JP2003301077A - Polyolefinic resin composition having biodegradability and sheet-shaped product having biodegradability - Google Patents
Polyolefinic resin composition having biodegradability and sheet-shaped product having biodegradabilityInfo
- Publication number
- JP2003301077A JP2003301077A JP2002109069A JP2002109069A JP2003301077A JP 2003301077 A JP2003301077 A JP 2003301077A JP 2002109069 A JP2002109069 A JP 2002109069A JP 2002109069 A JP2002109069 A JP 2002109069A JP 2003301077 A JP2003301077 A JP 2003301077A
- Authority
- JP
- Japan
- Prior art keywords
- component
- sheet
- resin composition
- polyolefin
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 36
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 28
- 239000000057 synthetic resin Substances 0.000 claims abstract description 28
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 14
- 239000004793 Polystyrene Substances 0.000 claims abstract description 11
- 229920002223 polystyrene Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 29
- 239000004626 polylactic acid Substances 0.000 claims description 29
- 229920005672 polyolefin resin Polymers 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004310 lactic acid Substances 0.000 abstract description 3
- 235000014655 lactic acid Nutrition 0.000 abstract description 3
- 238000005096 rolling process Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 229920006167 biodegradable resin Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 102100033007 Carbonic anhydrase 14 Human genes 0.000 description 2
- 101000867862 Homo sapiens Carbonic anhydrase 14 Proteins 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 101100316860 Autographa californica nuclear polyhedrosis virus DA18 gene Proteins 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000111 poly(butyric acid) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、土中や海水中等の
微生物により分解される合成樹脂およびそれからなるシ
ート状物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin which is decomposed by microorganisms in soil, seawater and the like, and a sheet-like product made of the synthetic resin.
【０００２】[0002]
【従来の技術】マルチシートをはじめとする農業・工業
用途シート状物は一般に安価であることが求められ、主
としてポリエチレン、ポリプロピレンなどのオレフィン
系樹脂を原料として生産されている。2. Description of the Related Art Sheet materials for agricultural and industrial use such as multi-sheets are generally required to be inexpensive and are mainly produced from olefin resins such as polyethylene and polypropylene as raw materials.
【０００３】しかしながら、これら農業・工業用シート
状物の回収・再生は、たとえば、様々な汚れ（たとえば
マルチシートの場合には泥などが付着する）のため、な
かなか捗っていないのが現状であり、廃棄により環境汚
染等様々な問題を引き起こすおそれがある。However, the current situation is that the recovery and regeneration of these agricultural and industrial sheet materials is not progressing due to various stains (for example, mud adheres in the case of multi-sheet). Yes, there is a risk that disposal will cause various problems such as environmental pollution.
【０００４】ここで、ポリ乳酸、ポリ酪酸等の生分解性
を有する樹脂を原料とすることにより、回収・再生を行
わず廃棄しても環境汚染等の問題を引きおこさない方法
が考えられる。しかし、これら生分解性を有する樹脂か
らなるシート状物は樹脂自体が高価であるためなかなか
その普及が進まない。Here, it is conceivable to use a biodegradable resin such as polylactic acid or polybutyric acid as a raw material so as not to cause problems such as environmental pollution even if the resin is discarded without being recovered or regenerated. However, the sheet-like material made of these biodegradable resins is not popular because the resin itself is expensive.
【０００５】ここで、本発明者等は安価な、ポリエチレ
ン、ポリプロピレン、及び、エチレン系共重合体、プロ
ピレン系共重合体、ポリオレフィン系熱可塑性エラスト
マーなどのポリオレフィン系樹脂をベースとしながら
も、生分解が可能なポリオレフィン系樹脂組成物に関す
る検討を行った。Here, the present inventors have made biodegradable products based on inexpensive polyolefin resins such as polyethylene, polypropylene, and ethylene copolymers, propylene copolymers, and thermoplastic polyolefin elastomers. A study was conducted on a polyolefin-based resin composition capable of achieving the above.
【０００６】生分解性成分として比較的安価で入手しや
すいポリ乳酸系生分解性合成樹脂を用い、ポリオレフィ
ン系重合体を配合したところ、充分な生分解性が得られ
ることが確認された。しかし、これらの樹脂組成物をシ
ート状またはフィルム状に加工する検討を行ったとこ
ろ、樹脂組成物を混合するロールの表面に樹脂成分が付
着して、その結果、混練ができず均一な樹脂組成物とな
らなかったり、あるいは、樹脂組成物自体は作製できた
ものの、平滑なシートあるいはフィルムを安定的に得る
ことができない場合があることが判った。It was confirmed that when a polylactic acid-based biodegradable synthetic resin, which is relatively inexpensive and easily available, was used as the biodegradable component and a polyolefin polymer was blended, sufficient biodegradability was obtained. However, as a result of studying processing of these resin compositions into a sheet shape or a film shape, the resin component adheres to the surface of the roll for mixing the resin composition, and as a result, a uniform resin composition cannot be kneaded. It has been found that there are cases in which a smooth sheet or film cannot be obtained in a stable manner, although it may not be obtained, or the resin composition itself can be produced.
