ester group.
The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as a methyl group, an ethyl group, various propyl groups, various butyl groups, various kinds. Pentyl group, various hexyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups And various nonadecyl groups and various icosyl groups.
The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 3 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as a vinyl group, various propenyl groups, various butenyl groups, various pentenyl groups, Various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadecenyl groups Groups and various icosenyl groups.

More specifically, as the hydroxyphenyltriazine compound represented by the general formula (1), R ¹¹ is an alkylene group having 1 to 20 carbon atoms, and R ¹² and R ¹⁵ are alkyl having 1 to 20 carbon atoms. An alkyl ester group which is a group, R ¹³ and R ¹⁴ are aryl groups having 6 to 20 carbon atoms, n ₁₁ and n ₁₂ are preferably hydroxyphenyl triazine compounds having 1 and R ¹¹ is 1 to 12 carbon atoms. The following alkylene groups, R ¹² and R ¹⁵ are alkyl ester groups having 2 to 16 carbon atoms, R ¹³ and R ¹⁴ are aryl groups having 6 to 12 carbon atoms, and n ₁₁ And a hydroxyphenyltriazine compound in which n ₁₂ is 1 is more preferable, R ¹¹ is an alkylene group having 1 to 8 carbon atoms, and R ¹² Is an alkyl ester group which is R ¹⁵ and an alkyl group having 6 to 12 carbon atoms, R ¹³ and R ¹⁴ are aryl groups having 6 to 10 carbon atoms, and n ₁₁ and n ₁₂ are 1 hydroxyphenyltriazine More preferably, the compound is an ester group in which R ¹¹ is an alkylene group having 1 to 4 carbon atoms, R ¹² and R ¹⁵ are alkyl groups having 8 carbon atoms, R ¹³ and R ¹⁴ are phenyl groups, n ₁₁ and _{n 12} is hydroxyphenyl triazine compound of 1 is particularly preferable.

More specifically, the hydroxyphenyltriazine compound represented by the general formula (1) is an ester group represented by the following chemical formula (2), wherein R ¹¹ is an ethylene group, and R ¹² and R ¹⁵ are isooctyl groups. Wherein R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n ₁₂ are 1, a hydroxyphenyl triazine compound, that is, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4, 6-bis (4-phenylphenyl) -1,3,5-triazine is preferred, and this hydroxyphenyltriazine compound is available as, for example, a commercial product (“TINUVIN479”, manufactured by BASF).

  The content of the ultraviolet absorber in the resin layer is preferably 0.1 parts by mass or more and 15 parts by mass or less, and 0.2 parts by mass with respect to 100 parts by mass of the resin constituting the resin layer, from the viewpoint of improving weather resistance. Part to 10 parts by mass is more preferable, and 0.3 part to 5 parts by mass is even more preferable.

  It is preferable that a resin layer contains a light stabilizer from a viewpoint of improving a weather resistance. As a light stabilizer, the light stabilizer illustrated as what can be used for a base material can be mentioned. The content of the light stabilizer can be exemplified by the same range as the content in the substrate from the viewpoint of improving the weather resistance.

  In addition, the resin layer may be blended with other additives in addition to weathering agents such as the above-described ultraviolet absorbers and light stabilizers, if necessary, additives that can be blended into the substrate, Examples thereof include inorganic fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants and foaming agents.

The thickness of the resin layer is preferably 10 μm or more and 150 μm or less, more preferably 30 μm or more and 120 μm or less, and even more preferably 50 μm or more and 100 μm or less from the viewpoints of protection of the decorative layer, processing characteristics, and improvement in scratch resistance and weather resistance.
Moreover, it is preferable to make it thicker than a base material sheet from a viewpoint of protecting a decoration layer and obtaining the outstanding scratch resistance.

The resin layer has a surface treatment such as a physical surface treatment such as an oxidation method or a roughening method, or a chemical surface treatment on one or both sides of the resin layer in order to improve interlayer adhesion between the resin layer and another layer. Can be applied. As these physical or chemical surface treatments, the same method as the above-mentioned surface treatment of the substrate is preferably exemplified.
In addition, in order to improve the interlayer adhesion between the resin layer and other layers, and further to suppress the effect on the weather resistance of the white pigment, a primer layer is formed on one or both sides of the resin layer. Processing may be performed. This primer layer will be described later.

(Primer layer)
The primer layer has different required effects depending on the location of the primer layer, and is mainly provided to improve the interlayer adhesion and to suppress the influence on the weather resistance of the white pigment. The primer layer preferably contains an ultraviolet absorber. When the intermediate resin layer has a single layer structure composed of a primer layer, it needs to contain an ultraviolet absorber. When the primer layer contains an ultraviolet absorber, more excellent weather resistance can be obtained.

For example, when the intermediate resin layer has a single layer structure of the primer layer and is provided between the base material and the surface protective layer, an effect of improving the interlayer adhesion between the base material and the surface protective layer can be obtained. In addition, when at least one of the base material and the surface protective layer contains a white pigment, there is a concern about weather resistance when the decorative sheet is used in an environment where it is exposed to direct sunlight. The influence on the weather resistance of the pigment is suppressed, and excellent weather resistance is obtained.
When the decorative layer is provided and the intermediate resin layer has a primer layer and a resin layer, and the primer layer is provided between the resin layer and the surface protective layer, the resin layer and the surface protection The effect of improving interlayer adhesion with the layer can be obtained. When at least one of the base material, the decoration layer, and the surface protective layer contains a white pigment, suppression of the influence on the weather resistance of the white pigment is suppressed, and excellent weather resistance is obtained. When the primer layer is provided between the decorative layer and the resin layer, an effect of improving the interlayer adhesion between the decorative layer and the resin layer can be obtained. Moreover, when a decoration layer contains a white pigment, the influence on the weather resistance of a white pigment is suppressed and the outstanding weather resistance is obtained.
From the above viewpoint, the intermediate resin layer preferably has a resin layer and a primer layer, and the decorative sheet of the present invention includes, for example, a base, an intermediate resin layer (resin layer, primer layer), and a surface protective layer in this order. It is preferable to have a base material, a decorative layer, an intermediate resin layer (resin layer, primer layer), and a surface protective layer in this order. The intermediate resin layer is also preferably a resin layer having a primer layer, a resin layer, and a primer layer in this order.

