WO2021065042A1 - Decorative material - Google Patents

Decorative material Download PDF

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Publication number
WO2021065042A1
WO2021065042A1 PCT/JP2020/014065 JP2020014065W WO2021065042A1 WO 2021065042 A1 WO2021065042 A1 WO 2021065042A1 JP 2020014065 W JP2020014065 W JP 2020014065W WO 2021065042 A1 WO2021065042 A1 WO 2021065042A1
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Prior art keywords
layer
cured product
region
decorative
base material
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PCT/JP2020/014065
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French (fr)
Japanese (ja)
Inventor
祥太 西根
小笠原 健
玲子 桜井
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大日本印刷株式会社
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Priority to JP2021551114A priority Critical patent/JPWO2021065042A1/ja
Publication of WO2021065042A1 publication Critical patent/WO2021065042A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/42Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class

Definitions

  • the present invention relates to a decorative material.
  • the surfaces of tables, counters, walls, floors, etc. are impregnated with an uncured resin solution of melamine resin in a porous base material such as titanium paper, laminated on phenol core paper or the like as necessary, and then impregnated resin.
  • a decorative material is used in which the liquid is cured by a hot press.
  • a decorative material impregnated and cured with such a melamine resin exhibits physical properties such as strength, hardness, and heat resistance.
  • the decorative material as described above is required to have a design showing a high-class feeling, and a visual three-dimensional effect is imparted by forming an uneven shape on the surface.
  • a decorative material having an uneven shape on the surface an embossed decorative material using an embossed plate (mirror surface plate with a texture) having an uneven shape has been proposed (see, for example, Patent Documents 1 and 2). ).
  • Patent Document 3 has been proposed as a decorative material having a surface uneven shape that does not use an embossed plate.
  • the decorative material of Patent Document 3 includes a paper base material, a release layer containing a cured product of an ionizing radiation curable resin provided on a part of the surface of the paper material base material, and the rest of the surface of the paper quality base material (paper quality). It is provided with a surface layer containing a cured product of a melamine resin provided on a portion of the surface of the base material on which a release layer is not provided).
  • the decorative board of Patent Document 3 is a step of providing a release layer on a part of the surface of a paper substrate, impregnating the paper substrate with an uncured melamine resin, and covering the release layer with the uncured melamine resin.
  • the decorative layer on the base material is worn over time because the thickness of the surface layer containing the cured product of the melamine resin cannot be increased. It was found that the design was reduced. Further, the present inventors have found that the reason why the thickness of the surface layer of the decorative material of Patent Document 3 cannot be increased is that the thickness of the release layer is thin. This is because when the thickness of the release layer is thin, if the thickness of the surface layer is increased, the thickness of the cured resin film on the release layer becomes thicker, and the cured resin film is peeled off when the cured resin film on the release layer is peeled off.
  • An object of the present invention is to provide the following [1] to [8].
  • a decorative material having a base material selected from a paper base material and a fiber base material, and the decorative material has a first region and a second region in a plane, and corresponds to the first region.
  • the decorative material at the portion to be subjected to has a permeation prevention layer and a first cured product layer having a releasable surface in this order on the base material, and the said portion corresponding to the second region.
  • the decorative material has a second cured product layer on the base material, the thickness of the permeation prevention layer is t0, the thickness of the first cured product layer is t1, and the thickness of the second cured product layer is t0.
  • t1 is more than 3.5 ⁇ m and 30.0 ⁇ m or less.
  • t2- (t0 + t1) is 2.0 ⁇ m or more and 50.0 ⁇ m or less.
  • the decorative material of the present invention is a decorative material having a base material selected from a paper base material and a fiber base material, and the decorative material has a first region and a second region in a plane, and the first region is described above.
  • the decorative material in a portion corresponding to one region has a permeation prevention layer and a first cured product layer having a releasable surface in this order on the base material, and corresponds to the second region.
  • the decorative material at the portion to be subjected to has a second cured product layer on the base material, the thickness of the permeation prevention layer is t0, the thickness of the first cured product layer is t1, and the second cured product. When the thickness of the layer is defined as t2, the relationship of t0 + t1 ⁇ t2 is satisfied.
  • FIG. 1 is a cross-sectional view showing an embodiment of the decorative material 100 of the present invention.
  • the decorative material 100 of FIG. 1 has a first region R1 and a second region R2 in a plane. Further, the decorative material 100 of FIG. 1 has a permeation prevention layer 31 and a first cured product layer 32 having a releasable surface in this order on the base material 10 at a portion corresponding to the first region R1. doing. Further, the decorative material 100 of FIG. 1 has a second cured product layer 22 on the base material 10 at a portion corresponding to the second region R2.
  • FIG. 1 is a cross-sectional view showing an embodiment of the decorative material 100 of the present invention.
  • the decorative material 100 of FIG. 1 has a first region R1 and a second region R2 in a plane. Further, the decorative material 100 of FIG. 1 has a permeation prevention layer 31 and a first cured product layer 32 having a releasable surface in this order on the base material 10 at a portion
  • t0 indicates the thickness of the permeation prevention layer 31
  • t1 indicates the thickness of the first cured product layer 32 having releasability
  • t2 indicates the thickness of the second cured product layer 22.
  • the decorative material 100 of FIG. 1 satisfies the relationship of t0 + t1 ⁇ t2.
  • the decorative material 100 of FIG. 1 has a first decorative layer 33 between the base material 10 and the permeation prevention layer 31 at a portion corresponding to the first region R1.
  • the decorative material 100 of FIG. 1 has a second decorative layer 23 between the base material 10 and the second cured product layer 22 at a portion corresponding to the second region R2.
  • flat surface means a surface on the side having the permeation prevention layer based on the base material of the decorative material of the present invention (the decorative material of FIG. 1 is visually recognized from the permeation prevention layer side with reference to the base material). It means (in the xy plane).
  • planar view means that the decorative material of the present invention is viewed vertically from the side having the permeation prevention layer with reference to the base material.
  • the base material is selected from a paper base material and a fiber base material, and a paper base material is preferable.
  • a curable resin By impregnating the paper base material and the fiber base material with a curable resin, excellent mechanical properties and the like can be imparted, and by extension, the pencil hardness of the surface of the decorative material is increased, and the surface of the decorative material is easily scratched. It is preferable in that it can be done.
  • the paper base material examples include kraft paper, titanium paper, linter paper, resin impregnated paper, thin paper and Japanese paper.
  • the fiber base material is composed of a fiber base material composed of inorganic fibers such as glass fiber, alumina fiber, silica fiber, and carbon fiber, and organic fiber of various synthetic resins such as polyester resin, acrylic resin, polyethylene resin, and polypropylene resin. Examples thereof include a fiber base material to be used, and a base material such as a composite thereof. Further, the fiber base material may be a non-woven fabric or a woven fabric.
  • the thickness of the base material is not particularly limited and may be appropriately selected according to the desired performance, and is usually about 10 to 150 ⁇ m, preferably 20 to 120 ⁇ m, more preferably 20 to 120 ⁇ m from the viewpoint of ensuring mechanical physical characteristics and handleability. It is 30 to 100 ⁇ m.
  • the basis weight thereof is usually about 20 to 150 g / m 2 , preferably 30 to 100 g / m 2 , from the same viewpoint.
  • the base material is preferably impregnated with a curable resin.
  • a curable resin such as a thermosetting resin or an ionizing radiation curable resin can be used, and the thermosetting resin is preferable from the viewpoint of handleability.
  • a melamine resin, a urea resin, a melamine-urea resin, a guanamine resin, and a sulfonamide resin are used from the viewpoint of further enhancing the texture of the decorative material and improving the mechanical strength of the decorative material.
  • Dialyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin and the like are preferable, and among them, melamine resin, urea resin, melamine-urea resin, phenol resin, guanamine resin and sulfonamide resin and the like.
  • the thermosetting resin of the above is preferable. Further, among the thermosetting resins, melamine resin, melamine-urea resin and phenol resin are preferable, and melamine resin is particularly preferable.
  • thermosetting resin examples include means for preparing a composition of an uncured thermosetting resin and impregnating the base material with the composition (for example, a step described later). (4).).
  • the impregnated composition becomes a cured product of a thermosetting resin by heating at an appropriate time point and curing it by a reaction such as a crosslinking reaction or a polymerization reaction (for example, step (6) described later).
  • thermosetting resin simply means a cured product obtained by curing an uncured product of a thermosetting resin.
  • curable resin composition simply means a cured product obtained by curing an uncured product of a thermosetting resin.
  • curable resin composition simply means a cured product obtained by curing an uncured product of a thermosetting resin.
  • curable resin composition means that they are uncured unless otherwise specified.
  • the base material is physically prepared on one or both sides of the base material, such as an oxidation method or an unevenness method, in order to improve the interlayer adhesion with other layers constituting the decorative material and to strengthen the adhesiveness with the adherend. It may be subjected to surface treatment such as surface treatment or chemical surface treatment, or a primer layer may be formed.
  • the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method and the like
  • the unevenness method include sandblasting method and solvent treatment method.
  • the decorative material of the present invention has a first region R1 and a second region R2 in a plane.
  • the thickness of the permeation prevention layer is defined as t0
  • the thickness of the first cured product layer is defined as t1
  • the thickness of the second cured product layer is defined as t2
  • t2- (t0 + t1) is the elevation of the first region R1 and the second. It is an index of the altitude difference from the altitude of the area R2. Therefore, by satisfying the relationship of t0 + t1 ⁇ t2, the first region R1 is visually recognized as being recessed, and the second region R2 is visually recognized as being raised, and the contrast between the two regions makes the three-dimensional appearance of the decorative material good. Can be.
  • t2- (t0 + t1) is preferably 2.0 ⁇ m or more and 50.0 ⁇ m or less, more preferably 5.0 ⁇ m or more and 35.0 ⁇ m or less, and further preferably 10.0 ⁇ m or more and 30.0 ⁇ m or less. ..
  • t2- (t0 + t1) is preferably 2.0 ⁇ m or more and 50.0 ⁇ m or less, more preferably 5.0 ⁇ m or more and 35.0 ⁇ m or less, and further preferably 10.0 ⁇ m or more and 30.0 ⁇ m or less. ..
  • t2- (t0 + t1) By setting t2- (t0 + t1) to 2.0 ⁇ m or more, it is possible to easily improve the three-dimensional effect. Further, by setting t2- (t0 + t1) to 50.0 ⁇ m or less, the first region and the second region can be stably produced easily.
  • t0, t1 and t2 are calculated as the average value of the thicknesses at 20 points.
  • the thickness can be calculated, for example, from a cross-sectional photograph of the decorative material. It is preferable that the 20 locations for calculating the average value are picked up so that there is no bias in the locations.
  • S2 / S1 is preferably 0.5 to 20, preferably 1.0 to 10. Is more preferable.
  • S2 / S1 is preferably 0.5 to 20, preferably 1.0 to 10. Is more preferable.
  • the first region is a region that is recessed and visually recognized as compared with the second region.
  • the first region has a permeation prevention layer and a first cured product layer having a releasable surface in this order on the base material.
  • the surface of the first region is preferably roughened. By roughening the surface of the first region, the first region is dented and easily visible, and the three-dimensional effect can be improved.
  • the permeation prevention layer is arranged between the base material and the first cured product layer.
  • the composition constituting the first cured product layer is suppressed from penetrating into the base material side, the thickness of the first cured product layer is secured, and the thickness of the second cured product layer can be increased. This makes it easier to improve the wear resistance of the decorative material.
  • the permeation prevention layer is provided on a part of the base material, not all on the base material. This is because when the permeation prevention layer is formed on the entire base material, it becomes difficult for the curable resin to impregnate the base material.
  • the area of the permeation prevention layer existing in the first region is preferably 90 or more, and is 95 or more. Is more preferable, 97 or more is further preferable, and 99 or more is even more preferable. In other words, it is preferable that the permeation prevention layer is substantially not present in a portion other than the first region in the plane of the decorative material.
  • the permeation prevention layer preferably contains a curable resin.
  • the permeation prevention layer preferably contains a cured product of an uncured curable resin composition.
  • the content of the curable resin is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more of the total solid content constituting the permeation prevention layer. It is preferably 90% by mass or more, and more preferably 90% by mass or more. Since the permeation prevention layer contains the curable resin, the sealing effect of the first cured product layer by the permeation prevention layer can be improved.
  • the composition forming the permeation prevention layer contains a thermoplastic resin.
  • the content of the thermoplastic resin is preferably 2 to 30 parts by mass and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the curable resin.
  • the thermoplastic resin include general-purpose thermoplastic resins such as acrylic resins, polyester resins, and cellulosic resins.
  • Examples of the curable resin of the permeation prevention layer include a thermosetting resin and an ionizing radiation curable resin, and an ionizing radiation curable resin is more preferable.
  • thermosetting resin As the thermosetting resin, the same ones as those exemplified as the thermosetting resin that can be impregnated in the base material can be preferably exemplified.
  • the ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation curable functional group.
  • the ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group is preferably mentioned. Be done.
  • ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and ⁇ -rays, and charged particle beams such as ⁇ -rays and ion rays are also included.
  • the ionizing radiation curable resin can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.
  • the ionizing radiation curable resin is preferably a polymerizable oligomer from the viewpoint of facilitating the suppression of the composition forming the permeation prevention layer from penetrating into the base material.
  • a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable.
  • “(meth) acrylate” means "acrylate or methacrylate”.
  • the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group.
  • An acrylate monomer having an acryloyl group is preferable from the viewpoint of obtaining a design property with a higher texture and better surface properties.
  • the number of functional groups is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and the upper limit is preferably 8 or less, more preferably 6 from the viewpoint of obtaining a higher quality design and better surface characteristics. It is as follows. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.
  • polymerizable monomers examples include bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate; trimethylol.
  • bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate; trimethylol.
  • dipentaerythritol such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate from the viewpoint of obtaining higher texture design and better surface characteristics.
  • a system-polymerizable monomer is preferable, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferable, and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are used in combination. Is particularly preferable.
  • the polymerizable oligomer examples include a (meth) acrylate oligomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group.
  • urethane (meth) acrylate oligomer epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, acrylic (meth) acrylate oligomer, polycaprolactone urethane (meth).
  • Acrylate oligomer polycaprolactone diol urethane (meth) acrylate and the like.
  • the number of functional groups of these polymerizable oligomers is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 8 or less, more preferably. It is 6 or less.
  • the weight average molecular weight of the polymerizable oligomer is preferably 500 or more, more preferably 1,000 or more, and the upper limit is preferably 80,000 or less, more preferably 50,000 or less.
  • the weight average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.
  • the permeation prevention layer preferably contains substantially no release agent from the viewpoint of facilitating the formation of the first cured product layer.
  • the fact that the release agent is substantially not contained means that the content of the release agent is less than 0.1% by mass of the total solid content of the permeation prevention layer, preferably 0.01% by mass or less. Yes, more preferably 0% by mass (does not contain a release agent).
  • the permeation prevention layer contains substantially no filler.
  • the fact that the filler is substantially not contained means that the content of the filler is less than 0.1% by mass of the total solid content of the permeation prevention layer, and is preferably 0.01% by mass or less, more preferably. Is 0% by mass (does not contain filler).
  • the thickness t0 of the permeation prevention layer is preferably 0.1 to 10.0 ⁇ m, more preferably 0.5 to 5.0 ⁇ m.
  • the first cured product layer is formed on at least a part of the permeation prevention layer and has a releasable surface. Since the surface of the first cured product layer has a releasable property, most of the second cured product layer on the first cured product layer is peeled off.
  • the second cured product layer on the first cured product layer is preferably completely peeled off from the viewpoint of improving the three-dimensional appearance due to the surface unevenness, but the second cured product layer is completely peeled off from the first cured product layer. In many cases, it cannot be done. Therefore, a small amount of the second cured product layer may remain on the first cured product layer as long as the effect of the present invention is not impaired.
  • the first cured product layer is preferably formed in synchronization with the pattern of the permeation prevention layer. For example, when the total area of the first cured product layer when the decorative material is viewed in a plan view is 100, the area of the first cured product layer existing on the permeation prevention layer is preferably 90 or more, preferably 95 or more. It is more preferably 97 or more, and even more preferably 99 or more.
  • the thickness t1 of the first cured product layer is preferably more than 3.5 ⁇ m and 30.0 ⁇ m or less, more preferably 5.0 ⁇ m or more and 25.0 ⁇ m or less, and 7.0 ⁇ m or more and 20.0 ⁇ m or less. Is even more preferable.
  • t1 By setting t1 to more than 3.5 ⁇ m, even if the thickness of the second cured product layer is increased, the second cured product layer is formed in the first region when the second cured product layer is peeled from the first region R1. Can be prevented from coagulating and breaking (see step (8) described later).
  • the thickness of the second cured product layer can be increased, and as a result, the wear resistance of the decorative material can be easily improved. Further, by setting t1 to 30.0 ⁇ m or less, the first cured product layer can be stably formed.