【０００７】そして、本発明者等は、検討の結果、ロー
ル表面への樹脂成分の付着は、ポリ乳酸系生分解性合成
樹脂成分の吸湿、及び、ポリオレフィン系重合体との組
み合わせに原因があることを見出した。As a result of the study by the present inventors, the adhesion of the resin component to the roll surface is caused by the moisture absorption of the polylactic acid-based biodegradable synthetic resin component and the combination with the polyolefin-based polymer. I found that.
【０００８】ポリ乳酸系生分解性樹脂成分はトウモロコ
シ等のでんぷんから得られる乳酸を原料とした合成樹脂
成分であるが、非常に吸湿性が高く、さらに、ポリオレ
フィン系重合体との相溶性が低いために、ポリ乳酸系生
分解性樹脂成分を水分がある状態でポリオレフィン系重
合体と混合してフィルム化、あるいは、シート化しよう
とするとロールの表面にこのポリ乳酸系生分解性樹脂成
分が付着することが判り、ポリ乳酸系生分解性樹脂成分
に水分がある状態でも安定してフィルム化、あるいは、
シート化できる方法について詳細に検討し、本発明に至
った。The polylactic acid-based biodegradable resin component is a synthetic resin component prepared from lactic acid obtained from starch such as corn, but has a very high hygroscopicity and a low compatibility with the polyolefin-based polymer. For this reason, when a polylactic acid-based biodegradable resin component is mixed with a polyolefin-based polymer in the presence of water to form a film or sheet, the polylactic acid-based biodegradable resin component adheres to the roll surface. It is found that the polylactic acid-based biodegradable resin component is stably formed into a film even when water is present, or
The present invention has been accomplished by studying in detail the method of forming a sheet.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、上記した従
来の問題点を改善する、すなわち、ロールによるシート
あるいはフィルム（本発明においてこれらを併せて「シ
ート状物」と云う）への加工に際して、ロール表面への
樹脂成分の付着が生ぜず、安定して生産できる生分解性
を有するポリオレフィン系樹脂組成物及び表面が平滑で
かつ安価な生分解性を有するポリオレフィン系樹脂組成
物、及び、生分解性を有するシート状物を提供すること
を目的とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, namely, in processing a sheet or film by a roll (these are collectively referred to as "sheet-like material" in the present invention). , A polyolefin-based resin composition having biodegradability capable of stable production without adhesion of a resin component to the roll surface, a polyolefin-based resin composition having a smooth surface and inexpensive biodegradability, and a raw material An object is to provide a sheet-like material having degradability.
【００１０】[0010]
【課題を解決するための手段】すなわち、本発明の樹脂
組成物は、請求項１に記載の通り、ベース成分としてポ
リオレフィン系樹脂、ａ成分としてポリ乳酸系合成樹脂
成分、及び、ｂ成分として酢酸ビニル・エチレン共重合
体、アクリル変成されたポリテトラフルオロエチレン及
びポリスチレン系共重合体から選ばれた１種以上を含む
ことを特徴とするポリオレフィン系樹脂組成物である。That is, the resin composition of the present invention has a polyolefin resin as a base component, a polylactic acid synthetic resin component as an a component, and an acetic acid as a b component, as described in claim 1. A polyolefin-based resin composition comprising one or more selected from vinyl-ethylene copolymer, acrylic modified polytetrafluoroethylene, and polystyrene-based copolymer.
【００１１】このような構成の樹脂組成物を用いること
により、安価でありながら充分な生分解性を有し、か
つ、原料に多少水分が含まれた状態であっても平滑な表
面を持つシート状物を得ることができる。By using the resin composition having such a structure, it is inexpensive and has sufficient biodegradability and has a smooth surface even when the raw material contains a little water. A substance can be obtained.