  For forming the primer layer, for example, a primer layer forming resin composition in which a weathering agent such as an ultraviolet absorber or a light stabilizer, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, or the like is appropriately mixed with the binder is used. It is done.

Examples of the UV absorber include UV absorbers exemplified as those that can be contained in the resin layer, for example, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, and the like. Among these agents, hydroxyphenyltriazine-based ultraviolet absorbers are more preferable, and hydroxyphenyltriazine-based ultraviolet absorbers represented by the following general formula (1) are more preferable.
The content of the ultraviolet absorber in the primer layer is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less, with respect to 100 parts by mass of the resin constituting the primer layer. The content is more preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or more and 25 parts by mass or less.

  The primer layer preferably contains a light stabilizer from the viewpoint of improving weather resistance. As a light stabilizer, the light stabilizer illustrated as what can be used for a base material can be mentioned. The content of the light stabilizer is preferably 0.5 parts by mass or more and 20 parts by mass or less, and preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin constituting the primer layer from the viewpoint of improving weather resistance. More preferably, it is 1.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 2 parts by mass or more and 8 parts by mass or less.

  Examples of the binder include those exemplified as the binder that can be used in the decorative layer, that is, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, Polycarbonate urethane-acrylic copolymer (urethane-acrylic copolymer derived from a polymer having a carbonate bond in the polymer main chain and having two or more hydroxyl groups in the terminal and side chains (polycarbonate polyol)), vinyl chloride Preferred examples include vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrified cotton), and cellulose acetate resins. These may be used alone or in combination. A combination of species can be used. For example, a mixture of a polycarbonate urethane-acrylic copolymer and an acrylic polyol resin can be used as a binder.

In addition to the one-component curing type, for example, curing of isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), xylylene diisocyanate (XDI), etc. Various types of resins, such as a two-component curable type with an agent, can be used.
In the present invention, from the viewpoint of containing more UV absorber in the intermediate resin layer, it is preferable to use a two-component curable resin as the binder used for forming the primer layer. By using a curable resin as a binder for the primer layer, it becomes possible to hold the UV absorber more firmly in the layer, and the hydroxyphenyl triazine UV absorber having the above branched structure is used as the UV absorber. Thus, since it is expected that the UV absorber is more strongly retained in the primer layer synergistically, more UV absorber can be contained.

  The thickness of the primer layer is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, from the viewpoint of improving interlayer adhesion, improving weather resistance, and further suppressing the effect on the weather resistance of the white pigment. More preferably, it is 3 μm or more and 6 μm or less.

(Surface protective layer)
The surface protective layer is a cured product of the curable resin composition, contains an ultraviolet absorber, and its content (M ₂ ) is more than the content (M ₁ ) of the ultraviolet absorber in the intermediate resin layer. It is a layer that needs to be small. The surface protective layer is a layer provided on the intermediate resin layer and located on the outermost surface of the decorative sheet of the present invention, and is a layer responsible for the development of surface characteristics such as scratch resistance as well as weather resistance.

The surface protective layer is composed of a cured product of a resin composition containing a curable resin.
As the curable resin used for forming the surface protective layer, an ionizing radiation curable resin or the like is preferably used in addition to a thermosetting resin such as a two-component curable resin. For example, ionizing radiation is used in combination. A so-called hybrid type may be used in which a curable resin and a thermosetting resin are used in combination, or a curable resin and a thermoplastic resin are used in combination.
As the curable resin, it is possible to increase the crosslink density of the resin constituting the surface protective layer and to suppress the bleed-out of the UV absorber not only in the surface protective layer but also in the intermediate resin layer, thereby obtaining excellent weather resistance. Furthermore, from the viewpoint of improving surface properties such as scratch resistance, ionizing radiation curable resins are preferred. Moreover, an electron beam curable resin is more preferable from the viewpoint that it can be applied without a solvent and is easy to handle.

(Ionizing radiation curable resin)
The ionizing radiation curable resin is a resin that crosslinks and cures when irradiated with ionizing radiation, and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. It is done. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Also included are electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams.
Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”.
Examples of the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group.
From the viewpoint of improving weather resistance and scratch resistance, and further processing characteristics, the number of functional groups is preferably 2 or more, 8 or less, more preferably 2 or more and 6 or less, further preferably 2 or more and 4 or less, and particularly preferably 2 or more and 3 or less. These polyfunctional (meth) acrylates may be used alone or in combination.

Examples of the polymerizable oligomer include a (meth) acrylate oligomer having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. Examples include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, acrylic (meth) acrylate oligomers, and the like.
Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  These polymerizable oligomers may be used alone or in combination of two or more. From the viewpoint of improving weather resistance and scratch resistance, and further processing characteristics, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate Oligomers and acrylic (meth) acrylate oligomers are preferred, urethane (meth) acrylate oligomers and polycarbonate (meth) acrylate oligomers are more preferred, and urethane (meth) acrylate oligomers are even more preferred.

The number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less from the viewpoint of improving weather resistance and scratch resistance, and further processing characteristics. The upper limit is more preferably 6 or less, and further preferably 4 or less. In particular, 3 or less is preferable.
Moreover, the weight average molecular weight of these polymerizable oligomers is preferably from 2,500 to 7,500, more preferably from 3,000 to 7,000, and even more preferably from 3,500 to 6,000. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted to standard polystyrene. In the present invention, by using a polymerizable oligomer having such a weight average molecular weight and having the number of functional groups, the bleedout of the UV absorber in the intermediate resin layer as well as the surface protective layer is suppressed, and more Excellent weather resistance can be obtained, and further, since the surface protective layer has an appropriate hardness, scratch resistance and processing characteristics can be improved.

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

  In the present invention, the ionizing radiation curable resin preferably contains a polymerizable oligomer from the viewpoint of improving weather resistance and scratch resistance, and further processing characteristics. The content of the polymerizable oligomer in the ionizing radiation curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

The surface protective layer needs to contain an ultraviolet absorber.
Examples of the UV absorber include UV absorbers exemplified as those that can be used for the substrate, for example, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, and the like. Of these, hydroxyphenyltriazine-based ultraviolet absorbers are more preferable, and hydroxyphenyltriazine-based ultraviolet absorbers represented by the general formula (1) are more preferable. Since the hydroxyphenyl triazine-based ultraviolet absorber has a branched structure, it is difficult to bleed out. Further, the hydroxyphenyl triazine-based ultraviolet absorber is further bleeded by a synergistic effect with the retention effect of the ultraviolet absorber by the cured product of the curable resin composition constituting the surface protective layer. Expected to be difficult to out, and excellent weather resistance can be obtained in the long term.

