JPH02199144A - Polyolefin resin composition - Google Patents
Polyolefin resin compositionInfo
- Publication number
- JPH02199144A JPH02199144A JP1776689A JP1776689A JPH02199144A JP H02199144 A JPH02199144 A JP H02199144A JP 1776689 A JP1776689 A JP 1776689A JP 1776689 A JP1776689 A JP 1776689A JP H02199144 A JPH02199144 A JP H02199144A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- copolymer
- component
- strength
- film
- 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 description 7
- 229920005672 polyolefin resin Polymers 0.000 title claims description 6
- -1 polypropylene Polymers 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 239000004743 Polypropylene Substances 0.000 claims abstract description 18
- 239000004711 α-olefin Substances 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 11
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000000806 elastomer Substances 0.000 claims abstract description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 5
- 229920001748 polybutylene Polymers 0.000 claims description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 3
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 claims description 3
- 229920012753 Ethylene Ionomers Polymers 0.000 claims description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 48
- 238000001125 extrusion Methods 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 10
- 229920000089 Cyclic olefin copolymer Polymers 0.000 abstract description 7
- 239000000155 melt Substances 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract description 4
- 229920001038 ethylene copolymer Polymers 0.000 abstract description 3
- 229920000554 ionomer Polymers 0.000 abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000113 differential scanning calorimetry Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 210000005036 nerve Anatomy 0.000 abstract 1
- 239000010408 film Substances 0.000 description 56
- 238000007789 sealing Methods 0.000 description 17
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000004806 packaging method and process Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000004708 Very-low-density polyethylene Substances 0.000 description 6
- 239000012785 packaging film Substances 0.000 description 6
- 229920006280 packaging film Polymers 0.000 description 6
- 229920001866 very low density polyethylene Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 229920001083 polybutene Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008094 contradictory effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229940105990 diglycerin Drugs 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- NUHSROFQTUXZQQ-UHFFFAOYSA-N isopentenyl diphosphate Chemical compound CC(=C)CCO[P@](O)(=O)OP(O)(O)=O NUHSROFQTUXZQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 235000003441 saturated fatty acids Nutrition 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 102100037709 Desmocollin-3 Human genes 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000968042 Homo sapiens Desmocollin-2 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000001993 dienes Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 210000005081 epithelial layer Anatomy 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、押出成型性、ヒートシール性、衝撃強度特性
、引張強度特性、透明性等に優れ、特に成型品の腰強度
と衝撃強度という相反する特性が同時に優れたポリオレ
フィン系樹脂組成物に関するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention has excellent extrusion moldability, heat sealability, impact strength characteristics, tensile strength characteristics, transparency, etc., and particularly improves the stiffness and impact strength of molded products. The present invention relates to a polyolefin resin composition that is excellent in contradictory properties at the same time.
これらは特に限定はしないが、例えばフィルム成型用の
単体層及び多層の少なくとも一層を構成する組成物とし
て有用なものである。Although these are not particularly limited, they are useful, for example, as a composition constituting at least one layer of a single layer or a multilayer for film molding.
従来、結晶性ポリプロピにン(以下、PPと略する)の
熱安定性、低温時の強度、衝撃強度等を改良するために
、エチレン−プロピレン共重合体ゴム(以下、EPRと
略する)を1部混合する方法が提案されている。しかし
、この方法ではPPとEPRの相溶性は必ずしも良好と
は言えず、薄いフィルム状に加工した場合混練が不均一
であったり、表面が荒れて光学特性が大きく悪化し、ま
た強度も不十分で商品価値の低いものしか得られなかっ
た。Conventionally, ethylene-propylene copolymer rubber (hereinafter referred to as EPR) was used to improve the thermal stability, strength at low temperatures, impact strength, etc. of crystalline polypropylene (hereinafter referred to as PP). A method of mixing one part has been proposed. However, in this method, the compatibility of PP and EPR is not necessarily good, and when processed into a thin film, the kneading is uneven, the surface is rough, the optical properties are greatly deteriorated, and the strength is insufficient. Therefore, only products with low commercial value could be obtained.
また、これらの問題を改良すべく非晶質のアタックティ
ックポリプロピレン類を更に混合する方法が提案されて
いるが、いずれもPPを主体として改良を進めたもので
あり、薄いフィルム状にした場合には未だ問題を有する
ものである。In addition, in order to improve these problems, a method of further mixing amorphous attack polypropylene has been proposed, but all of these are improvements based on PP, and when made into a thin film, still has problems.
また、更にこれら組成物の問題点を改良する組成として
、例えば、EVA、エチレン−α−オレフィン共重合体
エラストマー、ポリプロピレンの3元混合組成物を開示
する、特公昭59−38976号公報の提案がある。こ
の組成物は薄いフィルム状に加工した場合でも、従来の
ポリオレフィン系組成物に比べ、延伸加工性も優れ、低
温収縮性、耐熱性、ヒートシール性、機械強度等に優れ
たフィルムが得られている。しかしながら、包装の多様
化と包装スピードの高速化が急、速に進む現在、これら
組成物よりのフィルムでも物性が未だ不十分であり、特
にフィルムの腰強度が弱いという問題がある。Furthermore, as a composition to further improve the problems of these compositions, for example, Japanese Patent Publication No. 59-38976 discloses a ternary mixed composition of EVA, ethylene-α-olefin copolymer elastomer, and polypropylene. be. Even when processed into a thin film, this composition has superior stretchability compared to conventional polyolefin compositions, and produces films with excellent low-temperature shrinkability, heat resistance, heat sealability, mechanical strength, etc. There is. However, in today's world where the diversification of packaging and the speeding up of packaging are rapidly progressing, even films made from these compositions still have insufficient physical properties, and in particular, there is a problem that the film has low stiffness.
また、ポリプロピレンのような硬質樹脂の組成比を増や
し、腰強度を大きくしようとすると、押出成型性や延伸
性が低下し、厚み声が大きくなったり、引裂強度が低下
し、被包装物に突起等があると破れ易くなったり、衝撃
強度が低下して破れ易くなったりするという問題を有し
ている。In addition, if you try to increase the stiffness by increasing the composition ratio of hard resins such as polypropylene, extrusion moldability and stretchability will decrease, the thickness will increase, tear strength will decrease, and there will be protrusions on the packaged items. If there is such a problem, it becomes easy to tear, or the impact strength decreases, making it easy to tear.
以上のことから、本発明の目的は、これらの問題点がな
い、すなわち、押出成型性や延伸性に優れると共に衝撃
強度が大きくかつ成型品の腰強度も大きく、また、ヒー
トシール性、引裂強度特性、耐寒性、透明性等について
も優れたポリオレフィン系樹脂組成物、好ましくはフィ
ルム成型用ポリオレフィン系樹脂組成物を促供すること
である。Based on the above, the object of the present invention is to avoid these problems, that is, to have excellent extrusion moldability and stretchability, high impact strength, high stiffness of the molded product, and heat sealability and tear strength. The object of the present invention is to provide a polyolefin resin composition having excellent properties, cold resistance, transparency, etc., preferably a polyolefin resin composition for film molding.
