JP4156226B2 - Decorative sheet - Google Patents

Description

【００５９】
結果は、表１に示す如く、架橋したポリブタジエン樹脂層を少なくとも表面に有する実施例１〜実施例３は、いずれも、耐スクラッチ性、耐衝撃性、エンボス堅牢度、及び成形性の全てに於いて良好となった。しかし、比較例では、これら全ての性能を満たすものは無かった。
すなわち、実施例１に対してポリブタジエン樹脂層をＰＰ層に代えた比較例１は、耐衝撃性は良好であったが、耐スクラッチ性、エンボス堅牢度、及び成形性が不良となった。また、実施例１に対してポリブタジエン樹脂層をＰＰ層に代え、且つこのＰＰ層の上に表面保護層を設けた比較例２では、耐スクラッチ性は良くなるが、耐衝撃性が不良となり、残るエンボス堅牢度及び成形性も不良であった。また、実施例１に対して、ポリブタジエン樹脂層に対して電子線照射による架橋を施さなかった比較例３は、耐衝撃性及び成形性は良好であったが、耐スクラッチ性とエンボス堅牢度が不良となった。
【００６０】
【発明の効果】
（１）本発明の化粧シートによれば、表面に表面保護層を設ける事なく、耐スクラッチ性及び耐衝撃性が良好となる。しかも、同時に成形性も得られる。
（２）更に、最表面に凹凸模様を形成した構成では、より高意匠となる上、凹凸模様の凹凸形状が化粧シート成形時等の加熱により鈍化しない様なエンボス堅牢度も得られる。
（３）更に、ポリブタジエン樹脂層が、透明層のみ、又は透明層と不透明層との組合わせからなる構成の場合は、本発明の代表的な構成である。透明層のみの構成は、ポリブタジエン樹脂層とする樹脂シート裏面に装飾層等を形成すれば、上記効果に加えて、透明感、塗装感等の意匠感が得られる。一方、透明層と不透明層との組合わせの構成では、間に装飾層を挟んで裏面側に不透明層を表面側に透明層を配置すれば、前記効果に加えて、透明感、塗装感等の意匠感が得られ、更に被着体に対する隠蔽性も得られる。
【図面の簡単な説明】
【図１】本発明の化粧シートの或る２形態を例示する断面図。
【図２】本発明の化粧シートの別の１形態を例示する断面図。
【図３】本発明の化粧シートの別の１形態を例示する断面図。
【図４】本発明の化粧シートの別の１形態を例示する断面図。
【符号の説明】
１ ポリブタジエン樹脂層
１ａ、１ｂ ポリブタジエン樹脂層
２ 透明層
３ 非ポリブタジエン樹脂層
４ 不透明層
５ 装飾層
６ 接着層
６ａ、６ｂ 接着層
８ 凹凸模様
Ｓ 化粧シート[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet that can be used for surface cosmetics such as exteriors, interiors, fittings, furniture, and vehicle interiors of buildings.
[0002]
[Prior art]
As a conventional decorative sheet, a vinyl chloride resin sheet has been widely used as a resin sheet used for an opaque layer as a lower layer and a transparent resin layer as an upper layer. However, recently, from an environmental standpoint, a resin sheet made of a polyolefin resin such as polypropylene or an olefin thermoplastic elastomer has been used instead as a non-vinyl chloride resin sheet ( JP-A-54-62255, JP-A-6-210808, JP-A-11-221888, etc.). In addition to the decorative layer formation by printing or the like, the decorative treatment may be provided with uneven patterns such as a wood grain conduit groove on the decorative sheet surface by hot embossing in order to further enhance the design.
[0003]
[Problems to be solved by the invention]
However, if the decorative sheet surface is a resin sheet made of polyolefin resin or the like, the scratch resistance may be insufficient. Scratch resistance can be improved by applying a surface protective layer made of a curable resin such as urethane resin on the surface, but there are also problems such as an increase in the number of manufacturing processes and a new impact resistance. It was. In the case of using a conventional vinyl chloride resin sheet, when a decorative sheet is laminated on an adherend by bending or stretching it by V-cut processing, lapping processing, vacuum forming lamination processing, etc., the formability as workability is Was good. However, when a polyolefin resin sheet is used instead of the vinyl chloride resin sheet, it is easy to neck and the moldability may be inferior. In addition, when a decorative sheet is molded, the decorative sheet is usually heated. However, if the decorative sheet surface has a concavo-convex pattern, the concavo-convex shape may be blunted by heating, and the embossing fastness (embossing heat resistance) is weak. There was also a problem to say.
[0004]
That is, an object of the present invention is to provide a decorative sheet that has not only a special surface protective layer but also scratch resistance, impact resistance, and good moldability. Another object of the present invention is to provide a decorative sheet having an embossing fastness so that the uneven shape is not blunted by heating at the time of molding the decorative sheet even when the surface has an uneven pattern.
