JP2014113772A - Polyolefinic decorative sheet having antistatic function - Google Patents
Polyolefinic decorative sheet having antistatic function Download PDFInfo
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- JP2014113772A JP2014113772A JP2012270193A JP2012270193A JP2014113772A JP 2014113772 A JP2014113772 A JP 2014113772A JP 2012270193 A JP2012270193 A JP 2012270193A JP 2012270193 A JP2012270193 A JP 2012270193A JP 2014113772 A JP2014113772 A JP 2014113772A
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- polyolefin
- decorative sheet
- antistatic
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- antistatic agent
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- 239000002216 antistatic agent Substances 0.000 claims abstract description 40
- 239000011241 protective layer Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 21
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- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 63
- 229920005672 polyolefin resin Polymers 0.000 claims description 46
- 229920000098 polyolefin Polymers 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- -1 polypropylene Polymers 0.000 claims description 16
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- 230000004927 fusion Effects 0.000 claims description 5
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- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 32
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- 238000009408 flooring Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
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- 239000002023 wood Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
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- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
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- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 239000002519 antifouling agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は自然木・合板・集成材・アルミ材・鋼板材・石材・無機材・アスファルト・コンクリートなどの意匠性や耐久性を向上させる為に表面に貼り合せる化粧シートに関するものであり、特には、室内の床材表面に使用される帯電防止機能を有するポリオレフィン系化粧シートに関するものである。 The present invention relates to a decorative sheet to be bonded to the surface in order to improve the design and durability of natural wood, plywood, laminated wood, aluminum material, steel plate material, stone material, inorganic material, asphalt, concrete, etc. The present invention relates to a polyolefin-based decorative sheet having an antistatic function, which is used on the surface of indoor flooring.
化粧シートは、各種基材に意匠性を付与する為に貼り合せるものであり、当初は紙製あるいはポリ塩化ビニル樹脂製のものが主に製造・使用されていた。しかし近年の環境問題への関心の高まりから、ポリ塩化ビニル樹脂製の化粧シートは敬遠されており、それに置き換わる形で、ポリオレフィン系樹脂をベースにしたものが好適に使用されてきている。 The decorative sheet is bonded to various base materials in order to impart design properties. Initially, a decorative sheet made of paper or polyvinyl chloride resin was mainly manufactured and used. However, with the recent increase in interest in environmental problems, decorative sheets made of polyvinyl chloride resin have been avoided, and in place of them, those based on polyolefin resins have been used favorably.
化粧シートのポリ塩化ビニル樹脂製からポリオレフィン系樹脂製への切り替えに際しては、当初より様々な問題が指摘されていたが、技術の成熟によりその多くは解決されていった。しかし静電気帯電に関わる部分と難燃性に関わる部分では、ポリオレフィン系樹脂製化粧シートでポリ塩化ビニル樹脂製の化粧シートと同等の性能を付与することはこれまで困難であった。それゆえ、例えば前者の静電気帯電に関しては、特に湿度が低くなる冬場に化粧シート表層に静電気が帯電しやすい状態になる為、例えばカド部や隙間部などで埃が溜まりやすくなったり、また溜まった埃が取れにくくなったりといった問題が発生している。また、床材の表層や室内ドア、建具などに使用された場合に、帯電した静電気が放電(スパーク)しやすくなるなどで、住空間が不快な環境になってしまう。 Various problems have been pointed out at the time of switching from a polyvinyl chloride resin to a polyolefin resin for a decorative sheet, but many of them have been solved by the maturity of technology. However, it has been difficult to impart performance equivalent to that of a decorative sheet made of a polyolefin resin to a decorative sheet made of a polyolefin resin in a part related to electrostatic charging and a part related to flame retardancy. Therefore, for example, with regard to the former electrostatic charge, it becomes easy to charge static electricity on the surface of the decorative sheet, especially in the winter when the humidity is low. For example, dust easily collects or accumulates at the edges or gaps. There is a problem that it is difficult to remove dust. In addition, when used for the surface layer of flooring, indoor doors, joinery, etc., the static electricity is likely to be discharged (sparked), and the living space becomes uncomfortable.
ポリオレフィン系樹脂の高い帯電性は、その材質に由来する部分であり、根本的な対策は困難であるが、界面活性剤を表層に吹き付けるタイプや導電性材料を樹脂中に添加するタイプ、ポリエーテル−エステル−アミド系などの高分子型の帯電防止剤を添加するタイプ(例えば特許文献1を参照)などが提案されてきた。 The high chargeability of polyolefin resin is a part derived from its material, and fundamental countermeasures are difficult, but the type in which surfactant is sprayed on the surface layer, the type in which conductive material is added to the resin, and polyether A type in which a polymer type antistatic agent such as an ester-amide type is added (for example, see Patent Document 1) has been proposed.
しかし、例えば界面活性剤吹き付けタイプであれば、効果を長期間に渡って持続させることは難しく、また導電性材料添加や高分子型タイプであれば、導電性材料を相当量添加しないと効果が発現されないため、ポリオレフィン系樹脂の機械物性等への影響が高くなったり、透明性などの光学的性質への影響があったりするなどの問題がある。また、全てに共通する問題として、いずれも最表層へのアプローチでなければならず、中間層に上記の施策を施した場合には、帯電性を防止する効果は殆ど見られなかった。それゆえ、従来の帯電防止剤を使った処方では、長期間に渡る帯電防止効果の持続が難しかったり、帯電防止材料が化粧シートの物性に少なからず影響を与えてしまい、性能低下に繋がってしまったりするなどの問題があった。 However, it is difficult to maintain the effect over a long period of time, for example, with a surfactant spraying type, and if a conductive material is added or a polymer type is effective without adding a considerable amount of conductive material. Since it is not expressed, there is a problem that the influence on the mechanical properties and the like of the polyolefin resin is increased and the optical properties such as transparency are affected. Moreover, as a problem common to all, all must be approach to the outermost layer, and when the above measure was applied to the intermediate layer, the effect of preventing charging was hardly seen. For this reason, the prescription using conventional antistatic agents makes it difficult to maintain the antistatic effect over a long period of time, and the antistatic material has a considerable effect on the physical properties of the decorative sheet, leading to performance degradation. There was a problem, such as being loose.
