JP6679834B2 - Decorative sheet and veneer - Google Patents

Description

  The present invention relates to a decorative sheet and a decorative board.

  Conventionally, a decorative sheet is laminated on the surface of various articles in order to impart a design property. For example, a decorative sheet is laminated and used on the surface of a wall covering material used for a wall surface of a building, a floor decorative material used for a floor surface, furniture, and the like.

  In order to cope with the recent trend toward high-end products for consumers, a decorative sheet having a visual unevenness by providing a surface protective layer made of an ionizing radiation curable resin on a low-gloss pattern layer has been proposed (for example, , Patent Document 1). In the decorative sheet of Patent Document 1, a low-gloss area that is visually recognized as a concave portion is formed in the surface protective layer immediately above the low-gloss pattern layer and in the vicinity thereof, so that a glossy portion can be formed in accordance with a specific portion of the pattern. Erasing and visual unevenness are given, and it is possible to express an excellent design with high texture.

JP, 2006-95973, A

  However, the decorative sheet laminated on the surface of the article may be used under the condition that it frequently comes into contact with other articles in use, and higher scratch resistance is required depending on the use condition. If the scratch resistance of the decorative sheet is insufficient, there is a problem in that the gloss of the surface of the decorative sheet changes due to abrasion and the designability deteriorates. Since the surface protective layer of the decorative sheet of Patent Document 1 described above is formed of an ionizing radiation curable resin, it can exhibit a certain level of scratch resistance, but there is room for improvement in scratch resistance.

  Regarding this point, Patent Document 1 describes that the abrasion resistance is improved by adding an abrasion resistance improver to the surface protective layer. However, since the abrasion resistance improver often functions also as a matting agent, when the surface protective layer contains the abrasion resistance improver, the decorative sheet tends to have a low gloss as a whole. A low-gloss decorative sheet generally tends to be preferred because it has a high-class feeling, but as in Patent Document 1 above, a visual unevenness is caused by a difference in gloss between a low-gloss pattern layer forming portion and a non-forming portion. In the case of a decorative sheet that expresses, there is a problem that if the gloss is lowered too much, the difference in gloss becomes small and the design feeling is impaired.

  Further, Patent Document 1 describes that spherical α-alumina having a high hardness and a large effect on the improvement of wear resistance is preferable as the wear resistance improver. A wear resistance improver having an extremely high hardness, such as α-alumina, can be expected to have a sufficient improvement in wear resistance even in a small amount so as not to reduce the gloss too much.

  However, when a wear resistance improver having an extremely high hardness such as α-alumina is added, there is a problem that equipment such as a doctor blade is worn in the coating process and the equipment is damaged.

  On the other hand, in order to impart high scratch resistance to the decorative sheet, increasing the thickness of the surface protective layer has been studied.

  However, in the case of a decorative sheet that expresses a visual unevenness due to the difference in gloss between the portion where the low-gloss pattern layer is formed and the portion where the low-gloss pattern layer is formed, as in Patent Document 1, if the thickness of the surface protective layer is large, the difference in gloss There is a problem in that the feeling of design is lost and the design feeling is impaired.

  Therefore, there is a demand for the development of a decorative sheet that is excellent in scratch resistance and design, and that suppresses damage to the equipment during manufacturing.

  It is an object of the present invention to provide a decorative sheet and a decorative board that are excellent in scratch resistance and design, and that suppress damage to equipment during manufacturing.

  The present inventor, as a result of repeated diligent research, in a decorative sheet in which a low-gloss pattern layer and a surface protective layer are laminated at least in this order on a substrate sheet, the low-gloss pattern layer is formed in a pattern, And, it is laminated so as to be in contact with the surface protective layer, the thickness of the surface protective layer is in a specific range, the average particle diameter in a specific range, and the inclusion of wear-resistant filler showing Mohs hardness in a specific range The inventors have found that the above object can be achieved by using a composition containing a certain amount, and have completed the present invention.

That is, the present invention relates to the following decorative sheets and decorative plates.
1. A decorative sheet in which a low-gloss pattern layer and a surface protective layer are laminated at least in this order on a substrate sheet,
(1) The low-gloss pattern layer is formed in a pattern and is laminated so as to be in contact with the surface protective layer,
(2) The surface protective layer has a thickness of 2 to 15 μm,
(3) The surface protective layer contains an abrasion resistant filler having an average particle size of 25 μm or less,
(4) The wear resistant filler has a Mohs hardness of 8 or less,
(5) The content of the wear-resistant filler is 3 to 15 parts by mass with respect to 100 parts by mass of the resin component contained in the surface protective layer.
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the surface protective layer contains an ionizing radiation curable resin.
3. A decorative plate obtained by sticking the decorative sheet according to Item 1 or 2 to an adherend.

  INDUSTRIAL APPLICABILITY The decorative sheet of the present invention has excellent scratch resistance and designability, and damage to equipment during production is suppressed.

