JP2020175537A - Multilayer sheet and container using the same - Google Patents
Multilayer sheet and container using the same Download PDFInfo
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- JP2020175537A JP2020175537A JP2019077681A JP2019077681A JP2020175537A JP 2020175537 A JP2020175537 A JP 2020175537A JP 2019077681 A JP2019077681 A JP 2019077681A JP 2019077681 A JP2019077681 A JP 2019077681A JP 2020175537 A JP2020175537 A JP 2020175537A
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- mass
- polylactic acid
- multilayer sheet
- sheet
- parts
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- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 78
- 239000004626 polylactic acid Substances 0.000 claims abstract description 78
- 239000012792 core layer Substances 0.000 claims abstract description 52
- 239000010410 layer Substances 0.000 claims abstract description 52
- 239000011342 resin composition Substances 0.000 claims abstract description 43
- 239000002344 surface layer Substances 0.000 claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 100
- 229920005989 resin Polymers 0.000 claims description 56
- 239000011347 resin Substances 0.000 claims description 56
- 235000013305 food Nutrition 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 8
- 238000005187 foaming Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 229920001890 Novodur Polymers 0.000 abstract 4
- 238000000034 method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 239000004088 foaming agent Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000002093 peripheral effect Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- 229920005669 high impact polystyrene Polymers 0.000 description 5
- 239000004797 high-impact polystyrene Substances 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 5
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 235000021067 refined food Nutrition 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- -1 but in general Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
Description
本発明は、多層シート及びそれを用いた容器、前記多層シートの製造方法に関する。 The present invention relates to a multilayer sheet, a container using the multilayer sheet, and a method for producing the multilayer sheet.
従来からスーパーマーケット、コンビニエンスストア、デパート、弁当店等の店舗に
おいて、生鮮食料品や加工食品等を販売する際の包装に使用される容器として、合成樹脂製のシートを成形して得た容器が多く用いられている。
Traditionally, in stores such as supermarkets, convenience stores, department stores, and lunch boxes, many containers are obtained by molding synthetic resin sheets as containers used for packaging when selling fresh foods, processed foods, etc. It is used.
前記生鮮食料品や加工食品等を包装する合成樹脂製シートの容器は、一般には１回の使用後に焼却処分され、また自然環境中への廃棄や散逸も見逃せない状況であるため、近年では石油資源節約及び環境保護の観点から、合成樹脂そのものの使用量を減らす、或いは環境への負荷が少ない素材を、容器全体ではないにせよ、その一部に用いることが推奨されてきている。 Synthetic resin sheet containers for packaging fresh foods, processed foods, etc. are generally incinerated after one use, and disposal or dissipation into the natural environment cannot be overlooked. From the viewpoint of resource saving and environmental protection, it has been recommended to reduce the amount of synthetic resin itself used or to use a material having a low environmental load for a part of the container, if not the whole container.
環境への負荷を従来より減らすことができる素材として、当分野では植物を原料とするポリ乳酸が注目されている。但しポリ乳酸のみでは成形加工性が不十分であり、例えばポリ乳酸のシートを成形して食品用容器の製造を試みた場合に、目的とする容器の形に満足に賦形することには困難さが伴う。そのため、例えばポリ乳酸とスチレン系樹脂とを含む種々の樹脂組成物が開発され、それらは例えば特許文献１〜７に開示されている。 Polylactic acid made from plants is drawing attention in this field as a material that can reduce the burden on the environment. However, the molding processability is insufficient only with polylactic acid, and it is difficult to satisfactorily shape the desired container shape, for example, when a polylactic acid sheet is molded to manufacture a food container. Accompanied by. Therefore, various resin compositions containing, for example, polylactic acid and styrene-based resins have been developed, and they are disclosed in, for example, Patent Documents 1 to 7.
合成樹脂製のシートをさらに成形加工して得る容器、特に食品に直接接触する、例えば惣菜用の容器を製造する場合においては、衛生安全上の観点から、素材であるシートの表面に異物が付着してないことが前提である。合成樹脂を用いてシートを製造する場合には、合成樹脂やそれに含まれる添加剤に由来する粘着性異物（「目やに」と呼ばれることもある）が発生し、シート成膜で用いているダイスの吐出口（リップ）周縁部に溜まることがあり、シート成膜を進めると共に粘着性異物はしだいに滞留量を増して、ついには成膜しているシートに付着してその表面を汚染することがある。特にポリ乳酸を含む原料を用いると、粘着性異物の発生量は一般に増える傾向があり、シート表面を汚染する危険性がより高まる。そのため、リップ周縁部に滞留している粘着性異物を除去する作業の頻度も増え、生産効率も低下する。このような状況下で、ポリ乳酸を主要な原料として用いるが、粘着性異物の発生を抑制できるシート、前記シートを用いた容器の提供、及び前記シートの適切な製造方法の提供が求められていた。 In the case of manufacturing a container obtained by further molding a synthetic resin sheet, particularly a container for prepared foods, which comes into direct contact with food, foreign matter adheres to the surface of the sheet which is a material from the viewpoint of hygiene and safety. It is assumed that you have not done so. When a sheet is manufactured using a synthetic resin, sticky foreign substances (sometimes called "rheumatism") derived from the synthetic resin and the additives contained therein are generated, and the die used for forming the sheet is formed. It may accumulate on the periphery of the discharge port (lip), and as the sheet film formation progresses, the amount of sticky foreign matter gradually increases, and finally it adheres to the film-forming sheet and contaminates its surface. is there. In particular, when a raw material containing polylactic acid is used, the amount of sticky foreign matter generated generally tends to increase, and the risk of contaminating the sheet surface increases. Therefore, the frequency of work for removing the sticky foreign matter accumulated on the peripheral edge of the lip increases, and the production efficiency also decreases. Under such circumstances, polylactic acid is used as a main raw material, but it is required to provide a sheet capable of suppressing the generation of sticky foreign substances, a container using the sheet, and an appropriate manufacturing method of the sheet. It was.
本発明者はかかる状況に鑑み、課題を解決するための手段を検討し、本発明の完成に至った。即ち本発明は、以下に示す（１）〜（７）である。
（１）多層シート両面の最表面部に、ポリ乳酸とスチレン系樹脂とを含み、前記ポリ乳酸と前記スチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ１が、それぞれ５質量部以上３０質量部以下である樹脂組成物からなる最表面層と、多層シートの中間部に、ポリ乳酸とスチレン系樹脂とを含み、前記ポリ乳酸と前記スチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ２が、２５質量部以上５０質量部以下である樹脂組成物からなる中芯層とを含み、Ｘ２はＸ１より高い値である層構造を有する多層シート。
（２）中芯層の樹脂組成物において、ポリ乳酸とスチレン系樹脂の合計質量の割合が、前記中芯層の樹脂組成物全体の質量の８０質量％以上９９質量％以下である、（１）記載の多層シート。
（３）中芯層が、発泡倍率１．１倍以上２．０倍以下の発泡層である、（１）または（２）記載の多層シート。
（４）中芯層の厚さの割合が、多層シート全体の厚さに対して５０％以上９０％以下である、（１）〜（３）いずれか一項記載の多層シート。
（５）ダイス中で、多層シートの全ての層を一体化させて共押出し成形する、（１）〜（４）いずれか一項記載の多層シートの製造方法。
（６）（１）〜（４）いずれか一項記載の多層シートを成形した容器。
（７）食品用の容器である、（６）記載の容器。
In view of such a situation, the present inventor has examined means for solving the problem and has completed the present invention. That is, the present invention is (1) to (7) shown below.