  • the first cured product layer is a layer formed of a curable resin, more specifically, a layer formed of a cured product of an uncured curable resin composition.
  • a curable resin a thermosetting resin and an ionizing radiation curable resin are preferably mentioned, and an ionizing radiation curable resin is more preferable, from the viewpoint of obtaining a design property with a higher texture and better surface characteristics.
  • thermosetting resin the same ones as those exemplified as the thermosetting resin that can be impregnated in the base material can be preferably exemplified.
  • thermosetting resin the same ones as those exemplified as the thermosetting resin that can be impregnated in the base material can be preferably exemplified.
  • ionizing radiation curable resin the same ones as those exemplified for the permeation prevention layer can be preferably exemplified.
  • the first cured product layer preferably contains a release agent.
  • a release agent By containing a release agent, it can be peeled off even if another resin is laminated on the surface of the releasable ink decorative layer (the surface of the first cured product layer), while the other resin adheres to the second region. Since it is not peeled off, it is possible to easily give an elevation difference between the first region and the second region.
  • the release agent examples include a fluorine-based release agent, a silicone-based release agent, and the like, and a silicone-based release agent is preferable from the viewpoint of obtaining a design with a higher texture.
  • the silicone-based mold release agent examples include those having a polysiloxane structure as a basic structure, and among them, modified silicone oil in which an organic group is introduced into at least one of the side chain and the terminal thereof is preferable, and organic groups are present at both ends. The introduced modified silicone oil is more preferred.
  • a reactive functional group such as a (meth) acrylic group, an amino group, an epoxy group, a mercapto group, a carbinol group, a phenol group or a carboxyl group, or a polyether group
  • Non-reactive group functional groups such as aralkyl group, fluoroalkyl group, alkyl group, fatty acid amide group and phenyl group are preferably mentioned.
  • a reactive functional group is preferable, and a (meth) acrylic group is particularly preferable, that is, a (meth) acrylic-modified silicone oil is particularly preferable.
  • these organic groups may have substituents such as a nitrogen atom, a sulfur atom, a hydroxyl group and an alkyl group.
  • the content of the release agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and further preferably more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin forming the first cured product layer. It is 1 to 2 parts by mass. When the content of the release agent is within the above range, the effect of adding the release agent can be efficiently obtained.
  • the first cured product layer preferably contains an inorganic filler.
  • the inorganic filler include oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, zinc oxide and zirconia oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; magnesium carbonate and carbon dioxide. Carbonates such as calcium; sulfates such as calcium sulfate and barium sulfate; particles made of inorganic materials such as silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate.
  • oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide and zinc oxide are preferable, and silica is particularly preferable.
  • the average particle size of the inorganic filler is preferably 0.3 to 20 ⁇ m, more preferably 0.5 to 10 ⁇ m, from the viewpoint of facilitating Ra1 in the range described later.
  • the average particle size of the filler is a value measured by a laser diffraction / scattering method.
  • the content of the inorganic filler is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the curable resin forming the first cured product layer, from the viewpoint of facilitating Ra1 in the range described later. It is by mass, more preferably 20 to 35 parts by mass. When the content of the inorganic filler is within the above range, the effect of adding the inorganic filler can be efficiently obtained.
  • the decorative material of the present invention preferably has a first decorative layer at least in a part between the base material and the permeation prevention layer in a portion corresponding to the first region.
  • the first decorative layer may be formed in an arbitrary pattern in the first region.
  • the arbitrary pattern depends on the design to be imparted to the entire decorative material.
  • the first decorative layer preferably forms one or more patterns selected from conduits, autumn materials and knots.
  • the first region preferably forms one or more patterns selected from wood conduits, autumn wood and knots.
  • a duct is a cylindrical cell that serves as a passage for water, and the arrangement of minute conduits makes it appear to the human eye that a dark pattern is formed along the arrangement.
  • Autumn wood is a dark-colored part with narrow eyes that is formed from summer to autumn.
  • the part with a large mesh width made from spring to summer is called spring wood, and the annual rings of wood are formed by alternately repeating spring wood and autumn wood.
  • a node is a trace of a branch incorporated into the trunk, has a shape close to a circle or an ellipse, and has a darker color than the surrounding tissue.
  • the design given to the entire decorative material is a stone pattern such as travertine
  • the first decorative layer has a concave pattern.
  • the first region preferably forms a stone recessed pattern.
  • the design to be applied to the entire decorative material is a tile pattern or a brick pattern
  • the first decorative layer is a joint pattern.
  • the first region preferably forms a tile or brick joint pattern.
  • the first decorative layer can be formed, for example, by printing with an ink for forming the first decorative layer containing a colorant and a binder resin.
  • the colorant for the first decorative layer examples include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, valve handle, cadmium red, ultramarine blue, cobalt blue and other inorganic pigments, and quinacridone red. , Isoindolinone yellow, organic pigments such as phthalocyanine blue, dyes and the like.
  • the colorant of the first decorative layer preferably does not contain a bright pigment.
  • the binder resin of the first decorative layer is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral. Examples thereof include resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fibrous derivatives, rubber resins and the like.
  • the thickness of the first decorative layer can be appropriately adjusted in the range of about 0.1 to 20 ⁇ m in consideration of the desired design.
  • the arithmetic mean roughness Ra of JIS B0601: 1994 at a cutoff value of 0.8 mm on the surface of the first region is preferably 1.0 to 5.0 ⁇ m, more preferably 1.0 to 3.0 ⁇ m. preferable.
  • Ra of the first region By setting Ra of the first region to 1.0 ⁇ m or more, the first region can be recessed to make it easier to see. Further, by setting Ra of the first region to 5.0 ⁇ m or less, it is possible to suppress the appearance of the first region as whitish and facilitate the improvement of the design.
  • Ra in the first region can be adjusted by, for example, roughening the base material, roughening the layer formed on the base material (such as the first cured product layer described later), and the like.
  • the second region is a region that is visually recognized higher than the first region.
  • the second region has a second cured product layer on the substrate.
  • the second cured product layer is a layer formed of a curable resin, more specifically, a layer formed of a cured product of an uncured curable resin composition.
  • thermosetting resin and an ionizing radiation curable resin are preferably mentioned, and a thermosetting resin is more preferable, from the viewpoint of obtaining a design property with a higher texture.
  • curable resins may be used alone or in combination of two or more, for example, a thermosetting resin and an ionizing radiation curable resin may be used in combination, or these curable resins and thermoplastics may be used in combination. It may be used in combination with a resin.
  • thermosetting resin the same ones as those exemplified as the thermosetting resin that can be impregnated in the base material can be preferably exemplified, and the above-mentioned various thermosetting resins are preferable, and melamine resin is particularly preferable. It is the same.
  • a curable resin By using such a curable resin, a design property with a higher texture can be obtained, the adhesion to the base material is improved, and more excellent mechanical strength can be obtained.
  • the ionizing radiation curable resin include those similar to those exemplified in the permeation prevention layer.
  • the content of the curable resin with respect to the total of these resins is usually about 50% by mass or more and less than 100% by mass, preferably 60% by mass or more and 90% by mass or less. Is.
  • the second cured product layer preferably does not contain particles from the viewpoint of reducing diffusion.
  • the thickness t2 of the second cured product layer is preferably 5.0 ⁇ m or more and 50.0 ⁇ m or less, more preferably 10.0 ⁇ m or more and 40.0 ⁇ m or less, and 25.0 ⁇ m or more and 35.0 ⁇ m or less. Is even more preferable.
  • t2 By setting t2 to 5.0 ⁇ m or more, it is possible to easily improve the wear resistance of the decorative material. Further, by setting t2 to 50.0 ⁇ m or less, stable production becomes possible.
  • the second decorative layer can be formed, for example, by printing with an ink for forming a second decorative layer containing a colorant and a binder resin.
  • the colorant and binder resin of the second decorative layer include those exemplified by the colorant and binder resin of the first decorative layer described later.
  • the second decorative layer may be formed on the base material in an arbitrary pattern, for example.
  • the arbitrary pattern depends on the design to be imparted.
  • the arbitrary pattern is preferably a wood surface pattern (a portion other than the conduit groove pattern and / or the knot pattern) when a wood grain pattern is given to the entire decorative material, and the entire decorative material is made of stone such as travertin.
  • a pattern is given, it is preferable to use a pattern other than the recessed portion, and when giving a tile pattern or a brick pattern to the entire decorative material, it is preferable to use a tile portion or a brick portion.
  • the thickness of the second decorative layer can be appropriately adjusted in the range of about 0.1 to 20 ⁇ m in consideration of the desired design.
  • the arithmetic mean roughness Ra of JIS B0601: 1994 at a cutoff value of 0.8 mm on the surface of the second region is preferably 2.0 ⁇ m or less, and more preferably 0.5 to 1.5 ⁇ m.
  • the decorative material of the present invention preferably has a reinforcing layer on the surface opposite to the side having the permeation prevention layer of the base material.
  • a thermosetting resin decorative board having more excellent mechanical properties can be obtained by combining the reinforcing layers.
  • the reinforcing layer examples include a thermosetting resin impregnated sheet.
  • the types of the fiber base material and the paper base material used in the thermosetting resin impregnated sheet are not particularly limited as long as they are exemplified as the base material fiber base material and the paper base material, and the basis weight is preferably 100 to 100. It is 300 g / m 2 , more preferably 150 to 250 g / m 2 .
  • the thermosetting resin can be used without particular limitation as long as it can be impregnated in the base material in the state of the thermosetting resin composition, and a phenol resin is preferable. That is, a phenol resin impregnated paper is preferable as the reinforcing layer.
  • the phenol resin impregnated paper is produced by, for example, impregnating kraft paper having a basis weight of 150 to 250 g / m 2 with phenol resin so as to have an impregnation rate of about 20 to 60% and drying at about 100 to 140 ° C. Phenol formaldehyde is preferably used.
  • a primer layer can be provided between each layer in order to improve the adhesion of each layer.
  • the resin material forming the primer layer include urethane resin, polyester resin, acrylic resin, acrylic urethane resin, vinyl chloride-vinyl acetate copolymer resin and the like.
  • the thickness of the primer layer is usually about 0.1 to 15 ⁇ m, preferably 1 to 10 ⁇ m from the viewpoint of efficiently obtaining excellent adhesion.
  • the decorative material of the present invention may be one in which an adherend is laminated and integrated on the back surface of the base material (the side opposite to the side having the permeation prevention layer of the base material).
  • the adherend is, for example, a single wood board, a wood plywood board, a particle board, an MDF (medium density fiber board), a wood board such as an laminated material; a plaster board such as a plaster board or a plaster slag board; , Lightweight foamed concrete board, hollow extruded cement board, etc.; fiber cement board, pulp cement board, asbestos cement board, wood piece cement board, etc .; ceramic board, pottery, porcelain, earthenware, glass, amber, etc.
  • MDF medium density fiber board
  • Metal plates such as steel plates, polyvinyl chloride sol coated steel plates, aluminum plates and copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates and polycarbonate plates; phenol resin plates, urea resin plates and unsaturated polyester resin plates , Thermo-curable resin plate such as polyurethane resin plate, epoxy resin plate, melamine resin plate; resin such as phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin, glass fiber Examples thereof include a so-called FRP plate obtained by impregnating and curing a non-woven fabric, cloth, paper, or other various fibrous base materials to form a composite, and these may be used alone or as a composite substrate in which two or more of these are laminated. You may.
  • thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates and polycarbonate plates
  • the method of laminating the base material and various adherends is not particularly limited, and for example, a method of adhering a sheet to the adherend with an adhesive or the like can be adopted.
  • the adhesive may be appropriately selected from known adhesives according to the type of adherend and the like.
  • polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer and the like, as well as butadiene-acrylic nitrile rubber, neoprene rubber, natural rubber and the like can be mentioned.
  • the decorative material of the present invention is used, for example, as a top plate for various counters and desks; furniture; cabinets for kitchen products; residential building materials such as doors; and the like.
  • the members used in the parts including the horizontal surface such as the top plate used for the counter and the desk are required to have a visual three-dimensional effect as compared with the members used in the vertical surface. Since it is rubbed by various objects such as clothes, cleaning supplies, and watches, abrasion resistance is required, and it is preferable in that the effect of the decorative board of the present invention can be easily exhibited.
  • the decorative material of the present invention can be produced, for example, by the following steps (1) to (8).
  • a step of obtaining a laminate C which comprises arranging a release film on the uncured curable resin composition layer side of the laminate B.
  • the release film is peeled off from the laminate C, the second cured product layer on the first cured product layer of the second cured product layer is removed together with the release film, and the concave first.
  • the step (1) is a step of preparing the base material 10.
  • the step (2) is a step of forming the permeation prevention layer 31 on a part of the base material 10 (FIG. 2).
  • the curable resin composition used for forming the permeation prevention layer is preferably cured at this stage.
  • the decorative material 100 has the first decorative layer 33 and / or the second decorative layer 23
  • the first decorative layer 33 and / or the second decorative layer 23 is formed between the steps (1) and (2). It is preferable to have a step of performing (FIG. 2).
  • the step (3) is a step of obtaining a laminated body A (71) formed by forming a first cured product layer 32 having a releasable surface on a part of the permeation prevention layer 31 (FIG. 3).
  • the curable resin composition used for forming the first cured product layer 32 is preferably cured at this stage.
  • the portion where the first cured product layer 32 is formed on the permeation prevention layer 31 is a portion corresponding to the first region R1 of the decorative material obtained by the production method of the present invention.
  • the laminated body A is impregnated with the curable resin composition, and the uncured curable resin composition layer 22a is formed on the entire surface of the laminated body A on the side having the permeation prevention layer 31.
  • This is a step of obtaining the body B (72) (FIG. 4).
  • the base material 10 can be impregnated with the curable resin composition.
  • the step (5) is a step of obtaining a laminate C (73) formed by arranging the release film 80 on the uncured curable resin composition layer 22a side of the laminate B (FIG. 5).
  • the release film 80 is a second cured product layer on the first cured product layer 32 having a releasable surface among the second cured product layers obtained by curing the uncured curable resin composition layer 22a in the step (7) described later.
  • It has a role of removing the cured product layer. That is, the adhesive force between the release film 80 and the second cured product layer is A1, the second cured product layer and the layer located on the base material 10 side of the cured product layer (in the case of the first region R1, the first cured product).
  • the adhesive force with the second decorative layer 23 or the base material 10 is A2, A1> A2 in the first region R1 and A1 ⁇ A2 in the second region R2.
  • the material of the release film 80 is not particularly limited as long as the relationship is satisfied.
  • the release film 80 is a single layer of a sheet of various resins such as polyester resin such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resin such as polyethylene and polypropylene; acrylic resin; or a resin layer formed on these resin sheets. Things can be mentioned.
  • the decorative material 100 has the reinforcing layer 60
  • the laminated body C (73) is hot-pressed with both sides of the laminated body C (73) sandwiched between mirror plates to cure the uncured curable resin composition layer 22a.
  • This is a step of forming the bi-cured product layer 22.
  • the curable resin composition impregnated in the base material 10 can also be cured.
  • the conditions of the hot press may be appropriately adjusted according to the type of thermosetting resin used, and are not particularly limited, but are usually under temperature conditions of 100 to 200 ° C., pressure is 0.1 to 9.8 MPa, and time. Is 10 seconds to 120 minutes.
  • the step (7) is a step of taking out the laminated body C from between the mirror face plates.
  • the step (8) when the release film 80 is peeled off from the laminate C, the second cured product layer on the first cured product layer 32 of the second cured product layer is removed together with the release film 80, and the shape is concave.
  • This is a step of forming the first region R1 and forming the second region R2 in which the second cured product layer 22 remains (FIG. 1).
  • the thickness of the first cured product layer can be increased by having the permeation prevention layer. Therefore, even if the thickness of the second cured product layer is increased, the thickness of the second cured product layer can be increased in the step (8).
  • the second cured product layer on the first region R1 can be neatly peeled off without coagulation failure.
  • Example 1 Printing ink (manufactured by DIC Graphics Co., Ltd.) on a base material (titanium paper base paper for building materials, trade name "PM-67P” manufactured by KJ Special Paper Co., Ltd., basis weight: 80 g / m 2, thickness: 100 ⁇ m) Using "Ode SPTI”), a first decorative layer (conduit portion of wood grain) and a second decorative layer (bark portion of wood grain) having a thickness of 3 ⁇ m were formed by gravure printing.
  • the following curable resin composition for forming the permeation prevention layer is printed on the first decorative layer, irradiated with an electron beam (pressurized voltage: 165 KeV, 3Mrad (30 kGy)) and cured to obtain a thickness t0.
  • a 1.0 ⁇ m permeation prevention layer was formed.
  • the following curable resin composition for forming the first cured product layer is printed on the permeation prevention layer, irradiated with an electron beam (pressurized voltage: 165 KeV, 3Mrad (30 kGy)) and cured to obtain a thickness.
  • a laminated body A formed by forming a first cured product layer having t1 of 10.0 ⁇ m was obtained.
