JP2022129115A - Biaxially stretched polystyrene sheet and package - Google Patents
Biaxially stretched polystyrene sheet and package Download PDFInfo
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- JP2022129115A JP2022129115A JP2021027681A JP2021027681A JP2022129115A JP 2022129115 A JP2022129115 A JP 2022129115A JP 2021027681 A JP2021027681 A JP 2021027681A JP 2021027681 A JP2021027681 A JP 2021027681A JP 2022129115 A JP2022129115 A JP 2022129115A
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- 150000003505 terpenes Chemical class 0.000 claims abstract description 48
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- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical group C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000012887 quadratic function Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 238000007652 sheet-forming process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- IHPKGUQCSIINRJ-UHFFFAOYSA-N β-ocimene Natural products CC(C)=CCC=C(C)C=C IHPKGUQCSIINRJ-UHFFFAOYSA-N 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
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Landscapes
- Wrappers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、テルペン系樹脂を含有するポリスチレン系二軸延伸シート、及び、該シートを成形してなる包装体に関する。 TECHNICAL FIELD The present invention relates to a polystyrene-based biaxially oriented sheet containing a terpene-based resin, and a package formed by molding the sheet.
汎用ポリスチレン樹脂（ＧＰＰＳ）等からなる透明なポリスチレン系二軸延伸シートは、剛性、軽量性、透明性、成形性、リサイクル性などに優れ、食品包装容器や蓋材などの成形品として使用されている。
包装容器や蓋材等への成形は、公知の熱板接触加熱成形法、圧空成形法、真空成形法、真空圧空成形法、プラグアシスト成形法によって行われ、目的の形状に二次成形して好適に用いることができる。ＧＰＰＳ等からなる透明なポリスチレン系二軸延伸シートは、特に、弁当や総菜等の食品用の包装用透明蓋等に好適である。その他、工業部品等の小分けトレイや運搬容器などに用いることもできる。
Transparent polystyrene biaxially oriented sheets made of general-purpose polystyrene resin (GPPS) are excellent in rigidity, lightness, transparency, moldability, recyclability, etc., and are used as molded products such as food packaging containers and lid materials. there is
Forming into packaging containers, lid materials, etc. is carried out by known hot plate contact heat forming method, pressure forming method, vacuum forming method, vacuum pressure forming method, plug assist forming method, and secondary forming into the desired shape. It can be used preferably. A transparent polystyrene-based biaxially oriented sheet made of GPPS or the like is particularly suitable for packaging transparent lids for foods such as box lunches and side dishes. In addition, it can also be used for subdivision trays and transport containers for industrial parts and the like.
近年、環境問題に対する意識の高まりから、環境負荷を低減できる加工工程や生産性の向上を目的として、低温成形が求められている。低温成形は、従来の加工条件に比べて低い温度条件で加工できるため、加熱に必要なエネルギーを小さくできたり、加熱や離型に要する時間が短くできたりするため、環境負荷の低減や生産性の向上につながる。
低温成形を目的としたポリスチレン系二軸延伸シートとしては、例えば、特許文献１～３にスチレン－アクリル酸エステル共重合体を用いたシートが開示されている。
しかしながら、これらの技術は、共重合未反応物に起因するゲルが発生して押出成形不良が起こりやすく、ブツやメヤニ等のシート外観不良を発生させたり、共重合体の分岐鎖に起因して溶融張力が高くなりシート表面が荒れたりする等の問題があった。
In recent years, due to the growing awareness of environmental issues, low-temperature molding is required for the purpose of improving productivity and processing processes that can reduce the environmental load. Low-temperature molding can be processed under lower temperature conditions than conventional processing conditions, so the energy required for heating can be reduced, and the time required for heating and mold release can be shortened, reducing environmental impact and improving productivity. lead to improvement.
As a polystyrene biaxially oriented sheet intended for low temperature molding, for example, a sheet using a styrene-acrylic acid ester copolymer is disclosed in Patent Documents 1 to 3.
However, these techniques tend to cause poor extrusion molding due to the generation of gel due to the unreacted copolymer, and the occurrence of poor sheet appearance such as lumps and scum. There are problems such as a high melt tension and a rough sheet surface.
上記実情を鑑み、本発明の課題は、ゲル異物やシート表面荒れなどの外観不良が発生し難く、低温成形が可能なポリスチレン系二軸延伸シートおよびその包装体を提供することにある。 In view of the above circumstances, an object of the present invention is to provide a polystyrene-based biaxially oriented sheet that is less susceptible to appearance defects such as gel foreign matter and sheet surface roughness and that can be molded at a low temperature, and a package thereof.
本発明者らは、鋭意検討した結果、スチレン系樹脂とテルペン系樹脂とを所定の割合にて含有し、延伸により所定の配向緩和応力とすることで、シートの１００℃の損失正接を所定範囲とすることにより、上記課題を解決可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors found that the loss tangent of the sheet at 100 ° C. is reduced to a predetermined range by containing a styrene resin and a terpene resin in a predetermined ratio and by stretching to a predetermined orientation relaxation stress. By doing so, the inventors have found that the above problems can be solved, and have completed the present invention.
第１の本発明は、スチレン系樹脂（Ａ）５０．０～９９．０質量％とテルペン系樹脂（Ｂ）１．０～５０．０質量％とを含有するシートであって、シート厚みが０．０５ｍｍ以上０．５０ｍｍ以下であり、かつシート縦方向と横方向の配向緩和応力が共に０．１ＭＰａ以上１．２ＭＰａ以下であり、１００℃の損失正接が０．１５以上０．８０以下であることを特徴とするポリスチレン系二軸延伸シートである。 A first aspect of the present invention is a sheet containing 50.0 to 99.0% by mass of a styrene resin (A) and 1.0 to 50.0% by mass of a terpene resin (B), wherein the sheet thickness is 0.05 mm or more and 0.50 mm or less, the orientation relaxation stress in both the longitudinal direction and the transverse direction of the sheet is 0.1 MPa or more and 1.2 MPa or less, and the loss tangent at 100 ° C. is 0.15 or more and 0.80 or less. A polystyrene-based biaxially oriented sheet characterized by:
第１の本発明において、前記シートを１００．０質量％とした場合に、耐衝撃性ポリスチレン系樹脂（Ｃ）を０．１質量％以上５．０質量％以下含むことが好ましい。 In the first aspect of the present invention, it is preferable that the impact-resistant polystyrene resin (C) is contained in an amount of 0.1% by mass or more and 5.0% by mass or less when the sheet is 100.0% by mass.
第１の本発明において、前記シートのビカット軟化温度が７５℃以上１００℃未満であることが好ましい。 In the first invention, it is preferable that the sheet has a Vicat softening temperature of 75°C or more and less than 100°C.
第１の本発明において、前記シート厚みが０．１８ｍｍの場合に、ヘイズが１５．０％以下であることが好ましい。 In the first invention, when the sheet thickness is 0.18 mm, the haze is preferably 15.0% or less.
第２の本発明は、第１の本発明のポリスチレン系二軸延伸シートを用いてなる包装体である。 A second aspect of the present invention is a package using the polystyrene-based biaxially oriented sheet of the first aspect of the present invention.
本発明のポリスチレン系二軸延伸シートは、外観不良が発生し難いので、生産歩留まりが良好で経済効率が良く、また低温成形が可能であるので、成形加工のエネルギーを低減できる。 Since the polystyrene-based biaxially oriented sheet of the present invention hardly causes poor appearance, the production yield is good and economic efficiency is good, and low-temperature molding is possible, so that the energy for molding can be reduced.
以下、本発明の実施形態について説明する。なお、本発明の範囲は、以下に説明する実施形態に限定されるものではない。
＜ポリスチレン系二軸延伸シート＞
本発明のポリスチレン系二軸延伸シート（以下、本発明のシートと称することがある）は、スチレン系樹脂（Ａ）５０．０～９９．０質量％とテルペン系樹脂（Ｂ）１．０～５０．０質量％とを含有する。
なお、断り書きを設けない限り「△～△△」の表記は、「△以上△△以下」を意味し、好ましくは「△超△未満」を意味する。
Embodiments of the present invention will be described below. In addition, the scope of the present invention is not limited to the embodiments described below.
<Polystyrene biaxially oriented sheet>
The polystyrene-based biaxially oriented sheet of the present invention (hereinafter sometimes referred to as the sheet of the present invention) comprises styrene resin (A) 50.0 to 99.0% by mass and terpene resin (B) 1.0 to 50.0% by mass.
Unless otherwise specified, the notation "△ to △△" means "more than △ and less than △△", preferably "more than △ and less than △".
（スチレン系樹脂（Ａ））
本発明のシートに用いるスチレン系樹脂（Ａ）は、スチレン系モノマーを用いた重合体、スチレン系モノマーとそれらと共重合可能な他のモノマーとの共重合体を挙げることができる。
スチレン系モノマーとしては、スチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、４－エチルスチレン、４－ｔ－ブチルスチレン、２，４－ジメチルスチレン等のアルキル置換スチレン、α－メチルスチレン、α－メチル－４－メチルスチレン等のα－アルキル置換スチレン、２－クロロスチレン、４－クロロスチレン等のハロゲン化スチレン等を挙げることができる。これらスチレン系モノマーは、１種を単独で用いても良いし、２種以上を共重合させて用いてもよい。耐熱性向上の観点では、スチレンとαメチルスチレンとの共重合体が好ましい。
スチレン系モノマーと共重合可能な他のモノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸エステル、無水マレイン酸、酢酸ビニル、アクリロニトリルや、ブタジエン、イソプレン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエン、１，３－ペンタジエン、１，３－ヘキサジエン等の共役ジエン系炭化水素、エチレン、プロピレン、１－ブテン、１－ヘキセン、４－メチル－１－ペンテン、１－オクテン等のα－オレフィン等を挙げることができる。耐熱性向上の観点では、（メタ）アクリル酸、（メタ）アクリル酸エステル、無水マレイン酸、アクリロニトリルを用いることが好ましく、（メタ）アクリル酸、（メタ）アクリル酸エステルを用いることがより好ましく、（メタ）アクリル酸を用いることが特に好ましい。
(Styrene resin (A))
Examples of the styrene-based resin (A) used in the sheet of the present invention include polymers using styrene-based monomers and copolymers of styrene-based monomers and other monomers copolymerizable therewith.
Styrenic monomers include alkyl-substituted styrenes such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-t-butylstyrene, 2,4-dimethylstyrene, α-methyl Examples include styrene, α-alkyl-substituted styrenes such as α-methyl-4-methylstyrene, and halogenated styrenes such as 2-chlorostyrene and 4-chlorostyrene. These styrene-based monomers may be used alone, or two or more of them may be copolymerized and used. From the viewpoint of improving heat resistance, a copolymer of styrene and α-methylstyrene is preferred.
