JP2008087173A - Laminated resin sheet for molding - Google Patents

Laminated resin sheet for molding Download PDF

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JP2008087173A
JP2008087173A JP2006267201A JP2006267201A JP2008087173A JP 2008087173 A JP2008087173 A JP 2008087173A JP 2006267201 A JP2006267201 A JP 2006267201A JP 2006267201 A JP2006267201 A JP 2006267201A JP 2008087173 A JP2008087173 A JP 2008087173A
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resin sheet
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JP4888017B2 (en
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Sachiko Kagawa
幸子 香川
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Toppan Inc
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Toppan Printing Co Ltd
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<P>PROBLEM TO BE SOLVED: To provide a laminated resin sheet for molding which has no disappearing or falling-off risk when a sheet molded container 10 for a disposable sheet molded container 10 requiring no cap or lid material is subjected to vacuum/air-pressure forming and to which a matte surface decorative effect like a frosted glass bottle is applied. <P>SOLUTION: The molding laminated resin sheet is constituted by laminating a base material resin sheet 3 and a sealant layer through an adhesive layer and the sealant layer is obtained by laminating an ethylene/vinyl alcohol copolymer (EVOH) layer 4, a nylon layer 5 and the sealant layer 6 using a hot melt coextrusion method. A mixed resin coating layer 2 of a vinyl chloride/vinyl acetate copolymer (VCVA) containing fine acrylic resin particles a, a, a, etc., and polyurethane (PU) is laminated on the surface of the base material resin sheet 3. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、シャンプー,リンスや液体洗剤,柔軟剤や化粧品,化粧水などの試供品を収容する、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、基材樹脂シート３とエチレン-ビニルアルコール共重合体(EVOH)層４とナイロン層５とシーラント層６とを積層した、耐圧性や成型適性やガスバリア性などが優れた成型用積層樹脂シートにおいて、微細な合成樹脂粒子ａ,ａ,ａ,…を含有させた混合樹脂コート層２を積層して、マット調の表面加飾効果を付与した成型用積層樹脂シートに関する。   The present invention relates to a base resin sheet 3 and ethylene for a disposable sheet molding container 10 that contains samples such as shampoos, rinses, liquid detergents, softeners, cosmetics, and lotions, and does not require caps or lids. -In a laminated resin sheet for molding excellent in pressure resistance, moldability, gas barrier properties, etc., in which a vinyl alcohol copolymer (EVOH) layer 4, a nylon layer 5 and a sealant layer 6 are laminated, fine synthetic resin particles a, The present invention relates to a laminated resin sheet for molding to which a mixed resin coating layer 2 containing a, a,...

従来から、シャンプー,リンスや液体洗剤,柔軟剤や化粧品,化粧水などの試供品を収容する、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、基材樹脂シート３とシーラント層とを接着剤層を介して積層して成り、前記のシーラント層が、ガスバリア性などが優れたエチレン-ビニルアルコール共重合体(EVOH)層４と、耐圧強度や成型性が優れた結晶性ポリアミド(Ny-MXD6)などのナイロン層５と、熱融着性や液噛み密封性などが優れた線状低密度ポリエチレン(LLDPE)などのシーラント層６とを、熱溶融共押出し方法などで積層して成る、優れた耐圧性や成型適性やガスバリア性などを付与した、本願出願人に掛かる成型用積層シートの発明(特許文献１)のような、図３に示す成型用積層樹脂シートが広く用いられている。   Conventionally, a base resin sheet 3 and a sealant layer for a disposable sheet molding container 10 that contains samples such as shampoos, rinses, liquid detergents, softeners, cosmetics, and lotions, and does not require caps or lids. Are laminated via an adhesive layer, and the sealant layer is an ethylene-vinyl alcohol copolymer (EVOH) layer 4 having excellent gas barrier properties and a crystalline polyamide having excellent pressure strength and moldability. A nylon layer 5 such as (Ny-MXD6) and a sealant layer 6 such as linear low density polyethylene (LLDPE), which have excellent heat-fusibility and liquid-sealing sealing properties, are laminated by a hot-melt coextrusion method or the like. The molded laminated resin sheet shown in FIG. 3 is widely used, such as the invention of the laminated sheet for molding applied to the present applicant (Patent Document 1), which has excellent pressure resistance, molding suitability, gas barrier property and the like. It has been.