本発明に従えば、これらの問題点は;
低密度ポリエチレン、エチレン−酢酸ビニル共重合体、
エチレン−アクリル酸エチル共重合体、エチレン−アク
リル酸共重合体、エチレン−メタアクリル酸メチル共重
合体、エチレン−メタアクリル酸共重合体、アイオノマ
ー樹脂からなる群から選ばれる少なくとも一種の重合体
(A)15〜45wt%と、
ビカット軟化点60゛C以下の軟質エラストマー(B)
5〜15wL%と、
23℃における密度が0.880〜0.920g/cm
3、メルトインデックスが0.5〜5g/10分、示差
走査熱量計(DSC)による最高融点が110℃〜13
0℃であり、かつビカット軟化点が60℃〜95℃であ
るエチレンと炭素数4〜10のα−オレフィンとの共重
合体(C)2o〜55wt%と、
結晶性ポリプロピレン、結晶性ポリブテン−1のいずれ
か又はこれらの混合重合体(D)10〜40wL%と、
からなるポリオレフィン系樹脂組成物によって解決する
ことができる。According to the present invention, these problems are solved by: low density polyethylene, ethylene-vinyl acetate copolymer,
At least one polymer selected from the group consisting of ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, and ionomer resin ( A) Soft elastomer with a content of 15 to 45 wt% and a Vicat softening point of 60°C or less (B)
5-15wL% and density at 23℃ 0.880-0.920g/cm
3. Melt index is 0.5 to 5 g/10 minutes, maximum melting point by differential scanning calorimeter (DSC) is 110°C to 13
0°C and a Vicat softening point of 60°C to 95°C, a copolymer (C) of 20 to 55 wt% of ethylene and an α-olefin having 4 to 10 carbon atoms, crystalline polypropylene, crystalline polybutene- 1 or a mixed polymer (D) of 10 to 40 wL%, and a polyolefin resin composition comprising:
以下、本発明を具体的に説明する。The present invention will be specifically explained below.
本発明に用いる重合体(A)は、低密度ポリエチレン、
EVA、エチレン−アクリル酸エチル共重合体、エチレ
ン−アクリル酸共重合体、エチレン−メタアクリル酸メ
チル共重合体、エチレン−メタアクリル酸共重合体、ア
イオノマー樹脂のいずれか、又はこれらの混合物である
。The polymer (A) used in the present invention is low density polyethylene,
EVA, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylate copolymer, ionomer resin, or a mixture thereof. .
低密度ポリエチレンは、メルトインデックス0゜2〜2
0、好ましくは0.5〜10、密度0. 915〜0.
9:tOg/cdのもので、ビカット軟化点が95℃以
上のものである。Low density polyethylene has a melt index of 0°2~2
0, preferably 0.5-10, density 0. 915-0.
9: tOg/cd and Vicat softening point of 95°C or higher.
エチレン共重合体類はエチレン以外の単量体の量が2〜
12モル%、M−1が0. 2〜10のものである。こ
れらのうち、高圧法で製造された低密度ポリエチレン、
EVAが特に好ましい、又、これらはDSCによる融解
エネルギーより求めた結晶化度が40%、好ましくは4
5〜65%である。Ethylene copolymers contain monomers other than ethylene in an amount of 2 to 2.
12 mol%, M-1 is 0. 2 to 10. Among these, low-density polyethylene manufactured by high-pressure method,
EVA is particularly preferred, and these have a crystallinity of 40%, preferably 4, determined from the melting energy by DSC.
It is 5-65%.
次にビカット軟化点60’C以下の軟質エラストマー(
B)とは、1,2−ポリブタジェン、エチレンと炭素数
が3〜12のα−オレフィンから選ばれる一種又はそれ
以上のα−オレフィンとの軟質の共重合体のことを言い
、好ましくは後者であり、また場合によっては後者に更
に少量の、ポリエン構造を有する炭化水素、例えばジシ
クロペンタジェン、1.4−へキサジエン、エチリデン
−ノルボルネン等を更に共重合させても良い、α−オレ
フィンとしてはプロピレン、ブテン−1、ヘキセン−1
,4−メチルペンテン−11オクテン−1などであり、
好ましくはプロピレン、ブテン−1である。Next, a soft elastomer with a Vicat softening point of 60'C or less (
B) refers to 1,2-polybutadiene, a soft copolymer of ethylene and one or more α-olefins selected from α-olefins having 3 to 12 carbon atoms, preferably the latter. In some cases, the latter may be further copolymerized with a small amount of a hydrocarbon having a polyene structure, such as dicyclopentadiene, 1,4-hexadiene, ethylidene-norbornene, etc. As an α-olefin, Propylene, butene-1, hexene-1
, 4-methylpentene-11octene-1, etc.
Preferred are propylene and butene-1.
共重合体中のエチレン含量は、20〜93モル%、好ま
しくは40〜90モル%、より好ましくは65〜88モ
ル%である。The ethylene content in the copolymer is 20-93 mol%, preferably 40-90 mol%, more preferably 65-88 mol%.
こられの共重合体は、密度が0.900以下、好ましく
は0.890以下であり、ビカット軟化点(ASTMD
1525 (荷重1kgの値))が60″C以下であ
り、一般にゴム状の領域で実質的に非晶質のものであっ
て、前述A成分の低密度ポリエチレン、又は後述C成分
としての低密度の結晶性をもつものとは区別される。こ
こで実質的に非晶質とは結晶化度10%以下のものを言
う。These copolymers have a density of 0.900 or less, preferably 0.890 or less, and a Vicat softening point (ASTMD
1525 (value at a load of 1 kg)) is 60"C or less, and is generally substantially amorphous in a rubber-like region, and is a low-density polyethylene as the component A described above, or a low-density polyethylene as the component C described below. It is distinguished from those with crystallinity.Here, "substantially amorphous" refers to those with a crystallinity of 10% or less.
好ましいのは、エチレンとプロピレン又はブテン−1の
共重合体で、又はこれらに少量のジエン構造を有する化
合物を共重合体として含む場合で、例えばバナジウム化
合物と有機アルミニウム化合物系の触媒で重合したラン
ダム共重合体でメルトインデックスが0.1〜10、好
ましくは0. 2〜6の熱可塑性エラストマーである。Preferred is a copolymer of ethylene and propylene or butene-1, or a copolymer containing a small amount of a compound having a diene structure, such as a random copolymer polymerized with a vanadium compound and an organoaluminium compound catalyst. The copolymer has a melt index of 0.1 to 10, preferably 0. 2 to 6 thermoplastic elastomers.
これらは、一般の非加硫ゴムのようにブロック状でなく
、しかもコールド・ブローを起こさない、ペレット状で
供給され、単体でもフィルム状に押出加工できる程度の
十分な熱可塑性を有するものが好ましい。These are preferably supplied in the form of pellets that are not block-shaped like general non-vulcanized rubber and do not cause cold blowing, and have sufficient thermoplasticity to be able to be extruded into a film even when used alone. .
また、重合体(C)はエチレンと炭素数4〜10のα−
オレフィンとの共重合体である。α−オレフィンとして
は、ブテン−1、ヘキセン−1゜ヘフテン−1,4−メ
チルペンテン−1、オクテン−1などであり、好ましく
は4−メチルペンテン−1、オクテン−1である。共重
合体中のエチレン含量は85〜98モル%、好ましくは
90〜96モル%である。In addition, the polymer (C) is ethylene and α- having 4 to 10 carbon atoms.
It is a copolymer with olefin. Examples of the α-olefin include butene-1, hexene-1°hephtene-1,4-methylpentene-1, and octene-1, preferably 4-methylpentene-1 and octene-1. The ethylene content in the copolymer is 85-98 mol%, preferably 90-96 mol%.
これら共重合体の性質としては、23℃における密度が
0.880〜0.920g/c−であり、好ましくは0
.905〜0,915、より好ましくは0.907〜0
.913であり、また、メルトインデックスは0.5〜
5g/10分が好ましい、また、これら共重合体は、示
差走査熱量計(DSC)による最高融点が110℃〜1
30℃であり、かつビカット軟化点が60℃〜95℃で
あって、成分(B)のようなゴム状の領域で実質的に非
晶質なものとははっきり区別されて、低度の結晶性をも
つものであり、これらは、通常lO〜50%、好ましく
は15〜45%の結晶化度をもつものである。The properties of these copolymers include a density at 23°C of 0.880 to 0.920 g/c, preferably 0.
.. 905-0,915, more preferably 0.907-0
.. 913, and the melt index is 0.5~
5 g/10 minutes is preferable, and these copolymers have a maximum melting point of 110°C to 1°C by differential scanning calorimetry (DSC).
30°C, and a Vicat softening point of 60°C to 95°C, which is clearly distinguished from a substantially amorphous material in a rubbery region such as component (B), and has a low degree of crystallinity. These usually have a crystallinity of 10 to 50%, preferably 15 to 45%.