本発明の課題とするところは、上記の様に帯電性を防止する効果をポリオレフィン系樹脂の化粧シートに付与することで、ポリオレフィン系樹脂の材質に由来する帯電性を緩和させ、例えば床材表層装飾に使用した場合にも、カド部や隙間部などでの静電気由来の埃の堆積を抑制したり、同じく静電気由来のスパークを防止したりするなどの効果を発揮しつつ、化粧シートとしての基本性能、特に環境負荷のかかった後の表面保護層の密着性が維持されるような、帯電防止機能を有するポリオレフィン系化粧シートの仕様を設定することである。 The object of the present invention is to provide the effect of preventing charging as described above to the polyolefin resin decorative sheet, thereby reducing the charging property derived from the polyolefin resin material, for example, the flooring surface layer. Even when used for decoration, it is effective as a decorative sheet while suppressing the accumulation of static electricity-derived dust in the cadence and gaps, and also preventing static electricity-derived sparks. It is to set the specifications of the polyolefin-based decorative sheet having an antistatic function so that the performance, particularly the adhesion of the surface protective layer after being subjected to environmental load is maintained.
本発明はこの課題を解決したものでありすなわちその請求項1記載の発明は、少なくとも1層以上のポリオレフィン系樹脂層と表面保護層とを有するポリオレフィン系化粧シートにおいて、前記ポリオレフィン系樹脂層の少なくとも1層に、分子中に下記化学式1にて表される原子団1個と炭素数11〜22の直鎖型飽和炭化水素を最小限1個有する半極性有機化合物と、化学式2にて表される塩基性有機化合物とを混合させた組成物よりなる帯電防止剤を添加してなり、前記表面保護層には帯電防止剤を添加していないことを特徴とする帯電防止機能を有するポリオレフィン系化粧シートである。 The present invention solves this problem, that is, the invention according to claim 1 is a polyolefin-based decorative sheet having at least one polyolefin-based resin layer and a surface protective layer, wherein at least one of the polyolefin-based resin layers. In one layer, a semipolar organic compound having at least one atomic group represented by the following chemical formula 1 in the molecule and one straight-chain saturated hydrocarbon having 11 to 22 carbon atoms is represented by the chemical formula 2. A polyolefin-based cosmetic having an antistatic function, characterized in that an antistatic agent comprising a composition mixed with a basic organic compound is added, and no antistatic agent is added to the surface protective layer. It is a sheet.
その請求項2にかかる発明は、前記帯電防止剤の添加量が、前記ポリオレフィン系樹脂層中のポリオレフィン系樹脂100重量部に対して0.1〜5.0重量部であることを特徴とする、請求項1に記載の帯電防止機能を有するポリオレフィン系化粧シートである。 The invention according to claim 2 is characterized in that the addition amount of the antistatic agent is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the polyolefin resin in the polyolefin resin layer. A polyolefin-based decorative sheet having an antistatic function according to claim 1.
その請求項3にかかる発明は、前記表面保護層の厚みが3〜30μmであることを特徴とする、請求項1、2のいずれかに記載の帯電防止機能を有するポリオレフィン系化粧シートである。 The invention according to claim 3 is the polyolefin-based decorative sheet having an antistatic function according to claim 1, wherein the surface protective layer has a thickness of 3 to 30 μm.
その請求項4にかかる発明は、前記ポリオレフィン系樹脂層が2層以上の共押出により積層されており、そのうちの少なくとも1層が前記帯電防止剤を添加してなるポリオレフィン系樹脂層であることを特徴とする、請求項1〜3のいずれかに記載の帯電防止機能を有するポリオレフィン系化粧シートである。 The invention according to claim 4 is that the polyolefin resin layer is laminated by coextrusion of two or more layers, and at least one of them is a polyolefin resin layer to which the antistatic agent is added. The polyolefin decorative sheet having an antistatic function according to any one of claims 1 to 3.
その請求項5にかかる発明は、前記ポリオレフィン系樹脂層が3層の共押出により積層されており、その中間の層が前記帯電防止剤を添加してなるポリオレフィン系樹脂層であることを特徴とする、請求項1〜3のいずれか記載の帯電防止機能を有するポリオレフィン系化粧シートである。 The invention according to claim 5 is characterized in that the polyolefin resin layer is laminated by coextrusion of three layers, and an intermediate layer thereof is a polyolefin resin layer formed by adding the antistatic agent. A polyolefin-based decorative sheet having an antistatic function according to any one of claims 1 to 3.
その請求項6にかかる発明は、前記帯電防止剤を添加してなるポリオレフィン系樹脂層のポリオレフィン系樹脂がポリプロピレン樹脂を主体とする樹脂により構成されていることを特徴とする、請求項1〜5のいずれかに記載の帯電防止機能を有するポリオレフィン系化粧シートである。 The invention according to claim 6 is characterized in that the polyolefin resin of the polyolefin resin layer to which the antistatic agent is added is composed of a resin mainly composed of polypropylene resin. A polyolefin-based decorative sheet having an antistatic function according to any one of the above.
その請求項7にかかる発明は、前記ポリプロピレン樹脂の示差走査熱量分析測定による融解熱量が、70〜170J/gであることを特徴とする、請求項6に記載の帯電防止機能を有するポリオレフィン系化粧シートである。 The invention according to claim 7 is the polyolefin-based makeup having antistatic function according to claim 6, wherein the heat of fusion of the polypropylene resin by differential scanning calorimetry is 70 to 170 J / g. It is a sheet.
