JP2014184675A - Decorative sheet and decorative laminate using the same - Google Patents
Decorative sheet and decorative laminate using the same Download PDFInfo
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- JP2014184675A JP2014184675A JP2013061899A JP2013061899A JP2014184675A JP 2014184675 A JP2014184675 A JP 2014184675A JP 2013061899 A JP2013061899 A JP 2013061899A JP 2013061899 A JP2013061899 A JP 2013061899A JP 2014184675 A JP2014184675 A JP 2014184675A
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- Prior art keywords
- layer
- decorative sheet
- surface protective
- pattern ink
- ink layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 229930185605 Bisphenol Natural products 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
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- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 229910000004 White lead Inorganic materials 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
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- 230000000740 bleeding effect Effects 0.000 description 1
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- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Finishing Walls (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、化粧シート及びこれを用いた化粧板に関する。 The present invention relates to a decorative sheet and a decorative board using the decorative sheet.
家具や台所製品のキャビネット、床タイルや壁パネル、あるいは台所のシンク周り等に用いられる化粧板には、建材用基板に、例えば木目調柄等を印刷した化粧シートを接着剤で貼り合わせたものが一般に用いられている。
このような化粧板に使用される化粧シートには、ラミネート加工、ラッピング加工、Ｖカット加工等の二次加工のために、柔軟性、切削性、耐破断性等の加工適性や、耐汚染性、耐擦傷性、耐摩耗性、耐水性、耐薬品性、耐候性等の使用適性等の種々の特性が要求される。
こうした要求を満たすために、上記加工適性を十分に満足する基材を用い、該基材の表面に表面保護層を施すことが行われており、表面保護層としては、電離放射線硬化性樹脂が好ましく用いられている。
For decorative panels used in furniture, kitchen product cabinets, floor tiles, wall panels, and kitchen sinks, etc., a decorative sheet printed with a wood grain pattern, etc., is bonded to the building material substrate with an adhesive. Is commonly used.
The decorative sheet used for such a decorative plate is suitable for processing such as flexibility, machinability, rupture resistance, and stain resistance for secondary processing such as laminating, lapping, and V-cut. Various properties such as suitability for use such as scratch resistance, abrasion resistance, water resistance, chemical resistance and weather resistance are required.
In order to satisfy these requirements, a base material that sufficiently satisfies the processability is used, and a surface protective layer is applied to the surface of the base material. As the surface protective layer, an ionizing radiation curable resin is used. It is preferably used.
一方、近年の消費者の高級品指向により、床タイルや壁パネル、あるいは家具や台所製品のキャビネット等に対しても高級感が求められるようになり、これらに用いられる化粧板や化粧シートにおいても、高級感を与える外観を有するものが望まれている。
このような高級感を与える外観を有する化粧シートとして、特許文献１のような化粧シートが提案されている。
On the other hand, due to the recent trend toward consumer luxury goods, a sense of luxury has been demanded for floor tiles, wall panels, furniture and kitchen cabinets, etc. Those having a high-quality appearance are desired.
As a decorative sheet having an appearance that gives such a high-class feeling, a decorative sheet as in Patent Document 1 has been proposed.
特許文献１の化粧シートは、基材の表面に塗膜層、模様層、電離放射線硬化性樹脂が架橋硬化した表面保護層を有しており、模様層が塗膜層に比較して、電離放射線硬化性樹脂の浸透性を高く構成してなるものである。特許文献１の化粧シートによれば、電離放射線硬化性樹脂が模様の存在する部分により浸透しやすいため、該部分に凹部が形成され、表面に凹凸のある化粧材が得られる。
しかしながら、特許文献１の化粧シートは、模様層に十分な吸収浸透性を付与すべく、多量の体質顔料や多孔質材料を添加する必要があり、模様層が脆弱化するため、凹部の耐擦傷性及び耐摩耗性が低下するという問題がある。
The decorative sheet of Patent Document 1 has a coating layer, a patterned layer, and a surface protective layer in which an ionizing radiation curable resin is crosslinked and cured on the surface of the substrate. The patterned layer is ionized compared to the coated layer. It is configured to have high permeability of the radiation curable resin. According to the decorative sheet of Patent Document 1, since the ionizing radiation curable resin easily penetrates into a portion where a pattern exists, a concave portion is formed in the portion, and a decorative material having an uneven surface is obtained.
However, the decorative sheet of Patent Document 1 needs to add a large amount of extender pigment and porous material to impart sufficient absorption permeability to the pattern layer, and the pattern layer becomes brittle. There is a problem that the wear resistance and wear resistance are lowered.
上記問題を解決するために、特許文献２では、表面保護層に焼成カオリン粒子を含有し、耐摩耗性や耐擦傷性に対処する方法を提案している。
しかし、特許文献２の化粧シートは、耐擦傷性及び耐摩耗性には優れるものの、製造過程で経時的に化粧シートにスジムラ等の欠陥が生じ、意匠性を損なうという問題があった。
In order to solve the above problem, Patent Document 2 proposes a method for dealing with wear resistance and scratch resistance by containing calcined kaolin particles in the surface protective layer.
However, although the decorative sheet of Patent Document 2 is excellent in scratch resistance and abrasion resistance, there has been a problem that defects such as uneven stripes occur in the decorative sheet over time during the manufacturing process, thereby impairing the design.
本発明は、このような状況下で、表面に凹凸感を有し、耐擦傷性及び耐摩耗性に優れ、かつ製造過程で安定的な意匠性を付与できる化粧シート、及びこれを用いた化粧板を提供することを目的とする。 Under such circumstances, the present invention provides a decorative sheet that has an uneven feeling on the surface, is excellent in scratch resistance and abrasion resistance, and can impart a stable design in the manufacturing process, and a makeup using the same The purpose is to provide a board.
本発明者らは上記課題を解決すべく鋭意研究した結果、焼成カオリン粒子のような高硬度の粒子により耐擦傷性及び耐摩耗性を付与した場合、該高硬度粒子が塗工装置（グラビア印刷の場合、グラビア版胴やドクターブレード等）を摩耗することによって、化粧シートに欠陥が生じることを見出した。そして、さらに研究した結果、高硬度の焼成カオリン粒子を用いることなく、耐擦傷性及び耐摩耗性を満足できる構成を見出し、これを解決するに至った。 As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have provided high-hardness particles such as calcined kaolin particles with high hardness particles by applying a coating device (gravure printing). In the case of (3), it was found that the decorative sheet is defective when the gravure cylinder, doctor blade, etc.) are worn. As a result of further research, the inventors have found a structure that can satisfy the scratch resistance and the wear resistance without using high-hardness calcined kaolin particles, and have solved the problem.
すなわち、本発明は、
［１］基材上に、部分的に設けられた低艶絵柄インキ層と、該低艶絵柄インキ層上に存在してこれと接触すると共に、該低艶絵柄インキ層が形成された領域及び該低艶絵柄インキ層が形成されてない領域とを含む全面にわたって被覆する表面保護層を有してなり、
低艶絵柄インキ層が形成されていない部分の表面保護層の厚みをＨ、低艶絵柄インキ層上に存在する表面保護層の厚みをｈとした際に、Ｈが７〜１３μｍ、ｈが５〜１１μｍであり、かつＨ>ｈであり、
さらに、前記表面保護層が、樹脂成分及びシリカを含む表面保護層形成組成物から形成されてなり、該樹脂成分として電離放射線硬化性樹脂を含み、
前記シリカは、平均粒子径が８〜１２μｍでモース硬度が５〜７であり、含有量が前記樹脂成分１００質量部に対して１０〜２５質量部である、化粧シート、
［２］前記電離放射線硬化性樹脂が、重合性モノマー及びウレタンアクリレートオリゴマーを含む、上記［１］に記載の化粧シート、
［３］前記低艶絵柄インキ層が、非架橋性ウレタン樹脂を含む、上記［１］又は［２］に記載の化粧シート、
［４］前記基材と前記低艶絵柄インキ層との間に絵柄層を有する、上記［１］〜［３］の何れかに記載の化粧シート、
［５］前記基材と前記低艶絵柄インキ層との間にさらにプライマー層を有する、上記［１］〜［４］の何れかに記載の化粧シート、
［６］前記プライマー層が、架橋性ウレタン樹脂を含む、上記［５］に記載の化粧シート、
［７］上記［１］〜［６］の何れかに記載の化粧シートを基板に貼付した化粧板、
を提供するものである。
That is, the present invention
[1] A low gloss pattern ink layer partially provided on a substrate, a region present on and in contact with the low gloss pattern ink layer, and a region in which the low gloss pattern ink layer is formed; A surface protective layer covering the entire surface including the region where the low gloss pattern ink layer is not formed,
When the thickness of the surface protective layer where the low gloss pattern ink layer is not formed is H, and the thickness of the surface protective layer existing on the low gloss pattern ink layer is h, H is 7 to 13 μm and h is 5 ˜11 μm and H> h,
Furthermore, the surface protective layer is formed from a surface protective layer forming composition containing a resin component and silica, and includes an ionizing radiation curable resin as the resin component,
The silica has an average particle diameter of 8 to 12 μm, a Mohs hardness of 5 to 7, and a content of 10 to 25 parts by mass with respect to 100 parts by mass of the resin component,
[2] The decorative sheet according to [1], wherein the ionizing radiation curable resin includes a polymerizable monomer and a urethane acrylate oligomer,
[3] The decorative sheet according to the above [1] or [2], wherein the low gloss pattern ink layer contains a non-crosslinkable urethane resin,
[4] The decorative sheet according to any one of [1] to [3], which has a pattern layer between the base material and the low gloss pattern ink layer.