  Moreover, it is preferable that a light stabilizer is included from a viewpoint of improving the weather resistance of the decorative sheet of the present invention. As the light stabilizer, a hindered amine light stabilizer is preferable, and the hindered amine light stabilizer exemplified as the light stabilizer that can be used for the substrate can be used. From the viewpoint of weather resistance, decanedioic acid (sebacic acid) is derived. Hindered amine light stabilizers are preferred.

  These ultraviolet absorbers and light stabilizers can be used alone or in combination. Moreover, the ultraviolet absorber and the light stabilizer may have a reactive functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group.

Surface protective layer content of the ultraviolet absorber in (M _2), the content of the ultraviolet absorber of the intermediate resin layer is not particularly limited smaller than (M _1), but to obtain a more excellent weather resistance viewpoint From 0.1 parts by weight to 10 parts by weight, preferably 0.2 parts by weight to 5 parts by weight, more preferably 0.3 parts by weight to 3 parts by weight with respect to 100 parts by weight of the resin constituting the surface protective layer. Is more preferably 0.5 parts by mass or more and 2 parts by mass or less.
Further, the content of the light stabilizer in the surface protective layer is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface protective layer from the viewpoint of obtaining more excellent weather resistance. 0.5 parts by mass or more and 8 parts by mass or less are more preferable, 1 part by mass or more and 5 parts by mass or less are more preferable, and 1.5 parts by mass or more and 3 parts by mass or less are particularly preferable.

In the surface protective layer, as an additive, within the range that does not impair the object of the present invention, in addition to the above-mentioned ultraviolet absorbers, weathering agents such as light stabilizers, wear resistance improvers, polymerization inhibitors, crosslinking agents, infrared rays Absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, antiblocking agents, lubricants, solvents, colorants, etc. may be added. it can.
Moreover, as a coloring agent, it is preferable that the white pigment is contained as above-mentioned. In this case, the content of the white pigment in the surface protective layer is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface protective layer. 5 parts by mass or more and 10 parts by mass or less are more preferable.

Decorative sheet of the present invention, it is preferable Martens hardness of the surface protective layer is not more than 9N / mm ² or more 25 N / mm ^2. When the Martens hardness is within the above range, when the decorative sheet is subjected to processing such as bending, it becomes difficult for fine cracks to occur in the surface protective layer, and UV absorption in the surface protective layer is maintained even under long-term and severe environments. The bleeding out of the agent is suppressed, and further, the bleeding out of the ultraviolet absorber contained in the intermediate resin layer or the like is also suppressed. Therefore, excellent processing characteristics can be obtained together with excellent weather resistance. Further, when the Martens hardness is within the above range, when a white pigment is contained in the base material, the surface protective layer, etc., the influence on the weather resistance of the white pigment can be reduced, and excellent scratch resistance can be obtained.

In the present invention, the Martens hardness is specifically a value measured using an ultra-micro hardness meter, and at room temperature (23 ° C.), a pyramid-shaped diamond indenter is applied while continuously increasing the load. The surface area A (mm ² ) is calculated from the diagonal length of the pyramid-shaped depression formed on the surface (surface of the surface protective layer), and the test load F when the indentation depth reaches 2 μm ( This is a value calculated by dividing N) by the surface area A. For example, a micro hardness tester “Picodenter HM-500” (manufactured by Fischer Instrument Co.) may be used as the ultra micro hardness tester.

From the viewpoint of improving weather resistance, further processing characteristics and scratch resistance, the Martens hardness is preferably 10 N / mm ² or more and 22 N / mm ² or less, and more preferably 12 N / mm ² or more and 20 N / mm ² or less.

  The Martens hardness can be adjusted mainly by various configurations of the base material and the surface protective layer. For example, the Martens hardness can be arbitrarily selected from various configurations such as the material and thickness of the base material and the surface protective layer. The Martens hardness can be within the above range.

  The thickness of the surface protective layer is preferably 1.5 μm or more and 20 μm or less, more preferably 2 μm or more and 15 μm or less, and even more preferably 3 μm or more and 10 μm or less from the viewpoint of improving weather resistance, and further processing characteristics and scratch resistance.

(Decoration layer)
The decorative sheet of the present invention preferably has a decorative layer from the viewpoint of improving design properties. The decorative layer is not particularly limited as long as it is between the base material and the surface protective layer, but is preferably provided between the base material and the intermediate resin layer from the viewpoint of protecting the decorative layer.
The decorative layer may be, for example, a colored layer (so-called solid colored layer) covering the entire surface, or a pattern layer formed by printing various patterns using ink and a printing machine. It may be a combination thereof. For example, when the ground color of the adherend is colored and concealed, it is possible to improve the design property while concealing the color by making it a solid colored layer, and from the viewpoint of further improving the design property, solid coloring A layer and a pattern layer may be combined. On the other hand, when making use of the ground pattern of the adherend, only the pattern layer may be provided without using a solid colored layer.

As the ink used for the decoration layer, a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, or the like is appropriately used. Is done.
The binder is not particularly limited. For example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate urethane-acrylic copolymer (polymer main component) Urethane-acrylic copolymer derived from a polymer having a carbonate bond in the chain and having two or more hydroxyl groups in the terminal and side chains (polycarbonate polyol), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acetic acid Preferred examples include resins such as vinyl-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins, and these can be used alone or in combination. In addition to the one-component curing type, for example, curing of isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), xylylene diisocyanate (XDI), etc. Various types of resins, such as a two-component curable type with an agent, can be used.

  As the colorant, a white pigment exemplified as the colorant used for the substrate is preferably used from the viewpoint of concealing the background color of the adherend and improving the design. The content of the white pigment in the decoration layer is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the resin constituting the decoration layer. More preferred is 70 parts by mass or less.

  In addition, colorants other than white pigments, for example, inorganic pigments such as iron black, yellow lead, titanium yellow, petal, cadmium red, ultramarine, and cobalt blue; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; Colorants such as dyes; metallic pigments composed of scaly foils such as aluminum and brass; pearlescent pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate can also be used.