[0005]
[Means for Solving the Problems]
  Therefore, in order to solve the above problems, the decorative sheet of the present invention contains a syndiotactic 1,2-polybutadiene resin in a decorative sheet formed of a single layer or a multilayer resin layer and subjected to a decoration treatment.The thickness is 20 to 300 μm or 80 to 300 μmA polybutadiene resin layer is provided at least on the outermost surface, and at least the outermost polybutadiene resin layer is crosslinked by irradiation with ionizing radiation. Thus, the outermost surface layer of the decorative sheet is a layer of a cross-linked syndiotactic 1,2-polybutadiene resin, so that scratch resistance and impact resistance are good without providing a surface protective layer on the surface. It becomes. Moreover, moldability is also obtained at the same time.
Further, the decorative sheet of the present invention has a configuration in which the polybutadiene layer is formed by synthesizing a syndiotactic 1,2-polybutadiene resin by a melt extrusion method.
[0006]
Moreover, the decorative sheet of the present invention has a configuration in which an uneven pattern is formed on the outermost surface in the above configuration.
In this way, in the configuration having a concavo-convex pattern on the decorative sheet surface, the design becomes higher and the specific polybutadiene resin layer is cross-linked. Emboss fastness that does not slow down is also obtained.
[0007]
Further, in the decorative sheet of the present invention, in any one of the above-described configurations, the polybutadiene resin layer is configured by only a transparent layer or a combination of a transparent layer and an opaque layer.
Such a configuration is a typical configuration of the decorative sheet of the present invention. The configuration in which the polybutadiene resin layer is only a transparent layer is, for example, a configuration in which a decoration layer or the like is formed as a decoration process on the back surface of a single-layer resin sheet having only a polybutadiene resin layer. The effect as described above can be obtained for a decorative sheet to which a design feeling such as a feeling or a painting feeling is imparted. In addition, the configuration in which the polybutadiene resin layer is composed of a combination of a transparent layer and an opaque layer is, for example, applied as a decorative treatment on the front side surface of an opaque resin sheet made of a polybutadiene resin layer that is colored by adding a colorant to make an opaque layer. By forming a decorative layer, etc., and further laminating a polybutadiene resin layer as a transparent layer thereon by a melt extrusion method or the like, a concealing property to the adherend is imparted together with a sense of design such as a sense of transparency and a coating feeling With respect to the decorative sheet, the effects as described above can be obtained.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[0009]
〔Overview〕
In sectional drawing of FIG. 1, two examples are shown as a form example of the decorative sheet of this invention. The decorative sheet S illustrated in FIG. 1 (A) has a form of a multilayer resin layer, and has a polybutadiene resin layer 1 containing syndiotactic 1,2-polybutadiene resin as a transparent layer 2 on the surface side. The polybutadiene resin layer 1 is crosslinked by irradiation with ionizing radiation such as an electron beam. On the other hand, the non-polybutadiene resin layer 3 made of a resin other than the polybutadiene resin is provided as the opaque layer 4 on the back side. A decorative layer 5 and an adhesive layer 6 are provided between the opaque layer 4 and the transparent layer 2. The decorative sheet S having such a configuration is prepared by, for example, preparing a non-polybutadiene resin layer 3 as an opaque layer as a resin sheet, printing the decorative layer 5 on the resin sheet as a decorative treatment, and further applying an adhesive layer 6. After syndiotactic 1,2-polybutadiene resin is laminated at the same time as film formation by melt extrusion method to form the polybutadiene resin layer 1, the polybutadiene resin layer is crosslinked by irradiation with ionizing radiation such as an electron beam. ,Obtainable. In this way, by providing a syndiotactic 1,2-polybutadiene resin layer cross-linked with an electron beam or the like as the outermost surface layer of the decorative sheet, a special surface protective layer formed by coating or the like is not provided. In addition, a decorative sheet having good impact resistance and moldability as well as scratch resistance can be obtained.
[0010]
Note that the decorative sheet of the present invention may be a decorative sheet made of a single resin layer, and the decorative sheet S illustrated in FIG. 1B is a form example thereof. That is, the transparent layer 2 made of the specific polybutadiene resin layer 1 has a configuration in which the decorative layer 5 is formed as a decorative treatment on the back surface side and the concavo-convex pattern 8 is formed on the front surface side. Such a decorative sheet S is obtained by printing a decorative layer 5 on the back side of a transparent resin sheet used as a polybutadiene resin layer 1 and then forming a concavo-convex pattern 8 on the front side by a hot embossing method. It can be obtained by crosslinking the polybutadiene resin layer by irradiation with ionizing radiation such as.