[5] The decorative sheet according to any one of [1] to [4], further including a primer layer between the substrate and the low gloss pattern ink layer,
[6] The decorative sheet according to [5], wherein the primer layer contains a crosslinkable urethane resin.
[7] A decorative board in which the decorative sheet according to any one of [1] to [6] is attached to a substrate,
Is to provide.
本発明によれば、表面に凹凸感を有し、耐擦傷性及び耐摩耗性に優れ、かつ製造過程で安定的な意匠性を付与できる化粧シート、及びこれを用いた化粧板を得ることができる。 ADVANTAGE OF THE INVENTION According to this invention, it can obtain a decorative sheet | seat which has an uneven | corrugated feeling on the surface, is excellent in abrasion resistance and abrasion resistance, and can provide a stable design property in a manufacturing process, and a decorative board using the same. it can.
本発明の化粧シートは、基材上に、部分的に設けられた低艶絵柄インキ層と、該低艶絵柄インキ層上に存在してこれと接触すると共に、該低艶絵柄インキ層が形成された領域及び該低艶絵柄インキ層が形成されてない領域とを含む全面にわたって被覆する表面保護層を有してなり、
低艶絵柄インキ層が形成されていない部分の表面保護層の厚みをＨ、低艶絵柄インキ層上に存在する表面保護層の厚みをｈとした際に、Ｈが７〜１３μｍ、ｈが５〜１１μｍであり、かつＨ>ｈであり、
さらに、前記表面保護層が、樹脂成分及びシリカを含む表面保護層形成組成物から形成されてなり、該樹脂成分として電離放射線硬化性樹脂を含み、
前記シリカは、平均粒子径が８〜１２μｍでモース硬度が５〜７であり、含有量が前記樹脂成分１００質量部に対して１０〜２５質量部であるものである。
The decorative sheet of the present invention has a low gloss pattern ink layer partially provided on a substrate, and the low gloss pattern ink layer is formed on the low gloss pattern ink layer. A surface protective layer covering the entire surface including the formed region and the region where the low gloss pattern ink layer is not formed,
When the thickness of the surface protective layer where the low gloss pattern ink layer is not formed is H, and the thickness of the surface protective layer existing on the low gloss pattern ink layer is h, H is 7 to 13 μm and h is 5 ˜11 μm and H> h,
Furthermore, the surface protective layer is formed from a surface protective layer forming composition containing a resin component and silica, and includes an ionizing radiation curable resin as the resin component,
The silica has an average particle diameter of 8 to 12 μm, a Mohs hardness of 5 to 7, and a content of 10 to 25 parts by mass with respect to 100 parts by mass of the resin component.
図１及び２は本発明の化粧シート１０の実施の形態を示す断面図である。
図１の化粧シート１０は、基材１上に、低艶絵柄インキ層５、表面保護層６をこの順に有してなるものである。図２の化粧シート１０は、基材１上に、着色層２、絵柄層３、プライマー層４、低艶絵柄インキ層５、表面保護層６をこの順に有してなり、絵柄層３のパターンと低艶絵柄インキ層５とのパターンとが同調しているものである。
なお、図１及び２ともに、低艶絵柄インキ層５の直上部及びその近傍における表面保護層６には、低艶絵柄インキ層５と表面保護層６とが一部混合することによる低光沢領域７を形成している。後述するように、化粧シート１０において、低光沢領域７が凹部であるかの如く認知され、化粧シート１０に擬似立体感を与えるものである。特に、図２のように絵柄層３のパターンと低艶絵柄インキ層５とのパターンが同調した構成のものは、絵柄層３の絵柄に擬似立体感が付与された化粧シートとすることができる。
1 and 2 are sectional views showing an embodiment of a decorative sheet 10 of the present invention.
A decorative sheet 10 in FIG. 1 has a low gloss pattern ink layer 5 and a surface protective layer 6 in this order on a substrate 1. The decorative sheet 10 of FIG. 2 has a colored layer 2, a pattern layer 3, a primer layer 4, a low-gloss pattern ink layer 5, and a surface protective layer 6 in this order on the substrate 1. And the pattern of the low gloss pattern ink layer 5 are synchronized.
1 and 2, the surface protective layer 6 immediately above and near the low gloss pattern ink layer 5 has a low gloss area due to a partial mixing of the low gloss pattern ink layer 5 and the surface protective layer 6. 7 is formed. As will be described later, in the decorative sheet 10, the low gloss region 7 is recognized as if it is a recess, and gives the decorative sheet 10 a pseudo three-dimensional effect. In particular, as shown in FIG. 2, a structure in which the pattern of the pattern layer 3 and the pattern of the low gloss pattern ink layer 5 are synchronized can be a decorative sheet in which a pseudo three-dimensional effect is imparted to the pattern of the pattern layer 3. .
［基材］
基材１としては、通常化粧シートの基材として用いられるものであれば、特に限定されず、各種の紙類、プラスチックフィルム、金属箔、金属シート、金属板、木材等の木質系の板、窯業系素材等を用途に応じて適宜選択することができる。これらの材料はそれぞれ単独で使用してもよいが、紙同士の複合体や紙とプラスチックフィルムの複合体等、任意の組み合わせによる積層体であってもよい。
[Base material]
The base material 1 is not particularly limited as long as it is usually used as a base material for a decorative sheet. Various papers, plastic films, metal foils, metal sheets, metal plates, wood-based boards such as wood, A ceramic material or the like can be appropriately selected depending on the application. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper or a composite of paper and a plastic film.
これらの基材には、基材上に設けられる層との密着性を向上させるために、片面又は両面に、酸化法や凹凸化法等の物理的又は化学的表面処理を施すことができる。
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効果及び操作性等の面から好ましく用いられる。
また、該基材はプライマー層を形成する等の処理を施してもよいし、色彩を整えるための塗装や、デザイン的な観点での模様があらかじめ形成されていてもよい。
These base materials can be subjected to a physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides in order to improve adhesion to a layer provided on the base material.
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 sand blast method and solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
Further, the substrate may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.
基材として用いられる各種の紙類としては、薄葉紙、クラフト紙、チタン紙、コート紙、アート紙、硫酸紙、グラシン紙、パーチメント紙、パラフィン紙及び和紙、並びにこれら紙の紙間強化紙及び樹脂含浸紙等が挙げられる。これらの紙類の中でも、熱的安定性や強度の観点からは、薄葉紙、クラフト紙、チタン紙といった紙で構成されるものが好適であり、防湿性の観点からは、ポリエチレンフィルムを２枚の紙で挟み込んだポリサンド紙と呼ばれる紙とプラスチックフィルムの複合体が好適である。 Various papers used as the substrate include thin paper, kraft paper, titanium paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper and Japanese paper, and inter-paper reinforced paper and resin of these papers. Examples include impregnated paper. Among these papers, those composed of paper such as thin paper, kraft paper, and titanium paper are preferable from the viewpoint of thermal stability and strength. From the viewpoint of moisture resistance, two sheets of polyethylene film are used. A composite of paper and a plastic film called polysand paper sandwiched between papers is preferable.
プラスチックフィルムとしては、各種の合成樹脂からなるものが挙げられる。合成樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリメチルペンテン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリビニルアルコール樹脂、塩化ビニル−酢酸ビニル共重合樹脂、エチレン−酢酸ビニル共重合樹脂、エチレン−ビニルアルコール共重合樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンナフタレート−イソフタレート共重合樹脂、ポリメタクリル酸メチル樹脂、ポリメタクリル酸エチル樹脂、ポリアクリル酸ブチル樹脂、ナイロン６又はナイロン６６等で代表されるポリアミド樹脂、三酢酸セルロース樹脂、セロファン、ポリスチレン樹脂、ポリカーボネート樹脂、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、ポリアリレート樹脂、又はポリイミド樹脂等が挙げられる。
これらプラスチックフィルムの中では、熱的安定性や強度の観点からは、ポリエチレンテレフタレート樹脂を延伸処理したものが好適であり、防湿性の観点からは、ポリプロピレン樹脂を延伸処理したものが好適である。
As a plastic film, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 Polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyarylate resin, And polyimide resins.
Among these plastic films, a film obtained by stretching a polyethylene terephthalate resin is preferable from the viewpoint of thermal stability and strength, and a film obtained by stretching a polypropylene resin is preferable from the viewpoint of moisture resistance.