特許文献は、以下のとおりである。
特開２００５−１１１９２０号公報 The patent documents are as follows.
JP 2005-111920 A

ところが従来の、シャンプー,リンスや液体洗剤,柔軟剤や化粧品,化粧水などの試供品を収容する、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、図３に示す成型用積層樹脂シートについては、基材樹脂シート３の表面側又は内面側に、図示していない美麗な印刷層を設けた後に、真空,圧空成型して、図２に示す展示効果などが優れたシート成型容器１０を得ることができるものの、特に化粧品業界などにおいて、販売する本体容器に磨りガラス瓶を使用することが多いために、試供品を収容する使い捨てのシート成型容器１０であっても、磨りガラス瓶と同様の、マット調の表面加飾効果の要請が多かった。   However, the conventional laminate for molding a disposable sheet molding container 10 that contains samples such as shampoos, rinses, liquid detergents, softeners, cosmetics, and lotions, and does not require caps or lids. As for the resin sheet, after providing a beautiful printing layer (not shown) on the surface side or the inner surface side of the base resin sheet 3, vacuum molding and air pressure molding are performed, and the sheet molding with excellent display effects shown in FIG. Although the container 10 can be obtained, especially in the cosmetics industry and the like, a polished glass bottle is often used for the main body container to be sold. Therefore, even a disposable sheet-molded container 10 for storing a sample is used as a polished glass bottle. There were many requests for a similar matte surface decoration effect.

そこで、図３に示す成型用積層樹脂シートの、基材樹脂シート３の表面側に、通常の機械的なマット加工を施すなどして、また通常のマットニスをコーティングするなどして、成型用積層樹脂シートにマット調の表面加飾効果を付与したとしても、図２に示すシート成型容器１０を真空,圧空成型した時に、特に変形圧力や延伸倍率などが高いシート成型容器１０の角部において、通常の機械的なマット加工が消失するなどして、また通常のマットニスがひび割れして脱落するなどして、試供品を収容する使い捨てのシート成型容器１０の、マット調の表面加飾効果が失われることが問題であった。   Therefore, the laminated resin sheet for molding shown in FIG. 3 is subjected to normal mechanical mat processing on the surface side of the base resin sheet 3 or coated with a normal mat varnish, for example. Even when a mat-like surface decoration effect is imparted to the resin sheet, when the sheet molding container 10 shown in FIG. The mat-like surface decorating effect of the disposable sheet-molded container 10 containing the sample is lost because the normal mechanical mat processing disappears or the normal mat varnish cracks and falls off. It was a problem.

ところで、本発明の目的は、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、前述した本願出願人に掛かる成型用積層シートの発明のような、耐圧性や成型適性やガスバリア性などが優れた成型用積層樹脂シートにおいて、シート成型容器１０を真空,圧空成型した時に、消失したり脱落したりする恐れがない、磨りガラス瓶と同様の、マット調の表面加飾効果を付与した成型用積層樹脂シートを提供することにある。   By the way, the object of the present invention is to provide pressure resistance, molding suitability and gas barrier properties, such as the invention of the above-mentioned laminated sheet for molding according to the applicant of the present invention, for the disposable sheet molding container 10 that does not require a cap or a lid. In the laminated resin sheet for molding excellent in the above, a mat-like surface decorating effect similar to that of a polished glass bottle, which does not disappear or fall off when the sheet molding container 10 is formed by vacuum or pressure molding, is provided. The object is to provide a laminated resin sheet for molding.

本発明の請求項１に記載の成型用積層樹脂シートは、基材樹脂シート３とシーラント層とを接着剤層を介して積層して成る成型用積層樹脂シートにおいて、基材樹脂シート３の表面側に、微細な合成樹脂粒子ａ,ａ,ａ,…を含有させた混合樹脂コート層２を積層したことを特徴とする成型用積層樹脂シートである。   The laminated resin sheet for molding according to claim 1 of the present invention is a laminated resin sheet for molding formed by laminating a base resin sheet 3 and a sealant layer via an adhesive layer. A mixed resin coating layer 2 containing fine synthetic resin particles a, a, a,... Is laminated on the side.

本発明の請求項２に記載の成型用積層樹脂シートは、前記のシーラント層が、エチレン-ビニルアルコール共重合体(EVOH)層４とナイロン層５とシーラント層６とを、熱溶融共押出し方法などで積層して成ることを特徴とする成型用積層樹脂シートである。   In the laminated resin sheet for molding according to claim 2 of the present invention, the sealant layer comprises an ethylene-vinyl alcohol copolymer (EVOH) layer 4, a nylon layer 5, and a sealant layer 6. It is the laminated resin sheet for molding characterized by being laminated | stacked by the above.