It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the decorative sheet of this invention. It is a cross-sectional schematic diagram which shows an example of the laminated constitution of the decorative sheet of this invention.

  Hereinafter, the decorative sheet and the decorative plate of the present invention will be described in detail.

1. Decorative sheet The decorative sheet of the present invention is a decorative sheet in which a low-gloss pattern layer and a surface protective layer are laminated at least in this order on a base sheet, and (1) the low-gloss pattern layer is formed in a pattern. And is laminated so as to be in contact with the surface protective layer, (2) the surface protective layer has a thickness of 2 to 15 μm, and (3) the surface protective layer has an average particle diameter of 25 μm or less. A wear-resistant filler is contained, (4) the Mohs hardness of the wear-resistant filler is 8 or less, and (5) the content of the wear-resistant filler is 100 parts by mass of the resin component contained in the surface protective layer. It is characterized by being 3 to 15 parts by mass with respect to parts.

  In the decorative sheet of the present invention having the above characteristics, a low-gloss pattern layer and a surface protective layer are laminated at least in this order on a base sheet, the low-gloss pattern layer is formed in a pattern, and the surface is Since it is laminated so as to be in contact with the protective layer, it is possible to express a gloss matte design feeling having a low-gloss portion and a high-gloss portion and to exhibit excellent designability. Further, since the thickness of the surface protective layer is within a specific range, it is excellent in scratch resistance and designability, and further, curling and cracking of the surface protective layer are suppressed, which is excellent in processability in the manufacturing process. There is. Further, the surface protective layer contains a wear-resistant filler showing a specific range of average particle diameter and Mohs hardness in a specific content, thus exhibiting excellent scratch resistance and designability, and In this case, damage to equipment is suppressed, and the coating suitability of the resin composition for forming the surface protective layer is excellent.

  Hereinafter, each layer constituting the decorative sheet will be described. In the present specification, in the layer structure of the decorative sheet, the direction in which the surface protective layer is formed is referred to as "upper", "surface" or "front surface", and the surface protective layer in the layer structure of the decorative sheet. The side opposite to the direction in which is formed is referred to as "bottom" or "back surface".

Surface Protective Layer In the decorative sheet of the present invention, the surface protective layer has a thickness of 2 to 15 μm. If the thickness of the surface protective layer is less than 2 μm, the scratch resistance is poor. Further, when the thickness of the surface protective layer exceeds 15 μm, the design expressed by the low-gloss pattern layer and the pattern layer, which will be described later, becomes difficult to be visually recognized, and the designability is deteriorated. The thickness of the surface protective layer is preferably 3 to 12 μm.

  The surface protective layer constituting the decorative sheet of the present invention contains an abrasion resistant filler. The wear-resistant filler is not particularly limited as long as it can impart scratch resistance to the surface of the decorative sheet of the present invention and can adjust the Mohs hardness to 8 or less, and examples thereof include organic particles and inorganic particles. Can be used.

  As the organic particles, urethane beads, acrylic beads, nylon beads and the like can be used. As the inorganic particles, silica, alumina, chromium oxide, iron oxide, diamond, calcium carbonate, aluminum hydroxide, barium sulfate, talc, etc. can be used.

  As the wear-resistant filler, organic particles are preferably used because they have excellent scratch resistance and can suppress damage to equipment, and among them, urethane beads are more preferably used. Further, by using organic particles as the wear-resistant filler, even if the wear-resistant filler that has fallen off the surface of the surface protective layer is present on the surface of the decorative sheet, the organic particles are not too hard, so it has fallen off. Occurrence of scratches on the surface of the decorative sheet due to the wear resistant filler is suppressed. This can be confirmed when the scratch resistance is evaluated by the Martindale test described below.

  The wear-resistant filler has an average particle size of 25 μm or less. If the average particle size of the wear-resistant filler exceeds 25 μm, the surface protective layer becomes cloudy, making it difficult to visually recognize the low-gloss pattern layer described later and the design expressed by the pattern layer, and the decorative sheet has a good design property. descend. The average particle size of the wear resistant filler is preferably 20 μm or less. The average particle size of the wear resistant filler is preferably 5 μm or more, more preferably 8 μm or more. By setting the lower limit of the average particle diameter of the wear resistant filler to the above value, the decorative sheet of the present invention can exhibit more excellent scratch resistance. In the present specification, the average particle size of the wear-resistant filler is measured by a laser diffraction / scattering method using a laser diffraction / scattering particle size distribution measuring device LA ・ 910W (model number) manufactured by Horiba Ltd. It is the measured value.