好ましいのは、エチレンと4−メチルペンテン−1又は
オクテン−1との共重合体で、例えば、チタン化合物と
有機アルミニウム化合物系の触媒を用い、いわゆる中・
低圧法によって重合した低結晶性共重合体であり、通常
の線状低密度ポリエチレンと同等の最高融点を持ちなが
ら、ビカット軟化点が低く、60〜95℃の範囲にあっ
て、延伸加工等の成型性に優れたものである。これらに
は、例えばプラスチック・エンジニアリング第11巻、
P59〜62(’85)に記載されているようなVLD
PHのごときものがある。Preferably, a copolymer of ethylene and 4-methylpentene-1 or octene-1 is used, for example, using a titanium compound and an organoaluminum compound catalyst, so-called medium-copolymerization.
It is a low-crystalline copolymer polymerized by a low-pressure method, and has a maximum melting point equivalent to that of ordinary linear low-density polyethylene, but a low Vicat softening point in the range of 60 to 95°C, making it suitable for stretching, etc. It has excellent moldability. These include, for example, Plastic Engineering Volume 11;
VLD as described in P59-62 ('85)
There is something like PH.
また、成分(D)の結晶性ポリプロピレン、結晶性ポリ
ブテンとは、アイソタクシティの高い結晶性ポリマーで
ある。Moreover, the crystalline polypropylene and crystalline polybutene of component (D) are crystalline polymers with high isotacticity.
ポリプロビレ、ンはプロピレンの単独重合体、又は、プ
ロピレンと7モル%以下のα−オレフィンとの共重合体
を含むもので、M・1,0.5〜20のものである。Polypropylene contains a propylene homopolymer or a copolymer of propylene and 7 mol% or less of α-olefin, and has an M·1 of 0.5 to 20.
ポリブテンは、低分子量の液状、ワックス状のものと異
なり、ブテン−1含量93モル%以上で、他のモノマー
との共重合体をも含む高分子量のものである。これらは
、好ましくはピカット軟化点100 ”C以上の比較的
硬質の重合体である。Unlike low molecular weight liquid or waxy polybutenes, polybutene has a butene-1 content of 93 mol% or more and is a high molecular weight polybutene that also includes copolymers with other monomers. These are preferably relatively hard polymers with a Picat softening point of 100''C or higher.
本発明の組成物は、以上の各成分の(A)、(B)、(
C)、(D)の混合組成よりなり、これらの量の範囲は
、成分(A)が15〜45wL% であり、好ましくは
20〜40wL%、より好ましくは25〜35wt%で
ある。また、成分(B)の量の範囲は、5〜15wt%
であり、好ましくは10〜15wL%である。また、成
分(C)の量の範囲は、20〜55wL%であり、好ま
しくは25〜45wL%であり、より好ましくは30〜
40wL%である。また、成分(D)の量の範囲は、1
0〜40wt%であり、好ましくは20〜30wt%で
ある。The composition of the present invention comprises (A), (B), (
It consists of a mixed composition of C) and (D), and the range of the amount of component (A) is 15 to 45 wL%, preferably 20 to 40 wL%, and more preferably 25 to 35 wt%. Moreover, the range of the amount of component (B) is 5 to 15 wt%
and preferably 10 to 15 wL%. Further, the amount of component (C) ranges from 20 to 55 wL%, preferably from 25 to 45 wL%, and more preferably from 30 to 45 wL%.
It is 40wL%. Further, the range of the amount of component (D) is 1
The content is 0 to 40 wt%, preferably 20 to 30 wt%.
ここで低度の結晶性重合体成分である(C)の混合量が
少ない場合は、混合物としての、相乗効果を発揮できず
、押出成型性、衝撃強度特性、耐寒性、透明性等が低下
する。また、(C)の量が55wt%を越えても同様で
あり、成型品の腰強度及びシール特性等も低下するよう
になる。If the mixing amount of (C), which is a low-grade crystalline polymer component, is small, the mixture will not be able to exhibit a synergistic effect, and extrusion moldability, impact strength characteristics, cold resistance, transparency, etc. will deteriorate. do. The same thing will happen if the amount of (C) exceeds 55 wt%, and the stiffness and sealing properties of the molded product will also deteriorate.
成分(D)は、混合組成の引張強度、衝撃強度、耐熱性
、押出成型性、腰強度(弾性率)、ヒートシール温度範
囲を他の成分と共に相乗的に改良し、特に耐熱性、押出
成型性、腰強度(弾性率)ヒートシール温度範囲等にお
ける効果が大きい、これら効果は、混合量が少ない場合
は、例えば延伸加工時及びグイ内での流動特性による偏
肉が大きくなる。また、ヒートシール温度範囲、強度に
対する改良の効果が小さくなり、耐熱性も低下する。Component (D) synergistically improves the tensile strength, impact strength, heat resistance, extrusion moldability, waist strength (modulus), and heat sealing temperature range of the mixed composition with other components, and particularly improves heat resistance, extrusion moldability. These effects have a large effect on properties such as elasticity, stiffness (modulus of elasticity), and heat-sealing temperature range.If the mixing amount is small, for example, the uneven thickness due to the flow characteristics during stretching and within the gouer becomes large. Moreover, the effect of improvement on the heat sealing temperature range and strength becomes smaller, and the heat resistance also decreases.
一方、(D)成分が多過ぎると、押出成型性、透明性、
耐寒性、衝撃強度等に劣ってくる。On the other hand, if the amount of component (D) is too large, extrusion moldability, transparency,
Cold resistance, impact strength, etc. are inferior.
また、成分(A)は、特定の低密度ポリエチレン、エチ
レン系共重合体よりなり、混合組成の押出成型性、ヒー
トシール性、透明性等を他の成分と共に相乗的に改良す
るものであり、特に、ヒートシール性、透明性等におけ
る効果が大きい、成分(A)の混合量が少ない場合は、
押出成型性が悪くなり、成型品に厚み斑が生じたり、ま
た、ヒートシール温度範囲、衝撃強度に対する改良の効
果が小さ(なる。また、成分(A)の混合量が多過ぎて
も同様であり、成型品の腰強度及びヒートシール特性等
も低下するようになる。In addition, component (A) is made of a specific low-density polyethylene or ethylene copolymer, and synergistically improves the extrusion moldability, heat sealability, transparency, etc. of the mixed composition with other components, In particular, when the amount of component (A) mixed is small, which has a large effect on heat sealability, transparency, etc.
Extrusion moldability may deteriorate, thickness unevenness may occur in the molded product, and the effect of improving the heat sealing temperature range and impact strength may be small.Also, if the amount of component (A) mixed is too large, the same problem may occur. However, the stiffness and heat sealing properties of the molded product also decrease.
また、成分(B)の混合量が少ない場合も、混合物とし
ての相乗効果を発揮しなくなり、押出成型性、衝撃強度
特性、透明性等が低下する。また、(C)の混合量が多
過ぎても同様であり、成型品の腰強度、ヒートシール特
性、耐熱性等が低下するようになる。Furthermore, if the amount of component (B) mixed is small, the synergistic effect as a mixture will not be exhibited, and extrusion moldability, impact strength characteristics, transparency, etc. will deteriorate. The same thing will happen if the amount of (C) mixed is too large, and the stiffness, heat sealing properties, heat resistance, etc. of the molded product will deteriorate.
ここで成分(C)は、前述4成分(A)、(B)、(C
)、(D)の混合体の中で最も量の多い成分となること
が好ましい、4成分の内、成分(A)と成分(D)のみ
の混合では、混合性、相溶性が良くなく、前述の相乗効
果も期待し難い。Here, component (C) is the aforementioned four components (A), (B), (C
), (D) is preferably the component with the largest amount in the mixture. Mixing only component (A) and component (D) among the four components does not have good miscibility and compatibility; It is also difficult to expect the synergistic effects mentioned above.