金属箔、金属シート、又は金属板としては、例えばアルミニウム、鉄、ステンレス鋼、及び銅等が挙げられ、またこれらの金属をめっき処理したものも挙げられる。各種の木質系の板としては、木材の単板、合板、集成材、パーチクルボード及びＭＤＦ（中密度繊維板）等の木質繊維板が挙げられる。窯業系素材としては、石膏板、珪酸カルシウム板、木片セメント板等の窯業系建材、陶磁器、ガラス、琺瑯、焼成タイル等が挙げられる。 Examples of the metal foil, metal sheet, or metal plate include aluminum, iron, stainless steel, copper, and the like, and those obtained by plating these metals. Examples of the various wood-based boards include wood fiber boards such as wood single board, plywood, laminated wood, particle board, and MDF (medium density fiber board). Examples of ceramic materials include ceramic building materials such as gypsum plates, calcium silicate plates, and wood cement plates, ceramics, glass, firewood, and fired tiles.
基材の厚さについては特に制限はないが、プラスチックフィルムを用いる場合には、通常２０〜１５０μｍ程度、好ましくは３０〜１００μｍの範囲であり、紙基材を用いる場合には、坪量は、通常２０〜１５０ｇ／ｍ2程度、好ましくは３０〜１００ｇ／ｍ2の範囲である。 The thickness of the substrate is not particularly limited, but when a plastic film is used, it is usually in the range of about 20 to 150 μm, preferably 30 to 100 μm. When a paper substrate is used, the basis weight is Usually, it is about 20 to 150 g / m 2 , preferably 30 to 100 g / m 2 .
［着色層］
着色層２は、本発明の化粧シートの意匠性を高める目的で必要に応じて設けられる。着色層は、化粧シートの面方向の全部に形成することが好ましい。
着色層は、基材上の表面の色を整えることで、基材自身が着色していたり、色ムラがあるときに形成して、基材の表面に意図した色彩を与えるものである。着色層は隠蔽性を持たせるように形成することが多いが、透明色で形成し、下地が持っている模様を活かす場合もある。それに加えて、後述する低艶絵柄インキ層及び表面保護層を形成する成分が基材に浸透することを抑制できる。さらに後述する絵柄層の浸透も抑制でき、且つ浸透を抑制することで絵柄の滲みが少ない高い意匠性を得ることができる。前記の浸透抑制効果は、基材が紙や不織布等の浸透性基材である場合に特に有効である。
[Colored layer]
The colored layer 2 is provided as needed for the purpose of enhancing the design of the decorative sheet of the present invention. The colored layer is preferably formed on the entire surface of the decorative sheet.
The colored layer adjusts the color of the surface on the substrate, and is formed when the substrate itself is colored or has color unevenness, and gives the intended color to the surface of the substrate. The colored layer is often formed so as to have a concealing property, but may be formed of a transparent color and take advantage of the pattern of the base. In addition, it is possible to suppress penetration of the components forming the low-gloss pattern ink layer and the surface protective layer, which will be described later, into the substrate. Furthermore, the penetration of the pattern layer, which will be described later, can be suppressed, and by suppressing the penetration, a high design property with less bleeding of the pattern can be obtained. The permeation suppression effect is particularly effective when the base material is a permeable base material such as paper or nonwoven fabric.
着色層の形成に用いられるインキとしては、バインダーに顔料、染料等の着色剤、体質顔料、溶剤、安定剤、可塑剤、触媒、硬化剤等を適宜混合したものが使用される。
バインダーとしては特に制限はなく、例えば、ウレタン樹脂、塩化ビニル／酢酸ビニル系共重合体樹脂、塩化ビニル／酢酸ビニル／アクリル系共重合体樹脂、塩素化ポリプロピレン系樹脂、アクリル系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、ブチラール系樹脂、ポリスチレン系樹脂、ニトロセルロース系樹脂、酢酸セルロース系樹脂等の１種又は２種以上を用いることができる。これらの中でもウレタン樹脂が好適である。
As the ink used for forming the colored layer, an ink obtained by appropriately mixing a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is used.
The binder is not particularly limited. For example, urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin. One or more of polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins can be used. Among these, urethane resin is preferable.
ウレタン樹脂としては、アクリルポリオール、ポリエステルポリオール、ポリエーテルポリオール等のポリオールと、トリレンジイソシアネート、キシレンジイソシアネート、ジフェニルメタンジイソシアネート等の芳香族イソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、水添トリレンジイソシアネート等の脂肪族ないしは脂環式イソシアネート等のイソシアネートとを反応させてなるウレタン樹脂が挙げられる。通常ポリオール１分子中の水酸基数及びイソシアネート１分子中のイソシアネート基はそれぞれ平均２である。またウレタン樹脂の数平均分子量は１００００〜５００００程度であり、ガラス転移温度（Ｔｇ）は−７０〜６０℃程度のものが耐油性、耐スクラッチ性のために好ましい。
着色層の厚さは通常１〜２０μｍ程度である。
Urethane resins include polyols such as acrylic polyol, polyester polyol and polyether polyol, and aromatic isocyanates such as tolylene diisocyanate, xylene diisocyanate and diphenylmethane diisocyanate, aliphatics such as isophorone diisocyanate, hexamethylene diisocyanate and hydrogenated tolylene diisocyanate. Or the urethane resin formed by making it react with isocyanates, such as alicyclic isocyanate, is mentioned. Usually, the number of hydroxyl groups in one molecule of polyol and the number of isocyanate groups in one molecule of isocyanate are two on average. The number average molecular weight of the urethane resin is about 10,000 to 50,000, and the glass transition temperature (Tg) is preferably about −70 to 60 ° C. for oil resistance and scratch resistance.
The thickness of the colored layer is usually about 1 to 20 μm.
［絵柄層］
化粧シートは、基材自体が持つ意匠感や、後述する低艶絵柄インキ層と表面保護層とのグロスマット表現等によって、化粧シートとしての目的とする意匠感を表現できれば、絵柄層は設ける必要はない。しかし、通常は印刷等で絵柄を表現して高意匠とすべく、この絵柄層３を設ける（図２参照）。
絵柄層は、図２のように化粧シートの面方向の一部にパターン状に形成してもよいし、化粧シートの面方向の全部にパターン状に設けてもよい。
絵柄層の模様（絵柄パターン）としては、木目模様、大理石模様（例えばトラバーチン大理石模様）等の岩石の表面を模した石目模様、布目や布状の模様を模した布地模様、タイル貼模様、煉瓦積模様等があり、これらを複合した寄木、パッチワーク等の模様もある。
これらの模様は通常の黄色、赤色、青色、および黒色のプロセスカラーによる多色印刷によって形成される他、模様を構成する個々の色の版を用意して行う特色による多色印刷等によっても形成される。
絵柄層に用いる絵柄インキとしては、着色層に用いるインキと同様のものを用いることができる。
[Picture layer]
If the decorative sheet can express the desired design feeling as a decorative sheet by the design feeling of the base material itself or the gloss mat expression of the low gloss pattern ink layer and the surface protective layer described later, it is necessary to provide the pattern layer There is no. However, this pattern layer 3 is usually provided in order to express the pattern by printing or the like to make it a high design (see FIG. 2).
The pattern layer may be formed in a pattern on a part of the surface direction of the decorative sheet as shown in FIG. 2, or may be provided in a pattern on the entire surface direction of the decorative sheet.
As the pattern of the pattern layer (pattern pattern), a grain pattern imitating the surface of a rock such as a wood grain pattern, marble pattern (for example, travertine marble pattern), a fabric pattern imitating a cloth or cloth pattern, a tiled pattern, There are brickwork patterns, etc., and there are also patterns such as marquetry and patchwork that combine these.
These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates that make up the pattern. Is done.
As the pattern ink used for the pattern layer, the same ink as that used for the colored layer can be used.
後述するように、絵柄層の模様（絵柄パターン）と、低艶絵柄インキ層のパターンとを同調させることにより、擬似立体感の付与により意匠を高級化することができる。
絵柄層の厚さは通常１〜２０μｍ程度である。
As will be described later, by synchronizing the pattern of the pattern layer (pattern pattern) and the pattern of the low gloss pattern ink layer, the design can be upgraded by imparting a pseudo three-dimensional effect.
The thickness of the pattern layer is usually about 1 to 20 μm.
