JP2018123174A - Resin composition and molded body of the same - Google Patents
Resin composition and molded body of the same Download PDFInfo
- Publication number
- JP2018123174A JP2018123174A JP2017013771A JP2017013771A JP2018123174A JP 2018123174 A JP2018123174 A JP 2018123174A JP 2017013771 A JP2017013771 A JP 2017013771A JP 2017013771 A JP2017013771 A JP 2017013771A JP 2018123174 A JP2018123174 A JP 2018123174A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- group
- resin composition
- fatty acid
- acid
- 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 28
- 229920000098 polyolefin Polymers 0.000 claims abstract description 50
- -1 fatty acid ester Chemical class 0.000 claims abstract description 42
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 27
- 229930195729 fatty acid Natural products 0.000 claims abstract description 27
- 239000000194 fatty acid Substances 0.000 claims abstract description 27
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 13
- 239000005022 packaging material Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 10
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 239000004711 α-olefin Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 235000010746 mayonnaise Nutrition 0.000 description 7
- 239000008268 mayonnaise Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 5
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- PAZZVPKITDJCPV-UHFFFAOYSA-N 10-hydroxyoctadecanoic acid Chemical compound CCCCCCCCC(O)CCCCCCCCC(O)=O PAZZVPKITDJCPV-UHFFFAOYSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- RKHXDCVAPIMDMG-UHFFFAOYSA-N 9-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCC(O)CCCCCCCC(O)=O RKHXDCVAPIMDMG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XSXIVVZCUAHUJO-AVQMFFATSA-N (11e,14e)-icosa-11,14-dienoic acid Chemical compound CCCCC\C=C\C\C=C\CCCCCCCCCC(O)=O XSXIVVZCUAHUJO-AVQMFFATSA-N 0.000 description 1
- 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 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 229960003656 ricinoleic acid Drugs 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Abstract
Description
本発明は、樹脂組成物およびその成形体に関する。 The present invention relates to a resin composition and a molded body thereof.
熱可塑性樹脂は安価であることや成形が容易であることから、様々な場面で使用されている。しかし、熱可塑性樹脂を成形して包装材等として使用する場合、内容物が包装材に付着して取り出しにくい、あるいは取り出した後の包装材に付着した内容物は包装材とともに廃棄されてしまい歩留まりが低下するなどの問題がある。包装材に離型性を付与して内容物の付着を低減する目的で、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル等の脂肪酸エステルが用いられている。これらの脂肪酸エステルは安全性が高く、比較的安価であるため、例えば食品包装材等の汎用用途で好適に使用される。
特許文献1,2では、粘稠物が接するシーラント層に界面活性剤を配合することや、包装材の内面に予め界面活性剤を塗工して膜を形成することが記載されている。
Thermoplastic resins are used in various situations because they are inexpensive and easy to mold. However, when a thermoplastic resin is molded and used as a packaging material, the contents adhere to the packaging material and are difficult to remove, or the contents adhered to the packaging material after removal are discarded together with the packaging material and the yield There are problems such as lowering. Fatty acid esters such as glycerin fatty acid esters and sorbitan fatty acid esters are used for the purpose of imparting releasability to the packaging material and reducing adhesion of contents. Since these fatty acid esters are highly safe and relatively inexpensive, they are suitably used for general purposes such as food packaging materials.
Patent Documents 1 and 2 describe that a surfactant is blended in a sealant layer in contact with a viscous material, or that a film is formed by applying a surfactant in advance to the inner surface of a packaging material.
しかしながら、本発明者らが検討したところ、脂肪酸エステルを熱可塑性樹脂に配合した場合、脂肪酸エステルの樹脂への分散性が悪く、不均一な樹脂組成物になってしまいやすいことが判明した。そのため、得られた樹脂組成物を用いて作成したフィルム等の成形体は成形品表面に脂肪酸エステルが析出しやすくなり、成形品表面の平滑性が低下する、或いは成形品の外観が悪化する等の問題があることが判明した。また、脂肪酸エステルは成形体表面からブリードアウトしやすいため、その離型効果が低下しやすいことが懸念される。従って本発明の課題は、脂肪酸エステルを含んでいても、表面平滑性、外観、離型性に優れた成形体を得ることができる樹脂組成物を提供することと、表面平滑性、外観、離型性に優れた成形体を提供することである。 However, as a result of investigations by the present inventors, it has been found that when a fatty acid ester is added to a thermoplastic resin, the dispersibility of the fatty acid ester in the resin is poor and a non-uniform resin composition tends to be formed. Therefore, in a molded article such as a film prepared using the obtained resin composition, the fatty acid ester is likely to be precipitated on the surface of the molded article, the smoothness of the molded article surface is lowered, or the appearance of the molded article is deteriorated. It turns out that there is a problem. Moreover, since fatty acid ester is easy to bleed out from the surface of a molded object, there is a concern that the mold release effect tends to be lowered. Accordingly, an object of the present invention is to provide a resin composition capable of obtaining a molded article excellent in surface smoothness, appearance, and releasability even when a fatty acid ester is contained, and to provide surface smoothness, appearance, release properties. It is to provide a molded article having excellent moldability.
すなわち、本発明によれば、以下に示す樹脂組成物と成形体が提供される。
[1]熱可塑性樹脂、シリル化ポリオレフィン及び分子量が100〜10,000である脂肪酸エステルを含むことを特徴とする樹脂組成物。
[2]熱可塑性樹脂がポリオレフィンである、前記[1]に記載の樹脂組成物。
[3]前記[1]または[2]に記載の樹脂組成物から成形される成形体。
[4]成形体がフィルムまたはシートである、前記[3]に記載の成形体。
[5]容器または包装材である、前記[3]または[4]に記載の成形体。
That is, according to the present invention, the following resin composition and molded article are provided.
[1] A resin composition comprising a thermoplastic resin, a silylated polyolefin, and a fatty acid ester having a molecular weight of 100 to 10,000.