本発明の請求項３に記載の成型用積層樹脂シートは、前記の微細な球状の合成樹脂粒子ａ,ａ,ａ,…の合成樹脂が、アクリル樹脂であることを特徴とする成型用積層樹脂シートである。   The molding laminated resin sheet according to claim 3 of the present invention is characterized in that the synthetic resin of the fine spherical synthetic resin particles a, a, a,... Is an acrylic resin. It is a sheet.

本発明の請求項４に記載の成型用積層樹脂シートは、前記の微細な球状のアクリル樹脂粒子ａ,ａ,ａ,…の粒子径が、１〜５０μmであることを特徴とする成型用積層樹脂シートである。   The molding laminated resin sheet according to claim 4 of the present invention is characterized in that the fine spherical acrylic resin particles a, a, a,... Have a particle diameter of 1 to 50 μm. It is a resin sheet.

本発明の請求項５に記載の成型用積層樹脂シートは、前記の混合樹脂コート層２の混合樹脂が、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂であることを特徴とする成型用積層樹脂シートである。   In the laminated resin sheet for molding according to claim 5 of the present invention, the mixed resin of the mixed resin coat layer 2 is a mixed resin of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU). This is a laminated resin sheet for molding.

本発明の請求項６に記載の成型用積層樹脂シートは、前記の混合樹脂コート層２の混合樹脂の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合比が、９/１〜１/９であることを特徴とする成型用積層樹脂シートである。   In the laminated resin sheet for molding according to claim 6 of the present invention, the mixing ratio of the vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) of the mixed resin of the mixed resin coat layer 2 is as follows: The laminated resin sheet for molding is characterized by being 9/1 to 1/9.

本発明の成型用積層樹脂シートにおいては、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、基材樹脂シート３とシーラント層とを接着剤層を介して積層して成り、前記のシーラント層が、ガスバリア性などが優れたエチレン-ビニルアルコール共重合体(EVOH)層４と、耐圧強度や成型性が優れた結晶性ポリアミド(Ny-MXD6)などのナイロン層５と、熱融着性や液噛み密封性などが優れた線状低密度ポリエチレン(LLDPE)などのシーラント層６とを、熱溶融共押出し方法などで積層して成る、前述した図３に示す耐圧性や成型適性やガスバリア性などが優れた成型用積層樹脂シートにおいて、
図１Ａ,Ｂに示すように、基材樹脂シート３の表面側に、微細な合成樹脂粒子ａ,ａ,ａ,…を含有させた混合樹脂コート層２を積層したことによって、また前記の微細な合成樹脂粒子ａ,ａ,ａ,…が、粒子径が１〜５０μmの、微細な球状のアクリル樹脂粒子ａ,ａ,ａ,…であることによって、さらに前記の混合樹脂コート層２が、混合比が９/１〜１/９の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２であることによって、
図２に示すシート成型容器１０を真空,圧空成型した時に、粒子径が１〜５０μmの、耐熱性などが優れた微細なアクリル樹脂粒子ａ,ａ,ａ,…が、磨りガラス瓶と同様の、マット調の表面加飾効果を発揮して、柔軟性や強靭性などが優れた非晶性ポリエチレンテレフタレート(APET)などの基材樹脂シート３に適応した９/１〜１/９の混合比の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２が、基材樹脂シート３との密着性が優れている上に、耐圧,耐摩擦性や延伸,白化,ひび割れなどの成型適性が優れているために、特に変形圧力や延伸倍率などが高いシート成型容器１０の角部においても、微細なアクリル樹脂粒子ａ,ａ,ａ,…のマット調の表面加飾効果を保護して、消失したり脱落したりする恐れがない、磨りガラス瓶と同様の、安定したマット調の表面加飾効果を付与することができる。 In the laminated resin sheet for molding of the present invention, the base resin sheet 3 and the sealant layer for the disposable sheet molding container 10 that do not require a cap or a lid material are laminated via an adhesive layer, The sealant layer is composed of an ethylene-vinyl alcohol copolymer (EVOH) layer 4 having excellent gas barrier properties, a nylon layer 5 such as crystalline polyamide (Ny-MXD6) having excellent pressure strength and moldability, and heat fusion. 3. Pressure resistance and molding suitability shown in FIG. 3 described above, which is formed by laminating a sealant layer 6 such as linear low density polyethylene (LLDPE), which has excellent adhesion and liquid biting and sealing properties, by a hot melt coextrusion method or the like. In the laminated resin sheet for molding with excellent gas barrier properties, etc.
As shown in FIGS. 1A and 1B, by mixing the mixed resin coat layer 2 containing fine synthetic resin particles a, a, a,... The synthetic resin particles a, a, a,... Are fine spherical acrylic resin particles a, a, a,. By being a mixed resin coating layer 2 of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) having a mixing ratio of 9/1 to 1/9,
When the sheet molding container 10 shown in FIG. 2 is formed by vacuum and pressure molding, the fine acrylic resin particles a, a, a,... Having a particle diameter of 1 to 50 μm and excellent in heat resistance are the same as those in the polished glass bottle. A 9/1 to 1/9 mixing ratio suitable for a base resin sheet 3 such as amorphous polyethylene terephthalate (APET) that exhibits a matte surface decoration effect and is excellent in flexibility and toughness. In addition, the mixed resin coat layer 2 of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) has excellent adhesion to the base resin sheet 3 and is also resistant to pressure, friction and stretch. Because of the excellent moldability such as whitening and cracking, the matte surface of the fine acrylic resin particles a, a, a,... Polishing gas that protects the decorative effect and does not disappear or fall off Similar to scan the bottle, it can be imparted to the surface decorative effect stable matt.