また、成分(B)と成分(D)及び成分(C)と成分(
D)の混合は、相溶性は若干改良されるものの、前述の
相乗効果は期待し難く、特に、成型品の衝撃強度が未だ
不十分である。また、成分(A)と成分(B)と成分(
D)の混合物、成分(A)と成分(C)と成分(D)の
混合物、成分(B)と成分(C)と成分(D)の混合物
では、相溶性や成型加工性は改良され、ある特定の組成
で衝撃強度あるいは腰強度も改良れるが、両方同時に改
良することはできず、衝撃強度を改良しようとすると腰
強度が低下し、腰強度を改良しようとすると衝撃強度が
低下してしまう。In addition, component (B) and component (D), component (C) and component (
Mixing D) slightly improves the compatibility, but it is difficult to expect the synergistic effect described above, and in particular, the impact strength of the molded product is still insufficient. In addition, component (A), component (B), and component (
In the mixture of D), the mixture of component (A), component (C), and component (D), and the mixture of component (B), component (C), and component (D), compatibility and moldability are improved, A certain composition can improve either impact strength or waist strength, but it is not possible to improve both at the same time; attempting to improve impact strength will result in a decrease in waist strength, and attempting to improve waist strength will result in a decrease in impact strength. Put it away.
しかしながら、成分(A)、成分(B)、成分(D)に
成分(C)を加えると、それらの欠点を著しく改善し、
相溶性、成型加工性が良く、衝撃強度と腰強度が同時に
改良されると共に、成型品の透明性、ヒートシール性、
引張強度等も改良することができる。However, when component (C) is added to component (A), component (B), and component (D), these drawbacks are significantly improved,
It has good compatibility and moldability, and improves impact strength and waist strength at the same time, as well as transparency and heat sealability of molded products.
Tensile strength etc. can also be improved.
これらの理由は、混合体の各成分の結晶構造及び混合体
の分散状態あるいは配向状態等複雑な相互作用によるも
のと思われる。These reasons are thought to be due to complex interactions such as the crystal structure of each component of the mixture and the state of dispersion or orientation of the mixture.
例えば、成分(A)が主体の場合、上記各成分を混線能
力の優れた押出機で溶融混練押出を行い成型品とした場
合、成分(A)に分散している成分(D)の内部か周囲
に、成分(B)が複雑に分散しかつ、分散している成分
(D)同士を成分(C)が連結するように分散して相互
作用をしている状態等が考えられる。これらは、成型条
件により例えばフィルム、他成型品に加工して流動、配
向を与えると、各成分の状態も異なってくる。For example, when component (A) is the main component, if the above components are melt-kneaded and extruded using an extruder with excellent cross-mixing ability to form a molded product, the internal components of component (D) dispersed in component (A) A situation may be considered in which the component (B) is dispersed in a complicated manner in the surrounding area, and the component (C) is dispersed and interacts so as to connect the dispersed components (D) with each other. When these are processed into a film or other molded product depending on the molding conditions to impart fluidity and orientation, the state of each component also changes.
例えば、成分(D)の流動に適した比較的高温230〜
260℃で、上記混合物を小さなスリット、例えば1.
5mを有するフィルム、シート等用のグイから押出し、
一定のドロー比をかけた後に急冷してフィルムに加工し
た場合は、硬質成分(D)の量にもよるが、例えば成分
(D)として結晶性ポリプロピレンを30wt%混合し
て行った場合には、成分(D)の結晶性ポリプロピレン
は主成分(A)の中で流れ方向にその分散粒子を繊細状
に配向させ、かつ分散粒子を成分(B)、(C)が連結
した構造になり、非常に強度等緒特性の改善された性質
(特に衝撃強度、腰強度が共に改良された性質)を発揮
する場合もあると考えられる。この時、成分(C)は他
の成分に比べ流動配向性が低いため、配向成分と無配向
成分とがあたかも繊維で補強したような形になっている
と考えられる。For example, a relatively high temperature of 230~230°C suitable for the flow of component (D).
At 260°C, pass the above mixture through a small slit, e.g.
Extruded from a 5m long goo for films, sheets, etc.
When processed into a film by quenching after applying a certain draw ratio, it depends on the amount of hard component (D), but for example, when 30 wt% of crystalline polypropylene is mixed as component (D), , the crystalline polypropylene of component (D) has a structure in which the dispersed particles are finely oriented in the flow direction in the main component (A), and the components (B) and (C) are connected to the dispersed particles, It is thought that there may be cases where properties with significantly improved strength properties (particularly properties with improved impact strength and waist strength) are exhibited. At this time, since component (C) has a lower flow orientation than other components, it is considered that the oriented component and the non-oriented component are in a form as if they were reinforced with fibers.
本発明の組成物は、成型品、フィルム状として、又その
他接着剤的用途等に自由に使えるものとし、特に限定は
されないが、フィルム用として使用した方が好ましく、
例えば単体として円環状グイより通常の方法、例えば空
冷法、水冷法等によりインフレーションする方法、又は
T−グイからキャスト法等により成膜する方法、又これ
らを2軸に延伸する方法等により成型することができる
。The composition of the present invention can be freely used in the form of molded products, films, and other applications such as adhesives, and although it is not particularly limited, it is preferable to use it as a film.
For example, as a single body, it is molded from an annular goo by a conventional method such as air-cooling, water-cooling, etc., or by forming a film from a T-goo by a casting method, or by biaxially stretching these. be able to.
また、複合体として多層状に少なくともその構成層の内
の1層として成型した場合に、加工安定性、強度、シー
ル性、光学特性のあるフィルムとして、また、接着剤層
として内・外層に好ましく適用しうる。In addition, when molded as a multilayer composite as at least one of its constituent layers, it can be used as a film with processing stability, strength, sealing properties, and optical properties, and as an adhesive layer for the inner and outer layers. Applicable.
また、冷間で高度の配向を付与した成型体、例えばフィ
ルム状に加工するのにも、非常に加工性が良く好都合で
ある。Furthermore, it has very good processability and is convenient for processing into molded products, such as films, which have been given a high degree of cold orientation.
また、本発明の組成物は、有機パーオキサイド架橋剤や
エネルギー線を利用して架橋させても良く、得られた架
橋組成物は前述の優れた特性に加えて耐寒性、耐熱性を
改良できる。Further, the composition of the present invention may be crosslinked using an organic peroxide crosslinking agent or energy rays, and the resulting crosslinked composition can have improved cold resistance and heat resistance in addition to the above-mentioned excellent properties. .
また、本発明組成物の好ましい例として、本発明の組成
物に添加剤(E)として常温液体で沸点200℃以上の
非イオン系界面活性剤を0.5〜5wL%、好ましくは
0.8〜3wt%を混合した場合、更に好ましい性質が
相乗的に付与できる。Further, as a preferable example of the composition of the present invention, 0.5 to 5 wL%, preferably 0.8 wL%, preferably 0.8 wL% of a nonionic surfactant having a boiling point of 200°C or higher as a liquid at room temperature is added to the composition of the present invention as an additive (E). When ~3 wt% is mixed, further preferable properties can be imparted synergistically.
これら非イオン系界面活性剤としては、グリセリン、ソ
ルビトール、ペンタエリスリトール、ポリグリセリン等
の多価アルコールとアルキル基の炭素数5〜13の直鎖
状飽和脂肪酸あるいはアルキル基の炭素数17〜21の
直鎖状不飽和脂肪酸とのエステル類など、例えば、ジグ
リセリンモノオレート等;また、ポリオキシエチレンア
ルキルフェニルエーテル類、例えばポリオキシエチレン
ノニルエーテル又はポリエキシエチレンオクチルフェニ
ルエーテルなどがあり;また、ポリオキシエチレン脂肪
酸エステル類としてエチレンオキサイド3〜10単位の
ポリオキシエチレンを付加した前述の脂肪酸とのエステ
ルなどが好ましく、これらは、単独又は混合して用いら
れる。These nonionic surfactants include polyhydric alcohols such as glycerin, sorbitol, pentaerythritol, and polyglycerin, linear saturated fatty acids with an alkyl group of 5 to 13 carbon atoms, or linear saturated fatty acids with an alkyl group of 17 to 21 carbon atoms. There are also esters with chain unsaturated fatty acids, such as diglycerin monooleate; and polyoxyethylene alkylphenyl ethers, such as polyoxyethylene nonyl ether or polyoxyethylene octylphenyl ether; As the ethylene fatty acid esters, esters with the above-mentioned fatty acids to which polyoxyethylene of 3 to 10 units of ethylene oxide is added are preferable, and these may be used alone or in combination.
