JP2008138123A - Vinyl chloride-based resin composition and stretch film for food package - Google Patents
Vinyl chloride-based resin composition and stretch film for food package Download PDFInfo
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Abstract
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本発明は、塩化ビニル系樹脂組成物及びそれを用いた食品包装用ストレッチフィルムに関し、エポキシ基含有アクリル系化合物を用いることで、エポキシ基が塩化ビニル樹脂から成形加工中に脱離する塩化水素（ＨＣｌ）の捕捉、および不安定塩素の置換を行うことで熱安定性を向上させる効果があり、さらに得られた組成物を製膜することで昭和５７年厚生省告示２０号に定める蒸発残留物試験法にて測定したｎ−ヘプタン抽出量（以下、単にｎ−ヘプタン抽出量と呼ぶことがある）が極めて少ない塩化ビニル系樹脂組成物及び食品包装用ストレッチフィルムに関する。 TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition and a stretch film for food packaging using the same, and by using an epoxy group-containing acrylic compound, an epoxy group is detached from the vinyl chloride resin during molding (hydrogen chloride ( HCl) capture and replacement of unstable chlorine have the effect of improving thermal stability. Further, by forming a film of the obtained composition, the evaporation residue test stipulated in Ministry of Health and Welfare Notification No. 20 of 1982 The present invention relates to a vinyl chloride resin composition and a stretch film for food packaging, which have a very small n-heptane extract amount (hereinafter sometimes simply referred to as n-heptane extract amount) measured by the method.
食品の包装、特に精肉、鮮魚、青果等の生鮮食品の包装には、透明性、柔軟性およびヒートシール性に優れたストレッチフィルムが多数開発され、食品包装用フィルムとして広く使用されている。通常これらのフィルムは、ポリ塩化ビニル系樹脂にアジピン酸エステル系可塑剤とエポキシ化植物油とを可塑剤として使用したポリ塩化ビニル系樹脂組成物を成形したものが一般的である。
従来より、これらのフィルムは配合剤の衛生性、食品等への移行性が重要視されている。その衛生性では、米国のＦＤＡ規格（Ｆｏｏｄ ａｎｄ Ｄｒｕｇ Ａｄｍｉｎｉｓｔｒａｔｉｏｎ）や日本のＰＬ規格（塩化ビニル樹脂製包装容器包装等に関する自主規制基準）等に記載された添加剤より無毒化配合を確立し、また食品等への移行性については厚生省告示２０号試験により蒸発残留物試験法として抽出試験を行い確認している。
このような背景において従来は種々のものがある。しかしながら、可塑剤の種類や量、フィルム厚みによってはn−ヘプタン抽出量が規制値の１５０ｐｐｍに近くになったり、或は上回ったりする傾向があった。ｎ−ヘプタン抽出量を低下させるためにはフィルムを薄くする方法、可塑剤の量を減らす方法、抽出されにくい可塑剤に置き換える方法が上げられるが、塩化ビニル系樹脂からなる食品包装用ストレッチフィルムに用いられる可塑剤のうち、アジピン酸エステル系可塑剤は、ｎ−ヘプタンに抽出されにくいアジピン酸ポリエステル系可塑剤に置き換えることができるが、熱安定剤兼可塑剤として用いられるエポキシ化植物油からなる可塑剤の置き換えが困難であり、ｎ−ヘプタン抽出量を十分に低下させることが困難であった。
一方、エポキシ基含有アクリル系化合物を用いる例としては、以下の特許文献に示す例が挙げられる。しかし、エポキシ基含有アクリル系化合物を添加する目的は農業用フィルムの耐農薬性向上、べたつき改良、耐候性向上であり、本発明のように食品包装用ストレッチフィルムで用いられるエポキシ化植物油の添加量を０または極少量でも熱安定性に優れ、ｎ−ヘプタン抽出量を削減することは考慮されていない。
Many stretch films excellent in transparency, flexibility, and heat sealability have been developed and widely used as food packaging films for food packaging, particularly for fresh foods such as meat, fresh fish, and fruits and vegetables. Generally, these films are generally formed by molding a polyvinyl chloride resin composition using an adipate plasticizer and an epoxidized vegetable oil as a plasticizer on a polyvinyl chloride resin.
