JP6681724B2 - Slippery film and laminate using the same - Google Patents
Slippery film and laminate using the same Download PDFInfo
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- JP6681724B2 JP6681724B2 JP2016015559A JP2016015559A JP6681724B2 JP 6681724 B2 JP6681724 B2 JP 6681724B2 JP 2016015559 A JP2016015559 A JP 2016015559A JP 2016015559 A JP2016015559 A JP 2016015559A JP 6681724 B2 JP6681724 B2 JP 6681724B2
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- 239000000314 lubricant Substances 0.000 claims description 59
- -1 polypropylene Polymers 0.000 claims description 35
- 239000004743 Polypropylene Substances 0.000 claims description 23
- 229920001155 polypropylene Polymers 0.000 claims description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- 230000003068 static effect Effects 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 12
- 229920005604 random copolymer Polymers 0.000 claims description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229920006284 nylon film Polymers 0.000 claims description 2
- 150000002193 fatty amides Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 63
- 230000032683 aging Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000010030 laminating Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011091 composite packaging material Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Laminated Bodies (AREA)
Description
本発明は、ポリプロピレン系複合フィルムを備えた易滑性フィルムと、それを用いた積層体に関する。 TECHNICAL FIELD The present invention relates to a slippery film provided with a polypropylene-based composite film, and a laminate using the same.
例えば包装フィルムとしてポリプロピレン系フィルムが用いられることは広く知られており、ポリプロピレン系フィルムとそれとは異種のポリプロピレン系フィルム、ポリエチレンテレフタレート（ＰＥＴ）フィルムやナイロン（Ｎｙ）フィルム、とくに延伸ＰＥＴフィルムや延伸ナイロンフィルム（ＯＮｙ）を積層した積層体も広く知られている。 For example, it is widely known that a polypropylene film is used as a packaging film, and a polypropylene film and a polypropylene film different from the polypropylene film, a polyethylene terephthalate (PET) film or a nylon (Ny) film, particularly a stretched PET film or a stretched nylon. A laminated body in which films (ONy) are laminated is also widely known.
包装用に用いられる無延伸ポリプロピレンフィルムは一般的に有機滑剤が添加されており、製膜後に滑剤がフィルム表面に滲み出すことで良好な滑り性を発現している。従来の無延伸ポリプロピレンフィルムにおいては、接着剤を介して延伸ＰＥＴフィルムやＯＮｙなどのフィルムと貼り合わせ、接着剤を硬化させるために４０℃以上をかけてエージングすると、フィルム表面に滲み出た有機滑剤（とくに、脂肪酸アミド系滑剤）がフィルム中に再移行するため、滑りが悪くなる傾向があった。このため、延伸ＰＥＴフィルムやＯＮｙなどのフィルムと貼り合わせるときに、粉振りを行なって滑り性を保持することが行われているが、粉振りされる滑剤の量が多くなりすぎると、衛生面等の問題が発生することがあった。 An organic lubricant is generally added to an unstretched polypropylene film used for packaging, and the lubricant exudes on the surface of the film after film formation, thereby exhibiting good slipperiness. In a conventional unstretched polypropylene film, an organic lubricant that oozes out on the surface of a film when it is attached to a film such as a stretched PET film or ONy via an adhesive and aged at 40 ° C. or more to cure the adhesive. (Especially fatty acid amide lubricant) re-migrated into the film, so that slipping tended to become worse. For this reason, when laminating with a film such as a stretched PET film or ONy, it is performed to keep the slipperiness by dusting the powder. Such problems may occur.
したがって、とくにポリプロピレン系フィルムに他のフィルム等をラミネートして積層体とする際の工程安定性等を確保するためには、該ポリプロピレン系フィルムには、４０℃以上でエージングされる場合にあっても、そのフィルム表面が良好な滑り性、とくにあるレベル以下の静摩擦係数、例えば０．２以下の静摩擦係数を有することが望まれる。 Therefore, in order to ensure process stability when laminating a polypropylene film with another film to form a laminate, the polypropylene film may be aged at 40 ° C. or higher. However, it is desired that the film surface has good slipperiness, particularly a coefficient of static friction of a certain level or less, for example, a coefficient of static friction of 0.2 or less.