[0011]
Hereinafter, each layer will be described in detail.
[0012]
[Polybutadiene resin layer]
The polybutadiene resin layer 1 is a resin layer containing syndiotactic 1,2-polybutadiene resin as at least the outermost surface layer of the decorative sheet, and is a layer obtained by crosslinking the polybutadiene resin by irradiation with ionizing radiation such as an electron beam. is there. By using a polybutadiene resin for the resin of the resin layer, impact resistance and moldability can be obtained. Moreover, since the polybutadiene resin layer is crosslinked, in addition to these performances, further scratch resistance can be obtained. As the scratch resistance is improved, the impact resistance and moldability are not lowered. In addition, when an uneven pattern is provided on the surface of the decorative sheet, that is, the polybutadiene resin layer 1 as the outermost surface layer, the embossing fastness (embossing so that the uneven shape of the uneven pattern is not blunted by heat applied at the time of molding the decorative sheet, etc. Heat resistance). In addition, as a syndiotactic 1,2-polybutadiene resin, the product (for example, brand name "RB830") of JSR Corporation etc. can be used.
[0013]
Crosslinking is to improve the scratch resistance and emboss fastness of the decorative sheet surface. When the polybutadiene resin layer is the inner layer of the decorative sheet or on the back side, the polybutadiene resin layer is crosslinked. However, it may be a non-crosslinked layer.
The ionizing radiation may be applied to the polybutadiene resin layer before lamination, but is usually performed after the resin layer is laminated.
[0014]
As the ionizing radiation for crosslinking the syndiotactic 1,2-polybutadiene resin, electromagnetic waves or charged particles having energy capable of crosslinking the unsaturated double bond of the resin are used. Typically, an electron beam is used, but in addition, ultraviolet rays, X-rays, ion beams, and the like can be used. As the electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. are used, preferably 100 to 1000 keV, preferably That irradiates electrons having energy of 100 to 300 keV is used. As the ultraviolet light source, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp is used. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm is mainly used.
[0015]
In addition, the formation of the polybutadiene resin layer is (1) prepared as an uncured resin sheet, and after suitably forming a decoration layer or the like, it is crosslinked, or (2) is prepared as a crosslinked resin sheet, (3) A method of forming a film on a resin sheet as another resin layer by a melt extrusion method and then cross-linking may be used. These forming methods are appropriately selected according to the layer structure of the target decorative sheet.
[0016]
The polybutadiene resin layer 1 may be either a transparent layer or an opaque layer depending on the application. In either case, the layers may be colored by adding a colorant. However, when it is provided as the outermost surface layer, it is usually a transparent layer. For example, as illustrated in FIG. 1A, the decorative layer 5 is often provided on the lower side thereof, so that the decorative layer can be seen through. However, as an example of the case where the polybutadiene resin layer is opaque, for example, even when the polybutadiene resin layer is the outermost surface layer, when the decoration layer is dotted on the upper side (surface side) as a decoration process, the uneven pattern is formed. In some cases, the polybutadiene resin layer may be opaque. Further, as in the case of the decorative sheet S illustrated in FIG. 2, the polybutadiene resin layer has two layers, and the front-side polybutadiene resin layer 1 a is provided as the transparent layer 2. The polybutadiene resin layer 1b located below 5 is colored by adding a colorant and is provided as an opaque layer 4, and the polybutadiene resin layer is constituted by a combination of a transparent layer and an opaque layer. The transparent layer provides a sense of design such as a feeling of transparency and coating, and the opaque layer provides a concealing property to the adherend.
[0017]
In the polybutadiene resin layer, a resin other than the syndiotactic 1,2-polybutadiene resin may be used in combination for adjusting the physical properties. Examples thereof include thermoplastic resins such as acrylic resins, polycarbonate resins, polyolefin resins such as polyethylene and polypropylene, and elastomers such as olefin thermoplastic elastomers.
[0018]
Further, in the polybutadiene resin layer, known additives such as a matting agent such as calcium carbonate and silica, a lubricant such as alumina and silica, a coloring agent and a crosslinking agent may be added as necessary. . In addition, as a coloring agent, a well-known coloring agent, for example, what is listed by the below-mentioned decoration layer etc. can be used.
[0019]
In the case of the outermost surface layer, the thickness of the polybutadiene resin layer is usually 20 μm or more from the viewpoint of scratch resistance and impact resistance, and is usually about 20 to 300 μm considering the total thickness as a decorative sheet. However, when it is provided on the surface of the decorative sheet, in order to obtain the emboss fastness by the polybutadiene resin layer, it is preferable that the thickness be equal to or greater than the uneven depth of the uneven pattern.
On the other hand, in the case where the polybutadiene resin layer is an inner layer or outermost back layer of the decorative sheet and a portion that is not the outermost surface layer, the thickness is usually about 20 to 300 μm.