本発明はその請求項1記載の発明により、表面保護層に帯電防止剤を添加しなくとも、ポリオレフィン系樹脂層に、請求項1にて示した特定の構造を有する帯電防止剤を添加することにより、帯電防止効果が発現する。この効果が発現するメカニズムは、半極性有機化合物がドナー、塩基性有機化合物がアクセプターとなり、これらの間でクーロン力によりイオン伝導機構が働き、最表層に帯電した静電気が、該帯電防止剤の添加された層へとリークされる為である。そして表面保護層には帯電防止剤を添加していないので、化粧シートの表面物性に悪影響が出ることが無い。本発明の帯電防止機能を有するポリオレフィン系化粧シートを床材表面に用いることで、埃吸着防止や生活環境下でのスパーク(床材と室内履きのスリッパ裏面との間の摩擦により発生する静電気の放電)などを防止・抑制することが可能になる。 According to the first aspect of the present invention, the antistatic agent having the specific structure shown in the first aspect is added to the polyolefin resin layer without adding the antistatic agent to the surface protective layer. As a result, an antistatic effect is exhibited. The mechanism of this effect is that the semipolar organic compound is the donor and the basic organic compound is the acceptor, and the ion conduction mechanism works by the Coulomb force between them, and the static electricity charged on the outermost layer is added to the antistatic agent. It is because it leaks to the layer which was done. And since the antistatic agent is not added to the surface protective layer, the surface physical properties of the decorative sheet are not adversely affected. By using the polyolefin-based decorative sheet having the antistatic function of the present invention on the floor material surface, it is possible to prevent dust adsorption and to generate sparks under the living environment (static electricity generated by friction between the floor material and the back of the slippers of indoor shoes). Discharge) and the like can be prevented and suppressed.
本発明はその請求項2記載の発明により、帯電防止剤の添加量を制限することで、帯電防止機能を維持しつつ、ポリオレフィン系樹脂層の透明性を十分なものとすることで化粧シートとしての意匠性を向上させることが可能となる。 According to the second aspect of the present invention, the amount of the antistatic agent added is limited, so that the antistatic function is maintained and the transparency of the polyolefin-based resin layer is made sufficient as a decorative sheet. It becomes possible to improve the designability.
本発明はその請求項3記載の発明により、表面保護層の層厚を限定することで、帯電防止機能を維持しつつ、化粧シートとしての表面物性を維持することが可能となる。 According to the third aspect of the present invention, by limiting the layer thickness of the surface protective layer, it is possible to maintain the surface physical properties as a decorative sheet while maintaining the antistatic function.
本発明はその請求項4、5記載の発明により、帯電防止剤を添加したポリオレフィン系樹脂層を共押出で積層してなることにより、帯電防止剤のブリードアウトによる界面積層密着力の低下を最小限に抑えることが可能になる。 According to the present invention, the polyolefin resin layer to which the antistatic agent is added is laminated by coextrusion according to the inventions of the fourth and fifth aspects. It becomes possible to limit to the limit.
本発明はその請求項6、7記載の発明により、ポリエチレンなどの他のポリオレフィン系樹脂を使用した場合に比べて、帯電防止剤のブリードアウトによる界面積層密着力の低下、及び帯電防止剤の析出による効果低減を抑制することが可能になる。これはポリプロピレン樹脂の高い結晶性が、帯電防止剤の移動度を抑制する為である。 According to the present invention of the sixth and seventh aspects, compared with the case where other polyolefin resin such as polyethylene is used, the interfacial lamination adhesion force is reduced by bleeding out of the antistatic agent, and the antistatic agent is deposited. It becomes possible to suppress the effect reduction by. This is because the high crystallinity of the polypropylene resin suppresses the mobility of the antistatic agent.
以下、本発明を図面に基づき詳細に説明する。図1に本発明の帯電防止機能を有するポリオレフィン系化粧シートの一実施例の断面の構造を示す。基材シート1、絵柄模様層2、ポリオレフィン系樹脂層3(31,32)、表面保護層4の積層体からなる。 Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of an example of a polyolefin-based decorative sheet having an antistatic function of the present invention. It consists of the laminated body of the base material sheet 1, the pattern pattern layer 2, the polyolefin resin layer 3 (31, 32), and the surface protective layer 4.
基材シート1としては、後述する絵柄摸様層2を設けるのに適した厚みと材料からなるものであれば従来公知のものが使用可能である。特に限定するものではないが、ポリ塩化ビニル系樹脂ではなくポリオレフィン系樹脂からなるものが好ましい。化粧シートを貼り合わせる下地に対して隠蔽性を設けるために適宜着色することが好ましい。厚みとしては隠蔽性、ハンドリング性、経済性などを鑑みて、50〜100μm程度が好ましい。 As the base material sheet 1, a conventionally known material can be used as long as it is made of a material and a thickness suitable for providing the pattern bag-like layer 2 described later. Although it does not specifically limit, what consists of polyolefin resin instead of polyvinyl chloride resin is preferable. It is preferable to color appropriately in order to provide concealability to the base on which the decorative sheet is bonded. The thickness is preferably about 50 to 100 μm in view of concealing property, handling property, economy and the like.
絵柄摸様層2は、意匠性向上、あるいは隠蔽性の付与などの目的で、好適に設けられる。絵柄模様層2の材質は特に限定されるものではないが、アクリル系、オレフィン系、エステル系、ウレタン系、酢酸ビニル系等々のバインダーに染料または顔料などの着色剤や体質顔料などを添加し、さらに可塑剤、安定剤、ワックス、グリース、乾燥剤、硬化剤、増粘剤、分散剤、充填剤などを任意に添加してなるものが、好適に用いられる。上記材料を溶剤、希釈剤などで充分混練してなる塗工液を準備し、グラビア印刷、凹版印刷、フレキソ印刷、シルク印刷、静電印刷、インクジェット印刷などの公知の印刷方法、あるいはスプレーや刷毛などを使用した公知の塗装方法によって積層させることで設けることができる。絵柄模様層2の印刷は、後述するポリオレフィン系樹脂層3側に行なっても良いし、基材シート1側に行なってもよい。また、インキの密着力向上や隠蔽性の向上などを目的として、必要に応じてプライマーコート層(図示しない)を設ける方法も、好適に用いられる。 The pattern-like layer 2 is suitably provided for the purpose of improving design properties or imparting concealability. The material of the pattern layer 2 is not particularly limited, but a colorant such as a dye or pigment or an extender pigment is added to an acrylic, olefin, ester, urethane, vinyl acetate, or other binder. Further, those obtained by arbitrarily adding plasticizers, stabilizers, waxes, greases, drying agents, curing agents, thickeners, dispersants, fillers and the like are suitably used. Prepare a coating solution prepared by sufficiently kneading the above materials with a solvent, diluent, etc., and use a known printing method such as gravure printing, intaglio printing, flexographic printing, silk printing, electrostatic printing, inkjet printing, or spraying or brushing. It can provide by laminating | stacking by the well-known coating method using etc. The pattern pattern layer 2 may be printed on the polyolefin resin layer 3 side, which will be described later, or on the base sheet 1 side. In addition, a method of providing a primer coat layer (not shown) as needed is also preferably used for the purpose of improving the adhesion of the ink and improving the concealing property.