このような要望に関して、特許文献１には、ポリエチレン樹脂に、有機アミド二量体を１００〜３０００ｐｐｍ、無機充填剤を１０００〜１００００ｐｐｍ添加したシーラントフィルムおよびそれを用いた複合包装材が開示されているが、その実施例ではラミネート前後の摩擦係数が０．３／０．３と、十分に低い摩擦係数が得られるには至っていない。 Regarding such a demand, Patent Document 1 discloses a sealant film obtained by adding 100 to 3000 ppm of an organic amide dimer and 1000 to 10000 ppm of an inorganic filler to a polyethylene resin, and a composite packaging material using the sealant film. However, in the example, the friction coefficient before and after lamination is 0.3 / 0.3, which is not sufficiently low.
また、特許文献２には、融点７０〜９０℃の不飽和脂肪酸アマイド０．０２〜０．２重量％、融点１１５〜１３５℃の不飽和脂肪酸ビスアマイド０．０１〜０．１２重量％を含有する積層フィルムが開示されているが、エチレン・αオレフィンを使用しているため、耐熱性に劣り、本知見をポリプロピレン系に適応した場合、不飽和脂肪酸アマイド及び不飽和脂肪酸ビスアマイドの量を多くする必要があり、摩擦係数は低く抑えられるもののエージング処理後にフィルム表面の滑剤量が多くなりすぎ、衛生面や作業環境上の問題が生じる。 Further, Patent Document 2 contains 0.02 to 0.2% by weight of unsaturated fatty acid amide having a melting point of 70 to 90 ° C. and 0.01 to 0.12% by weight of unsaturated fatty acid bisamide having a melting point of 115 to 135 ° C. Although a laminated film is disclosed, it has poor heat resistance because it uses ethylene / α-olefins. When this finding is applied to polypropylene, it is necessary to increase the amount of unsaturated fatty acid amide and unsaturated fatty acid bisamide. However, although the coefficient of friction can be suppressed to a low level, the amount of lubricant on the film surface becomes too large after the aging treatment, resulting in problems in hygiene and working environment.
さらに、特許文献３には、両外層にエルカ酸アミドなどの最適エージング温度４０℃未満の滑剤を添加し、中間層にベヘン酸アミド、エチレンビスアミドなどの最適エージング温度４０℃以上の滑剤を添加し、その実施例に記載されているように、中間層にプロピレン―エチレンランダム共重合体、少なくとも一方の外層にプロピレン―エチレンランダム共重合体を用いて３層構成のポリプロピレン系多層フィルムおよび複合フィルムが開示されている。この特許文献３の各実施例では、各層に特殊な滑剤を添加した場合には、積層フィルムのエージング後の表面静摩擦係数として０．２以下が達成されている場合も見受けられるが、後述の如く本発明者らの知見によれば、通常一般の滑剤(例えば、通常一般の脂肪酸アミド系滑剤)を各層に添加する場合、特に表層に添加する場合、中間層、表層ともにプロピレン―エチレンランダム共重合体で構成されている場合には、エージング後の静摩擦係数として０．２以下を達成するのは困難である。その理由は、前述したように、プロピレン―エチレンランダム共重合体からなるフィルム層中に、添加した有機滑剤（とくに、脂肪酸アミド系滑剤）がフィルム表層から内部に移行し、滑りが悪くなる傾向があるからであると考えられる。 Further, in Patent Document 3, a lubricant having an optimum aging temperature of less than 40 ° C. such as erucic acid amide is added to both outer layers, and a lubricant having an optimum aging temperature of 40 ° C. or more such as behenic acid amide and ethylene bisamide is added to the intermediate layer. , A polypropylene-based multilayer film and a composite film having a three-layer structure using a propylene-ethylene random copolymer as an intermediate layer and a propylene-ethylene random copolymer as at least one outer layer, as described in the Examples. It is disclosed. In each of Examples of Patent Document 3, when a special lubricant is added to each layer, it can be seen that the surface static friction coefficient after aging of the laminated film is 0.2 or less, but as described below. According to the knowledge of the present inventors, when a general lubricant (for example, a general fatty acid amide lubricant) is added to each layer, particularly when added to the surface layer, both the intermediate layer and the surface layer propylene-ethylene random copolymer In the case of a united structure, it is difficult to achieve a static friction coefficient of 0.2 or less after aging. The reason is that, as described above, in the film layer made of the propylene-ethylene random copolymer, the added organic lubricant (particularly fatty acid amide-based lubricant) tends to migrate from the film surface layer to the inside and the slip tends to deteriorate. It is thought to be because there is.