(1) Polylactic acid and styrene-based resin are contained in the outermost surfaces of both sides of the multilayer sheet, and the mass number X 1 of polylactic acid with respect to a total of 100 parts by mass of the polylactic acid and the styrene-based resin is 5 parts by mass or more, respectively. The outermost surface layer made of a resin composition of 30 parts by mass or less and the intermediate portion of the multilayer sheet contain polylactic acid and a styrene resin, and the polylactic acid is contained in a total of 100 parts by mass of the polylactic acid and the styrene resin. A multilayer sheet having a layer structure in which the number of parts X 2 is 25 parts by mass or more and 50 parts by mass or less including a core layer made of a resin composition, and X 2 is a value higher than X 1 .
(2) In the resin composition of the core layer, the ratio of the total mass of the polylactic acid and the styrene resin is 80% by mass or more and 99% by mass or less of the total mass of the resin composition of the core layer (1). ) Described multi-layer sheet.
(3) The multilayer sheet according to (1) or (2), wherein the core layer is a foamed layer having a foaming ratio of 1.1 times or more and 2.0 times or less.
(4) The multilayer sheet according to any one of (1) to (3), wherein the ratio of the thickness of the core layer is 50% or more and 90% or less with respect to the thickness of the entire multilayer sheet.
(5) The method for producing a multilayer sheet according to any one of (1) to (4), wherein all the layers of the multilayer sheet are integrated and co-extruded in a die.
(6) A container formed by molding the multilayer sheet according to any one of (1) to (4).
(7) The container according to (6), which is a container for food.
本発明の実施により、環境負荷の少ないポリ乳酸を主要な成分として含み、衛生安全上の危険性も低減された、特に食品容器の用途に適した多層シートを提供することができる。さらにまた本発明の多層シートに適する製造方法を提供することができる。 By implementing the present invention, it is possible to provide a multilayer sheet particularly suitable for use in food containers, which contains polylactic acid having a low environmental load as a main component and has a reduced risk of hygiene and safety. Furthermore, it is possible to provide a manufacturing method suitable for the multilayer sheet of the present invention.
以下、本発明の好適な実施形態について詳細に説明する。但し、以下に説明する実施形態は、本発明の代表的な実施形態の一例を示したものであり、これにより本発明の範囲が狭く限定されて解釈されることはない。 Hereinafter, preferred embodiments of the present invention will be described in detail. However, the embodiments described below show an example of typical embodiments of the present invention, and the scope of the present invention is not narrowly and construed as a result.
＜層の構成＞
本発明の多層シートは、多層シート両面の最表面部に、ポリ乳酸とスチレン系樹脂とを含み、前記ポリ乳酸と前記スチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ１が、それぞれ５質量部以上３０質量部以下である樹脂組成物からなる最表面層と、多層シートの中間部に、ポリ乳酸とスチレン系樹脂とを含み、前記ポリ乳酸と前記スチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ２が、２５質量部以上４５質量部以下である樹脂組成物からなる中芯層とを含み、Ｘ２はＸ１より高い値である層構造を有する多層シートである。
<Layer structure>
The multilayer sheet of the present invention contains polylactic acid and a styrene resin on the outermost surfaces of both surfaces of the multilayer sheet, and the mass number X 1 of polylactic acid with respect to a total of 100 parts by mass of the polylactic acid and the styrene resin is The outermost surface layer made of a resin composition of 5 parts by mass or more and 30 parts by mass or less and the intermediate portion of the multilayer sheet contain polylactic acid and a styrene resin, and the total of 100 parts by mass of the polylactic acid and the styrene resin is contained. X 2 is a multilayer sheet having a layer structure having a layer structure having a value higher than X 1 including a core layer made of a resin composition in which the mass number X 2 of polylactic acid is 25 parts by mass or more and 45 parts by mass or less. ..
本発明の多層シートにおいて、最表面層はシートの両面合わせて２層あるが、前記最表面層はいずれも、ポリ乳酸とスチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ１が、それぞれ５質量部以上３０質量部以下である樹脂組成物からなるものである。両最表面層の化学組成は必ずしも同じである必要はなく、即ち一方の最表面層のＸ１の値と他方の最表面層のＸ１の値は、必ずしも同じ値である必要はない。 In the multilayer sheet of the present invention, the outermost surface layer has two layers including both sides of the sheet, and in each of the outermost surface layers, the mass number X 1 of polylactic acid with respect to 100 parts by mass of the total of polylactic acid and the styrene resin is large. Each of the resin compositions is composed of 5 parts by mass or more and 30 parts by mass or less. The chemical composition of both the outermost surface layer is not necessarily the same, i.e., the value of X 1 of one of the outermost surface layer X 1 value and the other outermost surface layer of, not necessarily the same values.
本発明のシート中間部とは、多層シートの最表面層を除いた部分である。また本発明の多層シートにおいて、中芯層はシート中間部にあり、前記中芯層は、ポリ乳酸とスチレン系樹脂とを含み、ポリ乳酸とスチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ２が、２５質量部以上５０質量部以下である樹脂組成物からなるものである。なお、本発明の多層シートでは、Ｘ２は、前記いずれのＸ１より高い値であることを特徴とする。また最表面層の樹脂組成物及び中芯層の樹脂組成物には、必要に応じ、本発明の効果を損なわない範囲の量で、着色剤、酸化防止剤、帯電防止剤、滑材、可塑剤など各種添加剤を含むことが可能である。また前記中芯層には、本発明の多層シートを製膜したり、成形加工したりするときに発生する端材を戻すことも可能である。 The sheet intermediate portion of the present invention is a portion of the multilayer sheet excluding the outermost surface layer. Further, in the multilayer sheet of the present invention, the core layer is located in the middle portion of the sheet, and the core layer contains polylactic acid and a styrene resin, and the mass of polylactic acid with respect to a total of 100 parts by mass of the polylactic acid and the styrene resin. It is composed of a resin composition in which the number of parts X 2 is 25 parts by mass or more and 50 parts by mass or less. The multilayer sheet of the present invention is characterized in that X 2 has a higher value than any of the above X 1 . Further, the resin composition of the outermost surface layer and the resin composition of the core layer are provided with a colorant, an antioxidant, an antistatic agent, a lubricant, and a plasticizer in an amount not impairing the effects of the present invention, if necessary. It is possible to include various additives such as agents. Further, it is also possible to return the scraps generated when the multilayer sheet of the present invention is formed or molded to the core layer.