[0020]
[Non-polybutadiene resin layer]
The non-polybutadiene resin layer 3 is a resin layer similar to the polybutadiene resin layer, but is a resin layer that is not located on the outermost surface provided as necessary, and the resin is syndiotactic 1,2- The resin layer does not contain a polybutadiene resin. In this respect, this resin layer is referred to as a non-polybutadiene resin layer in order to distinguish it from the polybutadiene resin layer.
[0021]
As the resin used for the non-polybutadiene resin layer 3, a resin corresponding to the application can be used. However, a thermoplastic resin is preferably used as the resin from the viewpoint of moldability. As the thermoplastic resin, a vinyl chloride resin may be used, but from the viewpoint of environmental consideration, a halogen-free resin such as chlorine is preferable. For example, polyolefin resin, ABS resin (acrylonitrile-butadiene-styrene copolymer) Copolyester resin, acrylic resin, cellulosic resin, etc. are used.
[0022]
Examples of the polyolefin resin include polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-butene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer, poly Methyl pentene, olefinic thermoplastic elastomer, ionomer and the like are used.
Examples of the copolymer polyester resin include an ethylene-isophthalate-terephthalate copolymer, a polyester-based thermoplastic elastomer (a hard crystalline high-melting aromatic polyester, a soft segment having a glass transition temperature of −70 ° C. For example, polybutylene terephthalate is used for the highly crystalline aromatic polyester having a high melting point, and polytetraethylene terephthalate is used for the amorphous polyether. Methylene glycol or the like is used), a completely amorphous polyester (typically, there is ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymer), or the like.
[0023]
In the non-polybutadiene resin layer, various known additives such as a colorant, a filler, a foaming agent, a flame retardant, and an antioxidant are added as necessary. In addition, as a coloring agent, a well-known coloring agent, for example, what is listed by the below-mentioned decoration layer etc. can be used.
The non-polybutadiene resin layer is formed as a transparent layer or an opaque layer depending on the application. Typically, as shown in FIG. 1 (A), the outermost surface layer of the decorative sheet is a polybutadiene resin layer 1, and this non-polybutadiene resin layer 3 is used as a layer on the back side, so that it is opaque to obtain concealment. Formed as layer 4. The non-polybutadiene resin layer may be colored.
[0024]
The non-polybutadiene resin layer is provided by forming a film by a melt extrusion method or the like on a polybutadiene resin layer prepared as a resin sheet in addition to the case of being provided as a resin sheet. In addition, the thickness of a non-polybutadiene resin layer is about 20-300 micrometers normally.
[0025]
[Decoration]
Any one of the resin layers constituting the decorative sheet is subjected to a decoration process such as printing and embossing. Typical examples of such decoration processing are described below.
(1) Addition of colorant into resin layer (colored transparent or colored opaque) [see FIG. 1 (A)],
(2) Formation of the decoration layer 5 by printing or the like expressing a pattern or the like [see FIG. 1 (A)],
(3) Shaping of the uneven pattern 8 by embossing or the like [see FIG. 1 (B)],
Etc. For such a decoration process, various conventionally known decoration processes for general decorative sheets can be appropriately employed. Moreover, these various decoration processes are used even if it combines suitably according to a use.
[0026]
(1) Coloring addition to the resin layer:
As an example of the color addition into the resin layer, the resin layer that is typically an opaque layer is colored. Further, even a resin layer that is a transparent layer may be colored transparent. The resin layer is a polybutadiene resin layer or a non-polybutadiene resin layer. In addition, the polybutadiene resin layer is typically a transparent layer in the outermost surface layer, and is typically an opaque layer in the back surface layer. In addition, a well-known colorant, for example, what is listed by the below-mentioned decoration layer, etc. can be used for a colorant.
[0027]
(2) Formation of decorative layer:
The decoration layer 5 is applied to the surface of the resin layer that can be a resin sheet having a shape maintaining function. The resin layer is a polybutadiene resin layer or a non-polybutadiene resin layer. The formation surface depends on the application, the lamination method, and the like. The decorative layer 5 is formed as a pattern printing layer, a metal thin film layer, or the like in order to impart a pattern or the like. The surface on which the decorative layer is formed is preferably provided on the outermost surface of the decorative sheet so that it can be protected from scratches and the like from the surface of the decorative sheet [see FIG. More preferably, it is provided on the inside avoiding the rearmost surface, for example, the surface between the resin layers [see FIG. 1 (A)].
[0028]
The pattern printing layer can be formed by a known printing method such as gravure printing, silk screen printing, offset printing, letterpress printing, flexographic printing, electrostatic printing, ink jet printing, transfer printing or the like. In addition, when the pattern of the decoration layer is solid all over, it can also be formed by a known coating method such as roll coating.