  The wear resistant filler has a Mohs hardness of 8 or less. When the Mohs hardness of the wear-resistant filler exceeds 8, the wear-resistant filler dropped from the surface of the surface protective layer by abrasion rubs against the surface of the decorative sheet, causing scratches on the surface of the decorative sheet. Further, when the wear-resistant filler having a Mohs hardness of more than 8 is used, the above-mentioned problems are less likely to occur because the fall-off due to wear is less likely to occur, but the equipment is damaged during the production. The Mohs hardness of the wear resistant filler is preferably 3 or more, more preferably 5 or more. By setting the lower limit value of the Mohs hardness of the wear resistant filler to the above value, the decorative sheet of the present invention can exhibit more excellent scratch resistance. In the present specification, the Mohs hardness of the wear resistant filler is a value measured by a 15-step Mohs hardness meter.

  The content of the wear resistant filler is 3 to 15 parts by mass based on 100 parts by mass of the resin component contained in the surface protective layer. When the content of the wear resistant filler is less than 3 parts by mass, the decorative sheet of the present invention is inferior in scratch resistance. Further, when the content of the wear-resistant filler exceeds 15 parts by mass, the gloss of the surface protective layer is excessively reduced, and the design due to the difference in gloss from the low gloss pattern layer described later or the pattern layer is expressed. The design becomes difficult to be visually recognized, and the designability of the decorative sheet deteriorates. The content of the wear resistant filler is preferably 4 to 8 parts by mass.

  The resin forming the surface protective layer is not particularly limited, but a thermosetting resin, an ionizing radiation curable resin (for example, an electron beam curable resin) or the like is preferable. In particular, ionizing radiation curable resins are preferable from the viewpoint of high surface hardness and productivity. Further, when an ionizing radiation curable resin is used, it is likely to cause an interaction with a low gloss pattern layer described later, and the decorative sheet of the present invention has a gloss matte design including a low gloss portion and a high gloss portion. It is also preferable from the viewpoint that the feeling can be more remarkably expressed and excellent designability can be exhibited.

  Examples of the thermosetting resin include unsaturated polyester resin, polyurethane resin (including two-component curing polyurethane), epoxy resin, amino alkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, and melamine. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator and a polymerization accelerator can be added to the resin. For example, as a curing agent, isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resin, polyurethane resin, etc., organic amine etc. can be added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile etc. Radical initiators can be added to unsaturated polyester resins.

  Examples of the method for forming the surface protective layer with the thermosetting resin include a method in which a solution of the thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, followed by drying and curing.

  The ionizing radiation-curable resin is not limited as long as it undergoes a cross-linking polymerization reaction upon irradiation with ionizing radiation and changes into a three-dimensional polymer structure. For example, one or more of prepolymers, oligomers and monomers having a polymerizable unsaturated bond or epoxy group in the molecule that can be cross-linked by irradiation with ionizing radiation can be used. Examples thereof include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; epoxy resins.

  The ionizing radiation includes visible rays, ultraviolet rays (near ultraviolet rays, vacuum ultraviolet rays, etc.), X-rays, electron beams, ion beams, etc. Among these, ultraviolet rays and / or electron beams are preferable.

  As the ultraviolet ray source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp lamp can be used. The wavelength of the ultraviolet light is about 190 to 380 nm.

  As the electron beam source, for example, various electron beam accelerators such as Cockcroft-Wald type, Van degraft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type and high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 1 to 15 Mrad, more preferably about 1 to 10 Mrad, still more preferably about 3 to 5 Mrad.

  The ionizing radiation-curable resin cures sufficiently when irradiated with an electron beam, but when it is cured by irradiating ultraviolet rays, it is preferable to add a photopolymerization initiator (sensitizer).

  Examples of the photopolymerization initiator in the case of a resin system having a radically polymerizable unsaturated group include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide. , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationically polymerizable functional group, for example, at least one kind of aromatic diazonium salt, aromatic sulfonium salt, metallocene compound, benzoinsulfonic acid ester, freeloxysulfoxonium diallyliodosyl salt, and the like Can be used.

  The addition amount of the photopolymerization initiator is not particularly limited, but is generally about 0.1 to 10 parts by mass relative to 100 parts by mass of the ionizing radiation-curable resin.

  The surface protective layer may contain silicone oil. When the surface protective layer contains silicone oil, the surface protective layer can be provided with slipperiness, and the scratch resistance of the decorative sheet of the present invention can be further improved. Examples of the silicone oil used in the surface protective layer include reactive silicone oil and non-reactive silicone oil.

  As the reactive silicone oil, among modified silicone oils having an organic group introduced at the side chain or terminal, a silicone oil having reactivity depending on the nature of the introduced organic group can be used. As the reactive silicone oil, specifically, in modified silicone oil side chain type, modified silicone oil both-end type, modified silicone oil one-end type, modified silicone oil side chain both-end type, etc., the organic group to be introduced is amino-modified. , Epoxy modified, mercapto modified, carboxyl modified, carbinol modified, phenol modified, methacrylic modified, different functional group modified, and the like. These reactive silicone oils can be used alone or in admixture of two or more.