  • the laminate A was impregnated with the curable resin composition for forming the second cured product layer below, and dried to obtain a laminate B (the amount of the cured resin composition at the time of drying was 80 g / m 2). Impregnated so that Next, the following release film is laminated on the surface of the laminate B opposite to the base material (the surface on the side having the uncured second cured product layer), and on the surface of the laminate B on the base material side.
  • Reinforcing layer kraft paper impregnated with a liquid uncured resin composition made of phenol resin and obtained by impregnating it with a phenol resin impregnated core paper having a basis weight of 245 g / m 2 (Ota Core manufactured by Ota Sangyo Co., Ltd.) 3
  • a laminated body C formed by laminating the sheets was obtained.
  • both sides of the laminate C are sandwiched between mirror plates (a mirror plate is placed on the reinforcing layer side and an embossed plate is placed on the release film side), and a hot press is used to form a molding temperature: 150 ° C. and a molding pressure: 100 kg / cm 2. For 10 minutes, heat and pressure molding was performed.
  • the laminate C was taken out from between the two mirror plates, and the release film was peeled from the laminate C to obtain the decorative plate of Example 1.
  • the release film was peeled off from the laminate C, the second cured product layer on the first cured product layer was removed together with the release film, and a concave first region was formed. ..
  • a second region was formed in which the second cured product layer remained in the portion having no first cured product layer.
  • the thickness t0 of the decorative material of Example 1 was 1.0 ⁇ m
  • t1 was 10.0 ⁇ m
  • t2 was 30 ⁇ m.
  • the ratio (S2 / S1) of the area S1 of the first region to the area S2 of the second region was about 5.0.
  • ⁇ Curable resin composition for forming an anti-penetration layer > ⁇ 90 parts by mass of hexafunctional acrylate-based oligomer ⁇ 10 parts by mass of cellulosic polymer ⁇ Appropriate amount of diluting solvent
  • ⁇ Curable resin composition for forming the first cured product layer Each of the following components was stirred with a process homogenizer (manufactured by SMT Co., Ltd., "PH91") at a rotation speed of 2000 rpm for 1 hour to obtain a resin composition.
  • a process homogenizer manufactured by SMT Co., Ltd., "PH91”
  • Ionizing radiation curable resin mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, trade name “Aronix M400” manufactured by Toa Synthetic Co., Ltd.
  • 60 parts by mass ⁇ Silicone-based mold release agent (both-terminal methacryloyloxyalkyl Modified organopolysiloxane, trade name "X-22-164B” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.9 parts by mass, silane coupling treated silica 18 parts by mass (average particle size 3.0 ⁇ m) ⁇ Methyl ethyl ketone 40 parts by mass
  • ⁇ Curable resin composition for forming a second cured product layer > ⁇ Melamine formaldehyde resin 60 parts by mass ⁇ Water 35 parts by mass ⁇ Isopropyl alcohol 5 parts by mass
  • ⁇ Making a release film> The following ionizing radiation curable resin composition is applied to the easy-adhesion surface of a 50 ⁇ m-thick polyethylene terephthalate film (trade name “Cosmoshine A4100” manufactured by Toyo Boseki Co., Ltd.), and an electron beam (pressurized voltage: 165 KeV, 5Mrad) is applied. (50 kGy)) was irradiated and cured to form a cured product layer having a thickness of 5 ⁇ m, and a release film was obtained.
  • a 50 ⁇ m-thick polyethylene terephthalate film trade name “Cosmoshine A4100” manufactured by Toyo Boseki Co., Ltd.
  • an electron beam pressurized voltage: 165 KeV, 5Mrad
  • Ionizing radiation curable resin composition >> -Ionizing radiation curable resin (ethylene bottom oxide modified product of trimethylolpropane triacrylate, trade name "Aronix M350” manufactured by Toa Synthetic Co., Ltd.) 100 parts by mass-Silicone-based mold release agent (both-terminal methacryloyloxyalkyl-modified organopoly) Siloxane, trade name "X-22-164B” manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass, silica particles (trade name "Silicia 450” manufactured by Fuji Silysia Chemical Ltd., average particle size: 5.2 ⁇ m) 8 parts by mass ⁇ 50 parts by mass of ethyl acetate
  • Example 2 to 4 The decorative materials of Examples 2 to 4 were obtained in the same manner as in Example 1 except that t0, t1 and t2 were changed to the values shown in Table 1.
  • Comparative Example 1 The decorative material of Comparative Example 1 was obtained by the same method as in Example 1 except that the first cured product layer was formed on the first decorative layer without forming the permeation prevention layer.
  • the reason why the t1 of the decorative material of Comparative Example 1 shows a value smaller than that of Example 1 is that the material for forming the first cured product layer permeated into the base material in Comparative Example 1.
  • Comparative Example 2 A decorative material of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that t1 and t2 were changed to the values shown in Table 1.
  • Base material 20 Second region forming layer 22: Second cured product layer 22a: Curable resin composition layer 23: Second decorative layer 30: First region forming layer 31: Penetration prevention layer 32: First cured product Layer 33: First decorative layer 60: Reinforcing layer 71: Laminated body A 72: Laminated body B 73: Laminated body C 80: Release film 100: Cosmetic material

Abstract

The present invention provides a decorative material which has a visual stereoscopic effect and high wear resistance. A decorative material includes a substrate selected from a paper substrate and a fibrous substrate. The decorative material has a first region and a second region in a plane. The decorative material at a point corresponding to the first region sequentially include, in this order, a penetration prevention layer and a first hardened material layer with mold releasability on the substrate. The decorative material at a point corresponding to the second region includes a second hardened material layer on the substrate. The relationship of t0 + t1 < t2 is satisfied where t0 is defined as the thickness of the penetration prevention layer, t1 is defined as the thickness of the first hardened material layer, and t2 is defined as the thickness of the second hardened material layer.

Description

化粧材Cosmetic material
 本発明は、化粧材に関する。 The present invention relates to a decorative material.
 従来、テーブル、カウンター、壁、床等の表面には、チタン紙等の多孔質基材にメラミン樹脂の未硬化樹脂液を含浸させ、必要に応じてフェノールコア紙等に積層した上で含浸樹脂液を熱プレスで硬化せしめてなる化粧材が使用されている。このようなメラミン樹脂を含浸及び硬化させた化粧材は、強度、硬さ、耐熱性等の物性を示す。 Conventionally, the surfaces of tables, counters, walls, floors, etc. are impregnated with an uncured resin solution of melamine resin in a porous base material such as titanium paper, laminated on phenol core paper or the like as necessary, and then impregnated resin. A decorative material is used in which the liquid is cured by a hot press. A decorative material impregnated and cured with such a melamine resin exhibits physical properties such as strength, hardness, and heat resistance.
 上述のような化粧材には、高級感を示す意匠が求められており、表面に凹凸形状を形成することにより視覚的な立体感を付与することが行われている。
 表面に凹凸形状を有する化粧材としては、凹凸形状が形成されたエンボス板(テクスチャーを付けた鏡面板)を用いて、エンボス処理した化粧材が提案されている(例えば、特許文献1及び2参照)。
The decorative material as described above is required to have a design showing a high-class feeling, and a visual three-dimensional effect is imparted by forming an uneven shape on the surface.
As a decorative material having an uneven shape on the surface, an embossed decorative material using an embossed plate (mirror surface plate with a texture) having an uneven shape has been proposed (see, for example, Patent Documents 1 and 2). ).
 しかしながら、特許文献1及び2に記載されている化粧材の表面に所望の凹凸模様の意匠感を付与する場合、模様ごとにエンボス板が必要であり、コストがかかり製造が困難であるという問題がある。また、この化粧材は、凹凸形状を下地の絵柄と同調させることが困難であり、高度な意匠性を付与しにくいという問題がある。 However, in order to impart a desired uneven pattern design feeling to the surface of the decorative material described in Patent Documents 1 and 2, there is a problem that an embossed plate is required for each pattern, which is costly and difficult to manufacture. is there. Further, this decorative material has a problem that it is difficult to synchronize the uneven shape with the pattern of the base, and it is difficult to impart a high degree of design.
 一方、エンボス板を用いない表面凹凸形状を有する化粧材として、特許文献3の化粧材が提案されている。 On the other hand, the decorative material of Patent Document 3 has been proposed as a decorative material having a surface uneven shape that does not use an embossed plate.
特開2015-193209号公報Japanese Unexamined Patent Publication No. 2015-193209 特開2017-87544号公報JP-A-2017-87544 国際公開第2016/148091号International Publication No. 2016/148091
 特許文献3の化粧材は、紙質基材と、紙質基材の表面の一部に設けられた、電離放射線硬化性樹脂の硬化物を含む離型層と、紙質基材の表面の残部(紙質基材の表面のうち、離型層が設けられていない部分)に設けられた、メラミン樹脂の硬化物を含む表面層とを備えるものである。特許文献3の化粧板は、紙質基材の表面の一部に離型層を設ける工程、紙質基材にメラミン樹脂の未硬化物を含浸させるとともにメラミン樹脂の未硬化物により離型層を被覆した後、加熱することによりメラミン樹脂の未硬化物を熱硬化させる工程、及び、離型層を被覆する硬化樹脂膜を剥離する工程を含む方法により製造される。
 特許文献3の化粧材はエンボス板を用いないため、特許文献1及び2の問題は解消できる。しかしながら、特許文献3の化粧材は、経時的に意匠性が低下するケースが頻発した。
 本発明は、このような状況下になされたもので、視覚的な立体感を有するとともに、耐摩耗性に優れた化粧材を提供することを目的とするものである。
The decorative material of Patent Document 3 includes a paper base material, a release layer containing a cured product of an ionizing radiation curable resin provided on a part of the surface of the paper material base material, and the rest of the surface of the paper quality base material (paper quality). It is provided with a surface layer containing a cured product of a melamine resin provided on a portion of the surface of the base material on which a release layer is not provided). The decorative board of Patent Document 3 is a step of providing a release layer on a part of the surface of a paper substrate, impregnating the paper substrate with an uncured melamine resin, and covering the release layer with the uncured melamine resin. After that, it is produced by a method including a step of thermosetting the uncured melamine resin by heating and a step of peeling off the cured resin film covering the release layer.
Since the decorative material of Patent Document 3 does not use an embossed plate, the problems of Patent Documents 1 and 2 can be solved. However, the cosmetic material of Patent Document 3 frequently deteriorates in design over time.
The present invention has been made under such circumstances, and an object of the present invention is to provide a decorative material having a visual three-dimensional effect and excellent wear resistance.
 本発明者らは鋭意研究した結果、特許文献3の化粧材は、メラミン樹脂の硬化物を含む表面層の厚みを厚くできないことにより、基材上の装飾層が経時的に摩耗してしまい、意匠性が低下することを見出した。
 また、本発明者らは、特許文献3の化粧材の表面層の厚みを厚くできない原因が、離型層の厚みが薄いためであることを見出した。これは、離型層の厚みが薄い場合に表面層の厚みを厚くすると、離型層上の硬化樹脂膜の厚みが厚くなり、離型層上の硬化樹脂膜を剥離する際に硬化樹脂膜が凝集破壊してしまうためである。
 さらに、本発明者らは、特許文献3の化粧材の離型層の厚みを厚くできない原因が、離型層を形成する際に離型層を構成する成分が基材に染み込むことにあることを見出し、基材上の一部に浸透防止層を形成することにより上記問題を解決するに至った。
As a result of diligent research by the present inventors, in the decorative material of Patent Document 3, the decorative layer on the base material is worn over time because the thickness of the surface layer containing the cured product of the melamine resin cannot be increased. It was found that the design was reduced.
Further, the present inventors have found that the reason why the thickness of the surface layer of the decorative material of Patent Document 3 cannot be increased is that the thickness of the release layer is thin. This is because when the thickness of the release layer is thin, if the thickness of the surface layer is increased, the thickness of the cured resin film on the release layer becomes thicker, and the cured resin film is peeled off when the cured resin film on the release layer is peeled off. This is because
Further, the present inventors cannot increase the thickness of the release layer of the decorative material of Patent Document 3 because the components constituting the release layer permeate into the base material when the release layer is formed. The above problem was solved by forming a permeation prevention layer on a part of the base material.
 本発明は、下記[1]~[8]を提供することを目的とする。
[1]紙基材及び繊維基材から選ばれる基材を有する化粧材であって、前記化粧材は、平面内に、第一領域と第二領域とを有し、前記第一領域に該当する箇所の前記化粧材は、前記基材上に、浸透防止層と、表面が離型性を有する第一硬化物層とをこの順に有してなり、前記第二領域に該当する箇所の前記化粧材は、前記基材上に、第二硬化物層を有してなり、前記浸透防止層の厚みをt0、前記第一硬化物層の厚みをt1、前記第二硬化物層の厚みをt2と定義した際に、t0+t1<t2の関係を満たす、化粧材。
[2]前記浸透防止層が電離放射線硬化性樹脂を含む、[1]に記載の化粧材。
[3]t1が3.5μm超30.0μm以下である、[1]又は[2]に記載の化粧材。
[4]t2-(t0+t1)が2.0μm以上50.0μm以下である、[1]~[3]の何れかに記載の化粧材。
[5]前記第一領域に該当する箇所の前記化粧材は、前記基材と前記浸透防止層との間の少なくとも一部に第一装飾層を有する、[1]~[4]の何れかに記載の化粧材。
[6]前記第二領域に該当する箇所の前記化粧材は、前記基材と前記第二硬化物層との間の少なくとも一部に第二装飾層を有する、[1]~[5]の何れかに記載の化粧材。
[7]前記第一硬化物層が離型剤を含む、[1]~[6]の何れかに記載の化粧材。
[8]前記第二硬化物層がメラミン樹脂を含む、[1]~[7]の何れかに記載の化粧材。
An object of the present invention is to provide the following [1] to [8].
[1] A decorative material having a base material selected from a paper base material and a fiber base material, and the decorative material has a first region and a second region in a plane, and corresponds to the first region. The decorative material at the portion to be subjected to has a permeation prevention layer and a first cured product layer having a releasable surface in this order on the base material, and the said portion corresponding to the second region. The decorative material has a second cured product layer on the base material, the thickness of the permeation prevention layer is t0, the thickness of the first cured product layer is t1, and the thickness of the second cured product layer is t0. A decorative material that satisfies the relationship of t0 + t1 <t2 when defined as t2.
[2] The decorative material according to [1], wherein the permeation prevention layer contains an ionizing radiation curable resin.
[3] The decorative material according to [1] or [2], wherein t1 is more than 3.5 μm and 30.0 μm or less.
[4] The decorative material according to any one of [1] to [3], wherein t2- (t0 + t1) is 2.0 μm or more and 50.0 μm or less.
[5] Any of [1] to [4], wherein the decorative material at a portion corresponding to the first region has a first decorative layer at least in a part between the base material and the permeation prevention layer. Cosmetic material described in.
[6] The decorative material in the portion corresponding to the second region has a second decorative layer at least in a part between the base material and the second cured product layer, according to [1] to [5]. The decorative material described in any of them.
[7] The decorative material according to any one of [1] to [6], wherein the first cured product layer contains a release agent.
[8] The decorative material according to any one of [1] to [7], wherein the second cured product layer contains a melamine resin.
 本発明によれば、視覚的な立体感を有するとともに、耐摩耗性に優れた化粧材を提供することができる。 According to the present invention, it is possible to provide a decorative material having a visual three-dimensional effect and excellent wear resistance.
本発明の化粧材の一実施形態を示す断面図である。It is sectional drawing which shows one Embodiment of the decorative material of this invention. 本発明の化粧材の製造方法の一工程を示す断面図である。It is sectional drawing which shows one step of the manufacturing method of the decorative material of this invention. 本発明の化粧材の製造方法の一工程を示す断面図である。It is sectional drawing which shows one step of the manufacturing method of the decorative material of this invention. 本発明の化粧材の製造方法の一工程を示す断面図である。It is sectional drawing which shows one step of the manufacturing method of the decorative material of this invention. 本発明の化粧材の製造方法の一工程を示す断面図である。It is sectional drawing which shows one step of the manufacturing method of the decorative material of this invention.
[化粧材]
 本発明の化粧材は、紙基材及び繊維基材から選ばれる基材を有する化粧材であって、前記化粧材は、平面内に、第一領域と第二領域とを有し、前記第一領域に該当する箇所の前記化粧材は、前記基材上に、浸透防止層と、表面が離型性を有する第一硬化物層とをこの順に有してなり、前記第二領域に該当する箇所の前記化粧材は、前記基材上に、第二硬化物層を有してなり、前記浸透防止層の厚みをt0、前記第一硬化物層の厚みをt1、前記第二硬化物層の厚みをt2と定義した際に、t0+t1<t2の関係を満たすものである。
[Cosmetic material]
The decorative material of the present invention is a decorative material having a base material selected from a paper base material and a fiber base material, and the decorative material has a first region and a second region in a plane, and the first region is described above. The decorative material in a portion corresponding to one region has a permeation prevention layer and a first cured product layer having a releasable surface in this order on the base material, and corresponds to the second region. The decorative material at the portion to be subjected to has a second cured product layer on the base material, the thickness of the permeation prevention layer is t0, the thickness of the first cured product layer is t1, and the second cured product. When the thickness of the layer is defined as t2, the relationship of t0 + t1 <t2 is satisfied.
