JP4654052B2 - Food packaging film - Google Patents
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- JP4654052B2 JP4654052B2 JP2005047483A JP2005047483A JP4654052B2 JP 4654052 B2 JP4654052 B2 JP 4654052B2 JP 2005047483 A JP2005047483 A JP 2005047483A JP 2005047483 A JP2005047483 A JP 2005047483A JP 4654052 B2 JP4654052 B2 JP 4654052B2
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Description
本発明は、食品包装用フィルムに関する。詳しくは、耐熱性、カット性、密着性、巻き剥離性等の食品包装用フィルムに要求される全特性が高位にバランスした、家庭用および業務用として食品の包装に使用される食品包装用フィルムに関する。 The present invention relates to a food packaging film. Specifically, food packaging films used for food packaging for home use and business use, with all the properties required for food packaging films such as heat resistance, cutability, adhesion, and roll peelability balanced at a high level. About.
従来、いわゆる家庭用および業務用として食品の包装に使用されている食品包装用フィルムとしては、ポリ塩化ビニル、ポリ塩化ビニリデン、又はポリエチレン等の比較的薄いフィルムからなるものが挙げられる。しかし、これらの食品包装用フィルムは、耐熱性に劣るため、例えば、油性の強い食品を直接包んで電子レンジなどで暖めて使用する場合、高温に晒されると形状を保持できずに破れて、包装した食品中に混入するなどの問題があった。 Conventionally, food packaging films used for food packaging for home and business use include films made of a relatively thin film such as polyvinyl chloride, polyvinylidene chloride, or polyethylene. However, since these food packaging films are inferior in heat resistance, for example, when directly using a food that is highly oily and wrapped in a microwave oven etc., when it is exposed to a high temperature, it can not be held and can be torn. There were problems such as contamination in the packaged food.
そこで、耐熱性に優れた包装用フィルムが提案されている。例えば、特開平05−239291号公報(特許文献1参照)、特開平06−032952号公報(特許文献2参照)、特開平07−165940号公報(特許文献3参照)等には、耐熱性に優れた4−メチル−1−ペンテン系重合体を主成分とする包装用フィルムが開示されている。しかし、これらの包装用フィルムは粘着性が不十分であるため、低温でステンレス製容器等を包装した際に使用中に剥離するなどの問題がある。 Therefore, a packaging film excellent in heat resistance has been proposed. For example, Japanese Patent Application Laid-Open No. 05-239291 (see Patent Document 1), Japanese Patent Application Laid-Open No. 06-032952 (see Patent Document 2), Japanese Patent Application Laid-Open No. 07-165940 (see Patent Document 3), etc. A packaging film containing an excellent 4-methyl-1-pentene polymer as a main component is disclosed. However, since these packaging films have insufficient adhesiveness, there are problems such as peeling during use when packaging stainless steel containers or the like at low temperatures.
また、特開平11−207893号公報(特許文献4参照)には、表面層、中間層及び表面層の少なくとも3層の積層構造をなすフィルムであって、表面層が、結晶性ポリプロピレン系樹脂、液状脂肪族炭化水素及び脂肪族多価アルコール脂肪酸エステルを含む樹脂組成物からなり、中間層が、ポリ(4−メチルペンテン−1)樹脂及び結晶性ポリプロピレン系樹脂を含む樹脂組成物、又は、ポリ(4−メチルペンテン−1)樹脂及び非晶性オレフィン系樹脂を含む樹脂組成物からなる自己粘着性包装用フィルムが開示されている。しかし、該包装用フィルムは粘着性が十分であるとは云えないものである。 JP-A-11-207893 (see Patent Document 4) discloses a film having a laminated structure of at least three layers of a surface layer, an intermediate layer, and a surface layer, the surface layer comprising a crystalline polypropylene resin, A resin composition comprising a liquid aliphatic hydrocarbon and an aliphatic polyhydric alcohol fatty acid ester, wherein the intermediate layer comprises a poly (4-methylpentene-1) resin and a crystalline polypropylene resin, or a poly A self-adhesive packaging film comprising a resin composition containing a (4-methylpentene-1) resin and an amorphous olefin resin is disclosed. However, the packaging film cannot be said to have sufficient adhesiveness.
更に、特開2003−200539号公報(特許文献5参照)には、メチル−1−ペンテン系重合体フィルム層の両面或いは片面に、エチレン・α−オレフィン共重合体およびメチル−1−ペンテン系重合体からなる樹脂組成物フィルムを積層した食品包装用フィルムが開示されている。しかし、該食品包装用フィルムは、伸び特性が過大でカット性が劣るため、小型収納箱から引き出して所望の寸法に切断する際の作業性に問題がある。 Furthermore, Japanese Patent Application Laid-Open No. 2003-200539 (see Patent Document 5) discloses that an ethylene / α-olefin copolymer and a methyl-1-pentene heavy polymer are formed on both sides or one side of a methyl-1-pentene polymer film layer. A food packaging film in which a resin composition film made of coalescence is laminated is disclosed. However, the film for food packaging has a problem in workability when it is pulled out from a small storage box and cut into a desired size because the film has an excessive elongation property and is inferior in cutability.
本発明の目的は、上記問題に鑑み、耐熱性、カット性、密着性、巻き剥離性等の食品包装用フィルムに要求される全特性が高位にバランスした、家庭用および業務用として食品の包装に使用される食品包装用フィルムを提供することにある。 In view of the above problems, the object of the present invention is to package food for home use and business use, with all the properties required for a film for food packaging such as heat resistance, cutability, adhesion, and releasability balanced at a high level. The object is to provide a film for food packaging used in packaging.
本発明者らは、鋭意検討した結果、耐熱性及びカット性に優れて、適度の剛性を有する樹脂層で中間層を形成し、防曇性に優れ、密着性と巻き剥離性とが高位でバランスした樹脂層で外層を形成し、且つ、中間層と外層と密着させるために両層間に接着性に優れた樹脂層で接着層を形成した、少なくとも5層から形成された積層体フィルムが、上記課題を解決し得る食品包装用フィルムであることを見出し、本発明に到った。 As a result of intensive studies, the inventors of the present invention formed an intermediate layer with a resin layer having excellent heat resistance and cutability and moderate rigidity, excellent antifogging properties, and high adhesion and releasability. A laminate film formed of at least five layers, in which an outer layer is formed with a balanced resin layer, and an adhesive layer is formed with a resin layer having excellent adhesiveness between both layers in order to adhere the intermediate layer and the outer layer, The present inventors have found that it is a food packaging film that can solve the above-mentioned problems, and have reached the present invention.