これらは、フィルムとした場合のブロッキング防止、帯
電防止、防曇効果を発揮し、包装用フィルムとして適し
たものである。また、これらの添加剤は、混合樹脂成分
中のどれかの成分に溶解しやすく、内層より表面層にこ
れらが徐々に浸透し、ブリードアウトしてくる等の効果
を発揮し、通常ポリオレフィン系のポリマーに見られが
ちな含有低分子を一度にはき出してしまい、表面がべと
つく等の問題もなく、また、表面が洗い流されても、効
果が持続する。These exhibit anti-blocking, anti-static, and anti-fog effects when made into a film, and are suitable as packaging films. In addition, these additives are easily dissolved in any of the components in the mixed resin component, and they gradually penetrate the surface layer from the inner layer and exhibit effects such as bleeding out. The low molecules that tend to be found in polymers are expelled all at once, so there is no problem with the surface becoming sticky, and the effect remains even after the surface is washed away.
また、更に本発明の組成物に添加剤(F)として、脂環
族飽和炭化水素、ロジン類、石油用脂、テルペン樹脂等
を添加しても良い。その好ましい範囲は、0.5〜l
Qwt%、より好ましくは1〜7wt%である。これら
は、単独又は混合して用いられ、前述の非イオン系界面
活性剤と併用すると、非イオン系界面活性剤のブリード
スピードを調整することができ、効果の持続性を更に保
持することができる。Furthermore, alicyclic saturated hydrocarbons, rosins, petroleum fats, terpene resins, etc. may be added to the composition of the present invention as additives (F). Its preferred range is 0.5-l
Qwt%, more preferably 1 to 7wt%. These can be used alone or in combination, and when used in combination with the nonionic surfactant mentioned above, the bleeding speed of the nonionic surfactant can be adjusted and the sustainability of the effect can be further maintained. .
このように本発明の組成物は、特にフィルム状に加工し
た場合に、加工安定性、強度、シール性、光学特性に優
れており、かつ衝撃強度と腰強度を同時に改良すること
ができる。また、冷間で高度の配向を付与することによ
り、低温収縮性を持たせることも可能であり、現在食品
の収縮包装分野で主に使われている塩ビ収縮フィルムと
同様の使い方が可能となって、包装の多様化と包装スピ
ードの高速化に対応したフィルムとすることが可能であ
る。As described above, the composition of the present invention, especially when processed into a film, has excellent processing stability, strength, sealing properties, and optical properties, and can simultaneously improve impact strength and stiffness. In addition, by imparting a high degree of cold orientation, it is possible to give it low-temperature shrinkability, making it possible to use it in the same way as PVC shrink film, which is currently mainly used in the food shrink packaging field. Therefore, it is possible to create a film that is compatible with the diversification of packaging and the increase in packaging speed.
また、収縮包装用フィルムとしての用途の他に、ストレ
ッチ−シュリンク包装用フィルム、その他色装用フィル
ム、農業用フィルム、多層としてバリヤー層を加えるこ
とによるバリヤーフィルム又はそのシュリンク包装用フ
ィルム等、その他、他種レジンとの多層フィルム等とす
ることができる。In addition to its use as a shrink packaging film, it is also used in stretch-shrink packaging films, other colored films, agricultural films, barrier films by adding a barrier layer as a multilayer, or shrink packaging films thereof, etc. It can be made into a multilayer film with a seed resin.
また、型成型品として使用しても良く、同様な効果が認
められ、特に衝撃強度に優れたものとなる。Moreover, it may be used as a molded product, and the same effect will be observed, and it will be particularly excellent in impact strength.
以下に実施例をあげて本発明の詳細な説明するが、これ
らは本発明の範囲を制限するものではない。EXAMPLES The present invention will be described in detail below with reference to Examples, but these are not intended to limit the scope of the present invention.
なお、本明細書及び本文実施例中の測定、評価は下記の
方法によった。Note that the measurements and evaluations in this specification and the main text examples were carried out by the following methods.
(評価方法)
ビカ・・ 占 °: ASTMD l 525−
58Tに準拠。(Evaluation method) Vika: ASTMD l 525-
Compliant with 58T.
断面積1m”の平らな先端をもつ針に1.000gの一
定荷重を加え、毎時50℃の速度で恒温油槽中で温度上
昇させ、針入深さが1mに達した温度をピカット軟化点
(℃)とした。A constant load of 1.000 g is applied to a needle with a flat tip with a cross-sectional area of 1 m", and the temperature is increased in a constant temperature oil bath at a rate of 50 °C per hour. The temperature at which the needle penetration depth reaches 1 m is called the Picat softening point ( ℃).
上皮ユ1Z4) : A S TM D 1505に
準拠。Epithelial layer 1Z4): Based on ASTM D 1505.
柴山製作所精密度勾配管を用い23℃で測定した。Measurements were made at 23°C using a precision gradient tube manufactured by Shibayama Seisakusho.
量l肚立利工):パーキンエルマー社製示差走査熱量計
MODEL DSC2型を用いて厚み100μ程度の
フィルム試料につき測定。Measured on a film sample with a thickness of about 100 μm using a differential scanning calorimeter MODEL DSC2 manufactured by PerkinElmer.
この試料を窒素気流下、150℃まで急速に加熱し、こ
の温度に5分間等温保持し、lO℃/分の速度で50℃
まで冷却し、次いで10’C/分の速度で再加熱した時
の吸熱ピーク温度を最高融点とした。(以後M、P、と
略す、)
梧益化度:上記DSCによる融解熱△Hを測定し、化学
便覧応用&1i(日本化学会4I)P、836の表11
.37の結晶成分の融解熱ΔHnを用い、結晶化度(%
)=ΔH/△HnXIQQより求めノこ。The sample was rapidly heated to 150°C under nitrogen flow, held isothermally at this temperature for 5 minutes, and then heated to 150°C at a rate of 10°C/min.
The highest melting point was defined as the endothermic peak temperature when the sample was cooled to 100° C. and then reheated at a rate of 10'C/min. (Hereinafter abbreviated as M, P) Degree of conversion: The heat of fusion △H was measured by the above DSC, and Table 11 of Chemical Handbook Application & 1i (Chemical Society of Japan 4I) P, 836
.. Using the heat of fusion ΔHn of the 37 crystal components, the crystallinity (%
)=ΔH/ΔHnXIQQ.
メル イン−゛ ス 10 :ASTMD1
23B−52Tに準拠。MEL IN-S 10:ASTMD1
Compliant with 23B-52T.
温度190”C2押出荷重2160±10gの条件で、
定常的に押出される樹脂の重量を10分間当たりの押出
しグラム数に喚算して表した。(以後M、1、と略す、
)
ルム の 二軸方向に20m*間隔で40
点厚みを測定し、これを流れ方向に3回繰り返したとき
、その平均厚みからの厚薄を±X%とした。Under the conditions of temperature 190"C2 extrusion load 2160±10g,
The weight of the resin constantly extruded was calculated into the number of grams extruded per 10 minutes. (Hereafter abbreviated as M,1,
) 40 meters at intervals of 20 m* in the two axes of the lum
The point thickness was measured, and when this was repeated three times in the machine direction, the thickness from the average thickness was defined as ±X%.
ルム の・ 0 8折幅を20mにわたって連続的
に測定し、その最大と最小の差R(閤)を平均折幅で割
り、100倍した偵。Measure the fold width of the room continuously over 20 meters, divide the difference R between the maximum and minimum by the average fold width, and multiply by 100.
会ニス」): ASTMD 1003−52に準拠して
測定した。varnish): Measured in accordance with ASTM D 1003-52.
久旦ムユK):ASTMD2457−70に準拠して測
定した。Kudan Muyu K): Measured in accordance with ASTM D2457-70.