Other monomers copolymerizable with styrene monomers include, for example, (meth)acrylic acid, (meth)acrylic acid ester, maleic anhydride, vinyl acetate, acrylonitrile, butadiene, isoprene, 2-methyl-1,3 -Conjugated diene hydrocarbons such as butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, ethylene, propylene, 1-butene, 1-hexene, 4-methyl- Examples include α-olefins such as 1-pentene and 1-octene. From the viewpoint of improving heat resistance, it is preferable to use (meth)acrylic acid, (meth)acrylic acid ester, maleic anhydride and acrylonitrile, and it is more preferable to use (meth)acrylic acid and (meth)acrylic acid ester. Particular preference is given to using (meth)acrylic acid.
スチレン系樹脂（Ａ）の重量平均分子量は、特に限定されるものではないが１５０，０００以上２，０００，０００以下が好ましく、１５０，０００以上１，８００，０００以下がより好ましい。係る範囲であると、溶融粘度特性から押出成形性が良好となる。また、１５０，０００以上であると、シートの機械的強度が十分となり、２，０００，０００以下であるとシートの弾性率が好適となり低温成形性が向上する。
スチレン系樹脂（Ａ）のＭＦＲは、１．５ｇ／１０分以上５．０ｇ／１０分以下が好ましく、２．０ｇ／１０分以上４．０ｇ／１０分以下がより好ましい。
The weight average molecular weight of the styrene resin (A) is not particularly limited, but is preferably 150,000 or more and 2,000,000 or less, more preferably 150,000 or more and 1,800,000 or less. Within such a range, good extrusion moldability is obtained from melt viscosity characteristics. Further, when it is 150,000 or more, the mechanical strength of the sheet becomes sufficient, and when it is 2,000,000 or less, the elastic modulus of the sheet becomes suitable and the low-temperature moldability is improved.
The MFR of the styrene resin (A) is preferably 1.5 g/10 min or more and 5.0 g/10 min or less, more preferably 2.0 g/10 min or more and 4.0 g/10 min or less.
スチレン系樹脂（Ａ）は、ガラス転移温度８０℃以上１４０℃以下が好ましく、上限は１３０℃以下がより好ましい。係る範囲であると、テルペン系樹脂（Ｂ）と配合した際に、シートの機械的強度と低温成形性のバランスに優れる。具体的には、８０℃以上により、シートに実用的な耐熱性を付加でき、１４０℃以下により低温成形性が良好となる。
ガラス転移温度は、ＪＩＳ Ｋ７１２１：２０１２に基づき、示差走査熱量測定により、１０℃／分で再昇温した際の値から求める。
The styrene-based resin (A) preferably has a glass transition temperature of 80° C. or higher and 140° C. or lower, and the upper limit is more preferably 130° C. or lower. Within such a range, when mixed with the terpene-based resin (B), the sheet has an excellent balance between mechanical strength and low-temperature moldability. Specifically, when the temperature is 80° C. or higher, practical heat resistance can be added to the sheet, and when the temperature is 140° C. or lower, low-temperature moldability is improved.
The glass transition temperature is obtained from the value when the temperature is reheated at 10° C./min by differential scanning calorimetry based on JIS K7121:2012.
（テルペン系樹脂（Ｂ））
本発明のシートに用いるテルペン系樹脂（Ｂ）は、単量体の主成分としてイソプレン（Ｃ５Ｈ８）の化学式を含む炭化水素及びその含酸素誘導体、例えば、モノテルペン（Ｃ１０化合物）、セスキテルペン（C１５化合物）、ジテルペン（C２０化合物）などのテルペンを基本骨格とする化合物（テルペン化合物）を重合して得られる樹脂である。
具体的には、テルペン化合物の単独重合体であるテルペン樹脂、テルペン化合物と芳香族化合物とを共重合して得られる芳香族変性テルペン樹脂、テルペン化合物とフェノール化合物との共重合体であるテルペンフェノール樹脂、それらの完全水素添加樹脂、または部分水素添加樹脂等を用いることができる。これらの中でも、入手のしやすさや価格の安さ、臭気の少なさなどから、テルペン樹脂、芳香族変性テルペン樹脂が好ましい。なお、これらは１種類を用いてもよいし、２種以上を用いてもよい。
(Terpene resin (B))
The terpene-based resin (B) used in the sheet of the present invention is a hydrocarbon containing a chemical formula of isoprene (C5H8) as a main monomer component and oxygen-containing derivatives thereof, such as monoterpene (C10 compound), sesquiterpene (C15 It is a resin obtained by polymerizing compounds (terpene compounds) having a terpene as a basic skeleton such as diterpenes (C20 compounds) and diterpenes (C20 compounds).
Specifically, terpene resins that are homopolymers of terpene compounds, aromatic modified terpene resins obtained by copolymerizing terpene compounds and aromatic compounds, and terpene phenols that are copolymers of terpene compounds and phenolic compounds Resins, their fully hydrogenated resins, or partially hydrogenated resins and the like can be used. Among these, terpene resins and aromatic modified terpene resins are preferred because of their availability, low price, low odor, and the like. In addition, these may use 1 type and may use 2 or more types.
テルペン化合物としては、特に限定されないが、例えばα―ピネン、β―ピネン、カルボン、カンフェン、２－カレン、３－カレン、ジペンテン、ｄ―リモネン、ミルセン、アロオシメン、オシメン、α―フェランドレン、α―イオノン、β―イオノン、β―シトロネレン、α―テルピネン、γ―テルピネン、テルピノレン、１，８－シネオール、１，４－シネオール、β―シトロネロール、α―テルピネオール、β―テルピネオール、γ―テルピネオール等が挙げられる。これらは１種類を用いてもよいし、２種以上を用いてもよい。
これらのテルペン化合物は、何れも植物源または動物源であり天然で生合成され、再生可能な資源である。
Examples of terpene compounds include, but are not limited to, α-pinene, β-pinene, carvone, camphene, 2-carene, 3-carene, dipentene, d-limonene, myrcene, alloocimene, ocimene, α-phellandrene, α- ionone, β-ionone, β-citronellen, α-terpinene, γ-terpinene, terpinolene, 1,8-cineol, 1,4-cineol, β-citronellol, α-terpineol, β-terpineol, γ-terpineol, etc. be done. One type of these may be used, or two or more types may be used.
All of these terpene compounds are of plant or animal origin, are naturally biosynthesized, and are renewable resources.
テルペン化合物の単独重合体であるテルペン樹脂としては、α―ピネン樹脂、β―ピネン樹脂、ジペンテン樹脂などを例示できる。これらはバイオマス割合が１００％に近い樹脂であるので、昨今の環境意識の高まりによるサーキュラーエコノミーの観点において有効に用いることができる。 Examples of the terpene resin, which is a homopolymer of a terpene compound, include α-pinene resin, β-pinene resin, and dipentene resin. Since these resins have a biomass ratio close to 100%, they can be effectively used from the viewpoint of a circular economy due to recent heightened environmental awareness.
芳香族変性テルペン樹脂は、テルペン化合物と芳香族化合物との共重合体である。テルペン化合物と共重合可能な芳香族化合物としては、スチレン、α―メチルスチレン、アルキルスチレン、アルコキシスチレン、ビニルトルエン、不飽和炭化水素基含有スチレンなどのスチレン誘導体であるクマロン、インデンなどが挙げられる。これらは１種を単独で用いても、２種以上で用いても良い。
芳香族変性テルペン樹脂としては、α―ピネン－スチレン共重合体、ジペンテン－スチレン共重合体、β―ピネン－スチレン共重合体、α―ピネン－α―スチレン共重合体、リモネン－スチレン共重合体等のスチレン単量体との共重合体が好ましい。
芳香族変性テルペン樹脂の共重合質量組成比のテルペン化合物／芳香族化合物は、５／９５～９９／１が好ましく、２０／８０～９５／５がより好ましく、４０／６０～９５／５がさらに好ましい。芳香族変性テルペン樹脂のバイオマス割合を高めるには、バイオマス由来の芳香族化合物を用いる、及び／又はテルペン化合物の共重合組成比を高くするとよい。バイオマス割合（単位％）は、樹脂の乾燥総重量に対するバイオマス原料由来成分の乾燥重量の比により求まる。
これらの共重合体は、例えばテルペン化合物と芳香族化合物とを有機溶媒中に混合し、フリーデルクラフツ型触媒存在下で共重合して得ることができる。
An aromatic modified terpene resin is a copolymer of a terpene compound and an aromatic compound. Examples of aromatic compounds copolymerizable with terpene compounds include styrene derivatives such as styrene, α-methylstyrene, alkylstyrene, alkoxystyrene, vinyltoluene, and unsaturated hydrocarbon group-containing styrene, coumarone, and indene. These may be used individually by 1 type, or may be used in 2 or more types.
Examples of aromatic modified terpene resins include α-pinene-styrene copolymers, dipentene-styrene copolymers, β-pinene-styrene copolymers, α-pinene-α-styrene copolymers, and limonene-styrene copolymers. A copolymer with a styrene monomer such as
The terpene compound/aromatic compound in the copolymerization mass composition ratio of the aromatic modified terpene resin is preferably 5/95 to 99/1, more preferably 20/80 to 95/5, and further 40/60 to 95/5. preferable. In order to increase the biomass ratio of the aromatic modified terpene resin, it is preferable to use a biomass-derived aromatic compound and/or increase the copolymer composition ratio of the terpene compound. The biomass ratio (unit %) is determined by the ratio of the dry weight of the biomass raw material-derived component to the total dry weight of the resin.
These copolymers can be obtained, for example, by mixing a terpene compound and an aromatic compound in an organic solvent and copolymerizing them in the presence of a Friedel-Crafts type catalyst.
テルペン系樹脂（Ｂ）の重量平均分子量は、特に限定されないが、上限は６０００以下が好ましく、５０００以下がより好ましく、４０００以下が更に好ましい。下限は３００以上が好ましく、５００以上がより好ましく、７００以上が更に好ましい。分子量６０００以下によりスチレン系樹脂（Ａ）との相溶性が良好になり、またテルペン系樹脂（Ｂ）の軟化点が低くなり、シートの低温成形性が向上する。分子量３００以上により、シートの機械強度や耐熱性が十分となる。 The weight average molecular weight of the terpene resin (B) is not particularly limited, but the upper limit is preferably 6,000 or less, more preferably 5,000 or less, and even more preferably 4,000 or less. The lower limit is preferably 300 or higher, more preferably 500 or higher, even more preferably 700 or higher. When the molecular weight is 6000 or less, the compatibility with the styrene resin (A) is improved, and the softening point of the terpene resin (B) is lowered, thereby improving the low-temperature moldability of the sheet. With a molecular weight of 300 or more, the sheet has sufficient mechanical strength and heat resistance.