すなわち、本発明は、少なくとも5層で構成された食品包装用フィルムであって、4−メチル−1−ペンテン系重合体から形成された中間層の表裏両面に、下記接着層樹脂組成物から形成された接着層が積層され、更にそれぞれの接着層の表面に下記外層樹脂組成物から形成された外層が積層されたことを特徴とする食品包装用フィルムである。
<接着層樹脂組成物>
密度が0.915〜0.935g/cm3の高圧法低密度ポリエチレン50〜85重量%、及び1−ブテン系重合体50〜15重量%を含む接着層樹脂組成物。
<外層樹脂組成物>
密度が0.915〜0.935g/cm3の高圧法低密度ポリエチレン85〜99重量%、防曇剤0.5〜5重量%、及び粘着付与剤0.5〜10重量%を含む外層樹脂組成物。
That is, the present invention is a food packaging film composed of at least five layers, which is formed from the following adhesive layer resin composition on both front and back surfaces of an intermediate layer formed from a 4-methyl-1-pentene polymer. The film for food packaging is characterized in that the adhesive layer thus formed is laminated, and an outer layer formed of the following outer resin composition is laminated on the surface of each adhesive layer.
<Adhesive layer resin composition>
An adhesive layer resin composition comprising 50 to 85% by weight of a high-pressure low-density polyethylene having a density of 0.915 to 0.935 g / cm 3 and 50 to 15% by weight of a 1-butene polymer.
<Outer layer resin composition>
Outer layer resin containing 85 to 99% by weight of high-pressure low-density polyethylene having a density of 0.915 to 0.935 g / cm 3 , 0.5 to 5% by weight of an antifogging agent, and 0.5 to 10% by weight of a tackifier Composition.
本発明に係わる食品包装用フィルムの各層の厚みについては、中間層の厚みが1〜10μm、接着層のそれぞれの厚みが0.5〜5μm、外層のそれぞれの厚みが1〜10μmであることが好ましい。 Regarding the thickness of each layer of the film for food packaging according to the present invention, the thickness of the intermediate layer is 1 to 10 μm, the thickness of each of the adhesive layers is 0.5 to 5 μm, and the thickness of each of the outer layers is 1 to 10 μm. preferable.
本発明の食品包装用フィルムは、耐熱性、カット性、密着性、巻き剥離性等の食品包装用フィルムに要求される全特性に優れ高位にバランスしている。そのため、家庭用および業務用として、食品の包装に好適に使用することができる。 The food packaging film of the present invention is excellent in all properties required for a food packaging film, such as heat resistance, cutability, adhesion, and peelability, and is well balanced. Therefore, it can be used suitably for food packaging for home use and business use.
以下、本発明について詳細に説明する。本発明の食品包装用フィルムは、中間層、該中間層の表裏両面に形成された接着層、該接着層のそれぞれの表面に形成された外層から構成された、少なくとも5層から構成された積層体フィルムからなる。 Hereinafter, the present invention will be described in detail. The film for food packaging of the present invention comprises an intermediate layer, an adhesive layer formed on both surfaces of the intermediate layer, and an outer layer formed on each surface of the adhesive layer. It consists of a body film.
先ず、中間層について説明する。本発明における中間層は、4−メチル−1−ペンテン系重合体で形成される。4−メチル−1−ペンテン系重合体としては、4−メチル−1−ペンテンの単独重合体、又は、4−メチル−1−ペンテンとそれ以外のα−オレフィンとの共重合体等が挙げられる。4−メチル−1−ペンテン以外のα−オレフィンとしては、例えば、エチレン、プロピレン、1−ブテン、1−ヘプテン、1−ヘキセン、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−エイコセン等の炭素数2〜20のα−オレフィンが挙げられる。これらのα−オレフィン単位は、4−メチル−1−ペンテン系共重合体中に単独で含まれていてもよいし、2種以上含まれていてもよい。
4−メチル−1−ペンテン系重合体の市販品としては、三井化学(株)製、商品名:TPX、MX002O等が挙げられる。
First, the intermediate layer will be described. The intermediate layer in the present invention is formed of a 4-methyl-1-pentene polymer. Examples of the 4-methyl-1-pentene polymer include a homopolymer of 4-methyl-1-pentene, or a copolymer of 4-methyl-1-pentene and other α-olefin. . Examples of the α-olefin other than 4-methyl-1-pentene include ethylene, propylene, 1-butene, 1-heptene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -C2-C20 alpha olefins, such as hexadecene, 1-octadecene, 1-eicosene, are mentioned. These α-olefin units may be contained alone in the 4-methyl-1-pentene copolymer, or two or more kinds thereof may be contained.
Examples of commercially available 4-methyl-1-pentene polymers include Mitsui Chemicals, trade names: TPX, MX002O, and the like.
本発明における接着層は、密度が0.915〜0.935g/cm3である高圧法低密度ポリエチレン(以下、HPLDという)50〜85重量%及び1−ブテン系重合体50〜15重量%を含む樹脂組成物から形成される。
HPLDは、いわゆる高圧法ラジカル重合により製造される長鎖分岐を有する分岐の多いポリエチレンであり、密度が0.915〜0.935g/cm3である。このHPLDは、190℃、2.16kg荷重におけるMFRが0.01〜100g/10分である。好ましくは0.05〜10g/10分、更に好ましくは0.1〜8g/10分である。
このHPLDは、長鎖分岐の度合を表わすスウェル比、すなわち、毛細管式流れ特性試験機を用い、190℃の条件下で内径(d)2.0mm、長さ15mmのノズルより押出速度10mm/分で押し出したストランドの径(ds)とノズル内径(d)との比(ds/d)が1.3以上であることが好ましい。HPLDの市販品としては、三井化学(株)製、商品名:ミラソン、住友化学(株)製、商品名:スミカセン等が挙げられる。
In the present invention, the adhesive layer comprises 50 to 85% by weight of a high-pressure low-density polyethylene (hereinafter referred to as HPLD) having a density of 0.915 to 0.935 g / cm 3 and 50 to 15% by weight of a 1-butene polymer. It is formed from the resin composition containing.