From the viewpoint of improving the weather resistance, the decorative layer preferably contains a weathering agent such as an ultraviolet absorber or a light stabilizer, and more preferably contains a light stabilizer.
Examples of the ultraviolet absorber and the light stabilizer include the ultraviolet absorber and the light stabilizer exemplified as those that can be contained in the substrate, the intermediate resin layer, and the surface protective layer. The content of the ultraviolet absorber can be exemplified by the same range as the content in the surface protective layer from the viewpoint of improving the weather resistance. Further, the content of the light stabilizer in the surface protective layer is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.2 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the resin constituting the surface protective layer. The following is more preferable, 0.3 to 3 parts by mass is further preferable, and 0.5 to 2 parts by mass is particularly preferable.

  In the case of having a pattern layer as a decoration layer, the pattern may be a wood grain pattern, a marble pattern (for example, travertine marble pattern), a stone pattern imitating the surface of a rock, a fabric pattern imitating a cloth or cloth pattern, or a tile There are pasting patterns, brickwork patterns, etc., and there are also patterns such as parquets and patchwork that combine these. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done.

  The thickness of the decoration layer may be appropriately selected according to the desired pattern, but is preferably 0.5 μm or more and 20 μm or less from the viewpoint of coloring and concealing the background color of the adherend and improving the design. It is more preferably 10 μm or less, and further preferably 2 μm or more and 5 μm or less.

(Back primer layer)
The decorative sheet of the present invention preferably has a primer layer (also referred to as a “back primer layer”) on the surface of the substrate opposite to the surface protective layer side. The effect of improving the interlayer adhesion between the substrate and the adherend can be obtained. Moreover, when a base material contains a white pigment, the effect which suppresses the influence to the adherend of a white pigment is acquired, and the outstanding weather resistance is acquired about a decorative sheet and a decorative material. In addition, this back surface primer is not a layer which can be contained in an intermediate | middle resin layer unlike said primer layer.

What is necessary is just to form a back surface primer layer using the resin composition which comprises the said primer layer, and may contain weathering agents, such as a ultraviolet absorber and a light stabilizer.
The thickness of the back primer layer is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, and further preferably 3 μm or more and 6 μm or less from the viewpoint of improving interlayer adhesion and suppressing the influence of the white pigment on the adherend. preferable.

(Adhesive layer)
The decorative sheet of the present invention can have an adhesive layer as necessary. In particular, when the decorative sheet of the present invention has a resin layer as an intermediate resin layer, it is effective to provide an adhesive layer in order to improve interlayer adhesion between the resin layer and the decorative layer. As an adhesive constituting the adhesive layer, an adhesive usually used in a decorative sheet can be used without limitation.

  Examples of the adhesive include urethane adhesives, acrylic adhesives, epoxy adhesives, and rubber adhesives. Among them, urethane adhesives are preferable in terms of adhesive strength. In addition, as a urethane type adhesive agent, the adhesive agent using two-component curable urethane resin containing various polyol compounds, such as polyether polyol, polyester polyol, an acrylic polyol, and hardening | curing agents, such as said various isocyanate compounds, is mentioned, for example. Is mentioned. Acrylic-polyester-vinyl acetate resins and the like are also suitable adhesives that can easily exhibit adhesiveness by heating and maintain adhesive strength even when used at high temperatures.

  The thickness of the adhesive layer is preferably from 0.1 μm to 30 μm, more preferably from 1 μm to 15 μm, and even more preferably from 2 μm to 10 μm from the viewpoint of obtaining sufficient adhesiveness.

(Concave)
The decorative sheet of the present invention preferably has a recess on the surface (also referred to as “surface on the surface side”) opposite to the substrate side surface of the surface protective layer. Since the decorative sheet of the present invention has a concave portion, a high-grade feeling associated with an improvement in texture (tactile feel) is obtained, and design properties are improved.

  As shown in FIG. 2, the concave portion only needs to exist on the surface of the surface protective layer opposite to the substrate side, and the depth of the concave portion may remain in the surface protective layer. In addition, there may be a material extending to the base material. From the viewpoint of obtaining an excellent texture (tactile sensation), it is preferable to combine not only those that remain in the surface protective layer but also those that reach the intermediate resin layer, those that reach the decorative layer, and those that reach the base material.

  The maximum depth D of the recesses and the total thickness T of the decorative sheet preferably have a relationship of 0.15 × T ≦ D ≦ T from the viewpoint of improving the design, that is, the depth D of the recesses The ratio D / T to the total thickness T of the decorative sheet is preferably 0.15 or more and 1 or less. From the same viewpoint, the relationship between the depth D of the recess and the total thickness T of the decorative sheet is more preferably 0.2 × T ≦ D ≦ 0.9 × T, and 0.25 × T ≦ More preferably, D ≦ 0.8 × T. That is, the ratio D / T between the depth D of the recess and the total thickness T of the decorative sheet is preferably 0.2 or more and 0.9 or less, and more preferably 0.25 or more and 0.8 or less.

  Further, the maximum depth of the concave portion can be relatively changed according to the total thickness T of the decorative sheet, but more specific depth is preferably 10 μm or more and 120 μm or less, more preferably 20 μm or more and 110 μm or less, 30 μm or more and 100 μm or less is more preferable. By having such a maximum depth, the decorative sheet will not be broken during the processing of the recess, for example, embossing, and the texture (tactile sensation) will not be finished as the recess is crushed. A sense of quality accompanying the improvement is obtained, and the design is improved.

  Here, the measurement of the maximum depth D of the concave portion is performed by measuring the height from the lowest point of the concave portion to the surface of the surface protective layer with respect to any 30 concave shapes using a surface roughness shape measuring machine. Cut-off value: 2.50 mm, cut-off filter type: 2RC, tilt correction method: measured under linear measurement conditions, with the deepest being the maximum depth.

  As a pattern of a recessed part, there are a grain board conduit groove, a stone board surface unevenness, a cloth surface texture, a satin texture, a grain, a hairline, a striated groove, etc., for example. From the viewpoint of improving the designability, it is preferable that the pattern of the recess is a pattern synchronized with the pattern of the decoration layer. For example, if the pattern layer is a wood grain pattern, selecting a wood grain plate conduit groove as the recess pattern, and synchronizing the grain of the pattern layer with the grain of the recess layer, it is more realistic and full of quality and has a high-class feeling A decorative sheet and a decorative material are obtained.