そこで本発明の課題は、とくに４０℃以上でエージングしてもフィルム表面の滑剤量を適切な範囲内に維持でき、それによってフィルム表面の静摩擦係数として望ましい値である０．２以下を達成できるポリプロピレン系複合フィルムを備えた易滑性フィルムと、それを用いた積層体を提供することにある。 Therefore, an object of the present invention is to provide a polypropylene that can maintain the amount of lubricant on the film surface within an appropriate range even if it is aged at 40 ° C. or higher, thereby achieving a desired value of the static friction coefficient of the film surface of 0.2 or less. An object of the present invention is to provide a slippery film provided with a base composite film and a laminate using the slippery film.
上記課題を解決するために、本発明に係る易滑性フィルムは、少なくともＡ／Ｂの２層を有するポリプロピレン系複合フィルムを備えた易滑性フィルムであって、Ａ層はプロピレンにエチレンまたはブテンをランダム共重合したプロピレン系ランダム共重合体を主成分とする層からなり、Ｂ層は第一工程でエチレンやブテンとプロピレンとを重合させてエチレン又はブテン含有量０〜１．５重量％のプロピレン−エチレン又はブテン共重合体（ａ成分）を全重合体の６０〜９０重量％製造し、次いで第二工程でエチレンまたはブテンとプロピレンとを重合させてエチレン又はブテン含有量２０〜５０重量％のプロピレンーエチレン又はブテン共重合体（ｂ成分）を全重合体の１０〜４０重量％製造して得られるポリプロピレン系共重合体（以下、プロピレン系ブロック共重合体と称す）を主成分とし、かつ、少なくとも脂肪酸アミド系滑剤を１００ｐｐｍ以上添加した層からなることを特徴とするものからなる。 In order to solve the above problems, the slippery film according to the present invention is a slippery film provided with a polypropylene-based composite film having at least two A / B layers, and the A layer is propylene with ethylene or butene. Of the propylene-based random copolymer obtained by random copolymerization of ethylene, but the B layer is obtained by polymerizing ethylene or butene and propylene in the first step to obtain an ethylene or butene content of 0 to 1.5% by weight. Propylene-ethylene or butene copolymer (a component) is produced in an amount of 60 to 90% by weight of the total polymer, and then ethylene or butene and propylene are polymerized in the second step to obtain an ethylene or butene content of 20 to 50% by weight. The polypropylene-based copolymer obtained by producing 10 to 40% by weight of the total propylene-ethylene or butene copolymer (component (b)) of , A main component referred to as a propylene block copolymer), and consist of, characterized in that a layer in which at least fatty acid amide lubricant was added over 100 ppm.
そしてこの本発明に係る易滑性フィルムにおいては、常温環境下でのフィルム表面の脂肪酸アミド系滑剤量が３〜２０ｍｇ／ｍ２の範囲であり、フィルムを４０℃以上でエージングしても表面の脂肪酸アミド系滑剤の量が３〜２０ｍｇ／ｍ２の範囲でかつ静摩擦係数が０．２以下であることが好ましい。 And, in this slippery film according to the present invention, the amount of the fatty acid amide-based lubricant on the film surface in a normal temperature environment is in the range of 3 to 20 mg / m 2 , and even if the film is aged at 40 ° C. or higher, It is preferable that the amount of the fatty acid amide lubricant is in the range of 3 to 20 mg / m 2 and the coefficient of static friction is 0.2 or less.