HPLD is a highly branched polyethylene having a long-chain branch produced by so-called high-pressure radical polymerization, and has a density of 0.915 to 0.935 g / cm 3 . This HPLD has an MFR of 0.01 to 100 g / 10 min at 190 ° C. and a load of 2.16 kg. Preferably it is 0.05-10 g / 10min, More preferably, it is 0.1-8g / 10min.
This HPLD uses a swell ratio representing the degree of long-chain branching, that is, a capillary flow characteristic tester, and an extrusion speed of 10 mm / min from a nozzle having an inner diameter (d) of 2.0 mm and a length of 15 mm under the condition of 190 ° C. It is preferable that the ratio (ds / d) between the diameter (ds) of the extruded strand and the nozzle inner diameter (d) is 1.3 or more. Examples of commercially available products of HPLD include Mitsui Chemical Co., Ltd., trade name: Mirason, Sumitomo Chemical Co., Ltd., trade name: Sumikasen.
接着層を形成するHPLDは、本発明の目的を損なわない範囲において、その一部をエチレンと炭素数5〜20のα−オレフィン共重合体で代替してもよい。好ましい代替量は50重量%以内である。エチレン・炭素数5〜20のα−オレフィン共重合体としては、X線回折法による結晶化度が約0〜50%程度、好ましくは5〜45%、さらに好ましくは10〜40%である。エチレン単位の含有量が80〜99モル%、好ましくは85〜97モル%、より好ましくは88〜95モル%のものが好ましい。 As long as the HPLD for forming the adhesive layer does not impair the object of the present invention, a part thereof may be replaced with ethylene and an α-olefin copolymer having 5 to 20 carbon atoms. A preferred alternative amount is within 50% by weight. The ethylene / C5-C20 α-olefin copolymer has a crystallinity of about 0 to 50%, preferably 5 to 45%, and more preferably 10 to 40% by X-ray diffraction. The ethylene unit content is preferably 80 to 99 mol%, preferably 85 to 97 mol%, more preferably 88 to 95 mol%.
上記エチレンと共重合する炭素数5〜20のα−オレフィンとしては、1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネン、1−デセン、3−メチル−1−ブテン、4−メチル−1−ペンテン等が例示される。コモノマーとしてのα−オレフィンは1種類に限らず、ターポリマーのように2種類以上用いたものもよい。 Examples of the α-olefin having 5 to 20 carbon atoms copolymerized with ethylene include 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, Examples include 4-methyl-1-pentene. The α-olefin as a comonomer is not limited to one type, and two or more types such as a terpolymer may be used.
このエチレン・炭素数5〜20のα−オレフィン共重合体は、通常、遷移金属触媒の存在下にエチレンとα−オレフィンを気相または液相下で共重合して得ることができる。例えば、チーグラー型触媒、フィリップス型触媒、メタロセン型触媒などが使用できるが、低温でのシール性、強度、弾性率、伸び等のバランスを考慮するとメタロセン型触媒が好ましい。また、重合方法などに特に制限はなく、気相法、溶液法、バルク重合法などの重合方法により重合することができる。エチレン・炭素数5〜20のα−オレフィン共重合体の市販品としては、三井化学(株)製、商品名:ネオゼックス、ウルトゼックス、エボリュー等が挙げられる。 This ethylene / C5-C20 α-olefin copolymer is usually obtained by copolymerizing ethylene and α-olefin in the gas phase or liquid phase in the presence of a transition metal catalyst. For example, a Ziegler type catalyst, a Phillips type catalyst, a metallocene type catalyst or the like can be used, but a metallocene type catalyst is preferred in consideration of a balance between sealing properties at low temperatures, strength, elastic modulus, elongation and the like. Moreover, there is no restriction | limiting in particular in the polymerization method etc., It can superpose | polymerize by superposition | polymerization methods, such as a gaseous-phase method, a solution method, and a bulk polymerization method. Examples of commercially available ethylene / C5-C20 α-olefin copolymers include Mitsui Chemicals, Inc., trade names: Neozex, Ultozex, Evolue and the like.
本発明における接着層の形成に用いる1−ブテン系重合体は、1−ブテンを主成分とする重合体であって、1−ブテンの単独重合体、あるいは、1−ブテンと1−ブテン以外のα−オレフィンとの共重合体が挙げられる。1−ブテン以外のα−オレフィンとしては,エチレン、プロピレン、1−ヘキセン、1−オクテン、1−テトラデセン、1−オクタデセンなどの炭素原子数2〜20の1−ブテン以外のαオレフィンが挙げられる。接着層を形成するHPLDとの相溶性が良好である点でエチレンが好ましい。また、1−ブテン系重合体は表面層と中間層の充分な接着強度を得るためには1−ブテン単位を80モル%以上含有することが好ましい。更に好ましくは90モル%以上含有するのことが望ましい。1−ブテン系重合体の市販品としては、三井化学(株)製、商品名:タフマー等が挙げられる。 The 1-butene polymer used for forming the adhesive layer in the present invention is a polymer containing 1-butene as a main component, and is a 1-butene homopolymer or other than 1-butene and 1-butene. Examples include copolymers with α-olefins. Examples of the α-olefin other than 1-butene include α-olefins other than 1-butene having 2 to 20 carbon atoms, such as ethylene, propylene, 1-hexene, 1-octene, 1-tetradecene, and 1-octadecene. Ethylene is preferred because of its good compatibility with HPLD forming the adhesive layer. Further, the 1-butene polymer preferably contains 80 mol% or more of 1-butene units in order to obtain sufficient adhesion strength between the surface layer and the intermediate layer. More preferably, it is 90% by mole or more. As a commercial item of 1-butene-type polymer, Mitsui Chemicals, Inc. make, brand name: Toughmer etc. are mentioned.