本発明におけるポリオレフィン系樹脂層3(31,32)の材質としては、炭素と酸素からなるポリオレフィン材料であれば、それ以外に特に制限を設けないが、耐傷付性や添加剤のブリードアウトのし易さ、更には経済性までをも含めた総合評価では、特にポリプロピレン材料を用いたものが望ましく、ホモポリプロピレンなどの高結晶の樹脂を使用したものが、機械物性や、後に示す融解潜熱を所定の数値範囲に設定するためにも、尚望ましい。 The material of the polyolefin resin layer 3 (31, 32) in the present invention is not particularly limited as long as it is a polyolefin material composed of carbon and oxygen, but it is resistant to scratching and bleeding out of additives. For comprehensive evaluation including ease and even economic efficiency, it is particularly desirable to use polypropylene materials, and those using highly crystalline resins such as homopolypropylene have predetermined mechanical properties and latent heat of fusion shown below. It is still desirable to set a numerical range of.
ポリプロピレン樹脂の結晶性の程度を示す指標としては、結晶を融解させる為に必要な熱量、所謂融解熱量が好適に用いられる。この融解潜熱が70J/g以下の場合は、充分な結晶成分が生成されてなく、非結晶成分が多いために、帯電防止剤のブリードがやや起き易い傾向になる。170J/g以上になることは、通常のポリプロピレン樹脂ではあり得ないが、仮になった場合には、非結晶部が少なすぎる為、添加剤が少ない非結晶部に偏在してしまうため、同じくブリードの問題が起き易い。 As an index indicating the degree of crystallinity of the polypropylene resin, the amount of heat necessary for melting the crystal, so-called heat of fusion, is preferably used. When the latent heat of fusion is 70 J / g or less, sufficient crystal components are not generated and there are many non-crystal components, so that antistatic agent bleeding tends to occur somewhat. If it is 170 J / g or more, it cannot be a normal polypropylene resin, but if it becomes temporary, since there are too few non-crystalline parts, it will be unevenly distributed in the non-crystalline part with a small amount of additives. The problem is likely to occur.
また、化粧シートの意匠性や質感を向上させる為に、ポリオレフィン系樹脂層3の表面には、木目、梨地、抽象模様等の様々な凹凸模様を設けてもよい。 In order to improve the design and texture of the decorative sheet, the surface of the polyolefin resin layer 3 may be provided with various uneven patterns such as wood grain, satin, and abstract pattern.
ポリオレフィン系樹脂層3(31、32)の少なくとも1層には、分子中に前記化学式1にて表される原子団1個と炭素数11〜22の直鎖型飽和炭化水素を最小限1個有する半極性有機化合物と、分子中に前記化学式2にて表される塩基性有機化合物とを混合させた組成物よりなる帯電防止剤が添加される。図では便宜上、ポリオレフィン系樹脂層3としてポリオレフィン系樹脂層31とポリオレフィン系樹脂層32の2層からなるように記載してあるが、単層でもよいし、3層以上の複層であってもよい。 At least one of the polyolefin-based resin layers 3 (31, 32) includes at least one atomic group represented by the above chemical formula 1 and a linear saturated hydrocarbon having 11 to 22 carbon atoms in the molecule. An antistatic agent comprising a composition obtained by mixing a semipolar organic compound having a basic organic compound represented by Chemical Formula 2 in the molecule is added. In the figure, for convenience, the polyolefin resin layer 3 is described as being composed of two layers of a polyolefin resin layer 31 and a polyolefin resin layer 32, but it may be a single layer or a multilayer of three or more layers. Good.
本発明における前記分子中に化学式1にて表される原子団1個と炭素数11〜22の直鎖型飽和炭化水素を最小限1個有する反極性有機化合物としては、具体的には下記化学式3、化学式4、化学式5、などがあげられる。後述する比較例で用いる化学式6では直鎖型飽和炭化水素の炭素数が11に満たないため好ましくない。 In the present invention, the antipolar organic compound having at least one atomic group represented by Chemical Formula 1 and one straight chain saturated hydrocarbon having 11 to 22 carbon atoms in the molecule is specifically represented by the following chemical formula. 3, Chemical Formula 4, Chemical Formula 5, and the like. Chemical formula 6 used in a comparative example described later is not preferable because the number of carbon atoms of the linear saturated hydrocarbon is less than 11.
本発明における前記化学式2にて表される塩基性有機化合物としては、具体的には下記化学式7、化学式8、化学式9、などがあげられる。後述する比較例で用いる化学式10では直鎖型飽和炭化水素の炭素数が11に満たないため好ましくない。 Specific examples of the basic organic compound represented by the chemical formula 2 in the present invention include the following chemical formula 7, chemical formula 8, chemical formula 9, and the like. Chemical formula 10 used in a comparative example described later is not preferable because the number of carbon atoms of the linear saturated hydrocarbon is less than 11.
帯電防止剤を添加するポリオレフィン系樹脂層は、全部のポリオレフィン系樹脂層であってもよいし、どれか一部だけでも良い。ポリオレフィン系樹脂層を複数層の積層体とする方法としては、共押出法による積層が層間の明確な界面ができないため、効率的に製造することが可能となる。特には3層構成としてその中間層のみに前記帯電防止剤を添加するようにすれば、添加剤成分のブリードによる密着強度低下や剥離などの問題が殆ど発生しない為、望ましいものとなる。 The polyolefin resin layer to which the antistatic agent is added may be all polyolefin resin layers or only a part of them. As a method of making a polyolefin resin layer into a laminate of a plurality of layers, lamination by a coextrusion method cannot form a clear interface between the layers, and thus it can be efficiently produced. In particular, if the antistatic agent is added only to the intermediate layer in a three-layer structure, problems such as a decrease in adhesion strength due to bleeding of the additive component and peeling hardly occur, which is desirable.