このような本発明に係る易滑性フィルムにおいては、滑り性が問題とされる外層を、プロピレンにエチレンやブテンをランダム共重合したプロピレン系ランダム共重合体を主成分とするＡ層とし、そのＡ層に対して内側に位置する層に、プロピレンにエチレンやブテンをブロック共重合したプロピレン系ブロック共重合体を主成分とするＢ層とから構成したものとなす。本発明者らの知見によれば、これら両層に脂肪酸アミド系滑剤を添加した場合、例えば４０℃以上に加熱してエージングした場合には、プロピレン系ランダム共重合体を主成分とする層では脂肪酸アミド系滑剤がフィルム層中に取り込まれて（移行されて）そのフィルム層表面における滑剤量が減少し、それに伴って静摩擦係数が悪化(上昇) する傾向にあり、一方、プロピレン系ブロック共重合体を主成分とする層では、逆に温度上昇に伴ってフィルム層中に添加されていた滑剤がブリードアウトされてそのフィルム層表面側に移行し、そのフィルム層表面における滑剤量が増加する傾向にある。本発明では、これらの傾向を考慮し、プロピレン系ブロック共重合体を主成分とするＢ層への脂肪酸アミド系滑剤の添加量を１００ｐｐｍ以上とすることで、４０℃以上に加熱してエージングされる場合にＢ層内の脂肪酸アミド系滑剤はＢ層表面側に、さらにはそこからＡ層内へと移行されることを可能としたものである。その結果、Ａ層内中に添加されていた滑剤が４０℃以上に加熱してエージングされる場合にＡ層内中に移行されようとする際に、Ａ層内中に移行されようとするＡ層内中に添加されていた滑剤と、Ｂ層からＡ層内へと移行されてきた滑剤とが、適切にバランスされ、結果的に滑り性が問題とされる外層としてのＡ層の表面における滑剤量が最適な範囲(例えば、常温環境下でのフィルム表面の脂肪酸アミド系滑剤量の範囲が３〜２０ｍｇ／ｍ２、４０℃以上のエージング後のフィルム表面の脂肪酸アミド系滑剤量の範囲が３〜２０ｍｇ／ｍ２、好ましくは５〜２０ｍｇ／ｍ２の範囲)に維持されることが可能になり、０．２以下の静摩擦係数の達成が実現される。なお、Ｂ層に使用するプロピレン系ブロック共重合体は、ポリプロピレン部の割合を示す２０℃キシレン不溶部の割合が７５〜８５重量％で、該不溶部の極限粘度（〔η〕Ｈ）が１．７〜２．２ｄｌ／ｇであり、エチレン・プロピレン共重合ゴム成分の割合を示すキシレン可溶部の極限粘度（〔η〕ＥＰ）が２．５〜３．４ｄｌ／ｇであることが好ましい。
ここで、上記２０℃キシレン不溶部、及び可溶部とは、上記プロピレン・エチレンブロック共重合体のペレットを沸騰キシレンに完全に溶解させた後２０℃に降温し、４時間以上放置し、その後これを析出物と溶液とに濾別した際、析出物を２０℃キシレン不溶部と称し、溶液部分（濾液）を乾固して減圧下７０℃で乾燥して得られる部分を可溶部と称す。
In such a slippery film according to the present invention, the outer layer whose slipperiness is a problem is an A layer containing a propylene-based random copolymer obtained by randomly copolymerizing propylene with ethylene or butene as its main component, and The layer located inside the A layer is composed of a B layer containing a propylene block copolymer obtained by block copolymerizing propylene with ethylene and butene as a main component. According to the knowledge of the present inventors, when a fatty acid amide lubricant is added to both layers, for example, when it is heated to 40 ° C. or higher and aged, the layer containing a propylene random copolymer as a main component is When the fatty acid amide lubricant is incorporated (migrated) into the film layer, the amount of lubricant on the surface of the film layer decreases, and the coefficient of static friction tends to deteriorate (increased) accordingly, while the propylene block copolymer On the contrary, in the layer mainly composed of coalescence, the lubricant added in the film layer is bleed out and moves to the film layer surface side as the temperature rises, and the lubricant amount on the film layer surface tends to increase. It is in. In the present invention, in consideration of these tendencies, the amount of the fatty acid amide-based lubricant added to the B layer containing the propylene-based block copolymer as the main component is 100 ppm or more, so that it is heated to 40 ° C. or more and aged. In this case, the fatty acid amide-based lubricant in the layer B can be transferred to the surface side of the layer B and further from there to the inside of the layer A. As a result, when the lubricant added in the A layer is heated