  The non-reactive silicone oil is not particularly limited as long as it is a silicone oil having no reactive functional group such as amino group, epoxy group, mercapto group, carboxy group, hydroxy group, (meth) acryloyl group and allyl group. As the non-reactive silicone oil, for example, silicone oil composed of polysiloxane, polyether modified silicone oil, aralkyl modified silicone oil, fluoroalkyl modified silicone oil, long chain alkyl modified silicone oil, higher fatty acid ester modified silicone oil, high grade Examples thereof include fatty acid amide modified silicone oil and phenyl modified silicone oil. These non-reactive silicone oils can be used alone or in admixture of two or more.

  The content of the silicone oil in the surface protective layer is about 0.1 to 50 parts by mass, preferably about 0.5 to 10 parts by mass, per 100 parts by mass of the resin forming the surface protective layer. By setting the content of the silicone oil within the above range, the surface protective layer can be sufficiently imparted with slipperiness, and the scratch resistance of the decorative sheet of the present invention can be further improved. The resin composition forming the surface protective layer, if necessary, a solvent, a dye, a coloring agent such as a pigment, a filler such as a filler, an antifoaming agent, a leveling agent, various additives such as a thixotropy imparting agent. Can be added.

  As a method for forming a surface protective layer with an ionizing radiation curable resin, for example, a solution of an ionizing radiation curable resin can be applied by a coating method such as a gravure coating method, a roll coating method, a gravure printing method, or a silk screen printing method. Good.

Low-gloss pattern layer The low-gloss pattern layer is a layer formed in a pattern and laminated so as to be in contact with the surface protective layer. The low-gloss pattern layer is formed in a pattern and is laminated so as to be in contact with the surface protective layer, so that the decorative sheet of the present invention has a gloss matte finish having a low-gloss portion and a high-gloss portion. The design feeling can be expressed, and excellent designability can be exhibited.

  By configuring the decorative sheet of the present invention as described above, it is possible to express a gloss matte design feeling having a low gloss portion and a high gloss portion, and it is possible to exhibit excellent designability. Although the reason for becoming is not clear, when applying an uncured resin composition for forming a surface protective layer on the surface of the low-gloss pattern layer, the resin component of the low-gloss pattern layer and the surface protective layer It is presumed that the resin composition for forming a part partially expresses interactions such as elution, dispersion, and mixing. At this time, the resin component of the low-gloss pattern layer and the resin composition for forming the surface protective layer do not become a complete compatible state in a short time but become a suspended state, and It is considered that the suspended portions existing immediately above and in the vicinity thereof scatter light to form a low gloss area. When such a state is fixed by curing the surface protective layer while maintaining this suspension state, a low-gloss area is partially formed in the surface protective layer, and that portion is visually illusion. It is presumed that it is visually recognized as if it were a recess.

  The ink forming the low-gloss pattern layer has a property of being eluted into the resin composition forming the surface protective layer, and is appropriately selected in relation to the resin composition (uncured product). Specifically, an ink having a non-crosslinking resin as a binder resin is preferable, and for example, a thermoplastic (non-crosslinking) urethane resin is suitable. Further, if necessary, in order to adjust the degree of expression of the low gloss area and the contrast of the gloss difference between the low gloss area and its surroundings, unsaturated polyester resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, etc. Can be mixed.

  A colorant may be added to the ink composition for forming the low-gloss pattern layer, but when the decorative sheet of the present invention has a colored hiding layer or a pattern layer, it forms a low-gloss pattern layer. It is not always necessary to add a colorant to the ink composition for coloring. That is, in the case where the decorative sheet of the present invention has a picture pattern layer, of the picture pattern to be expressed by the picture pattern layer, a portion where it is desired to deluster and visually express a concave portion and a low-gloss picture layer are provided. By synchronizing, it is possible to express a pattern having a visual recess due to a gloss difference. For example, when a wood grain pattern is to be represented by a picture pattern layer, a pattern in which the conduit portion is visually recessed due to the difference in gloss is represented by synchronizing the low-gloss pattern layer with the wood grain conduit portion. You can In addition, when trying to express the tile pasting pattern by the picture pattern layer, by synchronizing the low gloss picture layer to the joint groove portion of the tile pasting, the joint groove portion visually becomes a recess due to the gloss difference. It is possible to express patterns.

  The ink composition for forming the low gloss pattern layer may contain an extender pigment. When the ink composition for forming the low-gloss pattern layer contains an extender pigment, thixotropy can be imparted to the ink composition, and when the low-gloss pattern layer is printed using a plate, the ink composition The shape is maintained. As a result, in the low-gloss pattern layer, it is possible to emphasize the sharpness of the concavities and convexities at the end portion that transitions from the convex portion to the concave portion, and it is possible to achieve a sharp design expression.