−k ws” : AS’r’MD−882ニ準拠
して測定した。-kws": Measured in accordance with AS'r'MD-882.
1 mm+”);ASTMD−88
2に準拠して測定した。1 mm+”); ASTM D-88
Measured according to 2.
預1」」U創支工枯二工LL: ASTMDl 709
−67に準拠して測定した。Deposit 1” U Soshiko Kariniko LL: ASTMDl 709
-67.
エルメン′ル :ASTMD1922−
67に準拠して測定した。Elmen'le: ASTM D1922-
Measured in accordance with 67.
層:」」びシに1皿;バー・タイプシーラー(シール輻
5■)の温度を変え、これにより好ましくシールされる
温度範囲を示したものである。Layer: 1 plate per layer; The temperature range of the bar type sealer (sealing range: 5 cm) was changed to show the temperature range in which the seal could be preferably achieved.
その下限は剥離して一定の強度にシールされない温度で
あり、上限は熱により溶けて切れてしまい一定のシール
強度とすることができない耐熱性を示す値である。The lower limit is the temperature at which the seal will not peel and have a certain strength, and the upper limit is the temperature at which the seal will melt and break due to heat and will not have a certain seal strength.
なお、バー押圧は1kg/cdで時間は適宜調整し以下
、実施例に使用した樹脂を記す。The bar pressure was 1 kg/cd and the time was adjusted as appropriate.The resins used in the examples are described below.
a、: EVA (酢酸ビニル含量3.5モル%、M、
I、2.0)
a2 :低密度ポリエチレン(LDPE)[M。a,: EVA (vinyl acetate content 3.5 mol%, M,
I, 2.0) a2: Low density polyethylene (LDPE) [M.
1.2,0、密度0. 918 g/cd、M、 P
、 103℃]
a3 :エチレンーアクリル酸エチル共重合体(EEA
)(アクリル酸エチル含[5,0モル%、M、 I、
1. 5)
a4 ニアイオノマー樹JJI (to ) Cx−
f−レンーメタアクリル酸共重合体Na中和タイプ、メ
タアクリル酸含量6.6モル%、M、 I、 1.
O1中和度25%、ケン化度50%〕
bl :エチレンーα−オレフィン共重合体エラストマ
ー〔α−オレフィンがプロピレンで15モル%含有、エ
チリデンノルボルネン2wt%をランダム共重合、M、
1.0.45、密度0.88g / cd、ビカット軟
化点40゛C以下〕C3:低度な結晶性をもつエチレン
−αニオレフイン共重合体(VLDPE)CM、I、2
.2、密度0. 910 g/c+J、三片石油化学社
製ウルトゼックス1020L)
c、;VLDPE (M、I、3.6、密度0゜910
g/cd、三片石油化学社製ウルトゼックス1030L
)
C3: VLDPE (M、1.3.3、密度0゜91
2 g /cd、ダウ・ケミカル社製アテイン4002
〕
C,、VLDPE (M、I、1.0、密度0゜912
g/cd、ダウ・ケミカル社製アテイン40ca :
VLDPE (M、1.0.9、密度0゜909g/
c+j、住友化学社製エクセレンCNl0c、:VLD
PE (M、I、0.8、密度0゜906 g /cd
、ユニオン・カーバイド社製ナックフレックスDFDA
−1137NT)
dI :結晶性ポリプロピレン(IPP)(エチリンを
4wt%ランダム共重合、MFR3,3、ビカット軟化
点150℃〕
d富 ;結晶性ポリブテン−1(PB−1)(ブテン−
1含量96モル%、密度0. 905 g/d、M、
I、 1. 0)
d3 : IPP (エチレンを5wt%共重合、MF
R7,O1密度0. 900 g/cd、ビカット軟化
点125℃〕
実施例1
エチレン−酢酸ビニル共重合体(E V A 、 a
+):25wt%とエチレン−α−オレフィン共重合体
エストラマー(b+ )15wt%、結晶性エチレン−
α−オレフィン共重合体(VLDPE。1.2,0, density 0. 918 g/cd, M, P
, 103°C] a3: Ethylene-ethyl acrylate copolymer (EEA
) (contains ethyl acrylate [5.0 mol%, M, I,
1. 5) a4 Near ionomer tree JJI (to) Cx-
f-ren-methacrylic acid copolymer Na neutralized type, methacrylic acid content 6.6 mol%, M, I, 1.
O1 neutralization degree 25%, saponification degree 50%] bl: Ethylene-α-olefin copolymer elastomer [α-olefin contains 15 mol% of propylene, random copolymerization of 2 wt% ethylidene norbornene, M,
1.0.45, density 0.88 g/cd, Vicat softening point 40°C or less] C3: Ethylene-α niolefin copolymer (VLDPE) with low crystallinity CM, I, 2
.. 2. Density 0. 910 g/c+J, Mikata Petrochemical Co., Ltd. Ultzex 1020L) c, ;VLDPE (M, I, 3.6, density 0°910
g/cd, Mikata Petrochemical Co., Ltd. Urtozex 1030L
) C3: VLDPE (M, 1.3.3, density 0°91
2 g/cd, Attain 4002 manufactured by Dow Chemical Company
] C,, VLDPE (M, I, 1.0, density 0°912
g/cd, Attain 40ca manufactured by Dow Chemical Company:
VLDPE (M, 1.0.9, density 0゜909g/
c+j, Sumitomo Chemical Excellen CNl0c, :VLD
PE (M, I, 0.8, density 0゜906 g/cd
, Union Carbide Knackflex DFDA
-1137NT) dI: Crystalline polypropylene (IPP) (4 wt% random copolymerization of ethyline, MFR 3.3, Vicat softening point 150°C) dI: Crystalline polybutene-1 (PB-1) (butene-
1 content 96 mol%, density 0. 905 g/d, M,
I, 1. 0) d3: IPP (5 wt% copolymerization of ethylene, MF
R7, O1 density 0. 900 g/cd, Vicat softening point 125°C] Example 1 Ethylene-vinyl acetate copolymer (EVA, a
+): 25 wt% and ethylene-α-olefin copolymer elastomer (b+) 15 wt%, crystalline ethylene-
α-olefin copolymer (VLDPE).
ex)40wt%、結晶性ポリプロピレン(dl)20
wt%を混合し、65M径でL/D−37のミキシング
ヘッドタイプスクリューで、シリンダ部最高温度240
℃で可塑化混練した組成物を、10〇−径でスリット1
. 0■の環状ダイより押出して、内部に空気を入れる
ことによりインフレーシヨンし、急冷して、径400m
の厚み50μの均一なフィルムを得た。このフィルムを
連続的に巻き取ってロール状とした。ex) 40wt%, crystalline polypropylene (dl) 20
By mixing wt% with a 65M diameter L/D-37 mixing head type screw, the cylinder part maximum temperature was 240.
The composition that has been plasticized and kneaded at
.. It is extruded through a 0.0 mm annular die, inflated by introducing air inside, and rapidly cooled to a diameter of 400 m.
A uniform film with a thickness of 50 μm was obtained. This film was continuously wound up into a roll.
成膜加工性は良く安定して成膜でき、またそのフィルム
の幅方向の偏肉は上2゜5%であり、折幅の変動は4%
と均一であった。Film forming processability is good and stable film formation is possible, and the thickness deviation in the width direction of the film is 2.5% above, and the variation in fold width is 4%.
It was uniform.
このフィルムの特性は以下の通りであった。The properties of this film were as follows.
ヘイズ:1.6%、グロス:110%、落鍾衝撃強度(
以後ダート強度と略す):41kg−cm、腰強度(1
%引張弾性率、タテ/ヨコ)833/30 (kg/m
” )引張強度: 4. 5/4. O(kg/mっ
で、ヒートシール範囲は110〜260 ’Cと広く且
つ耐熱性もあった。Haze: 1.6%, Gloss: 110%, Drop impact strength (
(hereinafter abbreviated as dirt strength): 41 kg-cm, waist strength (1
% tensile modulus, vertical/horizontal) 833/30 (kg/m
) Tensile strength: 4.5/4.0 (kg/m), the heat sealing range was wide from 110 to 260'C, and the heat resistance was also high.