[2] The resin composition according to [1], wherein the thermoplastic resin is polyolefin.
[3] A molded article molded from the resin composition according to [1] or [2].
[4] The molded article according to [3], wherein the molded article is a film or a sheet.
[5] The molded article according to [3] or [4], which is a container or a packaging material.
本発明によれば、脂肪酸エステルを含んでいても、表面平滑性、外観、離型性に優れた成形体を得ることができる樹脂組成物と、表面平滑性、外観、離型性に優れた成形体を提供することができる。 According to the present invention, a resin composition capable of obtaining a molded article excellent in surface smoothness, appearance, and releasability even when containing a fatty acid ester, and excellent in surface smoothness, appearance, and releasability. A molded body can be provided.
以下に、本発明の実施形態について説明する。なお、文中の数値範囲を示す記号「a〜b」はとくに断りがない限り、a以上からb以下を表すものとする。 Hereinafter, embodiments of the present invention will be described. In addition, unless otherwise indicated, the symbol "ab" which shows the numerical range in a sentence shall express from a to b or less.
本発明の樹脂組成物は、熱可塑性樹脂とシリル化ポリオレフィンと分子量が100〜10,000である脂肪酸エステルを含む。
(熱可塑性樹脂)
熱可塑性樹脂としては、ポリオレフィン、ポリ塩化ビニル、ポリ塩化ビニリデン、エチレン・酢酸ビニル共重合体、エチレン・メタクリル酸共重合体、ポリエチレンテレフタレート等のポリエステル、ポリカーボネート、ポリアミド、ABS樹脂、ポリアセタール樹脂、ポリイミド、ポリウレタン、ポリ乳酸などが挙げられる。
中でもポリオレフィンが好ましい。ここで、ポリオレフィンとは、構成単位中にシリコーン鎖を含まないポリオレフィンを示す。ポリオレフィンとしては、例えば炭素数2〜20のオレフィンに由来する構造単位を含む重合体を挙げることができる。好ましいポリオレフィンとしては、エチレンの単独重合体または共重合体、プロピレンの単独重合体または共重合体を挙げることができる。
エチレンの単独または共重合体中のエチレン含量は50〜100モル%であることが好ましく、60〜100モル%がより好ましい。共重合成分としては、炭素数3以上のα−オレフィンが挙げられる。
エチレンの単独または共重合体のMFR(ASTM D1238、190℃、2.16kg荷重)は、例えば、0.01〜80g/10分が好ましく、0.1〜50g/10分がより好ましい。
低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン等も好ましいポリエチレンである。
プロピレンの単独または共重合体としては、プロピレン含量が50〜100モル%であることが好ましい。共重合成分としては、エチレン、炭素数4以上のα−オレフィン等が挙げられる。
The resin composition of the present invention includes a thermoplastic resin, a silylated polyolefin, and a fatty acid ester having a molecular weight of 100 to 10,000.
(Thermoplastic resin)
Examples of the thermoplastic resin include polyolefin, polyvinyl chloride, polyvinylidene chloride, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, polyester such as polyethylene terephthalate, polycarbonate, polyamide, ABS resin, polyacetal resin, polyimide, Examples thereof include polyurethane and polylactic acid.
Of these, polyolefin is preferable. Here, the polyolefin refers to a polyolefin containing no silicone chain in the structural unit. Examples of the polyolefin include a polymer containing a structural unit derived from an olefin having 2 to 20 carbon atoms. Preferred polyolefins include ethylene homopolymers or copolymers and propylene homopolymers or copolymers.
The ethylene content in the ethylene homopolymer or copolymer is preferably 50 to 100 mol%, more preferably 60 to 100 mol%. Examples of the copolymer component include α-olefins having 3 or more carbon atoms.
The MFR (ASTM D1238, 190 ° C., 2.16 kg load) of ethylene homopolymer or copolymer is preferably, for example, 0.01 to 80 g / 10 min, and more preferably 0.1 to 50 g / 10 min.
Low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene and the like are also preferable polyethylene.
As propylene homo- or copolymer, the propylene content is preferably 50 to 100 mol%. Examples of the copolymer component include ethylene and α-olefins having 4 or more carbon atoms.
また、MFR(ASTM D1238、230℃、2.16kg荷重)は、例えば、0.1〜100g/10分が好ましく、0.3〜50g/10分がより好ましい。
(シリル化ポリオレフィン)
シリル化ポリオレフィンは、シリコーン鎖とポリオレフィン鎖を有する限りどのような構造でもよい。例えばポリオレフィンにシリコーンがグラフトした構造であるシリコーングラフトポリオレフィン、ポリオレフィンとシリコーンとのブロック共重合体、シリコーンにポリオレフィンがグラフトした構造、前記ブロック共重合体のシリコーン部分にポリオレフィンがグラフトした構造を挙げることができる。
ブロック共重合体としては、(ポリオレフィン鎖)−(シリコーン鎖)の順に結合したブロック共重合体、 (ポリオレフィン鎖)−(シリコーン鎖)−(ポリオレフィン鎖)の順に結合したブロック共重合体を挙げることができる。
ポリオレフィン鎖は例えば炭素数2〜50、好ましくは炭素数2〜20のオレフィンに由来する構造単位を含む重合体鎖を例示できる。
なかでも下記式(1)で表される構造を有するものが好ましい。
The MFR (ASTM D1238, 230 ° C., 2.16 kg load) is, for example, preferably 0.1 to 100 g / 10 minutes, and more preferably 0.3 to 50 g / 10 minutes.
(Silylated polyolefin)
The silylated polyolefin may have any structure as long as it has a silicone chain and a polyolefin chain. For example, silicone grafted polyolefin having a structure in which silicone is grafted on polyolefin, block copolymer of polyolefin and silicone, structure in which polyolefin is grafted on silicone, structure in which polyolefin is grafted on the silicone part of the block copolymer it can.