【００１２】さらに、上記樹脂組成物において、ベース
成分、ａ成分及びｂ成分の含有比は請求項２に記載のよ
うに、ポリマー成分合計量を１００として上記ａ成分の
ポリ乳酸系合成樹脂成分の含有量を１０重量％以上と
し、かつ、ｂ成分の酢酸ビニル・エチレン共重合体の含
有量を０．５重量％以上とするか、または、請求項３に
記載のように、ポリマー成分合計量を１００として上記
ａ成分のポリ乳酸系合成樹脂成分の含有量を１０重量％
以上とし、かつ、ｂ成分のアクリル変成されたポリテト
ラフルオロエチレンの含有量を０．５重量％以上とする
か、あるいは、請求項４に記載のように、ポリマー成分
合計量を１００として上記ａ成分のポリ乳酸系合成樹脂
成分の含有量を１０重量％以上とし、かつ、ｂ成分のポ
リスチレン系共重合体の含有量を５重量％以上とするこ
とにより、より容易に生産性良く安定したシート生産が
可能となる。Further, in the above resin composition, the content ratio of the base component, the component a and the component b is, as described in claim 2, with the total amount of the polymer components being 100, of the polylactic acid type synthetic resin component of the component a. The content is 10% by weight or more and the content of the vinyl acetate / ethylene copolymer of the component b is 0.5% by weight or more, or the total amount of the polymer components is as described in claim 3. And the content of the polylactic acid-based synthetic resin component of the component a is 10% by weight.
And the content of the acrylic modified polytetrafluoroethylene of the component b is 0.5% by weight or more, or the total amount of the polymer components is 100 as described in claim 4, and A stable and easy-to-produce sheet with a polylactic acid-based synthetic resin component content of 10 wt% or more and a polystyrene copolymer content of b component of 5 wt% or more Production becomes possible.
【００１３】[0013]
【発明の実施の形態】本発明のポリオレフィン系樹脂組
成物においてベースとなる樹脂成分は、ポリエチレン、
ポリプロピレン、及び、エチレン系共重合体（エチレン
ユニットが主（８０％程度以上）のもの）、プロピレン
系共重合体、ポリオレフィン系熱可塑性エラストマーな
どのポリオレフィン系重合体の１種、あるいは２種以上
であることが必要である。BEST MODE FOR CARRYING OUT THE INVENTION The resin component serving as a base in the polyolefin resin composition of the present invention is polyethylene,
One or more of polypropylene and an ethylene-based copolymer (having an ethylene unit (mainly about 80% or more)), a propylene-based copolymer, or a polyolefin-based thermoplastic elastomer or other polyolefin-based polymer. It is necessary to be.
【００１４】これらポリオレフィン系重合体をベース樹
脂成分とすることにより、安価、軽量なシートあるいは
フィルムを得ることができ、かつ、万一焼却処理しても
ハロゲン、ダイオキシン等の有害ガスが発生しない。By using these polyolefin polymers as the base resin component, an inexpensive and lightweight sheet or film can be obtained, and no harmful gas such as halogen or dioxin is generated even if incinerated.
【００１５】本発明のポリオレフィン系樹脂組成物は、
ベース成分としてポリオレフィン系樹脂を含み、これに
ａ成分としてポリ乳酸系合成樹脂成分、及び、ｂ成分と
して酢酸ビニル・エチレン共重合体、アクリル変成され
たポリテトラフルオロエチレン又はポリスチレン系共重
合体からなる群より選ばれた１種以上を含むものであ
る。The polyolefin resin composition of the present invention is
Containing a polyolefin resin as a base component, a polylactic acid-based synthetic resin component as a component, and a vinyl acetate / ethylene copolymer, an acryl-modified polytetrafluoroethylene or polystyrene copolymer as a b component. It includes at least one selected from the group.
【００１６】ここで、ポリ乳酸系合成樹脂成分はトウモ
ロコシ等のでんぷんから得られる乳酸を原料とした合成
樹脂であり、市販されているものである。Here, the polylactic acid-based synthetic resin component is a synthetic resin obtained from lactic acid obtained from starch such as corn as a raw material, and is commercially available.
【００１７】ポリ乳酸系合成樹脂成分はポリオレフィン
系重合体、ポリ乳酸系合成樹脂成分及び酢酸ビニル・エ
チレン共重合体または／及びアクリル変成されたポリテ
トラフルオロエチレン等のポリマー成分の合計量を１０
０とした場合に、そのうち１０重量％以上とすることが
好ましい。The polylactic acid-based synthetic resin component is the total amount of the polyolefin polymer, the polylactic acid-based synthetic resin component and the vinyl acetate / ethylene copolymer or / and the polymer component such as acryl-modified polytetrafluoroethylene as 10 parts.
When it is set to 0, it is preferably 10% by weight or more.