Conventionally, these films have been regarded as important for the hygiene of the compounding agent and the transferability to foods. In terms of its hygiene, it has established a non-toxic formulation from the additives described in the US FDA standards (Food and Drug Administration) and Japanese PL standards (self-regulatory standards for vinyl chloride resin packaging containers, etc.) The transferability to foods, etc. is confirmed by conducting an extraction test as an evaporation residue test method by the Ministry of Health and Welfare Notification No. 20 test.
In this background, there are various conventional ones. However, depending on the type and amount of plasticizer and the film thickness, the n-heptane extraction amount tends to be close to or exceeding the regulated value of 150 ppm. In order to reduce the amount of n-heptane extracted, there are a method of thinning the film, a method of reducing the amount of plasticizer, and a method of replacing with a plasticizer that is difficult to extract, but for a stretch film for food packaging made of vinyl chloride resin. Of the plasticizers used, adipic acid ester plasticizers can be replaced by adipic acid polyester plasticizers that are difficult to extract into n-heptane, but plastics composed of epoxidized vegetable oils used as heat stabilizers and plasticizers. It was difficult to replace the agent, and it was difficult to sufficiently reduce the amount of n-heptane extracted.
On the other hand, the example shown in the following patent documents as an example using an epoxy-group-containing acrylic compound is mentioned. However, the purpose of adding an epoxy group-containing acrylic compound is to improve agricultural chemical resistance, stickiness, and weather resistance of agricultural films, and the amount of epoxidized vegetable oil used in food packaging stretch films as in the present invention Even if it is 0 or a very small amount, it is excellent in thermal stability, and it is not considered to reduce the amount of n-heptane extracted.
本発明は、このような状況下で、熱安定性に優れるとともに、ｎ−ヘプタン抽出性を少なくできる塩化ビニル系樹脂組成物及び食品包装用ストレッチフィルムを提供することを目的とするものである。 An object of the present invention is to provide a vinyl chloride resin composition and a stretch film for food packaging that are excellent in thermal stability and can reduce n-heptane extractability under such circumstances.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、塩化ビニル系樹脂に、エポキシ基を含有するアクリル系化合物を添加することで、エポキシ化植物油の添加量を０または極少量としても熱安定性に優れ、なおかつｎ−ヘプタン抽出量が少ないことを見出した。本発明は、係る知見に基づいて完成したものである。
すなわち本発明は、
１． ポリ塩化ビニル系樹脂１００質量部に対して、（Ａ）アジピン酸エステル系可塑剤０．１〜１０質量部、（Ｂ）アジピン酸ポリエステル系可塑剤１〜４０質量部、（Ｃ）重量平均分子量１，０００〜１５万であるエポキシ基含有アクリル系化合物０．１〜２０質量部からなる塩化ビニル系樹脂組成物
２． １に記載の塩化ビニル系樹脂組成物を製膜して得られるフィルムであって、フィルム厚みが５〜１０μｍで、昭和５７年厚生省告示２０号に定める蒸発残留物試験法にて測定したｎ−ヘプタン抽出量が５０ｐｐｍ以下であることを特徴とする食品包装用ストレッチフィルムを提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have added an acrylic compound containing an epoxy group to a vinyl chloride resin, thereby reducing the amount of epoxidized vegetable oil to 0 or extremely high. It has been found that even when the amount is small, the thermal stability is excellent and the amount of n-heptane extracted is small. The present invention has been completed based on such knowledge.
That is, the present invention
1. (A) 0.1 to 10 parts by mass of an adipic acid ester plasticizer, (B) 1 to 40 parts by mass of an adipic acid polyester plasticizer, and (C) a weight average molecular weight with respect to 100 parts by mass of the polyvinyl chloride resin. 1. A vinyl chloride resin composition comprising 0.1 to 20 parts by mass of an epoxy group-containing acrylic compound that is 1,000 to 150,000. 1. A film obtained by forming the vinyl chloride resin composition according to 1, wherein the film thickness is 5 to 10 μm and measured by an evaporation residue test method defined in Ministry of Health and Welfare Notification No. 20 in 1982. It is intended to provide a stretch film for food packaging, wherein the amount of heptane extracted is 50 ppm or less.
本発明によれば、熱安定性に優れｎ−ヘプタン抽出量を少なくできる塩化ビニル系樹脂組成物およびそれを用いた食品包装用ストレッチフィルムを提供することができる。 According to the present invention, it is possible to provide a vinyl chloride resin composition that is excellent in thermal stability and can reduce the amount of n-heptane extracted and a stretch film for food packaging using the same.