to 40 ° C. or higher and is aged, when it is transferred into the A layer, the lubricant tends to be transferred into the A layer. The lubricant added in the layer and the lubricant transferred from the B layer to the A layer are properly balanced, and as a result, the slipperiness is a problem. The optimum amount of the lubricant is (for example, the range of the amount of the fatty acid amide-based lubricant on the film surface at room temperature is 3 to 20 mg / m 2 , and the range of the amount of the fatty acid amide-based lubricant on the film surface after aging at 40 ° C. or higher is 3-20 mg / m < 2 >, preferably 5-20 mg / m < 2 >), and a static friction coefficient of 0.2 or less is achieved. The propylene-based block copolymer used for the layer B has a proportion of 20 ° C. xylene-insoluble portion showing the proportion of polypropylene portion of 75 to 85% by weight, and the intrinsic viscosity ([η] H ) of the insoluble portion is 1 It is preferable that the intrinsic viscosity ([η] EP ) of the xylene-soluble portion showing the ratio of the ethylene / propylene copolymer rubber component is 2.5 to 3.4 dl / g. .
Here, the 20 ° C. xylene-insoluble portion and the soluble portion are the pellets of the propylene / ethylene block copolymer completely dissolved in boiling xylene, the temperature is lowered to 20 ° C., and the mixture is allowed to stand for 4 hours or more. When this was separated into a precipitate and a solution by filtration, the precipitate was referred to as a 20 ° C. xylene-insoluble portion, and a portion obtained by drying the solution portion (filtrate) and drying at 70 ° C. under reduced pressure was referred to as a soluble portion. To call.
上記本発明に係る易滑性フィルムにおいては、前記Ｂ層への脂肪酸アミド系滑剤の添加量が１００ｐｐｍ以上２０００ｐｐｍ未満の範囲にあることが好ましい。上記の如く、４０℃以上のエージングによってＢ層からＡ層内へと移行されようとする滑剤の量とＡ層内中に移行されようとする滑剤の量とのバランスを、Ａ層表面における静摩擦係数の観点から適切に考慮すると良い。Ｂ層への脂肪酸アミド系滑剤の添加量が２０００ｐｐｍ以上になると、後述の比較例１に示すように、静摩擦係数は低く抑えられるものの、Ａ層表面の滑剤量が多くなりすぎ、衛生面や作業環境上の問題が生じるおそれがあるので注意を要する。 In the slippery film according to the present invention, the amount of the fatty acid amide lubricant added to the B layer is preferably in the range of 100 ppm or more and less than 2000 ppm. As described above, the balance between the amount of the lubricant that is about to be transferred from the B layer into the A layer and the amount of the lubricant that is about to be transferred into the A layer by aging at 40 ° C. or more is determined by the static friction on the surface of the A layer. It is good to consider it appropriately from the viewpoint of the coefficient. When the amount of the fatty acid amide-based lubricant added to the layer B is 2000 ppm or more, as shown in Comparative Example 1 below, the coefficient of static friction can be suppressed to a low level, but the amount of the lubricant on the surface of the layer A becomes too large, which results in hygiene and work. Be careful as it may cause environmental problems.