Examples of the block copolymer include a block copolymer bonded in the order of (polyolefin chain)-(silicone chain), and a block copolymer bonded in the order of (polyolefin chain)-(silicone chain)-(polyolefin chain). Can do.
Examples of the polyolefin chain include a polymer chain containing a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms.
Especially, what has a structure represented by following formula (1) is preferable.
(上記式(1)において、A1、A2およびA3は各々独立に、ポリオレフィン鎖または炭素数1〜20の炭化水素基である。Rは炭素数1〜20の炭化水素基である。各Rは同一でも異なっていてもよい。mは1〜10,000の整数である。A3が複数存在する場合、各A3は同一でも異なっていてもよい。ただし、A1、A2、A3のうち、少なくとも1つはポリオレフィン鎖を表す。)
上記A1、A2およびA3におけるポリオレフィン鎖は、例えば炭素数2〜50、好ましくは炭素数2〜20のオレフィンに由来する構造単位を含む重合体鎖である。
(In the above formula (1), A 1 , A 2 and A 3 are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different, m is an integer of 1 to 10,000, and when a plurality of A 3 are present, each A 3 may be the same or different, provided that A 1 , A 2 , A 3 represents at least one polyolefin chain.)
The polyolefin chain in A 1 , A 2 and A 3 is a polymer chain including a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, for example.
炭素数2〜50のオレフィンとしては、具体的には、エチレン、炭素数3〜50のα−オレフィン(プロピレン、1−ブテン、1−ペンテン、3−メチル−1−ブテン、1−ヘキセン、4−メチル−1−ペンテン、3−メチル−1−ペンテン、3,4−ジメチル−1−ペンテン、4−メチル−1−ヘキセン、3−エチル−1−ペンテン、3−エチル−4−メチル−1−ペンテン、3,4−ジメチル−1−ヘキセン、4−メチル−1−ヘプテン、3,4−ジメチル−1−ヘプテン、1−オクテン、1−デセン、1−ドデセン、1−テトラデセン、1−ヘキサデセン、1−オクタデセン、1−エイコセン、ビニルシクロヘキサン等)が挙げられる。 Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and an α-olefin having 3 to 50 carbon atoms (propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4 -Methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1 -Pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene 1-octadecene, 1-eicocene, vinylcyclohexane, etc.).
これらのうち、エチレン、炭素数3〜12のα−オレフィンが好ましく、エチレン、炭素数3〜8のα−オレフィンがより好ましく、エチレンが特に好ましい。
ポリオレフィン鎖は単独重合体鎖であっても、共重合体鎖であってもよい。
Among these, ethylene and an α-olefin having 3 to 12 carbon atoms are preferable, ethylene and an α-olefin having 3 to 8 carbon atoms are more preferable, and ethylene is particularly preferable.
The polyolefin chain may be a homopolymer chain or a copolymer chain.
なかでも、エチレンおよび炭素数3〜50のα−オレフィンから選ばれる炭素数2〜50のオレフィンのみから構成される重合体鎖が好ましく、さらには、エチレン単独重合体鎖、プロピレン単独重合体鎖、またはエチレン・炭素数3〜20のα−オレフィンの共重合体鎖が好ましい。エチレン・炭素数3〜20のα−オレフィンの共重合体鎖において、全構成単位を100モル%としたとき、炭素数3〜20のα−オレフィン由来の構造単位は、例えば0モル%を超え20モル%以下とすることができ、0モル%を超え10モル%以下とすることもできる。
また、上記ポリオレフィン鎖は所望により、他のオレフィン由来の構造単位を含んでもよい。他のオレフィンとしては、シス−2−ブテン等の内部二重結合を含むオレフィン;イソブテン等のビニリデン化合物;スチレン等のアリールビニル化合物;α−メチルスチレン等のアリールビニリデン化合物;メタクリル酸メチル等の官能基置換ビニリデン化合物;5−メチル−2−ノルボルネン、テトラシクロドデセン、シクロペンタジエン、ジシクロペンタジエン等の内部二重結合を含む脂肪族環状オレフィン;インデン等の芳香環を含有する環状オレフィン;ブタジエン、イソプレン、エチリデンノルボルネン、ビニルノルボルネン等の鎖状または環状のポリエン等が挙げられる。
他のオレフィン由来の構造単位の含有量は、ポリオレフィン鎖を構成する全構成単位を100モル%としたとき、0〜10モル%が好ましく、0〜5モル%がより好ましい。
上記ポリオレフィン鎖は、下記のGPC法により求めた数平均分子量が100以上500,000以下であることが好ましく、200以上100,000以下がさらに好ましく、500以上50,000以下がさらに好ましく、700以上10,000以下がさらに好ましい。
また、上記ポリオレフィン鎖は、下記のGPC法により求めた分子量分布(Mw/Mn)が1.1〜3.0の範囲にあることが好ましい。
Especially, the polymer chain comprised only from C2-C50 olefin chosen from ethylene and C3-C50 alpha olefin is preferable, Furthermore, ethylene homopolymer chain, propylene homopolymer chain, Alternatively, an ethylene / C3-C20 α-olefin copolymer chain is preferred. In the copolymer chain of ethylene / C3-C20 α-olefin, when all the structural units are 100 mol%, the structural unit derived from C3-C20 α-olefin exceeds, for example, 0 mol%. It can also be 20 mol% or less, and can also be over 0 mol% and 10 mol% or less.
Moreover, the said polyolefin chain may also contain the structural unit derived from another olefin as needed. Other olefins include olefins containing an internal double bond such as cis-2-butene; vinylidene compounds such as isobutene; aryl vinyl compounds such as styrene; arylvinylidene compounds such as α-methylstyrene; and functionalities such as methyl methacrylate. Group-substituted vinylidene compounds; aliphatic cyclic olefins containing internal double bonds such as 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, dicyclopentadiene; cyclic olefins containing an aromatic ring such as indene; butadiene, Examples thereof include linear or cyclic polyenes such as isoprene, ethylidene norbornene and vinyl norbornene.