＜ポリ乳酸＞
本発明の多層シートの両最表面層及び中芯層の樹脂組成物は、ポリ乳酸とスチレン系樹脂とを含む樹脂脂組成物である。前記ポリ乳酸は、乳酸が多数エステル結合してできた高分子である。乳酸には１つの不斉炭素に結合する官能基の立体配置の相違により、Ｌ体及びＤ体の２種の乳酸が存在し、従って、ポリ乳酸にもＤ体またはＬ体の単量体単位がほぼ単独で結合しているもの、Ｄ体単量体単位及びＬ体単量体単位が混合して結合しているもの、さらにＤ体単量体単位とＬ体単量体単位の結合についても、それらがランダムに結合しているもの、交互に結合しているもの、ブロック状に結合しているもの、いずれも用いることが可能である。但し、耐熱性の観点からは、Ｌ体単量体単位を９５質量％以上含むポリ乳酸であることが好ましい。なおポリ乳酸は、植物由来の原料から合成することができるカーボンニューラルな化合物として、環境保護の観点から近年注目を集めており、従って本発明で用いるポリ乳酸も、植物由来のポリ乳酸であることが好ましい。また、は特に限定は無く、スチレン系樹脂と溶融混合できればよいが、一般にはＭｗが５万以上のポリ乳酸が用いられる。なお、最表面層と中芯層とに用いるポリ乳酸は、必ずしも同一である必要はないが、特に必要がなければ、同一であることが好ましい。
<Polylactic acid>
The resin composition of both outermost surface layers and the core layer of the multilayer sheet of the present invention is a resin fat composition containing polylactic acid and a styrene resin. The polylactic acid is a polymer formed by ester-bonding a large number of lactic acids. There are two types of lactic acid, L-form and D-form, due to the difference in the configuration of the functional group bonded to one asymmetric carbon in lactic acid. Therefore, polylactic acid also has a D-form or L-form monomer unit. Are bonded almost alone, D-form monomer units and L-form monomer units are mixed and bonded, and D-form monomer units and L-form monomer units are bonded. It is also possible to use those in which they are randomly connected, those in which they are connected alternately, and those in which they are connected in a block shape. However, from the viewpoint of heat resistance, polylactic acid containing 95% by mass or more of L-form monomer units is preferable. Note that polylactic acid has been attracting attention in recent years as a carbon neural compound that can be synthesized from plant-derived raw materials from the viewpoint of environmental protection. Therefore, the polylactic acid used in the present invention is also a plant-derived polylactic acid. Is preferable. Further, there is no particular limitation, as long as it can be melt-mixed with a styrene resin, but in general, polylactic acid having an Mw of 50,000 or more is used. The polylactic acid used for the outermost surface layer and the core layer does not necessarily have to be the same, but it is preferable that they are the same unless there is a particular need.
＜スチレン系樹脂＞
本発明の多層シートの両最表面層及び中芯層の樹脂組成物は、ポリ乳酸とスチレン系樹脂とを含む樹脂脂組成物である。前記スチレン系樹脂は、スチレン、メチルスチレン、t−ブチルスチレン、α−メチルスチレンの群から選ばれる１種または２種以上のスチレン系単量体を重合または共重合した樹脂や、ＨＩＰＳやスチレンとブタジエンの共重合体（以降ＳＢＣと記す）として知られているゴム変性したスチレン系樹脂や、前記スチレン系単量体と、前記スチレン系単量体に共重合が可能な単量体、例えば、アクリル酸、メタクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸２−エチルヘキシルの群から選ばれる１種または２種以上の単量体を共重合させた樹脂が挙げられる。これらの中で、好ましいスチレン系樹脂としては、ＧＰＰＳ、ＨＩＰＳ、ＳＢＣ、ＭＳ樹脂、ＭＢＳ樹脂等が挙げられ、さらにこれら樹脂を混合した樹脂組成物が挙げられる。特に好ましいスチレン系樹脂は、ＧＰＰＳ及びＨＩＰＳである。なお最表面層を形成するスチレン系樹脂には、必要に応じ、本発明の効果を損なわない範囲の量で、着色剤、酸化防止剤、帯電防止剤、滑材、可塑剤など各種添加剤を含むことが可能である。これら各種添加剤は、予めスチレン系樹脂中に含まれていても良いし、多層シートを成膜する時点で新たに添加しても良い。
<Styrene resin>
The resin composition of both outermost surface layers and the core layer of the multilayer sheet of the present invention is a resin fat composition containing polylactic acid and a styrene resin. The styrene-based resin is a resin obtained by polymerizing or copolymerizing one or more styrene-based monomers selected from the group of styrene, methylstyrene, t-butylstyrene, and α-methylstyrene, and HIPS and styrene. A rubber-modified styrene resin known as a copolymer of butadiene (hereinafter referred to as SBC), or a monomer capable of copolymerizing the styrene monomer with the styrene monomer, for example. One or 2 selected from the group of acrylate, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate. Examples thereof include resins obtained by copolymerizing more than one kind of monomer. Among these, preferable styrene-based resins include GPPS, HIPS, SBC, MS resin, MBS resin and the like, and further examples thereof include a resin composition in which these resins are mixed. Particularly preferred styrene resins are GPPS and HIPS. If necessary, the styrene resin forming the outermost surface layer may contain various additives such as colorants, antioxidants, antistatic agents, lubricants, and plasticizers in an amount within a range that does not impair the effects of the present invention. It is possible to include. These various additives may be contained in the styrene resin in advance, or may be newly added at the time of forming the multilayer sheet.
前記スチレン系樹脂の分子量については特に制限はないが、ゲルパーミエーションクロマトグラフィー法を用い、標準分子量を有するＧＰＰＳを用いた検量線からの換算により算出した重量平均分子量（Ｍｗ）としては、１万以上５０万以下であることが好ましい。特に好ましくは、Ｍｗは３万以上４０万以下である。Ｍｗが５０万を超えるスチレン系樹脂は流動性が低いため、シート成形性が低下して、シート表面に鮫肌やモアレ模様が発生しやすくなる傾向がある。一方、Ｍｗが１万未満だとシートの耐熱性や耐衝撃性が劣るため好ましくない。 The molecular weight of the styrene resin is not particularly limited, but the weight average molecular weight (Mw) calculated by using the gel permeation chromatography method and converting from the calibration curve using GPPS having a standard molecular weight is 10,000. It is preferably 500,000 or less. Particularly preferably, Mw is 30,000 or more and 400,000 or less. Since a styrene resin having an Mw of more than 500,000 has low fluidity, the sheet formability is lowered, and shark skin and moire patterns tend to occur on the sheet surface. On the other hand, if Mw is less than 10,000, the heat resistance and impact resistance of the sheet are inferior, which is not preferable.