[0029]
The decorative layer pattern may be, for example, a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, characters, symbols, various abstract patterns, or the entire surface. Solid or the like, or a combination thereof.
[0030]
Moreover, well-known things can be used as the ink (or paint, the same shall apply hereinafter) used for the pattern printing layer. For example, ink binder resins include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, thermoplastic urethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, and cellulose resins. Curable resins such as thermoplastic resins such as two-component curable polyurethane resins, polyester resins, epoxy resins, or ionizing radiation curable resins that are cured by ionizing radiation such as ultraviolet rays and electron beams can be used. . Ink colorants include inorganic pigments such as titanium white, carbon black, petal, yellow lead and ultramarine, organic pigments such as aniline black, quinacridone, isoindolinone and phthalocyanine blue, and foil powder of titanium dioxide-coated mica. Or other pigments or other dyes.
[0031]
The metal thin film layer as the decoration layer is formed by using a metal such as aluminum, chromium, gold, silver, copper or the like by vacuum evaporation, sputtering, or the like. The metal thin film layer is partially provided in a pattern or on the entire surface.
[0032]
(3) Concave and convex pattern shaping:
The uneven pattern 8 is shaped by hairline processing, sandblasting, embossing, or the like. In particular, in the present invention, the heat resistance for maintaining the uneven shape of the uneven pattern is improved, which is particularly effective in the case of the uneven pattern by embossing using heat and pressure during shaping. The embossing is performed by pressing the embossed plate on the surface of the heat-softened resin layer using a hot press type sheet or rotary embossing machine.
As the uneven pattern, there are a wood grain plate conduit groove, a stone plate surface unevenness (such as a granite cleaved surface), a tiled or brickwork joint groove, a cloth surface texture, a satin texture, a grained grain, a hairline, a single line groove, and the like. Further, the uneven pattern may be a combination thereof.
[0033]
The surface on which the uneven pattern is shaped is usually the surface of the polybutadiene resin layer as the outermost surface layer. In this case, the polybutadiene resin layer may be formed directly on the resin sheet alone, but may be formed after the polybutadiene resin layer is laminated with other layers (decorative layer, non-polybutadiene resin layer, etc.). it can. However, it is preferable to shape the polybutadiene resin layer before crosslinking the resin layer. By cross-linking the polybutadiene resin after shaping, the embossing fastness of the shaped concavo-convex pattern can be improved easily.
In addition, the formation of the concavo-convex pattern can be performed simultaneously with the film formation by using an embossing / cooling roller having a concavo-convex pattern on the cooling surface as a cooling roller when forming the resin sheet by the melt extrusion method. In the same manner, for example, when the resin layer is laminated on the resin sheet at the same time as the film formation, it can be formed on the surface of the resin layer.
[0034]
The uneven pattern may be formed on the surface to be an interlayer inside the decorative sheet, in addition to being formed on the outermost surface of the polybutadiene resin layer serving as the outermost surface layer. However, since the concavo-convex pattern formed between the inner layers is a dense layer such as a resin layer on both sides of the concavo-convex (boundary) surface, there is essentially no problem of emboss fastness.
[0035]
[Adhesive layer]
In addition, it is preferable to perform an easy-adhesion process, when the adhesive improvement between a multilayer resin layer, the adhesive improvement between a decoration layer and a resin layer, or the adhesive improvement of a decorative sheet and a to-be-adhered body is required. As the easy adhesion treatment, known treatments such as corona discharge treatment, plasma treatment, adhesion layer (also referred to as primer layer or anchor layer) formation are appropriately performed. Further, the adhesive layer is also used as an adhesive when the resin sheets are laminated by a dry lamination method or the like. As these adhesive layers, those according to the material to be bonded may be appropriately used. For example, in addition to a curable resin such as a thermosetting resin, a resin such as a thermoplastic resin is used. As specific examples of the resin, for example, a two-component curable urethane resin, a polyester resin, an acrylic resin, or the like is used alone or as a mixture. The adhesive layer can be formed by a known coating method such as gravure coating or roll coating.
[0036]
If the example of use of an adhesive layer is shown, the adhesive layer 6 is provided between the polybutadiene resin layer 1 and the decoration layer 5 in the decorative sheet S illustrated in FIG. In the decorative sheet S illustrated in FIG. 3, an adhesive layer 6 a is provided between the polybutadiene resin 1 and the decorative layer 5, and an adhesive layer 6 b is provided on the back side of the lower non-polybutadiene resin layer 3. . Of course, the adhesive layer can be omitted if it is unnecessary.