接着層を形成する場合、HPLDと1−ブテン系重合体との混合比は、接着性、密着性、フィルム成形性などに影響を及ぼす。1−ブテン系重合体の混合量が15重量%未満であると、接着性が不十分となり中間層及び外層との接着強度が低下し、層間剥離を起こすことがあり好ましくない。また、1−ブテン系重合体の混合量が50重量%を超えるとフィルム成形性が低下し、表面状態が良好で均一厚みを有するフィルムが得難くなり好ましくない。かかる点を考慮すると、接着層を形成する両樹脂の混合割合は、HPLD50〜85重量%及び1−ブテン系重合体50〜15重量%であることが好ましい。 When forming an adhesive layer, the mixing ratio of HPLD and 1-butene polymer affects adhesiveness, adhesion, film formability, and the like. When the mixing amount of the 1-butene polymer is less than 15% by weight, the adhesiveness becomes insufficient, the adhesive strength between the intermediate layer and the outer layer is lowered, and delamination may occur. On the other hand, when the mixing amount of the 1-butene polymer exceeds 50% by weight, the film moldability is lowered, and it is difficult to obtain a film having a good surface state and a uniform thickness. Considering this point, the mixing ratio of both resins forming the adhesive layer is preferably 50 to 85% by weight of HPLD and 50 to 15% by weight of 1-butene polymer.
本発明における外層は、高圧法低密度ポリエチレン(HPLD)85〜99重量%、防曇剤0.5〜5重量%、及び粘着付与剤0.5〜10重量%を含む外層樹脂組成物から形成される。外層の形成に用いるHPLDは、接着層の形成に用いるHPLDと同様の樹脂で差し支えない。 The outer layer in the present invention is formed from an outer layer resin composition containing 85 to 99% by weight of high pressure method low density polyethylene (HPLD), 0.5 to 5% by weight of an antifogging agent, and 0.5 to 10% by weight of a tackifier. Is done. The HPLD used for forming the outer layer may be the same resin as the HPLD used for forming the adhesive layer.
外層樹脂組成物が含む防曇剤は、空気中の水分が凝縮してフィルムの表面を曇らせるのを防止するために配合される薬剤である。従って、食品包装用フィルムの表面を親水性にして、生じた水滴を拡がらせる作用を有するものであれば特に制限はなく、一般に防曇剤として用いられているものがそのまま使用できる。 The antifogging agent contained in the outer layer resin composition is a chemical compounded to prevent moisture in the air from condensing and fogging the surface of the film. Accordingly, there is no particular limitation as long as it has a function of making the surface of the food packaging film hydrophilic and spreading the generated water droplets, and those generally used as antifogging agents can be used as they are.
このような防曇剤としては、界面活性剤が用いられる。例えば、ソルビタンモノオレート、ソルビタンモノラウレート、ソルビタンモノベヘネート、ソルビタンモノステアレート等のソルビタン脂肪酸エステル;グリセリンモノオレート、グリセリンモノラウレート、グリセリンモノステアレート等のグリセリン脂肪酸エステル;ジグリセリンモノオレート、ジグリセリンセスキラウレート、ジグリセリンセスキオレート、テトラグリセリンモノオレート、テトラグリセリンモノステアレート、ヘキサグリセリンモノラウレート、ヘキサグリセリンモノオレート、デカグリセリンモノオレート、デカグリセリンモノラウレート等のポリグリセリン脂肪酸エステル;ポリオキシエチレンラウリルエーテル等のポリオキシアルキレンエーテル;ラウリルジエタノールアミン等の脂肪酸アミン;オレイン酸アミド等の脂肪酸アミドなどが挙げられる。これらに限定されるものではなく、またこれらは単独で、または混合物として使用される。 As such an antifogging agent, a surfactant is used. For example, sorbitan fatty acid esters such as sorbitan monooleate, sorbitan monolaurate, sorbitan monobehenate, sorbitan monostearate; glycerol fatty acid esters such as glycerol monooleate, glycerol monolaurate, glycerol monostearate; Polyglycerin fatty acid esters such as diglycerin sesquilaurate, diglycerin sesquiolate, tetraglycerin monooleate, tetraglycerin monostearate, hexaglycerin monolaurate, hexaglycerin monooleate, decaglycerin monooleate, decaglycerin monolaurate; Polyoxyalkylene ethers such as polyoxyethylene lauryl ether; fatty acid amines such as lauryl diethanolamine; olein And fatty acid amides such as amide. They are not limited to these and are used alone or as a mixture.
防曇剤の含有量は、外層樹脂組成物全体の0.5〜5重量%である。防曇剤の配合割合が0.5重量%未満である場合は、防曇効果が得られず、また、5重量%を超える場合は、防曇剤のブリードのために透明性が低下する。防曇剤は、予めHPLDの一部に混合してマスターバッチを形成し、これを残余のHPLDと混合して樹脂組成物を得ることが好ましい。 The content of the antifogging agent is 0.5 to 5% by weight of the entire outer layer resin composition. When the blending ratio of the antifogging agent is less than 0.5% by weight, the antifogging effect cannot be obtained, and when it exceeds 5% by weight, the transparency decreases due to bleeding of the antifogging agent. The antifogging agent is preferably mixed in advance with a part of HPLD to form a master batch, and this is mixed with the remaining HPLD to obtain a resin composition.
外層樹脂組成物が含む粘着付与剤としては、液状ポリブテン、非晶性ポリオレフィンや、脂肪族系炭化水素樹脂、芳香族系炭化水素樹脂、脂肪族・芳香族共重合系炭化水素樹脂、ジシクロペンタジエン系炭化水素樹脂、水添脂肪族系炭化水素樹脂、水添芳香族系炭化水素樹脂、水添脂肪族・芳香族共重合系炭化水素樹脂、水添ジシクロペンタジエン系炭化水素樹脂、合成テルペン系炭化水素樹脂、テルペン系炭化水素樹脂、水添テルペン系炭化水素樹脂、クマロンインデン系炭化水素樹脂、低分子量スチレン系樹脂、及びロジン系炭化水素樹脂等が挙げられる。1種類または2種類以上の混合物としてもよい。粘着付与剤の市販品としては、ヤスハラケミカル(株)製、商品名:クリアロン等が挙げられる。 Examples of the tackifier included in the outer layer resin composition include liquid polybutene, amorphous polyolefin, aliphatic hydrocarbon resin, aromatic hydrocarbon resin, aliphatic / aromatic copolymer hydrocarbon resin, dicyclopentadiene. Hydrocarbon resins, hydrogenated aliphatic hydrocarbon resins, hydrogenated aromatic hydrocarbon resins, hydrogenated aliphatic / aromatic copolymer hydrocarbon resins, hydrogenated dicyclopentadiene hydrocarbon resins, synthetic terpene resins Examples thereof include hydrocarbon resins, terpene hydrocarbon resins, hydrogenated terpene hydrocarbon resins, coumarone indene hydrocarbon resins, low molecular weight styrene resins, and rosin hydrocarbon resins. It is good also as a 1 type, or 2 or more types of mixture. Examples of commercially available tackifiers include Yasuhara Chemical Co., Ltd., trade name: Clearon.
