JP2016221745A5 - Decorative sheet and method for producing the decorative sheet - Google Patents
Decorative sheet and method for producing the decorative sheet Download PDFInfo
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- JP2016221745A5 JP2016221745A5 JP2015108409A JP2015108409A JP2016221745A5 JP 2016221745 A5 JP2016221745 A5 JP 2016221745A5 JP 2015108409 A JP2015108409 A JP 2015108409A JP 2015108409 A JP2015108409 A JP 2015108409A JP 2016221745 A5 JP2016221745 A5 JP 2016221745A5
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- decorative sheet
- nucleating agent
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- resin
- top coat
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- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000011347 resin Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 53
- 239000002667 nucleating agent Substances 0.000 claims description 26
- -1 polypropylene Polymers 0.000 claims description 24
- 239000004743 Polypropylene Substances 0.000 claims description 19
- 229920001155 polypropylene Polymers 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 239000010419 fine particle Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 150000003904 phospholipids Chemical class 0.000 claims description 6
- 239000002502 liposome Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940067631 Phospholipids Drugs 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、建築物の外装および内装に用いられる建装材、建具の表面、家電品の表面材などに用いられる化粧シートおよび化粧シートの製造方法に関するもので、特に、不飽和結合、水酸基またはアミノ基を有する分散剤がコーティングされた無機微粒子が添加されたトップコート層を備える化粧シートであって、超臨界逆相蒸発法によりベシクル化された造核剤が添加された透明樹脂層を備えた化粧シートおよび化粧シートの製造方法に関する。 TECHNICAL FIELD The present invention relates to a decorative sheet used for exterior and interior of buildings, the surface of fittings, the surface material of household electrical appliances, and a method for manufacturing the decorative sheet. A decorative sheet comprising a top coat layer to which inorganic fine particles coated with a dispersant having an amino group are added, comprising a transparent resin layer to which a nucleating agent vesicled by a supercritical reverse phase evaporation method is added The present invention relates to a decorative sheet and a method for manufacturing the decorative sheet .
本発明者等は鋭意検討の結果、トップコート層の下面に設けられた透明樹脂層に対して、超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルを添加することにより、透明樹脂層において造核剤の分散性を著しく向上させることに成功し、高い透明性と優れた耐傷性を示すことを見出した。 The present inventors have intensive studies results, added to the transparent resin layer provided on the lower surface of the top coat layer, the nucleating agent encapsulating vesicles encasing an nucleator into Therefore vesicle supercritical reverse phase evaporation method By doing so, the present inventors have succeeded in remarkably improving the dispersibility of the nucleating agent in the transparent resin layer, and found that it exhibits high transparency and excellent scratch resistance.
上記課題を解決するべく、本発明の第１の形態の化粧シートは、複数の樹脂層からなり、最表面の前記樹脂層が、不飽和結合、水酸基またはアミノ基を有する分散剤がコーティングされた無機微粒子が添加されたトップコート層を有する化粧シートであって、前記トップコート層の下面には、超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルを添加した結晶性ポリプロピレン樹脂を主成分とする透明樹脂層が形成されていることを特徴とする。 In order to solve the above problems, the decorative sheet according to the first aspect of the present invention comprises a plurality of resin layers, and the outermost resin layer is coated with a dispersant having an unsaturated bond, a hydroxyl group or an amino group. a decorative sheet having a top coat layer in which the inorganic fine particles are added, on the lower surface of the top coat layer, adding a nucleating agent encapsulating vesicles encasing an nucleator into Therefore vesicles supercritical reverse phase evaporation method The transparent resin layer which has the crystalline polypropylene resin as a main component is formed .
このような、本発明の第１の形態の化粧シートとすることにより、超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルを透明樹脂層の主成分である結晶性ポリプロピレン樹脂に対して添加することにより、当該造核剤内包ベシクルが凝集して結晶性ポリプロピレン樹脂が白濁することを防ぐことができるとともに、均一に分散した造核剤内包ベシクルに伴って結晶核が生じ結晶性ポリプロピレン樹脂の結晶化度が向上することにより硬度をより高くすることができるので、耐摩耗性はもちろんのこと、意匠性および耐傷性に優れた化粧シートを提供することを可能とする。 Such, by a decorative sheet of the first embodiment of the present invention is the main component of the transparent resin layer nucleating agent encapsulating vesicles encasing an nucleator into Therefore vesicle supercritical reverse phase evaporation method By adding to the crystalline polypropylene resin, it is possible to prevent the nucleating agent-encapsulating vesicles from agglomerating and causing the crystalline polypropylene resin to become cloudy, and the nucleating agent-encapsulating vesicles that are uniformly dispersed are crystallized. Since the nucleation and crystallinity of the crystalline polypropylene resin can improve the hardness, it is possible to provide a decorative sheet with excellent design and scratch resistance as well as wear resistance. And
本発明の第２の形態の化粧シートは、前記トップコート層は、硬化型樹脂を主成分とすることを特徴とする。また、本発明の第３の形態の化粧シートは、前記硬化型樹脂が、アクリルポリオールとイソシアネート化合物との反応物であることを特徴とする。 The decorative sheet according to the second aspect of the present invention is characterized in that the top coat layer contains a curable resin as a main component. The decorative sheet according to the third aspect of the present invention is characterized in that the curable resin is a reaction product of an acrylic polyol and an isocyanate compound.