本発明において帯電防止剤として用いる半極性有機化合物と塩基性有機化合物は、それぞれ単独で添加しただけでは効果を発現しない。必ず対になる状態で、両者が存在する必要がある。半極性有機化合物と塩基性有機化合物は、それぞれ同数存在する場合に最大の効果を発揮する。但し、実際には、完全に同数にすることは不可能に近く、添加量の比率が2:1〜1:2の範囲内であれば、実用的には効果が発現できる。 The semipolar organic compound and the basic organic compound used as an antistatic agent in the present invention do not exhibit an effect when they are added alone. Both must be present in a paired state. The semipolar organic compound and the basic organic compound exhibit the maximum effect when the same number exists. However, in practice, it is almost impossible to make the number completely the same, and if the ratio of the addition amount is in the range of 2: 1 to 1: 2, the effect can be practically expressed.
前記帯電防止剤の適正な添加量は、その合計量が、ポリオレフィン系樹脂100重量部に対して0.1〜5.0重量部が好適な範囲内である。0.1重量部よりも少ない添加量では帯電防止効果は期待できず、5.0重量部以上の添加量では、添加量を増やしても帯電防止効果の向上効果は得られずに、透明性の低下や経時でのブリードアウト、ポリオレフィン系樹脂の機械物性への影響などが起きてしまう為、好ましくない。 The appropriate amount of the antistatic agent added is preferably in the range of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the polyolefin resin. When the addition amount is less than 0.1 parts by weight, the antistatic effect cannot be expected. When the addition amount is 5.0 parts by weight or more, the improvement effect of the antistatic effect cannot be obtained even if the addition amount is increased, and the transparency is improved. This is not preferable because it causes a decrease in temperature, a bleed out with time, and an influence on the mechanical properties of the polyolefin resin.
本発明における表面保護層4の厚みは、帯電防止機能を効率的に発現させるためには、できる限り薄くすることが望ましいが、表面保護層の効果である耐傷性・耐候性・耐摩耗性などの付与を考慮すると、ある一定以上の厚みを設けてあるほうが望ましい。一方で、一定以上の厚みがある場合には、表層に帯電した静電気の内部へのリークが発生しづらくなる為、帯電防止効果が充分に発揮されなくなる。これらのバランスを考慮すると、表面保護層の厚みが3〜30μmの範囲内にあることが望ましい。 The thickness of the surface protective layer 4 in the present invention is desirably as thin as possible in order to efficiently exhibit the antistatic function, but scratch resistance, weather resistance, abrasion resistance, etc., which are the effects of the surface protective layer, etc. In view of the provision of the above, it is desirable to provide a certain thickness or more. On the other hand, when the thickness exceeds a certain level, it becomes difficult to cause leakage of static electricity charged on the surface layer, and thus the antistatic effect is not sufficiently exhibited. Considering these balances, it is desirable that the thickness of the surface protective layer be in the range of 3 to 30 μm.
本発明における表面保護層4は、その材質に制限はないが、(メタ)アクリレート系材料をイソシアネート硬化剤で架橋硬化させたり、紫外線照射や電子線照射などを用いて架橋硬化させたりしたものを用いると、硬質かつ強靭性のある表面保護層4が得られるため、好適である。(メタ)アクリレート系材料としては、例えば適度な柔軟性を付与してハンドリング性をアップさせたい場合などは、ウレタン(メタ)アクリレート材料なども好適に用いられる。例えばイソシアネート硬化剤を用いて架橋させる場合には、イソシアネートと反応させるために、(メタ)アクリレート樹脂には水酸基が付与され、紫外線照射を用いて反応させる場合には、光重合開始剤が適宜添加される。電子線を用いて硬化をさせる場合には、(メタ)アクリレート樹脂であれば、特段の添加剤は必ずしも必要ではないが、より高効率に架橋を進めるために、架橋助剤の添加は好適に用いられる。尚、(メタ)アクリレート材料の分子量には特に規定はなく、モノマー、オリゴマー、プレポリマー状のものなどが、任意に選択できる。またこれらを複数種混合して使用することも可能である。 The material of the surface protective layer 4 in the present invention is not limited, but a material obtained by crosslinking and curing a (meth) acrylate material with an isocyanate curing agent, or crosslinking and curing using ultraviolet irradiation, electron beam irradiation, or the like. If used, the hard and tough surface protective layer 4 is obtained, which is preferable. As the (meth) acrylate-based material, for example, when it is desired to impart appropriate flexibility and improve handling properties, a urethane (meth) acrylate material or the like is also preferably used. For example, in the case of crosslinking using an isocyanate curing agent, a hydroxyl group is added to the (meth) acrylate resin in order to react with isocyanate, and in the case of reaction using ultraviolet irradiation, a photopolymerization initiator is appropriately added. Is done. In the case of curing using an electron beam, a special additive is not necessarily required if it is a (meth) acrylate resin. However, in order to advance crosslinking more efficiently, it is preferable to add a crosslinking aid. Used. The molecular weight of the (meth) acrylate material is not particularly limited, and monomers, oligomers, prepolymers and the like can be arbitrarily selected. It is also possible to use a mixture of a plurality of these.
表面保護層4としてアクリル系樹脂を主原料とすれば、元より高い耐候性能を持つものとなるが、更なる性能付与の為に、紫外線吸収剤及びラジカル補足剤の添加が好適に用いられる。紫外線吸収剤として使用されるものとしては、有機系のもでは、ベンゾトリアゾール系、ベンゾフェノン系、ベンゾエート系、ヒドロキシフェニルトリアジン系などがあり、それ以外にも無機系の紫外線カット剤も、有機系紫外線吸収剤と同様に作用する添加剤として使用される。ラジカル補足剤としては、ヒンダードフェノール系及びヒンダードアミン系のうち、特定の構造を持つものが、光励起によって発生した、材料劣化の原因となるフリーラジカルの増殖を抑えて無害化する効果がある。特に、ヒンダードアミン系のラジカル補足剤はその効果が大きく、また長期間に渡って効果が持続するという特徴を有するので、適量を添加することで、表面保護層4としての性能を損なうことなく、耐候性能を付与することができる。尚、紫外線吸収剤は、その構造によって吸収波長域などに特徴があるので、複数種の併用使用も好適に行われており、時に相乗効果が期待できる。同様にラジカル補足剤も複数種の併用使用が時に好適である。 If an acrylic resin is used as a main raw material for the surface protective layer 4, it will have higher weather resistance than the original, but the addition of an ultraviolet absorber and a radical scavenger is suitably used for further performance. As organic UV absorbers, there are benzotriazoles, benzophenones, benzoates, hydroxyphenyltriazines, etc., as well as inorganic UV-blocking agents, organic UV Used as an additive that acts like an absorbent. As the radical scavenger, those having a specific structure among hindered phenols and hindered amines have an effect of detoxifying the growth of free radicals that are caused by photoexcitation and cause material deterioration. In particular, the hindered amine-based radical scavenger has the characteristics that the effect is large and the effect lasts for a long period of time. Therefore, by adding an appropriate amount, the weather resistance is not impaired without impairing the performance as the surface protective layer 4. Performance can be imparted. In addition, since an ultraviolet absorber has the characteristics in an absorption wavelength range etc. according to the structure, multiple types of combined use is also performed suitably and a synergistic effect can be anticipated sometimes. Similarly, radical scavengers are sometimes suitable for use in combination of a plurality of types.