実施例2〜1!
実施例1と同様な方法で、表1の組成でフィルムとし、
得られた特性を表2に示す。Examples 2-1! In the same manner as in Example 1, a film was prepared with the composition shown in Table 1,
The properties obtained are shown in Table 2.
表1
いずれも成膜の加工安定性は良く、フィルムの幅方向の
偏肉も少なく、ダート強度及び腰強度(1%引張弾性率
)における改良効果が大きい。Table 1 In all cases, the processing stability of film formation is good, there is little thickness deviation in the width direction of the film, and there is a large improvement effect in dart strength and waist strength (1% tensile modulus).
また、各々ヒートシール温度範囲も広<110〜260
℃であり、シール強度も強く、シール部に穴があく等の
問題は、この温度範囲では見られない。In addition, each heat sealing temperature range is wide <110 to 260
℃, the seal strength is strong, and problems such as holes in the seal are not observed in this temperature range.
実施例12〜26
実施例1と同様の方法を用い、実施例1の樹脂組成でそ
の組成比を表3のように変えてフィルムを成膜し、得ら
れた特性を表4に示す。Examples 12 to 26 Using the same method as in Example 1, films were formed using the resin composition of Example 1 with the composition ratios changed as shown in Table 3, and the obtained properties are shown in Table 4.
その結果、いずれの組成比の場合も成膜の加工安定性は
良く、偏肉や折幅変動は小さかった。As a result, the process stability of the film formation was good for all composition ratios, and thickness deviations and fold width fluctuations were small.
また、この組成比の範囲内では、透明性、光沢も優れて
おり、ダート強度と腰強度(1%引張弾性率)という通
常相反する特性が共に優れた成型品を得ることができる
ことがわかる。また、更にこれら組成比の範囲では、各
々ヒートシール温度範囲も広<110〜260℃であり
、シール強度も強いものであった。It is also seen that within this composition ratio range, it is possible to obtain a molded product that has excellent transparency and gloss, and is excellent in both dart strength and waist strength (1% tensile modulus), which are usually contradictory properties. Furthermore, within these composition ratio ranges, the heat sealing temperature range was wide (<110 to 260°C), and the sealing strength was strong.
なお、実施例19の組成で、各組成成分の配向状態を偏
光蛍光法で調べたところ、EVA、ポリプロピレン、エ
チレン−α−オレフィン共重合体エラストマーは流れ方
向に配向しているものの、部分結晶性エチレン−α−オ
レフィン共重合体はほとんど配向していないことが観察
された。この組成のダート強度は、42kg−dと実施
例の組成の中で最も強いものであった。In addition, when the orientation state of each composition component in the composition of Example 19 was examined using a polarized fluorescence method, it was found that although EVA, polypropylene, and ethylene-α-olefin copolymer elastomer were oriented in the flow direction, they were partially crystalline. It was observed that the ethylene-α-olefin copolymer was hardly oriented. The dart strength of this composition was 42 kg-d, which was the strongest among the compositions of Examples.
実施例27〜42
実施例1の組成及び実施例12〜26の組成(表3)を
、実施例1と同じ押出機を用い溶融可塑化し、押出機の
途中から液状添加剤として、ジグリセリンーモノオレー
トを2,0wt%注入し、混練した組成物を同様に押出
し、急冷して厚み90μの原反を得た。引き続き、この
原反を70″Cの熱風を用いて加熱し、タテ3.2倍、
ヨコ4゜0倍に内部に空気を吹き込んで、冷間延伸し、
折り畳んだ後、40℃の熱風を用いてヒートセットして
、厚み11μのフィルムを得た。Examples 27 to 42 The compositions of Example 1 and Examples 12 to 26 (Table 3) were melt-plasticized using the same extruder as Example 1, and diglycerin was added as a liquid additive from the middle of the extruder. A composition in which 2.0 wt % of monooleate was injected and kneaded was extruded in the same manner and rapidly cooled to obtain an original fabric having a thickness of 90 μm. Subsequently, this original fabric was heated using hot air at 70″C, and the vertical size was increased by 3.2 times.
Air is blown into the inside at 4° width and cold stretched.
After folding, heat setting was performed using hot air at 40° C. to obtain a film having a thickness of 11 μm.
得られたフィルムの特性を表5に示す。Table 5 shows the properties of the obtained film.
いずれも成膜の安定性は良く、偏肉及び折幅の変動も小
さかった。In all cases, the stability of film formation was good, and variations in thickness unevenness and fold width were also small.
またいずれのフィルムも厚みが11μと薄いにもかかわ
らず、ダート強度が30kg−c鳳を越え、腰強度(1
%引張弾性率)も強(、更に引裂強度についても非常に
優れたものであった。又、これらフィルムは各々ヒート
シール温度範囲も広く110〜260℃であり、シール
強度も強いものであった。また、得られたフィルムは、
60℃での収縮率20〜30%、熱収縮応力100〜1
50g/cj(タテ/ヨコ平均)とシュリンク包装用フ
ィルムとして、十分な低温収縮性を持っており、ダート
強度、腰強度、引張強度、引裂強度、透明性、ヒートシ
ール性等の優れた特性と相まって、シュリンク包装の多
様化及び包装スピードの高速化に対応した包装用フィル
ムとして非常に有用なものである。In addition, despite the thickness of both films being as thin as 11 μm, the dart strength exceeds 30 kg-c, and the waist strength (1
% tensile modulus) (and tear strength was also very excellent. Also, each of these films had a wide heat sealing temperature range of 110 to 260°C, and the sealing strength was also strong. .Also, the obtained film is
Shrinkage rate at 60℃ 20-30%, heat shrinkage stress 100-1
50g/cj (vertical/horizontal average), it has sufficient low-temperature shrinkability as a shrink packaging film, and has excellent properties such as dart strength, waist strength, tensile strength, tear strength, transparency, and heat sealability. In combination, the film is extremely useful as a packaging film that can accommodate the diversification of shrink packaging and the increased packaging speed.
比較例1〜10
実施例1と同様な方法で、組成については表6の組成の
フィルムを成膜し、得られた特性を表7に示す。Comparative Examples 1 to 10 Films having the compositions shown in Table 6 were formed in the same manner as in Example 1, and the obtained properties are shown in Table 7.
表6
表8
その結果、成膜加工安定性については、比較例N[L7
を除いて問題があり、偏肉もあまり良いものではなかっ
た。Table 6 Table 8 As a result, regarding the film forming process stability, Comparative Example N [L7
There was a problem with everything except for the unevenness of the meat, which was not very good.
特に、比較例1.2.3は混練も不均一であり、光学特
性(ヘイズ、グロス)が悪いものであった。In particular, in Comparative Examples 1.2.3, the kneading was uneven and the optical properties (haze, gloss) were poor.
また、比較例4.5.6.9はフィルムの腰強度が小さ
いため、取扱いが難しい。In addition, Comparative Examples 4,5,6,9 are difficult to handle because the film has low stiffness.
また、比較例7.8.10のフィルムは、光学特性が他
のものに比較して良くはなっているものの、未だダート
強度、腰強度共に不十分であった。Furthermore, although the films of Comparative Examples 7, 8, and 10 had better optical properties than the others, they still had insufficient dart strength and stiffness.
ヒートシール温度範囲は、比較例1.2.3.8.10
が160〜230″Cと高温領域であって、強度もあま
り強いものではなかった。比較例4.5.6.9は10
0〜150 ”Cと低温領域でシールできるが、耐熱性
がなく穴があき易いものであった。The heat sealing temperature range is Comparative Example 1.2.3.8.10
was in the high temperature range of 160 to 230"C, and the strength was not very strong. Comparative example 4.5.6.9 was 10
Although it can be sealed in the low temperature range of 0 to 150"C, it has no heat resistance and is prone to holes.
比較例11〜20
実施例1と同様な方法で、組成については表8の組成の
フィルムを成膜し、得られたフィルムの特性を表9に示
す。Comparative Examples 11 to 20 Films having the compositions shown in Table 8 were formed in the same manner as in Example 1, and the properties of the obtained films are shown in Table 9.