テルペン系樹脂（Ｂ）の軟化点は、６０℃以上１６０℃以下が好ましく、７０℃以上１５０℃以下がより好ましく、８０℃以上１４０℃以下が更に好ましい。６０℃以上により、シートに実用的な耐熱性を付与できる。１６０℃以下により、シートのビカット軟化温度およびガラス転移温度が低くなり、低温成形性を向上できる。テルペン系樹脂（Ｂ）の軟化点は、ＪＩＳ Ｋ５９０２：２００６に準じて測定される。 The softening point of the terpene-based resin (B) is preferably 60°C or higher and 160°C or lower, more preferably 70°C or higher and 150°C or lower, even more preferably 80°C or higher and 140°C or lower. A temperature of 60° C. or higher can impart practical heat resistance to the sheet. When the temperature is 160° C. or less, the Vicat softening temperature and glass transition temperature of the sheet are lowered, and low-temperature moldability can be improved. The softening point of the terpene resin (B) is measured according to JIS K5902:2006.
（シートの組成）
本発明のシートは、スチレン系樹脂（A）とテルペン系樹脂（Ｂ）とを混合することで、シートの低温成形性を発現させることができる。これは、テルペン系樹脂（Ｂ）のガラス転移温度や軟化点が分子量により制御し易いからである。また、芳香族変性テルペン樹脂、特にスチレン変性テルペン樹脂は、スチレン系樹脂（Ａ）との共通成分であるスチレンにより、スチレン系樹脂（Ａ）とテルペン系樹脂（Ｂ）との相溶性を調整できるので、両者の樹脂組成物からなるシートのガラス転移温度やビカット軟化温度の制御がし易いからである。
(Seat composition)
By mixing the styrene resin (A) and the terpene resin (B), the sheet of the present invention can exhibit low-temperature moldability of the sheet. This is because the glass transition temperature and softening point of the terpene resin (B) can be easily controlled by the molecular weight. In addition, the aromatic modified terpene resin, particularly the styrene modified terpene resin, can adjust the compatibility between the styrene resin (A) and the terpene resin (B) by styrene, which is a common component with the styrene resin (A). Therefore, it is easy to control the glass transition temperature and the Vicat softening temperature of the sheet composed of both resin compositions.
本発明のシートは、シートを１００．０質量％とする場合、スチレン系樹脂（Ａ）とテルペン系樹脂（Ｂ）との混合質量組成比は、５０．０～９９．０：１．０～５０．０である。テルペン系樹脂（Ｂ）の混合質量組成比が１．０質量％以上によりシートの低温成形性が向上し、５０．０質量％以下によりスチレン系樹脂（Ａ）との相溶性が良好となり、シート表面荒れ等が起き難くシート外観が向上する。
中でも、スチレン系樹脂（Ａ）とテルペン系樹脂（Ｂ）との混合質量組成比が８０．０～９９．０：１．０～２０．０であると、シートの無色透明性が高くなり、例えば容器の蓋などの成形品で内容物の視認性や美観を求められる包装体用途に好適となる。９０．０～９９．０：１．０～１０．０がより好ましく、９５．０～９９．０：１．０～５．０が更に好ましい。
また、スチレン系樹脂（Ａ）とテルペン系樹脂（Ｂ）との混合質量組成比が５０．０～８０．０：２０．０～５０．０であると、シートの白色度が増し文字や絵柄の印刷等が映えるため、意匠性の高いシートや底容器などの成形品からなる包装体用途に好適となる。５０．０～７０．０：３０．０～５０．０がより好ましい。
また、石油由来樹脂の使用量を低減させ、環境負荷の軽減させる観点では、バイオマス由来のテルペン系樹脂（Ｂ）の混合比が高いほど好ましい。例えば、シートのバイオマス度は、０．５％以上が好ましく、２．５％以上がより好ましい。なお、バイオマス度（単位％）は、製品の乾燥重量に対する、使用したバイオマスの乾燥重量の比から求まる。
In the sheet of the present invention, when the sheet is 100.0% by mass, the mixed mass composition ratio of the styrene resin (A) and the terpene resin (B) is 50.0 to 99.0: 1.0 to 50.0. When the mixed mass composition ratio of the terpene resin (B) is 1.0% by mass or more, the low-temperature moldability of the sheet is improved, and when it is 50.0% by mass or less, compatibility with the styrene resin (A) is improved, and the sheet Surface roughness and the like are less likely to occur, and the appearance of the sheet is improved.
Above all, when the mixing mass composition ratio of the styrene-based resin (A) and the terpene-based resin (B) is 80.0 to 99.0:1.0 to 20.0, the sheet has high colorless transparency, For example, molded products such as container lids are suitable for package applications where the visibility and beauty of the contents are required. 90.0 to 99.0: 1.0 to 10.0 is more preferred, and 95.0 to 99.0: 1.0 to 5.0 is even more preferred.
Further, when the mixing mass composition ratio of the styrene-based resin (A) and the terpene-based resin (B) is 50.0 to 80.0:20.0 to 50.0, the whiteness of the sheet increases and characters and patterns can be obtained. Since the printing etc. of , etc. shine, it is suitable for use as a package made of a molded product such as a highly designed sheet or a bottom container. 50.0-70.0: 30.0-50.0 is more preferred.
In addition, from the viewpoint of reducing the amount of petroleum-derived resin used and reducing the environmental load, it is preferable that the mixing ratio of the biomass-derived terpene-based resin (B) is as high as possible. For example, the biomass degree of the sheet is preferably 0.5% or more, more preferably 2.5% or more. The degree of biomass (unit: %) is determined from the ratio of the dry weight of biomass used to the dry weight of the product.
（耐衝撃性ポリスチレン系樹脂（Ｃ））
本発明のシートは、耐衝撃性ポリスチレン系樹脂（Ｃ）を含有することができる。耐衝撃性ポリスチレン系樹脂（Ｃ）の含有により、シートの耐ブロッキング性と耐衝撃性が向上する。耐衝撃性ポリスチレン樹脂（Ｃ）の含有率は、シートを１００．０質量％とした場合、０．１質量％以上５．０質量％以下が好ましく、０．５質量％以上４．０質量％以下がより好ましい。
(Impact-resistant polystyrene resin (C))
The sheet of the present invention can contain an impact-resistant polystyrene resin (C). The inclusion of the impact-resistant polystyrene resin (C) improves the blocking resistance and impact resistance of the sheet. The content of the impact-resistant polystyrene resin (C) is preferably 0.1% by mass or more and 5.0% by mass or less, and 0.5% by mass or more and 4.0% by mass, when the sheet is 100.0% by mass. The following are more preferred.
耐衝撃性ポリスチレン系樹脂（Ｃ）としては、ゴム等の成分が含まれるポリスチレン系樹脂であれば良く、スチレンの単独重合体中にゴム成分が含まれているもの等を好適に用いることができる。ゴム成分としては、例えば、ポリブタジエン、スチレン－ブタジエン共重合体、ポリイソプレン、ブタジエン－イソプレン共重合体などが挙げられる。ゴム成分は、マトリックス樹脂となるポリスチレン中に、独立してゴム成分が粒子状になって分散していているもの、あるいは、ポリスチレンにグラフト重合して粒子状に分散しているものであってもよい。 The impact-resistant polystyrene-based resin (C) may be any polystyrene-based resin containing a component such as rubber, and a styrene homopolymer containing a rubber component can be suitably used. . Examples of rubber components include polybutadiene, styrene-butadiene copolymers, polyisoprene, and butadiene-isoprene copolymers. The rubber component may be one in which the rubber component is dispersed in polystyrene as a matrix resin in the form of particles independently, or one in which the rubber component is dispersed in the form of particles by graft polymerization on polystyrene. good.
耐衝撃性ポリスチレン系樹脂（Ｃ）のゴム成分の含有率は、耐衝撃性と延伸成形性とを両立する観点から、耐衝撃性ポリススチレン系樹脂（Ｃ）を１００．０質量％とする場合、１．０質量％以上１５．０質量％以下が好ましく、３．０質量％以上１５．０質量％以下がより好ましく、５．０質量％以上１５．０質量％以下が更に好ましい。
ゴム成分の含有率は、一塩化ヨウ素、ヨウ化カリウムおよびチオ硫酸ナトリウム標準液を用いた電位差滴定でジエン含有量を測定し、ジエン含有量をゴム状重合体の含有量として計算される。測定方法は、例えば、日本分析化学会高分子分析研究懇談会編、「新版 高分子分析ハンドブック」、紀伊國屋書店（１９９５年度版）、Ｐ．６５９（３）ゴム含量に記載されている。
耐衝撃性ポリスチレン系樹脂（Ｃ）のＭＦＲは、１．５ｇ／１０分以上５．０ｇ／１０分以下が好ましく、２．０ｇ／１０分以上４．０ｇ／１０分以下がより好ましい。
The content of the rubber component in the impact-resistant polystyrene resin (C) is 100.0% by mass of the impact-resistant polystyrene resin (C) from the viewpoint of achieving both impact resistance and stretch moldability. , preferably 1.0% by mass or more and 15.0% by mass or less, more preferably 3.0% by mass or more and 15.0% by mass or less, and even more preferably 5.0% by mass or more and 15.0% by mass or less.
The content of the rubber component is calculated by measuring the diene content by potentiometric titration using iodine monochloride, potassium iodide and sodium thiosulfate standard solutions, and taking the diene content as the content of the rubbery polymer. The measurement method is described, for example, by the Japan Society for Analytical Chemistry, Polymer Analysis Research Council, "New Edition Polymer Analysis Handbook", Kinokuniya Shoten (1995 edition), p. 659(3) rubber content.
The MFR of the impact-resistant polystyrene resin (C) is preferably 1.5 g/10 minutes or more and 5.0 g/10 minutes or less, more preferably 2.0 g/10 minutes or more and 4.0 g/10 minutes or less.