本発明の第４の形態の化粧シートは、前記ベシクルが、リン脂質からなる外膜を具備するリポソームであることを特徴とする。このような、本発明の第４の形態の化粧シートとすることにより、透明樹脂層の主成分である結晶性ポリプロピレン樹脂とリポソームとの相溶性をより良好なものとすることができるので、その結果、当該結晶性ポリプロピレン樹脂中への造核剤の分散性を向上させて結晶化度を高めて極めて耐傷性に優れた化粧シートを提供することを可能とする。 The decorative sheet according to the fourth aspect of the present invention is characterized in that the vesicle is a liposome having an outer membrane made of phospholipid. By using the decorative sheet of the fourth aspect of the present invention, the compatibility between the crystalline polypropylene resin, which is the main component of the transparent resin layer, and the liposome can be improved, so that As a result, it is possible to improve the dispersibility of the nucleating agent in the crystalline polypropylene resin, increase the crystallinity, and provide a decorative sheet having extremely excellent scratch resistance.
本発明の化粧シートの製造方法は、複数の樹脂層からなり、最表面の前記樹脂層が、不飽和結合、水酸基またはアミノ基を有する分散剤がコーティングされた無機微粒子が添加されたトップコート層を有する化粧シートの製造方法であって、前記トップコート層の下面に、超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルを添加した結晶性ポリプロピレン樹脂を主成分とする透明樹脂層を形成することを特徴とする。The method for producing a decorative sheet of the present invention comprises a top coat layer comprising a plurality of resin layers, wherein the outermost resin layer is coated with inorganic fine particles coated with a dispersant having an unsaturated bond, a hydroxyl group or an amino group. The main component is a crystalline polypropylene resin in which a nucleating agent-encapsulating vesicle in which a nucleating agent is encapsulated in a vesicle by a supercritical reverse phase evaporation method is added to the lower surface of the top coat layer. A transparent resin layer is formed.
本発明においては、耐摩耗性に優れたトップコート層を備えるとともに、意匠性および耐傷性に優れた透明樹脂層を備える化粧シートおよび化粧シートの製造方法を提供することを可能とする。 In this invention, while providing the topcoat layer excellent in abrasion resistance, it becomes possible to provide the manufacturing method of a decorative sheet and a decorative sheet provided with the transparent resin layer excellent in designability and scratch resistance.
本発明の化粧シートは、複数の樹脂層からなり、最表面の樹脂層が、不飽和結合、水酸基またはアミノ基を有する分散剤がコーティングされた無機微粒子が添加されたトップコート層とされた化粧シートにおいて、当該トップコート層の下面には、超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルを添加した結晶性ポリプロピレン樹脂を主成分とする透明樹脂層が形成されていることが重要である。 The decorative sheet of the present invention comprises a plurality of resin layers, and the outermost resin layer is a topcoat layer to which inorganic fine particles coated with a dispersant having an unsaturated bond, a hydroxyl group or an amino group are added. In the sheet, on the lower surface of the top coat layer, a transparent resin layer mainly composed of a crystalline polypropylene resin in which a nucleating agent-encapsulating vesicle in which a nucleating agent is encapsulated in a vesicle is added by a supercritical reverse phase evaporation method is formed. It is important that
透明樹脂層は、結晶性ポリプロピレン樹脂を主成分とし、後述する超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルが添加されている。 Transparent resin layer is composed mainly of crystalline polypropylene resin, nucleating agent encapsulating vesicles encasing an nucleator into the supercritical reverse phase evaporation method thus vesicles to be described later is added.