The content of structural units derived from other olefins is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, assuming that all the structural units constituting the polyolefin chain are 100 mol%.
The polyolefin chain preferably has a number average molecular weight of 100 or more and 500,000 or less, more preferably 200 or more and 100,000 or less, further preferably 500 or more and 50,000 or less, and more preferably 700 or more. 10,000 or less is more preferable.
The polyolefin chain preferably has a molecular weight distribution (Mw / Mn) determined by the following GPC method in the range of 1.1 to 3.0.
GPC測定法:
GPC測定は、温度140℃、オルトジクロロベンゼンを溶媒として使用して測定し、ポリエチレン換算値として分析値(重量平均分子量(Mw)、数平均分子量(Mn)およびMw/Mn)を得ることができる。
測定は以下の条件で行うことができる。また、分子量は、市販の単分散標準ポリスチレンを用いて検量線を作成し、下記の換算法に基づいて求めることができる。
装置:ゲル浸透クロマトグラフAllianceGPC2000型(Waters社製)
溶剤:o−ジクロロベンゼン
カラム:TSKgelカラム(東ソー社製)×4
流速:1.0ml/分
試料:0.15mg/mLo−ジクロロベンゼン溶液
温度:140℃
分子量換算:PS換算/汎用較正法
なお、汎用較正の計算には、以下に示すMark−Houwink粘度式の係数を用いることができる。
ポリスチレン(PS)の係数:KPS=1.38×10−4,aPS=0.70
ポリエチレン(PE)の係数:KPE=5.06×10−4,aPE=0.70
GPC measurement method:
GPC measurement can be performed at a temperature of 140 ° C. using orthodichlorobenzene as a solvent, and analytical values (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn) can be obtained as polyethylene conversion values. .
The measurement can be performed under the following conditions. The molecular weight can be determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mLo-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PS conversion / general-purpose calibration method The coefficient of the Mark-Houwink viscosity equation shown below can be used for calculation of general-purpose calibration.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 −4 , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 −4 , aPE = 0.70
上記A1、A2、A3およびRにおいて、炭素数1〜20、このましくは炭素数1〜10の炭化水素基としては、アルキル基、アリールアルキル基、アルケニル基、アリール基が挙げられる。 In the above A 1 , A 2 , A 3 and R, examples of the hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms include an alkyl group, an arylalkyl group, an alkenyl group and an aryl group. .
アルキル基としては、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、2−エチルヘキシル基、オクチル基、デシル基、オクタデシル基等の直鎖状または分岐状アルキル基;シクロペンチル基、シクロヘキシル基、ノルボルニル基等のシクロアルキル基等が挙げられる。
アリールアルキル基としては、ベンジル基、フェニルエチル基、フェニルプロピル基等が挙げられる。
アルケニル基としては、ビニル基、プロペニル基、シクロヘキセニル基等が挙げられる。
アリール基としては、フェニル基、トリル基、ジメチルフェニル基、トリメチルフェニル基、エチルフェニル基、プロピルフェニル基、ナフチル基等が挙げられる。
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, and octadecyl group. A linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a norbornyl group;
Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group.
Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.
Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a naphthyl group.
上記式(1)において、mは1〜10,000の整数である。mは5以上が好ましく、10以上がより好ましい。また、mは1,000以下が好ましく、300以下がより好ましく、50以下がより好ましい。 In the above formula (1), m is an integer of 1 to 10,000. m is preferably 5 or more, and more preferably 10 or more. Further, m is preferably 1,000 or less, more preferably 300 or less, and even more preferably 50 or less.
上記A1、A2、単数または複数のA3は、全てがポリオレフィン鎖であってもよいし、一部の基がポリオレフィン鎖でその他は炭素数1〜20の炭化水素基であってもよい。 All of A 1 , A 2 , and one or plural A 3 may be polyolefin chains, or some groups may be polyolefin chains and others may be hydrocarbon groups having 1 to 20 carbon atoms. .
上記式(1)において、mが2以上であり、A3のうちの少なくとも1つが他のA3と異なる場合、複数種の下記ユニットが存在するが、その並ぶ順序に特に制限はなく、ブロック的であってもランダム的であってもよい。 In the above formula (1), m is equal to or greater than 2, when at least one of A 3 that is different from the other A 3, but plural kinds of the following units are present, not particularly limited in its aligned sequence, block Or random.
上記式(1)としては、下記(1A)、(1B)または(1C)で表される構造体が好ましく、その中でも(1A)がより好ましい。
(1A)上記式(1)において、A1およびA2がポリオレフィン鎖であり、A3が炭素数1〜20の炭化水素基である、構造体。
(1B)上記式(1)において、A1、A2の一方がポリオレフィン鎖であり、他方が炭素数1〜20の炭化水素基であり、A3が炭素数1〜20の炭化水素基である、構造体。
(1C)上記式(1)において、A1およびA2が炭素数1〜20の炭化水素基であり、A3のうち少なくとも1つがポリオレフィン鎖である、構造体。
As said formula (1), the structure represented by following (1A), (1B) or (1C) is preferable, and (1A) is more preferable among these.
(1A) In the above formula (1), A 1 and A 2 are polyolefin chains, and A 3 is a hydrocarbon group having 1 to 20 carbon atoms.
(1B) In the above formula (1), one of A 1 and A 2 is a polyolefin chain, the other is a hydrocarbon group having 1 to 20 carbon atoms, and A 3 is a hydrocarbon group having 1 to 20 carbon atoms. There is a structure.
(1C) In the above formula (1), A 1 and A 2 are hydrocarbon groups having 1 to 20 carbon atoms, and at least one of A 3 is a polyolefin chain.