（相溶化剤）
本発明のシートは、スチレン系樹脂（Ａ）とテルペン系樹脂（Ｂ）との相溶性を向上させ均質なシートを得るために、相溶化剤を用いてもよい。相溶化剤としては、スチレン系樹脂（Ａ）とテルペン系樹脂（Ｂ）との相溶効果が得られる成分であれば特に限定されないが、例えば、スチレン系熱可塑性エラストマーが挙げられ、具体例としてはスチレン－ブタジエン－スチレンブロック共重合体（ＳＢＳ）、スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン－エチレン－プロピレン－スチレンブロック共重合体（ＳＥＰＳ）、スチレン－ブタジエン－ブチレン－スチレンブロック共重合体（ＳＢＢＳ）、スチレン－イソプレン－スチレンブロック共重合体（ＳＩＳ）、スチレン－イソブチレン－スチレンブロック共重合体（ＳＩＢＳ）等が挙げられる。
相溶化剤の含有率は、シートを１００質量％とする場合、０～３０質量％が好ましく、１～２０質量％がより好ましく、２～１０質量％が更に好ましい。相溶化剤が３０質量％以下であることにより、スチレン系熱可塑性エラストマー中のエチレン、プロピレン、ブチレン、イソブチレン、ブタジエン、イソプレン等のゴム成分が、シート製膜工程や二次加工時に熱劣化し難く、シート外観、二軸延伸性、低温成形性が良好となる。
(Compatibilizer)
A compatibilizing agent may be used in the sheet of the present invention in order to improve compatibility between the styrene resin (A) and the terpene resin (B) and obtain a homogeneous sheet. The compatibilizer is not particularly limited as long as it is a component capable of obtaining a compatibility effect between the styrene resin (A) and the terpene resin (B). Specific examples thereof include styrene thermoplastic elastomers. is styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butadiene-butylene- Styrene block copolymer (SBBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene-styrene block copolymer (SIBS) and the like.
The content of the compatibilizer is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 10% by mass when the sheet is 100% by mass. When the content of the compatibilizing agent is 30% by mass or less, rubber components such as ethylene, propylene, butylene, isobutylene, butadiene, and isoprene in the styrene-based thermoplastic elastomer are less likely to be thermally deteriorated during the sheet film forming process and secondary processing. , sheet appearance, biaxial stretchability, and low temperature moldability are improved.
（他の成分）
本発明のシートは、本発明の効果を損ねない範囲で、上記した樹脂以外の他の樹脂や添加剤等の他の成分を含有することができる。
他の樹脂としては、ポリオレフィン系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、塩素化ポリエチレン系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリアセタール系樹脂、アクリル系樹脂、エチレン酢酸ビニル共重合体、ポリメチルペンテン系樹脂、ポリビニルアルコール系樹脂、環状オレフィン系樹脂、ポリ乳酸系樹脂、ポリブチレンサクシネート系樹脂、ポリアクリロニトリル系樹脂、ポリエチレンオキサイド系樹脂、セルロース系樹脂、ポリイミド系樹脂、ポリウレタン系樹脂、ポリフェニレンスルフィド系樹脂、ポリフェニレンエーテル系樹脂、ポリビニルアセタール系樹脂、ポリブタジエン系樹脂、ポリブテン系樹脂、ポリアミドイミド系樹脂、ポリアミドビスマレイミド系樹脂、ポリアリレート系樹脂、ポリエーテルイミド系樹脂、ポリエーテルエーテルケトン系樹脂、ポリエーテルケトン系樹脂、ポリエーテルスルホン系樹脂、ポリケトン系樹脂、ポリサルフォン系樹脂、アラミド系樹脂、フッ素系樹脂等が挙げられる。
また、シート製造工程で発生するシート耳のトリミングロス等を用いたリサイクル樹脂を含有することもできる。
(other ingredients)
The sheet of the present invention may contain other components such as resins other than the above-described resins and additives as long as the effects of the present invention are not impaired.
Other resins include polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, chlorinated polyethylene resins, polyester resins, polycarbonate resins, polyamide resins, polyacetal resins, acrylic resins, and ethylene acetate. Vinyl copolymer, polymethylpentene resin, polyvinyl alcohol resin, cyclic olefin resin, polylactic acid resin, polybutylene succinate resin, polyacrylonitrile resin, polyethylene oxide resin, cellulose resin, polyimide resin , polyurethane resins, polyphenylene sulfide resins, polyphenylene ether resins, polyvinyl acetal resins, polybutadiene resins, polybutene resins, polyamideimide resins, polyamide bismaleimide resins, polyarylate resins, polyetherimide resins, Examples include polyetheretherketone-based resins, polyetherketone-based resins, polyethersulfone-based resins, polyketone-based resins, polysulfone-based resins, aramid-based resins, fluorine-based resins, and the like.
Further, it is also possible to contain a recycled resin obtained by using trimming loss of sheet tabs generated in the sheet manufacturing process.
添加剤としては、加工助剤、溶融粘度改良剤、酸化防止剤、老化防止剤、熱安定剤、光安定剤、耐候性安定剤、紫外線吸収剤、中和剤、核剤、架橋剤、滑材、アンチブロッキング剤、鉱油、スリップ剤、防曇剤、抗菌剤、消臭剤、難燃剤、帯電防止剤、着色剤および顔料などが挙げられる。 Additives include processing aids, melt viscosity improvers, antioxidants, anti-aging agents, heat stabilizers, light stabilizers, weather stabilizers, ultraviolet absorbers, neutralizers, nucleating agents, cross-linking agents, lubricants, materials, anti-blocking agents, mineral oils, slip agents, anti-fogging agents, antimicrobial agents, deodorants, flame retardants, antistatic agents, colorants and pigments.
アンチブロッキング剤としては、無機粒子、有機粒子が挙げられる。無機粒子としては、例えばシリカ、ガラスビーズ等、及びそれらの表面に化学的処理を施したもの等が挙げられる。有機粒子としては、例えばポリスチレン、ポリメタクリル酸メチル等、及びそれらに熱処理、化学処理を施したもの等が挙げられる。中でも、化学的に安定であり、触媒作用によって樹脂を変性させないこと、後述のシート表面への離型剤シリコーンオイルの塗布性の点から、酸化珪素を主体成分とする球状シリカが好ましい。
アンチブロッキング剤のシート中の含有率は５０～５００ｐｐｍが好ましい。平均粒子径は１～２０μｍが好ましい。
Anti-blocking agents include inorganic particles and organic particles. Examples of inorganic particles include silica, glass beads, etc., and those whose surfaces have been chemically treated. Examples of organic particles include polystyrene, polymethyl methacrylate, and the like, and those obtained by subjecting them to heat treatment or chemical treatment. Among them, spherical silica containing silicon oxide as a main component is preferred because it is chemically stable, does not denature the resin by catalytic action, and is easy to apply a release agent silicone oil to the sheet surface, which will be described later.
The content of the antiblocking agent in the sheet is preferably 50-500 ppm. The average particle size is preferably 1-20 μm.
（防曇層、離型層）
本発明のシートは、表面に防曇剤、離型剤などを含む塗布液を塗布し乾燥して防曇層、離型層を設けることができる。シートの一方の面に防曇層、他方の面に離型層を設けると、蓋、容器などの包装体を成形、使用する際の離型性が良好となり、食品等の水分を含む内容物を収容した際の防曇性が良好となる。
防曇剤としては、公知の界面活性剤が使用可能で、ショ糖脂肪酸エステル、ポリグリセリン脂肪酸エステル等の多価アルコール脂肪酸エステルが好ましく、更にポリビニルアルコール、アクリルポリマー、ポリオキシエチレンポリオキシプロピレンブロック共重合体等の水溶性高分子および／またはメチルセルロース、シクロデキストリン等の多糖類混合物を加えるとシート表面における多価アルコール脂肪酸エステルの分散性や保持が良好になり防曇性向上の点で好ましい。
離型剤としては、シリコーンオイルが好ましく、安全性、離型性等の点から、アルキルポリシロキサンが好ましく、ポリジメチルシロキサンが特に好ましい。
防曇層、離型層の厚みは、特に制限されないが、それら性能を十分発現する点で、防曇層は２０～１００ｎｍ、離型層は１～５０ｎｍが好ましい。
(Anti-fogging layer, release layer)
The sheet of the present invention can be provided with an antifogging layer and a release layer by applying a coating liquid containing an antifogging agent, a release agent, etc. on the surface and drying it. By providing an anti-fogging layer on one side of the sheet and a release layer on the other side, the releasability is improved when packaging bodies such as lids and containers are molded and used. The antifogging property is improved when the is accommodated.
As the anti-fogging agent, known surfactants can be used, and polyhydric alcohol fatty acid esters such as sucrose fatty acid esters and polyglycerol fatty acid esters are preferable. Addition of a water-soluble polymer such as a polymer and/or a mixture of polysaccharides such as methylcellulose and cyclodextrin improves the dispersibility and retention of the polyhydric alcohol fatty acid ester on the surface of the sheet, which is preferable from the viewpoint of improving the antifogging property.
As the release agent, silicone oil is preferable, alkylpolysiloxane is preferable, and polydimethylsiloxane is particularly preferable from the viewpoints of safety and releasability.
The thicknesses of the antifogging layer and the release layer are not particularly limited, but the antifogging layer preferably has a thickness of 20 to 100 nm, and the release layer preferably has a thickness of 1 to 50 nm, in order to fully exhibit their properties.
（シートの製造方法）
本発明のポリスチレン系二軸延伸シートは、公知の方法によって製造できる。例えば、原材料を押出機で溶融混練してダイからシート状に押出し、冷却ロールや空冷、水冷にて冷却固化して未延伸シートを作製し、次いで、縦方向及び横方向に延伸処理し、二軸延伸シートを得ることできる。
(Manufacturing method of sheet)
The polystyrene-based biaxially oriented sheet of the present invention can be produced by a known method. For example, raw materials are melted and kneaded in an extruder, extruded into a sheet from a die, cooled and solidified by cooling rolls, air cooling, or water cooling to produce an unstretched sheet, then stretched in the longitudinal direction and the transverse direction, An axially stretched sheet can be obtained.
未延伸シートの製造方法の詳細例としては、シートを構成する原材料を混合した後、単軸押出機、異方向二軸押出機、同方向二軸押出機などの押出機を使用し、組成物の均一な分散分配を促す。原材料は、タンブラーミキサー、ミキシングロール、バンバリーミキサー、リボンブレンダ―、スーパーミキサーなどの混合機で混合した後、押出機に投入してもよいし、または、他の混練機の先端にストランドダイを接続し、ストランドカット、ダイカットなどの方法により一旦ペレット化した後、得られたペレットを押出機に投入してもよい。
次いで、押出機により溶融された樹脂組成物を、押出機の先端にＴダイなどの口金を接続し、シート状に成型した後、冷却ロールで冷却固化する。押出温度は、１８０～２６０℃程度が好ましく、１９０～２５０℃がより好ましい。
As a detailed example of the method for producing an unstretched sheet, after mixing the raw materials that make up the sheet, using an extruder such as a single screw extruder, a counter-rotating twin-screw extruder, or a co-rotating twin screw extruder, the composition Promotes uniform distribution of Raw materials may be mixed in a mixer such as a tumbler mixer, mixing roll, Banbury mixer, ribbon blender, super mixer, etc., and then fed into an extruder, or a strand die may be connected to the tip of another mixer. Alternatively, after pelletizing by a method such as strand cutting or die cutting, the obtained pellets may be fed into an extruder.