粘着付与剤の含有量は、外層樹脂組成物全体の0.5〜10重量%である。粘着付与剤の配合割合が0.5重量%未満である場合は、充分な密着力が得られないため好ましくない。また、10重量%を超える場合は、ブロッキングして巻剥離力が過大となるため好ましくない。 The content of the tackifier is 0.5 to 10% by weight of the entire outer layer resin composition. When the mixing ratio of the tackifier is less than 0.5% by weight, it is not preferable because sufficient adhesion cannot be obtained. On the other hand, if it exceeds 10% by weight, it is not preferable because it is blocked and the winding peeling force becomes excessive.
本発明に係わる食品包装用フィルムは、上記樹脂組成物を使用して、Tダイ付押出機を用いる押出成形法、円形ダイを用いるインフレーション成形法等で製造することが可能である。Tダイ押出成形法では、配向防止処理として、例えば、成形温度200〜270℃、ドラフト比(ドラフト距離内での延伸比)40〜130、ドラフト距離(ダイ先からフィルムが冷却ロールに接触するまでの距離)50〜120mmとし、フィルム温度40〜70℃で延伸倍率1.2倍以下にして巻き取るような多層押出成形法が好ましい。 The food packaging film according to the present invention can be produced by using the above resin composition by an extrusion molding method using an extruder with a T die, an inflation molding method using a circular die, or the like. In the T-die extrusion molding method, for example, a molding temperature of 200 to 270 ° C., a draft ratio (stretch ratio within a draft distance) of 40 to 130, and a draft distance (from the die tip until the film contacts the cooling roll) The distance is preferably 50 to 120 mm, and a multilayer extrusion molding method in which the film temperature is 40 to 70 ° C. and the film is wound at a draw ratio of 1.2 times or less is preferable.
本発明の食品包装用フィルムを構成する各層の厚みは、特に限定されるものでなく、任意に選択することができる。好ましくは、中間層の厚みが1〜10μm、接着層の厚みがそれぞれ0.5〜5μm、外層の厚みがそれぞれ1〜10μmの範囲に形成する。また、積層体としての総厚みは約5〜30μmの範囲である。 The thickness of each layer which comprises the film for food packaging of this invention is not specifically limited, It can select arbitrarily. Preferably, the intermediate layer has a thickness of 1 to 10 μm, the adhesive layer has a thickness of 0.5 to 5 μm, and the outer layer has a thickness of 1 to 10 μm. Moreover, the total thickness as a laminated body is the range of about 5-30 micrometers.
上記のように、本発明に係わる食品包装用フィルムは、外層/接着層/中間層/接着層/外層の順に積層された少なくとも5層からなる層構成を有する。本発明の目的を損なわない範囲において、上記組成の中間層及び接着層を更に増やした層構成でもよい。また、他の組成からなる層を積層してもよい。その場合、各層間には接着層を設けることが好ましい。5層を超える層構成とした場合であっても、積層フィルムの表裏最外層は上記外層樹脂組成物から形成された外層であることが好ましい。 As described above, the food packaging film according to the present invention has a layer structure composed of at least five layers laminated in the order of outer layer / adhesive layer / intermediate layer / adhesive layer / outer layer. In the range not impairing the object of the present invention, a layer structure in which the intermediate layer and the adhesive layer having the above composition are further increased may be used. Moreover, you may laminate | stack the layer which consists of another composition. In that case, it is preferable to provide an adhesive layer between the respective layers. Even if it is a case where it is set as the layer structure exceeding five layers, it is preferable that the front and back outermost layers of a laminated film are the outer layers formed from the said outer layer resin composition.
以下、実施例を示して本発明について更に詳細に説明する。尚、実施例に示した各種特性値は下記方法により測定した。
(1)メルトフローレート(MFR)(g/10分)
ASTM D1238に規定される方法により測定する。
(2)密度(g/cm3)
ASTM D1505に規定される方法により測定する。
Hereinafter, the present invention will be described in more detail with reference to examples. Various characteristic values shown in the examples were measured by the following methods.
(1) Melt flow rate (MFR) (g / 10 min)
Measured by the method specified in ASTM D1238.
(2) Density (g / cm 3 )
Measured by the method specified in ASTM D1505.
(3)カット性
市販の家庭用ラップ収納小箱〔三井化学プラテック(株)製、家庭用ハイラップ収納箱、ポリ乳酸樹脂製カット刃付〕に、実施例又は比較例で得られたフィルムの紙管巻物(20m巻、幅:30cm)を収納する。収納箱からフィルムを引き出し、収納箱に取り付けられたカット刃で長さ約30cmに切断する。この操作を収納フィルムがなくなるまで繰り返す。この評価を20名の評価員が実施する。<評価基準>○:16人以上の評価員が切断し易いと判定したフィルム。△:7〜15人の評価員が切断し易いと判定したフィルム。×:6人以下の評価員が切断し易いと判定したフィルム。
(3) Cut property Film paper obtained in Examples or Comparative Examples on commercially available household wrapping small boxes (made by Mitsui Chemicals Platec Co., Ltd., household high wrap storage box, with polylactic acid resin cutting blade) A tube roll (20 m roll, width: 30 cm) is stored. The film is pulled out from the storage box and cut to a length of about 30 cm with a cutting blade attached to the storage box. This operation is repeated until the storage film runs out. This evaluation is carried out by 20 evaluators. <Evaluation Criteria> ◯: A film determined by 16 or more evaluators to be easily cut. (Triangle | delta): The film judged that 7-15 evaluators are easy to cut | disconnect. X: The film which 6 or less evaluators determined that it was easy to cut | disconnect.
(4)密着性
前項と同様の操作で切断したフィルム(長さ:30cm、幅:30cm)20枚をそれぞれ20個のステンレス製容器(開口部:一辺20cmの正方形)の開口部を覆うように被せ、フィルムの外縁部を容器の形状に合わせて折り曲げて密着させる。30分間放置した後、フィルムの剥離発生の有無を観察する。<評価基準>○:4枚以下のフィルムに剥離が認められたもの。△:5〜14枚のフィルムに剥離が認められたもの。×:15枚以上のフィルムに剥離が認められたもの。
(4) Adhesiveness Each of 20 films (length: 30 cm, width: 30 cm) cut by the same operation as in the previous section covers the openings of 20 stainless steel containers (openings: squares with sides of 20 cm). Cover and fold the outer edge of the film to fit the shape of the container. After leaving for 30 minutes, the presence or absence of film peeling is observed. <Evaluation Criteria> ○: No more than 4 films with peeling. (Triangle | delta): The thing by which peeling was recognized by 5-14 films. X: Peeling was observed on 15 or more films.