本発明に係るシリル化ポリオレフィンにおいて、シリコーン鎖/ポリオレフィン鎖(重量比)は特に限定されるものではないが、例えば、好ましくは5/95〜99/1であり、より好ましくは10/90〜95/5である。 In the silylated polyolefin according to the present invention, the silicone chain / polyolefin chain (weight ratio) is not particularly limited, but is preferably 5/95 to 99/1, and more preferably 10/90 to 95, for example. / 5.
本発明に係るシリル化ポリオレフィンの製造方法は特に限定されるものではないが、例えば、WO2012/098865号公報の段落0089〜0145や段落0196〜0207等に記載された方法により製造することができる。 Although the manufacturing method of the silylated polyolefin based on this invention is not specifically limited, For example, it can manufacture by the method described in paragraphs 0089-0145, paragraphs 0196-0207, etc. of WO2012 / 098865 gazette.
(脂肪酸エステル)
脂肪酸エステルとしては、脂肪酸とアルコールとの反応物であるエステルが挙げられる。
脂肪酸としては、炭素数が6〜22の飽和あるいは不飽和、直鎖あるいは分岐の脂肪酸が好ましい。具体的に示すと、例えば、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、パルミトレイン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、ノナデカン酸、アラキン酸、ガドレイン酸、エイコサジエン酸、アラキドン酸、ベヘン酸、エルカ酸、ドコサジエン酸、リグノセリン酸、イソステアリン酸、リシノレイン酸、12−ヒドロキシステアリン酸、9−ヒドロキシステアリン酸、10−ヒドロキシステアリン酸、水素添加ヒマシ油脂肪酸(12−ヒドロキシステアリン酸の他に少量のステアリン酸及びパルミチン酸を含有する脂肪酸)等が挙げられる。これらの中では、カプリル酸、カプリン酸、ステアリン酸が好ましい。
一方、アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、tert−ブタノール、ヘキサノール、オクタノール等の1価のアルコール;エチレングリコール、プロピレングリコール、ジエチレングリコール、1,4−ブタンジオール、ポリアルキレングリコール、ソルビトール、ショ糖、グリセリン、ポリグリセリン等の多価アルコールが挙げられる。アルコールとしては、多価アルコールが好ましく、ポリグリセリンがより好ましい。
(Fatty acid ester)
Examples of the fatty acid ester include esters that are a reaction product of a fatty acid and an alcohol.
The fatty acid is preferably a saturated or unsaturated, linear or branched fatty acid having 6 to 22 carbon atoms. Specifically, for example, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, nonadecanoic acid, Arachidic acid, gadoleic acid, eicosadienoic acid, arachidonic acid, behenic acid, erucic acid, docosadienoic acid, lignoceric acid, isostearic acid, ricinoleic acid, 12-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, hydrogenated Castor oil fatty acid (fatty acid containing a small amount of stearic acid and palmitic acid in addition to 12-hydroxystearic acid) and the like. Among these, caprylic acid, capric acid, and stearic acid are preferable.
On the other hand, as alcohols, monovalent alcohols such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, hexanol, octanol; ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, polyalkylene glycol, sorbitol And polyhydric alcohols such as sucrose, glycerin and polyglycerin. As the alcohol, polyhydric alcohol is preferable, and polyglycerin is more preferable.
本発明に用いられる脂肪酸エステルの分子量は、100〜10,000であり、200〜5,000であることが好ましく、400〜2,000であることがより好ましい。 The molecular weight of the fatty acid ester used in the present invention is from 100 to 10,000, preferably from 200 to 5,000, and more preferably from 400 to 2,000.
(樹脂組成物)
前記樹脂組成物は、熱可塑性樹脂(A)とシリル化ポリオレフィン(B)と分子量100〜10000の脂肪酸エステル(C)との含有割合(質量比)は(A)/(B)/(C)=60〜99.45/0.5〜30/0.05〜10であることが好ましく、72〜98.9/1.0〜20/0.1〜8.0であることがより好ましく、85〜97.5/2.0〜10/0.5〜5.0であることが更に好ましい。
(Resin composition)
In the resin composition, the content ratio (mass ratio) of the thermoplastic resin (A), the silylated polyolefin (B), and the fatty acid ester (C) having a molecular weight of 100 to 10,000 is (A) / (B) / (C). = 60 to 99.45 / 0.5 to 30 / 0.05 to 10, more preferably 72 to 98.9 / 1.0 to 20 / 0.1 to 8.0, More preferably, it is 85-97.5 / 2.0-10 / 0.5-5.0.
該樹脂組成物は熱可塑性樹脂とシリル化ポリオレフィンと分子量100〜10000の脂肪酸エステルのみにより構成されていてもよいが、所望により、本発明の目的を損なわない範囲で、さらに他の樹脂や添加剤等を含むことができる。添加剤としては、例えば、可塑剤、紫外線安定化剤、着色防止剤、艶消し剤、消臭剤、難燃剤、耐候剤、帯電防止剤、糸摩擦低減剤、スリップ剤、離型剤、抗酸化剤、イオン交換剤、および着色顔料等を添加することができる。
また、必要に応じて他のオイル類を添加することができる。他のオイル類としては、食用油、シリコーンオイルなどを挙げることができる。これらオイル類は、樹脂組成物全体に対して、好ましくは0.05〜10質量%、好ましくは0.1〜5質量%の範囲で添加される。
The resin composition may be composed only of a thermoplastic resin, a silylated polyolefin, and a fatty acid ester having a molecular weight of 100 to 10000, but if desired, other resins and additives may be added as long as the object of the present invention is not impaired. Etc. can be included. Examples of additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like can be added.
Moreover, other oils can be added as needed. Examples of other oils include edible oil and silicone oil. These oils are added in an amount of preferably 0.05 to 10% by mass, preferably 0.1 to 5% by mass with respect to the entire resin composition.