［プライマー層］
プライマー層４は、所望により設けられる層であって、主として各層の密着性を高める役割を有する。プライマー層４の位置としては、基材と低艶絵柄インキ層との間であれば特に制限されることはない。化粧シートが着色層及び絵柄層を有する場合には、プライマー層４の位置は、絵柄層３と低艶絵柄インキ層５との間（図２）、基材１と着色層２との間、着色層２と絵柄層３との間が挙げられる。化粧シートが着色層及び絵柄層を有する場合の好ましいプライマー層の位置は、低艶絵柄インキ層及び表面保護層の密着性を高める観点から、絵柄層と低艶絵柄インキ層との間である。なお、プライマー層４の位置は２箇所以上であってもよい。
[Primer layer]
The primer layer 4 is a layer provided as desired, and mainly has a role of improving the adhesion of each layer. The position of the primer layer 4 is not particularly limited as long as it is between the base material and the low gloss pattern ink layer. When the decorative sheet has a colored layer and a pattern layer, the position of the primer layer 4 is between the pattern layer 3 and the low gloss pattern ink layer 5 (FIG. 2), between the base material 1 and the colored layer 2, The space between the colored layer 2 and the pattern layer 3 is mentioned. A preferable primer layer position when the decorative sheet has a colored layer and a pattern layer is between the pattern layer and the low gloss pattern ink layer from the viewpoint of enhancing the adhesion between the low gloss pattern ink layer and the surface protective layer. In addition, the position of the primer layer 4 may be two or more.
プライマー層は、主として樹脂成分を含むプライマー層形成組成物から形成することができ、該樹脂成分としては、着色層のバインダー成分と同様の樹脂を用いることができる。
また、プライマー層の樹脂成分は、熱硬化性樹脂を含むことが好ましい。熱硬化性樹脂を含むことにより、密着性を向上させつつ、耐擦傷性及び耐摩耗性を良好にでき、さらに、低艶絵柄インキ層及び表面保護層を形成する成分が基材に浸透することを抑制できる。前記の浸透抑制効果は、基材が紙や不織布等の浸透性基材である場合に特に有効である。
また、熱硬化性樹脂としては、耐擦傷性及び耐摩耗性の観点から、架橋性ウレタン樹脂が特に好適である。
The primer layer can be formed mainly from a primer layer forming composition containing a resin component, and the same resin as the binder component of the colored layer can be used as the resin component.
Moreover, it is preferable that the resin component of a primer layer contains a thermosetting resin. By including a thermosetting resin, it is possible to improve the scratch resistance and wear resistance while improving adhesion, and further, the components that form the low-gloss pattern ink layer and the surface protective layer penetrate into the substrate. Can be suppressed. The permeation suppression effect is particularly effective when the base material is a permeable base material such as paper or nonwoven fabric.
Moreover, as a thermosetting resin, a crosslinkable urethane resin is especially suitable from a viewpoint of abrasion resistance and abrasion resistance.
［低艶絵柄インキ層］
本発明の化粧シートに設けられる低艶絵柄インキ層５は、化粧シートの面方向において部分的に存在し、図１に示すように基材１に直接積層されるか、または図２に示すように、必要に応じて設けられた着色層２、絵柄層３、プライマー層４等の上に積層されるものである。そして、該低艶絵柄インキ層５の直上部及びその近傍における表面保護層６には、低光沢領域７が形成される。
本発明の化粧シートを表面保護層側から見ると、低光沢領域は艶が低く、その周辺の艶との差によって視覚的に凹部として認識されるため、全体として、この低光沢領域によって視覚的に凹凸模様として認識される。
表面保護層６中に形成される低光沢領域７の広がりの程度については、本発明の効果を奏する範囲内であれば特に限定されず、図１及び図２に示すように、低艶絵柄インキ層５の表面から表面保護層６の厚み方向の途中で留まっていてもよく、表面保護層６の最表面に達するものであってもよい。
[Low gloss pattern ink layer]
The low gloss pattern ink layer 5 provided on the decorative sheet of the present invention is partially present in the surface direction of the decorative sheet, and is directly laminated on the substrate 1 as shown in FIG. 1 or as shown in FIG. And laminated on the colored layer 2, the pattern layer 3, the primer layer 4, and the like provided as necessary. A low gloss region 7 is formed in the surface protective layer 6 immediately above and near the low gloss pattern ink layer 5.
When the decorative sheet of the present invention is viewed from the surface protective layer side, the low gloss region has a low gloss, and is visually recognized as a concave portion due to a difference with the gloss on the periphery thereof. Is recognized as an uneven pattern.
The extent of spreading of the low gloss region 7 formed in the surface protective layer 6 is not particularly limited as long as it is within the range where the effects of the present invention can be achieved. As shown in FIG. 1 and FIG. It may stay in the middle of the thickness direction of the surface protective layer 6 from the surface of the layer 5 or may reach the outermost surface of the surface protective layer 6.
低光沢領域とその周辺とにおける艶差の発生機構やその広がりの程度の強弱の発生機構については、十分解明されるには至っていないが、艶差の発生機構については、各種実験と観察、測定の結果から、低艶絵柄インキ層の表面に表面保護層を形成するための電離放射線硬化性樹脂の未硬化物を塗工した際に、各材料の組合せ、塗工条件の適当な選択によって、低艶絵柄インキ層の樹脂成分と表面保護層が、一部溶出、分散、混合等の相互作用を発現することによるものと推測される。この際、低艶絵柄インキ層のインキと電離放射線硬化性樹脂の未硬化物におけるそれぞれの樹脂成分は、短時間には完全相溶状態にならずに懸濁状態となって、低艶絵柄インキ層の直上部及びその近傍に存在し、該懸濁状態となった部分が光を散乱して低光沢領域をなすものと考えられる。この懸濁状態を有したまま、表面保護層を架橋硬化させることにより、かかる状態が固定されると、表面保護層中に低光沢領域が部分的に形成され、目の錯覚により、その部分が凹部であるかのように認知されるものと推測される。 The mechanism of gloss difference in the low-gloss area and its surroundings and the mechanism of the intensity of the extent of the spread have not been fully elucidated, but the mechanism of gloss difference has been variously tested, observed, and measured. From the results, when an uncured product of ionizing radiation curable resin for forming a surface protective layer on the surface of the low gloss pattern ink layer was coated, by appropriate selection of the combination of each material and coating conditions, It is presumed that the resin component of the low gloss pattern ink layer and the surface protective layer are partly expressed by interactions such as elution, dispersion, and mixing. At this time, each resin component in the ink of the low gloss pattern ink layer and the uncured product of the ionizing radiation curable resin becomes a suspended state instead of being completely compatible in a short time. It is considered that the portion present in the immediate upper part of the layer and in the vicinity thereof and in the suspended state scatters light to form a low gloss region. When this state is fixed by crosslinking and curing the surface protective layer with this suspended state, a low-gloss region is partially formed in the surface protective layer. It is presumed to be recognized as if it were a recess.
本発明の化粧シートにおいては、この低艶絵柄インキ層の特徴をいかして、好ましく設けられる絵柄層との組合せにより、絵柄層が表現しようとする模様のうち、艶を消して視覚的に凹部を表現したい部分と低艶絵柄インキ層とを同調させることによって、艶差による視覚的凹部を有する模様が得られる。例えば、絵柄層によって木目模様を表現しようとする場合には、木目の導管部分に低艶絵柄インキ層のインキ部分を同調させることにより、艶差により導管部分が視覚的に凹部となった模様が得られる。また、絵柄層によってタイル貼模様を表現しようとする場合には、タイル貼の目地溝部分に低艶絵柄インキ層のインキ部分を同調させることにより、艶差によって、目地溝部分が視覚的に凹部となった模様が得られる。 In the decorative sheet of the present invention, by utilizing the characteristics of this low gloss pattern ink layer, by combining with the pattern layer that is preferably provided, among the patterns that the pattern layer intends to express, the gloss is erased visually and the concave portion is visually displayed. By synchronizing the portion to be expressed with the low gloss pattern ink layer, a pattern having visual recesses due to gloss difference can be obtained. For example, when a wood grain pattern is to be expressed by a pattern layer, by synchronizing the ink part of the low gloss pattern ink layer with the grain part of the grain, a pattern in which the conduit part is visually concave due to the difference in gloss is formed. can get. In addition, when a tiled pattern is to be expressed by the pattern layer, the joint groove portion is visually recessed due to the gloss difference by synchronizing the ink portion of the low gloss pattern ink layer with the tile groove joint portion. The resulting pattern is obtained.
低艶絵柄インキ層を形成する組成物は、表面保護層形成組成物に含まれる電離放射線硬化性樹脂との間で溶出、分散、混合等の相互作用を発現し得る性質を有するものであり、該電離放射線硬化性樹脂（未硬化物）との関連で適宜選定されるものである。
このような低艶絵柄インキ層形成組成物は少なくともバインダー樹脂を含む。また、バインダー樹脂として非架橋性樹脂を含むことが好ましい。
The composition for forming the low gloss pattern ink layer has a property capable of expressing an interaction such as elution, dispersion, and mixing with the ionizing radiation curable resin contained in the surface protective layer forming composition. It is appropriately selected in relation to the ionizing radiation curable resin (uncured product).
Such a low gloss pattern ink layer forming composition contains at least a binder resin. Moreover, it is preferable that non-crosslinkable resin is included as binder resin.