【００１８】ポリ乳酸系合成樹脂成分の含有量が１０重
量％以上であると充分な生分解性を得ることができ、あ
るいは、分解までに必要な期間が短縮できる。ポリ乳酸
系合成樹脂成分の含有量は好ましくは１０重量％以上７
５重量％以下である。しかし、本発明の趣旨からポリ乳
酸系合成樹脂成分の含有量は３０重量％以下であれば充
分であり、コスト面でも有利である。When the content of the polylactic acid-based synthetic resin component is 10% by weight or more, sufficient biodegradability can be obtained, or the period required for decomposition can be shortened. The content of the polylactic acid-based synthetic resin component is preferably 10% by weight or more 7
It is 5% by weight or less. However, for the purpose of the present invention, it is sufficient if the content of the polylactic acid-based synthetic resin component is 30% by weight or less, which is advantageous in terms of cost.
【００１９】ポリ乳酸系合成樹脂成分は吸湿性が高く、
開封後放置により２０００重量％程度、吸湿する場合が
あるが、本発明においてはその特有の構成により、２０
００重量％程度までの吸湿であれば、その水分を予め乾
燥することなく配合して用いることができる。The polylactic acid-based synthetic resin component has high hygroscopicity,
Although it may absorb about 2000% by weight of moisture when left unopened after being opened, in the present invention, due to its unique structure,
If the moisture absorption is up to about 00% by weight, the moisture can be blended and used without being dried in advance.
【００２０】一方、酢酸ビニル・エチレン共重合体を添
加する際には、ポリマー成分の合計量を１００として好
ましくは０．５重量％含有するように添加する。このよ
うに極めて少量の添加でも充分な効果が得られるので、
コストへの影響は極めて小さい。酢酸ビニル・エチレン
共重合体の含有量が０．５重量％以上であるとポリ乳酸
系合成樹脂成分中の残留水分による影響が小さくなり、
フィルム化、シート化時のロールへの付着防止効果が高
くなり、良品の安定生産が可能となるからである。On the other hand, when the vinyl acetate-ethylene copolymer is added, the total amount of the polymer components is 100, and preferably 0.5 wt% is added. In this way, even if added in an extremely small amount, a sufficient effect can be obtained,
The impact on cost is extremely small. When the content of the vinyl acetate / ethylene copolymer is 0.5% by weight or more, the influence of the residual water in the polylactic acid-based synthetic resin component becomes small,
This is because the effect of preventing adherence to rolls when forming a film or sheet becomes high, and stable production of non-defective products becomes possible.
【００２１】酢酸ビニル・エチレン共重合体の含有量
は、通常５０重量％以下とすることが望ましい。５０重
量％以下がコスト的に有利で、またロールへの粘着など
の問題が特におこりにくいからである。The content of the vinyl acetate / ethylene copolymer is usually preferably 50% by weight or less. This is because 50% by weight or less is advantageous in terms of cost, and problems such as sticking to rolls are particularly unlikely to occur.
【００２２】本発明で用いる酢酸ビニル・エチレン共重
合体（「ＶＡＥ」とも云う）は酢酸ビニルとエチレンと
からなる共重合体であるが、エチレン系共重合体である
一般的なエチレン−酢酸ビニル共重合体（酢酸ビニルユ
ニットは通常１５％以上２０重量％以下）とは異なり、
酢酸ビニルユニット含有量がエチレンユニット含有量に
対して相対的に多いもの（酢酸ビニルユニット含有率は
５５％以上、通常７０％以下）である。このような酢酸
ビニル・エチレン共重合体の例として、日本合成化学工
業製ソアブレンＢＨ、ＣＨ、ＣＩ及び大日本インキ化学
工業製エバスレン４１０−Ｐ、４２０−Ｐ、４５０−
Ｐ、３５０−Ｐ、３１０−Ｐなどが挙げられる。The vinyl acetate / ethylene copolymer (also referred to as "VAE") used in the present invention is a copolymer composed of vinyl acetate and ethylene, and is a general ethylene-vinyl acetate which is an ethylene-based copolymer. Unlike the copolymer (vinyl acetate unit is usually 15% to 20% by weight),
The vinyl acetate unit content is relatively large relative to the ethylene unit content (vinyl acetate unit content is 55% or more, usually 70% or less). Examples of such vinyl acetate / ethylene copolymers include Soaburen BH, CH and CI manufactured by Nippon Synthetic Chemical Industry and Ebaslene 410-P, 420-P and 450-manufactured by Dainippon Ink and Chemicals.
P, 350-P, 310-P and the like.