本発明の樹脂組成物において、ポリ塩化ビニル系樹脂としては、平均重合度７００〜１，７００程度の塩化ビニル単独重合体が好ましく用いられる。平均重合度が７００未満では引張強度、伸び等の機械物性が劣り、平均重合度が１，７００を越えると溶融粘度が上昇し、発熱による分解が顕著となり成形加工が困難となる。より好ましくは８００〜１，５００である。
本発明における塩化ビニル系樹脂とは、上記塩化ビニル単独重合体のほか、塩化ビニルと共重合可能な単量体との共重合体（以下、塩化ビニル共重合体とする）、該塩化ビニル共重合体以外の重合体に塩化ビニルをグラフト共重合させたグラフト共重合体等も用いることができる。これらの共重合体は、共重合体中の塩化ビニル以外の構成単位の含有量が多くなると機械的特性が低下するので、塩化ビニル単位を６．０質量％以上含有するものが好ましい。なお、上記各重合体は乳化重合法、懸濁重合法、溶液重合法、塊状重合法等いずれの重合方法で得られたものでもよく、それぞれの単独又は２種以上の重合体の組み合わせで使用される。
In the resin composition of the present invention, as the polyvinyl chloride resin, a vinyl chloride homopolymer having an average degree of polymerization of about 700 to 1,700 is preferably used. If the average degree of polymerization is less than 700, mechanical properties such as tensile strength and elongation are inferior. If the average degree of polymerization exceeds 1,700, the melt viscosity increases, decomposition due to heat generation becomes remarkable, and molding processing becomes difficult. More preferably, it is 800-1500.
In the present invention, the vinyl chloride resin refers to a copolymer of a monomer copolymerizable with vinyl chloride (hereinafter referred to as vinyl chloride copolymer), the vinyl chloride copolymer, in addition to the above vinyl chloride homopolymer. A graft copolymer obtained by graft copolymerizing vinyl chloride with a polymer other than the polymer can also be used. These copolymers are preferably those containing 6.0% by mass or more of vinyl chloride units because the mechanical properties are lowered when the content of constituent units other than vinyl chloride in the copolymer increases. Each polymer may be obtained by any polymerization method such as emulsion polymerization method, suspension polymerization method, solution polymerization method, bulk polymerization method, etc., and used alone or in combination of two or more polymers. Is done.
上記の塩化ビニルと共重合可能な単量体としては、分子中に反応性二重結合を有するものであればよく、例えば、エチレン、プロピレン、ブチレン等のα−オレフィン類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；ブチルビニルエーテル、セチルビニルエーテル等のビニルエーテル類；アクリル酸、メタクリル酸等の不飽和カルボン酸類；アクリル酸メチル、メタクリル酸エチル、メタクリル酸フェニル等のアクリル酸又はメタクリル酸のエステル類；スチレン、α−メチルスチレン等の芳香族ビニル類；塩化ビニリデン、フッ化ビニル等のハロゲン化ビニル類；Ｎ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等のＮ−置換マレイミド類；等が挙げられ、これらは１種単独又は２種以上の組み合わせで用いられる。また、上記塩化ビニル共重合体以外の重合体としては、塩化ビニルをグラフト共重合できるものであればよく、例えば、エチレン・酢酸ビニル共重合体、エチレン・酢酸ビニル・一酸化炭素共重合体、エチレン・エチルアクリレート共重合体、エチレン・エチルアクリレート・一酸化炭素共重合体、エチレン・メチルメタクリレート共重合体、エチレン・プロピレン共重合体、アクリロニトリル・ブタジエン共重合体、ポリウレタン、塩素化ポリエチレン、塩素化ポリプロピレン等が挙げられ、これらは１種単独又は２種以上の組み合わせで用いられる。 The monomer copolymerizable with vinyl chloride is not particularly limited as long as it has a reactive double bond in the molecule. For example, α-olefins such as ethylene, propylene, butylene; vinyl acetate, propionic acid Vinyl esters such as vinyl; Vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; Unsaturated carboxylic acids such as acrylic acid and methacrylic acid; Esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl methacrylate, and phenyl methacrylate Aromatic vinyls such as styrene and α-methylstyrene; vinyl halides such as vinylidene chloride and vinyl fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Are used singly or in combination of two or more. The polymer other than the vinyl chloride copolymer may be any polymer that can be graft copolymerized with vinyl chloride, such as an ethylene / vinyl acetate copolymer, an ethylene / vinyl acetate / carbon monoxide copolymer, Ethylene / ethyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / methyl methacrylate copolymer, ethylene / propylene copolymer, acrylonitrile / butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated Polypropylene etc. are mentioned, These are used individually by 1 type or in combination of 2 or more types.