非架橋性樹脂としては、ポリエステルウレタン樹脂等の熱可塑性（非架橋性）ウレタン樹脂や、アクリル樹脂、ポリエステル樹脂、不飽和ポリエステル樹脂、塩化ビニル−酢酸ビニル共重合体等が挙げられ、なかでもポリエステルウレタン樹脂等の熱可塑性（非架橋性）ウレタン樹脂が好ましい。
また、必要に応じて、低光沢領域の発現の程度、低光沢領域とその周囲との艶差のコントラストを調整するため、不飽和ポリエステル樹脂、アクリル樹脂、又は塩化ビニル−酢酸ビニル共重合体等を混合することができる。
る。
Examples of non-crosslinkable resins include thermoplastic (non-crosslinkable) urethane resins such as polyester urethane resins, acrylic resins, polyester resins, unsaturated polyester resins, vinyl chloride-vinyl acetate copolymers. A thermoplastic (non-crosslinkable) urethane resin such as a urethane resin is preferred.
If necessary, unsaturated polyester resin, acrylic resin, vinyl chloride-vinyl acetate copolymer, etc. are used to adjust the degree of expression of the low gloss region and the contrast of the gloss difference between the low gloss region and its surroundings. Can be mixed.
The
低艶絵柄インキ層形成組成物は、着色剤を含有することができ、それ自体でも絵柄模様を与えることができる。なお、図２に示すような着色層２や絵柄層３を有する場合には、必ずしも着色剤を添加して着色する必要はない。
低艶絵柄インキに用いられる着色剤としては、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又は染料、アルミニウム、真鍮等の鱗片状箔片からなる金属顔料、二酸化チタン被覆雲母、塩基性炭酸鉛等の鱗片状箔片からなる真珠光沢（パール）顔料等の各種顔料が用いられる。これら顔料の中ではシリカが好適である。
顔料の平均粒子径は、０．１〜５μｍの範囲が好ましい。また、低艶絵柄インキ層形成組成物における顔料の含有量は、５〜１５質量％の範囲であることが好ましい。
The low gloss pattern ink layer forming composition can contain a colorant, and can provide a pattern pattern by itself. In addition, when it has the colored layer 2 and the pattern layer 3 as shown in FIG. 2, it is not necessary to add a coloring agent and to color.
Colorants used in low gloss design inks include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue, metallic pigments composed of scaly foils such as aluminum and brass, pearl luster composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate (pearl) ) Various pigments such as pigments are used. Of these pigments, silica is preferred.
The average particle diameter of the pigment is preferably in the range of 0.1 to 5 μm. Moreover, it is preferable that content of the pigment in a low gloss pattern ink layer forming composition is the range of 5-15 mass%.
低艶絵柄インキ層の厚みは、後述する表面保護層の厚みとのバランスもあるため一概にはいえないが、０．５〜８μｍであることが好ましい。０．５μｍ以上とすることにより、化粧シート表面の十分な艶差を出しやすくなり、８μｍ以下とすることにより、低艶絵柄インキの印刷に際して機械的制約がなく、また経済的にも有利である。 The thickness of the low gloss pattern ink layer cannot be generally specified because of the balance with the thickness of the surface protective layer described later, but is preferably 0.5 to 8 μm. By setting the thickness to 0.5 μm or more, it becomes easy to produce a sufficient gloss difference on the surface of the decorative sheet. By setting the thickness to 8 μm or less, there is no mechanical restriction when printing low-gloss pattern ink, and it is economically advantageous. .
［表面保護層］
表面保護層６は、樹脂成分及び特定のシリカを含む表面保護層形成組成物から形成されてなるものである。また、樹脂成分としては電離放射線硬化性樹脂を必須成分として含む。
ここで、電離放射線硬化性樹脂とは、電磁波または荷電粒子線の中で分子を架橋、重合させ得るエネルギー量子を有するもの、すなわち、紫外線または電子線等を照射することにより、架橋、硬化する樹脂成分を指す。
[Surface protective layer]
The surface protective layer 6 is formed from a surface protective layer forming composition containing a resin component and specific silica. Moreover, ionizing radiation curable resin is included as an essential component as a resin component.
Here, the ionizing radiation curable resin has an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, a resin that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Refers to ingredients.
電離放射線硬化性樹脂は、従来電離放射線硬化性の樹脂として慣用されている重合性モノマー及び重合性オリゴマーないしはプレポリマーの中から適宜選択して用いることができるが、良好な硬化特性を得る観点から、ブリードアウトしにくく、固形分基準として９５〜１００％程度としても塗工性を有し、かつ硬化する際に硬化収縮を生じにくいものが好ましい。そのような電離放射線硬化性樹脂の代表例を以下に記載する。なお、「（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。 The ionizing radiation curable resin can be appropriately selected from a polymerizable monomer and a polymerizable oligomer or prepolymer conventionally used as an ionizing radiation curable resin, but from the viewpoint of obtaining good curing characteristics. It is preferable that it is difficult to bleed out, has a coating property even if it is about 95 to 100% as a solid content, and does not easily cause curing shrinkage when cured. Representative examples of such ionizing radiation curable resins are described below. “(Meth) acrylate” means “acrylate or methacrylate”.
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）アクリレート単量体が好適であり、なかでも分子内にエチレン性不飽和結合を２個以上有するような多官能性（メタ）アクリレートが好ましく、１種を単独で、あるいは２種以上を組み合わせて用いて用いればよい。官能基数としては、２〜８が好ましく、２〜６がより好ましく、３〜４がさらに好ましい。 As the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and in particular, a polyfunctionality having two or more ethylenically unsaturated bonds in the molecule ( (Meth) acrylate is preferred, and one kind may be used alone, or two or more kinds may be used in combination. As a functional group number, 2-8 are preferable, 2-6 are more preferable, and 3-4 are more preferable.
本発明においては、前記多官能性（メタ）アクリレートとともに、その粘度を調整する等の目的で、メチル（メタ）アクリレート等の単官能性（メタ）アクリレートを、本発明の目的を損なわない範囲で適宜併用することができる。単官能性（メタ）アクリレートは１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 In the present invention, monofunctional (meth) acrylates such as methyl (meth) acrylate and the like for the purpose of adjusting the viscosity together with the polyfunctional (meth) acrylate, as long as the object of the present invention is not impaired. It can be used together as appropriate. A monofunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.
次に、重合性オリゴマーとしては、分子中にラジカル重合性不飽和基を持つオリゴマー、例えば、エポキシ（メタ）アクリレート系、ウレタン（メタ）アクリレート系、ポリエステル（メタ）アクリレート系、ポリエーテル（メタ）アクリレート系のオリゴマー等が好ましく挙げられる。これらのオリゴマーのうち、多官能性の重合性オリゴマーが好ましく、官能基数としては、２〜１６が好ましく、２〜８がより好ましく、２〜６がさらに好ましい。 Next, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) Preferred are acrylate oligomers and the like. Among these oligomers, polyfunctional polymerizable oligomers are preferable, and the number of functional groups is preferably 2 to 16, more preferably 2 to 8, and still more preferably 2 to 6.
さらに、重合性オリゴマーとしては、他にポリブタジエンオリゴマーの側鎖に（メタ）アクリレート基をもつ疎水性の高いポリブタジエン（メタ）アクリレート系オリゴマー、主鎖にポリシロキサン結合をもつシリコーン（メタ）アクリレート系オリゴマー、小さな分子内に多くの反応性基をもつアミノプラスト樹脂を変性したアミノプラスト樹脂（メタ）アクリレート系オリゴマー、あるいはノボラック型エポキシ樹脂、ビスフェノール型エポキシ樹脂、脂肪族ビニルエーテル、芳香族ビニルエーテル等の分子中にカチオン重合性官能基を有するオリゴマー等がある。これらの重合性オリゴマーは、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group. These polymerizable oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.
本発明では、耐擦傷性及び耐摩耗性の観点から、電離放射線硬化性樹脂として、重合性モノマー及び重合性オリゴマーを含むことが好ましい。該組み合わせの場合、重合性オリゴマーとしては、ウレタンアクリレートオリゴマーが好適である。
［重合性モノマー／重合性オリゴマー］の質量比は、オリゴマー成分を添加することにより表面保護層を硬質化すること、及びオリゴマー成分が過剰になることにより表面保護層形成組成物が高粘度化することを防止する観点から、１．０〜５．０であることが好ましく、２．０〜３．０であることがより好ましい。
In this invention, it is preferable that a polymerizable monomer and a polymerizable oligomer are included as ionizing radiation curable resin from a viewpoint of abrasion resistance and abrasion resistance. In the case of this combination, a urethane acrylate oligomer is suitable as the polymerizable oligomer.
The mass ratio of [polymerizable monomer / polymerizable oligomer] is such that the surface protective layer is hardened by adding the oligomer component, and the surface protective layer forming composition is increased in viscosity by the excess of the oligomer component. From the viewpoint of preventing this, it is preferably 1.0 to 5.0, and more preferably 2.0 to 3.0.
電離放射線硬化性樹脂として紫外線硬化性樹脂を用いる場合には、光重合用開始剤を紫外線硬化性樹脂１００質量部に対して、０．１〜５質量部程度添加することが望ましい。光重合用開始剤としては、従来慣用されているものから適宜選択することができ、特に限定されない。 When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the ultraviolet curable resin. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.