  The extender pigment is not particularly limited and is appropriately selected from silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. Among these, silica, which is a material having a high degree of freedom in material design such as oil absorption, particle size, and pore volume, and excellent in designability, whiteness, and coating stability as an ink composition, is preferable. Is more preferred. The particle size of silica is preferably in the range of 0.1 to 5 μm. When it is 0.1 μm or more, the thixotropy of the ink composition does not become extremely high when it is added to the ink composition, and the viscosity of the ink composition does not increase too much, which makes it easy to control printing. In addition, when trying to express the mattness of the conduit pattern part, the coating thickness of the low-gloss pattern on the conduit pattern part is usually 5 μm or less, and if the particle size of silica is smaller than the coating thickness, the cue of the particles is relatively high. Since it is pressed down and is inconspicuous, it is difficult for visual discomfort to occur.

  The content of the extender pigment in the low-gloss pattern layer is preferably 5 to 15% by mass. When the amount is 5% by mass or more, the ink composition can be provided with sufficient thixotropy, and when the amount is 15% by mass or less, the effect of imparting a low gloss feeling is less likely to decrease.

The coating amount of the ink composition forming the low-gloss pattern layer is preferably ² to ²⁰ g / m ² . When the coating amount of the ink composition is 2 g / m ² or more, the amount of the above-mentioned ink composition eluted into the resin composition forming the surface protective layer is sufficient, and a low gloss area is sufficiently obtained, so that the makeup is improved. The sheet has a sufficient gloss matte feeling. On the other hand, when the coating amount of the ink composition is 20 g / m ² or less, there are no mechanical restrictions when printing the ink composition, and it is economically advantageous. The coating amount of the ink composition forming the low-gloss pattern layer is more preferably 5 to 10 g / m ² .

  In the decorative sheet of the present invention, the low-gloss pattern layer is formed in a pattern. The pattern is not particularly limited, for example, wood grain pattern, stone pattern, grain pattern, tile pasting pattern, brick pattern, cloth pattern, leather pattern, geometric pattern, letters, symbols, abstract pattern, flower pattern, etc. Can be selected according to the purpose.

  The low-gloss pattern layer can be formed, for example, by printing the pattern using the ink composition described above. Examples of printing methods include gravure printing, flexo printing, silk screen printing, offset printing, and the like.

Base Material Sheet The base material sheet is not limited, and a fibrous sheet, a plastic base material, a metal base material, a wood base material, or the like can be used.

  As the fibrous sheet, known fibrous sheets such as thin paper, inter-paper reinforcing paper, impregnated paper, titanium paper, coated paper, corrugated paper, linter paper, kraft paper, and fine paper can be used.

  Specifically, general paper for wallpaper (pulp-based sheet size-treated with a known sizing agent); flame-retardant paper (pulp-based sheet treated with a flame retardant such as guanidine sulfamate or guanidine phosphate). ); Inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; Fine paper; Thin paper; Fiber mixed paper (paper made by mixing pulp and synthetic fibers). Note that the fibrous sheet used in the present invention also includes those that correspond to non-woven fabrics in terms of classification.

  As the plastic substrate, polyolefin resin sheets such as polyethylene and polypropylene; polyester resin sheets such as polyethylene terephthalate and polybutylene terephthalate; acrylonitrile butadiene styrene; various plastic sheets and films such as polyvinyl chloride can be used. Of these, polyolefin resin sheets are preferable. Further, it is desirable that the plastic substrate is colored. As the metal base material, it is possible to commercialize a base material that is a steel plate, aluminum, stainless steel or the like on which a colorant is undercoated. Examples of the wood-based base material include plywood, particle board, and medium-density fiber board.

Although the basis weight of the base sheet is not critical, preferably about 20 to 300 g / ^{m 2,} more preferably about 50 to 300 g / ^{m 2,} about 50~130g / ^{m 2} is more preferable.

(Layer composition of decorative sheet)
The decorative sheet of the present invention has a low-gloss pattern layer and a surface protective layer, which are laminated at least in this order on a substrate sheet, and the low-gloss pattern layer is formed in a pattern, and is in contact with the surface protective layer. As long as they are laminated, the specific configuration (layer configuration) is not limited. For example, at least a picture pattern layer, a low-gloss picture layer and a surface protective layer are laminated in this order on a base sheet, and the low-gloss picture layer is formed in a pattern and is laminated so as to be in contact with the surface protective layer. The decorative sheet that has been used.

  FIG. 1 shows the above example of the layer structure of the decorative sheet of the present invention. In FIG. 1, a decorative sheet 1 of the present invention comprises a base sheet 2, a pattern layer 3, a low-gloss pattern layer 4 and a surface protective layer 5 laminated in this order, and the low-gloss pattern layer 4 is patterned. And formed so as to be in contact with the surface protection layer 5. Further, in the decorative sheet of the present invention, as shown in FIG. 2, a colored hiding layer 6 may be further formed between the base material sheet 2 and the picture pattern layer 3, and the picture pattern layer 3 and the low gloss picture pattern may be formed. The transparent resin layer 7 may be formed between the layer 4 and the back surface, and the back surface primer layer 8 may be formed on the back surface of the base sheet 2.