以上、本発明の成型用積層樹脂シートにおいては、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、前述した本願出願人に掛かる成型用積層シートの発明のような、耐圧性や成型適性やガスバリア性などが優れた成型用積層樹脂シートにおいて、基材樹脂シート３の表面側に、粒子径が１〜５０μmの、微細なアクリル樹脂粒子ａ,ａ,ａ,…を含有させた、混合比が９/１〜１/９の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２を積層したことによって、
シート成型容器１０を真空,圧空成型した時に、耐熱性などが優れた微細なアクリル樹脂粒子ａ,ａ,ａ,…が、磨りガラス瓶と同様の、マット調の表面加飾効果を発揮して、基材樹脂シート３との密着性などが優れた塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２が、特に変形圧力や延伸倍率などが高いシート成型容器１０の角部においても、微細なアクリル樹脂粒子ａ,ａ,ａ,…のマット調の表面加飾効果を保護して、消失したり脱落したりする恐れがない、磨りガラス瓶と同様の、安定したマット調の表面加飾効果を付与した成型用積層樹脂シートを提供することができる。 As described above, in the laminated resin sheet for molding according to the present invention, the pressure resistance and the like of the above-described invention for the laminated sheet for molding according to the applicant of the present invention for the disposable sheet molding container 10 that does not require a cap or a lid material. In the laminated resin sheet for molding excellent in moldability and gas barrier properties, fine acrylic resin particles a, a, a,... Having a particle diameter of 1 to 50 μm are contained on the surface side of the base resin sheet 3. By laminating the mixed resin coating layer 2 of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) having a mixing ratio of 9/1 to 1/9,
When the sheet-molded container 10 is vacuum-formed or vacuum-formed, the fine acrylic resin particles a, a, a,... Excellent in heat resistance and the like exhibit a matte-like surface decoration effect similar to a polished glass bottle. A mixed resin coating layer 2 of a vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) having excellent adhesion to the base resin sheet 3 is a sheet molding container having particularly high deformation pressure and stretch ratio. Even at the 10 corners, the matte-like surface decoration effect of the fine acrylic resin particles a, a, a,... Is protected, and there is no fear of disappearing or dropping off. A laminated resin sheet for molding to which a mat-like surface decorating effect is imparted can be provided.

本発明の成型用積層樹脂シートにおける、混合樹脂コート層２に含有させる微細な合成樹脂粒子ａ,ａ,ａ,…については、磨りガラス瓶と同様の、細かいマット調や粗いマット調などの表面加飾効果の要請に応じて、粒子径が１〜５０(望ましくは１０〜３０)μmの、含有させる混合樹脂コート層２の５〜５０(望ましくは１０〜２０)Wt％の、耐熱性などが優れた微細なアクリル樹脂粒子ａ,ａ,ａ,…を、後述する塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２に、特に制約なく含有させることができる。   In the laminated resin sheet for molding according to the present invention, the fine synthetic resin particles a, a, a,... Contained in the mixed resin coating layer 2 have surface treatments such as a fine matte tone and a rough matte tone similar to those of a polished glass bottle. Depending on the demand for the decoration effect, the particle diameter is 1 to 50 (preferably 10 to 30 μm), the mixed resin coating layer 2 to be contained has a heat resistance of 5 to 50 (preferably 10 to 20) Wt%. ... Excellent fine acrylic resin particles a, a, a,... Can be contained in the mixed resin coat layer 2 of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) described later without any particular limitation. it can.