Next, the resin composition melted by the extruder is connected to a mouthpiece such as a T-die at the tip of the extruder, molded into a sheet, and then cooled and solidified by cooling rolls. The extrusion temperature is preferably about 180 to 260°C, more preferably 190 to 250°C.
未延伸シートの延伸方法の詳細例としては、シートの流れ方向（縦方向、ＭＤ）へのロール延伸や、シートの流れ方向に対して垂直方向（横方向、ＴＤ）へのテンター延伸等により、二軸延伸することが好ましい。また、縦方向に延伸後、横方向に延伸してもよいし、横方向に延伸後、縦方向に延伸してもよい。また、縦方向及び横方向に延伸処理されていれば、同じ方向に２回以上延伸してもよい。さらには、縦方向に延伸後、横方向に延伸し、さらに縦方向に延伸してもよい。また、同時二軸延伸機により縦方向、横方向に同時に延伸されてもよい。さらには、未延伸シートを裁断し、バッチ式の延伸機により二軸延伸してもよい。 As a detailed example of the stretching method of the unstretched sheet, roll stretching in the sheet flow direction (longitudinal direction, MD), tenter stretching in the direction perpendicular to the sheet flow direction (transverse direction, TD), etc. Biaxial stretching is preferred. Further, after stretching in the longitudinal direction, the film may be stretched in the horizontal direction, or after stretching in the horizontal direction, it may be stretched in the vertical direction. In addition, as long as the film is stretched in the longitudinal direction and the transverse direction, it may be stretched twice or more in the same direction. Furthermore, after stretching in the longitudinal direction, the film may be stretched in the transverse direction and then further stretched in the longitudinal direction. Alternatively, the film may be stretched simultaneously in the machine direction and the transverse direction by a simultaneous biaxial stretching machine. Furthermore, an unstretched sheet may be cut and biaxially stretched by a batch-type stretching machine.
二軸延伸シートの延伸倍率は、シートの縦方向、横方向共に１．１倍以上４．０倍以下が好ましく、１．５倍以上３．０倍以下がより好ましく、２．０倍以上２．５倍以下が更に好ましい。延伸倍率１．１倍以上により、シートを成形加工した成形品が十分な衝撃強度を有し、４．０倍以下により、シートを熱成形する際の賦形性、型再現性が良好となる。
本発明における延伸倍率は、二軸延伸シートの試験片に直線を記して熱収縮させ、その直線長さの収縮前後の変化率から求められる。具体的には、［延伸倍率＝Ｙ／Ｚ］の式によって算出される値であり、この式において、Ｙは、二軸延伸シートの試験片に定規および筆記用具を用いてシート縦方向および横方向に描いた直線の長さ（ｍｍ）であり、Ｚは、ＪＩＳ Ｋ７２０６に準拠して測定した当該シートのビカット軟化温度より４０℃高い温度のシリコンオイルバスに試験片を１０分間浸漬させ収縮させた後の直線の長さ（ｍｍ）である。
The draw ratio of the biaxially stretched sheet is preferably 1.1 times or more and 4.0 times or less in both the longitudinal direction and the transverse direction of the sheet, more preferably 1.5 times or more and 3.0 times or less, and 2.0 times or more2. 0.5 times or less is more preferable. When the draw ratio is 1.1 times or more, the molded article formed by molding the sheet has sufficient impact strength, and when it is 4.0 times or less, the shapeability and mold reproducibility when thermoforming the sheet are improved. .
The draw ratio in the present invention is obtained by drawing a straight line on a test piece of a biaxially stretched sheet, heat shrinking the straight line, and calculating the rate of change in the length of the straight line before and after shrinkage. Specifically, it is a value calculated by the formula [stretch ratio = Y / Z], in which Y is a test piece of a biaxially stretched sheet with a ruler and a writing utensil. The length (mm) of the straight line drawn in the direction, Z is the test piece was immersed in a silicone oil bath at a temperature 40 ° C higher than the Vicat softening temperature of the sheet measured in accordance with JIS K7206 for 10 minutes and contracted. is the length (mm) of the straight line after
（シートの厚み）
本発明のシートの厚みは、０．０５ｍｍ以上０．５０ｍｍ以下である。係る範囲において、包装体等の成形品を作製する二次加工工程における取り扱い容易性や、成形品の強度が良好となり、０．１０ｍｍ以上０．４０ｍｍ以下が好ましく、０．１５ｍｍ以上０．３ｍｍ以下がより好ましい。０．０５ｍｍ以上により、成形品が十分な機械的強度を有し、０．５０ｍｍ以下により、二次加工成形し易い。
(sheet thickness)
The thickness of the sheet of the present invention is 0.05 mm or more and 0.50 mm or less. In such a range, the ease of handling in the secondary processing step of producing a molded product such as a package and the strength of the molded product are improved, and the thickness is preferably 0.10 mm or more and 0.40 mm or less, and 0.15 mm or more and 0.3 mm or less. is more preferred. With a thickness of 0.05 mm or more, the molded article has sufficient mechanical strength, and with a thickness of 0.50 mm or less, it is easy to perform secondary processing.
（シートの物性）
・透明性
本発明のシートを、例えば容器の蓋などの成形品で内容物の視認性や美観を求められる包装体に用いる場合は、シートの透明性が高いほど良い。
シートの高透明性としては、例えば、シート厚みが０．１８ｍｍの場合に、ヘイズ１５．０％以下が好ましく、ヘイズ１０．０％以下がより好ましく、５．０％以下がさらに好ましく、２．０％以下が特に好ましい。全光線透過率は８０％以上が好ましく、８４％以上がより好ましく、９０％以上が更に好ましい。
他方、シートのバイオマス度を高めるためにテルペン系樹脂（Ｂ）の混合組成比を増大させる場合、薄肉成形品の強度を強めるために耐衝撃性ポリスチレン系樹脂（Ｃ）の混合組成比を増大させる場合、シートを構成する樹脂の相溶性向上のために相溶化剤を含有する場合は、シートの白色度が高くなり易い。これらの場合は、文字や絵柄の印刷等が映える意匠性の高いシートや底容器等の包装体に好適に使用することができる。ヘイズは、例えば、シート厚みが０．１８ｍｍの場合に、１０．０％超７０．０％以下となりやすく、１５．０％以上５０．０％以下となりやすく、シートの機械的強度、耐熱性と両立する点から、１５．０％以上３０．０％以下が好ましい。
ヘイズは、ＪＩＳ Ｋ７１３６：２０００に準拠して測定でき、全光線透過率に対する拡散透過率の比である。全光線透過率は、ＪＩＳ Ｋ７３６１－１：１９９７に準拠して測定できる。
(Physical properties of sheet)
- Transparency When the sheet of the present invention is used for a package, such as a container lid, which requires good visibility and beauty of the contents, the transparency of the sheet is preferably as high as possible.
As for the high transparency of the sheet, for example, when the sheet thickness is 0.18 mm, the haze is preferably 15.0% or less, more preferably 10.0% or less, and further preferably 5.0% or less. 0% or less is particularly preferable. The total light transmittance is preferably 80% or higher, more preferably 84% or higher, even more preferably 90% or higher.
On the other hand, when the mixed composition ratio of the terpene resin (B) is increased in order to increase the biomass degree of the sheet, the mixed composition ratio of the impact-resistant polystyrene resin (C) is increased in order to increase the strength of the thin molded product. In this case, if a compatibilizer is included to improve the compatibility of the resin constituting the sheet, the whiteness of the sheet tends to increase. In these cases, it can be suitably used for a highly designed sheet on which printed characters and patterns can be printed, and for packages such as bottom containers. For example, when the sheet thickness is 0.18 mm, the haze tends to be more than 10.0% and 70.0% or less, and tends to be 15.0% or more and 50.0% or less. From the viewpoint of compatibility, the content is preferably 15.0% or more and 30.0% or less.
Haze can be measured according to JIS K7136:2000, and is the ratio of diffuse transmittance to total light transmittance. Total light transmittance can be measured according to JIS K7361-1:1997.
・ビカット軟化温度、ガラス転移温度
本発明のシートは、テルペン系樹脂（Ｂ）の含有によりビカット軟化温度、ガラス転移温度が低くなり、市場で流通しているホモポリスチレンからなる二軸延伸シートに比べ低温成形性に優れる。
ビカット軟化温度の上限は、シートの低温成形性の点から、１００℃未満が好ましく、９９℃以下がより好ましく、９８℃以下が更に好ましい。下限は、実用的な耐熱性の点から、７５℃以上が好ましく、８０℃以上がより好ましく、８５℃以上がさらに好ましい。
ガラス転移温度の上限は、シートの低温成形性の点から、１００℃未満が好ましく、９９℃以下がより好ましい。下限は、実用的な耐熱性の点から、８０℃以上が好ましく、８５℃以上がより好ましい。
ビカット軟化温度は、ＪＩＳ Ｋ７２０６：２０１６に準拠して測定できる。
ガラス転移温度は、ＪＩＳ Ｋ７１２１：２０１２に基づき、示差走査熱量分析装置を用い、１０℃／分で再昇温した際のガラス転移温度で求まる。
ビカット軟化温度とガラス転移温度の測定対象物は、シートを構成する樹脂組成物、未延伸シート、二軸延伸シートの加熱収縮物の何れでもよい。
- Vicat softening temperature and glass transition temperature The sheet of the present invention has a lower Vicat softening temperature and glass transition temperature due to the inclusion of the terpene resin (B), and is compared to commercially available biaxially oriented homopolystyrene sheets. Excellent low temperature moldability.
The upper limit of the Vicat softening temperature is preferably less than 100° C., more preferably 99° C. or less, and even more preferably 98° C. or less, from the viewpoint of low-temperature moldability of the sheet. From the viewpoint of practical heat resistance, the lower limit is preferably 75°C or higher, more preferably 80°C or higher, and even more preferably 85°C or higher.
The upper limit of the glass transition temperature is preferably less than 100°C, more preferably 99°C or less, from the viewpoint of low-temperature moldability of the sheet. From the viewpoint of practical heat resistance, the lower limit is preferably 80°C or higher, more preferably 85°C or higher.
The Vicat softening temperature can be measured according to JIS K7206:2016.
The glass transition temperature is obtained by reheating at 10° C./min using a differential scanning calorimeter based on JIS K7121:2012.
The object to be measured for the Vicat softening temperature and the glass transition temperature may be a resin composition constituting a sheet, an unstretched sheet, or a heat-shrink product of a biaxially stretched sheet.