(Manufacturing method of decorative sheet)
About the manufacturing method of the decorative sheet of the present invention, which is one of the preferred embodiments as the decorative sheet of the present invention, a back primer layer, a substrate, a decorative layer, an adhesive layer, an intermediate resin layer (resin layer and primer layer), and a surface Taking a decorative sheet having a protective layer in order as an example, the production method will be described.
The decorative sheet of the present invention includes, for example, a step (1) of providing a decorative layer on a substrate, a step (2) of providing a resin layer on the decorative layer, and a curable resin composition on the resin layer, It can manufacture by passing through the process (3) which hardens | cures and forms a surface protective layer in order.

  Step (1) is a step of providing a decorative layer on the substrate. The decorative layer is formed by applying an ink used for forming the decorative layer on a base material to provide a desired colored layer and 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 surface treatment is applied to the base material, a decoration layer is formed. When a primer layer is provided between the base material and the decoration layer, it may be provided before the formation of the decoration layer. When providing a back surface primer layer in the surface (back surface) on the opposite side to the decoration layer side of a material, you may provide after formation of a decoration layer. The primer layer is formed by applying a resin composition constituting the 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 do.

  Step (2) is a step of providing a resin layer on the decorative layer. The resin layer is formed by applying an adhesive to the base material having the decorative layer as necessary to form an adhesive layer, and then using the resin composition constituting the resin layer to extrude and dry laminate the resin layer. It can be formed by laminating by adhesion and pressure bonding by methods such as wet lamination and thermal lamination.

When surface treatment is performed on the resin layer, the surface treatment may be performed after the resin layer is provided.
Moreover, when providing a primer layer between a resin layer and a surface protective layer, what is necessary is just to provide a primer layer using the resin composition which comprises a primer layer after providing a resin layer.

Step (3) is a step in which a curable resin composition is applied on the resin layer and cured to form a surface protective layer.
The surface protective layer is obtained by applying and curing an ionizing radiation curable resin composition containing the ionizing radiation curable resin on a resin layer or a primer layer provided on the resin layer as desired. It is done. In addition, when not providing a resin layer, after providing a decoration layer in a base material sheet, a curable resin composition may be apply | coated and hardened to form a surface protective layer.

  Application of the resin composition for forming the surface protective layer is preferably a known gravure coat, bar coat, roll coat, reverse roll coat, comma coat, etc. so that the thickness after curing is a predetermined thickness. More preferably, gravure coating is used.

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

The irradiation dose is preferably such that the crosslinking 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, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, 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. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

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

In the case where the concave portion is formed in the surface protective layer, it is preferable to employ embossing in consideration of easiness of work. The embossing may be performed by a normal method using a known single-wafer or rotary embossing machine.
When embossing, for example, the decorative sheet is preferably heated to 80 ° C. or higher and 260 ° C. or lower, more preferably 85 ° C. or higher and 160 ° C. or lower, more preferably 100 ° C. or higher and 140 ° C. or lower, and the embossed plate is pressed on the decorative sheet. Thus, embossing can be performed.

[Cosmetics]
The decorative material of the present invention has an adherend and the decorative sheet of the present invention, and specifically, a surface that requires decoration of the adherend and a surface on the base material side of the decorative sheet. They are stacked in opposition. That is, the decorative material of the present invention has at least an adherend, a base material, and a surface protective layer in this order. In FIG. 3, the schematic diagram which shows the cross section of an example of the preferable aspect of the decorative material of this invention is shown. The decorative material 20 of the present invention shown in FIG. 3 includes an adherend 21, an adhesive layer 22, and the decorative sheet 10 of the present invention in this order.

(Substrate)
Examples of the adherend include plate materials such as flat plates and curved plates, three-dimensional articles, sheets (or films), and the like. For example, wood members used as plate materials such as timber veneers, wood plywood, particle board, MDF (medium density fiber board) such as cedar, bamboo, pine, lauan, etc. Metal members used as plate materials such as iron and aluminum, steel plates, three-dimensional shaped articles, or sheets; Non-cement ceramic materials such as glass, ceramics such as ceramics, gypsum, and non-ceramics such as ALC (lightweight cellular concrete) plates Ceramic materials used as ceramic materials, etc., such as plate materials and three-dimensional shaped articles; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride Plate material such as resin, cellulose resin, rubber, three-dimensional article, or sheet Resin member or the like used as the like. Moreover, these members can be used individually or in combination of multiple types.

  The adherend may be appropriately selected from the above according to the intended use, such as interior materials for buildings such as walls, ceilings and floors, window frames, doors, handrails, skirting boards, surrounding edges, moldings such as malls, etc. When using artificial members, those made of at least one member selected from wooden members, metal members, and resin members are preferable. When using exterior members such as entrance doors, window frames, doors, and other fittings. Is preferably made of at least one member selected from a metal member and a resin member.

  What is necessary is just to select the thickness of a to-be-adhered material suitably according to a use and material, 0.1 mm or more and 10 mm or less are preferable, 0.3 mm or more and 5 mm are more preferable, 0.5 mm or more and 3 mm or less are still more preferable.

(Adhesive layer)
In order to obtain excellent adhesion, the adherend and the decorative sheet are preferably bonded together via an adhesive layer. That is, the decorative material of the present invention is preferably a member having at least an adherend, an adhesive layer, a base material, and a surface protective layer in this order.

It does not specifically limit as an adhesive agent used for an adhesive bond layer, A well-known adhesive agent can be used, For example, adhesive agents, such as a heat sensitive adhesive and a pressure sensitive adhesive, are mentioned preferably. Examples of the resin used for the adhesive constituting the adhesive layer include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acryl copolymer resin, and polyester resin. , Polyamide resins, and the like, and these can be used alone or in combination. Further, a two-component curable polyurethane adhesive or polyester adhesive using an isocyanate compound or the like as a curing agent can also be applied.
An adhesive can also be used for the adhesive layer. As the pressure-sensitive adhesive, an acrylic, urethane, silicone, rubber, or other pressure-sensitive adhesive can be appropriately selected and used.

The adhesive layer is formed by applying and drying the above resin in a form that can be applied, such as a solution or emulsion, by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. can do.
Although there is no restriction | limiting in particular in the thickness of an adhesive bond layer, from a viewpoint of obtaining the outstanding adhesiveness, 1 micrometer or more and 100 micrometers or less are preferable, 5 micrometers or more and 50 micrometers or less are more preferable, and 10 micrometers or more and 30 micrometers or less are still more preferable.