(5)巻き剥離性
前3項のカット性の評価を最後のフィルムまで実施する際に、フィルムを最後まで収納箱からスムーズに取り出せるかどうかを評価員20人が評価する。<評価基準>○:16人以上が取り出し易いと判定したフィルム。△:7〜15人が取り出し易いと判定したフィルム。×:6人以下が取り出し易いと判定したフィルム。
(5) Winding releasability When the evaluation of the cutting property in the previous three items is performed up to the last film, 20 evaluators evaluate whether the film can be smoothly taken out from the storage box. <Evaluation criteria> ◯: A film determined by 16 or more people to be easily taken out. (Triangle | delta): The film which 7-15 persons determined that it was easy to take out. X: The film which 6 or less persons judged to be easy to take out.
(6)層間剥離
実施例又は比較例で得られたフィルムの表裏両面に市販の粘着テープ(ニチバン(株)製、商品名:セロテープ(登録商標)、長さ:35cm、幅:17mm)を貼り付け、引き剥がした時に層間剥離が発生するかどうかを観察する。10枚のフィルムについて評価する。<評価基準>○:層間剥離が全く発生しない。×:少なくとも1枚に層間剥離が発生した。
(6) Delamination A commercially available adhesive tape (manufactured by Nichiban Co., Ltd., trade name: cello tape (registered trademark), length: 35 cm, width: 17 mm) is pasted on both sides of the film obtained in Example or Comparative Example. Observe whether delamination occurs when attached and peeled off. Evaluate 10 films. <Evaluation criteria> ○: No delamination occurs. X: Delamination occurred on at least one sheet.
(7)耐熱温度(℃)
東京都生活文化局消費者部適正表示課発行の品質表示要領〔ラップ(食品包装用ラップフィルム)〕に従って測定する。
<試料>
実施例又は比較例で得られたフィルム(MD方向長さ:14cm、TD方向長さ:3cm)及び板目紙(長さ:2.5cm、幅:3cm)を用意する。粘着テープを用いて、フィルムのMD方向の両端部の2.5cmずつの部分に板目紙を重ね合わせて固定して試料とする。
<測定法>
フィルムと板目紙が重なった両端部2.5cmずつの部分の上部を治具に固定し、下端に10gの荷重をかける。所定温度に調整したエアーオーブン中に迅速に入れ、1時間加熱した後、フィルムの切断の有無を調べる。試験温度は5℃刻みに設定する。試料が切断しなかった場合は、温度を5℃上げて前記の操作を繰り返す。試料が切断されない最高温度を耐熱温度とする。
(7) Heat-resistant temperature (℃)
Measured according to the quality labeling guidelines issued by the Consumer Affairs Department, Tokyo Metropolitan Life and Culture Bureau Consumer Labeling Section [wrapping (wrapping film for food packaging)].
<Sample>
A film (MD direction length: 14 cm, TD direction length: 3 cm) and board paper (length: 2.5 cm, width: 3 cm) obtained in Examples or Comparative Examples are prepared. Using a pressure-sensitive adhesive tape, a piece of paper is overlapped and fixed on each 2.5 cm portion at both ends in the MD direction of the film to prepare a sample.
<Measurement method>
The upper part of each 2.5 cm end portion where the film and board are overlapped is fixed to a jig, and a load of 10 g is applied to the lower end. After quickly putting in an air oven adjusted to a predetermined temperature and heating for 1 hour, the presence or absence of cutting of the film is examined. The test temperature is set in increments of 5 ° C. If the sample does not cut, raise the temperature by 5 ° C. and repeat the above operation. The maximum temperature at which the sample is not cut is defined as the heat resistant temperature.
実施例1
<中間層樹脂>
中間層を構成する4−メチル−1ペンテン樹脂として、三井化学(株)製、商品名:TPX MX002O〔4−メチル−1−ペンテンと炭素数16及び18のα−オレフィンとの共重合体、密度:0.83g/cm3、MFR:23g/10分(260℃、荷重:5kg)〕を使用した。
Example 1
<Interlayer resin>
As 4-methyl-1 pentene resin constituting the intermediate layer, manufactured by Mitsui Chemicals, Inc., trade name: TPX MX002O [copolymer of 4-methyl-1-pentene and α-olefin having 16 and 18 carbon atoms, Density: 0.83 g / cm 3 , MFR: 23 g / 10 min (260 ° C., load: 5 kg)].
<接着層樹脂組成物>
中間層の表裏両面に積層する接着層を構成する高圧法低密度ポリエチレンとして、住友化学工業(株)製、商品名:スミカセンCE3506(密度:0.931g/cm3、MFR:5g/10分)85重量部、1−ブテン系重合体として、三井化学(株)製、商品名:タフマーBL3450(密度0.9g/cm3、MFR:4g/10分、1−ブテンとエチレンとの共重合体)15重量部を使用し、ブレンドして接着層を構成する樹脂組成物を得た。
<Adhesive layer resin composition>
As a high-pressure method low-density polyethylene constituting an adhesive layer laminated on the front and back surfaces of the intermediate layer, Sumitomo Chemical Co., Ltd., trade name: Sumikasen CE3506 (density: 0.931 g / cm 3 , MFR: 5 g / 10 minutes) 85 parts by weight, 1-butene polymer, manufactured by Mitsui Chemicals, Inc., trade name: Tafmer BL3450 (density 0.9 g / cm 3 , MFR: 4 g / 10 min, copolymer of 1-butene and ethylene ) 15 parts by weight was blended to obtain a resin composition constituting an adhesive layer.