本発明の成型用積層樹脂シートにおける、基材樹脂シート３の表面側に積層する混合樹脂コート層２については、柔軟性や強靭性などが優れた非晶性ポリエチレンテレフタレート(APET),延伸ポリエチレンテレフタレート(OPET),ポリエチレン(PE),ポリプロピレン(PP),ポリ塩化ビニル(PVC),ポリ塩化ビニリデン(PVDC)などの単層又は多層の基材樹脂シート３に適応した、基材樹脂シート３との密着性が向上するような９/１〜１/９(望ましくは７/３〜３/７)の混合(Wt)比の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂を用いて、熱溶融した状態で、前述した微細な球状のアクリル樹脂粒子ａ,ａ,ａ,…の適量を含有させてよく混練りして、そのまま熱押出しコーティングするなどして、また一旦フィルム状に成型してドライラミネートするなどして、基材樹脂シート３の表面側に、１〜１５(望ましくは２〜６)g/m2の、基材樹脂シート３との密着性が優れている上に、耐圧,耐摩擦性や延伸,白化,ひび割れなどの成型適性が優れた混合樹脂コート層２を積層することができる。 In the laminated resin sheet for molding of the present invention, the mixed resin coat layer 2 laminated on the surface side of the base resin sheet 3 is amorphous polyethylene terephthalate (APET), stretched polyethylene terephthalate having excellent flexibility and toughness. (OPET), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), etc. A vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) having a mixed (Wt) ratio of 9/1 to 1/9 (preferably 7/3 to 3/7) to improve adhesion. Using the mixed resin, in a state of being hot melted, the above-mentioned fine spherical acrylic resin particles a, a, a,... Also once molded into a film and dry laminated And Runado, on the surface side of the base resin sheet 3, on which 1 to 15 (preferably 2~6) g / m 2, the adhesion between the base resin sheet 3 has excellent withstand voltage, resistance The mixed resin coating layer 2 having excellent moldability such as friction, stretching, whitening, and cracking can be laminated.

なお、塩化ビニル−酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２については、ポリウレタン(PU)の硬化を促進して、混合樹脂コート層２の耐圧,耐摩擦性などがより向上するように、ポリウレタン(PU)混合量の５Wt％程度のポリイソシアネートを添加することが望ましい。   For the mixed resin coat layer 2 of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU), curing of the polyurethane (PU) is promoted and the pressure resistance and friction resistance of the mixed resin coat layer 2 are increased. It is desirable to add polyisocyanate of about 5 Wt% of the amount of polyurethane (PU) mixed so that the above can be improved.

例えば、アクリル樹脂が溶解しない有機溶剤であるエステル／ケトン／芳香族炭化水素／アルコール混合溶剤の様な有機溶剤に、塩化ビニル−酢酸ビニル共重合体(VCVA)とポリウレタン(PU)とを分散して、基材樹脂シート３の表面側に、１〜１５g/m2(dry)の混合樹脂コート層２をコーティングする。 For example, vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) are dispersed in an organic solvent such as ester / ketone / aromatic hydrocarbon / alcohol mixed solvent, which is an organic solvent that does not dissolve acrylic resin. Then, the mixed resin coating layer 2 of 1 to 15 g / m 2 (dry) is coated on the surface side of the base resin sheet 3.

本発明の実施例１,２及び比較例１,２における、図１Ａは、成型用積層樹脂シートの断面図であって、図１Ｂは、成型用積層樹脂シートの混合樹脂コート層２の拡大断面図であ
る。 また図２は、成型用積層樹脂シートを用いて成型した、キャップや蓋材などを必要としない使い捨てシート成型容器１０の斜視図である。 In Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention, FIG. 1A is a sectional view of a laminated resin sheet for molding, and FIG. FIG. FIG. 2 is a perspective view of a disposable sheet molding container 10 that is molded using a laminated resin sheet for molding and does not require a cap or a lid.