本発明においては、造核剤に対して超臨界逆相蒸発法を用いてベシクル化することによって、造核剤がナノサイズのカプセル内に内包された造核剤内包ベシクル構造とされており、これによって造核剤内包ベシクル同士が２次凝集することを防止して結晶性ポリプロピレン樹脂中への高い分散性を実現している。また、結晶性ポリプロピレン樹脂中においては、当該造核剤内包ベシクルは外膜の一部またはすべてが崩壊して内包物が露出した状態とされている。当該内包物が樹脂と相溶する物質の場合には、さらに当該樹脂中に内包物が溶けて分散し、内容物が樹脂と相溶しない物質の場合には、内容物が樹脂中に液滴もしくは固体の状態で存在することとされている。 In the present invention, the nucleating agent is vesicled using a supercritical reverse phase evaporation method to form a nucleating agent-encapsulating vesicle structure in which the nucleating agent is encapsulated in a nano-sized capsule, As a result, secondary flocculation of the nucleating agent-encapsulating vesicles is prevented, and high dispersibility in the crystalline polypropylene resin is realized. Further, in the crystalline polypropylene resin, the nucleating agent-encapsulating vesicle is in a state in which part or all of the outer membrane is collapsed and the inclusion is exposed. When the inclusion is a substance that is compatible with the resin, the inclusion is further dissolved and dispersed in the resin, and when the contents are a substance that is not compatible with the resin, the contents are dropped into the resin. Or it is supposed to exist in a solid state.
本発明においては、リン脂質からなる外膜を具備する造核剤内包ベシクルとすることが重要であり、リン脂質からなる外膜を備える造核剤内包ベシクルとすることにより、透明樹脂層の主成分である結晶性ポリプロピレン樹脂との相溶性を向上させて造核剤内包ベシクルの結晶性ポリプロピレン樹脂への分散性をさらに良好なものとすることができ、その結果、均一に分散した造核剤内包ベシクルによって結晶性ポリプロピレン樹脂の結晶化度を向上させ、透明樹脂層の硬度をさらに高くすることができる。 In the present invention, it is important to nucleating agent encapsulating vesicles comprising an outer membrane made of phospholipid, by a nucleating agent encapsulating vesicles comprising outer membrane composed of phospholipids, mainly of the transparent resin layer It is possible to improve the compatibility with the crystalline polypropylene resin as a component to further improve the dispersibility of the nucleating agent-encapsulating vesicles in the crystalline polypropylene resin. As a result, the nucleating agent is uniformly dispersed. The crystallinity of the crystalline polypropylene resin can be improved by the inclusion vesicle , and the hardness of the transparent resin layer can be further increased.
透明樹脂層４としては、結晶性ポリプロピレン樹脂を主成分として形成し、さらに、超臨界逆相蒸発法によりベシクルに造核剤を内包させた造核剤内包ベシクルが添加されている。造核剤内包ベシクルは、結晶性ポリプロピレン樹脂１００重量部に対して、０．０１〜０．５重量部の割合で添加されていることが好ましい。 As the transparent resin layer 4, a nucleating agent-encapsulating vesicle formed of a crystalline polypropylene resin as a main component and further encapsulating a nucleating agent in a vesicle by a supercritical reverse phase evaporation method is added. The nucleating agent-containing vesicle is preferably added at a ratio of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the crystalline polypropylene resin.
以上のように、本発明の化粧シート１においては、不飽和結合、水酸基またはアミノ基を有する分散剤によって表面がコーティングされた無機微粒子を添加したトップコート層５を備えることによって優れた耐摩耗性を実現しているとともに、結晶性ポリプロピレン樹脂を主成分として超臨界逆相蒸発法によりベシクルに造核剤を内包させた造核剤内包ベシクルが添加された透明樹脂層４を備えることによって意匠性および耐傷性にも優れた化粧シート１を提供することを可能とする。 As described above, the decorative sheet 1 of the present invention has excellent wear resistance by including the top coat layer 5 to which inorganic fine particles whose surface is coated with a dispersant having an unsaturated bond, a hydroxyl group or an amino group are added. And having a transparent resin layer 4 containing a nucleating agent-encapsulating vesicle in which a nucleating agent is encapsulated in a vesicle by a supercritical reverse phase evaporation method with a crystalline polypropylene resin as a main component. Further, it is possible to provide the decorative sheet 1 having excellent scratch resistance.