<外層樹脂組成物>
それぞれの接着層の表面に形成される外層を構成する高圧法低密度ポリエチレンとして、住友化学工業(株)製、商品名:スミカセンCE3506(密度:0.931g/cm3、MFR:5g/10分)92重量部、防曇剤としてジグリセリンオレート〔理研ビタミン(株)製、商品名:O−71DE〕3重量部、粘着付与剤として、水添テルペン樹脂〔ヤスハラケミカル(株)製、商品名:クリアロンP−125〕5重量部を使用し、口径30mm、L/Dが26の二軸押出機を用いて樹脂温度200℃で混練し、造粒して外層を構成する樹脂組成物を得た。
<Outer layer resin composition>
As a high-pressure method low-density polyethylene constituting the outer layer formed on the surface of each adhesive layer, Sumitomo Chemical Co., Ltd., trade name: Sumikasen CE3506 (density: 0.931 g / cm 3 , MFR: 5 g / 10 minutes) ) 92 parts by weight, 3 parts by weight of diglycerin oleate [manufactured by Riken Vitamin Co., Ltd., trade name: O-71DE] as an antifogging agent, and hydrogenated terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name: Clearon P-125] 5 parts by weight, kneaded at a resin temperature of 200 ° C. using a twin screw extruder having a diameter of 30 mm and an L / D of 26, and granulated to obtain a resin composition constituting the outer layer .
<フィルムの製造及び評価>
上記樹脂及び樹脂組成物を使用して、積層フィルムの層構成が外層/接着層/中間層/接着層/外層となるようにし、また、各層の厚み構成比が上記の順に3/1/2/1/3、合計厚みが10μmの3種5層の積層フィルムをフィードブロック型Tダイ押出成形機を用いて、樹脂温度280℃、ドラフト比50、ドラフト距離80mmとして、キャストロール温度を40℃とし、バキュームチャンバー方式で延伸倍率1.2倍、巻取速度250m/分で食品包装用フィルムを製造した。得られたフィルムについて、上記方法により各種特性を評価した。主な製造条件及び評価結果を表1に示す。
<Production and evaluation of film>
Using the resin and the resin composition, the layer structure of the laminated film is outer layer / adhesive layer / intermediate layer / adhesive layer / outer layer, and the thickness constitution ratio of each layer is 3/1/2 in the above order. / 1/3, 3 types and 5 layers of laminated film with a total thickness of 10 μm, using a feed block type T-die extruder, resin temperature 280 ° C., draft ratio 50, draft distance 80 mm, cast roll temperature 40 ° C. The film for food packaging was manufactured by a vacuum chamber method at a draw ratio of 1.2 times and a winding speed of 250 m / min. About the obtained film, various characteristics were evaluated by the said method. Table 1 shows the main production conditions and evaluation results.
実施例2〜7、比較例1〜5
使用原料及び製造条件を表1〜3に示した通りに変更した以外は、実施例1と同様にして樹脂組成物を製造し、得られた樹脂組成物から食品包装用フィルムを製造した。各種特性を実施例1と同様にして評価した。主な製造条件及び評価結果を表1〜3にそれぞれ示す。
Examples 2-7, Comparative Examples 1-5
A resin composition was produced in the same manner as in Example 1 except that the raw materials used and production conditions were changed as shown in Tables 1 to 3, and a food packaging film was produced from the obtained resin composition. Various characteristics were evaluated in the same manner as in Example 1. Main production conditions and evaluation results are shown in Tables 1 to 3, respectively.
実施例8
環状5層ダイが装着された共押出インフレーション成形機を使用し、樹脂温度280℃、ブローアップ比4.5で共押出インフレーション製膜し、巻き取り速度40m/分として共押出インフレーション成形を行った以外、実施例1と同様にして食品包装用フィルムを製造した。得られたフィルムについて、上記方法により各種特性を評価した。主な製造条件及び評価結果を表2に示す。
Example 8
Using a coextrusion inflation molding machine equipped with an annular five-layer die, a coextrusion inflation film was formed at a resin temperature of 280 ° C. and a blow-up ratio of 4.5, and a coextrusion inflation molding was performed at a winding speed of 40 m / min. Except for the above, a food packaging film was produced in the same manner as in Example 1. About the obtained film, various characteristics were evaluated by the said method. Table 2 shows the main production conditions and evaluation results.
<表1〜表3の記載の説明>
(1)A1、D1:高圧法低密度ポリエチレン〔三井化学(株)製、商品名:ミラソンF212、密度0.924g/cm3、190℃、荷重2.16kgにおけるMFR2.0g/10分〕。
(2)A2、D2:高圧法低密度ポリエチレン〔住友化学工業(株)製、商品名:スミカセンCE3506(密度:0.931g/cm3MFR:5g/10分)。
(3)B:ジグリセリンオレート〔理研ビタミン(株)製、商品名:リケマールO−71DE〕
(4)C1:水添テルペン樹脂〔ヤスハラケミカル(株)製、商品名:クリアロンP−125〕
(5)C2:液状ポリブテン〔新日本石油化学(株)製、商品名:日石ポリブテンHV−300F、100℃における動粘度590cSt〕。
(6)TPX:4−メチル−1−ペンテン・炭素数16及び18のα−オレフィンとの共重合体〔三井化学(株)製、商品名:TPX MX002O、密度:0.83g/cm3、260℃、荷重:5kgにおけるMFR:23g/10分〕
(7)PP:プロピレン重合体〔三井化学(株)製、商品名:三井ポリプロF122、密度:0.90g/cm3、230℃、荷重2.16kgにおけるMFR:2.2g/分〕。
(8)E1:1−ブテン・エチレン共重合体〔三井化学(株)製、商品名:タフマーBL3450、密度0.9g/cm3、190℃、荷重2.16kgにおけるMFR:4g/10分〕。
(9)E2:エチレン・1−ブテン共重合体〔三井化学(株)製、商品名:タフマーA−4085、密度:0.88g/cm3、190℃、荷重2.16kgにおけるMFR:3.6g/分〕。
(10)E3:プロピレン・1−ブテン共重合体〔三井化学(株)製、商品名:タフマーXR110T、密度:0.89g/cm3、190℃、荷重2.16kgにおけるMFR:3.2g/分〕。
(11)E4:エチレン・プロピレン共重合体〔三井化学(株)製、商品名:タフマーP−0180、密度:0.87g/cm3、190℃、荷重2.16kgにおけるMFR:4.5g/分〕。
(12)外層、中間層、及び接着層の各層の配合比の単位:重量部
<Description of Tables 1 to 3>
(1) A1, D1: High-pressure method low-density polyethylene [Mitsui Chemicals, Inc., trade name: Mirason F212, density 0.924 g / cm 3 , 190 ° C., MFR 2.0 g / 10 min at a load of 2.16 kg].