・粘弾性
本発明のシートは、動的粘弾性測定装置を用い振動周波数１０Ｈｚ条件で測定した１００℃における損失正接（ｔａｎδ）が０．１５以上であり、０．２０以上が好ましい。損失正接（ｔａｎδ）の上限は０．８０以下であり、０．７０以下が好ましく、０．６０以下がより好ましい。
損失正接（ｔａｎδ）は、貯蔵弾性率（Ｅ’) に対する損失弾性率（Ｅ”）の比、すなわち損失正接（ｔａｎδ＝Ｅ”／Ｅ’）である。損失正接（ｔａｎδ）が高いと、その温度領域では、材料の損失弾性率（Ｅ”）、すなわち粘性の寄与率が大きいことを意味する。
本発明のシートは低温成形性に優れるものであるが、ポリスチレン系二軸延伸シートの一般的な成形温度は１００℃～１４０℃前後であることから、粘弾性の温度指標を１００℃とすることで、損失正接（ｔａｎδ）の大小からシートの熱成形性を考察できる。損失正接（ｔａｎδ）が０．１５以上により、シートを加熱して包装体に成形する時にシートが適度に変形するため成形性が向上する。損失正接（ｔａｎδ）が０．８０以下により、シートを包装体に加熱成形する時のシートの変形が大きくなり過ぎず、破れや厚みムラなどの成形不良が生じ難い。
損失正接（ｔａｎδ）は、一般的には材料のガラス転移温度、分子構造、分子配向などで制御される。本発明では、ガラス転移温度の低いテルペン系樹脂（Ｂ）の混合組成比を好適化にすることで、シートの損失正接（ｔａｎδ）を所望の範囲に調整できる。具体的には、テルペン系樹脂（B）の混合量を増やすことで、ガラス転移温度が低温側にシフトし損失正接を大きくすることができる。このとき、テルペン系樹脂（B）の混合量は上述した１．０～５０．０％の範囲が好適である。
Viscoelasticity The sheet of the present invention has a loss tangent (tan δ) at 100° C. measured at a vibration frequency of 10 Hz using a dynamic viscoelasticity measuring device of 0.15 or more, preferably 0.20 or more. The upper limit of the loss tangent (tan δ) is 0.80 or less, preferably 0.70 or less, and more preferably 0.60 or less.
Loss tangent (tan .delta.) is the ratio of loss modulus (E'') to storage modulus (E'), or loss tangent (tan .delta.=E''/E'). A high loss tangent (tan δ) means that the loss elastic modulus (E″) of the material, that is, the contribution of viscosity, is large in that temperature range.
The sheet of the present invention is excellent in low-temperature moldability, but since the general molding temperature of polystyrene-based biaxially oriented sheets is around 100°C to 140°C, the temperature index of viscoelasticity should be 100°C. , the thermoformability of the sheet can be considered from the magnitude of the loss tangent (tan δ). When the loss tangent (tan δ) is 0.15 or more, the sheet is appropriately deformed when the sheet is heated and molded into a package, so that the moldability is improved. When the loss tangent (tan δ) is 0.80 or less, deformation of the sheet is not excessively increased when the sheet is heat-formed into a package, and forming defects such as tearing and thickness unevenness are less likely to occur.
The loss tangent (tan δ) is generally controlled by the glass transition temperature, molecular structure, molecular orientation, etc. of the material. In the present invention, by optimizing the mixing composition ratio of the terpene resin (B) having a low glass transition temperature, the loss tangent (tan δ) of the sheet can be adjusted within a desired range. Specifically, by increasing the mixed amount of the terpene-based resin (B), the glass transition temperature can be shifted to the low temperature side, and the loss tangent can be increased. At this time, the mixing amount of the terpene-based resin (B) is preferably in the above-mentioned range of 1.0 to 50.0%.
・配向緩和応力
本発明のシートは、縦方向と横方向の配向緩和応力が共に０．１ＭＰａ以上１．２ＭＰａ以下であり、０．２ＭＰａ以上１．０ＭＰａ以下が好ましく、０．３ＭＰａ以上０．８ＭＰａ以下がより好ましい。
０．１ＭＰａ以上により、シートおよび成形品、包装体の耐衝撃性が向上して割れ難く、破れ難くなり、また、シートを熱板加熱式圧空成形等で熱成形する際に、金型外周の枠部分で裂ける等の成形不良が発生し難くなる。１．２ＭＰａ以下により、熱成形時の賦形性、型再現性が良好となる。
また、シートの縦方向と横方向の物性の異方性による熱成形時の不良を少なくする観点から、配向緩和応力の縦方向と横方向との絶対値差は０．６ＭＰａ以下が好ましく、０．４ＭＰａ以下がより好ましく、０．１ＭＰａ以下が更に好ましい。
シートの配向緩和応力は、二軸延伸によって樹脂の分子を配向させることによって有する物性であり、縦延伸温度、横延伸温度を下げて延伸すると縦方向、横方向の配向緩和応力が増大し、縦延伸温度、横延伸温度を上げて延伸すると縦方向、横方向の配向緩和応力が低減する。縦方向と横方向の配向緩和応力を共に０．１ＭＰａ以上１．２ＭＰａ以下にするには、縦延伸温度を１００～１３０℃、縦延伸倍率を１．１～４．０倍、横延伸温度を１００～１４０℃、横延伸倍率を１．１～４．０倍にするとよい。
シートの配向緩和応力は、ＡＳＴＭ Ｄ １５０４に準拠し、１５ｍｍ幅の試験片をシートのビカット軟化温度より３０℃高い温度のシリコンオイルバス中に浸漬させた際に発生する収縮応力の最大値を測定して求まる。
- Orientation Relaxation Stress In the sheet of the present invention, the orientation relaxation stress in both the longitudinal direction and the transverse direction is 0.1 MPa or more and 1.2 MPa or less, preferably 0.2 MPa or more and 1.0 MPa or less, and 0.3 MPa or more and 0.8 MPa. The following are more preferred.
At 0.1 MPa or more, the impact resistance of the sheet, molded product, and package is improved, making it difficult to crack and tear. Molding defects such as tearing at the frame portion are less likely to occur. When the pressure is 1.2 MPa or less, good shapeability and mold reproducibility during thermoforming are obtained.
In addition, from the viewpoint of reducing defects during thermoforming due to anisotropy of physical properties in the longitudinal direction and the lateral direction of the sheet, the difference in absolute value of the orientation relaxation stress in the longitudinal direction and the lateral direction is preferably 0.6 MPa or less, and 0 4 MPa or less is more preferable, and 0.1 MPa or less is even more preferable.
The orientation relaxation stress of a sheet is a physical property obtained by orienting resin molecules by biaxial stretching. When the stretching temperature and the transverse stretching temperature are raised and the film is stretched, the orientation relaxation stress in the longitudinal direction and the transverse direction is reduced. In order to make the orientation relaxation stress in both the longitudinal direction and the transverse direction 0.1 MPa or more and 1.2 MPa or less, the longitudinal stretching temperature is 100 to 130 ° C., the longitudinal stretching ratio is 1.1 to 4.0 times, and the transverse stretching temperature is It is preferable to set the temperature to 100 to 140° C. and the transverse stretching ratio to 1.1 to 4.0 times.
The orientation relaxation stress of the sheet conforms to ASTM D 1504, and measures the maximum shrinkage stress generated when a 15 mm wide test piece is immersed in a silicone oil bath at a temperature 30°C higher than the Vicat softening temperature of the sheet. and found.
・耐衝撃性
本発明のシートは、二次加工時のシートの割れや、包装体の取り扱い時の割れや破れを起こり難くする観点から、耐衝撃性として、ＪＩＳ Ｋ７１２４－２：１９９９に準拠して測定される最大衝撃点エネルギーが０．５Ｊ以上であることが好ましく、０．７Ｊ以上がより好ましい。
・Impact resistance The sheet of the present invention conforms to JIS K7124-2: 1999 as impact resistance from the viewpoint of preventing cracking of the sheet during secondary processing and cracking and tearing during handling of the package. It is preferable that the maximum impact point energy as measured by 1 is 0.5 J or more, more preferably 0.7 J or more.
・引張弾性率
本発明のシートは、ＪＩＳ Ｋ７１６１－１：２０１４に準拠して雰囲気温度２３℃で測定される引張弾性率が２．０GＰａ以上であることが好ましく、２．２GＰａ以上がより好ましく、２．５GＰａ以上がさらに好ましい。上限は、特に制限されないが、一般に６．０GＰａ以下である。引張弾性率が２．０ＧＰａ以上であれば、シートや包装体の剛性が十分高く、特にシート厚みを薄くした場合でも、外力に対する変形が抑制され好適である。
Tensile modulus The sheet of the present invention preferably has a tensile modulus of 2.0 GPa or more, more preferably 2.2 GPa or more, measured at an ambient temperature of 23° C. in accordance with JIS K7161-1:2014. 2.5 GPa or more is more preferable. Although the upper limit is not particularly limited, it is generally 6.0 GPa or less. If the tensile modulus is 2.0 GPa or more, the rigidity of the sheet or package is sufficiently high, and deformation against external force is suppressed even when the sheet thickness is reduced, which is preferable.
＜包装体＞
本発明のシートは、成形加工して包装体に利用できる。
包装体は、各種用途に応じた形状に成形して用いられる。例えば、用途は、生鮮、総菜、乾物、菓子などの食品や工業部品を収容する包装体であり、形状は、箱型底容器、コップ、皿、トレイ、蓋つき容器、蓋などが挙げられる。
本発明のシートは、公知の方法で成形できる。例えば、熱板接触加熱成形法、圧空成形法、真空成形法、真空圧空成形法、プラグアシスト成形法、等である。中でも、成形品の厚みの均等性、成形生産効率の観点から、熱板接触加熱成形法が好ましい。シートの成形加工は、シートロールを用いて連続的に行っても良いし、カット版シートを用い１ショット毎に成形しても良い。
<Package>
The sheet of the present invention can be molded and used as a package.
The package is used after being molded into a shape suitable for various uses. For example, it is used as a package for housing foods such as fresh foods, side dishes, dried foods, confectionery, and industrial parts, and its shape includes box-bottom containers, cups, plates, trays, containers with lids, lids, and the like.
The sheet of the present invention can be molded by known methods. For example, hot plate contact heating molding method, pressure molding method, vacuum molding method, vacuum pressure molding method, plug assist molding method, and the like. Among them, the hot plate contact heating molding method is preferable from the viewpoint of the uniformity of the thickness of the molded product and the efficiency of molding production. The sheet forming process may be performed continuously using a sheet roll, or may be formed for each shot using a cut plate sheet.