 図1は、本発明の化粧材100の一実施形態を示す断面図である。
 図1の化粧材100は、平面内に、第一領域R1と第二領域R2とを有している。また、図1の化粧材100は、第一領域R1に該当する箇所において、基材10上に、浸透防止層31と、表面が離型性を有する第一硬化物層32とをこの順に有している。また、図1の化粧材100は、第二領域R2に該当する箇所において、基材10上に、第二硬化物層22を有している。
 図1において、t0は浸透防止層31の厚み、t1は離型性を有する第一硬化物層32の厚み、t2は第二硬化物層22の厚みを示している。図1の化粧材100は、t0+t1<t2の関係を満たしている。
 また、図1の化粧材100は、第一領域R1に該当する箇所において、基材10と浸透防止層31との間に第一装飾層33を有している。また、図1の化粧材100は、第二領域R2に該当する箇所において、基材10と第二硬化物層22との間に第二装飾層23を有している。
FIG. 1 is a cross-sectional view showing an embodiment of the decorative material 100 of the present invention.
The decorative material 100 of FIG. 1 has a first region R1 and a second region R2 in a plane. Further, the decorative material 100 of FIG. 1 has a permeation prevention layer 31 and a first cured product layer 32 having a releasable surface in this order on the base material 10 at a portion corresponding to the first region R1. doing. Further, the decorative material 100 of FIG. 1 has a second cured product layer 22 on the base material 10 at a portion corresponding to the second region R2.
In FIG. 1, t0 indicates the thickness of the permeation prevention layer 31, t1 indicates the thickness of the first cured product layer 32 having releasability, and t2 indicates the thickness of the second cured product layer 22. The decorative material 100 of FIG. 1 satisfies the relationship of t0 + t1 <t2.
Further, the decorative material 100 of FIG. 1 has a first decorative layer 33 between the base material 10 and the permeation prevention layer 31 at a portion corresponding to the first region R1. Further, the decorative material 100 of FIG. 1 has a second decorative layer 23 between the base material 10 and the second cured product layer 22 at a portion corresponding to the second region R2.
 本明細書において「平面」とは、本発明の化粧材の基材を基準とした浸透防止層を有する側の面(図1の化粧材を、基材を基準として浸透防止層側から視認したxy面内)を意味する。また、本明細書において「平面視」とは、本発明の化粧材を、基材を基準として浸透防止層を有する側から垂直に視認することを意味する。 In the present specification, the term "flat surface" means a surface on the side having the permeation prevention layer based on the base material of the decorative material of the present invention (the decorative material of FIG. 1 is visually recognized from the permeation prevention layer side with reference to the base material). It means (in the xy plane). Further, in the present specification, "planar view" means that the decorative material of the present invention is viewed vertically from the side having the permeation prevention layer with reference to the base material.
<基材>
 基材は、紙基材及び繊維基材から選ばれるものであり、紙基材が好ましい。
 紙基材及び繊維基材は、硬化性樹脂を含浸することにより優れた機械的物性等を付与することができ、ひいては化粧材の表面の鉛筆硬度を高め、化粧材表面を傷付き難くしやすくできる点で好ましい。
<Base material>
The base material is selected from a paper base material and a fiber base material, and a paper base material is preferable.
By impregnating the paper base material and the fiber base material with a curable resin, excellent mechanical properties and the like can be imparted, and by extension, the pencil hardness of the surface of the decorative material is increased, and the surface of the decorative material is easily scratched. It is preferable in that it can be done.
 紙基材としては、例えばクラフト紙、チタン紙、リンター紙、樹脂含浸紙、薄葉紙及び和紙等が挙げられる。
 繊維基材としては、ガラス繊維、アルミナ繊維、シリカ繊維、炭素繊維等の無機繊維で構成される繊維基材、ポリエステル樹脂、アクリル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂等の各種合成樹脂の有機繊維で構成される繊維基材、またこれらの複合体等の基材が挙げられる。また、繊維基材は、不織布であってもよいし、織布であってもよい。
Examples of the paper base material include kraft paper, titanium paper, linter paper, resin impregnated paper, thin paper and Japanese paper.
The fiber base material is composed of a fiber base material composed of inorganic fibers such as glass fiber, alumina fiber, silica fiber, and carbon fiber, and organic fiber of various synthetic resins such as polyester resin, acrylic resin, polyethylene resin, and polypropylene resin. Examples thereof include a fiber base material to be used, and a base material such as a composite thereof. Further, the fiber base material may be a non-woven fabric or a woven fabric.
 基材の厚さは、特に制限はなく、所望の性能に応じて適宜選択すればよく、機械的物性の確保、取扱性の観点から通常10~150μm程度、好ましくは20~120μm、更に好ましくは30~100μmである。また、基材として紙基材を用いる場合、これと同様の観点から、その坪量は、通常20~150g/m程度、好ましくは30~100g/mである。 The thickness of the base material is not particularly limited and may be appropriately selected according to the desired performance, and is usually about 10 to 150 μm, preferably 20 to 120 μm, more preferably 20 to 120 μm from the viewpoint of ensuring mechanical physical characteristics and handleability. It is 30 to 100 μm. When a paper base material is used as the base material, the basis weight thereof is usually about 20 to 150 g / m 2 , preferably 30 to 100 g / m 2 , from the same viewpoint.
 基材は硬化性樹脂を含浸してなるものが好ましい。かかる構成により、化粧材の機械的強度を向上することができ、ひいては化粧材の表面の鉛筆硬度を高め、化粧材表面を傷付き難くしやすくできる。
 硬化性樹脂としては、熱硬化性樹脂、電離放射線硬化性樹脂等の硬化性樹脂を用いることができ、取り扱い性の観点から熱硬化性樹脂が好ましい。
The base material is preferably impregnated with a curable resin. With such a configuration, the mechanical strength of the decorative material can be improved, and thus the pencil hardness of the surface of the decorative material can be increased, and the surface of the decorative material can be easily scratched.
As the curable resin, a curable resin such as a thermosetting resin or an ionizing radiation curable resin can be used, and the thermosetting resin is preferable from the viewpoint of handleability.
 基材に含浸させる硬化性樹脂としては、化粧材の質感をより高めるとともに、化粧材の機械的強度の向上を図る観点から、メラミン樹脂、尿素樹脂、メラミン-尿素樹脂、グアナミン樹脂、スルホンアミド樹脂、ジアリルフタレート樹脂、ポリエステル樹脂、フェノール樹脂、エポキシ樹脂、アミノアルキッド樹脂、ケイ素樹脂及びポリシロキサン樹脂等が好ましく、中でもメラミン樹脂、尿素樹脂、メラミン-尿素樹脂、フェノール樹脂、グアナミン樹脂及びスルホンアミド樹脂等の熱硬化性樹脂が好ましい。また、熱硬化性樹脂の中でもメラミン樹脂、メラミン-尿素樹脂及びフェノール樹脂が好ましく、特にメラミン樹脂が好ましい。 As the curable resin to be impregnated in the base material, a melamine resin, a urea resin, a melamine-urea resin, a guanamine resin, and a sulfonamide resin are used from the viewpoint of further enhancing the texture of the decorative material and improving the mechanical strength of the decorative material. , Dialyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin and the like are preferable, and among them, melamine resin, urea resin, melamine-urea resin, phenol resin, guanamine resin and sulfonamide resin and the like. The thermosetting resin of the above is preferable. Further, among the thermosetting resins, melamine resin, melamine-urea resin and phenol resin are preferable, and melamine resin is particularly preferable.
 基材中に熱硬化性樹脂を含浸する手段としては、未硬化の熱硬化性樹脂の組成物を用意し、該組成物を該基材中に含浸させる手段が挙げられる(例えば、後述の工程(4)。)。
 含浸した該組成物は、適宜の時点において、加熱して架橋反応、重合反応等の反応により硬化させることで、熱硬化性樹脂の硬化物となる(例えば、後述の工程(6)。)。
Examples of means for impregnating the base material with the thermosetting resin include means for preparing a composition of an uncured thermosetting resin and impregnating the base material with the composition (for example, a step described later). (4).).
The impregnated composition becomes a cured product of a thermosetting resin by heating at an appropriate time point and curing it by a reaction such as a crosslinking reaction or a polymerization reaction (for example, step (6) described later).
 なお、本明細書において、単に「熱硬化性樹脂」と称する場合は、熱硬化性樹脂の未硬化物を硬化させてなる硬化物を意味する。電離放射線硬化性樹脂等の他の硬化性樹脂についても同様である。
 また、本明細書において、硬化性樹脂組成物、熱硬化性樹脂組成物、電離放射線硬化性樹脂組成物と称する場合は、特に断りのない限り、未硬化であることを意味する。
In the present specification, the term "thermosetting resin" simply means a cured product obtained by curing an uncured product of a thermosetting resin. The same applies to other curable resins such as ionizing radiation curable resins.
Further, in the present specification, the terms curable resin composition, thermosetting resin composition, and ionizing radiation curable resin composition mean that they are uncured unless otherwise specified.
 基材は、化粧材を構成する他の層との層間密着性の向上、被着材との接着性の強化等のために、その片面又は両面に、酸化法、凹凸化法等の物理的表面処理、又は化学的表面処理等の表面処理を施したり、プライマー層を形成したりしたものであってもよい。
 酸化法としては、例えばコロナ放電処理、クロム酸化処理、火炎処理、熱風処理、オゾン-紫外線処理法等が挙げられ、凹凸化法としては、例えばサンドブラスト法、溶剤処理法等が挙げられる。これらの表面処理は、基材の種類に応じて適宜選択されるが、一般にはコロナ放電処理法が、表面処理の効果及び操作性等の面から好ましく用いられる。
The base material is physically prepared on one or both sides of the base material, such as an oxidation method or an unevenness method, in order to improve the interlayer adhesion with other layers constituting the decorative material and to strengthen the adhesiveness with the adherend. It may be subjected to surface treatment such as surface treatment or chemical surface treatment, or a primer layer may be formed.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method and the like, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments are appropriately selected depending on the type of the base material, but in general, the corona discharge treatment method is preferably used from the viewpoints of the effect and operability of the surface treatment.
<領域>
 本発明の化粧材は、平面内に、第一領域R1と第二領域R2とを有する。
 浸透防止層の厚みをt0、第一硬化物層の厚みをt1、第二硬化物層の厚みをt2と定義した際に、t2-(t0+t1)は、第一領域R1の標高と、第二領域R2との標高との標高差の指標となる。
 よって、t0+t1<t2の関係を満たすことにより、第一領域R1は凹んで視認され、第二領域R2は浮かび上がって視認されることとなり、両領域のコントラストにより化粧材の立体感を良好なものとすることができる。
<Area>
The decorative material of the present invention has a first region R1 and a second region R2 in a plane.
When the thickness of the permeation prevention layer is defined as t0, the thickness of the first cured product layer is defined as t1, and the thickness of the second cured product layer is defined as t2, t2- (t0 + t1) is the elevation of the first region R1 and the second. It is an index of the altitude difference from the altitude of the area R2.
Therefore, by satisfying the relationship of t0 + t1 <t2, the first region R1 is visually recognized as being recessed, and the second region R2 is visually recognized as being raised, and the contrast between the two regions makes the three-dimensional appearance of the decorative material good. Can be.
 t2-(t0+t1)は、2.0μm以上50.0μm以下であることが好ましく、5.0μm以上35.0μm以下であることがより好ましく、10.0μm以上30.0μm以下であることがさらに好ましい。
 t2-(t0+t1)を2.0μm以上とすることにより、立体感を良好にしやすくできる。また、t2-(t0+t1)を50.0μm以下とすることにより、第一領域及び第二領域を安定して製造しやすくできる。
t2- (t0 + t1) is preferably 2.0 μm or more and 50.0 μm or less, more preferably 5.0 μm or more and 35.0 μm or less, and further preferably 10.0 μm or more and 30.0 μm or less. ..
By setting t2- (t0 + t1) to 2.0 μm or more, it is possible to easily improve the three-dimensional effect. Further, by setting t2- (t0 + t1) to 50.0 μm or less, the first region and the second region can be stably produced easily.
 t0、t1及びt2は、20箇所の厚みの平均値として算出することが好ましい。厚みは、例えば化粧材の断面写真から算出できる。なお、平均値を算出するための20箇所は、場所の偏りがないようにピックアップすることが好ましい。 It is preferable to calculate t0, t1 and t2 as the average value of the thicknesses at 20 points. The thickness can be calculated, for example, from a cross-sectional photograph of the decorative material. It is preferable that the 20 locations for calculating the average value are picked up so that there is no bias in the locations.
 化粧材の第一領域R1の面積をS1、第二領域R2の面積をS2と定義した際に、S2/S1が、0.5~20であることが好ましく、1.0~10であることがより好ましい。
 S2/S1を0.5以上とすることにより、化粧材の平面内の標高の高い割合が増加するため、化粧材の耐摩耗性を良好にしやすくできる。また、S2/S1を20以下とすることにより、凹んで視認される箇所と浮かび上がって視認される箇所との割合のバランスを適切な範囲として、意匠性を良好にしやすくできる。
When the area of the first region R1 of the decorative material is defined as S1 and the area of the second region R2 is defined as S2, S2 / S1 is preferably 0.5 to 20, preferably 1.0 to 10. Is more preferable.
By setting S2 / S1 to 0.5 or more, the high proportion of the altitude of the decorative material in the plane increases, so that the wear resistance of the decorative material can be easily improved. Further, by setting S2 / S1 to 20 or less, it is possible to easily improve the design by setting the balance of the ratio between the portion visually recognized as recessed and the portion visually recognized as raised as an appropriate range.
《第一領域》
 第一領域は、第二領域と比べて凹んで視認される領域である。
 第一領域は、基材上に、浸透防止層と、表面が離型性を有する第一硬化物層とをこの順に有する。
《First area》
The first region is a region that is recessed and visually recognized as compared with the second region.
The first region has a permeation prevention layer and a first cured product layer having a releasable surface in this order on the base material.
 第一領域は、表面が粗面化されてなることが好ましい。第一領域の表面を粗面化することにより、第一領域が凹んで見えやすくなり、立体感をより良好にしやすくできる。 The surface of the first region is preferably roughened. By roughening the surface of the first region, the first region is dented and easily visible, and the three-dimensional effect can be improved.
-浸透防止層-
 浸透防止層は、基材と第一硬化物層との間に配置される。かかる構成により、第一硬化物層を構成する組成物が基材側に浸透することが抑制され、第一硬化物層の厚みが確保され、ひいては第二硬化物層の厚みを厚くすることができるようになり、化粧材の耐摩耗性を良好にしやすくできる。
 浸透防止層は基材上の全部ではなく、基材上の一部に有することが肝要である。基材上の全部に浸透防止層を形成した場合、基材中に硬化性樹脂が含浸しにくくなるためである。このため、化粧材を平面視した際の浸透防止層の全面積を100とした際に、第一領域内に存在する浸透防止層の面積が90以上であることが好ましく、95以上であることがより好ましく、97以上であることがさらに好ましく、99以上であることがよりさらに好ましい。言い換えると、化粧材の平面内において、浸透防止層は、第一領域以外の箇所に実質的に存在しないことが好ましい。
-Penetration prevention layer-
The permeation prevention layer is arranged between the base material and the first cured product layer. With such a structure, the composition constituting the first cured product layer is suppressed from penetrating into the base material side, the thickness of the first cured product layer is secured, and the thickness of the second cured product layer can be increased. This makes it easier to improve the wear resistance of the decorative material.
It is important that the permeation prevention layer is provided on a part of the base material, not all on the base material. This is because when the permeation prevention layer is formed on the entire base material, it becomes difficult for the curable resin to impregnate the base material. Therefore, when the total area of the permeation prevention layer when the decorative material is viewed in a plan view is 100, the area of the permeation prevention layer existing in the first region is preferably 90 or more, and is 95 or more. Is more preferable, 97 or more is further preferable, and 99 or more is even more preferable. In other words, it is preferable that the permeation prevention layer is substantially not present in a portion other than the first region in the plane of the decorative material.
 浸透防止層は、硬化性樹脂を含むことが好ましい。言い換えると、浸透防止層は、未硬化の硬化性樹脂組成物の硬化物を含むことが好ましい。
 また、硬化性樹脂の含有量は、浸透防止層を構成する全固形分の50質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることがさらに好ましく、90質量%以上であることがさらに好ましい。
 浸透防止層が硬化性樹脂を含むことにより、浸透防止層による第一硬化物層の目止め効果を良好にすることができる。
The permeation prevention layer preferably contains a curable resin. In other words, the permeation prevention layer preferably contains a cured product of an uncured curable resin composition.