【００２３】また、アクリル変成されたポリテトラフル
オロエチレンを添加する際にはポリマー成分の合計量を
１００として０．５重量％以上含有するように添加する
ことが望ましい。このように極めて少量の添加でも充分
な効果が得られるので、コストへの影響は極めて小さ
い。アクリル変成されたポリテトラフルオロエチレンの
含有量が０．５重量％以上であるとポリ乳酸系合成樹脂
成分中の残留水分による影響が小さくなり、フィルム
化、シート化時のロールへの付着が起きにくく、良品の
安定生産が可能となるからである。When the acrylic modified polytetrafluoroethylene is added, it is desirable to add it in an amount of 0.5% by weight or more based on 100 as the total amount of the polymer components. As described above, a sufficient effect can be obtained even with the addition of an extremely small amount, so that the influence on the cost is extremely small. When the content of polytetrafluoroethylene modified with acrylic acid is 0.5% by weight or more, the influence of residual water content in the polylactic acid-based synthetic resin component becomes small, and adhesion to the roll occurs when forming a film or sheet. This is because it is difficult and stable production of good products is possible.
【００２４】アクリル変成されたポリテトラフルオロエ
チレンの含有量は通常２０重量％以下とすることが望ま
しい。２０重量％以下がコスト的に有利だからである。
ここでアクリル変成されたポリテトラフルオロエチレン
は、三菱レイヨン等から入手できる。It is desirable that the content of polytetrafluoroethylene modified with acrylic resin is usually 20% by weight or less. This is because 20% by weight or less is advantageous in terms of cost.
The polytetrafluoroethylene that has been acrylic modified here can be obtained from Mitsubishi Rayon or the like.
【００２５】一方、ポリスチレン系共重合体は、ハード
セグメントとしてのソフトスチレンにソフトセグメント
としてのビニルポリイソプレンとが結合した共重合体
（ＳＩＳ）で、例えばクラレからハイブラー７１２５な
どとして入手可能である。On the other hand, the polystyrene-based copolymer is a copolymer (SIS) in which soft styrene as a hard segment and vinyl polyisoprene as a soft segment are bound to each other, and it is available from Kuraray Co., Ltd. as Hybler 7125 or the like.
【００２６】また、ソフトセグメントとしてポリ（エチ
レン−プロピレン）が結合したポリスチレン系共重合体
（ＳＥＰＳ）なども用いることができ、このようなポリ
スチレン系共重合体は、クラレからセプトン２０６３、
２００７、１００１、１０５０、１０４等として入手可
能である。なお、ポリスチレン系共重合体としては上記
のものを２種以上混合して用いることもできる。Further, a polystyrene-based copolymer (SEPS) having poly (ethylene-propylene) bonded as a soft segment can also be used. Such a polystyrene-based copolymer can be obtained from Kuraray to Septon 2063,
It is available as 2007, 1001, 1050, 104, etc. The polystyrene-based copolymer may be a mixture of two or more of the above.
【００２７】これらポリオレフィン系重合体、ａ成分及
びｂ成分は、ニーダー、バンバリーミキサー等により均
一になるよう混練、混合され、本発明のポリオレフィン
系樹脂組成物を得ることができるが、この樹脂組成物は
必要に応じて押し出し成形等によりペレットとすること
ができる。The polyolefin-based polymer, the component a and the component b are kneaded and mixed uniformly by a kneader, Banbury mixer or the like to obtain the polyolefin-based resin composition of the present invention. Can be formed into pellets by extrusion molding or the like, if necessary.
【００２８】本発明のポリオレフィン系樹脂組成物に
は、上記ポリオレフィン系重合体、ａ成分及びｂ成分か
らなる基本樹脂組成物以外に、その混練時、あるいはフ
ィルム化加工、シート化加工などの際に、本発明の効果
を大きく損なわない限りにおいて、酸化防止剤、滑剤等
を適宜添加することができる。The polyolefin-based resin composition of the present invention contains, in addition to the basic resin composition comprising the above-mentioned polyolefin-based polymer, the components a and b, during kneading, film forming, sheet forming, etc. As long as the effects of the present invention are not significantly impaired, antioxidants, lubricants and the like can be added as appropriate.
【００２９】このようにして得られたポリオレフィン系
樹脂組成物を用いて、Ｔダイ押出成形、カレンダー加工
などにより、フィルム化、シート化して本発明のシート
状物を得ることができる。The polyolefin resin composition thus obtained can be formed into a film or sheet by T-die extrusion molding, calendering or the like to obtain the sheet-like product of the present invention.