＜超臨界逆相蒸発法によりベシクルに造核剤を内包させた造核剤内包ベシクルの調製＞
以下に、超臨界逆相蒸発法によりベシクルに造核剤を内包させた造核剤内包ベシクルの詳しい調製方法を説明する。まず、メタノール１００重量部、造核剤としてのリン酸エステル金属塩系造核剤（アデカスタブＮＡ−１１；ＡＤＥＫＡ社製）８２重量部、ベシクルの外膜を構成するリン脂質としてのホスファチジルコリン５重量部を６０℃に保たれた高圧ステンレス容器に入れて密閉し、圧力が２０ＭＰａになるように当該容器内に二酸化炭素を注入して超臨界状態とする。その後、当該容器内を激しく攪拌するとともに、イオン交換水１００重量部を注入する。温度と圧力を超臨界状態に保ちながらさらに１５分間攪拌混合後、二酸化炭素を容器から排出して大気圧に戻すことで造核剤を内包したリン脂質からなる外膜を具備する造核剤リポソームが得られる。なお、ベシクルの外膜を分散剤などの物質とする場合には、ホスファチジルコリンに替えて上述の分散剤を用いることにより得られる。
<Preparation of a nucleating agent-encapsulating vesicle in which a nucleating agent is encapsulated in a vesicle by the supercritical reverse phase evaporation method>
Below, the detailed preparation method of the nucleating agent inclusion | inner_cover vesicle which included the nucleating agent in the vesicle by the supercritical reverse phase evaporation method is demonstrated . First, 100 parts by weight of methanol, 82 parts by weight of a phosphate ester metal salt nucleating agent as a nucleating agent (Adeka Stub NA-11; manufactured by ADEKA), 5 parts by weight of phosphatidylcholine as a phospholipid constituting the outer membrane of the vesicle Is put in a high-pressure stainless steel container maintained at 60 ° C. and sealed, and carbon dioxide is injected into the container so that the pressure becomes 20 MPa to obtain a supercritical state. Thereafter, the inside of the container is vigorously stirred and 100 parts by weight of ion exchange water is injected. A nucleating agent liposome comprising an outer membrane composed of a phospholipid encapsulating a nucleating agent by stirring and mixing for 15 minutes while maintaining temperature and pressure in a supercritical state, and then discharging carbon dioxide from the container to return to atmospheric pressure. Is obtained. When the outer membrane of the vesicle is used as a substance such as a dispersant, it can be obtained by using the above-mentioned dispersant instead of phosphatidylcholine.
本発明の化粧シートおよび化粧シートの製造方法は、上記の実施形態および実施例に限定されるものではなく、発明の特徴を損なわない範囲において、種々の変更が可能である。 The decorative sheet and the method for manufacturing the decorative sheet of the present invention are not limited to the above-described embodiments and examples, and various modifications can be made without departing from the characteristics of the invention.
Claims (5)
最表面の前記樹脂層が、不飽和結合、水酸基またはアミノ基を有する分散剤がコーティングされた無機微粒子が添加されたトップコート層を有する化粧シートであって、
前記トップコート層の下面には、超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルを添加した結晶性ポリプロピレン樹脂を主成分とする透明樹脂層が形成されていることを特徴とする化粧シート。 Consisting of multiple resin layers,
The outermost resin layer is a decorative sheet having a top coat layer to which inorganic fine particles coated with a dispersant having an unsaturated bond, a hydroxyl group or an amino group are added,
The lower surface of the top coat layer, a transparent resin layer mainly composed of the added crystalline polypropylene resin nucleating agent containing vesicles encasing an nucleator into Therefore vesicle supercritical reverse phase evaporation method is formed A decorative sheet characterized in that
前記トップコート層の下面に、超臨界逆相蒸発法によってベシクルに造核剤を内包させた造核剤内包ベシクルを添加した結晶性ポリプロピレン樹脂を主成分とする透明樹脂層を形成することを特徴とする化粧シートの製造方法。 A transparent resin layer mainly composed of a crystalline polypropylene resin containing a nucleating agent-encapsulating vesicle in which a nucleating agent is encapsulated in a vesicle is formed on the lower surface of the top coat layer by a supercritical reverse phase evaporation method. A method for producing a decorative sheet.
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| JP7007546B2 (en) * | 2017-03-01 | 2022-01-24 | 凸版印刷株式会社 | Decorative sheets and transparent resin sheets, and their manufacturing methods |
| JP7031126B2 (en) * | 2017-03-01 | 2022-03-08 | 凸版印刷株式会社 | Decorative sheet and manufacturing method of decorative sheet |
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| JP2000289162A (en) * | 1999-04-13 | 2000-10-17 | Toppan Printing Co Ltd | Decorative sheet |
| JP2004268374A (en) * | 2003-03-07 | 2004-09-30 | Toppan Printing Co Ltd | Decorative sheet and decorative material |
| JP2007077345A (en) * | 2005-09-16 | 2007-03-29 | Masamitsu Nagahama | Resin material, manufacturing method of resin material and use of liposome |
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