(2) A2, D2: High-pressure method low-density polyethylene [manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikasen CE3506 (density: 0.931 g / cm 3 MFR: 5 g / 10 min).
(3) B: Diglycerin oleate [Riken Vitamin Co., Ltd., trade name: Riquemar O-71DE]
(4) C1: Hydrogenated terpene resin [manufactured by Yashara Chemical Co., Ltd., trade name: Clearon P-125]
(5) C2: Liquid polybutene [manufactured by Nippon Petrochemical Co., Ltd., trade name: Nisseki Polybutene HV-300F, kinematic viscosity at 100 ° C. 590 cSt].
(6) TPX: 4-methyl-1-pentene / copolymer with α-olefin having 16 and 18 carbon atoms [manufactured by Mitsui Chemicals, trade name: TPX MX002O, density: 0.83 g / cm 3 , 260 ° C, load: MFR at 5 kg: 23 g / 10 min]
(7) PP: Propylene polymer [Mitsui Chemicals, Inc., trade name: Mitsui Polypro F122, density: 0.90 g / cm 3 , 230 ° C., MFR at load 2.16 kg: 2.2 g / min].
(8) E1: 1-butene-ethylene copolymer [Mitsui Chemicals, trade name: Tafmer BL3450, density 0.9 g / cm 3 , 190 ° C., MFR at 2.16 kg load: 4 g / 10 min] .
(9) E2: ethylene / 1-butene copolymer [manufactured by Mitsui Chemicals, Inc., trade name: Tafmer A-4085, density: 0.88 g / cm 3 , 190 ° C., MFR at 2.16 kg load: 3. 6 g / min].
(10) E3: Propylene / 1-butene copolymer [Mitsui Chemicals, trade name: Tafmer XR110T, density: 0.89 g / cm 3 , 190 ° C., MFR at a load of 2.16 kg: 3.2 g / Min].
(11) E4: Ethylene / propylene copolymer [Mitsui Chemical Co., Ltd., trade name: Tafmer P-0180, density: 0.87 g / cm 3 , 190 ° C., MFR at 2.16 kg load: 4.5 g / Min].
(12) Unit of blending ratio of each layer of outer layer, intermediate layer, and adhesive layer: parts by weight
家庭用および業務用の食品包装用フィルムとして好適に使用できる。 It can be suitably used as a food packaging film for home use and business use.
Claims (2)
前記中間層の樹脂成分は、4-メチル-1-ペンテン単独重合体および/または4-メチル-1-ペンテンとαオレフィンとの共重合体からなる、食品包装用フィルム。
<接着層樹脂組成物>
密度が0.915〜0.935g/cm3の高圧法低密度ポリエチレン50〜85重量% 、及び1−ブテン系重合体50〜15重量%を含む接着層樹脂組成物。
<外層樹脂組成物>
密度が0.915〜0.935g/cm3の高圧法低密度ポリエチレン85〜99重量%、防曇剤0.5〜5重量%、及び粘着付与剤0.5〜10重量%を含む外層樹脂組成物。 A food packaging film composed of at least five layers, on both sides of the middle-layer, an adhesive layer formed from the following adhesive layer resin composition is laminated below the outer layer resin further on a surface of each of the adhesive layers The outer layer formed from the composition is laminated ,
The resin component of the intermediate layer is a food packaging film comprising 4-methyl-1-pentene homopolymer and / or a copolymer of 4-methyl-1-pentene and α-olefin .
<Adhesive layer resin composition>
An adhesive layer resin composition comprising 50 to 85% by weight of a high-pressure low-density polyethylene having a density of 0.915 to 0.935 g / cm 3 and 50 to 15% by weight of a 1-butene polymer.
<Outer layer resin composition>
Outer layer resin containing 85 to 99% by weight of high-pressure low-density polyethylene having a density of 0.915 to 0.935 g / cm 3 , 0.5 to 5% by weight of an antifogging agent, and 0.5 to 10% by weight of a tackifier Composition.
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JP6517066B2 (en) * | 2014-03-31 | 2019-05-22 | 三井化学株式会社 | Resin composition and use thereof |
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JPH10100343A (en) * | 1996-09-30 | 1998-04-21 | Kohjin Co Ltd | Laminated stretch shrink film |
JPH1129670A (en) * | 1997-07-09 | 1999-02-02 | Kao Corp | Wrap film |
JPH11198315A (en) * | 1998-01-12 | 1999-07-27 | Mitsui Chem Inc | Poly(4-methyl-1-pentene)-based resin laminate |
JPH11240068A (en) * | 1998-02-26 | 1999-09-07 | Mitsui Chem Inc | Preparation of multi-layer inflation film, multi-layer inflation film, and packaging material consisting of multi-layer inflation film |
JP2001225431A (en) * | 2000-02-15 | 2001-08-21 | Mitsui Chemicals Inc | 4-methyl-1-pentene resin laminate |
JP2002146343A (en) * | 2000-08-22 | 2002-05-22 | Mitsui Chemicals Inc | Sealant resin composition, sealant film and its use |
JP2004291609A (en) * | 2003-02-12 | 2004-10-21 | Mitsui Kagaku Platech Co Ltd | Stretched polyolefinic film |
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Patent Citations (7)
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JPH10100343A (en) * | 1996-09-30 | 1998-04-21 | Kohjin Co Ltd | Laminated stretch shrink film |
JPH1129670A (en) * | 1997-07-09 | 1999-02-02 | Kao Corp | Wrap film |
JPH11198315A (en) * | 1998-01-12 | 1999-07-27 | Mitsui Chem Inc | Poly(4-methyl-1-pentene)-based resin laminate |
JPH11240068A (en) * | 1998-02-26 | 1999-09-07 | Mitsui Chem Inc | Preparation of multi-layer inflation film, multi-layer inflation film, and packaging material consisting of multi-layer inflation film |
JP2001225431A (en) * | 2000-02-15 | 2001-08-21 | Mitsui Chemicals Inc | 4-methyl-1-pentene resin laminate |
JP2002146343A (en) * | 2000-08-22 | 2002-05-22 | Mitsui Chemicals Inc | Sealant resin composition, sealant film and its use |
JP2004291609A (en) * | 2003-02-12 | 2004-10-21 | Mitsui Kagaku Platech Co Ltd | Stretched polyolefinic film |
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