各成分は、公知の方法、例えば単軸や二軸の押出機、ニーダー、ヘンシェルミキサー、バンバリーミキサー、タンブラーミキサー等を用いて溶融混練することができ、必要に応じてペレット化して使用することもできる。
また、シリル化ポリオレフィンの濃度が高いマスターバッチを調整し、マスターバッチをポリオレフィンで希釈して使用してもよい。
Each component can be melt-kneaded using a known method, for example, a single-screw or twin-screw extruder, a kneader, a Henschel mixer, a Banbury mixer, a tumbler mixer, etc., and may be used after being pelletized as necessary. it can.
Further, a master batch having a high concentration of silylated polyolefin may be prepared, and the master batch may be diluted with polyolefin and used.
(成形体)
本発明の成形体はどのような形状でも構わないが、フィルムまたはシートであることが好ましい。
本発明の成形体は、前記樹脂組成物を、押出成形法、射出成形法、溶融流涎法、インフレーション成形法、圧縮成形法、トランスファー成形法、注型成形法等の公知の方法により成形することができる。
また本発明の成形体は、共押出成形や貼り合わせ等の公知の方法により、前記樹脂組成物からなる層と他の層とを積層した積層体であってもよい。前記樹脂組成物層や他の層は各々1層であっても2層以上でもよい。また他の層を構成する材料も樹脂、金属、紙、布等の種々の材料を用途に応じて適宜選択できる。
(Molded body)
The shaped product of the present invention may have any shape, but is preferably a film or a sheet.
The molded body of the present invention is obtained by molding the resin composition by a known method such as an extrusion molding method, an injection molding method, a melt casting method, an inflation molding method, a compression molding method, a transfer molding method, or a casting molding method. Can do.
Moreover, the molded body of the present invention may be a laminated body in which a layer made of the resin composition and another layer are laminated by a known method such as coextrusion molding or bonding. The resin composition layer and other layers may each be one layer or two or more layers. Further, the materials constituting the other layers can be appropriately selected from various materials such as resin, metal, paper, and cloth depending on the application.
(用途)
本発明の成形体の用途としては、例えば以下が例示されるが、これらに限定されるものではない。
撥水フィルム;撥油フィルム;容器、包装材(食品用、その他);表面保護フィルム;
(Use)
Examples of uses of the molded article of the present invention include, but are not limited to, the following.
Water repellent film; oil repellent film; container, packaging material (for food, etc.); surface protective film;
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。
以下の実施例・比較例において、各種の分析方法は以下の手順により行った。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof.
In the following examples and comparative examples, various analysis methods were performed according to the following procedures.
<表面自由エネルギー>
23℃、50%RHの条件で、プレスシートの表面について、固液界面解析システム(DropMaster500画像処理式、協和界面科学株式会社製)を使用して、水、ジヨードメタン、ブロモナフタレンとの静的接触角を測定した。各液体試料について、それぞれ5回ずつ測定しその平均値をサンプルの接触角とし、各液体試料の表面張力成分値を用いて、Fowkesの拡散式よりシートの表面自由エネルギー(mN/m)を算出した。
<Surface free energy>
Static contact with water, diiodomethane, and bromonaphthalene using the solid-liquid interface analysis system (DropMaster500 image processing type, manufactured by Kyowa Interface Science Co., Ltd.) on the surface of the press sheet under the conditions of 23 ° C. and 50% RH The corner was measured. For each liquid sample, measure 5 times each and use the average value as the contact angle of the sample, and calculate the surface free energy (mN / m) of the sheet from the Fowkes diffusion formula using the surface tension component value of each liquid sample. did.
<算術表面粗さRa>
プレスシートの表面について、表面粗さ測定機(サーフコム130A、株式会社東京精密製)を使用して、算術平均粗さRa(μm)を5回測定しその平均値を算出した。
<Arithmetic surface roughness Ra>
About the surface of the press sheet, arithmetic mean roughness Ra (micrometer) was measured 5 times using the surface roughness measuring machine (Surfcom 130A, Tokyo Seimitsu make), and the average value was computed.
<外観>
プレスシートを目視で観察し、下記評価基準に従って外観を評価した。ここで、添加剤の分散不良により生じたとみられる、シート面内での透明性の不均一や流れムラなどの外観不良をあわせて、めらめら感と定義した。
―外観の評価基準―
○:めらめら感なし(シート面内の外観が均一)
×:めらめら感あり
<Appearance>
The press sheet was visually observed and the appearance was evaluated according to the following evaluation criteria. Here, it was defined as a feeling of glittering together with appearance defects such as non-uniformity of transparency within the sheet surface and flow unevenness, which may be caused by poor dispersion of the additive.
―Appearance evaluation criteria―
○: No glare (uniform appearance in the sheet surface)
×: Glittering
<身離れ性>
プレスシートを110mm×100mmの長方形にカットし、直径35mm、高さ100mmの円筒形サンプルを作製した。得られた円筒形サンプルの内面にマヨネーズ25gを広げたあと、円筒形サンプルを立てて、内面に付着しているマヨネーズの落下の様子を60分間観察した。
60分経過前後での、内面にマヨネーズが付着している部分の最上部の高さの変化をマヨネーズの落下量とし、比較例1の×評価に対して、下記評価基準に従って身離れ性の評価結果とした。
―身離れ性の評価基準―
◎:極めて良好(マヨネーズの落下量が比較例1の300%以上)
○:良好(マヨネーズの落下量が比較例1の150%以上300%未満)
×:不良(マヨネーズの落下量が比較例1の150%未満)
<Separation>
The press sheet was cut into a 110 mm × 100 mm rectangle to produce a cylindrical sample with a diameter of 35 mm and a height of 100 mm. After 25 g of mayonnaise was spread on the inner surface of the obtained cylindrical sample, the cylindrical sample was erected, and the appearance of the mayonnaise falling on the inner surface was observed for 60 minutes.