(Manufacturing method of cosmetic material)
A decorative material can be manufactured through the process of laminating a decorative sheet and an adherend.
This step is a step of laminating the adherend and the decorative sheet of the present invention, in which the surface that requires decoration of the adherend and the surface of the decorative sheet on the base material side are opposed to each other. Examples of the method of laminating the adherend and the decorative sheet include, for example, a laminating method in which a decorative sheet is pressed onto a plate-shaped adherend with a pressure roller and an adhesive is interposed therebetween. The decorative sheet is supplied through the wrapping process in which the decorative sheet is sequentially pressure-bonded and laminated on the plurality of side surfaces constituting the adherend by a plurality of different rollers, and fixed to the fixed frame. Heat up with a heater through a silicone rubber sheet until the decorative sheet softens, and press the vacuum molding die against the heated and softened decorative sheet. At the same time, suck air from the vacuum molding die with a vacuum pump. The vacuum forming process etc. which make a decorative sheet closely_contact | adhere to a vacuum forming die etc. are mentioned preferably.

  When a hot melt adhesive (heat sensitive adhesive) is used in laminating or wrapping, the heating temperature is preferably 160 ° C. or higher and 200 ° C. or lower depending on the type of resin constituting the adhesive. For the adhesive, 100 ° C. or higher and 130 ° C. or lower is preferable. Moreover, in the case of a vacuum forming process, it is common to carry out with heating, 80 to 130 degreeC is preferable, More preferably, it is 90 to 120 degreeC.

  The decorative material obtained as described above can be arbitrarily cut and subjected to optional decoration such as grooving and chamfering on the surface and the end of the mouth using a cutting machine such as a router or a cutter. Moreover, after sticking a decorative sheet to a steel plate or the like, bending processing such as V-cut processing or lapping processing can also be performed. And various uses, for example, interior materials or exterior members of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, edges, moldings, and other furniture, furniture, kitchens, furniture Or it can use for the surface decorative board of cabinets, such as a weak electrical product and OA apparatus, the interior material of a vehicle, or an exterior member.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation and measurement method)
(1) Evaluation of weather resistance About the decorative material obtained in each Example and Comparative Example, using a sunshine weather meter ("WEL-300", manufactured by Suga Test Instruments Co., Ltd.), a black panel temperature of 63 ° C, 120 minutes A weathering test was conducted by leaving it for 6000 hours under the condition of middle 18 minutes rain. The appearance of the decorative material after the weather resistance test was visually observed and evaluated according to the following criteria. In addition, in this specification, when “+” is described together with the following criteria in the table, “+” means “better, but it does not lead to a one-step evaluation”. . For example, “B ⁺ ” is superior to “B”, but does not reach “A”.
A: Appearance change was not confirmed.
B: A very slight color change was confirmed.
C: A slight change in color tone was confirmed.
D: At least one of remarkable color tone change, floating between layers, and cracking was confirmed.
(2) Evaluation of scratch resistance For the decorative sheets obtained in each of the examples and comparative examples, 300 g / m of steel wool ("Bonster # 0000", manufactured by Nippon Steel Wool Co., Ltd.) is used on the surface. ^A rubbing test was performed by 10 reciprocations with a load of ² . The surface condition after the test was visually observed and evaluated according to the following criteria.
A: There was no damage and no change in gloss was confirmed.
B: Very slight scratches and very slight changes in gloss were confirmed.
C: Minor scratches and slight changes in gloss were confirmed.
D: Scratches were confirmed, and significant gloss change was confirmed.
(3) Evaluation of processing characteristics (lapping process) About the decorative material obtained by each Example and the comparative example, the state of the corner | angular part (bending part) was observed visually, and the following references | standards evaluated.
A: Appearance change was not confirmed in a corner | angular part (bending part).
B: Slight whitening was confirmed at the corner (bending portion), but no crack was confirmed.
C: Slight whitening and cracks were confirmed at the corners (bending parts).
D: Remarkable whitening and cracks were confirmed at the corner (bending portion).
(4) Evaluation of design property About the decorative material obtained by each Example and the comparative example, the design property was evaluated on the following references | standards.
A: High designability due to excellent texture due to the recess was confirmed.
B: Sufficient design properties were confirmed due to the texture of the recesses.
C: Although the texture by a recessed part is few, the designability was confirmed.
D: There was no texture by a recessed part and the design property was low.
(5) Measurement of Martens hardness About the decorative sheet obtained by each Example and the comparative example, Martens hardness was measured with the following method.
Using an ultra-micro hardness tester (micro-hardness tester, “Picodenter HM-500”, manufactured by Fischer Instruments Co., Ltd.), pyramidal diamonds while increasing the load continuously at room temperature (23 ° C.) The indenter is pushed into the sample (surface of the surface protective layer), the test load F (N) when the indentation depth reaches 2 μm is measured, and the surface area A is calculated from the length of the diagonal of the pyramidal depression formed on the surface. Martens hardness was calculated by calculating (mm ² ) and dividing the test load F (N) by the surface area A.

Example 1
Polypropylene resin sheet (thickness: 60 μm, white colored resin sheet (white pigment: rutile titanium oxide (average particle size: 0.25 μm), content: 10 mass%)) subjected to double-sided corona discharge treatment as a base material And gravure printing on one surface of the substrate with a two-component curable acrylic-urethane resin binder (containing 40% by mass of rutile titanium oxide (average particle size: 0.25 μm) as a white pigment) Apply the coating method to provide a wood grain decorative layer (thickness: 3 μm), and apply the two-component curable urethane-nitrified cotton mixed resin composition on the other side to form the back primer layer (thickness: 2 μm) did.
A transparent polyurethane resin adhesive is applied on the decorative layer to form an adhesive layer (thickness after drying: 3 μm), and the transparent polypropylene resin is heated and melt-extruded by a T-die extruder to obtain a transparent layer. A resin layer (thickness: 80 μm) was formed.
Next, after subjecting the surface of the resin layer to corona discharge treatment, a composition obtained by mixing 100 parts by mass of the following primer layer-forming resin composition and 5 parts by mass of hexamethylene diisocyanate (curing agent) is obtained by a gravure printing method. Was applied to form a primer layer (thickness after drying: 4 μm).
Further, the following ionizing radiation curable resin composition is applied onto the primer layer by a roll coating method to form an uncured resin layer, and irradiated with an electron beam (pressurized voltage: 175 KeV, 5 Mrad (50 kGy)). The uncured resin layer was cured to obtain a surface protective layer (thickness: 5 μm). Thereafter, embossing was performed from the surface protective layer side to form a wood grain conduit pattern having a concave portion with a maximum depth of 50 μm to obtain a decorative sheet.