【００３０】[0030]
【実施例】以下に本発明のポリオレフィン系樹脂組成物
およびそれよりなるシート状物について具体的に説明す
る。表１に示す原料を用い、表２〜５に示す含有率（重
量比）となるよう８インチテストロールを用いて混練し
て、本発明のポリオレフィン系樹脂組成物を製造すると
同時に、厚さ０．２ｍｍのシートを作製した。EXAMPLES The polyolefin resin composition of the present invention and the sheet-like material comprising the same will be specifically described below. Using the raw materials shown in Table 1, kneading was carried out using an 8-inch test roll so that the contents (weight ratio) shown in Tables 2 to 5 were obtained to produce the polyolefin resin composition of the present invention, and at the same time, the thickness was 0. A 2 mm sheet was prepared.
【００３１】なお、ポリ乳酸系合成樹脂成分は通常アル
ミシート内装袋付紙袋の荷姿で入手されるが、同一種類
のものを、開封直後に使用した場合（表２〜５における
「＊１」、及び、開封後冷暗倉庫に３か月保管した場合
（表２〜５における「＊２」、水分率：１９１６重量
％：カールフィッシャー法により測定）の２つをそれぞ
れ用いている（配合は乾燥重量をベースとして行っ
た）。The polylactic acid-based synthetic resin component is usually obtained in the form of a paper bag with an aluminum sheet-containing bag, but when the same type is used immediately after opening (“* 1” in Tables 2 to 5). , And when stored for 3 months in a cold and dark warehouse after opening (“* 2” in Tables 2 to 5, moisture content: 1916% by weight: measured by Karl Fischer method). It was done based on weight).
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【表３】 [Table 3]
【００３５】[0035]
【表４】 [Table 4]
【００３６】[0036]
【表５】 [Table 5]
【００３７】表２における比較例３のポリオレフィン系
樹脂組成物を用いた場合には、ロールに組成物の成分が
付着して平滑なシートができなかったために、以下の評
価を行わなかった。また、比較例４及び５のポリオレフ
ィン系樹脂組成物を用いた場合には、前ロール表面及び
後ロール表面にフィルム長さ方向に平行に筋状の「取
れ」（ロールにより形成されるシートの一部分がそのロ
ール表面から剥離されずに残留したために形成されたシ
ートの瑕疵）が発生し、安定な生産ができなかった。When the polyolefin resin composition of Comparative Example 3 in Table 2 was used, the components of the composition adhered to the roll and a smooth sheet could not be formed. Therefore, the following evaluation was not performed. When the polyolefin-based resin compositions of Comparative Examples 4 and 5 were used, streak-shaped “strike” was formed on the front roll surface and the rear roll surface parallel to the film length direction (a part of the sheet formed by the roll. Was not peeled off from the roll surface and remained, so that the formed sheet was flawed and stable production could not be performed.
【００３８】このように安定的に生産ができない場合を
「×」として評価した。また、後ロール表面に点状の
「取れ」が発生したものの、安定生産が可能であると判
断されたものは「△」、また、安定生産が可能であると
判断されたものの後ロール表面（鏡面仕上げ）に剥離せ
ずに「曇」状の樹脂組成物の付着が見られたものを「○
〜△」として評価した。The case where stable production was not possible was evaluated as "x". In addition, although dot-like "stripping" occurred on the surface of the rear roll, it was judged as "△" when stable production was possible, and when the surface of the rear roll was judged to be possible for stable production ( "Mirror finish" shows that the "cloudy" resin composition adhered without peeling and was marked with "○".
~ △ "was evaluated.
【００３９】これらシートについて、引張強度、引裂強
度及び生分解性についてそれぞれ評価を行った。ただ
し、上記安定生産性評価が、「×」、「△」及び「○〜
△」と評価された組成物によるシートの内、その幅
（横）方向の機械的強度の測定に使用可能な大きさのサ
ンプルが得られない場合には、長さ方向（縦方向）のみ
について評価した。Each of these sheets was evaluated for tensile strength, tear strength and biodegradability. However, the above stable productivity evaluation is "x", "△" and "○ ~
If a sample having a size usable for measuring the mechanical strength in the width (horizontal) direction cannot be obtained among the sheets of the composition evaluated as “Δ”, only in the longitudinal direction (longitudinal direction) evaluated.
【００４０】引張強度及び引裂強度はＪＩＳ Ｋ６７２
３に準じて評価した。なお「縦」とはシート長さ方向、
「横」はシート長さ方向に垂直な方向をそれぞれ示す。The tensile strength and tear strength are JIS K672.
Evaluation was made according to 3. Note that "vertical" means the sheet length direction,
“Horizontal” indicates a direction perpendicular to the sheet length direction.