[0037]
[Adherent]
In addition, as a to-be-adhered body which sticks a decorative sheet, the thing according to a use is used. Specific examples of the adherend include plate materials made of various materials, plate materials such as curved plates, three-dimensional articles, sheets (or films), and the like. For example, wood board materials such as wood veneer, such as wood veneer, wood plywood, particle board, MDF (medium density fiber board), etc. Ceramic materials used as plate materials and three-dimensional articles such as metal materials used as sheets, ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates Material, acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber plate, three-dimensional shape Resin materials used as articles or sheets, or exclusively Paper such as high-quality paper, Japanese paper, etc., non-woven fabric or woven fabric made of carbon, asbestos, glass, synthetic resin, or a composite material of these two or more materials, for example, a plate material or a three-dimensional article Used as a composite (element) material such as FRP (fiber reinforced plastic), which is typically made of wood powder plastic, paper powder plastic, or a fiber reinforced with unsaturated polyester resin Combinations are listed.
[0038]
[Use of decorative sheet]
There is no restriction | limiting in particular as a use of the decorative sheet of this invention. For example, interior materials for buildings such as walls, floors, ceilings, exterior walls, roofs, door exteriors, exterior materials for buildings such as window frames, furniture surface materials such as fences, shelves, desks, curbs, baseboards, It is a structural member such as a door frame, a housing (cabinet) of an electric device such as a television receiver, a surface material of household appliances such as a refrigerator door, and a vehicle interior material such as an automobile, a train, and a ship.
[0039]
【Example】
Next, the present invention will be described in more detail with reference to examples and comparative examples.
[0040]
[Example 1]
A decorative sheet S as shown in the sectional view of FIG. 3 was produced as follows.
First, as the non-polybutadiene resin layer 3 made of a resin other than the polybutadiene resin used as the opaque layer 4, a polyethylene resin film having a thickness of 60 μm and made opaque brown by adding a colorant (trade name “E-5” manufactured by Okura Kogyo Co., Ltd.) After applying a corona discharge treatment to both surfaces of this resin film to obtain a wetting index of 45 mN / m (45 dyn / cm), a gravure printing method is used on the front surface to decorate the wood grain pattern with urethane resin ink 5. As the easy adhesion treatment, an adhesive layer 6a on the entire surface with a polyester adhesive was sequentially formed. Next, the adhesive layer 6b of the whole surface by urethane resin-type ink was formed in the surface made into the back side of this resin film by the gravure printing method as an easily bonding process, and the printing sheet was produced.
[0041]
Next, syndiotactic 1,2-polybutadiene resin (manufactured by JSR Corporation, trade name “RB830”) is formed on the surface of the printed sheet on which the decorative layer 5 is formed to form the polybutadiene resin layer 1 to be the transparent layer 2. By a melt extrusion coating method using a T die, a film was formed so as to have a thickness of 80 μm and an uncrosslinked resin layer was laminated to obtain a laminated sheet.
[0042]
Next, the unevenness pattern 8 of the wood grain conduit groove is shaped by hot embossing on the surface of the laminated sheet on the uncrosslinked resin layer (polybutadiene resin layer 1) side, and then the shaped surface is irradiated with an electron beam ( Acceleration voltage 175 keV, irradiation dose 600 kGy (60 Mrad)), the resin layer was cross-linked to obtain a desired decorative sheet S as shown in the cross-sectional view of FIG.
[0043]
Then, the decorative sheet S is laminated on a 2.5 mm thick MDF (medium fiber board) using a urethane resin two-component curable adhesive, and the adhesive is cured to produce a decorative board. The performance was evaluated with a decorative board. The results are summarized in Table 1.
[0044]
[Example 2]
A decorative sheet S as shown in the sectional view of FIG. 2 was produced as follows.
First, a syndiotactic 1,2-polybutadiene resin (trade name “RB830” manufactured by JSR Corporation) is formed into a film having a thickness of 150 μm by a melt extrusion method using a T-die, and is an uncrosslinked resin. The resin sheet which consists of was prepared.
Next, a corona discharge treatment is applied to the back surface of the resin sheet to obtain a wetting index of 45 mN / m (45 dyn / cm), and then a wood grain decorative layer 5 made of urethane resin ink by gravure printing. As a result, a pattern sheet and a colored concealing solid layer were sequentially formed to prepare a printed sheet.
[0045]
Next, in the same manner as in Example 1, the concave and convex pattern 8 is formed on the surface to be the front side of the printed sheet, and then the polybutadiene resin is crosslinked by electron beam irradiation to obtain a desired decorative sheet S as shown in FIG. Obtained (see Table 1). Furthermore, using this decorative sheet, a decorative board was produced in the same manner as in Example 1, and the performance was evaluated.
[0046]
Example 3
A decorative sheet S as shown in the sectional view of FIG. 4 was produced as follows.