また、上記においては少なくともＡ／Ｂの２層構成を有する場合について説明したが、本発明に係る易滑性フィルムは、上記ポリプロピレン系複合フィルムが少なくともＡ／Ｂ／Ｃの３層を有し、Ｃ層がプロピレンにエチレンおよび／またはブテンをランダム共重合したプロピレン系ランダム共重合体を主成分とする層からなる場合を含む。 Moreover, although the case where it has a two-layer structure of at least A / B has been described above, in the slippery film according to the present invention, the polypropylene-based composite film has at least three layers of A / B / C, This includes the case where the C layer is composed of a layer containing, as a main component, a propylene-based random copolymer obtained by randomly copolymerizing propylene with ethylene and / or butene.
本発明は、上記のような易滑性フィルムの一面に、少なくとも、二軸延伸ポリエチレンテレフタレートフィルム、二軸延伸ポリプロピレンフィルム、二軸延伸ナイロンフィルム、またはアルミニウム箔のいずれか一つがラミネートされた積層体についても提供する。この場合、ラミネート時等の工程安定性のみを考えれば、二軸延伸ポリエチレンテレフタレートフィルム等のラミネート面としてはＡ／Ｂの２層のいずれの層の表面側でも可能であるが、ラミネート後の積層体の一面の良好な滑り性まで考慮するのであれば、Ａ／Ｂの２層の場合にはＢ層表面側にラミネートされることが好ましい。ラミネート方法としては、例えば、接着剤を使ったドライラミネート法がある。 The present invention is a laminated body in which at least one of a biaxially stretched polyethylene terephthalate film, a biaxially stretched polypropylene film, a biaxially stretched nylon film, or an aluminum foil is laminated on one surface of the slippery film as described above. Will also be provided. In this case, considering only the process stability at the time of lamination, the biaxially stretched polyethylene terephthalate film or the like can be laminated on either side of the two layers A / B. In consideration of the good slipperiness of one side of the body, in the case of two layers of A / B, it is preferable to laminate on the surface side of the B layer. As a laminating method, for example, there is a dry laminating method using an adhesive.
このように、本発明によれば、４０℃以上でエージングしてもフィルム表面の滑剤量を適切な範囲内に維持でき、それによってフィルム表面の静摩擦係数を０．２以下に抑えることが可能なポリプロピレン系複合フィルムを備えた易滑性フィルムを実現できる。 Thus, according to the present invention, the amount of lubricant on the film surface can be maintained within an appropriate range even if it is aged at 40 ° C. or higher, and thereby the coefficient of static friction on the film surface can be suppressed to 0.2 or less. A slippery film provided with a polypropylene-based composite film can be realized.
また、本発明に係る積層体によれば、包装材として好適な、例えば、袋の開口性が求められるレトルト食品などの包装用材料を提供することができ、本発明に係る積層体はその他にも、絞り成型で易滑性が求められるリチウムイオン電池の包装などにも好適に使用することが可能である。 Further, according to the laminate according to the present invention, it is possible to provide a packaging material suitable for a packaging material, for example, a packaging material such as a retort food in which opening property of a bag is required. Also, it can be suitably used for packaging of lithium-ion batteries which are required to have slipperiness by drawing.