表面保護層4の積層方法に制限はなく、例えばその原料が液体であれば、公知のコーティング方法を用いて積層すればよい。また、機能性の付与や面状態の改善等の為に、表面保護層4を複層化してもよい。無論、同じ材料を複数回に分けて積層してもよい。 There is no restriction | limiting in the lamination | stacking method of the surface protection layer 4, For example, if the raw material is a liquid, what is necessary is just to laminate | stack using a well-known coating method. Further, the surface protective layer 4 may be formed in multiple layers for the purpose of imparting functionality or improving the surface state. Of course, the same material may be laminated in a plurality of times.
表面保護層4には、さらに機能性を付与する為に、前述の紫外線吸収剤やラジカル補足剤の他にも、様々な添加剤が適宜添加される。例えば、抗菌剤、防汚剤、艶消し剤、沈降防止剤、ワックス、難燃材、各種顔料、各種染料、遮熱剤、有機フィラー、無機フィラーなどが好適に使用される。表面保護層4の架橋方法としてイソシアネート架橋を選択する場合には、硬化剤の添加が必須であり、紫外線架橋を選ぶ場合は、光重合開始剤の添加は必須である。尚、イソシアネート硬化剤は、公知のものを使用して良いが、その選定にあたっては、使用用途を考えて、無黄変タイプまたは難黄変タイプのものから適宜選択するのが望ましい。 In addition to the ultraviolet absorber and the radical scavenger described above, various additives are appropriately added to the surface protective layer 4 in order to impart further functionality. For example, antibacterial agents, antifouling agents, matting agents, antisettling agents, waxes, flame retardants, various pigments, various dyes, heat shields, organic fillers, inorganic fillers, and the like are preferably used. When isocyanate crosslinking is selected as the crosslinking method of the surface protective layer 4, addition of a curing agent is essential, and when ultraviolet crosslinking is selected, addition of a photopolymerization initiator is essential. In addition, although a well-known thing may be used for an isocyanate hardening | curing agent, it is desirable to select suitably from the thing of a non-yellowing type or a non-yellowing type considering the use use.
また、表面保護層4の硬度を補強する目的で、各種無機材料の添加も好適に行なわれる。特に中空状のガラスビーズを添加すると、表面を硬質にする為に擦り傷に対する耐性が向上し、更に中空状にする為に、押し傷に対してもクッション性を発揮して、傷が付きにくくなる。 Further, various inorganic materials are preferably added for the purpose of reinforcing the hardness of the surface protective layer 4. In particular, when hollow glass beads are added, resistance to scratches is improved to make the surface hard, and further, cushioning properties are exerted against pressing wounds to make the surface harder, making it difficult to be damaged. .
以上のようにして得た本発明の帯電防止機能を有するポリオレフィン系化粧シートを、木質材、アスファルト、コンクリート、金属材、無機材、などに貼り合わせることで、高い意匠性・耐久性・防滑性など保持しつつ、帯電防止機能に優れた床材を得ることができる。帯電防止機能に優れているため、表面に静電気が長期間に渡って存在することがなく、床材の継ぎ目に埃が溜まりにくく、また溜まった埃も簡単な掃除で取り除くことができる。また、特に湿度の低い冬場などにおいて、帯電した静電気のスパーク放電を防止することができる。 The polyolefin-based decorative sheet having the antistatic function of the present invention obtained as described above is bonded to a wood material, asphalt, concrete, a metal material, an inorganic material, etc., and has high designability / durability / slip resistance. Etc., and a flooring material having an excellent antistatic function can be obtained. Since it has an excellent antistatic function, static electricity does not exist on the surface for a long period of time, and it is difficult for dust to collect at the joint of the flooring material, and the accumulated dust can be removed by simple cleaning. In addition, it is possible to prevent electrostatic discharge of charged static electricity particularly in winter when the humidity is low.
<実施例1〜7>
ランダムポリプロピレン樹脂(プライムポリプロ_S235WC:株式会社プライムポリマー製)を85重量部、低密度ポリエチレン樹脂(ノバテックLD_LC600A:日本ポリエチレン株式会社製)を10重量部、酸化チタン(CR−60:石原産業株式会社製)を5重量部の割合で押出機を用いて混練し、Tダイ製膜機を用いて厚み70μmで製膜を行ない、基材シート1を作成した。
<Examples 1-7>
85 parts by weight of random polypropylene resin (Prime Polypro_S235WC: manufactured by Prime Polymer Co., Ltd.), 10 parts by weight of low density polyethylene resin (Novatech LD_LC600A: manufactured by Nippon Polyethylene Co., Ltd.), titanium oxide (CR-60: manufactured by Ishihara Sangyo Co., Ltd.) ) Was kneaded using an extruder at a ratio of 5 parts by weight, and film formation was performed at a thickness of 70 μm using a T-die film forming machine to prepare a substrate sheet 1.