また、前記スチレン系樹脂の溶融時の流動性の指標として、ＪＩＳ Ｋ７２１０のＨ法に準拠した方法で測定される２００℃、５ｋｇｆにおけるＭＦＲ値が１（ｇ／１０分）以上１５（ｇ／１０分）以下であることが好ましく、２（ｇ／１０分）以上８（ｇ／１０分）以下であることがさらに好ましい。 Further, as an index of the fluidity of the styrene resin at the time of melting, the MFR value at 200 ° C. and 5 kgf measured by a method based on the H method of JIS K7210 is 1 (g / 10 min) or more and 15 (g / 10). Minutes) or less, more preferably 2 (g / 10 minutes) or more and 8 (g / 10 minutes) or less.
＜最表面層におけるポリ乳酸とスチレン系樹脂に対するポリ乳酸の質量割合＞
本発明の多層シートの両最表面層の樹脂組成物は、ポリ乳酸とスチレン系樹脂とを含み、ポリ乳酸とスチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ１は、それぞれ５質量部以上３０質量部以下である樹脂組成物である。またＸ１は、それぞれ５質量部以上２０質量部以下であることがより好ましい。Ｘ１が５質量部未満であると、多層シートの端材を中芯層の原料に戻すような場合に、中芯材の樹脂組成物に含まれるポリ乳酸の割合が望まれる以上に低下する可能性がある。一方、Ｘ１が３０質量部を超えると、本発明の効果である、多層シート成膜時における粘着性異物の発生が抑制できない。
<Mass ratio of polylactic acid to styrene resin in the outermost surface layer>
The resin composition of both outermost surface layers of the multilayer sheet of the present invention contains polylactic acid and a styrene resin, and the mass number X 1 of polylactic acid with respect to a total of 100 parts by mass of polylactic acid and styrene resin is 5 mass each. It is a resin composition having a part or more and 30 parts by mass or less. Further, it is more preferable that X 1 is 5 parts by mass or more and 20 parts by mass or less, respectively. When X 1 is less than 5 parts by mass, the proportion of polylactic acid contained in the resin composition of the core material is lowered more than desired when the end material of the multilayer sheet is returned to the raw material of the core layer. there is a possibility. On the other hand, if X 1 exceeds 30 parts by mass, the generation of sticky foreign matter at the time of forming a multilayer sheet, which is an effect of the present invention, cannot be suppressed.
＜中芯層におけるポリ乳酸とスチレン系樹脂合計質量に対するポリ乳酸の質量割合＞
本発明の多層シートの中芯層の樹脂組成物は、ポリ乳酸とスチレン系樹脂とを含み、ポリ乳酸とスチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ２は、それぞれ２５質量部以上５０質量部以下である樹脂組成物である。Ｘ１は、それぞれ２５質量部以上４５質量部以下であることがより好ましい。Ｘ１が、２５質量部未満であると、本発明の多層シートに占めるポリ乳酸の割合が少なくなるため、環境負荷を低減させたシートの提供ができなくなる。一方、Ｘ１が、５０質量部を超えると、多層シートの成形加工性が低下し、食品容器の製造が困難になる傾向がある。
<Mass ratio of polylactic acid to the total mass of polylactic acid and styrene resin in the core layer>
The resin composition of the core layer of the multilayer sheet of the present invention contains polylactic acid and a styrene resin, and the mass number X 2 of polylactic acid with respect to a total of 100 parts by mass of polylactic acid and styrene resin is 25 parts by mass, respectively. The resin composition is 50 parts by mass or less. It is more preferable that X 1 is 25 parts by mass or more and 45 parts by mass or less, respectively. If X 1 is less than 25 parts by mass, the proportion of polylactic acid in the multilayer sheet of the present invention is small, so that it is not possible to provide a sheet with a reduced environmental load. On the other hand, when X 1 exceeds 50 parts by mass, the molding processability of the multilayer sheet is lowered, and the production of a food container tends to be difficult.
＜最表面層及び中芯層の組成物全体に占めるポリ乳酸＋スチレン系樹脂の質量割合＞
本発明の多層シートでは、さらに最表面層及び中芯層を構成する樹脂組成物においては、ポリ乳酸とスチレン系樹脂以外に、必要に応じて着色剤、酸化防止剤、帯電防止剤、滑材、可塑剤、相溶化材、流動化材、ブロッキング防止材、結晶核材を含む樹脂組成物であることが可能であり、中芯層を構成する樹脂組成物に含まれるポリ乳酸とスチレン系樹脂の合計質量の割合が、中芯層を構成する樹脂組成物全体の質量の８０質量％以上９９質量％以下、好ましくは８５質量％以上９５質量％以下である多層シートとすることができる。特に前記相溶化材として、具体的には、例えばスチレンとブタジエンのブロック共重合体、ポリブタジエンにメタクリル酸メチル及びスチレンをグラフト共重合させたグラフト共重合体、メタクリル酸メチルとｎ−アクリル酸ブチルのブロック共重合体、等を挙げることができる。
<Mass ratio of polylactic acid + styrene resin to the entire composition of the outermost surface layer and the core layer>
In the multilayer sheet of the present invention, in the resin composition constituting the outermost surface layer and the core layer, in addition to the polylactic acid and the styrene resin, a colorant, an antioxidant, an antistatic agent, and a lubricant are required. , A plasticizer, a compatibilizer, a fluidizing material, an antiblocking material, and a crystal nucleating material, which can be a resin composition containing polylactic acid and a styrene resin contained in the resin composition constituting the core layer. A multilayer sheet having a total mass ratio of 80% by mass or more and 99% by mass or less, preferably 85% by mass or more and 95% by mass or less of the total mass of the resin composition constituting the core layer can be obtained. In particular, as the compatibilizer, specifically, for example, a block copolymer of styrene and butadiene, a graft copolymer obtained by graft-copolymerizing methyl methacrylate and styrene on polybutadiene, and methyl methacrylate and butyl n-acrylate. Block copolymers, etc. can be mentioned.
また、前記最表面層及び中芯層を構成するポリ乳酸とスチレン系樹脂とを含む樹脂組成物の、溶融時の流動性の指標として、ＪＩＳ Ｋ７２１０のＨ法に準拠した方法で測定される２００℃、５ｋｇｆにおけるＭＦＲ値は、１（ｇ／１０分）以上１５（ｇ／１０分）以下であることが好ましく、５（ｇ／１０分）以上１２（ｇ／１０分）以下であることがさらに好ましい。 Further, as an index of the fluidity at the time of melting of the resin composition containing the polylactic acid and the styrene resin constituting the outermost surface layer and the core layer, it is measured by a method based on the H method of JIS K7210 200. The MFR value at ° C. and 5 kgf is preferably 1 (g / 10 minutes) or more and 15 (g / 10 minutes) or less, and 5 (g / 10 minutes) or more and 12 (g / 10 minutes) or less. More preferred.