いずれのフィルムも成膜加工安定性が悪くかつ偏肉の大
きなものしか得られなかった。All of the films had poor film-forming stability and only had large thickness deviations.
また、これらフィルムは各組成樹脂の相溶性が比較的良
く、光学特性は良いものの、ダート強度が弱く、腰強度
も小さいため、取扱いの難しいものであった。Further, although these films have relatively good compatibility of each constituent resin and good optical properties, they have low dart strength and low stiffness, making them difficult to handle.
比較例21〜30
比較例11〜20の組成(表8)を実施例27と同様の
方法でフィルムを成膜し、平均厚み11μのフィルムを
得た。得られたフィルムの特性を表10に示す。Comparative Examples 21 to 30 Films were formed using the compositions of Comparative Examples 11 to 20 (Table 8) in the same manner as in Example 27 to obtain films with an average thickness of 11 μm. Table 10 shows the properties of the obtained film.
その結果、いずれのフィルムも成膜加工安定性が悪く、
またフィルムの偏肉も大きなものであった。また、これ
らのフィルムは光学特性は比較的良いものの、ダート強
度が弱く、更に引裂強度もあまり強くないため、突起物
のある内容物を包装しようとしたり、包装スピードを上
げようとするとフィルムが破れたり、穴がおいてしまい
、使用できないものであった。As a result, both films had poor film-forming stability.
Furthermore, the thickness of the film was also large. In addition, although these films have relatively good optical properties, their dart strength is low and their tear strength is also not very strong, so if you try to package contents with protrusions or increase the packaging speed, the film may tear. They were unusable because they had holes in them.
特に、比較例21.25.26.30は、腰強度も弱い
ため、上記の問題の他取扱い難いという問題があるもの
であった。In particular, Comparative Examples 21, 25, 26, and 30 had a problem in that they were difficult to handle in addition to the above-mentioned problems because of their weak waist strength.
なかでも特にシート、フィルム成型用の組成物として非
常に有用なものである。Among these, it is particularly useful as a composition for forming sheets and films.
以上のように、本発明による組成物は、押出成型性に優
れると共に、ヒートシール性、衝撃強度特性、引張強度
特性、透明性等に優れたものである。As described above, the composition according to the present invention has excellent extrusion moldability, as well as excellent heat sealability, impact strength characteristics, tensile strength characteristics, transparency, and the like.
Claims (1)
エチレン−アクリル酸エチル共重合体、エチレン−アク
リル酸共重合体、エチレン−メタアクリル酸メチル共重
合体、エチレン−メタアクリル酸共重合体、アイオノマ
ー樹脂からなる群から選ばれる少なくとも一種の重合体
(A)15〜45wt%と、 ビカット軟化点60℃以下の軟質エラストマー(B)5
〜15wt%と、 23℃における密度が0.880〜0.920g/cm
^3、メルトインデックスが0.5〜5g/10分、示
差走査熱量計(DSC)による最高融点が110℃〜1
30℃であり、かつビカット軟化点が60〜95℃であ
るエチレンと炭素数4〜10のα−オレフィンとの共重
合体(C)20〜55wt%と、 結晶性ポリプロピレン、結晶性ポリブテン−1のいずれ
か又はこれらの混合重合体(D)10〜40wt%と、 からなるポリオレフィン系樹脂組成物。[Claims] Low density polyethylene, ethylene-vinyl acetate copolymer,
At least one polymer selected from the group consisting of ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, and ionomer resin ( A) Soft elastomer with a content of 15 to 45 wt% and a Vicat softening point of 60°C or less (B) 5
~15wt% and density at 23°C of 0.880~0.920g/cm
^3, melt index is 0.5~5g/10min, maximum melting point by differential scanning calorimeter (DSC) is 110℃~1
30°C and a Vicat softening point of 60 to 95°C, 20 to 55 wt% of a copolymer (C) of ethylene and an α-olefin having 4 to 10 carbon atoms, crystalline polypropylene, crystalline polybutene-1 A polyolefin resin composition comprising: or 10 to 40 wt% of a mixed polymer (D) thereof.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1776689A JP2772655B2 (en) | 1989-01-30 | 1989-01-30 | Polyolefin resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1776689A JP2772655B2 (en) | 1989-01-30 | 1989-01-30 | Polyolefin resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02199144A true JPH02199144A (en) | 1990-08-07 |
JP2772655B2 JP2772655B2 (en) | 1998-07-02 |
Family
ID=11952833
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1776689A Expired - Lifetime JP2772655B2 (en) | 1989-01-30 | 1989-01-30 | Polyolefin resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2772655B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0816428A4 (en) * | 1995-03-13 | 1999-05-06 | Mitsui Petrochemical Ind | 4-methyl-1-pentene polymer composition |
US6693237B2 (en) * | 2000-05-23 | 2004-02-17 | Canon Kabushiki Kaisha | Sealing composition for sealing solar cell, and solar cell module and building material-integral type solar cell module using said composition |
JP4953269B2 (en) * | 2000-04-28 | 2012-06-13 | 三井化学株式会社 | Thermoplastic resin molded body and composition |
-
1989
- 1989-01-30 JP JP1776689A patent/JP2772655B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0816428A4 (en) * | 1995-03-13 | 1999-05-06 | Mitsui Petrochemical Ind | 4-methyl-1-pentene polymer composition |
JP4953269B2 (en) * | 2000-04-28 | 2012-06-13 | 三井化学株式会社 | Thermoplastic resin molded body and composition |
US6693237B2 (en) * | 2000-05-23 | 2004-02-17 | Canon Kabushiki Kaisha | Sealing composition for sealing solar cell, and solar cell module and building material-integral type solar cell module using said composition |
Also Published As
Publication number | Publication date |
---|---|
JP2772655B2 (en) | 1998-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5443765A (en) | Method for producing a highly stretched multi-layered film | |
JPS6079932A (en) | High-orientation stretchable multi-layer film and manufacture thereof | |
JP5049122B2 (en) | Resin composition, film or sheet or laminate comprising resin composition | |
US6727000B2 (en) | Multilayer heat-shrinkable sealable films | |
JPH07276584A (en) | Laminated sheet | |
JP2001162737A (en) | Multi-layer film for packaging | |
JP5826035B2 (en) | Film for stretch wrapping | |
JP2002240210A (en) | Film for packaging food | |
JP2974198B2 (en) | Polyolefin-based shrink laminated film and method for producing the same | |
JPS5938976B2 (en) | improved composition | |
DE112020001602T5 (en) | RESIN COMPOSITION FOR SEALING MATERIAL, MULTI-LAYER BODY, PACKING MATERIAL AND PACKING CONTAINER | |
JPH02199144A (en) | Polyolefin resin composition | |
JPH0577371A (en) | Laminated film | |
JP2001145987A (en) | Multilayered film for packaging | |
JP2003220675A (en) | Polyolefin stretched film and method of manufacturing the same | |
JP2009138139A (en) | Stretched film of olefin polymer | |
EP2918409B1 (en) | Stretch wrapping film | |
KR100550313B1 (en) | Polypropylene Resin Composition Having Good Low Heat Sealing Property, Good Transparency and Good Tear Strength | |
JPS5950172B2 (en) | improved composition | |
JP4311973B2 (en) | Polyolefin-based stretch film | |
JPH07232417A (en) | Polyolefoinic heat-shrinkable laminated film and manufacture thereof | |
JPWO2004020195A1 (en) | Polypropylene wrap film | |
JP2946100B2 (en) | Polyolefin-based multilayer stretched film | |
JP2019001139A (en) | Multilayer biaxially oriented film and transfer film | |
JP2022150852A (en) | Multilayer biaxially stretched film |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080424 Year of fee payment: 10 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090424 Year of fee payment: 11 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090424 Year of fee payment: 11 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090424 Year of fee payment: 11 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
EXPY | Cancellation because of completion of term | ||
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090424 Year of fee payment: 11 |