  A polyurethane-based heat-sensitive adhesive (hot melt adhesive, “PUR704”, manufactured by Kreiberit Japan Co., Ltd.) is applied to the base material of the obtained decorative sheet to form an adhesive layer (thickness: 20 μm) and bonded. Before the agent layer is solidified, the decorative sheet is made to follow the L-shaped adherend (material: vinyl chloride), and the adherent and the decorative sheet are adhered to produce the decorative material. did. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

(Primer layer forming resin composition)
Binder: Mixture of polycarbonate urethane-acrylic copolymer and acrylic polyol resin UV absorber A: 3% by mass of hydroxyphenyltriazine compound (“TINUVIN479”, manufactured by BASF) represented by the above general formula (2) (of the above resin) (3.7 parts by mass with respect to 100 parts by mass of the mixture)
Ultraviolet absorber B: Hydroxyphenyltriazine compound represented by the following general formula (3) (“TINUVIN400”, manufactured by BASF) 12% by mass (14.6 parts by mass with respect to 100 parts by mass of the above resin mixture)

Light stabilizer a: Hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, “TINUVIN123”, manufactured by BASF) 3% by mass
(Ionizing radiation curable resin composition)
Ionizing radiation curable resin A: urethane acrylate oligomer (weight average molecular weight: 4,000, number of functional groups: 3)
Ultraviolet absorber A: Hydroxyphenyltriazine compound represented by the above general formula (2) (“TINUVIN479”, manufactured by BASF) 1% by mass (1.0 part by mass with respect to 100 parts by mass of the resin mixture)
Light stabilizer a: hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, “TINUVIN123”, manufactured by BASF) 2% by mass

Examples 2 and 3
In Example 1, the cosmetics of Examples 2 and 3 were the same as Example 1 except that the ionizing radiation curable resins in the ionizing radiation curable resin composition were changed to the following ionizing radiation curable resins B and C. Sheets and decorative materials were prepared. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.
Ionizing radiation curable resin B: urethane acrylate oligomer (weight average molecular weight: 7,000, number of functional groups: 3)
Ionizing radiation curable resin C: urethane acrylate oligomer (weight average molecular weight: 3,000, number of functional groups: 3)

Example 4
In Example 1, the above-mentioned light stabilizer a (hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate), “TINUVIN123”, manufactured by BASF A decorative sheet and a decorative material were produced in the same manner as in Example 1 except that 1% by mass)) was added. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Example 5
In Example 1, the above-described light stabilizer a (hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate) was added to the printing ink used for forming the decorative layer. A decorative sheet and a cosmetic material were produced in the same manner as in Example 1 except that “TINUVIN123” (manufactured by BASF)) was contained in an amount of 1% by mass. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Example 6
In Example 1, the light stabilizer a (hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)) was added to the printing ink used for forming the base material and the decorative layer. A decorative sheet and a cosmetic material were produced in the same manner as in Example 1 except that 1% by mass of Sebacate, “TINUVIN123” (manufactured by BASF) was included. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Example 7
In Example 1, the resin composition for forming the primer layer was replaced with a resin composition not containing the light stabilizer a, and the embossing with a maximum depth of 140 μm was performed in the same manner as in Example 1. A decorative sheet and a decorative material were prepared. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Example 8
In Example 1, the ultraviolet absorber A in the ionizing radiation curable resin composition was changed to an ultraviolet absorber C (benzotriazole-based ultraviolet absorber, 2- (5-chloro-benzotriazolyl) -6-tert-butyl- A decorative sheet and a decorative material of Example 8 were produced in the same manner as in Example 1 except that p-cresol, “TINUVIN 326” (manufactured by BASF) was used. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Example 9
In Example 1, a decorative sheet and a decorative material were produced in the same manner as in Example 1, except that embossing with a maximum depth of the concave portion of 10 μm was performed. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Example 10
In Example 1, 3 mass% and 12 mass% of the ultraviolet absorbers A and B in the resin composition for forming a primer layer were set to 3.1 mass% and 6.9 mass%, respectively (into 100 mass parts of resin) In contrast, 3.6 mass parts and 7.9 mass parts, respectively, total 11.5 mass parts), and 1 mass% of the ultraviolet absorber A in the ionizing radiation curable resin composition is 7.1 mass%. A decorative sheet and a decorative material were produced in the same manner as in Example 1, except that the amount was 7.8 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Example 11
In Example 1, a decorative sheet and a cosmetic material were produced in the same manner as in Example 1 except that 3 parts by mass of the ultraviolet absorber A was added to 100 parts by mass of the polypropylene resin. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Comparative Example 1
In Example 1, a decorative sheet and a cosmetic material were produced in the same manner as in Example 1 except that the ultraviolet absorbent A in the ionizing radiation curable resin composition was omitted. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

Comparative Example 2
In Example 1,
The contents of the UV absorbers A and B in the primer layer-forming resin composition are both 1% by mass (1.1 parts by mass and 1.1 parts by mass with respect to 100 parts by mass of the resin, respectively, for a total of 2.2). Mass part), and the content of the ultraviolet absorber A in the ionizing radiation curable resin composition was set to 15% by mass (18.1 parts by mass with respect to 100 parts by mass of the resin). A decorative sheet and a decorative material were prepared. Said evaluation is performed about the obtained decorative sheet and a decorative member, and the evaluation result is shown in Table 1.