熱板接触加熱成形法の場合、熱板温度条件は、低温成形性の観点からシートのビカット軟化温度＋１０℃～＋３０℃が好ましく、上限は＋２０℃以下がより好ましく、＋１５℃以下が更に好ましい。金型形状が複雑な場合や深い場合は、ビカット軟化温度＋１６℃～＋２０℃とするとよい。シートの低温成形性の観点からより熱板温度条件は十分な賦形性が得られる範囲で低いほど好ましい。熱板温度条件をビカット軟化温度＋３０℃以下とすることにより、成形サイクル時間の短時間化と成形品のレインドロップの発生抑制を両立し易い。
上述の各種成形法の加熱時間条件は、０．５～１０．０秒が好ましく、０．５秒～５．０秒がより好ましい。なお、加熱時間とは、シートを真空及び／又は圧空で熱板に接触させている時間と、次いでシートを金型へ延展するために所望の真空及び／又は圧空状態になるまでの遅れ時間の合計を云う。
In the case of the hot plate contact heating molding method, the hot plate temperature condition is preferably the Vicat softening temperature of the sheet +10 ° C. to +30 ° C. from the viewpoint of low temperature moldability, the upper limit is more preferably +20 ° C. or less, and +15 ° C. or less. If the shape of the mold is complex or deep, the Vicat softening temperature should be +16°C to +20°C. From the viewpoint of the low-temperature formability of the sheet, the lower the temperature of the hot plate, the better, as long as sufficient formability can be obtained. By setting the hot plate temperature condition to Vicat softening temperature +30° C. or less, it is easy to achieve both shortening of the molding cycle time and suppression of the occurrence of rain drops in the molded product.
The heating time conditions for the various molding methods described above are preferably 0.5 to 10.0 seconds, more preferably 0.5 to 5.0 seconds. The heating time is the time during which the sheet is brought into contact with the hot plate in vacuum and/or compressed air, and the delay time until the desired vacuum and/or compressed air state is reached in order to spread the sheet to the mold. Say the total.
以下、実施例により本発明を詳しく説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。
＜原材料＞
実施例比較例に用いた原材料の成分、物性、略号は、以下の通りである。
なお、スチレン系樹脂（Ａ）、耐衝撃性ポリスチレン系樹脂（Ｃ）のメルトフローレート（ＭＦＲ）はＪＩＳ Ｋ７２１０－１：２０１４に準じ、温度２００℃、荷重５ｋｇｆの条件で測定された値である。相溶化剤のＭＦＲは、ＪＩＳ Ｋ７２１０－１：２０１４に準じ、温度２３０℃、荷重２．１６ｋｇｆの条件で測定された値である。
テルペン樹脂（Ｂ）の軟化点は、ＪＩＳ Ｋ５９０２：２００６に準じて測定された値である。
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
<Raw materials>
The ingredients, physical properties, and abbreviations of the raw materials used in Examples and Comparative Examples are as follows.
The melt flow rate (MFR) of the styrene resin (A) and the impact-resistant polystyrene resin (C) is a value measured according to JIS K7210-1:2014 under conditions of a temperature of 200°C and a load of 5 kgf. . The MFR of the compatibilizer is a value measured under conditions of a temperature of 230° C. and a load of 2.16 kgf according to JIS K7210-1:2014.
The softening point of the terpene resin (B) is a value measured according to JIS K5902:2006.
（スチレン系樹脂（A））
Ａ－１； スチレン単独重合体、ＭＦＲ３．５ｇ／１０分
（テルペン系樹脂（B））
Ｂ－１； 芳香族変性テルペン樹脂、ヤスハラケミカル社製ＹＳレジンＴＯ１２５、軟化点１２５℃、バイオマス割合７０％、重量平均分子量１５００
Ｂ－２； β―ピネン樹脂、軟化点１１５℃、バイオマス割合９０％、重量平均分子量３４００
(Styrene resin (A))
A-1; Styrene homopolymer, MFR 3.5 g/10 min (terpene resin (B))
B-1; aromatic modified terpene resin, YS resin TO125 manufactured by Yasuhara Chemical Co., softening point 125 ° C., biomass ratio 70%, weight average molecular weight 1500
B-2; β-pinene resin, softening point 115° C., biomass ratio 90%, weight average molecular weight 3400
（耐衝撃性ポリスチレン系樹脂（C））
Ｃ－１； スチレン－ポリブタジエンゴムグラフト共重合体、ポリブタジエンゴム含有率９．０質量％、ＭＦＲ３．０ｇ／１０分
（相溶化剤）；
Ｄ－１； スチレン－エチレン－ブチレン－スチレンブロック共重合体（ＳＥＢＳ）、スチレン含有比率６７質量％、ＭＦＲ２．０ｇ／１０分
(Impact-resistant polystyrene resin (C))
C-1; Styrene-polybutadiene rubber graft copolymer, polybutadiene rubber content 9.0% by mass, MFR 3.0 g/10 min (compatibilizer);
D-1; Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene content ratio 67% by mass, MFR 2.0 g/10 min
＜実施例１～８、比較例１＞
表１に示すシート組成の原材料を単軸押出機に投入し、設定温度２００℃で溶融混練した後、単軸押出機の先端に接続したＴダイにてシート状に押出し、設定温度１００℃のキャスティングロールに引き取り、冷却固化させて未延伸シートを得た。その後、得られた未延伸シートを表１に示す延伸温度で同時二軸延伸機を用い、縦方向２．５倍、横方向２．５倍の延伸処理を行い、二軸延伸シートを得た。
シートのバイオマス度は、シートの質量を１００％としたときの、テルペン系樹脂（Ｂ）の混合質量組成比にテルペン系樹脂（Ｂ）のバイオマス割合を乗じて算出し、表１に記した。
<Examples 1 to 8, Comparative Example 1>
The raw materials of the sheet composition shown in Table 1 are put into a single screw extruder, melt-kneaded at a set temperature of 200 ° C., then extruded into a sheet with a T die connected to the tip of the single screw extruder, and set at a temperature of 100 ° C. It was taken up by casting rolls and solidified by cooling to obtain an unstretched sheet. Thereafter, the obtained unstretched sheet was stretched 2.5 times in the machine direction and 2.5 times in the transverse direction using a simultaneous biaxial stretching machine at the stretching temperature shown in Table 1 to obtain a biaxially stretched sheet. .
The biomass degree of the sheet was calculated by multiplying the mixed mass composition ratio of the terpene-based resin (B) by the biomass ratio of the terpene-based resin (B) when the mass of the sheet was 100%, and is shown in Table 1.
＜評価＞
実施例、比較例で得られたシートについて、以下の評価を行い表１に纏めた。
（１）シート厚み
二軸延伸シートについて、ＪＩＳ Ｋ７１３０：１９９９に準拠して、スタンドタイプ定圧厚さ測定器にて測定した。
（２）シート外観
二軸延伸シートから、縦方向２５０ｍｍ、横方向２５０ｍｍの試験片を５枚切り出し、ゲル異物や未溶融ブツ、メヤニなど外観不良の欠点数を数え、試験片５枚の合計数を以下の基準で評価した。
良 ：欠点数が3個未満
可 ：欠点数が３個以上8個未満
不可：欠点数が8個以上
（３）透明性（ヘイズ、全光線透過率）
二軸延伸シートについて、日本電色工業株式会社製ヘイズメーターＮＤＨ－５０００を用いて、ＪＩＳ Ｋ７１３６：２０００に準拠してヘイズを、ＪＩＳ Ｋ７３６１：１９９７に準拠して全光線透過率を測定した。
<Evaluation>
The sheets obtained in Examples and Comparative Examples were evaluated as follows and summarized in Table 1.
(1) Sheet Thickness A biaxially stretched sheet was measured using a stand-type constant pressure thickness gauge in accordance with JIS K7130:1999.
(2) Sheet appearance From the biaxially stretched sheet, 5 test pieces of 250 mm in the vertical direction and 250 mm in the horizontal direction are cut out, and the number of defects such as gel foreign matter, unmelted spots, and resin deposits is counted, and the total number of 5 test pieces. was evaluated according to the following criteria.
Good: Less than 3 defects Acceptable: 3 to 8 defects Poor: 8 or more defects (3) Transparency (haze, total light transmittance)
The biaxially stretched sheet was measured for haze according to JIS K7136:2000 and total light transmittance according to JIS K7361:1997 using a haze meter NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd.
（４）ビカット軟化温度
二軸延伸する前の未延伸シートを用いて、ＪＩＳ Ｋ７２０６：２０１６に準拠して測定した。
（５）ガラス転移温度
ＪＩＳ Ｋ７１２１：２０１２に基づき、パーキンエルマー製ＤＳＣ８５００を用いて、二軸延伸シート約１０ｍｇを昇温速度１０℃／分で０℃から２００℃まで昇温し、２００℃で１分間保持した後、降温速度１０℃／分で０℃まで降温し、再度、昇温速度１０℃／分で２００℃まで昇温し、再昇温時のガラス転移温度を分析した。
(4) Vicat softening temperature Measured according to JIS K7206:2016 using an unstretched sheet before biaxially stretching.
(5) Glass transition temperature Based on JIS K7121:2012, using a PerkinElmer DSC8500, about 10 mg of a biaxially oriented sheet is heated from 0 ° C. to 200 ° C. at a heating rate of 10 ° C./min, and 1 at 200 ° C. After holding for 1 minute, the temperature was lowered to 0° C. at a rate of temperature drop of 10° C./min, and the temperature was raised again to 200° C. at a rate of temperature rise of 10° C./min, and the glass transition temperature at the time of reheating was analyzed.
（５）粘弾性
二軸延伸シートの幅方向について、ＪＩＳ Ｋ７２４４：１９９９に基づき、動的粘弾性測定装置を用いて、振動周波数１０Ｈｚ、ひずみ０．１％の条件で、－１００℃から２００℃まで昇温した時の粘弾性カーブを測定し、１００℃と１１５℃における貯蔵弾性率（Ｅ’）および損失正接（ｔａｎδ）を求めた。また、損失正接（ｔａｎδ）がピークを示す温度を損失正接（ｔａｎδ）のピーク温度とした。
（６）配向緩和応力
二軸延伸シートを用い、縦方向に平行に幅１５ｍｍ、長さ約１２０ｍｍの試験片と、横方向に平行に幅１５ｍｍ、長さ約１２０ｍｍの試験片をそれぞれ切り出し、各試験片についてＡＳＴＭ Ｄ－１５０４に準拠し、シートのビカット軟化温度より３０℃高い温度のシリコンオイルバス中で収縮応力を測定し、その際の最大値を配向緩和応力とした。
(5) Viscoelasticity Regarding the width direction of the biaxially stretched sheet, using a dynamic viscoelasticity measuring device based on JIS K7244: 1999, under the conditions of a vibration frequency of 10 Hz and a strain of 0.1%, -100 ° C. to 200 ° C. The viscoelastic curve was measured when the temperature was raised to 100° C. and the storage elastic modulus (E′) and loss tangent (tan δ) at 100° C. and 115° C. were determined. The temperature at which the loss tangent (tan δ) peaked was taken as the peak temperature of the loss tangent (tan δ).