The content of the curable resin is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more of the total solid content constituting the permeation prevention layer. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
Since the permeation prevention layer contains the curable resin, the sealing effect of the first cured product layer by the permeation prevention layer can be improved.
 なお、浸透防止層を形成する組成物が基材に浸透しにくくするために、浸透防止層を形成する組成物は熱可塑性樹脂を含むことが好ましい。熱可塑性樹脂の含有量は、硬化性樹脂100質量部に対して2~30質量部であることが好ましく、5~15質量部であることがより好ましい。
 熱可塑性樹脂は、アクリル系樹脂、ポリエステル系樹脂及びセルロース系樹脂等の汎用の熱可塑性樹脂が挙げられる。
In addition, in order to make it difficult for the composition forming the permeation prevention layer to permeate into the base material, it is preferable that the composition forming the permeation prevention layer contains a thermoplastic resin. The content of the thermoplastic resin is preferably 2 to 30 parts by mass and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the curable resin.
Examples of the thermoplastic resin include general-purpose thermoplastic resins such as acrylic resins, polyester resins, and cellulosic resins.
 浸透防止層の硬化性樹脂としては、熱硬化性樹脂、電離放射線硬化性樹脂が好ましく挙げられ、電離放射線硬化性樹脂がより好ましい。 Examples of the curable resin of the permeation prevention layer include a thermosetting resin and an ionizing radiation curable resin, and an ionizing radiation curable resin is more preferable.
 熱硬化性樹脂としては、上記基材に含浸し得る熱硬化性樹脂として例示したものと同じものを好ましく例示することができる。
 電離放射線硬化性樹脂は、電離放射線を照射することにより、架橋、硬化する樹脂のことであり、電離放射線硬化性官能基を有するものである。ここで、電離放射線硬化性官能基とは、電離放射線の照射によって架橋硬化する基であり、(メタ)アクリロイル基、ビニル基、アリル基等のエチレン性二重結合を有する官能基等が好ましく挙げられる。また、電離放射線とは、電磁波又は荷電粒子線のうち、分子を重合あるいは架橋し得るエネルギー量子を有するものを意味し、通常、紫外線(UV)又は電子線(EB)が用いられるが、その他、X線、γ線などの電磁波、α線、イオン線などの荷電粒子線も含まれる。
 電離放射線硬化性樹脂としては、具体的には、従来電離放射線硬化性樹脂として慣用されている重合性モノマー、重合性オリゴマーの中から適宜選択して用いることができる。なお、浸透防止層を形成する組成物が基材に浸透することを抑制しやすくする観点から、電離放射線硬化性樹脂は重合性オリゴマーが好ましい。
As the thermosetting resin, the same ones as those exemplified as the thermosetting resin that can be impregnated in the base material can be preferably exemplified.
The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group is preferably mentioned. Be done. Further, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.
Specifically, the ionizing radiation curable resin can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins. The ionizing radiation curable resin is preferably a polymerizable oligomer from the viewpoint of facilitating the suppression of the composition forming the permeation prevention layer from penetrating into the base material.
 重合性モノマーとしては、分子中にラジカル重合性不飽和基を持つ(メタ)アクリレート系モノマーが好ましく、中でも多官能性(メタ)アクリレートモノマーが好ましい。ここで「(メタ)アクリレート」とは「アクリレート又はメタクリレート」を意味する。
 多官能性(メタ)アクリレートモノマーとしては、分子中に2つ以上の電離放射線硬化性官能基を有し、かつ該官能基として少なくとも(メタ)アクリロイル基を有する(メタ)アクリレートモノマーが挙げられ、より質感の高い意匠性及びより優れた表面特性を得る観点から、アクリロイル基を有するアクリレートモノマーが好ましい。
 より質感の高い意匠性及びより優れた表面特性を得る観点から、官能基数は好ましくは2以上、より好ましくは3以上、さらに好ましくは4以上であり、上限として好ましくは8以下、より好ましくは6以下である。これらの多官能性(メタ)アクリレートは、単独で、又は複数種を組み合わせて用いてもよい。
As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. Here, "(meth) acrylate" means "acrylate or methacrylate".
Examples of the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. An acrylate monomer having an acryloyl group is preferable from the viewpoint of obtaining a design property with a higher texture and better surface properties.
The number of functional groups is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and the upper limit is preferably 8 or less, more preferably 6 from the viewpoint of obtaining a higher quality design and better surface characteristics. It is as follows. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.
 このような重合性モノマーとしては、エチレングリコールジ(メタ)アクリレート、ビスフェノールAテトラエトキシジアクリレート、ビスフェノールAテトラプロポキシジアクリレート、1,6-ヘキサンジオールジアクリレート等の二官能(メタ)アクリレート;トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、イソシアヌル酸変性トリ(メタ)アクリレート等の三官能以上の(メタ)アクリレート;が好ましく挙げられる。中でも、より質感の高い意匠性及びより優れた表面特性を得る観点から、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等のジペンタエリスリトール系重合性モノマーが好ましく、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレートがより好ましく、ジペンタエリスリトールペンタ(メタ)アクリレートとジペンタエリスリトールヘキサ(メタ)アクリレートとを併用することが特に好ましい。 Examples of such polymerizable monomers include bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate; trimethylol. Propanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trifunctional or higher (meth) acrylates such as isocyanuric acid-modified tri (meth) acrylates; are preferred. Among them, dipentaerythritol such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate from the viewpoint of obtaining higher texture design and better surface characteristics. A system-polymerizable monomer is preferable, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferable, and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are used in combination. Is particularly preferable.
 重合性オリゴマーとしては、例えば、分子中に2つ以上の電離放射線硬化性官能基を有し、かつ該官能基として少なくとも(メタ)アクリロイル基を有する(メタ)アクリレートオリゴマーが挙げられる。例えば、ウレタン(メタ)アクリレートオリゴマー、エポキシ(メタ)アクリレートオリゴマー、ポリエステル(メタ)アクリレートオリゴマー、ポリエーテル(メタ)アクリレートオリゴマー、ポリカーボネート(メタ)アクリレートオリゴマー、アクリル(メタ)アクリレートオリゴマー、ポリカプロラクトンウレタン(メタ)アクリレートオリゴマー、ポリカプロラクトンジオールウレタン(メタ)アクリレート等が挙げられる。 Examples of the polymerizable oligomer include a (meth) acrylate oligomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. For example, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, acrylic (meth) acrylate oligomer, polycaprolactone urethane (meth). ) Acrylate oligomer, polycaprolactone diol urethane (meth) acrylate and the like.
 より質感の高い意匠性及びより優れた表面特性を得る観点から、これらの重合性オリゴマーの官能基数は、好ましくは2以上、より好ましくは3以上であり、上限として好ましくは8以下、より好ましくは6以下である。 From the viewpoint of obtaining a higher quality design and better surface properties, the number of functional groups of these polymerizable oligomers is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 8 or less, more preferably. It is 6 or less.
 重合性オリゴマーの重量平均分子量は、500以上が好ましく、より好ましくは1,000以上であり、上限として好ましくは80,000以下、より好ましくは50,000以下である。本明細書において、重量平均分子量は、GPC分析によって測定され、かつ標準ポリスチレンで換算された平均分子量である。 The weight average molecular weight of the polymerizable oligomer is preferably 500 or more, more preferably 1,000 or more, and the upper limit is preferably 80,000 or less, more preferably 50,000 or less. As used herein, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.
 浸透防止層は、第一硬化物層を形成しやすくする観点から、離型剤を実質的に含有しないことが好ましい。離型剤を実質的に含有しないとは、離型剤の含有量が、浸透防止層の全固形分の0.1質量%未満であることを意味し、好ましくは0.01質量%以下であり、より好ましくは0質量%(離型剤を含有しない)である。 The permeation prevention layer preferably contains substantially no release agent from the viewpoint of facilitating the formation of the first cured product layer. The fact that the release agent is substantially not contained means that the content of the release agent is less than 0.1% by mass of the total solid content of the permeation prevention layer, preferably 0.01% by mass or less. Yes, more preferably 0% by mass (does not contain a release agent).
 浸透防止層は、フィラーを実質的に含有しないことが好ましい。フィラーを実質的に含有しないとは、フィラーの含有量が、浸透防止層の全固形分の0.1質量%未満であることを意味し、好ましくは0.01質量%以下であり、より好ましくは0質量%(フィラーを含有しない)である。 It is preferable that the permeation prevention layer contains substantially no filler. The fact that the filler is substantially not contained means that the content of the filler is less than 0.1% by mass of the total solid content of the permeation prevention layer, and is preferably 0.01% by mass or less, more preferably. Is 0% by mass (does not contain filler).
 浸透防止層の厚みt0は、0.1~10.0μmであることが好ましく、0.5~5.0μmであることがより好ましい。
 t0を0.1μm以上とすることにより、第一硬化物層形成用インキに含まれる未硬化の硬化性樹脂組成物が基材側に浸透することを抑制しやすくできる。また、t0を10.0μm以下とすることにより、他領域に影響を与えることなく安定的に浸透防止層を形成できる。
The thickness t0 of the permeation prevention layer is preferably 0.1 to 10.0 μm, more preferably 0.5 to 5.0 μm.
By setting t0 to 0.1 μm or more, it is possible to easily suppress the penetration of the uncured curable resin composition contained in the ink for forming the first cured product layer into the substrate side. Further, by setting t0 to 10.0 μm or less, the permeation prevention layer can be stably formed without affecting other regions.
―第一硬化物層―
 第一硬化物層は、浸透防止層上の少なくとも一部に形成され、表面が離型性を有するものである。第一硬化物層は表面が離型性を有するため、第一硬化物層上の第二硬化物層は殆どが剥離される。第一硬化物層上の第二硬化物層は、表面凹凸による立体感を良好にする観点から完全に剥離することが好ましいが、第一硬化物層上から第二硬化物層を完全に剥離できない場合も多い。このため、本発明の効果を阻害しない範囲であれば、第一硬化物層上に微量の第二硬化物層が残存していてもよい。
 第一硬化物層を浸透防止層上に形成することにより、第一硬化物層の厚みを確保することができ、ひいては第二領域の第二硬化物層の厚みを厚くすることができるようになり、化粧材の耐摩耗性を良好にしやすくできる。
 第一硬化物層は、浸透防止層のパターンに同調して形成することが好ましい。例えば、化粧材を平面視した際の第一硬化物層の全面積を100とした際に、浸透防止層上に存在する第一硬化物層の面積が90以上であることが好ましく、95以上であることがより好ましく、97以上であることがさらに好ましく、99以上であることがよりさらに好ましい。
-First cured product layer-
The first cured product layer is formed on at least a part of the permeation prevention layer and has a releasable surface. Since the surface of the first cured product layer has a releasable property, most of the second cured product layer on the first cured product layer is peeled off. The second cured product layer on the first cured product layer is preferably completely peeled off from the viewpoint of improving the three-dimensional appearance due to the surface unevenness, but the second cured product layer is completely peeled off from the first cured product layer. In many cases, it cannot be done. Therefore, a small amount of the second cured product layer may remain on the first cured product layer as long as the effect of the present invention is not impaired.
By forming the first cured product layer on the permeation prevention layer, the thickness of the first cured product layer can be secured, and by extension, the thickness of the second cured product layer in the second region can be increased. Therefore, the wear resistance of the decorative material can be easily improved.
The first cured product layer is preferably formed in synchronization with the pattern of the permeation prevention layer. For example, when the total area of the first cured product layer when the decorative material is viewed in a plan view is 100, the area of the first cured product layer existing on the permeation prevention layer is preferably 90 or more, preferably 95 or more. It is more preferably 97 or more, and even more preferably 99 or more.
 第一硬化物層の厚みt1は、3.5μm超30.0μm以下であることが好ましく、5.0μm以上25.0μm以下であることがより好ましく、7.0μm以上20.0μm以下であることがさらに好ましい。 
 t1を3.5μm超とすることにより、第二硬化物層の厚みを厚くしても、第一領域R1から第二硬化物層を剥離する際に、第一領域内で第二硬化物層が凝集破壊することを抑制することができる(後述の工程(8)参照。)。すなわち、t1を3.5μm超とすることにより、第二硬化物層の厚みを厚くすることが可能となり、その結果、化粧材の耐摩耗性を良好にしやすくできる。
 また、t1を30.0μm以下とすることにより、安定的に第1硬化物層を形成することができる。
The thickness t1 of the first cured product layer is preferably more than 3.5 μm and 30.0 μm or less, more preferably 5.0 μm or more and 25.0 μm or less, and 7.0 μm or more and 20.0 μm or less. Is even more preferable.
By setting t1 to more than 3.5 μm, even if the thickness of the second cured product layer is increased, the second cured product layer is formed in the first region when the second cured product layer is peeled from the first region R1. Can be prevented from coagulating and breaking (see step (8) described later). That is, by setting t1 to more than 3.5 μm, the thickness of the second cured product layer can be increased, and as a result, the wear resistance of the decorative material can be easily improved.
Further, by setting t1 to 30.0 μm or less, the first cured product layer can be stably formed.
 第一硬化物層は、硬化性樹脂により形成される層、より具体的には、未硬化の硬化性樹脂組成物の硬化物により形成される層である。
 硬化性樹脂としては、より質感の高い意匠性及びより優れた表面特性を得る観点から、熱硬化性樹脂、電離放射線硬化性樹脂が好ましく挙げられ、電離放射線硬化性樹脂がより好ましい。
The first cured product layer is a layer formed of a curable resin, more specifically, a layer formed of a cured product of an uncured curable resin composition.
As the curable resin, a thermosetting resin and an ionizing radiation curable resin are preferably mentioned, and an ionizing radiation curable resin is more preferable, from the viewpoint of obtaining a design property with a higher texture and better surface characteristics.
 熱硬化性樹脂としては、上記基材に含浸し得る熱硬化性樹脂として例示したものと同じものを好ましく例示することができる。
 電離放射線硬化性樹脂としては、浸透防止層で例示したものと同じものを好ましく例示することができる。
As the thermosetting resin, the same ones as those exemplified as the thermosetting resin that can be impregnated in the base material can be preferably exemplified.
As the ionizing radiation curable resin, the same ones as those exemplified for the permeation prevention layer can be preferably exemplified.
 第一硬化物層は、離型剤を含むことが好ましい。離型剤を含むことにより、離型性インキ装飾層の表面(第一硬化物層の表面)に他の樹脂を積層しても剥離できる一方で、第二領域には他の樹脂が接着して剥離されないため、第一領域と第二領域とに標高差を付与しやすくできる。 The first cured product layer preferably contains a release agent. By containing a release agent, it can be peeled off even if another resin is laminated on the surface of the releasable ink decorative layer (the surface of the first cured product layer), while the other resin adheres to the second region. Since it is not peeled off, it is possible to easily give an elevation difference between the first region and the second region.
 離型剤としては、フッ素系離型剤、シリコーン系離型剤等が挙げられ、より質感の高い意匠性を得る観点から、シリコーン系離型剤が好ましい。
 シリコーン系離型剤としては、ポリシロキサン構造を基本構造とするものが挙げられ、中でもその側鎖及び末端の少なくともいずれかに有機基が導入された変性シリコーンオイルが好ましく、両末端に有機基が導入された変性シリコーンオイルがより好ましい。有機基としては、より質感の高い意匠性を得る観点から、(メタ)アクリル基、アミノ基、エポキシ基、メルカプト基、カルビノール基、フェノール基、カルボキシル基等の反応性官能基、ポリエーテル基、アラルキル基、フロロアルキル基、アルキル基、脂肪酸アミド基、フェニル基等の非反応性基官能基等が好ましく挙げられる。中でも反応性官能基が好ましく、特に(メタ)アクリル基が好ましい、すなわち特に(メタ)アクリル変性シリコーンオイルが好ましい。また、これらの有機基は窒素原子、硫黄原子、水酸基、アルキル基等の置換基を有していてもよい。
Examples of the release agent include a fluorine-based release agent, a silicone-based release agent, and the like, and a silicone-based release agent is preferable from the viewpoint of obtaining a design with a higher texture.
Examples of the silicone-based mold release agent include those having a polysiloxane structure as a basic structure, and among them, modified silicone oil in which an organic group is introduced into at least one of the side chain and the terminal thereof is preferable, and organic groups are present at both ends. The introduced modified silicone oil is more preferred. As the organic group, from the viewpoint of obtaining a design with a higher texture, a reactive functional group such as a (meth) acrylic group, an amino group, an epoxy group, a mercapto group, a carbinol group, a phenol group or a carboxyl group, or a polyether group , Non-reactive group functional groups such as aralkyl group, fluoroalkyl group, alkyl group, fatty acid amide group and phenyl group are preferably mentioned. Of these, a reactive functional group is preferable, and a (meth) acrylic group is particularly preferable, that is, a (meth) acrylic-modified silicone oil is particularly preferable. Further, these organic groups may have substituents such as a nitrogen atom, a sulfur atom, a hydroxyl group and an alkyl group.