From the results of Examples 1 to 11, it was confirmed that the decorative sheet of the present invention and the decorative material using the decorative sheet are excellent in weather resistance. Moreover, it was confirmed that it is excellent also in scratch resistance, processing characteristics, and design properties. From the comparison between Examples 1 and 10, when the content of the ultraviolet absorber contained in the decorative sheet is the same, Example 1 in which the content of the ultraviolet absorber contained in the intermediate resin layer is higher. It was confirmed that the weather resistance was excellent. Moreover, it was confirmed from the comparison with Example 1 and 11 that the more excellent weather resistance is obtained by containing a ultraviolet absorber in the resin layer in an intermediate resin layer.
In Example 8, the ultraviolet absorber in the ionizing radiation curable resin composition was a benzotriazole-based ultraviolet absorber, but by comparison with other examples, a hydroxyphenyltriazine compound, particularly represented by the general formula (2), was used. It was confirmed that better weather resistance can be obtained by using a specific hydroxyphenyltriazine compound.
Moreover, about recessed part maximum depth (D), 50 micrometers (the recessed part maximum depth (D) is decorative sheet thickness (T) and (D) = 0.32 * (T) ((D) / (T) = 0.32))) and 140 μm ((D) = 0.90 × (T), (D) / (T) = 0.90). The decorative sheet of Example 7 has a richer texture than that of Example 9 with 10 μm ((D) = 0.06 × (T), (D) / (T) = 0.06). It was confirmed that it was excellent in design.

  On the other hand, the decorative sheet of Comparative Example 1 which does not contain an ultraviolet absorber in the surface protective layer does not provide weather resistance, and the content of the ultraviolet absorber in the primer layer is the content of the ultraviolet absorber in the surface protective layer. The weather resistance of the decorative sheet of Comparative Example 2 smaller than the amount was not obtained.

  The decorative sheet of the present invention has excellent processing characteristics, weather resistance and scratch resistance, and a decorative material using the decorative sheet has excellent weather resistance and scratch resistance. Therefore, in addition to interior or exterior members of buildings such as walls, ceilings and floors, window frames, doors, handrails, skirting boards, edges, moldings, and other fittings or construction parts, kitchens, furniture or light electrical appliances, OA It is suitably used for a surface decorative plate of a cabinet such as a device, an interior material or exterior member of a vehicle. In particular, by using its excellent scratch resistance and weather resistance, it is suitably used for members used in an environment exposed to direct sunlight, such as exterior members such as entrance doors, window frames, doors and other fittings.

10. Cosmetic sheet 11. Base material 12. Decorative layer 13. Adhesive layer 14. Intermediate resin layer 14a. Resin layer 14b. Primer layer 15. Surface protective layer 16. Back primer layer 17. UV absorber 18. White pigment 19. Recess 20. Cosmetic material 21. Substrate 22. Adhesive layer

Claims (22)

It has a base material, an intermediate resin layer, and a surface protective layer in order, the surface protective layer is a cured product of the curable resin composition, the intermediate resin layer and the surface protective layer contain an ultraviolet absorber, The ultraviolet absorber content (M ₁ ) relative to 100 parts by mass of the resin constituting the intermediate resin layer is greater than the ultraviolet absorber content (M ₂ ) relative to 100 parts by mass of the resin constituting the surface protective layer. Makeup sheet. The decorative sheet according to claim 1, wherein the total (M ₁ + M ₂ ) of the content (M ₁ ) and the content (M ₂ ) is 0.5 parts by mass or more and 40 parts by mass or less. The decorative sheet according to claim 1 or 2, wherein a ratio (M ₁ / M ₂ ) between the content (M ₁ ) and the content (M ₂ ) is 1.1 or more and 35 or less.   The decorative sheet according to any one of claims 1 to 3, wherein at least one of the substrate and the surface protective layer contains a white pigment.   The decorative sheet according to any one of claims 1 to 4, further comprising a decorative layer between the base material and the surface protective layer, wherein at least one of the base material and the decorative layer contains a white pigment.   The decorative sheet according to claim 5, wherein the base material and the decorative layer contain a white pigment.   The decorative sheet according to any one of claims 4 to 6, wherein the white pigment is titanium oxide.   The decorative sheet according to claim 7, wherein the titanium oxide is a rutile type titanium oxide.   The decorative sheet according to any one of claims 4 to 8, wherein the content of the white pigment in the substrate is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin constituting the substrate.   The decorative sheet according to any one of claims 5 to 8, wherein the content of the white pigment in the decoration layer is 5 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the resin constituting the decoration layer.   The decorative sheet according to any one of claims 1 to 10, wherein the ultraviolet absorber contained in at least one of the intermediate resin layer and the surface protective layer contains a triazine-based ultraviolet absorber. The decorative sheet according to claim 11, wherein the triazine-based ultraviolet absorber contains a hydroxyphenyltriazine compound represented by the following general formula (1).

(In the general formula (1), R ¹¹ is a divalent organic group, R ¹² is an ester group represented by —C (═O) OR ¹⁵ , and R ¹³ , R ¹⁴ and R ¹⁵ are each independently And n ₁₁ and n ₁₂ are each independently an integer of 1 to 5.) The ultraviolet absorber is an alkyl ester group in the general formula (1), wherein R ¹¹ is an alkylene group having 1 to 20 carbon atoms, and R ¹² and R ¹⁵ are alkyl groups having 1 to 20 carbon atoms, ^13. The decorative sheet according to claim 12, wherein R ¹³ and R ¹⁴ are aryl groups having 6 to 20 carbon atoms, and n ₁₁ and n ₁₂ are 1 hydroxyphenyl triazine compounds.   The decorative sheet according to any one of claims 1 to 13, wherein the curable resin is an ionizing radiation curable resin.   The curable resin is an ionizing radiation curable resin containing a urethane (meth) acrylate oligomer having a functional group number of 2 or more and 8 or less and a weight average molecular weight of 2,500 or more and 7,500 or less. The decorative sheet according to claim 1.   The decorative sheet according to any one of claims 1 to 15, wherein at least one of the substrate and the surface protective layer contains a light stabilizer.   The decorative sheet according to any one of claims 5 to 16, wherein the decorative layer contains a light stabilizer.   The decorative sheet according to claim 16 or 17, wherein the light stabilizer is a hindered amine light stabilizer.   The decorative sheet according to any one of claims 1 to 18, wherein the decorative sheet has a concave portion on the surface opposite to the surface on the substrate side of the surface protective layer.   The decorative sheet according to claim 19, wherein the maximum depth D of the concave portion and the thickness T of the decorative sheet have a concave portion having a relationship of 0.15 × T ≦ D ≦ T.   A decorative material comprising an adherend and the decorative sheet according to any one of claims 1 to 20.   The decorative material according to claim 21, wherein the adherend comprises at least one member selected from a metal member and a resin member.