以下に、本発明について、実施例、比較例を主体に説明する。
本発明に係る易滑性フィルムは、前述したように、少なくともＡ／Ｂの２層を有するポリプロピレン系複合フィルムを備えた易滑性フィルムであるが、実施例ではＡ／Ｂ／Ｃの３層フィルムを作製した。表１に示すように、Ａ層とＣ層にエチレン含量３．８重量％、融点１４２℃のプロピレン―エチレンランダム共重合体（「ＥＰＣ」と表示）を用い、Ｂ層に２０℃キシレン可溶部２０重量％、該可溶部の極限粘度［η］ＥＰ３．２ｄｌ／ｇ、２０℃キシレン不溶部８０重量％、該不溶部の極限粘度［η］H１．９ｄｌ／ｇのプロピレン系ブロック共重合体（「ＢＰＰ」と表示）を用いて易滑性フィルムを作製し、実施例１〜比較例２はＡ層／Ｂ層／Ｃ層の３層構成であり、それぞれの層の厚みは、１０／４０／１０μｍとした。比較例３、４は、Ａ層のみの単層フィルムであり、厚みは６０μｍとした。
Hereinafter, the present invention will be described mainly with reference to Examples and Comparative Examples.
As described above, the slippery film according to the present invention is a slippery film provided with a polypropylene-based composite film having at least two A / B layers, but in the examples, three A / B / C layers are used. A film was made. As shown in Table 1, a propylene-ethylene random copolymer (indicated as "EPC") having an ethylene content of 3.8% by weight and a melting point of 142 ° C was used for the A layer and the C layer, and 20 ° C xylene was soluble in the B layer.
尚、２０℃キシレン可溶部の含有量は、ポリプロピレンペレット５ｇを沸騰キシレン（関東化学（株）製１級）５００ｍｌに完全に溶解させた後に、２０℃に降温し、４時間以上放置する。その後、これを析出物と溶液とに濾過して、可溶部と不溶部に分離した。可溶部は濾液を減圧下で固化した後、７０℃で乾燥し、その重量を測定して含有量（重量％）を求めた。また、２０℃キシレン不溶部および可溶部の極限粘度は、可溶部と不溶部に分離したサンプルを用い、ウベローデ型粘度計を用いて、１３５℃テトラリン中で測定を行った。 Regarding the content of the 20 ° C. xylene-soluble portion, 5 g of polypropylene pellets was completely dissolved in 500 ml of boiling xylene (Kanto Kagaku Co., Ltd. grade 1), then the temperature was lowered to 20 ° C. and the mixture was allowed to stand for 4 hours or more. Then, this was filtered into a precipitate and a solution to separate a soluble portion and an insoluble portion. The soluble portion was obtained by solidifying the filtrate under reduced pressure, drying it at 70 ° C., and measuring its weight to determine the content (% by weight). The intrinsic viscosities of the 20 ° C. xylene-insoluble part and the soluble part were measured in 135 ° C. tetralin using an Ubbelohde viscometer using a sample separated into the soluble part and the insoluble part.
上記Ａ、Ｂ、Ｃ層に、表１に示す量の脂肪酸アミド系滑剤を添加した。脂肪酸アミド系滑剤としては、例えば、オレイン酸アミドやエルカ酸アミド、ベヘン酸アミド等が使用可能であり、各実施例、比較例ではエルカ酸アミドを使用した。 The fatty acid amide lubricants in the amounts shown in Table 1 were added to the A, B and C layers. As the fatty acid amide lubricant, for example, oleic acid amide, erucic acid amide, behenic acid amide and the like can be used, and erucic acid amide was used in each Example and Comparative Example.
各実施例、比較例における各サンプルを表１に示すそれぞれのエージング温度（２３℃、４０℃、５０℃）で３日間保存した直後に表面滑剤量を定量した。表面滑剤の採取は、各サンプルで内寸が２０ｃｍ×２５ｃｍの袋を作り、その中に５０ｍｌのエタノールを入れ、３分間攪拌してエタノール中に溶解させた。滑剤が溶解したエタノールを、水素炎イオン検出器付薄層クロマトグラフィー（ＬＳＩメディエンス製のイアトロスキャン）を用い、定量分析を行った。表面滑剤量の変化を図１に示した。また、表面滑剤量と静摩擦係数の関係を図２に示した。静摩擦係数の測定は、JIS K 7125に準拠し、フィルム対フィルムで行った。 The amount of surface lubricant was quantified immediately after storing each sample in each Example and Comparative Example at each aging temperature (23 ° C, 40 ° C, 50 ° C) shown in Table 1 for 3 days. For collecting the surface lubricant, a bag having an inner size of 20 cm × 25 cm was prepared for each sample, 50 ml of ethanol was put therein, and the mixture was stirred for 3 minutes and dissolved in ethanol. The ethanol in which the lubricant was dissolved was subjected to quantitative analysis using thin layer chromatography with a hydrogen flame ion detector (Iatroscan manufactured by LSI Medience). The change in the amount of surface lubricant is shown in FIG. The relationship between the amount of surface lubricant and the coefficient of static friction is shown in FIG. The static friction coefficient was measured film by film in accordance with JIS K 7125.