 離型剤の含有量は、第一硬化物層を形成する硬化性樹脂100質量部に対して、好ましくは0.1~5質量部、より好ましくは0.5~3質量部、更に好ましくは1~2質量部である。離型剤の含有量が上記範囲内であると、効率的に離型剤の添加効果が得られる。 The content of the release agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and further preferably more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin forming the first cured product layer. It is 1 to 2 parts by mass. When the content of the release agent is within the above range, the effect of adding the release agent can be efficiently obtained.
 第一硬化物層は、無機フィラーを含むことが好ましい。第一硬化物層が無機フィラーを含むことにより、第一領域の表面を粗面化して、化粧材の視覚的な立体感を良好にしやすくできる。
 無機フィラーとしては、酸化アルミニウム、酸化マグネシウム、シリカ、酸化カルシウム、酸化チタン、酸化亜鉛、酸化ジルコニア等の酸化物;水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム等の水酸化物;炭酸マグネシウム、炭酸カルシウム等の炭酸塩;硫酸カルシウム、硫酸バリウム等の硫酸塩;ケイ酸マグネシウム、ケイ酸アルミニウム、ケイ酸カルシウム、アルミノケイ酸等のケイ酸塩等の無機材料からなる粒子が挙げられる。中でも、酸化アルミニウム、酸化マグネシウム、シリカ、酸化カルシウム、酸化チタン、酸化亜鉛等の酸化物が好ましく、特にシリカが好ましい。
The first cured product layer preferably contains an inorganic filler. When the first cured product layer contains an inorganic filler, the surface of the first region can be roughened, and the visual three-dimensional appearance of the decorative material can be easily improved.
Examples of the inorganic filler include oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, zinc oxide and zirconia oxide; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; magnesium carbonate and carbon dioxide. Carbonates such as calcium; sulfates such as calcium sulfate and barium sulfate; particles made of inorganic materials such as silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate. Of these, oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide and zinc oxide are preferable, and silica is particularly preferable.
 無機フィラーの平均粒径は、Ra1を後述する範囲としやすくする観点から、好ましくは0.3~20μm、より好ましくは0.5~10μmである。本明細書において、フィラーの平均粒径は、レーザー回折散乱法により測定される値である。 The average particle size of the inorganic filler is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, from the viewpoint of facilitating Ra1 in the range described later. In the present specification, the average particle size of the filler is a value measured by a laser diffraction / scattering method.
 無機フィラーの含有量は、Ra1を後述する範囲としやすくする観点から、第一硬化物層を形成する硬化性樹脂100質量部に対して、好ましくは1~50質量部、より好ましくは10~40質量部、更に好ましくは20~35質量部である。無機フィラーの含有量が上記範囲内であると、効率的に無機フィラーの添加効果が得られる。 The content of the inorganic filler is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the curable resin forming the first cured product layer, from the viewpoint of facilitating Ra1 in the range described later. It is by mass, more preferably 20 to 35 parts by mass. When the content of the inorganic filler is within the above range, the effect of adding the inorganic filler can be efficiently obtained.
―第一装飾層―
 本発明の化粧材は、第一領域に該当する箇所において、基材と浸透防止層との間の少なくとも一部に第一装飾層を有することが好ましい。
-First decorative layer-
The decorative material of the present invention preferably has a first decorative layer at least in a part between the base material and the permeation prevention layer in a portion corresponding to the first region.
 第一装飾層は、第一領域内に任意のパターンで形成すればよい。該任意のパターンは、化粧材全体で付与したい意匠によって異なる。
 例えば、化粧材全体で付与する意匠が木材の模様の場合、第一装飾層は、導管、秋材及び節から選ばれる1種以上の模様を形成してなることが好ましい。言い換えると、第一領域は、木材の導管、秋材及び節から選ばれる1種以上の模様を形成してなることが好ましい。導管とは、水分の通路となる円筒形の細胞であり、微小な導管が配列することにより、人の目には該配列に沿って濃色の絵柄が形成されているようにみえる。秋材とは、夏から秋にかけて形成される目幅が狭く色の濃い部分のことである。なお、春から夏にかけてつくられる目幅の大きな部分は春材と称し、春材と秋材とが交互に繰り返されることで木材の年輪が形成される。節とは、幹に取り込まれた枝の痕跡であり、円形又は楕円形に近い形状をしており、周辺組織よりも濃い色を有している。
 また、化粧材全体で付与する意匠がトラバーチン等の石の模様の場合、第一装飾層は凹陥部模様とすることが好ましい。言い換えると、第一領域は、石の凹陥部模様を形成してなることが好ましい。
 また、化粧材全体で付与する意匠がタイル模様又はレンガ模様の場合、第一装飾層は目地模様とすることが好ましい。言い換えると、第一領域は、タイル又はレンガの目地模様を形成してなることが好ましい。
 第一装飾層により付与する意匠を上記のようにすることにより、第一領域が窪んで見えやすくなり、視覚的な立体感をより良好なものとすることができる。
The first decorative layer may be formed in an arbitrary pattern in the first region. The arbitrary pattern depends on the design to be imparted to the entire decorative material.
For example, when the design to be applied to the entire decorative material is a wood pattern, the first decorative layer preferably forms one or more patterns selected from conduits, autumn materials and knots. In other words, the first region preferably forms one or more patterns selected from wood conduits, autumn wood and knots. A duct is a cylindrical cell that serves as a passage for water, and the arrangement of minute conduits makes it appear to the human eye that a dark pattern is formed along the arrangement. Autumn wood is a dark-colored part with narrow eyes that is formed from summer to autumn. The part with a large mesh width made from spring to summer is called spring wood, and the annual rings of wood are formed by alternately repeating spring wood and autumn wood. A node is a trace of a branch incorporated into the trunk, has a shape close to a circle or an ellipse, and has a darker color than the surrounding tissue.
Further, when the design given to the entire decorative material is a stone pattern such as travertine, it is preferable that the first decorative layer has a concave pattern. In other words, the first region preferably forms a stone recessed pattern.
Further, when the design to be applied to the entire decorative material is a tile pattern or a brick pattern, it is preferable that the first decorative layer is a joint pattern. In other words, the first region preferably forms a tile or brick joint pattern.
By making the design given by the first decorative layer as described above, the first region is dented and easily visible, and the visual three-dimensional effect can be improved.
 第一装飾層は、例えば、着色剤及びバインダー樹脂を含む第一装飾層形成用インキを用いた印刷により形成することができる。 The first decorative layer can be formed, for example, by printing with an ink for forming the first decorative layer containing a colorant and a binder resin.
 第一装飾層の着色剤としては、例えば、カーボンブラック(墨)、鉄黒、チタン白、アンチモン白、黄鉛、チタン黄、弁柄、カドミウム赤、群青、コバルトブルー等の無機顔料、キナクリドンレッド、イソインドリノンイエロー、フタロシアニンブルー等の有機顔料、あるいは染料等が挙げられる。第一装飾層の着色剤は光輝性顔料を含まないことが好ましい。
 第一装飾層のバインダー樹脂としては特に制限はなく、例えば、アクリル系樹脂、スチレン系樹脂、ポリエステル系樹脂、ウレタン系樹脂、塩素化ポリオレフィン系樹脂、塩化ビニル-酢酸ビニル共重合体系樹脂、ポリビニルブチラール樹脂、アルキド系樹脂、石油系樹脂、ケトン樹脂、エポキシ系樹脂、メラミン系樹脂、フッ素系樹脂、シリコーン系樹脂、繊維素誘導体、ゴム系樹脂等が挙げられる。
Examples of the colorant for the first decorative layer include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, valve handle, cadmium red, ultramarine blue, cobalt blue and other inorganic pigments, and quinacridone red. , Isoindolinone yellow, organic pigments such as phthalocyanine blue, dyes and the like. The colorant of the first decorative layer preferably does not contain a bright pigment.
The binder resin of the first decorative layer is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral. Examples thereof include resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fibrous derivatives, rubber resins and the like.
 第一装飾層の厚みは、目的とする意匠性を考慮して、0.1~20μm程度の範囲で適宜調整することができる。 The thickness of the first decorative layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the desired design.
―表面形状―
 第一領域の表面のカットオフ値0.8mmにおけるJIS B0601:1994の算術平均粗さRaは、1.0~5.0μmであることが好ましく、1.0~3.0μmであることがより好ましい。
 第一領域のRaを1.0μm以上とすることにより、第一領域を凹んで見えやすくすることができる。また、第一領域のRaを5.0μm以下とすることにより、第一領域が白っぽく見えることを抑制し、意匠性を良好にしやすくできる。
-Surface shape-
The arithmetic mean roughness Ra of JIS B0601: 1994 at a cutoff value of 0.8 mm on the surface of the first region is preferably 1.0 to 5.0 μm, more preferably 1.0 to 3.0 μm. preferable.
By setting Ra of the first region to 1.0 μm or more, the first region can be recessed to make it easier to see. Further, by setting Ra of the first region to 5.0 μm or less, it is possible to suppress the appearance of the first region as whitish and facilitate the improvement of the design.
 第一領域のRaは、例えば、基材を粗面化すること、基材上に形成する層(後述する第一硬化物層等)を粗面化すること、などにより調整できる。 Ra in the first region can be adjusted by, for example, roughening the base material, roughening the layer formed on the base material (such as the first cured product layer described later), and the like.
《第二領域》
 第二領域は、第一領域と比べて高く視認される領域である。
 第二領域は、基材上に第二硬化物層を有する。
《Second area》
The second region is a region that is visually recognized higher than the first region.
The second region has a second cured product layer on the substrate.
―第二硬化物層―
 第二硬化物層は、硬化性樹脂により形成される層、より具体的には、未硬化の硬化性樹脂組成物の硬化物により形成される層である。
-Second cured product layer-
The second cured product layer is a layer formed of a curable resin, more specifically, a layer formed of a cured product of an uncured curable resin composition.
 第二硬化物層の硬化性樹脂としては、より質感の高い意匠性を得る観点から、熱硬化性樹脂、電離放射線硬化性樹脂が好ましく挙げられ、熱硬化性樹脂がより好ましい。これらの硬化性樹脂は、単独で、又は複数種を組み合わせて用いてもよく、例えば熱硬化性樹脂と電離放射線硬化性樹脂とを併用してもよいし、またこれらの硬化性樹脂と熱可塑性樹脂とを併用してもよい。
 熱硬化性樹脂としては、基材に含浸し得る熱硬化性樹脂として例示したものと同じものを好ましく例示することができ、上記の各種熱硬化性樹脂が好ましいこと、特にメラミン樹脂が好ましいことも同じである。このような硬化性樹脂を用いることで、より質感の高い意匠性が得られるとともに、基材との密着性が向上し、より優れた機械的強度が得られる。電離放射線硬化性樹脂については、浸透防止層で例示したものと同様のものが挙げられる。
 硬化性樹脂と熱可塑性樹脂とを併用する場合、これらの樹脂の合計に対する硬化性樹脂の含有量は、通常50質量%以上100質量%未満程度であり、好ましくは60質量%以上90質量%以下である。
As the curable resin of the second cured product layer, a thermosetting resin and an ionizing radiation curable resin are preferably mentioned, and a thermosetting resin is more preferable, from the viewpoint of obtaining a design property with a higher texture. These curable resins may be used alone or in combination of two or more, for example, a thermosetting resin and an ionizing radiation curable resin may be used in combination, or these curable resins and thermoplastics may be used in combination. It may be used in combination with a resin.
As the thermosetting resin, the same ones as those exemplified as the thermosetting resin that can be impregnated in the base material can be preferably exemplified, and the above-mentioned various thermosetting resins are preferable, and melamine resin is particularly preferable. It is the same. By using such a curable resin, a design property with a higher texture can be obtained, the adhesion to the base material is improved, and more excellent mechanical strength can be obtained. Examples of the ionizing radiation curable resin include those similar to those exemplified in the permeation prevention layer.
When the curable resin and the thermoplastic resin are used in combination, the content of the curable resin with respect to the total of these resins is usually about 50% by mass or more and less than 100% by mass, preferably 60% by mass or more and 90% by mass or less. Is.
 第二硬化物層は、拡散を低減する観点から粒子を含まないことが好ましい。 The second cured product layer preferably does not contain particles from the viewpoint of reducing diffusion.
 第二硬化物層の厚みt2は、5.0μm以上50.0μm以下であることが好ましく、10.0μm以上40.0μm以下であることがより好ましく、25.0μm以上35.0μm以下であることがさらに好ましい。
 t2を5.0μm以上とすることにより、化粧材の耐摩耗性を良好にしやすくできる。また、t2を50.0μm以下とすることにより、安定的な生産が可能となる。
The thickness t2 of the second cured product layer is preferably 5.0 μm or more and 50.0 μm or less, more preferably 10.0 μm or more and 40.0 μm or less, and 25.0 μm or more and 35.0 μm or less. Is even more preferable.
By setting t2 to 5.0 μm or more, it is possible to easily improve the wear resistance of the decorative material. Further, by setting t2 to 50.0 μm or less, stable production becomes possible.
―第二装飾層―
 第二装飾層は、例えば、着色剤及びバインダー樹脂を含む第二装飾層形成用インキを用いた印刷により形成することができる。
 第二装飾層の着色剤及びバインダー樹脂としては、後述する第一装飾層の着色剤及びバインダー樹脂で例示するものが挙げられる。
-Second decorative layer-
The second decorative layer can be formed, for example, by printing with an ink for forming a second decorative layer containing a colorant and a binder resin.
Examples of the colorant and binder resin of the second decorative layer include those exemplified by the colorant and binder resin of the first decorative layer described later.
 第二装飾層は、例えば、基材上に任意のパターンで形成すればよい。
 該任意のパターンは、付与したい意匠によって異なる。例えば、該任意のパターンは、化粧材全体で木目模様を付与する場合には木肌模様(導管溝模様及び/又は節目模様以外の部分)とすることが好ましく、化粧材全体でトラバーチン等の石の模様を付与する場合には凹陥部以外の模様とすることが好ましく、化粧材全体でタイル模様又はレンガ模様を付与する場合にはタイル部分又はレンガ部分とすることが好ましい。
The second decorative layer may be formed on the base material in an arbitrary pattern, for example.
The arbitrary pattern depends on the design to be imparted. For example, the arbitrary pattern is preferably a wood surface pattern (a portion other than the conduit groove pattern and / or the knot pattern) when a wood grain pattern is given to the entire decorative material, and the entire decorative material is made of stone such as travertin. When a pattern is given, it is preferable to use a pattern other than the recessed portion, and when giving a tile pattern or a brick pattern to the entire decorative material, it is preferable to use a tile portion or a brick portion.
 第二装飾層の厚みは、目的とする意匠性を考慮して、0.1~20μm程度の範囲で適宜調整することができる。 The thickness of the second decorative layer can be appropriately adjusted in the range of about 0.1 to 20 μm in consideration of the desired design.
-表面形状-
 第二領域の表面のカットオフ値0.8mmにおけるJIS B0601:1994の算術平均粗さRaは、2.0μm以下であることが好ましく、0.5~1.5μmであることがより好ましい。
-Surface shape-
The arithmetic mean roughness Ra of JIS B0601: 1994 at a cutoff value of 0.8 mm on the surface of the second region is preferably 2.0 μm or less, and more preferably 0.5 to 1.5 μm.
<補強層>
 本発明の化粧材は、化粧材を補強するために、基材の浸透防止層を有する側とは反対側の面に補強層を有することが好ましい。
 特に、基材として、熱硬化性樹脂を含浸させた繊維基材又は紙基材を採用した場合、補強層を組み合わせることで、より機械的物性に優れる熱硬化性樹脂化粧板が得られる。
<Reinforcing layer>
In order to reinforce the decorative material, the decorative material of the present invention preferably has a reinforcing layer on the surface opposite to the side having the permeation prevention layer of the base material.
In particular, when a fiber base material or a paper base material impregnated with a thermosetting resin is used as the base material, a thermosetting resin decorative board having more excellent mechanical properties can be obtained by combining the reinforcing layers.
 補強層としては、熱硬化性樹脂含浸シートが挙げられる。
 熱硬化性樹脂含浸シートに用いられる繊維基材、紙基材の種類としては、基材の繊維基材、紙基材として例示したものであれば特に制限はなく、坪量は好ましくは100~300g/m、より好ましくは150~250g/mである。また、熱硬化性樹脂としては、熱硬化性樹脂組成物の状態で基材に含浸し得るものであれば特に限定することなく使用することができ、フェノール樹脂が好ましい。すなわち、補強層としてはフェノール樹脂含浸紙が好ましい。
 フェノール樹脂含浸紙としては、例えば坪量150~250g/mのクラフト紙に、フェノール樹脂を含浸率20~60%程度となるように含浸させて、100~140℃程度で乾燥させることにより製造されるものが好ましく用いられる。
Examples of the reinforcing layer include a thermosetting resin impregnated sheet.