本発明における（Ａ）アジピン酸エステル系可塑剤とは、炭素数１０以下のアルキル基を有する単独または２種以上の脂肪族アルコールとアジピン酸との混合アジピン酸エステル系可塑剤であって、単独アジピン酸エステル系可塑剤としては、ジイソノニルアジペート：ＤＩＮＡ（炭素数９のもの）、ジオクチルアジペート：ＤＯＡ（炭素数８のもの）等が挙げられ、混合アジピン酸エステル系可塑剤としてはＣ８，１０アジペート（炭素数８、１０のアルキル基を有するアルコールの混合エステル）、Ｃ７，８アジペート（同７、９のもの）、Ｃ６，８，１０アジペート（同６、８、１０のもの）等が挙げられ、１種単独または２種以上の組み合わせて用いても良い。本発明におけるアジピン酸エステル系可塑剤の添加量は０．１〜１０質量部である。０．１重量部未満では十分な柔軟性付与効果が得られず、また成形加工時の溶融粘度が高くなりすぎて剪断発熱が多く熱劣化し易くなる。１０質量部を越えると、成形後のフィルム厚みを１０μｍ以下としてもｎ−ヘプタン抽出量を５０ｐｐｍ以下に下げることが困難となる。より好ましくは１〜５質量部である。 The (A) adipate ester plasticizer in the present invention is a single adipate ester plasticizer having an alkyl group having 10 or less carbon atoms or a mixture of two or more aliphatic alcohols and adipic acid. Examples of adipate plasticizers include diisononyl adipate: DINA (9 carbon atoms), dioctyl adipate: DOA (8 carbon atoms), and mixed adipate plasticizers are C8,10 adipates. (Mixed esters of alcohols having an alkyl group with 8 or 10 carbon atoms), C7,8 adipate (7,9), C6,8,10 adipate (6,8,10), etc. You may use individually by 1 type or in combination of 2 or more types. The addition amount of the adipic acid ester plasticizer in the present invention is 0.1 to 10 parts by mass. If the amount is less than 0.1 parts by weight, a sufficient flexibility imparting effect cannot be obtained, and the melt viscosity at the time of molding becomes too high, resulting in a large amount of shearing heat and easy thermal degradation. If it exceeds 10 parts by mass, it will be difficult to reduce the n-heptane extract to 50 ppm or less even if the film thickness after molding is 10 μm or less. More preferably, it is 1-5 mass parts.
本発明における（Ｂ）アジピン酸ポリエステル系可塑剤とは、アジピン酸と二価アルコールとの反応物であり、二価アルコールとしてはエチレングリコール、プロピレングリコール、ブタンジオール、１、６−ヘキサンジオール等があり、アジピン酸と１種類または２種類以上の二価アルコールとの反応生成物であり、具体的にはポリ（プロピレングリコール、アジピン酸）エステル、ポリ（ブタンジオール、アジピン酸）エステル、ポリ（エチレングリコール、アジピン酸）エステル、ポリ（１、６−ヘキサンジオール、ブタンジオール、アジピン酸）エステル、ポリ（ブタンジオール、エチレングリコール、アジピン酸）エステル、ポリ（エチレングリコール、プロピレングリコール、ブタンジオール、アジピン酸）エステル等が挙げられる。この平均分子量は１０００〜３０００のものが効果的に使用されるが、これが１０００未満ではｎ−ヘプタン抽出性が大きい。一方、平均分子量が３０００を越えると押出成形性が大幅に低下するとともにストレッチフィルムの耐寒性が低下してしまう。物性の向上、押出成形性の点において、平均分子量２０００前後のものが好適に使用される。本発明におけるアジピン酸ポリエステル系可塑剤の添加量は１〜４０質量部である。１重量部未満では柔軟性付与効果が得られず、成形加工も困難となる。また４０質量部を越えると１０μｍ以下の厚みで成形したフィルムの腰（剛性）がなく、包装の仕上がりが悪化するだけでなく、不経済である。より好ましくは５〜３０質量部である。 The (B) adipic acid polyester plasticizer in the present invention is a reaction product of adipic acid and a dihydric alcohol. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, butanediol, and 1,6-hexanediol. Yes, a reaction product of adipic acid and one or more dihydric alcohols, specifically, poly (propylene glycol, adipic acid) ester, poly (butanediol, adipic acid) ester, poly (ethylene Glycol, adipic acid) ester, poly (1,6-hexanediol, butanediol, adipic acid) ester, poly (butanediol, ethylene glycol, adipic acid) ester, poly (ethylene glycol, propylene glycol, butanediol, adipic acid ) Ester etc. That. An average molecular weight of 1000 to 3000 is effectively used, but if it is less than 1000, n-heptane extractability is large. On the other hand, when the average molecular weight exceeds 3000, the extrusion moldability is significantly lowered and the cold resistance of the stretch film is lowered. Those having an average molecular weight of about 2000 are preferably used in terms of improving physical properties and extrudability. The addition amount of the adipic acid polyester plasticizer in the present invention is 1 to 40 parts by mass. If it is less than 1 part by weight, the effect of imparting flexibility cannot be obtained, and the molding process becomes difficult. On the other hand, if it exceeds 40 parts by mass, the film formed with a thickness of 10 μm or less will not have a low stiffness (rigidity), and the finish of the packaging will be deteriorated, and it will be uneconomical. More preferably, it is 5-30 mass parts.
本発明における（Ｃ）アクリル系重合体とは、重量平均分子量１，０００〜１５万で分子内にエポキシ基を５０〜９０質量％含有するアクリル系重合体である。重量平均分子量が５，０００未満ではｎ−ヘプタン抽出量を抑制する効果が小さく、１０万を越えると溶融粘度を低減させる効果が少なく、成形加工性が悪化する。より好ましくは５，０００〜１０万である。また、本発明におけるアクリル系重合体は、分子内にエポキシ基を５０〜９０質量％含有している。エポキシ基が５０質量％未満では十分な熱安定性付与効果が得られず、９０質量％を越えると成形加工中にアクリル系重合体同士または分子内で架橋してしまいブツやフィッシュアイ不良の原因となる。より好ましくは６０〜８０質量％である。これらのアクリル系重合体の添加量は０．１〜２０質量部である。０．１質量部未満では十分な熱安定性向上効果が得られず、２０質量部を越えるとアクリル臭気や架橋の問題が発生する。より好ましくは５〜１８質量部である。 The (C) acrylic polymer in the present invention is an acrylic polymer having a weight average molecular weight of 1,000 to 150,000 and containing 50 to 90% by mass of an epoxy group in the molecule. If the weight average molecular weight is less than 5,000, the effect of suppressing the extraction amount of n-heptane is small, and if it exceeds 100,000, the effect of reducing the melt viscosity is small and the molding processability deteriorates. More preferably, it is 5,000 to 100,000. Moreover, the acrylic polymer in this invention contains 50-90 mass% of epoxy groups in a molecule | numerator. If the epoxy group is less than 50% by mass, a sufficient effect of imparting thermal stability cannot be obtained, and if it exceeds 90% by mass, the acrylic polymer may be cross-linked with each other or in the molecule during the molding process, causing defects and fisheye defects It becomes. More preferably, it is 60-80 mass%. The addition amount of these acrylic polymers is 0.1-20 mass parts. If the amount is less than 0.1 parts by mass, a sufficient effect of improving the heat stability cannot be obtained, and if it exceeds 20 parts by mass, problems of acrylic odor and crosslinking occur. More preferably, it is 5-18 mass parts.