The change in the height of the uppermost part of the part where the mayonnaise adheres to the inner surface after about 60 minutes is regarded as the amount of fall of the mayonnaise, and the evaluation of the separability according to the following evaluation criteria with respect to the × evaluation of Comparative Example 1 As a result.
―Evaluation criteria for personality―
A: Very good (the amount of mayonnaise falling is 300% or more of Comparative Example 1)
○: Good (the amount of mayonnaise falling is 150% or more and less than 300% of Comparative Example 1)
X: Defect (the amount of mayonnaise falling is less than 150% of Comparative Example 1)
[合成例1]
国際公開第2012/098865号の合成例2に記載の方法により片末端ビニル基含有エチレン系重合体(P−1)を合成した。この片末端ビニル基含有エチレン系重合体(P−1)(単体)の物性は以下の通りであった。
融点(Tm)127℃
Mw=4800、Mn=2087、Mw/Mn=2.3(GPC)
末端不飽和率 97%
[Synthesis Example 1]
One-end vinyl group-containing ethylene polymer (P-1) was synthesized by the method described in Synthesis Example 2 of International Publication No. 2012/098865. The physical properties of this one-end vinyl group-containing ethylene polymer (P-1) (single unit) were as follows.
Melting point (Tm) 127 ° C
Mw = 4800, Mn = 2087, Mw / Mn = 2.3 (GPC)
Terminal unsaturation 97%
[合成例2]
300mlの2ツ口フラスコに、[合成例1]で得た片末端ビニル基含有エチレン系重合体(P−1)25.1g(11.8mmol)を装入し、窒素雰囲気下、ヒドロシランA(Gelest,Inc.製、DMS−H112)6.2g(5.9mmol;Si−H基として11.8mmol相当)と、国際公開第2012/098865号の合成例3に従い調製した白金触媒組成物(C−1)をヒドロシランAで200倍希釈したもの150μl(Pt換算で1.4×10−6mmol)を装入した。予め内温130℃に昇温しておいた油浴中に、上記反応器をセットし、撹拌した。油浴中にて6時間撹拌した後に冷却し、メタノール約200mlを加え、300mlビーカーに内容物を取り出し2時間攪拌した。その後、固体をろ取し乾燥させることにより、式(1)において、A1、A2がエチレン単独重合体鎖であり、A3がメチル基であり、Rがメチル基であり、mが12〜13である白色固体のシリル化ポリオレフィン(B−1)33.5gを得た。NMR解析の結果、得られたシリル化ポリオレフィン(B−1)は収率99%、オレフィン転化率100%、異性化率1%であった。GPCで分析した数平均分子量は5,000であった。
ヒドロシランA:HSi(CH3)2O−(−Si(CH3)2−O−)n−Si(CH3)2H
(n=12〜13)
[Synthesis Example 2]
A 300 ml two-necked flask was charged with 25.1 g (11.8 mmol) of the one-end vinyl group-containing ethylene polymer (P-1) obtained in [Synthesis Example 1], and hydrosilane A ( 6.2 g (5.9 mmol; equivalent to 11.8 mmol as Si-H group) of Gelest, Inc., DMS-H112) and a platinum catalyst composition prepared according to Synthesis Example 3 of International Publication No. 2012/098865 (C 150 μl (1.4 × 10 −6 mmol in terms of Pt) of -1) diluted 200-fold with hydrosilane A was charged. The reactor was set in an oil bath that had been heated to an internal temperature of 130 ° C. in advance, and stirred. The mixture was stirred in an oil bath for 6 hours and then cooled, about 200 ml of methanol was added, and the contents were taken out into a 300 ml beaker and stirred for 2 hours. Thereafter, the solid is collected by filtration and dried, whereby in formula (1), A 1 and A 2 are ethylene homopolymer chains, A 3 is a methyl group, R is a methyl group, and m is 12 33.5 g of white solid silylated polyolefin (B-1) which was ˜13 was obtained. As a result of NMR analysis, the obtained silylated polyolefin (B-1) had a yield of 99%, an olefin conversion rate of 100%, and an isomerization rate of 1%. The number average molecular weight analyzed by GPC was 5,000.
Hydrosilane A: HSi (CH 3) 2 O - (- Si (CH 3) 2 -O-) n -Si (CH 3) 2 H
(N = 12-13)
[実施例1]
ポリプロピレン(プライムポリマー社製ポリプロピレン、F300SP)89重量部、合成例2で得られたシリル化ポリオレフィン(B−1)10重量部、パナセート810(日油株式会社製、トリ(カプリル・カプリン酸)グリセリル)1重量部を、ラボプラストミル(株式会社東洋精機製作所社製)を用いて、温度200℃で5分間溶融混練し、樹脂組成物を得た。その後、神藤金属工業所社製油圧式熱プレス機を用いて、樹脂組成物に対し、温度200℃で5分間加圧した後、温度20℃に設定した別の神藤金属工業所社製油圧式熱プレス機を用いて、3分間加圧し、厚さ200μmのプレスシートを得た。得られたプレスシートの各種物性測定結果を表1に示す。
[Example 1]
89 parts by weight of polypropylene (polypropylene manufactured by Prime Polymer Co., Ltd., F300SP), 10 parts by weight of silylated polyolefin (B-1) obtained in Synthesis Example 2, Panaceto 810 (manufactured by NOF Corporation, tri (capryl / capric acid) glyceryl) ) 1 part by weight was melt kneaded at a temperature of 200 ° C. for 5 minutes using a lab plast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a resin composition. Then, using a hydraulic heat press machine manufactured by Shin-Fuji Metal Industry Co., Ltd., pressurizing the resin composition at a temperature of 200 ° C. for 5 minutes, and then setting it at a temperature of 20 ° C., another hydraulic heat press manufactured by Shin-Fuji Metal Industry Co., Ltd. Using a press, the pressure was applied for 3 minutes to obtain a press sheet having a thickness of 200 μm. Table 1 shows the measurement results of various physical properties of the obtained press sheet.