【００４１】また、生分解性についてはコンポスト試験
として松下電工製生ゴミ分解処理機ＥＨ４３２ＡＨを用
いて、この装置の通常条件で運転したときの分解状況を
目視で判定し、試験前の状態から変化が見られなかった
場合を「×」、若干分解されて部分的に亀裂が入った状
態となった場合を「△」、分解が進んで亀裂が全体に入
った状態となっている場合を「○」として評価した。こ
れら評価結果を表２〜５に併せて記載した。As for the biodegradability, the composting test was carried out by visually observing the decomposition state of the apparatus when the apparatus was operated under normal conditions, using a garbage disintegration processing machine EH432AH manufactured by Matsushita Electric Works. When the cracks were not seen, it was marked with an X, when it was disassembled slightly and partially cracked, it was marked with a triangle, and when the decomposition proceeded and the cracks were in full, it was marked. It was evaluated as "○". These evaluation results are also shown in Tables 2-5.
【００４２】表２〜表５により、本発明に係るポリオレ
フィン系樹脂組成物を用いてなるシート状物は、高い生
分解性を維持しながら、開封後時間が経過したポリ乳酸
系合成樹脂成分を用いた場合であっても良品の安定生産
が可能であり、さらに、引張強度、引裂強度とも、従来
のオレフィン系−ポリ乳酸系のポリオレフィン系樹脂組
成物を用いてなるシート状物より高いことが判る。As shown in Tables 2 to 5, the sheet-like material using the polyolefin resin composition according to the present invention contains a polylactic acid-based synthetic resin component which has been kept open for a long time while maintaining high biodegradability. Even when used, stable production of non-defective products is possible, and further, the tensile strength and the tear strength are both higher than those of the sheet-shaped material using the conventional olefin-polylactic acid-based polyolefin resin composition. I understand.
【００４３】なお、上記実施例１〜２１のうち、シート
の安定生産性評価が「○」であったポリオレフィン系樹
脂組成物について、カレンダーによって、それぞれ厚さ
１００μｍのフィルムを作製したが、その際も安定生産
が可能であり、得られたフィルムの機械的特性も、比較
例２のポリオレフィン系樹脂組成物から同様に作製した
フィルムと同等以上であった。With respect to the polyolefin-based resin compositions of Examples 1 to 21 in which the stable productivity evaluation of the sheet was “◯”, films each having a thickness of 100 μm were produced by a calendar. Stable production was possible, and the mechanical properties of the obtained film were equal to or higher than those of the film similarly prepared from the polyolefin resin composition of Comparative Example 2.
【００４４】[0044]
【発明の効果】本発明のポリオレフィン系樹脂組成物
は、ベース成分としてポリオレフィン系樹脂、ａ成分と
してポリ乳酸系合成樹脂成分、及び、ｂ成分として酢酸
ビニル・エチレン共重合体、アクリル変成されたポリテ
トラフルオロエチレン又はポリスチレン系共重合体から
なる群より選ばれた１種以上を含む構成を有しているた
め、シート状物の安定生産が可能で、かつ、この樹脂組
成物から得られる本発明のシート状物も、充分な生分解
性を維持しながら、引張強度、引裂強度等の機械的強度
に優れたものとすることができる。The polyolefin resin composition of the present invention comprises a polyolefin resin as a base component, a polylactic acid type synthetic resin component as a component, a vinyl acetate / ethylene copolymer as a component b, and an acrylic-modified poly. The present invention, which has a structure containing at least one selected from the group consisting of tetrafluoroethylene or polystyrene-based copolymers, enables stable production of a sheet-like product, and is obtained from this resin composition. The sheet-like product can also have excellent mechanical strength such as tensile strength and tear strength while maintaining sufficient biodegradability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 67/04 Ｃ０８Ｌ 67/04 // Ｃ０８Ｌ 101/16 101/16 (72)発明者 田代 千秋 神奈川県座間市相模が丘１−27−10 (72)発明者 松井 政裕 大阪府大阪市北区南森町１丁目４番19号 カネボウ化成株式会社内 (72)発明者 石田 昌也 大阪府大阪市北区南森町１丁目４番19号 カネボウ化成株式会社内 Ｆターム(参考） 4F071 AA14 AA15X AA22 AA27 AA28X AA43 AA78 BA01 BB04 BB06 BC01 4J002 BB03W BB04W BB12W BC03Y BD18Y BF03Y CF18X 4J200 AA04 AA06 BA14 CA01 DA01 DA16 EA11 EA20 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08L 67/04 C08L 67/04 // C08L 101/16 101/16 (72) Inventor Chiaki Tashiro Zama, Kanagawa Prefecture 1-27-10 Sagamigaoka City (72) Inventor Masahiro Matsui 1-4-19 Minamimorimachi, Kita-ku, Osaka City, Osaka Prefecture Kanebo Kasei Co., Ltd. (72) Masaya Ishida 1-chome, Minamimorimachi, Kita-ku, Osaka City, Osaka Prefecture No. 4-19 Kanebo Kasei Co., Ltd. F term (reference) 4F071 AA14 AA15X AA22 AA27 AA28X AA43 AA78 BA01 BB04 BB06 BC01 4J002 BB03W BB04W BB12W BC03Y BD18Y BF03Y CF18X 4J200 AA04 AA20 DA16 CA14 CA01 CA14 CA14