The types of the fiber base material and the paper base material used in the thermosetting resin impregnated sheet are not particularly limited as long as they are exemplified as the base material fiber base material and the paper base material, and the basis weight is preferably 100 to 100. It is 300 g / m 2 , more preferably 150 to 250 g / m 2 . Further, the thermosetting resin can be used without particular limitation as long as it can be impregnated in the base material in the state of the thermosetting resin composition, and a phenol resin is preferable. That is, a phenol resin impregnated paper is preferable as the reinforcing layer.
The phenol resin impregnated paper is produced by, for example, impregnating kraft paper having a basis weight of 150 to 250 g / m 2 with phenol resin so as to have an impregnation rate of about 20 to 60% and drying at about 100 to 140 ° C. Phenol formaldehyde is preferably used.
<プライマー層>
 本発明の化粧材は、各層の密着性向上のため、各層間にプライマー層を設けることができる。
 プライマー層を形成する樹脂材料としては、ウレタン樹脂、ポリエステル樹脂、アクリル樹脂、アクリルウレタン樹脂、塩化ビニル-酢酸ビニル共重合体樹脂等が挙げられる。また、プライマー層の厚さは、優れた密着性を効率よく得る観点から、通常0.1~15μm程度、好ましくは1~10μmである。
<Primer layer>
In the decorative material of the present invention, a primer layer can be provided between each layer in order to improve the adhesion of each layer.
Examples of the resin material forming the primer layer include urethane resin, polyester resin, acrylic resin, acrylic urethane resin, vinyl chloride-vinyl acetate copolymer resin and the like. The thickness of the primer layer is usually about 0.1 to 15 μm, preferably 1 to 10 μm from the viewpoint of efficiently obtaining excellent adhesion.
<被着材>
 本発明の化粧材は、基材の裏面(基材の浸透防止層を有する側とは反対側の面)に被着材を積層して一体化したものであってもよい。
<Adhesion material>
The decorative material of the present invention may be one in which an adherend is laminated and integrated on the back surface of the base material (the side opposite to the side having the permeation prevention layer of the base material).
 被着材は、例えば、木材単板、木材合板、パーチクルボード、MDF(中密度繊維板)、集成材等の木質板;石膏板、石膏スラグ板等の石膏系板;珪酸カルシウム板、石綿スレート板、軽量発泡コンクリート板、中空押出セメント板等のセメント板;パルプセメント板、石綿セメント板、木片セメント板等の繊維セメント板;陶器、磁器、土器、硝子、琺瑯等のセラミックス板;鉄板、亜鉛メッキ鋼板、ポリ塩化ビニルゾル塗布鋼板、アルミニウム板、銅板等の金属板;ポリオレフィン樹脂板、アクリル樹脂板、ABS板、ポリカーボネート板等の熱可塑性樹脂板;フェノール樹脂板、尿素樹脂板、不飽和ポリエステル樹脂板、ポリウレタン樹脂板、エポキシ樹脂板、メラミン樹脂板等の熱硬化型樹脂板;フェノール樹脂、尿素樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、メラミン樹脂、ジアリルフタレート樹脂等の樹脂を、硝子繊維不織布、布帛、紙、その他の各種繊維質基材に含浸硬化して複合化したいわゆるFRP板等が挙げられ、これらを単独で用いてもよく、これらの2種以上を積層した複合基板として用いてもよい。 The adherend is, for example, a single wood board, a wood plywood board, a particle board, an MDF (medium density fiber board), a wood board such as an laminated material; a plaster board such as a plaster board or a plaster slag board; , Lightweight foamed concrete board, hollow extruded cement board, etc.; fiber cement board, pulp cement board, asbestos cement board, wood piece cement board, etc .; ceramic board, pottery, porcelain, earthenware, glass, amber, etc. Metal plates such as steel plates, polyvinyl chloride sol coated steel plates, aluminum plates and copper plates; thermoplastic resin plates such as polyolefin resin plates, acrylic resin plates, ABS plates and polycarbonate plates; phenol resin plates, urea resin plates and unsaturated polyester resin plates , Thermo-curable resin plate such as polyurethane resin plate, epoxy resin plate, melamine resin plate; resin such as phenol resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, diallyl phthalate resin, glass fiber Examples thereof include a so-called FRP plate obtained by impregnating and curing a non-woven fabric, cloth, paper, or other various fibrous base materials to form a composite, and these may be used alone or as a composite substrate in which two or more of these are laminated. You may.
 基材と各種被着材との積層方法としては特に限定されるものではなく、例えば接着剤によりシートを被着材に貼着する方法等を採用することができる。接着剤は、被着材の種類等に応じて公知の接着剤から適宜選択すれば良い。例えば、ポリ酢酸ビニル、ポリ塩化ビニル、塩化ビニル-酢酸ビニル共重合体、エチレン-アクリル酸共重合体、アイオノマー等のほか、ブタジエン-アクリルニトリルゴム、ネオプレンゴム、天然ゴム等が挙げられる。 The method of laminating the base material and various adherends is not particularly limited, and for example, a method of adhering a sheet to the adherend with an adhesive or the like can be adopted. The adhesive may be appropriately selected from known adhesives according to the type of adherend and the like. For example, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer and the like, as well as butadiene-acrylic nitrile rubber, neoprene rubber, natural rubber and the like can be mentioned.
<用途>
 本発明の化粧材は、例えば、各種カウンター及び机等の天板;家具;台所製品のキャビネット;ドア等の住宅用建材;等に用いられる。この中でも、カウンター及び机等に用いられる天板等の水平面を含む部位にて使用される部材は、垂直面にて使用される部材と比して、視覚的な立体感が求められ、かつ、衣服、清掃用品及び時計等の様々なもので擦られるため耐摩耗性が求められることから、本発明の化粧板の効果を発揮しやすい点で好ましい。
<Use>
The decorative material of the present invention is used, for example, as a top plate for various counters and desks; furniture; cabinets for kitchen products; residential building materials such as doors; and the like. Among these, the members used in the parts including the horizontal surface such as the top plate used for the counter and the desk are required to have a visual three-dimensional effect as compared with the members used in the vertical surface. Since it is rubbed by various objects such as clothes, cleaning supplies, and watches, abrasion resistance is required, and it is preferable in that the effect of the decorative board of the present invention can be easily exhibited.
[化粧材の製造方法]
 本発明の化粧材は、例えば、下記(1)~(8)の工程で製造することができる。
(1)基材を準備する工程。
(2)前記基材上の一部に浸透防止層を形成する工程。
(3)前記浸透防止層上の少なくとも一部に、表面が離型性を有する第一硬化物層を形成してなる、積層体Aを得る工程。
(4)前記積層体Aを硬化性樹脂組成物に含浸し、前記積層体Aの浸透防止層を有する側の全面に、未硬化の硬化性樹脂組成物層を形成してなる積層体Bを得る工程。
(5)前記積層体Bの前記未硬化の硬化性樹脂組成物層側に剥離フィルムを配置してなる、積層体Cを得る工程。
(6)前記積層体Cの両面を鏡面板で挟んだ状態で熱プレスし、前記未硬化の硬化性樹脂組成物層を硬化してなる第二硬化物層を形成する工程。
(7)前記鏡面板の間から前記積層体Cを取り出す工程。
(8)前記積層体Cから前記剥離フィルムを剥離除去する際に、前記剥離フィルムとともに前記第二硬化物層のうち第一硬化物層上の第二硬化物層を除去し、凹状の第一領域を形成するとともに、前記第二硬化物層が残存してなる第二領域を形成する工程。
[Manufacturing method of decorative material]
The decorative material of the present invention can be produced, for example, by the following steps (1) to (8).
(1) Step of preparing a base material.
(2) A step of forming a permeation prevention layer on a part of the base material.
(3) A step of obtaining a laminated body A formed by forming a first cured product layer having a releasable surface on at least a part of the permeation prevention layer.
(4) A laminate B formed by impregnating the curable resin composition with the laminate A and forming an uncured curable resin composition layer on the entire surface of the laminate A on the side having the permeation prevention layer. The process of obtaining.
(5) A step of obtaining a laminate C, which comprises arranging a release film on the uncured curable resin composition layer side of the laminate B.
(6) A step of heat-pressing the laminated body C with both sides sandwiched between mirror plates to form a second cured product layer obtained by curing the uncured curable resin composition layer.
(7) A step of taking out the laminated body C from between the mirror surface plates.
(8) When the release film is peeled off from the laminate C, the second cured product layer on the first cured product layer of the second cured product layer is removed together with the release film, and the concave first. A step of forming a region and forming a second region in which the second cured product layer remains.
 工程(1)は、基材10を準備する工程である。
 工程(2)は、基材10上の一部に浸透防止層31を形成する工程である(図2)。浸透防止層の形成に用いる硬化性樹脂組成物は、この段階で硬化することが好ましい。
The step (1) is a step of preparing the base material 10.
The step (2) is a step of forming the permeation prevention layer 31 on a part of the base material 10 (FIG. 2). The curable resin composition used for forming the permeation prevention layer is preferably cured at this stage.
 化粧材100が第一装飾層33及び/又は第二装飾層23を有する場合、工程(1)と工程(2)との間に、第一装飾層33及び/又は第二装飾層23を形成する工程を有することが好ましい(図2)。 When the decorative material 100 has the first decorative layer 33 and / or the second decorative layer 23, the first decorative layer 33 and / or the second decorative layer 23 is formed between the steps (1) and (2). It is preferable to have a step of performing (FIG. 2).
 工程(3)は、浸透防止層31上の一部に、表面が離型性を有する第一硬化物層32を形成してなる積層体A(71)を得る工程である(図3)。第一硬化物層32の形成に用いる硬化性樹脂組成物は、この段階で硬化することが好ましい。
 浸透防止層31上に第一硬化物層32を形成した箇所が、本発明の製造方法により得られた化粧材の第一領域R1に相当する箇所となる。
The step (3) is a step of obtaining a laminated body A (71) formed by forming a first cured product layer 32 having a releasable surface on a part of the permeation prevention layer 31 (FIG. 3). The curable resin composition used for forming the first cured product layer 32 is preferably cured at this stage.
The portion where the first cured product layer 32 is formed on the permeation prevention layer 31 is a portion corresponding to the first region R1 of the decorative material obtained by the production method of the present invention.
 工程(4)は、積層体Aを硬化性樹脂組成物に含浸し、積層体Aの浸透防止層31を有する側の全面に、未硬化の硬化性樹脂組成物層22aを形成してなる積層体B(72)を得る工程である(図4)。
 なお、工程(4)の最中に、基材10の中に硬化性樹脂組成物を含浸させることができる。
In the step (4), the laminated body A is impregnated with the curable resin composition, and the uncured curable resin composition layer 22a is formed on the entire surface of the laminated body A on the side having the permeation prevention layer 31. This is a step of obtaining the body B (72) (FIG. 4).
During the step (4), the base material 10 can be impregnated with the curable resin composition.
 工程(5)は、積層体Bの未硬化の硬化性樹脂組成物層22a側に剥離フィルム80を配置してなる積層体C(73)を得る工程である(図5)。
 剥離フィルム80は、後述の工程(7)において、未硬化の硬化性樹脂組成物層22aを硬化した第二硬化物層のうち、表面が離型性を有する第一硬化物層32上の第二硬化物層を除去する役割を有する。すなわち、剥離フィルム80と第二硬化物層との接着力をA1、第二硬化物層と、該硬化物層の基材10側に位置する層(第一領域R1の場合は第一硬化物層32、第二領域R2の場合は第二装飾層23又は基材10)との接着力をA2とした際に、第一領域R1ではA1>A2、第二領域R2ではA1<A2、の関係を満たすものであれば、剥離フィルム80の材質等は特に限定されない。
The step (5) is a step of obtaining a laminate C (73) formed by arranging the release film 80 on the uncured curable resin composition layer 22a side of the laminate B (FIG. 5).
The release film 80 is a second cured product layer on the first cured product layer 32 having a releasable surface among the second cured product layers obtained by curing the uncured curable resin composition layer 22a in the step (7) described later. (Ii) It has a role of removing the cured product layer. That is, the adhesive force between the release film 80 and the second cured product layer is A1, the second cured product layer and the layer located on the base material 10 side of the cured product layer (in the case of the first region R1, the first cured product). In the case of the layer 32 and the second region R2, when the adhesive force with the second decorative layer 23 or the base material 10) is A2, A1> A2 in the first region R1 and A1 <A2 in the second region R2. The material of the release film 80 is not particularly limited as long as the relationship is satisfied.
 剥離フィルム80としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル樹脂;ポリエチレン、ポリプロピレン等のポリオレフィン樹脂;アクリル樹脂;等の各種樹脂のシートの単層、あるいは、これら樹脂シート上に樹脂層を形成したものが挙げられる。 The release film 80 is a single layer of a sheet of various resins such as polyester resin such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resin such as polyethylene and polypropylene; acrylic resin; or a resin layer formed on these resin sheets. Things can be mentioned.
 化粧材100が補強層60を有する場合、工程(5)において、積層体Bの基材10側に補強層60を配置することが好ましい。 When the decorative material 100 has the reinforcing layer 60, it is preferable to arrange the reinforcing layer 60 on the base material 10 side of the laminated body B in the step (5).
 工程(6)は、積層体C(73)の両面を鏡面板で挟んだ状態で、積層体C(73)を熱プレスし、未硬化の硬化性樹脂組成物層22aを硬化してなる第二硬化物層22を形成する工程である。
 工程(6)の最中に、基材10中に含浸した硬化性樹脂組成物も硬化させることができる。
In the step (6), the laminated body C (73) is hot-pressed with both sides of the laminated body C (73) sandwiched between mirror plates to cure the uncured curable resin composition layer 22a. This is a step of forming the bi-cured product layer 22.
During the step (6), the curable resin composition impregnated in the base material 10 can also be cured.
 熱プレスの条件は、使用する熱硬化性樹脂の種類に応じて適宜調整すればよく、特に制限はないが、通常100~200℃の温度条件で、圧力は0.1~9.8MPa、時間は10秒から120分間である。 The conditions of the hot press may be appropriately adjusted according to the type of thermosetting resin used, and are not particularly limited, but are usually under temperature conditions of 100 to 200 ° C., pressure is 0.1 to 9.8 MPa, and time. Is 10 seconds to 120 minutes.
 工程(7)は、鏡面板の間から積層体Cを取り出す工程である。
 工程(8)は、積層体Cから剥離フィルム80を剥離除去する際に、剥離フィルム80とともに第二硬化物層のうち第一硬化物層32上の第二硬化物層を除去し、凹状の第一領域R1を形成するとともに、第二硬化物層22が残存してなる第二領域R2を形成する工程である(図1)。
 本発明の化粧材の製造方法は、浸透防止層を有することによって第一硬化物層の厚みを厚くできるため、第二硬化物層の厚みを厚くしても、工程(8)の際に、第一領域R1上の第二硬化物層が凝集破壊することなく綺麗に剥離することができる。
The step (7) is a step of taking out the laminated body C from between the mirror face plates.
In the step (8), when the release film 80 is peeled off from the laminate C, the second cured product layer on the first cured product layer 32 of the second cured product layer is removed together with the release film 80, and the shape is concave. This is a step of forming the first region R1 and forming the second region R2 in which the second cured product layer 22 remains (FIG. 1).
In the method for producing a decorative material of the present invention, the thickness of the first cured product layer can be increased by having the permeation prevention layer. Therefore, even if the thickness of the second cured product layer is increased, the thickness of the second cured product layer can be increased in the step (8). The second cured product layer on the first region R1 can be neatly peeled off without coagulation failure.
 次に、本発明を実施例により、さらに詳細に説明するが、本発明は、この例によってなんら限定されるものではない。 Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.
1.評価
1-1.耐摩耗性
 東洋精機製作所社製の商品名「ロータリーアブレージョンテスタ」を用いて、JIS K6902:2008の「6.2 耐摩耗B法」に準拠して、実施例及び比較例で得られた化粧材の耐摩耗性を評価した。研磨材は、JIS R6252に準拠した研磨紙「品番:S-42、3M company」を用いた。化粧材の印刷模様の50%が消し去られたときの回転盤の回転数を表1に示す。
1. 1. Evaluation 1-1. Abrasion resistance Decorative materials obtained in Examples and Comparative Examples using the trade name "Rotary Ablation Tester" manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with "6.2 Abrasion Resistance B Method" of JIS K6902: 2008. The wear resistance of was evaluated. As the polishing material, a polishing paper "Product No .: S-42, 3M company" conforming to JIS R6252 was used. Table 1 shows the number of rotations of the turntable when 50% of the printed pattern of the decorative material is erased.
1-2.第二硬化物層の剥離性
 実施例及び比較例で得られた化粧材について、第二硬化物層の剥離性を目視で評価した。第一領域上に第二硬化物層が残存していないものを「A」、剥離フィルムを剥離する際に、第一領域上で第二硬化物層が凝集破壊してしまい、第一領域上の一部に第二硬化物層が残存しているものを「C」とした。結果を表1に示す。
1-2. Peelability of the second cured product layer The peelability of the second cured product layer was visually evaluated for the decorative materials obtained in Examples and Comparative Examples. "A" is the one in which the second cured product layer does not remain on the first region, and when the release film is peeled off, the second cured product layer is coagulated and broken on the first region, and is on the first region. The one in which the second cured product layer remained in a part of the above was designated as "C". The results are shown in Table 1.