＜発泡倍率＞
本発明の多層シートでは、各層における発泡状態には特に限定はなく、目的とする用途に応じて発泡させても良いし、発泡させなくても良い。また特定の層のみを発泡層とすることも可能である。発泡倍率は１．１倍以上１０倍以下、好ましくは１．１倍以上５倍以下、より好ましくは１．１倍以上２倍以下が一般的である。発泡させる場合には 泡は連通している泡であってもよいし、独立泡であっても良く、また、両者が混在する発泡状態であっても良い。例えば中芯層を発泡させることにより、より軽量で、熱伝導率がより低い多層シートや容器を得ることができるようになる。また、例えば最表面層を発泡させない層とすれば、よりシート表面の平滑性が高く、印刷適正や光沢に優れた多層シートを得ることができる。
<Foam magnification>
In the multilayer sheet of the present invention, the foaming state in each layer is not particularly limited, and may or may not be foamed depending on the intended use. It is also possible to use only a specific layer as a foam layer. The foaming ratio is generally 1.1 times or more and 10 times or less, preferably 1.1 times or more and 5 times or less, and more preferably 1.1 times or more and 2 times or less. In the case of foaming, the bubbles may be continuous bubbles, independent bubbles, or a mixed foam state. For example, by foaming the core layer, it becomes possible to obtain a multi-layer sheet or container that is lighter and has a lower thermal conductivity. Further, for example, if the outermost surface layer is a layer that does not foam, a multilayer sheet having higher smoothness on the sheet surface and excellent printability and gloss can be obtained.
多層シート中の特定の層を発泡層とする場合には、多層シートの成膜時に、発泡層とする層の原料樹脂とは別に、さらに発泡剤を添加して多層シートを成膜するのが好ましい製造方法である。発泡剤の種類に特に限定はないが、無機系化学発泡剤や有機系化学発泡剤が好ましく用いられる。また発泡剤の添加方法にも特に限定はなく、例えば発泡剤を単独で添加することも、また発泡剤を含む樹脂マスターバッチを添加することも可能である。また発泡剤の添加量は、多層シートの目標とする厚さや発泡倍率により、適宜調整することができるが、通常は中芯層の樹脂組成物１００質量部に対して、０．３以上３質量部以下の範囲で添加する。 When a specific layer in the multilayer sheet is used as a foam layer, when the multilayer sheet is formed, a foaming agent is further added in addition to the raw material resin of the layer to be the foam layer to form the multilayer sheet. This is a preferred manufacturing method. The type of foaming agent is not particularly limited, but an inorganic chemical foaming agent and an organic chemical foaming agent are preferably used. Further, the method of adding the foaming agent is not particularly limited, and for example, the foaming agent can be added alone, or a resin masterbatch containing the foaming agent can be added. The amount of the foaming agent added can be appropriately adjusted depending on the target thickness and foaming ratio of the multilayer sheet, but is usually 0.3 or more and 3 mass with respect to 100 parts by mass of the resin composition of the core layer. Add in the range below.
本発明の多層シートでは、シート全体の厚さについて特に限定はないが、全体の厚さは、０．２ｍｍ以上３．０ｍｍ以下であることが好ましく、０．４ｍｍ以上１．５ｍｍ以下であることがより好ましい。本発明の多層シートは、食品容器用のシート素材として好ましく用いられるが、全体の厚さが０．２ｍｍ未満であると、絶対的な強度が不足する。一方３．０ｍｍを超えるとその厚さの故に賦形性、柔軟性が低下するため、食品容器への成形加工が一般的に困難になり、またシートをロール状に巻くことも困難になる。 In the multilayer sheet of the present invention, the thickness of the entire sheet is not particularly limited, but the overall thickness is preferably 0.2 mm or more and 3.0 mm or less, and 0.4 mm or more and 1.5 mm or less. Is more preferable. The multilayer sheet of the present invention is preferably used as a sheet material for food containers, but if the total thickness is less than 0.2 mm, the absolute strength is insufficient. On the other hand, if it exceeds 3.0 mm, the shapeability and flexibility are lowered due to its thickness, so that it is generally difficult to mold the food container, and it is also difficult to roll the sheet into a roll.
また、本発明の多層シートでは、シート全体の厚さに対する各層の厚さの割合について特に限定はない。ただし、本発明の多層シートの中芯層は、特にポリ乳酸を含むことを必須としている層であり、中芯層はシート全体の厚さに対して５０％以上９０％以下であることが好ましい。中芯層の厚さ割合が５０％未満であると、ポリ乳酸の割合が少なく、環境保護の目的からは逸脱してしまう。また中芯層の厚さ割合が９０％を超えると、最表面層が途切れる部分が生じ易くなり、シートの外観も損なわれる可能性が高まる。なお、最表面層は２層存在するが、この２層は必ずしも同じ厚さである必要はない。 Further, in the multilayer sheet of the present invention, the ratio of the thickness of each layer to the thickness of the entire sheet is not particularly limited. However, the core layer of the multilayer sheet of the present invention is a layer that is indispensable to contain polylactic acid, and the core layer is preferably 50% or more and 90% or less with respect to the thickness of the entire sheet. .. If the thickness ratio of the core layer is less than 50%, the ratio of polylactic acid is small, which deviates from the purpose of environmental protection. Further, when the thickness ratio of the core layer exceeds 90%, a portion where the outermost surface layer is interrupted is likely to occur, and the possibility that the appearance of the sheet is impaired increases. There are two outermost layers, but the two layers do not necessarily have the same thickness.