Claims (5)
脂、ａ成分としてポリ乳酸系合成樹脂成分、及び、ｂ成
分として酢酸ビニル・エチレン共重合体、アクリル変成
されたポリテトラフルオロエチレン又はポリスチレン系
共重合体からなる群より選ばれた１種以上を含むことを
特徴とするポリオレフィン系樹脂組成物。1. A polyolefin resin as a base component, a polylactic acid-based synthetic resin component as a component, and a vinyl acetate / ethylene copolymer as an b component, an acryl-modified polytetrafluoroethylene or polystyrene-based copolymer. A polyolefin-based resin composition comprising at least one selected from the group consisting of:
ａ成分のポリ乳酸系合成樹脂成分の含有量が１０重量％
以上であり、ｂ成分の酢酸ビニル・エチレン共重合体の
含有量が０．５重量％以上であることを特徴とする請求
項１に記載のポリオレフィン系樹脂組成物。2. The content of the polylactic acid-based synthetic resin component of the component a is 10% by weight, with the total amount of the polymer components being 100.
The polyolefin resin composition according to claim 1, wherein the content of the vinyl acetate / ethylene copolymer as the component b is 0.5% by weight or more.
ａ成分のポリ乳酸系合成樹脂成分の含有量が１０重量％
以上であり、ｂ成分のアクリル変成されたポリテトラフ
ルオロエチレンの含有量が０．５重量％以上であること
を特徴とする請求項１に記載のポリオレフィン系樹脂組
成物。3. The content of the polylactic acid-based synthetic resin component of the component a is 10% by weight, with the total amount of the polymer components being 100.
The polyolefin resin composition according to claim 1, wherein the content of the acrylic modified polytetrafluoroethylene of the component b is 0.5% by weight or more.
ａ成分のポリ乳酸系合成樹脂成分の含有量が１０重量％
以上であり、ｂ成分のポリスチレン系共重合体の含有量
が５重量％以上であることを特徴とする請求項１に記載
のポリオレフィン系樹脂組成物。4. The content of the polylactic acid-based synthetic resin component of the component a is 10% by weight, with the total amount of the polymer components being 100.
The polyolefin resin composition according to claim 1, wherein the content of the polystyrene copolymer as the component b is 5% by weight or more.
レフィン系樹脂組成物からなることを特徴とするシート
状物。5. A sheet-like material comprising the polyolefin-based resin composition according to any one of claims 1 to 4.
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| JP2002109069A JP3735310B2 (en) | 2002-04-11 | 2002-04-11 | Biodegradable polyolefin resin composition and biodegradable sheet-like material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002109069A JP3735310B2 (en) | 2002-04-11 | 2002-04-11 | Biodegradable polyolefin resin composition and biodegradable sheet-like material |
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|---|---|
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| JP2005232228A (en) * | 2004-02-17 | 2005-09-02 | Tosoh Corp | Resin composition |
| JP2006131716A (en) * | 2004-11-04 | 2006-05-25 | Mitsui Chemicals Inc | Thermoplastic resin composition |
| JP2006348060A (en) * | 2005-06-13 | 2006-12-28 | Cp Kasei Kk | Thermoplastic resin foam sheet and method for producing the sheet container |
| JP2007063435A (en) * | 2005-08-31 | 2007-03-15 | Toyota Motor Corp | Polylactic acid composition |
| WO2007063973A1 (en) | 2005-11-30 | 2007-06-07 | Mitsubishi Plastics, Inc. | Thermally shrinkable polyolefin film, molded article using the film, thermally shrinkable label, and container |
| WO2008001917A1 (en) * | 2006-06-30 | 2008-01-03 | Mitsubishi Plastics, Inc. | Film, heat shrinkable film, molded article using the heat shrinkable film, heat shrinkable label, and container using the molded article or attached with the label |
| WO2008023758A1 (en) * | 2006-08-23 | 2008-02-28 | Jsr Corporation | Thermoplastic resin composition and molded article obtained from the same |
| JP2008044365A (en) * | 2006-07-19 | 2008-02-28 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable laminated film, molded product using the film, heat-shrinkable label, and container equipped with the molded product or heat-shrinkable label |
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