本発明においては、電離放射線硬化性樹脂として電子線硬化性樹脂を用いることが好ましい。これは、表面保護層形成組成物に紫外線吸収剤が含まれる場合は、紫外線硬化性樹脂を用いると紫外線照射量の不足を防ぐために照射する紫外線の波長や照射量の調製を要することがあるが、電子線硬化性樹脂を用いるとそのような調製は不要であり、安定した硬化特性が効率的に得られるからである。 In the present invention, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. This is because when the surface protective layer-forming composition contains an ultraviolet absorber, the use of an ultraviolet curable resin may require adjustment of the wavelength and dose of the irradiated ultraviolet rays in order to prevent shortage of the ultraviolet dose. This is because, when an electron beam curable resin is used, such preparation is unnecessary and stable curing characteristics can be obtained efficiently.
また、表面保護層形成組成物の樹脂成分としては、物性調整等の為に更に必要に応じ適宜、塩化ビニル−酢酸ビニル共重合体、酢酸ビニル樹脂、アクリル樹脂、セルロース系樹脂等の熱可塑性樹脂を混合使用しても良い。 In addition, as a resin component of the surface protective layer forming composition, a thermoplastic resin such as a vinyl chloride-vinyl acetate copolymer, a vinyl acetate resin, an acrylic resin, or a cellulose resin may be appropriately used to adjust physical properties. May be used in combination.
（表面保護層の厚み）
本発明においては、低艶絵柄インキ層５が形成されていない部分の表面保護層６の厚みをＨ、低艶絵柄インキ層５上に存在する表面保護層６の厚みをｈとした際に、Ｈが７〜１３μｍ、ｈが５〜１１μｍであり、かつＨ>ｈであることを要する（図１、図２）。
Ｈが７μｍ未満であると、耐擦傷性及び耐摩耗性を満足することができず、Ｈが１３μｍを超えると、下方に位置する意匠の視認性が低下して、化粧シートの凹凸感が損なわれてしまう。また、ｈが５μｍ未満であると、低光沢領域の耐擦傷性及び耐摩耗性が劣り、ｈが１１μｍを超えると、低艶絵柄インキ層の直上部及びその近傍における表面保護層を十分に低光沢とすることができず、また、絵柄層を有する場合には絵柄層の視認性が低下することにより、化粧シートの意匠性が低下してしまう。
前記Ｈは８〜１２μｍであることが好ましい。また、前記ｈは６〜１１μｍであることが好ましい。
また、［前記Ｈ−前記ｈ］は、０．５μｍ以上であることが好ましく、１．０〜２．５μｍであることがより好ましい。
(Thickness of the surface protective layer)
In the present invention, when the thickness of the surface protective layer 6 where the low gloss pattern ink layer 5 is not formed is H, and the thickness of the surface protective layer 6 present on the low gloss pattern ink layer 5 is h, It is necessary that H is 7 to 13 μm, h is 5 to 11 μm, and H> h (FIGS. 1 and 2).
When H is less than 7 μm, the scratch resistance and wear resistance cannot be satisfied. When H exceeds 13 μm, the visibility of the design located below is lowered, and the unevenness of the decorative sheet is impaired. It will be. Further, if h is less than 5 μm, the scratch resistance and wear resistance of the low gloss region are inferior, and if h exceeds 11 μm, the surface protective layer in the immediate upper part of the low gloss pattern ink layer and its vicinity is sufficiently low. It cannot be made glossy, and when it has a pattern layer, the visibility of the pattern layer is lowered, so that the design of the decorative sheet is lowered.
The H is preferably 8 to 12 μm. The h is preferably 6 to 11 μm.
[H-said h] is preferably 0.5 μm or more, and more preferably 1.0 to 2.5 μm.
（シリカ）
表面保護層形成組成物は、モース硬度が５〜７のシリカを含む。
シリカのモース硬度が５未満であると、耐擦傷性及び耐摩耗性が不十分となり、シリカのモース硬度が７を超えると、塗工装置（グラビア印刷の場合、グラビア版胴やドクターブレード等）が摩耗することにより、化粧シートに欠陥が生じる。シリカのモース硬度は、６〜７であることが好ましい。
また、該シリカの平均粒子径は、８〜１２μｍのものを用いる。平均粒子径が８μｍ未満であると、表面保護層の表面からシリカが露出しづらくなり、表面保護層の耐擦傷性及び耐摩耗性が不十分となる。また、シリカの平均粒子径が１２μｍを超えると、表面保護層の表面からシリカが露出し過ぎてシリカのバインド力が低下し、表面保護層の耐擦傷性及び耐摩耗性が不十分となるとともに、光散乱性が高まり意匠の視認性が低下して、化粧シートの凹凸感が損なわれてしまう。シリカの平均粒子径は、９〜１１μｍであることが好ましい。
なお、本発明における平均粒子径は、レーザー回折・散乱法により測定したものである。
(silica)
The surface protective layer forming composition contains silica having a Mohs hardness of 5 to 7.
When the Mohs hardness of silica is less than 5, the scratch resistance and wear resistance are insufficient, and when the Mohs hardness of silica exceeds 7, a coating device (in the case of gravure printing, a gravure plate cylinder, a doctor blade, etc.) As a result, the decorative sheet becomes defective. The Mohs hardness of silica is preferably 6-7.
The average particle diameter of the silica is 8 to 12 μm. When the average particle size is less than 8 μm, silica is difficult to be exposed from the surface of the surface protective layer, and the scratch resistance and wear resistance of the surface protective layer are insufficient. On the other hand, if the average particle diameter of silica exceeds 12 μm, the silica is excessively exposed from the surface of the surface protective layer, the silica binding force is reduced, and the scratch resistance and wear resistance of the surface protective layer become insufficient. In addition, the light scattering property is increased and the visibility of the design is lowered, and the unevenness of the decorative sheet is impaired. The average particle diameter of silica is preferably 9 to 11 μm.
The average particle diameter in the present invention is measured by a laser diffraction / scattering method.
また、上記シリカの含有量は、表面保護層形成組成物の樹脂成分１００質量部に対して１０〜２５質量部である。１０質量部未満となると、表面保護層の耐擦傷性及び耐摩耗性が不十分となり、２５質量部を超えると、シリカのバインド力が低下して表面保護層の耐擦傷性及び耐摩耗性が低下する傾向となるとともに、化粧シートの意匠性が低下して、化粧シートの凹凸感が損なわれてしまう。
上記シリカの含有量は、表面保護層形成組成物の樹脂成分１００質量部に対して１３〜１８質量部であることが好ましい。
Moreover, content of the said silica is 10-25 mass parts with respect to 100 mass parts of resin components of a surface protective layer forming composition. When the amount is less than 10 parts by mass, the scratch resistance and wear resistance of the surface protective layer are insufficient. When the amount exceeds 25 parts by mass, the binding force of silica is reduced, and the scratch resistance and wear resistance of the surface protective layer are reduced. While it becomes the tendency to fall, the design property of a decorative sheet falls and the uneven | corrugated feeling of a decorative sheet will be impaired.
It is preferable that content of the said silica is 13-18 mass parts with respect to 100 mass parts of resin components of a surface protective layer forming composition.
（添加剤）
表面保護層形成組成物には、耐候性改善剤、耐摩耗性向上剤、重合禁止剤、架橋剤、赤外線吸収剤、帯電防止剤、接着性向上剤、レベリング剤、チクソ性付与剤、カップリング剤、可塑剤、消泡剤、充填剤、溶剤、着色剤等の添加剤を含有させてもよい。耐候性改善剤としては、紫外線吸収剤や光安定剤を用いることができる。また、表面保護層形成組成物中には、低艶絵柄インキ層に添加するような艶消剤（シリカ等）を少量添加してもよい。
(Additive)
The surface protective layer forming composition includes a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, and a coupling. You may contain additives, such as an agent, a plasticizer, an antifoamer, a filler, a solvent, and a coloring agent. As the weather resistance improving agent, an ultraviolet absorber or a light stabilizer can be used. Moreover, you may add a small amount of matting agents (silica etc.) which are added to a low gloss pattern ink layer in a surface protective layer forming composition.
（表面保護層の形成方法）
表面保護層は、重合性モノマーや重合性オリゴマー等の電離放射線硬化性樹脂、上述した特定のシリカ、及び必要に応じて添加される添加剤を、それぞれ所定の割合で均質に混合して、表面保護層形成組成物を調製し、グラビアコート、バーコート、ロールコート、リバースロールコート、コンマコート等の公知の方式により、塗布し、必要に応じて乾燥し、電離放射線を照射することにより形成することができる。
電離放射線の線源としては、紫外線源としては、超高圧水銀燈、メタルハライドランプ等の光源が使用できる。紫外線の波長としては通常１９０〜３８０ｎｍの波長域が主として用いられる。電子線源としては、コッククロフトワルトン型、高周波型等の各種電子線加速器を用い、１００〜１０００ｋｅＶのエネルギーをもつ電子を照射するもの等が使用できる。電子線の照射線量は、通常２０〜１５０ｋＧｙ程度である。
(Method for forming surface protective layer)
The surface protective layer is prepared by uniformly mixing an ionizing radiation curable resin such as a polymerizable monomer or polymerizable oligomer, the above-described specific silica, and an additive that is added as necessary, in a predetermined ratio, respectively. A protective layer-forming composition is prepared and applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., dried as necessary, and formed by irradiation with ionizing radiation. be able to.