  Hereinafter, each layer will be specifically described by using a decorative sheet having such a layer structure as a typical example.

Picture Pattern Layer In the decorative sheet of the present invention, a picture pattern layer may be formed on the base sheet or the colored hiding layer described later, if necessary.

  The picture pattern layer imparts a design property to the decorative sheet. As the picture pattern, for example, wood pattern, stone pattern, sand pattern, tile pattern, brick pattern, texture pattern, leather pattern, geometric pattern, letters, symbols, abstract patterns, flower patterns, etc., It can be selected according to the purpose.

  The picture pattern layer can be formed by printing a picture pattern, for example. Examples of printing methods include gravure printing, flexo printing, silk screen printing, offset printing, and the like. A printing ink containing a colorant, a binder resin, and a solvent can be used as the printing ink. Known or commercially available inks may be used as these inks.

  The colorant is not particularly limited, and a known inorganic pigment or organic pigment can be used. Examples of the inorganic pigment include titanium oxide, zinc oxide, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (benji), and cadmium. Examples include red, ultramarine blue, navy blue, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo-based (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, Quinacridone, perylene, diketopyrrolopyrrole, dibromanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine) and the like. The content of the pigment is preferably about 10 to 100 parts by mass, more preferably about 15 to 50 parts by mass with respect to 100 parts by mass of the resin component.

  The binder resin can be set according to the type of the base sheet. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Examples thereof include resin, melamine resin, fluorine resin, silicone resin, fibrin derivative and rubber resin.

  Examples of the solvent (or dispersion medium) are petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid-2. -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents; and water. These solvents (or dispersion media) can be used alone or as a mixture.

  Although the thickness of the picture pattern layer differs depending on the kind of the picture pattern, it is generally preferable to be about 0.1 to 20 μm.

Transparent Resin Layer In the decorative sheet of the present invention, a transparent resin layer may be formed on the pattern layer for the purpose of adjusting gloss. The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless transparent, colored transparent, translucent and the like. Examples of the resin forming the transparent resin layer include phenol resin, urea resin, diallyl phthalate, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensate. , Silicon resin, polysiloxane, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ionomer, polymethylpentene , Acrylic acid ester, methacrylic acid ester, polycarbonate, cellulose triacetate and the like. Moreover, you may use the ionizing radiation hardening type resin mentioned above. These resins can be used alone or in combination of two or more.

  Fine particles of silica, alumina, kaolin, etc., beads such as urethane beads, acrylic beads, etc. may be added to the transparent resin layer for adjusting gloss.

  The transparent resin layer may be colored as long as it has transparency, but it is particularly preferable not to add a coloring agent.

  The thickness of the transparent resin layer is usually about 5 to 50 μm, but may exceed the above range depending on the application of the decorative sheet.

A colored hiding layer may be formed on the colored hiding layer base sheet, if necessary. The colored hiding layer is formed as a solid printing layer on the entire surface of the base material sheet. The colored hiding layer can be, for example, a layer containing a pigment and a binder resin. The colored hiding layer can be formed by a known printing method such as gravure printing, flexographic printing, silk screen printing, offset printing, etc., using a printing ink containing a coloring material, a binder resin, and a solvent. Known or commercially available inks may be used as these inks.

  As the coloring material, the binder resin and the solvent, those used for the above-mentioned pattern layer can be used.

  The thickness of the colored hiding layer is preferably about 1 to 4 μm.

A primer layer may be formed on the primer layer base sheet, the colored hiding layer, the pattern layer or the transparent resin layer, if necessary, for the purpose of improving interlayer adhesion.

  As the resin contained in the primer layer, for example, acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like can be used, but especially acrylic, chlorinated polypropylene and the like. Is desirable.

  Examples of acryl include methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate- (meth) acrylic acid. (Meth) such as butyl copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-methyl (meth) acrylate copolymer An acrylic resin made of a homopolymer or a copolymer containing an acrylate ester can be used.

  Polyurethane is a composition containing a polyol (polyhydric alcohol) as a main agent and an isocyanate as a crosslinking agent (curing agent).

  The polyol has two or more hydroxyl groups in the molecule, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

  Further, as the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate and 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated diphenylmethane diisocyanate. ) Isocyanates are used.

  The thickness of the primer layer is not limited, but is preferably about 0.1 to 10 μm, more preferably about 0.1 to 5 μm.

Back surface primer layer A back surface primer layer may be provided on the back surface of the base sheet, if necessary. The back surface primer layer is effective when the decorative sheet of the present invention and the adherend are laminated to produce a decorative plate.