First, as a polybutadiene resin layer 1b to be the opaque layer 4, a colored resin kneaded by adding iron oxide as a colorant to a syndiotactic 1,2-polybutadiene resin (manufactured by JSR Corporation, trade name “RB830”), A resin sheet made of an uncrosslinked colored opaque resin was prepared by melt extrusion using a T-die so as to have a thickness of 60 μm.
[0047]
Next, similarly to Example 1, after corona discharge treatment was performed on both surfaces of the resin sheet to obtain a wetting index of 45 mN / m (45 dyn / cm), the surface of the front side was subjected to a urethane resin system by gravure printing. A decorative layer 5 of a wood grain pattern with ink and an adhesive layer 6a on the entire surface with a polyester-based adhesive were formed in order as an easy adhesion treatment. Next, the adhesive layer 6b of the whole surface by urethane resin-type ink was formed in the surface made into the back side of this resin film by the gravure printing method as an easily bonding process, and the printing sheet was produced.
[0048]
Next, in the same manner as in Example 1, a syndiotactic 1,2-polybutadiene resin (manufactured by JSR Corporation) was used to form a polybutadiene resin layer 1a to be the transparent layer 2 on the decorative layer 5 formation surface of the printing sheet. The product name “RB830”) was formed into a film having a thickness of 80 μm by a melt (multilayer) extrusion coating method using a T die, and an uncrosslinked resin layer was laminated to obtain a laminated sheet.
[0049]
Further, similarly to Example 1, the unevenness pattern 8 of the wood grain conduit groove was shaped by hot embossing on the surface of the resin layer (polybutadiene resin layer 1a) on the surface side of the laminated sheet, and then the electron beam was applied to the shaped surface. (Acceleration voltage 175 keV, irradiation dose 600 kGy (60 Mrad)), the resin layer was cross-linked to obtain a desired decorative sheet S as shown in the sectional view of FIG. 4 as a polybutadiene resin layer 1a (see Table 1). ). And the decorative board was produced like Example 1 using this decorative sheet, and performance evaluation was carried out.
[0050]
[Comparative Example 1]
In Example 1, instead of the polybutadiene resin layer, the transparent layer is a non-polybutadiene resin layer 3 having a thickness of 80 μm made of random polypropylene resin (trade name “TX1950”, manufactured by Nippon Polychem Co., Ltd.) (no electron beam irradiation) A decorative sheet was produced in the same manner as in Example 1 (see Table 1). Furthermore, using this decorative sheet, a decorative board was produced in the same manner as in Example 1, and the performance was evaluated.
[0051]
[Comparative Example 2]
In Example 1, instead of the polybutadiene resin layer, the non-polybutadiene resin layer 3 having a thickness of 60 μm made of a random polypropylene resin (manufactured by Nippon Polychem Co., Ltd., trade name “TX1950”) was used as the transparent layer (there was no electron beam irradiation). A decorative sheet (same as Comparative Example 1) was produced in the same manner as in Example 1 except that. Further, an electron beam curable resin coating was applied to the surface of the decorative sheet and crosslinked and cured by electron beam irradiation to form a surface protective layer having a thickness of 15 μm to obtain a final decorative sheet (Table 1). reference). Furthermore, using this decorative sheet, a decorative board was produced in the same manner as in Example 1, and the performance was evaluated.
[0052]
[Comparative Example 3]
In Example 1, a decorative sheet was prepared in the same manner as in Example 1 except that the crosslinking by electron beam irradiation was omitted and the polybutadiene resin layer was left uncrosslinked (see Table 1). Furthermore, using this decorative sheet, a decorative board was produced in the same manner as in Example 1, and the performance was evaluated.
[0053]
[Performance evaluation results]
The scratch resistance, impact resistance, embossing fastness, and moldability were evaluated as follows. The evaluation results are summarized in Table 1.
[0054]
(1) Scratch resistance: Using a Hoffman scratch tester (manufactured by BYK-Gardner, USA), the surface was observed for damage when tested under a load of 7.85 N (800 gf), and there was no damage. Was evaluated as good and scratched.
In the test, a scratch blade (a cylindrical edge portion having a diameter of 7 mm) is set so as to be in contact with the surface of the test body at an angle of 45 degrees, and the scratch blade is moved so as to be pulled, and the surface is rubbed. At that time, the load applied to the scratch blade is changed, and the load when the surface of the specimen is damaged is read. The Hoffman scratch test is in the standards of the Naval Research Laboratory (NRL) Specification of the US Navy Research Laboratories. It is said to be close to the way.
[0055]
(2) Impact resistance: An impact resistance test (test load: 4.91 N (500 gf), test height: 300 mm) was carried out by a test method based on JIS K 5400 using a DuPont impact tester, and surface cracks were generated. The presence or absence was observed, and it was evaluated that no crack was good and that there was a crack.