As an ionizing radiation source, an ultra-high pressure mercury lamp, a metal halide lamp or the like can be used as an ultraviolet ray source. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm is mainly used. As the electron beam source, various electron beam accelerators such as a Cockcroft-Walton type and a high frequency type, which irradiate electrons having energy of 100 to 1000 keV can be used. The electron beam irradiation dose is usually about 20 to 150 kGy.
＜化粧板＞
本発明の化粧シートは、各種基板に貼付して化粧板として使用することができる。
被着体となる基板は、プラスチックシート、金属板、木材等の木質系の板、窯業系素材等を用途に応じて適宜選択することができる。化粧シートと基板とは接着剤を介して貼り合わせることができる。貼り合わせ時には必要に応じて、密着性を向上するために、化粧シート若しくは基板側に、物理的処理や化学的処理を行ってもよい。
化粧板は、壁、天井、床等の建築物の内装または外装材、窓枠、扉、手すり、幅木、廻り縁、モール等の建具の表面化粧板、キッチン、家具又は弱電、ＯＡ機器等のキャビネットの表面化粧板、車両の内装、外装等に用いることができる。
<Decorative board>
The decorative sheet of the present invention can be used as a decorative plate by sticking to various substrates.
As a substrate to be an adherend, a plastic sheet, a metal plate, a wooden board such as wood, a ceramic material, or the like can be appropriately selected depending on the application. A decorative sheet and a board | substrate can be bonded together through an adhesive agent. At the time of bonding, a physical treatment or a chemical treatment may be performed on the decorative sheet or the substrate side as necessary in order to improve the adhesion.
The decorative panels are interior and exterior materials for buildings such as walls, ceilings, and floors, window frames, doors, handrails, skirting boards, edges, and decorative panels for furniture such as malls, kitchens, furniture, light electrical appliances, OA equipment, etc. It can be used for a surface decorative board of a cabinet, an interior or exterior of a vehicle.
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、これらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
（評価方法）
各実施例及び比較例で得られた化粧シートについて、以下の方法で評価した。
（１）意匠性
化粧シートの外観を下記基準で目視評価した。
Ａ；艶消部分が明確に凹として認識できる。
Ｂ；艶消部分がある程度凹として認識できる。
Ｃ；艶消部分が全く凹として認識できない。
(Evaluation method)
The decorative sheets obtained in each Example and Comparative Example were evaluated by the following methods.
(1) Designability The appearance of the decorative sheet was visually evaluated according to the following criteria.
A: The matte portion can be clearly recognized as a concave.
B: The matte part can be recognized as being concave to some extent.
C: The matte part cannot be recognized as a concave at all.
（２）耐摩耗性
ＪＡＳ合板Ｂ試験に準拠して、化粧シートに対して、テーバー摩耗機で５０回摩耗試験を行った。摩耗紙はＳ−４２を使用し、荷重は５００ｇとした。摩耗試験後の化粧シートの外観を下記基準で目視評価した。
ＡＡ＋；基材の露出が無く、絵柄パターンが取られていない。
ＡＡ ；基材の露出が無く、絵柄パターンが１０％取られている。
Ａ ；基材の軽微な露出があり、絵柄パターンが２５％取られている。
Ｂ ；基材の軽微な露出があり、絵柄パターンが３５％取られている。
Ｃ ；基材の軽微な露出があり、絵柄パターンが４５％取られている。
Ｃ− ；基材の露出があり、絵柄パターンが５０％以上取られている。
Ｄ ；基材の著しい露出があり、絵柄パターンが全て（１００％）取られている。
(2) Abrasion resistance In accordance with the JAS plywood B test, the decorative sheet was subjected to an abrasion test 50 times with a Taber abrasion machine. The worn paper was S-42 and the load was 500 g. The appearance of the decorative sheet after the abrasion test was visually evaluated according to the following criteria.
AA +: The substrate is not exposed and the pattern is not taken.
AA: There is no exposure of the substrate, and 10% of the pattern is taken.
A: There is slight exposure of the base material, and 25% of the pattern is taken.
B: There is a slight exposure of the substrate, and 35% of the pattern is taken.
C: There is slight exposure of the substrate, and 45% of the pattern is taken.
C-: Substrate exposed and pattern pattern taken 50% or more.
D: There is significant exposure of the substrate, and all (100%) of the pattern is taken.
（３）耐擦傷性
２９．４ｋＰａ（３００ｇ／ｃｍ2）の荷重となるように調整された重りに、スチールウール(♯0000)を取り付けて、化粧シートの表面を５０回擦り、該表面の艶の変化を下記基準で目視評価した。
Ａ＋；全く艶変化がない。
Ａ ；軽微な艶変化がある。
Ｂ ；艶変化がある。
Ｃ ；大きな艶変化がある。
Ｄ ；著しい艶変化がある。
(3) Scratch resistance Steel wool (# 0000) is attached to a weight adjusted to a load of 29.4 kPa (300 g / cm 2 ), and the surface of the decorative sheet is rubbed 50 times. Was visually evaluated according to the following criteria.
A +: No gloss change at all.
A: There is a slight gloss change.
B: There is a gloss change.
C: There is a large gloss change.
D: Significant gloss change.
（４）塗布装置の摩耗性
円周１２４０ｍｍのグラビア版を用い、ラインスピード１００ｍ／ｍｉｎの印刷速度で３００００ｍ2の基材へのグラビア印刷を想定して、次のように試験を行った。
円周１２４０ｍｍのグラビア版を持つグラビア輪転機にドクターブレードを設置し、表面保護層形成組成物をインキパンに入れ、グラビア版を８０．６ｒｐｍで５時間空回しした。５時間空回しした後の表面保護層形成組成物を１時間放置し、該組成物に当初から含まれる物を除く沈殿物を下記基準で目視評価した。
Ａ ；沈殿物が全く確認できない。
Ｂ ；沈殿物がわずかに確認できる。
Ｃ ；沈殿物が多く確認できる。
(4) Abrasion of coating apparatus Using a gravure plate having a circumference of 1240 mm, a test was conducted as follows assuming gravure printing on a substrate of 30000 m 2 at a printing speed of 100 m / min.
A doctor blade was installed in a gravure rotary press having a gravure plate with a circumference of 1240 mm, the surface protective layer forming composition was put in an ink pan, and the gravure plate was spun at 80.6 rpm for 5 hours. The composition for forming a surface protective layer after idling for 5 hours was allowed to stand for 1 hour, and the precipitates excluding those originally contained in the composition were visually evaluated according to the following criteria.
A: Precipitate cannot be confirmed at all.
B: A slight precipitate can be confirmed.
C: Many precipitates can be confirmed.
［実施例１］
基材として、米秤量３０ｇ／ｍ2の建材用一般紙を用い、その片面にアクリル樹脂と硝化綿をバインダーとし、チタン白、弁柄、黄鉛を着色剤とするインキを用いて、塗工量５ｇ／ｍ2の（全面ベタ）層をグラビア印刷にて施して着色層とした。その上に硝化綿をバインダーとし、弁柄を主成分とする着色剤を含有するインキを用いて、木目模様の絵柄層をグラビア印刷にて形成した。
次いで、数平均分子量２０，０００、ガラス転移温度（Ｔｇ）−５９．８℃のポリエステルウレタン樹脂とトリレンジイソシアネートからなるポリイソシアネートをバインダーとする塗料組成物を用いて、塗工量５ｇ／ｍ2で全面にグラビア印刷してプライマー層を形成した。
次いで、数平均分子量３０，０００、ガラス転移温度（Ｔｇ）−６２．８℃の非架橋性ポリエステルウレタン樹脂をバインダーとし、平均粒子径１．５μｍのシリカ微粒子をバインダー１００質量部に対して１０質量部配合した低艶絵柄インキを用いて木目模様の導管部分に位置同調するようにグラビア印刷にて、厚み１μｍの低艶絵柄インキ層を形成した。
次いで、樹脂成分として、２官能アクリレートモノマーと６官能アクリレートオリゴマーとを７０：３０の質量割合で含む電離放射線硬化性樹脂１００質量部に対して、硬質シリカ（モース硬度７、平均粒子径１０μｍ）を１６質量部、艶消剤（表面処理シリカ、平均粒子径７μｍ）を７質量部含む表面保護層形成組成物を、低艶絵柄インキ層が形成されていない部分の厚みが９μｍとなるようにグラビアオフセットコータ法により塗工した。
塗工後、加速電圧１７５ｋＶ、照射線量５０ｋＧｙの電子線を照射して、表面保護層形成組成物を硬化させて、表面保護層とした。
次いで、７０℃で２４時間の養生を行い、化粧シートを得た。
[Example 1]
As a base material, a general paper for building materials with a weight of 30 g / m 2 is used as the base material, and coated on one side using an ink containing acrylic resin and nitrified cotton as a binder and titanium white, petal, and yellow lead as colorants. A (full-surface solid) layer having an amount of 5 g / m 2 was applied by gravure printing to form a colored layer. A woodgrain pattern layer was formed by gravure printing using an ink containing a nitrified cotton as a binder and a colorant mainly composed of a petiole.