  The back surface primer layer can be formed by applying a known primer agent to the base material sheet. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane-based resin) or the like, a urethane-cellulosic resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton). ), A resin-based primer agent composed of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers and light stabilizers. The amount of the additive compounded can be appropriately set according to the product characteristics.

The coating amount of the primer agent is not particularly limited, but is usually about 0.1 to 100 g / m ² , and preferably about 0.1 to 50 g / m ² . The thickness of the back surface primer layer is not particularly limited, but is usually about 0.01 to 10 μm, preferably about 0.1 to 1 μm.

2. Decorative plate A decorative plate can be obtained by pasting the decorative sheet of the present invention on an adherend. The adherend is not limited and may be the same as that used for a known decorative plate. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet can be suitably used for wood materials. Specific examples of wood materials include veneer made from various materials such as cedar, cypress, keyaki (zelkova), pine, lauan, teak, and melapee, wood veneer, wood plywood, particle board, medium density fiberboard (MDF). , A chipboard, or a composite substrate in which chipboards are laminated, and the like. As the wood material, it is preferable to use wood plywood, particle board, and medium density fiberboard (MDF).

  The method of sticking the decorative sheet onto the adherend is not limited, and for example, a method of sticking the decorative sheet onto the adherend with an adhesive can be employed. The adhesive may be appropriately selected from known adhesives according to the type of adherend. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer and the like, as well as butadiene / acrylonitrile rubber, neoprene rubber and natural rubber. These adhesives are used alone or in combination of two or more.

  The veneer produced in this manner is, for example, interior materials for buildings such as walls, ceilings and floors; exterior materials such as balconies and balconies; surface veneers and furniture for fittings such as window frames, doors and handrails; Alternatively, it can be used as a surface decorative plate of a cabinet for light electric power, OA equipment and the like.

3. Manufacturing method of decorative sheet As a manufacturing method of a decorative sheet, for example, a manufacturing method of laminating a low-gloss pattern layer and a surface protective layer on a base material sheet can be mentioned. The method for laminating the low-gloss pattern layer on the substrate sheet is not particularly limited, but using the ink composition for forming the low-gloss pattern layer described above, gravure printing, flexographic printing, silk screen printing, offset printing It may be laminated by a method of printing in a pattern by a coating method such as.

  The method for laminating the surface protective layer on the low-gloss pattern layer is not particularly limited, but an uncured resin composition for forming the surface protective layer is applied on the low-gloss pattern layer formed in a pattern. Then, after the resin component of the low-gloss pattern layer and the resin composition for forming the surface protective layer exhibit interactions such as partial elution, dispersion, and mixing, the resin composition is cured to provide surface protection. The layers may be laminated according to the method of forming the layers. When the surface protective layer is laminated on the low-gloss pattern layer by such a method, the decorative sheet of the present invention remarkably expresses a gloss matte design feeling having a low-gloss portion and a high-gloss portion. It is possible to exhibit excellent designability.

  When the decorative sheet of the present invention has a colored hiding layer, a pattern layer, a primer layer and a transparent resin layer, the resin composition for forming these layers is gravure printing, flexographic printing, silk screen printing, These layers may be appropriately formed by applying by a known printing method such as offset printing or extrusion molding.

  The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
As a base sheet, a general paper for building materials with a rice weighing of 30 g / m ² is prepared, an acrylic resin and nitrified cotton are used as binders on one side of the paper, and inks using titanium white, red valves, and yellow lead as colorants are used. A (overall solid) layer having a coating amount of 5 g / m ² was applied by gravure printing to form a colored hiding layer. On top of that, a wood grain pattern layer was formed by gravure printing using an ink containing nitrified cotton as a binder and a coloring agent having a valve pattern as a main component.

Next, using acrylic polyol resin as a binder, 10 parts by mass of silica particles were blended with 100 parts by mass of the binder, and 5 parts by mass of urethane beads were blended with 100 parts by mass of the binder to prepare a coating composition, and a coating amount of 5 g / Gravure printing was performed on the entire surface with m ² to form a transparent resin layer.

  Then, next, for transparent ink (conduit ink) using a polyester urethane resin having a number average molecular weight of 30,000 and a glass transition temperature (Tg) of 62.8 ° C. as a binder, silica having an average particle diameter of 1.5 μm. A low-gloss pattern layer was formed by gravure printing using an ink composition containing 10% by mass of particles so as to align with the conduit portion having a wood pattern.

  Next, as a resin component, 5 parts by mass of urethane beads (average particle diameter 5 μm, Mohs hardness 3) as a wear-resistant filler is contained with respect to 100 parts by mass of an ionizing radiation curable resin composed of a hexafunctional urethane acrylate, and a silicone. An ionizing radiation curable resin composition containing 2% by mass of oil with respect to 100% by mass of the ionizing radiation curable resin composition was applied by a gravure direct coater method.

  After the coating, an electron beam having an accelerating voltage of 125 kV and an irradiation dose of 30 kGy was irradiated to cure the ionizing radiation curable resin to form a surface protective layer having a thickness of 4 μm.