1-3.立体感
 実施例及び比較例で得られた化粧材について、蛍光灯の照明下で、任意の成人20人に、立体感を有するか否かについて目視評価をさせた。結果を表1に示す。
 A:立体感の高い意匠性を有すると答えた人が18人以上であった。
 B:立体感の高い意匠性を有すると答えた人が15~17人であった。
 C:立体感の高い意匠性を有すると答えた人が14人以下であった。
1-3. Three-dimensional effect The cosmetic materials obtained in Examples and Comparative Examples were visually evaluated by any 20 adults under the illumination of a fluorescent lamp to see if they had a three-dimensional effect. The results are shown in Table 1.
A: More than 18 people answered that they had a highly three-dimensional design.
B: 15 to 17 people answered that they had a highly three-dimensional design.
C: The number of people who answered that they had a high three-dimensional design was 14 or less.
2.化粧材の作製
[実施例1]
 基材(建材用チタン紙原紙、KJ特殊紙株式会社製の商品名「PM-67P」、坪量:80g/m、厚さ:100μm)上に、印刷インキ(DICグラフィックス株式会社製、「オーデSPTI」)を用いて、グラビア印刷により厚さ3μmの第一装飾層(木目の導管部分)及び第二装飾層(木目の木肌部分)を形成した。
 次いで、第一装飾層上に、下記の浸透防止層形成用の硬化性樹脂組成物を印刷し、電子線(加圧電圧:165KeV、3Mrad(30kGy))を照射して硬化させ、厚みt0が1.0μmの浸透防止層を形成した。
 次いで、浸透防止層上に、下記の第一硬化物層形成用の硬化性樹脂組成物を印刷し、電子線(加圧電圧:165KeV、3Mrad(30kGy))を照射して硬化させて、厚みt1が10.0μmの第一硬化物層を形成してなる積層体Aを得た。
 次いで、積層体Aを下記の第二硬化物層形成用の硬化性樹脂組成物に含浸し、乾燥させてなる積層体Bを得た(乾燥時の硬化樹脂組成物の量が80g/mとなるように含浸)。
 次いで、積層体Bの基材とは反対側の面(未硬化の第二硬化物層を有する側の面)上に、下記の剥離フィルムを積層し、積層体Bの基材側の面に、補強層(クラフト紙にフェノール樹脂からなる液体状の未硬化樹脂組成物に含浸させて得られた坪量245g/mのフェノール樹脂含浸コア紙(太田産業株式会社製、太田コア)を3枚重ねたもの)を積層してなる積層体Cを得た。
 次いで、積層体Cの両面を鏡面板で挟み(補強層側に鏡面板、剥離フィルム側にエンボス板を配置)、熱プレス機を用いて、成形温度:150℃、成形圧力:100kg/cmで10分間、加熱加圧成形を行った。成形後、2枚の鏡面板の間から積層体Cを取り出し、積層体Cから剥離用フィルムを剥離することにより、実施例1の化粧板を得た。
 なお、積層体Cから剥離フィルムを剥離除去する際に、剥離フィルムとともに第二硬化物層のうち第一硬化物層上の第二硬化物層が除去され、凹状の第一領域が形成された。また、第一硬化物層を有さない箇所には第二硬化物層が残存してなる第二領域が形成された。
 実施例1の化粧材の厚みt0は1.0μm、t1は10.0μm、t2は30μmであった。また、第一領域の面積S1と、第二領域の面積S2との比(S2/S1)は約5.0であった。
2. Preparation of decorative material [Example 1]
Printing ink (manufactured by DIC Graphics Co., Ltd.) on a base material (titanium paper base paper for building materials, trade name "PM-67P" manufactured by KJ Special Paper Co., Ltd., basis weight: 80 g / m 2, thickness: 100 μm) Using "Ode SPTI"), a first decorative layer (conduit portion of wood grain) and a second decorative layer (bark portion of wood grain) having a thickness of 3 μm were formed by gravure printing.
Next, the following curable resin composition for forming the permeation prevention layer is printed on the first decorative layer, irradiated with an electron beam (pressurized voltage: 165 KeV, 3Mrad (30 kGy)) and cured to obtain a thickness t0. A 1.0 μm permeation prevention layer was formed.
Next, the following curable resin composition for forming the first cured product layer is printed on the permeation prevention layer, irradiated with an electron beam (pressurized voltage: 165 KeV, 3Mrad (30 kGy)) and cured to obtain a thickness. A laminated body A formed by forming a first cured product layer having t1 of 10.0 μm was obtained.
Next, the laminate A was impregnated with the curable resin composition for forming the second cured product layer below, and dried to obtain a laminate B (the amount of the cured resin composition at the time of drying was 80 g / m 2). Impregnated so that
Next, the following release film is laminated on the surface of the laminate B opposite to the base material (the surface on the side having the uncured second cured product layer), and on the surface of the laminate B on the base material side. , Reinforcing layer (kraft paper impregnated with a liquid uncured resin composition made of phenol resin and obtained by impregnating it with a phenol resin impregnated core paper having a basis weight of 245 g / m 2 (Ota Core manufactured by Ota Sangyo Co., Ltd.) 3 A laminated body C formed by laminating the sheets) was obtained.
Next, both sides of the laminate C are sandwiched between mirror plates (a mirror plate is placed on the reinforcing layer side and an embossed plate is placed on the release film side), and a hot press is used to form a molding temperature: 150 ° C. and a molding pressure: 100 kg / cm 2. For 10 minutes, heat and pressure molding was performed. After molding, the laminate C was taken out from between the two mirror plates, and the release film was peeled from the laminate C to obtain the decorative plate of Example 1.
When the release film was peeled off from the laminate C, the second cured product layer on the first cured product layer was removed together with the release film, and a concave first region was formed. .. In addition, a second region was formed in which the second cured product layer remained in the portion having no first cured product layer.
The thickness t0 of the decorative material of Example 1 was 1.0 μm, t1 was 10.0 μm, and t2 was 30 μm. The ratio (S2 / S1) of the area S1 of the first region to the area S2 of the second region was about 5.0.
<浸透防止層形成用の硬化性樹脂組成物>
・6官能アクリレート系オリゴマー 90質量部
・セルロース系ポリマー 10質量部
・希釈溶剤 適量
<Curable resin composition for forming an anti-penetration layer>
・ 90 parts by mass of hexafunctional acrylate-based oligomer ・ 10 parts by mass of cellulosic polymer ・ Appropriate amount of diluting solvent
<第一硬化物層形成用の硬化性樹脂組成物>
 以下の各成分を、プロセスホモジナイザー(株式会社エスエムテー製、「PH91」)を用いて、回転数:2000rpmで1時間撹拌して樹脂組成物を得た。
・電離放射線硬化性樹脂(ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物、東亞合成株式会社製の商品名「アロニックスM400」) 60質量部
・シリコーン系離型剤(両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、信越化学株式会社製の商品名「X-22-164B」) 0.9質量部
・シランカップリング処理シリカ 18質量部
(平均粒子径3.0μm)
・メチルエチルケトン 40質量部
<Curable resin composition for forming the first cured product layer>
Each of the following components was stirred with a process homogenizer (manufactured by SMT Co., Ltd., "PH91") at a rotation speed of 2000 rpm for 1 hour to obtain a resin composition.
・ Ionizing radiation curable resin (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, trade name “Aronix M400” manufactured by Toa Synthetic Co., Ltd.) 60 parts by mass ・ Silicone-based mold release agent (both-terminal methacryloyloxyalkyl Modified organopolysiloxane, trade name "X-22-164B" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.9 parts by mass, silane coupling treated silica 18 parts by mass (average particle size 3.0 μm)
・ Methyl ethyl ketone 40 parts by mass
<第二硬化物層形成用の硬化性樹脂組成物>
・メラミンホルムアルデヒド樹脂 60質量部
・水 35質量部
・イソプロピルアルコール 5質量
<Curable resin composition for forming a second cured product layer>
Melamine formaldehyde resin 60 parts by mass ・ Water 35 parts by mass ・ Isopropyl alcohol 5 parts by mass
<剥離フィルムの作製>
 厚さ50μmのポリエチレンテレフタレートフィルム(東洋紡株式会社製の商品名「コスモシャイン A4100」)の易接着面に、下記の電離放射線硬化性樹脂組成物を塗布し、電子線(加圧電圧:165KeV、5Mrad(50kGy))を照射して硬化し、厚さ5μmの硬化物層を形成し、剥離フィルムを得た。
<<電離放射線硬化性樹脂組成物>>
・電離放射線硬化性樹脂(トリメチロールプロパントリアクリレートのエチレンボトムオキシド変性物、東亞合成株式会社製の商品名「アロニックスM350」) 100質量部
・シリコーン系離型剤(両末端メタクリロイルオキシアルキル変性オルガノポリシロキサン、信越化学株式会社製の商品名「X-22-164B」) 2質量部
・シリカ粒子(富士シリシア化学株式会社製の商品名「サイリシア450」、平均粒径:5.2μm) 8質量部
・酢酸エチル 50質量部
<Making a release film>
The following ionizing radiation curable resin composition is applied to the easy-adhesion surface of a 50 μm-thick polyethylene terephthalate film (trade name “Cosmoshine A4100” manufactured by Toyo Boseki Co., Ltd.), and an electron beam (pressurized voltage: 165 KeV, 5Mrad) is applied. (50 kGy)) was irradiated and cured to form a cured product layer having a thickness of 5 μm, and a release film was obtained.
<< Ionizing radiation curable resin composition >>
-Ionizing radiation curable resin (ethylene bottom oxide modified product of trimethylolpropane triacrylate, trade name "Aronix M350" manufactured by Toa Synthetic Co., Ltd.) 100 parts by mass-Silicone-based mold release agent (both-terminal methacryloyloxyalkyl-modified organopoly) Siloxane, trade name "X-22-164B" manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass, silica particles (trade name "Silicia 450" manufactured by Fuji Silysia Chemical Ltd., average particle size: 5.2 μm) 8 parts by mass・ 50 parts by mass of ethyl acetate
[実施例2~4]
 t0、t1及びt2を表1の値に変更した以外は、実施例1と同様にして、実施例2~4の化粧材を得た。
[Examples 2 to 4]
The decorative materials of Examples 2 to 4 were obtained in the same manner as in Example 1 except that t0, t1 and t2 were changed to the values shown in Table 1.
[比較例1]
 浸透防止層を形成せず、第一装飾層上に第一硬化物層を形成した以外は、実施例1と同様の手法で比較例1の化粧材を得た。比較例1の化粧材のt1が実施例1よりも小さい値を示す理由は、比較例1では第一硬化物層の形成材料が基材中に浸透したためである。
[Comparative Example 1]
The decorative material of Comparative Example 1 was obtained by the same method as in Example 1 except that the first cured product layer was formed on the first decorative layer without forming the permeation prevention layer. The reason why the t1 of the decorative material of Comparative Example 1 shows a value smaller than that of Example 1 is that the material for forming the first cured product layer permeated into the base material in Comparative Example 1.
[比較例2]
 t1及びt2を表1の値に変更した以外は、比較例1と同様にして、比較例2の化粧材を得た。
[Comparative Example 2]
A decorative material of Comparative Example 2 was obtained in the same manner as in Comparative Example 1 except that t1 and t2 were changed to the values shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1の結果から、実施例1~4の化粧材は、視覚的な立体感を有するとともに、耐摩耗性に優れたものであることが確認できる。
 なお、比較例1はt1が小さいため、第一領域R1から第二硬化物層を剥離する際に、第一領域内で第二硬化物層が凝集破壊してしまい、第一領域内に第二硬化物層が残存することにより、第一領域と第二領域との段差が小さくなってしまうものであった。
From the results in Table 1, it can be confirmed that the decorative materials of Examples 1 to 4 have a visual three-dimensional effect and are excellent in abrasion resistance.
Since t1 is small in Comparative Example 1, when the second cured product layer is peeled from the first region R1, the second cured product layer is coagulated and broken in the first region, and the second cured product layer is contained in the first region. Due to the remaining cured product layer, the step between the first region and the second region becomes smaller.
 10:基材
 20:第二領域形成層
 22:第二硬化物層
22a:硬化性樹脂組成物層
 23:第二装飾層
 30:第一領域形成層
 31:浸透防止層
 32:第一硬化物層
 33:第一装飾層
 60:補強層
 71:積層体A
 72:積層体B
 73:積層体C
 80:剥離フィルム
100:化粧材
10: Base material 20: Second region forming layer 22: Second cured product layer 22a: Curable resin composition layer 23: Second decorative layer 30: First region forming layer 31: Penetration prevention layer 32: First cured product Layer 33: First decorative layer 60: Reinforcing layer 71: Laminated body A
72: Laminated body B
73: Laminated body C
80: Release film 100: Cosmetic material

Claims (8)

  1.  紙基材及び繊維基材から選ばれる基材を有する化粧材であって、
     前記化粧材は、平面内に、第一領域と第二領域とを有し、
     前記第一領域に該当する箇所の前記化粧材は、前記基材上に、浸透防止層と、表面が離型性を有する第一硬化物層とをこの順に有してなり、
     前記第二領域に該当する箇所の前記化粧材は、前記基材上に、第二硬化物層を有してなり、
     前記浸透防止層の厚みをt0、前記第一硬化物層の厚みをt1、前記第二硬化物層の厚みをt2と定義した際に、t0+t1<t2の関係を満たす、化粧材。
    A decorative material having a base material selected from a paper base material and a fiber base material.
    The decorative material has a first region and a second region in a plane, and has a first region and a second region.
    The decorative material at a portion corresponding to the first region has a permeation prevention layer and a first cured product layer having a releasable surface on the base material in this order.
    The decorative material in the portion corresponding to the second region has a second cured product layer on the base material.
    A decorative material satisfying the relationship of t0 + t1 <t2 when the thickness of the permeation prevention layer is defined as t0, the thickness of the first cured product layer is defined as t1, and the thickness of the second cured product layer is defined as t2.
  2.  前記浸透防止層が電離放射線硬化性樹脂を含む、請求項1に記載の化粧材。 The decorative material according to claim 1, wherein the permeation prevention layer contains an ionizing radiation curable resin.
  3.  t1が3.5μm超30.0μm以下である、請求項1又は2に記載の化粧材。 The decorative material according to claim 1 or 2, wherein t1 is more than 3.5 μm and 30.0 μm or less.
  4.  t2-(t0+t1)が2.0μm以上50.0μm以下である、請求項1~3の何れか1項に記載の化粧材。 The decorative material according to any one of claims 1 to 3, wherein t2- (t0 + t1) is 2.0 μm or more and 50.0 μm or less.
  5.  前記第一領域に該当する箇所の前記化粧材は、前記基材と前記浸透防止層との間の少なくとも一部に第一装飾層を有する、請求項1~4の何れか1項に記載の化粧材。 The decorative material in a portion corresponding to the first region has a first decorative layer at least in a part between the base material and the permeation prevention layer, according to any one of claims 1 to 4. Cosmetic material.
  6.  前記第二領域に該当する箇所の前記化粧材は、前記基材と前記第二硬化物層との間の少なくとも一部に第二装飾層を有する、請求項1~5の何れか1項に記載の化粧材。 The decorative material in a portion corresponding to the second region has a second decorative layer at least in a part between the base material and the second cured product layer, according to any one of claims 1 to 5. The listed cosmetic material.
  7.  前記第一硬化物層が離型剤を含む、請求項1~6の何れか1項に記載の化粧材。 The decorative material according to any one of claims 1 to 6, wherein the first cured product layer contains a release agent.
  8.  前記第二硬化物層がメラミン樹脂を含む、請求項1~7の何れか1項に記載の化粧材。 The decorative material according to any one of claims 1 to 7, wherein the second cured product layer contains a melamine resin.
PCT/JP2020/014065 2019-09-30 2020-03-27 Decorative material WO2021065042A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57163522A (en) * 1981-04-01 1982-10-07 Toppan Printing Co Ltd Preparation of embossed decorative sheet
JP2005042373A (en) * 2003-07-28 2005-02-17 Dainippon Printing Co Ltd Decorated material provided with contact aptitude
WO2016148091A1 (en) * 2015-03-13 2016-09-22 大日本印刷株式会社 Decorative panel and manufacturing method for same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57163522A (en) * 1981-04-01 1982-10-07 Toppan Printing Co Ltd Preparation of embossed decorative sheet
JP2005042373A (en) * 2003-07-28 2005-02-17 Dainippon Printing Co Ltd Decorated material provided with contact aptitude
WO2016148091A1 (en) * 2015-03-13 2016-09-22 大日本印刷株式会社 Decorative panel and manufacturing method for same

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