Next, using a coating composition having a polyisocyanate composed of a polyester urethane resin having a number average molecular weight of 20,000 and a glass transition temperature (Tg) of −59.8 ° C. and tolylene diisocyanate, a coating amount of 5 g / m 2. The primer layer was formed by gravure printing on the entire surface.
Next, a non-crosslinkable polyester urethane resin having a number average molecular weight of 30,000 and a glass transition temperature (Tg) of −62.8 ° C. is used as a binder, and silica fine particles having an average particle diameter of 1.5 μm are 10 masses per 100 mass parts of the binder. A low-gloss pattern ink layer having a thickness of 1 μm was formed by gravure printing so as to synchronize the position with the wood grain pattern conduit using the low-gloss pattern ink blended in part.
Next, as a resin component, hard silica (Mohs hardness 7, average particle diameter 10 μm) is added to 100 parts by mass of an ionizing radiation curable resin containing a bifunctional acrylate monomer and a hexafunctional acrylate oligomer in a mass ratio of 70:30. A composition for forming a surface protective layer containing 16 parts by mass and 7 parts by mass of a matting agent (surface-treated silica, average particle diameter: 7 μm) is gravure so that the thickness of the part where the low gloss pattern ink layer is not formed is 9 μm Coating was performed by an offset coater method.
After coating, the surface protective layer-forming composition was cured by irradiating an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 50 kGy to obtain a surface protective layer.
Next, curing was performed at 70 ° C. for 24 hours to obtain a decorative sheet.
［実施例２〜５］及び［比較例１〜８］
実施例１において、表面保護層形成組成物中の硬質シリカの添加量及び／又は種類を表１のものとして、Ｈ及び／又はｈを表１の条件とした以外は、実施例１と同様にして化粧シートを得た。
[Examples 2 to 5] and [Comparative Examples 1 to 8]
In Example 1, except that the addition amount and / or type of hard silica in the surface protective layer forming composition is as shown in Table 1, and H and / or h are as shown in Table 1, the same as in Example 1. A decorative sheet was obtained.
実施例１〜７の化粧シートは、表面の凹凸感がはっきりしており、意匠性が良好であった。また、表面保護層の耐擦傷性及び耐摩耗性に優れつつ、塗工装置の摩耗が生じるものではなく、塗工装置の摩耗を原因とする化粧シートの欠陥も生じないものであった。 The decorative sheets of Examples 1 to 7 had clear surface irregularities and good design properties. In addition, the surface protective layer was excellent in scratch resistance and abrasion resistance, but the coating apparatus was not worn, and the decorative sheet was not defective due to the wear of the coating apparatus.
比較例１の化粧シートは、硬質シリカのモース硬度が５未満であることから、表面保護層の耐擦傷性及び耐摩耗性に劣るものであった。比較例２の化粧シートは、硬質シリカのモース硬度が７を超えることから、塗工装置を摩耗してしまうものであった。なお、比較例２の化粧シートは、テーブルテストでは意匠性は良好であるが、連続生産する場合には塗工装置の摩耗に伴い、化粧シートに欠陥が生じ、安定した意匠性が得られないものであった。
比較例３の化粧シートは、表面保護層の厚みに対して硬質シリカの平均粒子径が小さいことから、表面保護層の耐擦傷性及び耐摩耗性に劣るものであった。比較例４の化粧シートは、表面保護層の厚みに対して硬質シリカの平均粒子径が大きすぎて、硬質シリカのバインド力が弱くなり、表面保護層の耐擦傷性及び耐摩耗性が不十分となるとともに、光散乱性が高まり意匠の視認性が低下して、化粧シートの凹凸感が損なわれるものであった。
The decorative sheet of Comparative Example 1 had inferior scratch resistance and abrasion resistance of the surface protective layer because the Mohs hardness of the hard silica was less than 5. Since the decorative sheet of Comparative Example 2 had a Mohs hardness of hard silica exceeding 7, the coating device was worn. In addition, the decorative sheet of Comparative Example 2 has good design properties in the table test, but in the case of continuous production, a defect occurs in the decorative sheet due to wear of the coating apparatus, and stable design properties cannot be obtained. It was a thing.
The decorative sheet of Comparative Example 3 was inferior in the scratch resistance and abrasion resistance of the surface protective layer because the average particle diameter of the hard silica was small with respect to the thickness of the surface protective layer. In the decorative sheet of Comparative Example 4, the average particle diameter of the hard silica is too large with respect to the thickness of the surface protective layer, the binding force of the hard silica becomes weak, and the scratch resistance and abrasion resistance of the surface protective layer are insufficient. At the same time, the light scattering property is increased and the visibility of the design is lowered, and the unevenness of the decorative sheet is impaired.
比較例５の化粧シートは、硬質シリカの含有量が多すぎて、硬質シリカのバインド力が弱くなり、表面保護層の耐摩耗性に劣るとともに、意匠の視認性が低下して、化粧シートの凹凸感が損なわれるものであった。比較例６の化粧シートは、硬質シリカの含有量が少なすぎて、表面保護層の耐擦傷性及び耐摩耗性に劣るものであった。
比較例７の化粧シートは、Ｈが１３μｍを超えることから、下方に位置する意匠の視認性が低下して、化粧シートの凹凸感が損なわれるものであった。比較例８の化粧シートは、Ｈやｈが薄いことから、耐擦傷性及び耐摩耗性に劣るものであった。
The decorative sheet of Comparative Example 5 has too much hard silica content, and the binding force of the hard silica becomes weak, the wear resistance of the surface protective layer is inferior, and the visibility of the design is reduced. The feeling of unevenness was impaired. The decorative sheet of Comparative Example 6 had too little hard silica content and was inferior in the scratch resistance and abrasion resistance of the surface protective layer.
In the decorative sheet of Comparative Example 7, since H exceeds 13 μm, the visibility of the design located below is lowered, and the unevenness of the decorative sheet is impaired. The decorative sheet of Comparative Example 8 was inferior in scratch resistance and wear resistance because H and h were thin.
本発明の化粧シート及び化粧板は、表面に凹凸感を有し、耐擦傷性及び耐摩耗性に優れ、かつ製造過程で安定的な意匠性を付与できることから、建築物の内装または外装材、建具の表面化粧板、家具の表面化粧板、及び車両の内装、外装等に好適に用いられる。 Since the decorative sheet and decorative plate of the present invention have an uneven feeling on the surface, are excellent in scratch resistance and wear resistance, and can provide a stable design in the manufacturing process, the interior or exterior material of a building, It is suitably used for surface decorative panels for joinery, furniture decorative panels for furniture, and interiors and exteriors of vehicles.
１：基材
２：着色層
３：絵柄層
４：プライマー層
５：低艶絵柄インキ層
５１：低艶粒子
６：表面保護層
７：低光沢領域
１０：化粧シート
1: base material 2: colored layer 3: picture layer 4: primer layer 5: low gloss pattern ink layer 51: low gloss particles 6: surface protective layer 7: low gloss region 10: decorative sheet
Claims (7)
低艶絵柄インキ層が形成されていない部分の表面保護層の厚みをＨ、低艶絵柄インキ層上に存在する表面保護層の厚みをｈとした際に、Ｈが７〜１３μｍ、ｈが５〜１１μｍであり、かつＨ>ｈであり、
さらに、前記表面保護層が、樹脂成分及びシリカを含む表面保護層形成組成物から形成されてなり、該樹脂成分として電離放射線硬化性樹脂を含み、
前記シリカは、平均粒子径が８〜１２μｍでモース硬度が５〜７であり、含有量が前記樹脂成分１００質量部に対して１０〜２５質量部である、化粧シート。 A low-gloss pattern ink layer provided partially on the substrate, and a region on the low-gloss pattern ink layer that is present on and in contact with the low-gloss pattern ink layer and the low-gloss pattern ink layer It has a surface protective layer covering the entire surface including the area where the pattern ink layer is not formed,
When the thickness of the surface protective layer where the low gloss pattern ink layer is not formed is H, and the thickness of the surface protective layer existing on the low gloss pattern ink layer is h, H is 7 to 13 μm and h is 5 ˜11 μm and H> h,
Furthermore, the surface protective layer is formed from a surface protective layer forming composition containing a resin component and silica, and includes an ionizing radiation curable resin as the resin component,
The silica is a decorative sheet having an average particle diameter of 8 to 12 μm, a Mohs hardness of 5 to 7, and a content of 10 to 25 parts by mass with respect to 100 parts by mass of the resin component.
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