  Finally, curing was performed at 70 ° C. for 24 hours to obtain a decorative sheet.

Examples 2-9, Comparative Examples 1-7
Makeup was performed in the same manner as in Example 1 except that the thickness of the surface protective layer, the resin contained in the surface protective layer, the amount of the wear-resistant filler added, the type, the Mohs hardness, and the average particle diameter were changed as shown in Table 1. Sheets were prepared.

  The following evaluations were performed on the above Examples and Comparative Examples.

Scratch resistance (Martindale test)
The decorative sheets prepared in Examples and Comparative Examples were attached to MDF to prepare decorative plates. The veneer was attached to the friction table of a Martindale abrasion tester ("Martindale 1300 series model 1302 (model number)" by James Heal), and the Scotch-Bright industrial pad 7446 (3M Japan (Ltd.) ) Was applied, a load of 6 N was applied, and a friction test was performed by Lissajous figure motion under the condition of friction of 100 times. The appearance after the test was visually observed to evaluate the Lissajous mark and the change in gloss according to the following evaluation criteria.
(Lissajous mark)
○: Lissajous mark is not seen △: Minor Lissajous mark is seen, but there is no problem in actual use ×: Lissajous mark is noticeable (gloss change)
◯: No change in gloss is seen Δ: A slight change in gloss is seen, but there is no problem in actual use ×: Significant change in gloss is seen

Design (Gloss Matte Evaluation)
The gloss matte feeling on the surface of the decorative sheet was visually observed and evaluated according to the following evaluation criteria.
◎: Gloss matte is sufficiently expressed ○: Gloss matte is expressed △: Gloss matte is slightly expressed, but poor in design ×: Gloss matte is not expressed (Low (Glossiness evaluation)
With respect to the decorative sheets prepared in Examples and Comparative Examples, the gloss level at an incident angle of 85 degrees was measured by using a VG-2000 type (model number) manufactured by Nippon Denshoku Industries Co., Ltd. by a measuring method according to ASTM D523. . The evaluation was performed according to the following evaluation criteria based on the measured glossiness. In the following evaluation, if the evaluation is Δ or more, it can be determined that there is no problem in practical use.
A: Gloss is less than 7 B: Gloss is 7 or more and 10 or less B: Gloss is more than 10 and less than 20 X: Gloss is 20 or more

Equipment damage evaluation The suitability for mass production in the manufacturing process was observed and evaluated according to the following evaluation criteria.
○: The equipment (doctor blade) is not damaged before and after production, and the appearance (luster) of the product is stable. ×: The equipment (doctor blade) is damaged before and after production, and the appearance (luster) of the product also changes. are doing

In the processability manufacturing process, the state of the decorative sheet was observed, it was judged whether or not the post-process could proceed, and the evaluation was performed according to the following evaluation criteria.
◯: Curling of the decorative sheet and cracking of the surface protective layer are suppressed, and the post-process can proceed. Δ: Curling of the decorative sheet and cracking of the surface protective layer occur slightly, but the post-process can proceed. And there is no problem in actual use. ×: Curling of the decorative sheet, cracking of the surface protective layer occur, and subsequent process cannot proceed.

Applicability (Transition stability)
When the ionizing radiation-curable resin composition for forming the surface protective layer was applied, the state of surface transition was visually observed and the coating suitability was evaluated according to the following evaluation criteria.
◯: The ionizing radiation curable resin composition is stably transferred to the coated surface
Δ: Some unevenness in the transition is confirmed, but there is no problem in actual use ×: There is a gap on the coated surface of the ionizing radiation curable resin composition or the thickness is unstable. Shown in.

1. Decorative sheet 2. Base sheet 3. Pattern layer 4. Low gloss pattern layer 5. Surface protective layer 6. Colored hiding layer 7. Transparent resin layer 8. Back primer layer

Claims (3)

A decorative sheet having a relatively low-gloss portion and a relatively high-gloss portion,
On the substrate sheet, a low-gloss pattern layer and a surface protective layer forming a relatively low-gloss portion are laminated at least in this order,
(1) The low-gloss pattern layer is formed in a pattern and is laminated so as to be in contact with the surface protective layer,
(2) The thickness of the surface protective layer is 2 to 12 μm,
(3) the surface protective layer contains a wear-resistant filler having an average particle diameter of. 15 to 25.mu. m,
(4) The wear resistant filler has a Mohs hardness of 8 or less,
(5) The content of the wear resistant filler is 3 to 15 parts by mass with respect to 100 parts by mass of the resin component contained in the surface protective layer,
(6) The wear resistant filler is organic particles,
A decorative sheet characterized by that.   The decorative sheet according to claim 1, wherein the surface protective layer contains an ionizing radiation curable resin.   A decorative board obtained by sticking the decorative sheet according to claim 1 or 2 to an adherend.