グラビアインキ(XS−756;DICグラフィックス株式会社製)にイソシアネート硬化剤を添加し、メチルエチルケトン溶剤で粘度調整を行った塗工液を準備し、前記の通り作製した基材シート1の片面に、グラビア印刷法を用いて絵柄模様層2を印刷した。基材シート1の反対側の面には、前記グラビアインキから顔料成分を抜いたものを準備し、更にシリカを適量添加したものを、グラビアコーターを用いて、塗布量1g/m2(ドライ)狙いで塗工した。その後、40℃のオーブン下で3日間の養生を行なった。 An isocyanate curing agent was added to gravure ink (XS-756; manufactured by DIC Graphics Co., Ltd.), and a coating solution was prepared by adjusting the viscosity with a methyl ethyl ketone solvent. On one side of the base sheet 1 produced as described above, The pattern layer 2 was printed using a gravure printing method. On the other side of the base sheet 1, a gravure ink with a pigment component removed is prepared, and an appropriate amount of silica added is applied using a gravure coater to a coating amount of 1 g / m 2 (dry). I painted it with my aim. Thereafter, curing was performed in an oven at 40 ° C. for 3 days.
養生後の基材シート1の絵柄模様層2を設けた側に、アンカーコート剤(タケラック_A3210:三井化学株式会社製)にイソシアネート硬化剤を添加し、更に酢酸エチル溶剤で固形分が25%になるように希釈し、バーコーターを用いて塗布量1g/m2(ドライ)狙いで塗工した後、Tダイ3種3層共押出ラミネータを用いて、下記表1の通りに配合したポリプロピレン樹脂を共押出ラミネートした。その後コロナ処理を行い、表面保護層4として、アクリレート系コート剤(UCクリヤー_W480E:DICグラフィックス株式会社製)に、ヘキサメチレンジイソシアネート系硬化剤と希釈溶剤としてメチルエチルケトンを適宜添加して、バーコーターを用いて塗布量6±1g/m2(ドライ)の範囲内に収まるように塗工した。その後、40℃のオーブン下で3日間の養生を行なった。このようにして実施例1〜7の帯電防止機能を有するポリオレフィン系化粧シートを作製した。 An isocyanate curing agent is added to an anchor coating agent (Takelac_A3210: manufactured by Mitsui Chemicals, Inc.) on the side of the substrate sheet 1 after curing on which the pattern layer 2 is provided, and the solid content is reduced to 25% with an ethyl acetate solvent. After diluting to the extent that it is coated with the aim of a coating amount of 1 g / m 2 (dry) using a bar coater, a polypropylene resin blended as shown in Table 1 below using a T-die type 3 layer co-extrusion laminator Was coextruded. After that, corona treatment is performed, and as the surface protective layer 4, a hexamethylene diisocyanate curing agent and methyl ethyl ketone as a diluent solvent are appropriately added to an acrylate coating agent (UC Clear_W480E: manufactured by DIC Graphics Co., Ltd.), and a bar coater is used. The coating amount was applied so that it was within the range of 6 ± 1 g / m 2 (dry). Thereafter, curing was performed in an oven at 40 ° C. for 3 days. Thus, the polyolefin type decorative sheet having the antistatic function of Examples 1 to 7 was produced.
<実施例8〜13>
表2に示すように、バーコーターの番手を変更したり重ね塗工回数を増やしたりするなどして、表面保護層4の厚みを変えた以外は実施例1と同様にして実施例8〜13の帯電防止機能を有するポリオレフィン系化粧シートを作製した。
<Examples 8 to 13>
As shown in Table 2, Examples 8 to 13 were carried out in the same manner as in Example 1 except that the thickness of the surface protective layer 4 was changed by changing the number of the bar coater or increasing the number of times of repeated coating. A polyolefin-based decorative sheet having an antistatic function was prepared.
<比較例1〜2>
表1の実施例1で示す配合の代わりに、表3の比較例で示す配合にする事により、比較例1〜2の化粧シートを作製した。
<Comparative Examples 1-2>
Instead of the formulation shown in Example 1 of Table 1, cosmetic sheets of Comparative Examples 1 and 2 were prepared by using the formulation shown in the Comparative Example of Table 3.
<性能評価>
このようにして作製した、実施例及び比較例の化粧シートを、水系エマルジョン接着剤(リカボンドBA−10L:中央理化工業株式会社製)を介して合板基材に貼り合わせて、化粧板を作製した。作製した床面材に対して、下記の通り物性評価を行ない、性能の優劣を確認した。
<Performance evaluation>
The decorative sheets of Examples and Comparative Examples thus prepared were bonded to a plywood substrate via an aqueous emulsion adhesive (Rikabond BA-10L: manufactured by Chuo Rika Kogyo Co., Ltd.) to prepare a decorative board. . The physical properties of the produced floor surface material were evaluated as follows, and the superiority or inferiority of the performance was confirmed.
<表面抵抗測定>
実施例及び比較例を使用したそれぞれの化粧板について、表面抵抗計(ST−4:シムコジャパン株式会社製)を用いて、温度25℃湿度60%の環境下で、表面抵抗の測定を行なった。
<Surface resistance measurement>
About each decorative board using an Example and a comparative example, the surface resistance was measured in the environment of temperature 25 degreeC humidity 60% using the surface resistance meter (ST-4: manufactured by Simco Japan Co., Ltd.). .
<表面帯電静電気量測定>
実施例及び比較例を使用したそれぞれの化粧板について、チャージマスターシステム(シムコジャパン株式会社製の直流高電圧発生装置ECM−20(Lite)とHDRチャージングアプリケーターからなる静電気帯電装置)を用いて強制的に帯電状態を起こし、静電気測定器(FMX−003:シムコジャパン株式会社製)を用いて表層の電位を経時的に測定して、帯電電位が10kVから5kVに低下するまでの時間を計った。尚、この測定は、合板基材に貼り合せる前のシートの状態で行なった。
<Measurement of electrostatic charge on the surface>
For each decorative board using Examples and Comparative Examples, a charge master system (electrostatic charging device comprising a DC high voltage generator ECM-20 (Lite) manufactured by Simco Japan Co., Ltd. and an HDR charging applicator) is forcibly used. The charged state was caused and the surface potential was measured over time using an electrostatic meter (FMX-003: manufactured by Simco Japan Co., Ltd.), and the time until the charged potential decreased from 10 kV to 5 kV was measured. . In addition, this measurement was performed in the state of the sheet | seat before bonding on a plywood base material.