本発明の多層シートは、その層構成として、シート両面の最表面部に、ポリ乳酸とスチレン系樹脂とを含み、前記ポリ乳酸と前記スチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ１が、それぞれ５質量部以上３０質量部以下である樹脂組成物からなる最表面層と、シート中間部に、ポリ乳酸とスチレン系樹脂とを含み、前記ポリ乳酸と前記スチレン系樹脂の合計１００質量部に対するポリ乳酸の質量部数Ｘ２が、２５質量部以上５０質量部以下である樹脂組成物からなる中芯層とを含み、Ｘ２はＸ１より高い値である層構造を有する多層シートであれば、その他は特に限定は無く、最表面層と中芯層以外の層をさらに含んでいても良い。再表面層に含まれるポリ乳酸は少ないほど本発明の効果が発揮されやすいため、Ｘ１の好ましい範囲は５質量部以上２５質量部以下であり、５質量部以上２０質量部以下であることがさらに好ましい。但し、好ましい多層シートの層構成としては、最表面層／中芯層／最表面層の順に各層が積層されている３層構造の多層シートである。多層シートの層構成を本発明の要件で規定することにより、これまで課題となっていた、ポリ乳酸を多く含むシートの製造時における、Ｔダイのリップ周縁部への粘着性異物の付着が抑制され、シート汚染を防ぐことが可能な層構成を有する多層シート、またそれを用いた容器を得ることができる。 The multilayer sheet of the present invention contains polylactic acid and a styrene resin on the outermost surfaces of both sides of the sheet as its layer structure, and the mass number of polylactic acid X based on 100 parts by mass of the polylactic acid and the styrene resin in total. 1 contains a polylactic acid and a styrene-based resin in the outermost surface layer made of a resin composition of 5 parts by mass or more and 30 parts by mass or less, respectively, and the intermediate portion of the sheet, and the total of the polylactic acid and the styrene-based resin is 100. A multilayer sheet having a layer structure in which the number of parts X 2 of polylactic acid with respect to parts by mass includes a core layer made of a resin composition of 25 parts by mass or more and 50 parts by mass or less, and X 2 is a value higher than X 1. If so, the other is not particularly limited, and layers other than the outermost surface layer and the core layer may be further included. Since the effect of the present invention is more likely to be exhibited as the amount of polylactic acid contained in the surface reconstruction layer is smaller, the preferable range of X 1 is 5 parts by mass or more and 25 parts by mass or less, and 5 parts by mass or more and 20 parts by mass or less. More preferred. However, a preferable layer structure of the multilayer sheet is a multilayer sheet having a three-layer structure in which each layer is laminated in the order of the outermost surface layer / core layer / outermost surface layer. By defining the layer structure of the multilayer sheet in the requirements of the present invention, the adhesion of sticky foreign matter to the lip peripheral portion of the T-die during the production of a sheet containing a large amount of polylactic acid, which has been a problem so far, is suppressed. It is possible to obtain a multilayer sheet having a layered structure capable of preventing sheet contamination, and a container using the same.
＜シートの製造方法＞
本発明の多層シートの製造方法は、一般的な共押出多層法であるフィードブロック方式やマルチマニホールド方式により、ダイス中で、多層シートの全ての層を一体化させて、吐出口のリップから一枚のシート状に押し出し、冷却ロールの間を通して固化させ、シートを巻き取る製造方法が好ましい。ダイスは、Ｔダイス（Ｔダイともいう）が好ましく用いられる。なお、一般的な共押出し方法で多層シートを製造する際は、各層の流動性を合わせた樹脂を使用することが好ましい。
<Sheet manufacturing method>
The method for manufacturing a multi-layer sheet of the present invention is a feed block method or a multi-manifold method, which is a general coextrusion multi-layer method, in which all layers of the multi-layer sheet are integrated in a die and one from the lip of the discharge port. A manufacturing method in which the sheet is extruded into a sheet, solidified through the cooling rolls, and the sheet is wound up is preferable. As the die, a T die (also referred to as a T die) is preferably used. When producing a multilayer sheet by a general coextrusion method, it is preferable to use a resin having a combined fluidity of each layer.
＜容器＞
本発明の多層シートを成形加工して得た容器もまた、本発明のひとつの実施形態である。多層シートの成形加工方法は特に限定はないが、例えば、真空成形や圧空成形等の公知の成形加工方法によって、得ることができる。本発明の容器は、特に食品用の容器であることが好ましい。
<Container>
A container obtained by molding the multilayer sheet of the present invention is also an embodiment of the present invention. The forming method of the multilayer sheet is not particularly limited, but it can be obtained by, for example, a known forming method such as vacuum forming or compressed air forming. The container of the present invention is particularly preferably a container for food.
以下、実施例に基づいて本発明の多層シートを更に詳細に説明するとともに、本発明の効果を検証した結果を示す。なお、以下に説明する実施例は、本発明の代表的な実施例を示したものであり、これにより本発明の範囲が狭く解釈されることはない。 Hereinafter, the multilayer sheet of the present invention will be described in more detail based on Examples, and the results of verifying the effects of the present invention will be shown. It should be noted that the examples described below show typical examples of the present invention, and the scope of the present invention is not narrowly interpreted by this.
＜シートの成膜＞
実施例１〜１３、及び比較例１〜５の多層シートを、表１〜３に記載した層構成で成膜した。このうち実施例１３、比較例５の多層シートは、特に中芯層を発泡させた多層シートである。以下に成膜方法をさらに具体的に記載する。
<Sheet film formation>
The multilayer sheets of Examples 1 to 13 and Comparative Examples 1 to 5 were formed into a film having the layer structure shown in Tables 1 to 3. Of these, the multilayer sheets of Examples 13 and 5 are particularly multilayer sheets in which the core layer is foamed. The film forming method will be described more specifically below.
＜実施例1＞
実施例１の多層シートの最表面層として用いた樹脂組成物を、予め以下の方法で準備した。即ち、ポリ乳酸（ＲＥＶＯＤＡ１１０、海正生物材料社製）の５質量部と、ＨＩＰＳ（トーヨースチロールＨＩ Ｅ６４０Ｎ、東洋スチレン社製）の９５質量部と、相溶化材（メタブレンＣ−２２３Ａ、三菱ケミカル社製）の１０質量部、滑材と流動化材の合計３質量部を、ヘンシェルミキサーで予備混合し、次いで二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）を用いて溶融混練し、さらにストランドをペレタイザーに通して、実施例１の多層シートの中芯層用樹脂組成物のペレットを得た。なお、二軸押出機のシリンダー設定温度は２００℃、樹脂組成物の突出量は、３０ｋｇ／時間の条件で運転した。
<Example 1>
The resin composition used as the outermost surface layer of the multilayer sheet of Example 1 was prepared in advance by the following method. That is, 5 parts by mass of polylactic acid (REVODA110, manufactured by Kaisei Biomaterials Co., Ltd.), 95 parts by mass of HIPS (Toyostyrol HI E640N, manufactured by Toyo Styron Co., Ltd.), and a compatibilizer (Metabrene C-223A, Mitsubishi Chemical Co., Ltd.). 10 parts by mass of (manufactured by Toshiba Machine Co., Ltd.) and a total of 3 parts by mass of lubricating material and fluidizing material are premixed with a Henschel mixer, and then melt-kneaded using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM26SS) to further prepare strands. Through a pelletizer, pellets of the resin composition for the core layer of the multilayer sheet of Example 1 were obtained. The cylinder set temperature of the twin-screw extruder was 200 ° C., and the protrusion amount of the resin composition was 30 kg / hour.