基材樹脂シート３とシーラント層とを接着剤層を介して積層して成り、前記のシーラント層が、エチレン-ビニルアルコール共重合体(EVOH)層４とナイロン層５とシーラント層６とを、熱溶融共押出し方法などで積層して成る成型用積層樹脂シート、
すなわち、柔軟性や強靭性などが優れた非晶性ポリエチレンテレフタレート(APET,250μm)の基材樹脂シート３と、ガスバリア性などが優れたエチレン-ビニルアルコール共重合体(EVOH,10μm)層４と、耐圧強度や成型性が優れた結晶性ポリアミド(Ny-MXD6,10μm)のナイロン層５と、熱融着性や液噛み密封性などが優れた線状低密度ポリエチレン(LLDPE,30μm)のシーラント層６とを、エチレン-ビニルアルコール共重合体(EVOH)層４とナイロン層５とシーラント層６とは熱溶融共押出し方法で、続いて基材樹脂シート３とエチレン-ビニルアルコール共重合体(EVOH)層４とはドライラミネート方法で、それぞれ図示していない適宜の接着剤層を介して積層して、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、前述した本願出願人に掛かる成型用積層シートの発明のような、耐圧性や成型適性やガスバリア性などが優れた成型用積層樹脂シートを作製した。 A base resin sheet 3 and a sealant layer are laminated via an adhesive layer, and the sealant layer includes an ethylene-vinyl alcohol copolymer (EVOH) layer 4, a nylon layer 5, and a sealant layer 6. A laminated resin sheet for molding, which is laminated by a hot-melt coextrusion method,
That is, an amorphous polyethylene terephthalate (APET, 250 μm) base resin sheet 3 excellent in flexibility and toughness, and an ethylene-vinyl alcohol copolymer (EVOH, 10 μm) layer 4 excellent in gas barrier properties, etc. , Nylon layer 5 of crystalline polyamide (Ny-MXD6, 10μm) with excellent compressive strength and moldability, and sealant of linear low density polyethylene (LLDPE, 30μm) with excellent heat fusion and liquid-tight sealing Layer 6 and ethylene-vinyl alcohol copolymer (EVOH) layer 4, nylon layer 5 and sealant layer 6 are produced by a hot melt coextrusion method, followed by base resin sheet 3 and ethylene-vinyl alcohol copolymer ( EVOH) layer 4 is a dry laminating method, and is laminated through an appropriate adhesive layer (not shown), and the above-mentioned applicant for the disposable sheet molding container 10 that does not require a cap or a lid. For molding Such as in the invention of the layer sheet, such as pressure resistance and molding suitability and gas barrier properties to produce excellent molding laminated resin sheet.

次に、表１に示す基材樹脂シート３との密着性が向上するような混合(Wt)比の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂を用いて、それぞれ熱溶融した状態で、表１に示す粒子径の、耐熱性などが優れた微細な球状のアクリル樹脂(又はシリカ樹脂)粒子ａ,ａ,ａ,…の、表１に示す適量を含有させてよく混練りして、それぞれそのまま熱押出しコーティングして、非晶性ポリエチレンテレフタレート(APET,250μm)の基材樹脂シート３の表面側に、それぞれ５g/m2の混合樹脂コート層２を積層することによって、本発明の実施例１,２及び比較例１,２における、図１Ａ,Ｂに示す成型用積層樹脂シートを作製した。 Next, a mixed resin of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) having a mixing (Wt) ratio that improves adhesion to the base resin sheet 3 shown in Table 1 is used. The appropriate amount shown in Table 1 of the fine spherical acrylic resin (or silica resin) particles a, a, a,. Mix well and knead and heat-extrusion coating as it is, and a mixed resin coating layer 2 of 5 g / m 2 is formed on the surface side of the base resin sheet 3 of amorphous polyethylene terephthalate (APET, 250 μm). The laminated resin sheets for molding shown in FIGS. 1A and 1B in Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention were produced by lamination.