(6) Orientation Relaxation Stress Using a biaxially oriented sheet, cut out a test piece with a width of 15 mm and a length of about 120 mm parallel to the machine direction and a test piece with a width of 15 mm and a length of about 120 mm in the horizontal direction. According to ASTM D-1504, the contraction stress of the test piece was measured in a silicon oil bath at a temperature 30° C. higher than the Vicat softening temperature of the sheet, and the maximum value at that time was taken as the orientation relaxation stress.
（７）引張弾性率
二軸延伸シートについて、縦方向に幅１０ｍｍ、長さ１００ｍｍの試験片を３本切り出し、ＪＩＳ Ｋ７１６１－１：２０１４に準拠して、引張試験機を用い、雰囲気温度２３℃、引張速度５ｍｍ／分の条件で測定し、３本の測定値の平均を算出した。
（８）引張破断伸度
二軸延伸シートについて、ＪＩＳ Ｋ７１２７：１９９９に準拠し、シートの縦方向、横方向に各５本ずつ計１０本のダンベル状試験片（試験片タイプ５、狭い平行部の幅６ｍｍ）を切断刃で打ち抜き、狭い平行部に標線間距離２５ｍｍで標線を記し、チャック間初期距離８０ｍｍ、測定雰囲気温度２３℃、試験速度２００ｍｍ／ｍｉｎの条件で、引張試験を行い、１０本の引張破断伸度の平均値を算出した。
（９）耐衝撃性（面衝撃強度）
二軸延伸シートについて、ＪＩＳ Ｋ７１２４－２：１９９９に準拠し、１００ｍｍ×１００ｍｍの試験片５枚を切断刃にて打ち抜き、測定雰囲気温度２３℃において、衝撃速度３．０ｍ／秒の条件で衝撃試験を行い、５枚の面衝撃強度（最大衝撃点エネルギー）の平均値を算出した。
(7) Tensile modulus For the biaxially stretched sheet, cut out three test pieces with a width of 10 mm and a length of 100 mm in the longitudinal direction, and use a tensile tester in accordance with JIS K7161-1: 2014, at an ambient temperature of 23 ° C. , and the tensile speed was 5 mm/min, and the average of the three measured values was calculated.
(8) Tensile elongation at break Regarding the biaxially stretched sheet, in accordance with JIS K7127: 1999, a total of 10 dumbbell-shaped test pieces (specimen type 5, narrow parallel part (width 6 mm) is punched out with a cutting blade, a gauge line is marked on the narrow parallel part with a gauge distance of 25 mm, and a tensile test is performed under the conditions of an initial chuck distance of 80 mm, a measurement atmosphere temperature of 23 ° C, and a test speed of 200 mm / min. , the average value of the tensile elongation at break of 10 pieces was calculated.
(9) Impact resistance (surface impact strength)
Regarding the biaxially stretched sheet, according to JIS K7124-2: 1999, five test pieces of 100 mm × 100 mm were punched out with a cutting blade, and an impact test was performed under the conditions of an impact speed of 3.0 m / sec at a measurement atmosphere temperature of 23 ° C. was performed, and the average value of the plane impact strength (maximum impact point energy) of the five sheets was calculated.
（１０）低温成形性
二軸延伸シートを用い、縦方向２５０ｍｍ、横方向２５０ｍｍの正方形の試験片を切り出し、関西自動成形機社製、熱板加熱式圧空成形機ＰＫ－４５０型に、評価用金型を取り付け、加熱時間２．０秒、加熱圧力１．０ｋｇ／ｃｍ２、成形時間１．０秒、成形圧力３．０ｋｇ／ｃｍ２、金型温度６０℃の条件で、熱板温度条件を変化させて、試験片に対して成形試験を行い、成形されたシートを観察し、型の再現忠実性（型再現性）を評価した。
熱板温度条件は、８８℃～１０８℃の間の４℃毎の温度と、１１６℃、１２４℃である。
成形試験に用いた評価用金型は、長辺２００ｍｍ、短辺１５０ｍｍの長方形で、長辺はシート縦方向に平行に合わせ、短辺はシート横方向に平行に合わせる。長方形内に、開口幅１０ｍｍ、長さ５０～７０ｍｍの溝が、縦方向、横方向に各１０本あり、１０本は、溝の開口幅に対する最大深さで表される絞り比が０．３から１．２まで、０．１刻みに異なるものである。絞り比が大きいほど型再現性の難度が高く、試験片１枚につき、縦方向と横方向のそれぞれの型再現性の良好な最大絞り比が求められる。型再現性は、成形されたシートの溝を凹と表現すると、シートを反転させて溝（凹）を上向き（凸）にして照明を当てて観察し、溝の深さに相当する凸の高さが溝の全長に亘って均一であるか否かの良否を調べ、良評価の溝の絞り比で最大のものを最大絞り比とした。
評価は、先ず、熱板温度条件ごとに試験片２枚を成形し、２枚の各縦方向、横方向の最大絞り比、計４点を求め平均値を算出する。次に、横軸に熱板温度、縦軸に最大絞り比をとったグラフに、各熱板温度条件の最大絞り比平均値をプロットし、２次関数近似曲線を用いて最大絞り比が０．６となる熱板温度を読み取る。この温度が低いほど、低温成形性が優れていると評価できる。なお、縦方向、横方向の最大絞り比、計４点全てが０．３未満の場合と、成形したシートのレインドロップが酷い場合は、グラフにプロットしない。
(10) Low temperature moldability Using a biaxially oriented sheet, cut out a square test piece of 250 mm in the vertical direction and 250 mm in the horizontal direction, and use a hot plate heating type pressure molding machine PK-450 manufactured by Kansai Automatic Molding Machine Co., Ltd. for evaluation. The mold was attached, and the heating time was 2.0 seconds, the heating pressure was 1.0 kg/cm 2 , the molding time was 1.0 seconds, the molding pressure was 3.0 kg/cm 2 , and the mold temperature was 60°C. A molding test was carried out on the test piece by changing , the molded sheet was observed, and the mold reproducibility (mold reproducibility) was evaluated.
Hot plate temperature conditions are between 88°C and 108°C in 4°C increments and 116°C and 124°C.
The mold for evaluation used in the molding test was a rectangle with long sides of 200 mm and short sides of 150 mm. In the rectangle, there are 10 grooves with an opening width of 10 mm and a length of 50 to 70 mm in the vertical direction and the horizontal direction. to 1.2 in steps of 0.1. The higher the drawing ratio, the more difficult the mold reproducibility becomes, and the maximum drawing ratio with good mold reproducibility in both the vertical and horizontal directions is required for each test piece. If the grooves of the molded sheet are expressed as concave, the mold reproducibility is measured by turning the sheet over so that the grooves (concave) face upward (convex) and observing under illumination. The quality of the uniformity over the entire length of the sag groove was examined, and the maximum drawing ratio of the grooves evaluated as good was taken as the maximum drawing ratio.
For the evaluation, first, two test pieces were molded for each hot plate temperature condition, and the maximum drawing ratios of the two sheets in each of the vertical and horizontal directions were obtained, and the average value was calculated. Next, the maximum drawing ratio average value for each hot plate temperature condition is plotted on a graph with the hot plate temperature on the horizontal axis and the maximum drawing ratio on the vertical axis, and the maximum drawing ratio is 0 using a quadratic function approximation curve. Read the hot plate temperature to be .6. It can be evaluated that the lower this temperature, the better the low-temperature moldability. If the maximum drawing ratio in the vertical direction and the horizontal direction is less than 0.3 in total for all four points, and if the raindrop of the formed sheet is severe, it is not plotted on the graph.
表１より、実施例１～８のシートは、テルペン系樹脂（Ｂ）を含有することにより、ビカット軟化温度、ガラス転移温度が比較例１よりも低下し、低温成形性に優れた。これは、テルペン系樹脂を含有し、かつ配向緩和応力を１．２ＭＰａ以下となるように延伸した結果、１００℃における損失正接（ｔａｎδ）が０．１５以上と高くなり、熱成形時にシートが容易に変形するようになったためである。また、ゲル状物やメヤニなどが少なく、シート外観はいずれも良好であった。
実施例１、２、３、５、７は、ヘイズ１０．０％以下であり、食品用包装体として好適な透明性を示した。
From Table 1, the sheets of Examples 1 to 8 had a lower Vicat softening temperature and a glass transition temperature than those of Comparative Example 1 due to the inclusion of the terpene resin (B), and were excellent in low-temperature moldability. As a result of containing a terpene resin and being stretched so that the orientation relaxation stress is 1.2 MPa or less, the loss tangent (tan δ) at 100 ° C. is as high as 0.15 or more, and the sheet can be easily formed during thermoforming. This is because it began to transform into In addition, the appearance of the sheet was good with little gel-like matter and die build-up.
Examples 1, 2, 3, 5, and 7 had a haze of 10.0% or less, exhibiting transparency suitable for food packaging.
本発明のポリスチレン系二軸延伸シートは、外観不良が発生し難いので、生産歩留まりが良好で経済効率が良く、また低温成形が可能であるので、成形加工のエネルギーを低減できる。
更に、バイオマス由来のテルペン原料を用いた樹脂を使用することからも、環境負荷の低減に大いに役立つ。
Since the polystyrene-based biaxially oriented sheet of the present invention hardly causes poor appearance, the production yield is good and economic efficiency is good, and low-temperature molding is possible, so that the energy for molding can be reduced.
Furthermore, the use of a resin using a biomass-derived terpene raw material also greatly contributes to the reduction of the environmental load.
Claims (5)
シート厚みが０．０５ｍｍ以上０．５０ｍｍ以下であり、かつ
シート縦方向と横方向の配向緩和応力が共に０．１ＭＰａ以上１．２ＭＰａ以下であり、
１００℃の損失正接が０．１５以上０．８０以下である
ことを特徴とするポリスチレン系二軸延伸シート。 A sheet containing 50.0 to 99.0% by mass of styrene resin (A) and 1.0 to 50.0% by mass of terpene resin (B),
The sheet thickness is 0.05 mm or more and 0.50 mm or less, and the orientation relaxation stress in both the longitudinal direction and the transverse direction of the sheet is 0.1 MPa or more and 1.2 MPa or less,
A polystyrene-based biaxially oriented sheet having a loss tangent at 100°C of 0.15 or more and 0.80 or less.
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