表１に示すように、実施例１では、常温２３℃から５０℃の範囲で表面滑剤量が３〜２０ｍｇ／ｍ２の範囲であり、静摩擦係数は０．２以下で良好な滑り性であり、加工時に滑剤付着が指摘される（滑剤量が多すぎる）２０ｍｇ／ｍ２を超えないものであった。実施例２，３についても同様の結果であった。 As shown in Table 1, in Example 1, the surface lubricant amount was in the range of 3 to 20 mg / m 2 in the range of room temperature of 23 ° C. to 50 ° C., and the static friction coefficient was 0.2 or less, which was good slipperiness. However, the adhesion of the lubricant was pointed out during processing (the amount of the lubricant was too large), and the amount did not exceed 20 mg / m 2 . Similar results were obtained for Examples 2 and 3.
比較例１では、４０℃以上のエージングで２０ｍｇ／ｍ２を超えるレベルであった。静摩擦係数は０．２以下で良好な滑り性であるが、表面滑剤量が多すぎ、加工時に滑剤付着が指摘されるレベルを超えていた。比較例２では、４０℃以上でエージングしても滑剤が３ｍｇ／ｍ２を超えることはなく、静摩擦係数が０．２を超えるものであった。比較例３では、常温２３℃で表面滑剤量が３ｍｇ／ｍ２以上であったが、５０℃にエージングすると表面滑剤量が３ｍｇ／ｍ２を下回り、静摩擦係数が０．２を超えるものであった。比較例４では、５０℃にエージングしても表面滑剤量が３ｍｇ／ｍ２を下回ることはなかったが、常温２３℃では表面滑剤量が加工時に滑剤付着が指摘される２０ｍｇ／ｍ２を超えるものであった。 In Comparative Example 1, the level was over 20 mg / m 2 with aging at 40 ° C. or higher. The coefficient of static friction was 0.2 or less, indicating good slipperiness, but the amount of surface lubricant was too large, which exceeded the level at which lubricant adhesion was noted during processing. In Comparative Example 2, the lubricant did not exceed 3 mg / m 2 even after aging at 40 ° C. or higher, and the coefficient of static friction exceeded 0.2. In Comparative Example 3, the amount of surface lubricant was 3 mg / m 2 or more at room temperature of 23 ° C., but when aged at 50 ° C., the amount of surface lubricant was less than 3 mg / m 2, and the coefficient of static friction exceeded 0.2. It was In Comparative Example 4, the amount of surface lubricant did not fall below 3 mg / m 2 even after aging at 50 ° C., but at room temperature 23 ° C., the amount of surface lubricant exceeded 20 mg / m 2 at which lubricant adhesion was pointed out during processing. It was a thing.
本発明に係る易滑性フィルムおよびそれを用いた積層体は、各種包装材として、例えば、袋の開口性が求められるレトルト食品などの包装用材料として、さらには通常の包装材以外にも、例えば、絞り成型で易滑性が求められるリチウムイオン電池の包装などにも好適なものである。 The slippery film and the laminate using the same according to the present invention are various packaging materials, for example, packaging materials such as retort foods in which bag opening properties are required, and in addition to ordinary packaging materials, For example, it is also suitable for packaging lithium-ion batteries, which are required to have slipperiness by drawing.
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