また実施例１の多層シートの中芯層として用いた樹脂組成物も同様に、予め以下の方法で準備した。即ち、ポリ乳酸（ＲＥＶＯＤＡ１１０、海正生物材料社製）の３５質量部と、ＨＩＰＳ（トーヨースチロールＨＩ Ｅ６４０Ｎ、東洋スチレン社製）の６５質量部と、相溶化材（メタブレンＣ−２２３Ａ、三菱ケミカル社製）の１０質量部、滑材と流動化材の合計３質量部を、ヘンシェルミキサーで予備混合し、次いで二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）を用いて溶融混練し、さらにストランドをペレタイザーに通して、実施例１の多層シートの中芯層用樹脂組成物のペレットを得た。なお、二軸押出機のシリンダー設定温度は２００℃、樹脂組成物の突出量は、３０ｋｇ／時間の条件で運転した。 Similarly, the resin composition used as the core layer of the multilayer sheet of Example 1 was also prepared in advance by the following method. That is, 35 parts by mass of polylactic acid (REVODA110, manufactured by Kaisei Biomaterials Co., Ltd.), 65 parts by mass of HIPS (Toyostyrol HI E640N, manufactured by Toyo Styron Co., Ltd.) and a compatibilizer (Metabrene C-223A, Mitsubishi Chemical Co., Ltd.). 10 parts by mass of (manufactured by Toshiba Machine Co., Ltd.) and a total of 3 parts by mass of lubricating material and fluidizing material are premixed with a Henschel mixer, and then melt-kneaded using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM26SS) to further prepare strands. Through a pelletizer, pellets of the resin composition for the core layer of the multilayer sheet of Example 1 were obtained. The cylinder set temperature of the twin-screw extruder was 200 ° C., and the protrusion amount of the resin composition was 30 kg / hour.
次いで、実施例１の多層シートの中芯層として、６５ｍｍ押出機を用い、前記中芯層用の樹脂組成物を押し出し、また実施例１の両最表面層として、４０ｍｍ押出し機を２台使用して前記両表層用の樹脂組成物を押し出し、それぞれの溶融樹脂をフィードブロックを経由させて、幅７００ｍｍのＴダイ中に送り、中芯層と最表面層を全て一体化させた２種３層とし、冷却後のシート全体の厚さが０．４ｍｍ、及び全体の厚さに対する最表面層／中芯層／最表面層の厚さの割合が、１５％／７０％／１５％とした層構成を有する３層の多層シートを押し出した。なお実施例１の層構成は表１にも示した。Ｔダのリップから押し出された前記実施例１の多層シートは、その後３本のロールを用いて冷却し、巻取機にて巻き取りした。実施例１の多層シートの成膜は、途中で中断することなく１時間連続的に実施した。 Next, a 65 mm extruder was used as the core layer of the multilayer sheet of Example 1, the resin composition for the core layer was extruded, and two 40 mm extruders were used as both outermost surface layers of Example 1. Then, the resin compositions for both surface layers are extruded, and each molten resin is sent into a T-die having a width of 700 mm via a feed block, and the core layer and the outermost surface layer are all integrated into two types 3 As a layer, the thickness of the entire sheet after cooling was 0.4 mm, and the ratio of the thickness of the outermost surface layer / core layer / outermost surface layer to the total thickness was 15% / 70% / 15%. A three-layer multilayer sheet having a layer structure was extruded. The layer structure of Example 1 is also shown in Table 1. The multilayer sheet of Example 1 extruded from the lip of T-da was then cooled using three rolls and wound up by a winder. The film formation of the multilayer sheet of Example 1 was continuously carried out for 1 hour without interruption in the middle.
＜実施例２〜６、比較例１〜４＞
実施例２〜６、比較例１〜４の多層シートは、両最表面層、及び中芯層の化学組成、シート全体の厚さに対する最表面層／中芯層／最表面層の厚さを表１に示したように設定し、成膜装置の各ヒーター温度、吐出量、リップ幅は適宜調整したが、基本的には実施例１と同じ手順で、同じ装置を用い、実施例２〜６、比較例１〜４の多層シートを成膜した。これら実施例、比較例の多層シートのＴダイからの押し出しも、途中で中断することなく実施例１と同様に１時間連続的に実施した。また実施例２〜６の層構成は表１に、比較例１〜４の層構成は表２に示した。
<Examples 2 to 6, Comparative Examples 1 to 4>
The multilayer sheets of Examples 2 to 6 and Comparative Examples 1 to 4 have the chemical composition of both outermost surface layers and the core layer, and the thickness of the outermost surface layer / core layer / outermost surface layer with respect to the thickness of the entire sheet. The settings were made as shown in Table 1, and each heater temperature, discharge amount, and lip width of the film forming apparatus were appropriately adjusted. However, basically, the same procedure as in Example 1 was used, and Examples 2 to 2 were used. 6. The multilayer sheets of Comparative Examples 1 to 4 were formed. The extruding of the multilayer sheets of these Examples and Comparative Examples from the T-die was also continuously carried out for 1 hour in the same manner as in Example 1 without interruption. The layer structures of Examples 2 to 6 are shown in Table 1, and the layer structures of Comparative Examples 1 to 4 are shown in Table 2.
＜実施例７〜１２＞
実施例７〜１２の多層シートは、両最表面層、及び中芯層の化学組成、シート全体の厚さに対する最表面層／中芯層／最表面層の厚さを表２に示したように設定し、成膜装置の各ヒーター温度、吐出量、リップ幅は適宜調整したが、基本的には実施例１と同じ手順で、同じ装置を用い、実施例７〜１２の多層シートを成膜した。これら実施例の多層シートのＴダイからの押し出しも、途中で中断することなく実施例１と同様に１時間連続的に実施した。また実施例７〜１２の層構成は表３にまとめて示した。
<Examples 7 to 12>
In the multilayer sheets of Examples 7 to 12, the chemical compositions of both outermost surface layers and the core layer, and the thickness of the outermost surface layer / core layer / outermost surface layer with respect to the thickness of the entire sheet are shown in Table 2. The temperature, discharge rate, and lip width of each heater of the film forming apparatus were adjusted as appropriate, but basically the same procedure as in Example 1 was used to form the multilayer sheets of Examples 7 to 12. Membrane. The extrusion of the multilayer sheet of these examples from the T-die was also continuously carried out for 1 hour in the same manner as in Example 1 without interruption. The layer structures of Examples 7 to 12 are summarized in Table 3.