続いて、従来の通常の成型,充填工程で、図１Ａ,Ｂに示す実施例１,２及び比較例１,２の成型用積層樹脂シートを用いて、化粧水の１５mlの試供品を収容しながら、図２に示すキャップや蓋材などを必要としない使い捨てシート成型容器１０の、それぞれ１００個を真空,圧空成型して、図１Ｂに示す成型用積層樹脂シートの混合樹脂コート層２の、表２に示す延伸,白化,ひび割れなどの成型適性を目視で評価した後に、真空,圧空成型したそれぞれ１００個のシート成型容器１０について、ＪＩＳ-Ｚ-０２００に準拠した振動テストを実施して、表２に示す混合樹脂コート層２の密着性や耐圧,耐摩擦性などの輸送適性を評価した。   Subsequently, in the conventional normal molding and filling process, a 15 ml sample of the skin lotion was stored using the molded resin sheets of Examples 1 and 2 and Comparative Examples 1 and 2 shown in FIGS. 1A and 1B. However, 100 of each of the disposable sheet molding containers 10 that do not require a cap or a lid shown in FIG. 2 are formed by vacuum and pressure molding, and the mixed resin coating layer 2 of the laminated resin sheet for molding shown in FIG. After visually evaluating the suitability for molding such as stretching, whitening, and cracking shown in Table 2, a vibration test in accordance with JIS-Z-0200 was performed on each of the 100 sheet-molded containers 10 formed by vacuum and pressure forming. The transportability such as adhesion, pressure resistance, and friction resistance of the mixed resin coating layer 2 shown in Table 2 was evaluated.

以上、本発明の実施例１,２の成型用積層樹脂シートにおいては、キャップや蓋材などを必要としない使い捨てシート成型容器１０用の、耐圧性や成型適性やガスバリア性などが優れた成型用積層樹脂シートにおいて、基材樹脂シート３の表面側に、粒子径が１０〜３０μmの、含有させる混合樹脂コート層２の１０〜２０Wt％の、耐熱性などが優れた微細なアクリル樹脂粒子ａ,ａ,ａ,…を含有させた、基材樹脂シート３との密着性が向上するような９０/１０〜７０/３０の混合(Wt)比の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２を積層したことによって、
シート成型容器１０を真空,圧空成型した時に、耐熱性などが優れた微細なアクリル樹脂粒子ａ,ａ,ａ,…が、粗いマット調,細かいマット調の表面加飾効果を発揮して、基材樹脂シート３との密着性などが優れた塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂コート層２が、微細なアクリル樹脂粒子ａ,ａ,ａ,…のマット調の表面加飾効果を保護して、ひび割れ,逆艶, 白化,摩擦傷などの恐れがない、磨りガラス瓶と同様の、安定したマット調の表面加飾効果を付与した成型用積層樹脂シートを得ることができた。 As described above, in the laminated resin sheets for molding according to Examples 1 and 2 of the present invention, for the disposable sheet molding container 10 that does not require a cap or a lid, etc., it is excellent in pressure resistance, molding suitability, gas barrier properties, and the like. In the laminated resin sheet, on the surface side of the base resin sheet 3, fine acrylic resin particles a, having a particle diameter of 10 to 30 μm, 10 to 20 Wt% of the mixed resin coating layer 2 to be contained, excellent in heat resistance, etc. A vinyl chloride-vinyl acetate copolymer (VCVA) containing 90,10 to 70/30, which contains a, a,... and improves adhesion to the base resin sheet 3. By laminating a mixed resin coating layer 2 of polyurethane and PU (PU),
When the sheet molding container 10 is vacuum-formed or vacuum-formed, the fine acrylic resin particles a, a, a,... Excellent in heat resistance and the like exhibit a surface decoration effect with a rough matte tone and a fine matte tone. The mixed resin coating layer 2 of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) having excellent adhesion to the resin sheet 3 is made of fine acrylic resin particles a, a, a,. A laminated resin sheet for molding that provides a stable matte surface decoration effect similar to a polished glass bottle that protects the matte surface decoration effect and prevents the occurrence of cracks, reverse luster, whitening, and scratches. Could get.

Figure 2008087173
Figure 2008087173

Figure 2008087173
Figure 2008087173

本発明の実施例１,２及び比較例１,２における、図１Ａは、成型用積層樹脂シートの断面図であって、図１Ｂは、成型用積層樹脂シートの混合樹脂コート層２の拡大断面図である。In Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention, FIG. 1A is a cross-sectional view of a laminated resin sheet for molding, and FIG. 1B is an enlarged cross section of a mixed resin coat layer 2 of the laminated resin sheet for molding FIG. 本発明の実施例１,２及び比較例１,２における、成型用積層樹脂シートを用いて成型した、キャップや蓋材などを必要としない使い捨てシート成型容器１０の斜視図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a perspective view of a disposable sheet molding container 10 that is molded using a molding laminated resin sheet in Examples 1 and 2 and Comparative Examples 1 and 2 of the present invention and does not require a cap or a lid. 従来の、成型用積層樹脂シートの断面図である。It is sectional drawing of the conventional laminated resin sheet for shaping | molding.