[0056]
(3) Embossing fastness: Embossing fastness was performed on the decorative sheet, not on the decorative sheet. After immersing the decorative sheet in glycerin heated to 130 ° C. for 30 seconds, the presence or absence of the concavo-convex pattern on the surface was observed. What was done was evaluated as bad.
[0057]
(4) Formability: Evaluated by formability in the vacuum forming lamination method (vacuum press forming). The shape of the adherend is a substantially rectangular parallelepiped shape, and is a plate-like substrate having a thickness of 15 mm made of MDF (medium fiberboard) having three-dimensional corners of 5 mmR in all directions. The adherend was molded at a membrane temperature of 110 ° C. and a vacuum press time of 1 min, and the presence or absence of necking was observed. Necking appears as a phenomenon in which only the concaves and convexes on the surface are extremely extended. No necking occurred, and those that occurred were considered bad.
[0058]
[Table 1]

[0059]
As shown in Table 1, the results of Examples 1 to 3 having at least a crosslinked polybutadiene resin layer on the surface are all in terms of scratch resistance, impact resistance, emboss fastness, and moldability. And became good. However, none of the comparative examples satisfy all these performances.
That is, in Comparative Example 1 in which the polybutadiene resin layer was replaced with a PP layer compared to Example 1, the impact resistance was good, but the scratch resistance, emboss fastness, and moldability were poor. Further, in Comparative Example 2 in which the polybutadiene resin layer was replaced with a PP layer with respect to Example 1 and a surface protective layer was provided on the PP layer, the scratch resistance was improved, but the impact resistance was poor, The remaining embossing fastness and moldability were also poor. Moreover, although the comparative example 3 which did not perform the bridge | crosslinking by electron beam irradiation with respect to Example 1 with respect to the polybutadiene resin layer was good in impact resistance and moldability, it had scratch resistance and emboss fastness. It became defective.
[0060]
【The invention's effect】
(1) According to the decorative sheet of the present invention, scratch resistance and impact resistance are improved without providing a surface protective layer on the surface. Moreover, moldability is also obtained at the same time.
(2) Further, in the configuration in which the concavo-convex pattern is formed on the outermost surface, the embossing fastness is obtained such that the concavo-convex shape of the concavo-convex pattern is not blunted by heating during molding of a decorative sheet.
(3) Furthermore, in the case where the polybutadiene resin layer has a configuration consisting of only a transparent layer or a combination of a transparent layer and an opaque layer, this is a typical configuration of the present invention. In the configuration of only the transparent layer, if a decorative layer or the like is formed on the back side of the resin sheet as the polybutadiene resin layer, in addition to the above effects, a design feeling such as a transparency and a coating feeling can be obtained. On the other hand, in the configuration of a combination of a transparent layer and an opaque layer, if an opaque layer is arranged on the back side with a decorative layer in between and a transparent layer is arranged on the front side, in addition to the above effects, a sense of transparency, a feeling of painting The design feeling is obtained, and further, the concealability to the adherend is also obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating two forms of a decorative sheet according to the present invention.
FIG. 2 is a cross-sectional view illustrating another embodiment of the decorative sheet of the present invention.
FIG. 3 is a cross-sectional view illustrating another embodiment of the decorative sheet of the present invention.
FIG. 4 is a cross-sectional view illustrating another embodiment of the decorative sheet of the present invention.
[Explanation of symbols]
1 Polybutadiene resin layer
1a, 1b Polybutadiene resin layer
2 Transparent layer
3 Non-polybutadiene resin layer
4 Opaque layer
5 decoration layers
6 Adhesive layer
6a, 6b Adhesive layer
8 Uneven pattern
S decorative sheet

Claims (5)

In a decorative sheet composed of a single layer or multiple layers of resin and decorated.
A decorative sheet comprising at least the outermost polybutadiene resin layer containing syndiotactic 1,2-polybutadiene resin and having a thickness of 20 to 300 μm , and at least the outermost polybutadiene resin layer is crosslinked by irradiation with ionizing radiation. . In a decorative sheet composed of a single layer or multiple layers of resin and decorated.
A decorative sheet comprising at least the outermost polybutadiene resin layer containing syndiotactic 1,2-polybutadiene resin and having a thickness of 80 to 300 μm, and at least the outermost polybutadiene resin layer is cross-linked by irradiation with ionizing radiation. . The decorative sheet according to claim 1 or 2, wherein the polybutadiene layer is formed by melt extrusion of a syndiotactic 1,2-polybutadiene resin. The decorative sheet according to any one of claims 1 to 3 , wherein a concavo-convex pattern is formed on the outermost surface. The decorative sheet according to any one of claims 1 to 4, wherein the polybutadiene resin layer comprises only a transparent layer or a combination of a transparent layer and an opaque layer.

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