＜実施例１３＞
実施例１３の多層シートは、実施例２と同じ原料、手順、装置を用いるが、中芯層の樹脂組成物として、さらに発泡剤マスターバッチ（ポリスレンＥＳ４０５、永和化成社製）を０．８質量部、タルク０．３質量部を添加し、成膜装置の各ヒーター温度、吐出量、リップ幅は適宜調整して、全体の厚さが０．６ｍｍで、中芯層が１．３倍に発泡している多層シートを成膜した。実施例１３の多層シートのＴダイからの押し出しも、途中で中断することなく１時間連続的に実施した。実施例１３の層構成は表４に示した。
<Example 13>
The multilayer sheet of Example 13 uses the same raw materials, procedures, and equipment as those of Example 2, but uses 0.8 mass of a foaming agent masterbatch (Polyslen ES405, manufactured by Eiwa Kasei Co., Ltd.) as the resin composition of the core layer. By adding 0.3 parts by mass of talc and adjusting the temperature, discharge rate, and lip width of each heater of the film forming apparatus as appropriate, the overall thickness is 0.6 mm and the core layer is 1.3 times larger. A foamed multilayer sheet was formed. The extrusion of the multilayer sheet of Example 13 from the T-die was also carried out continuously for 1 hour without interruption in the middle. The layer structure of Example 13 is shown in Table 4.
＜比較例５＞
比較例５の多層シートは、両最表面層及び中芯層は比較例２と同じ樹脂組成物を用い、成膜装置の各ヒーター温度、吐出量、リップ幅は適宜微調整したが、基本的には実施例１３と同じ装置を用い、中芯層を発泡させた多層シートである。比較例５のＴダイからのシート押し出しも、途中で中断することなく実施例１３と同様に１時間連続的に実施した。比較例５の層構成も表４に示した。
<Comparative example 5>
In the multilayer sheet of Comparative Example 5, both outermost surface layers and the core layer used the same resin composition as in Comparative Example 2, and each heater temperature, discharge amount, and lip width of the film forming apparatus were finely adjusted as appropriate, but basically. Is a multilayer sheet in which the core layer is foamed using the same apparatus as in Example 13. The sheet extrusion from the T-die of Comparative Example 5 was also carried out continuously for 1 hour in the same manner as in Example 13 without interruption in the middle. The layer structure of Comparative Example 5 is also shown in Table 4.
＜粘着性異物の発生状況＞
実施例１〜１３、比較例１〜５の各多層シートの成膜押し出しする間に、Ｔダイのリップ周縁部に滞留してくる粘着性異物の発生状態、さらにリップ周縁部に溜まった前記粘着性異物が、押出し中のシート表面へ付着したか否か、ビデオカメラによる撮影記録を補助的に利用して目視観察した。勿論、粘着性異物の発生が少なければ少ないほど、本発明の効果を反映している多層シートであることを示す。評価の段階としては、成膜開始直後から成膜終了まで、Ｔリップ周縁部に粘着性異物の付着が全く観られない場合を最良「Ａ」とし、リップ周縁部への粘着性異物が顕著に観られ、さらに成膜中のシートに表面にも付着してしまう場合が１回でも起きれば「Ｅ」とした。その中間段階、即ち粘着性異物のリップ付着が僅かに観られる場合は「Ｂ」、リップ付着が「Ｂ」より多く観られる場合は「Ｃ」、シートへの粘着性異物の付着は起きないまでも、リップ周縁部への粘着性異物の滞留が顕著である場合は「Ｄ」とした。「Ａ」〜「Ｃ」の評価であれば、本発明の効果を発現しているとした。
<Status of occurrence of sticky foreign matter>
During the film formation extrusion of each of the multilayer sheets of Examples 1 to 13 and Comparative Examples 1 to 5, the state of generation of sticky foreign matter staying on the lip peripheral portion of the T-die, and the adhesive accumulated on the lip peripheral portion. Whether or not the foreign matter adhered to the surface of the sheet being extruded was visually observed by using a video camera recording as an auxiliary. Of course, the smaller the amount of sticky foreign matter generated, the more the multilayer sheet reflects the effect of the present invention. As the evaluation stage, the best case is "A" when no sticky foreign matter is observed on the peripheral edge of the T-lip from immediately after the start of film formation to the end of film formation, and the sticky foreign matter on the peripheral edge of the lip is remarkable. It was rated as "E" if it was observed and even once it adhered to the surface of the sheet being filmed. In the middle stage, that is, "B" when a slight amount of sticky foreign matter adheres to the lip, "C" when more lip adhesion is observed than "B", until the sticky foreign matter does not adhere to the sheet. However, when the sticky foreign matter was remarkably retained on the peripheral edge of the lip, it was rated as "D". If the evaluation is "A" to "C", it is considered that the effect of the present invention is exhibited.
＜多層シートの賦形性の評価＞
実施例１〜１３、比較例１〜５の多層シートについて、開口部の横幅が２７０ｍｍ、開口部の縦長さが２００ｍｍ、深さが３０ｍｍであり、各コーナー部に丸みを設けた角形容器に成形加工する金型を用いて、真空成形によりヒーター温度（間接加熱）上／下５００℃の条件のもと角形容器サンプルを作製した。作製した角形容器については、金型の設計通り成形されている場合は「Ａ」、成形できているが角部の再現性等が「Ａ」には及ばないような場合は「Ｂ」とした。さらに賦形性は「Ｂ」に達しないが、割れなく成形できた場合を「Ｃ」、容器の表面に割れや裂けが生じたりした場合は「Ｄ」と、賦形性を４段階で比較評価した。賦形性に関しては、容器の形状にも左右されるため、本試験では、「Ａ」〜「Ｃ」の評価であれば、本発明の効果を発現しているとした。
<Evaluation of formability of multi-layer sheet>
For the multilayer sheets of Examples 1 to 13 and Comparative Examples 1 to 5, the width of the opening is 270 mm, the length of the opening is 200 mm, and the depth is 30 mm, and the multi-layer sheet is formed into a square container having rounded corners. Using the mold to be processed, a square container sample was prepared by vacuum forming under the condition of heater temperature (indirect heating) above / below 500 ° C. Regarding the manufactured square container, "A" was given if it was molded according to the design of the mold, and "B" was given if it was molded but the reproducibility of the corners did not reach "A". .. Furthermore, the shapeability does not reach "B", but the shapeability is compared in 4 stages, with "C" when molding is possible without cracking and "D" when cracking or tearing occurs on the surface of the container. evaluated. Since the shapeability depends on the shape of the container, in this test, it was considered that the effect of the present invention was exhibited if the evaluation was "A" to "C".
実施例１〜１３、比較例１〜５の評価結果については表１〜３の該当欄に合わせて記載した。これらの評価結果から、本発明の実施により、環境負荷の少ないポリ乳酸を成分として含み、成膜時における粘着性異物のリップ周縁部への付着が少なく、衛生安全上の危険性も低減された、特に食品容器の用途に適した多層シートを提供できることが確認された。 The evaluation results of Examples 1 to 13 and Comparative Examples 1 to 5 are described in the corresponding columns of Tables 1 to 3. Based on these evaluation results, the implementation of the present invention has reduced the risk of hygiene and safety by containing polylactic acid, which has a low environmental load, as a component, and the adhesion of sticky foreign matter to the lip peripheral portion during film formation is small. , Especially, it was confirmed that it is possible to provide a multilayer sheet suitable for the use of food containers.
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