符号の説明Explanation of symbols

２ …混合樹脂コート層
３ …基材樹脂シート
４ …エチレン-ビニルアルコール共重合体(EVOH)層
５ …ナイロン層
６ …シーラント層
１０ …シート成型容器
ａ …微細な合成樹脂粒子,微細な球状のアクリル樹脂粒子 2 ... Mixed resin coating layer 3 ... Base resin sheet 4 ... Ethylene-vinyl alcohol copolymer (EVOH) layer 5 ... Nylon layer 6 ... Sealant layer 10 ... Sheet molding container a ... Fine synthetic resin particles, fine spherical Acrylic resin particles

Claims (6)

基材樹脂シート３とシーラント層とを接着剤層を介して積層して成る成型用積層樹脂シートにおいて、基材樹脂シート３の表面側に、微細な合成樹脂粒子ａ,ａ,ａ,…を含有させた混合樹脂コート層２を積層したことを特徴とする成型用積層樹脂シート。   In the laminated resin sheet for molding formed by laminating the base resin sheet 3 and the sealant layer through the adhesive layer, fine synthetic resin particles a, a, a,. A laminated resin sheet for molding, wherein the mixed resin coating layer 2 contained is laminated. 前記のシーラント層が、エチレン-ビニルアルコール共重合体(EVOH)層４とナイロン層５とシーラント層６とを、熱溶融共押出し方法などで積層して成ることを特徴とする、請求項１に記載の成型用積層樹脂シート。   2. The sealant layer according to claim 1, wherein the sealant layer is formed by laminating an ethylene-vinyl alcohol copolymer (EVOH) layer 4, a nylon layer 5, and a sealant layer 6 by a hot melt coextrusion method or the like. The laminated resin sheet for molding described. 前記の微細な合成樹脂粒子ａ,ａ,ａ,…の合成樹脂が、アクリル樹脂であることを特徴とする、請求項１又は請求項２に記載の成型用積層樹脂シート。   The laminated resin sheet for molding according to claim 1 or 2, wherein the synthetic resin of the fine synthetic resin particles a, a, a, ... is an acrylic resin. 前記の微細なアクリル樹脂粒子ａ,ａ,ａ,…の粒子径が、１〜５０μmであることを特徴とする、請求項３に記載の成型用積層樹脂シート。   The molded resin sheet for molding according to claim 3, wherein a particle diameter of the fine acrylic resin particles a, a, a, ... is 1 to 50 µm. 前記の混合樹脂コート層２の混合樹脂が、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合樹脂であることを特徴とする、請求項１から請求項４のどれかに記載の成型用積層樹脂シート。   The mixed resin of the mixed resin coating layer 2 is a mixed resin of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU), according to any one of claims 1 to 4. A laminated resin sheet for molding as described in 1. 前記の混合樹脂コート層２の混合樹脂の、塩化ビニル-酢酸ビニル共重合体(VCVA)とポリウレタン(PU)との混合比が、９/１〜１/９であることを特徴とする、請求項５に記載の成型用積層樹脂シート。   The mixing ratio of vinyl chloride-vinyl acetate copolymer (VCVA) and polyurethane (PU) in the mixed resin of the mixed resin coating layer 2 is 9/1 to 1/9, Item 6. A laminated resin sheet for molding according to Item 5.
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CN103935576A (en) * 2014-04-09 2014-07-23 卓高泰(广州)包装有限公司 Plastic-vacuum-forming container allowed to be resealed
US9315064B2 (en) 2012-02-20 2016-04-19 Avery Dennison Corporation Multilayer film for multi-purpose inkjet systems
US10703131B2 (en) 2010-03-04 2020-07-07 Avery Dennison Corporation Non-PVC film and non-PVC film laminate
US11485162B2 (en) 2013-12-30 2022-11-01 Avery Dennison Corporation Polyurethane protective film

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US10703131B2 (en) 2010-03-04 2020-07-07 Avery Dennison Corporation Non-PVC film and non-PVC film laminate
US9315064B2 (en) 2012-02-20 2016-04-19 Avery Dennison Corporation Multilayer film for multi-purpose inkjet systems
US11485162B2 (en) 2013-12-30 2022-11-01 Avery Dennison Corporation Polyurethane protective film
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CN103935576A (en) * 2014-04-09 2014-07-23 卓高泰(广州)包装有限公司 Plastic-vacuum-forming container allowed to be resealed

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