[実施例2]
樹脂組成物の組成を、ポリプロピレン(プライムポリマー社製ポリプロピレン、F300SP)85重量部、合成例2で得られたシリル化ポリオレフィン(B−1)10重量部、パナセート810(日油株式会社製、トリ(カプリル・カプリン酸)グリセリル)5重量部に変更したこと以外は実施例1と同様の操作を行った。
結果を表1に示す。
[Example 2]
The resin composition was composed of 85 parts by weight of polypropylene (polypropylene manufactured by Prime Polymer, F300SP), 10 parts by weight of silylated polyolefin (B-1) obtained in Synthesis Example 2, and panacet 810 (manufactured by NOF Corporation, Tri (Capryl / capric acid) glyceryl) The same operation as in Example 1 was performed except that the amount was changed to 5 parts by weight.
The results are shown in Table 1.
[実施例3]
パナセート810の代わりにサンソフトQ−18S(太陽化学株式会社製、モノステアリン酸デカグリセリン)以外は実施例1と同様の操作を行った。
結果を表1に示す。
[Example 3]
The same operation as in Example 1 was performed except that Sunsoft Q-18S (manufactured by Taiyo Kagaku Co., Ltd., decaglycerin monostearate) was used instead of panacet 810.
The results are shown in Table 1.
[実施例4]
パナセート810の代わりにサンソフトQ−1810S(太陽化学株式会社製、デカステアリン酸デカグリセリン)以外は実施例1と同様の操作を行った。
結果を表1に示す。
[Example 4]
The same operation as in Example 1 was performed except for Sunsoft Q-1810S (manufactured by Taiyo Kagaku Co., Ltd., decastearate decaglycerin) instead of panacet 810.
The results are shown in Table 1.
[比較例1]
ポリプロピレン(プライムポリマー社製ポリプロピレン、F300SP)を、神藤金属工業所社製油圧式熱プレス機を用いて、温度200℃で5分間加圧した後、温度20℃に設定した別の神藤金属工業所社製油圧式熱プレス機を用いて、3分間加圧し、厚さ200μmのプレスシートを得た。得られたプレスシートの各種物性測定結果を表1に示す。
[Comparative Example 1]
Another Kamito Metal Industry Co., Ltd., which was set at a temperature of 20 ° C. after pressurizing polypropylene (polypropylene manufactured by Prime Polymer Co., Ltd., F300SP) at a temperature of 200 ° C. for 5 minutes using a hydraulic hot press machine manufactured by Kamito Metal Industry Co., Ltd. Pressing was performed for 3 minutes using a hydraulic hot press machine manufactured to obtain a press sheet having a thickness of 200 μm. Table 1 shows the measurement results of various physical properties of the obtained press sheet.
[比較例2]
シリル化ポリオレフィン(B−1)を用いず、樹脂組成物の組成を、ポリプロピレン(プライムポリマー社製ポリプロピレン、F300SP)99重量部、パナセート810(日油株式会社製、トリ(カプリル・カプリン酸)グリセリル)1重量部に変更したこと以外は実施例1と同様の操作を行った。
結果を表1に示す。
[Comparative Example 2]
Without using silylated polyolefin (B-1), the composition of the resin composition was 99 parts by weight of polypropylene (polypropylene manufactured by Prime Polymer Co., Ltd., F300SP), panacet 810 (manufactured by NOF Corporation, tri (capryl / capric acid) glyceryl). ) The same operation as in Example 1 was performed except that the amount was changed to 1 part by weight.
The results are shown in Table 1.
[比較例3]
パナセート810の代わりにサンソフトQ−18S(太陽化学株式会社製、モノステアリン酸デカグリセリン)以外は比較例2と同様の操作を行った。
結果を表1に示す。
[Comparative Example 3]
The same operation as in Comparative Example 2 was performed except that Sunsoft Q-18S (manufactured by Taiyo Kagaku Co., Ltd., decaglycerin monostearate) was used instead of Panacet 810.
The results are shown in Table 1.
[比較例4]
パナセート810の代わりにサンソフトQ−1810S(太陽化学株式会社製、デカステアリン酸デカグリセリン)以外は比較例2と同様の操作を行った。
結果を表1に示す。
[Comparative Example 4]
The same operation as in Comparative Example 2 was performed except for Sunsoft Q-1810S (manufactured by Taiyo Kagaku Co., Ltd., decastearate decaglycerin) instead of panacet 810.
The results are shown in Table 1.
表1に示すように、実施例1〜4で得られたサンプルは、比較例1と比較して、外観を損なうことなく、表面自由エネルギーが低下した。さらに、実施例1および実施例3で得られたサンプルは、比較例1と比較して、身離れ性に優れていた。
また、実施例1〜4と比較例2〜4の比較から明らかなように、シリル化ポリオレフィンと脂肪酸エステル系添加剤の組合せにより、脂肪酸エステルのみをポリオレフィンに添加した場合と比較して、成形品の表面自由エネルギー、表面粗さ、身離れ性、外観が向上した。
As shown in Table 1, the samples obtained in Examples 1 to 4 had a reduced surface free energy as compared with Comparative Example 1 without deteriorating the appearance. Furthermore, the samples obtained in Example 1 and Example 3 were superior in the ability to leave compared to Comparative Example 1.
In addition, as is clear from the comparison between Examples 1 to 4 and Comparative Examples 2 to 4, the molded article was compared with the case where only the fatty acid ester was added to the polyolefin by the combination of the silylated polyolefin and the fatty acid ester-based additive. Improved surface free energy, surface roughness, detachability and appearance.
Claims (5)
The molded article according to claim 3 or 4, which is a container or a packaging material.
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