<表面保護層の密着性>
実施例及び比較例の各種化粧板を、25℃(室温)×192時間、60℃×192時間加熱、80℃×192時間加熱、80℃2時間と−20℃2時間を100サイクル、の各環境下に置いた後に暴露試験を行なった後、セロハンテープ剥離試験をおこなって、表面保護層の剥離状態を確認した。以上の結果を表4に示す。
<Adhesion of surface protective layer>
Each of the decorative panels of Examples and Comparative Examples, 25 ° C. (room temperature) × 192 hours, 60 ° C. × 192 hours heating, 80 ° C. × 192 hours heating, 80 ° C. 2 hours and −20 ° C. 2 hours, 100 cycles each After the exposure test was performed after being placed in the environment, a cellophane tape peel test was performed to confirm the peeled state of the surface protective layer. The results are shown in Table 4.
表4で明らかなように、本発明の実施例の帯電防止機能を有するポリオレフィン系化粧シートは、比較例1の化粧シートに比べて、帯電電位が低下する時間が短くなっていることがわかる。これは、ポリオレフィンに添加した帯電防止剤の効果であるといえる。尚、表面への帯電のし易さを示す指標である表面抵抗の値は、実施例及び比較例の全てにおいて、差が分らないほどに高い値であった。これは、比較例はもちろん、実施例の帯電防止機能を有するポリオレフィン系化粧シートにおいても、その最表層には帯電防止剤が添加されていない為である。これは即ち、実施例の帯電防止機能を有するポリオレフィン系化粧シートも、強制帯電させた直後には帯電するが、その後、シート内部に帯電した電荷がリークされていると考えられる。帯電電位が低下する時間は、帯電した電荷が内部にリークしていく速度を示す指標と考えられる。また実施例3の結果と比較例2の結果の比較から、本発明の構造、特に化学式2にて表される塩基性有機化合物を使用した効果により、トップコートの密着性が大きく向上している事がわかる。これは、本発明の化学式2に示す塩基性有機化合物が、ポリプロピレン樹脂と絡み合うことにより、ブリードアウトしにくくなっている為と考えられる。 As is apparent from Table 4, it can be seen that the polyolefin-based decorative sheet having the antistatic function of the example of the present invention has a shorter time for the charging potential to be lowered than the decorative sheet of Comparative Example 1. This can be said to be an effect of the antistatic agent added to the polyolefin. Incidentally, the value of the surface resistance, which is an index indicating the ease of charging the surface, was high enough that no difference was found in all of the examples and comparative examples. This is because the antistatic agent is not added to the outermost layer in the polyolefin-based decorative sheet having the antistatic function as well as the comparative example. That is, it is considered that the polyolefin-based decorative sheet having the antistatic function of the example is charged immediately after being forcibly charged, but thereafter, the charged charge is leaked inside the sheet. The time during which the charging potential is lowered is considered to be an index indicating the rate at which the charged charge leaks inside. Moreover, from the comparison of the results of Example 3 and the results of Comparative Example 2, the adhesion of the top coat is greatly improved by the effect of using the basic organic compound represented by the structure of the present invention, particularly Chemical Formula 2, I understand that. This is presumably because the basic organic compound represented by Chemical Formula 2 of the present invention is difficult to bleed out due to entanglement with the polypropylene resin.
<実施例14〜17>
表5に示すように、帯電防止剤Aの代わりに帯電防止剤B〜Eを添加した以外は実施例1と同様にして、実施例14〜17の帯電防止機能を有するポリオレフィン系化粧シートを作製した。
<Examples 14 to 17>
As shown in Table 5, polyolefin-type decorative sheets having antistatic functions of Examples 14 to 17 were prepared in the same manner as Example 1 except that antistatic agents B to E were added instead of the antistatic agent A. did.
<比較例3〜4>
帯電防止剤Aの代わりに、帯電防止剤F〜Gを添加した他は、実施例3と同じように静電気防止剤を添加する事で、表6に示すように比較例3〜4の化粧シートを作製した。
<Comparative Examples 3-4>
In addition to adding antistatic agents F to G instead of antistatic agent A, the antistatic agent was added in the same manner as in Example 3, so that the decorative sheets of Comparative Examples 3 to 4 as shown in Table 6 were used. Was made.
<性能評価>
実施例14〜17と比較例3〜4の化粧シートについて、前記と同じ方法で表面抵抗測定、表面帯電静電気量測定の測定を行なった。結果を表7に示す。炭素数10以下の直鎖型飽和炭化水素しか有さない比較例3及び比較例4の化粧シートにおいては、表面保護層の密着性低下がみられている。これは帯電防止剤とポリプロピレン樹脂との相容性に問題があり、ブリードアウトを起こしてトップコート層との界面に偏析した為と考えられる。
<Performance evaluation>
About the decorative sheet of Examples 14-17 and Comparative Examples 3-4, the surface resistance measurement and the measurement of the amount of electrostatic charge of the surface were performed by the same method as the above. The results are shown in Table 7. In the decorative sheets of Comparative Example 3 and Comparative Example 4 having only linear saturated hydrocarbons having 10 or less carbon atoms, the adhesiveness of the surface protective layer is reduced. This is presumably because there was a problem in the compatibility between the antistatic agent and the polypropylene resin, and bleed out and segregated at the interface with the topcoat layer.
本発明の帯電防止機能を有するポリオレフィン系化粧シートは、塩化ビニルを一切使用しないため環境問題の心配もない。更には、帯電防止機能が付与されている為、埃が付き難い、付いた埃を掃き取り易い、静電気のスパークによる不快適性を感じない、などの効果が得られる。 Since the polyolefin-based decorative sheet having an antistatic function of the present invention does not use any vinyl chloride, there is no concern about environmental problems. Furthermore, since an antistatic function is provided, it is possible to obtain effects such as being hard to get dust, easy to sweep off the attached dust, and not feeling uncomfortable due to static sparks.
1…基材シート
2…絵柄模様層
3(31,32)…ポリオレフィン系樹脂層
4…表面保護層
DESCRIPTION OF SYMBOLS 1 ... Base material sheet 2 ... Pattern pattern layer 3 (31, 32) ... Polyolefin-type resin layer 4 ... Surface protective layer
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WO2008041649A1 (en) * | 2006-09-28 | 2008-04-10 | Toppan Printing Co., Ltd. | Decorative sheet and method for producing the same |
JP2011079918A (en) * | 2009-10-05 | 2011-04-21 | Boron Laboratory Co Ltd | Donor-acceptor hybrid-based internally kneaded type antistatic agent stably exhibiting antistatic property |
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