このような特徴を有するアクリル系重合体としては、グリシジルメタクリレートのホモポリマー、グリシジルメタクリレートモノマーをポリマー分子中に１個以上含有しており、グリシジルメタクリレートと共重合可能なモノマーとの共重合体が挙げられる。グリシジルメタクリレートと共重合可能なモノマーとしては、ヒドロキシメチルアクリレート、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、３−ヒドロキシプロピルアクリレート、２−ヒドロキシブチルアクリレート、４−ヒドロキシブチルアクリレート、２−ヒドロキシペンチルアクリレート、６−ヒドロキシペンチルアクリレート等のヒドロキシアクリル酸エステル；ヒドロキシメチルメタクリレート、２−ヒドロキシエチルメタクリレート、２−ヒドロキシプロピルメタクリレート、３−ヒドロキシプロピルメタクリレート、２−ヒドロキシブチルメタクリレート、４−ヒドロキシブチルメタクリレート、２−ヒドロキシペンチルメタクリレート、６−ヒドロキシペンチルメタクリレート等のヒドロキシメタクリル酸エステル；アクリル酸、メタクリル酸等のα，β−不飽和カルボン酸；メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、ｉ−プロピルアクリレート、ｎ−ブチルアクリレート、ｉ−ブチルアクリレート、シクロヘキシルアクリレート、２−エチルヘキシルアクリレート、デシルアクリレート、ドデシルアクリレート、トリデシルアクリレート、ステアリルアクリレート等のアクリル酸エステル；メチルメタクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、ｉ−プロピルメタクリレート、ｎ−ブチルメタクリレート、ｉ−ブチルメタクリレート、シクロヘキシルメタクリレート、２−エチルヘキシルメタクリレート、デシルメタクリレート、ドデシルメタクリレート、トリデシルメタクリレート、ステアリルメタクリレート等のメタクリル酸エステル；スチレン、アクリロニトリル、メタクリロニトリル、酢酸ビニル、プロピオン酸ビニル、ジアクリロアミド、Ｎ−ブトキシメタクリロアミド等が挙げられる。 Examples of the acrylic polymer having such characteristics include a homopolymer of glycidyl methacrylate and a copolymer of glycidyl methacrylate and a monomer that contains at least one glycidyl methacrylate monomer and can be copolymerized with glycidyl methacrylate. It is done. Monomers copolymerizable with glycidyl methacrylate include hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxypentyl acrylate , Hydroxyacrylic esters such as 6-hydroxypentyl acrylate; hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy Hydroxyl such as pentyl methacrylate and 6-hydroxypentyl methacrylate Methacrylic acid ester; α, β-unsaturated carboxylic acid such as acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, cyclohexyl acrylate, 2 -Acrylic acid esters such as ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, tridecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, cyclohexyl methacrylate 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, tridecyl methacrylate Rate, methacrylic acid esters such as stearyl methacrylate; styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, Jiakuriroamido, like N- but-Kishime Taku Lilo amides.
その他本発明において、熱安定剤は種々用いることができるが、エポキシ基による熱安定性を向上させるためにはＣａ−Ｚｎ系安定剤を用いることがより好ましい。Ｃａ−Ｚｎ系安定剤とは、カルシウムの脂肪酸塩と亜鉛の脂肪酸塩の混合物であり、その添加量は０．１〜２．０質量部である。０．１質量部未満では熱安定性の効果が発揮されず、２．０質量部を越えると亜鉛焼けと呼ばれる急激な分解が起こる。より好ましくは０．３〜１．８質量部である。
本発明に用いられるカルシウム、亜鉛と塩をつくる脂肪酸としては、ベヘニン酸、ステアリン酸、ラウリン酸、オレイン酸、パルミチン酸、リシノール酸、安息香酸等が挙げられ、目的に応じて２種以上組み合わせて用いることもできるが、成形加工時の滑性とプレートアウトのバランスからステアリン酸塩とするのが好ましい。また、カルシウムと亜鉛の比率は質量比で１：２〜１：３である。亜鉛の比率がカルシウムに対して２より少ないとカルシウム塩特有の赤味が出てしまい、亜鉛の比率がカルシウムに対して３よりも多いと、成形加工中に生成する塩化亜鉛が塩化ビニル系樹脂の分解触媒となり、「亜鉛焼け」と呼ばれる急激な黒化、分解が生じる。
In the present invention, various heat stabilizers can be used, but a Ca—Zn-based stabilizer is more preferably used in order to improve the thermal stability due to the epoxy group. The Ca—Zn stabilizer is a mixture of a fatty acid salt of calcium and a fatty acid salt of zinc, and the addition amount is 0.1 to 2.0 parts by mass. If it is less than 0.1 parts by mass, the effect of thermal stability is not exhibited, and if it exceeds 2.0 parts by mass, rapid decomposition called zinc burn occurs. More preferably, it is 0.3-1.8 mass parts.
Examples of the fatty acid that forms a salt with calcium and zinc used in the present invention include behenic acid, stearic acid, lauric acid, oleic acid, palmitic acid, ricinoleic acid, benzoic acid, and the like. Although it can also be used, it is preferable to use a stearate from the balance between the slipperiness at the time of molding and the plate-out. Moreover, the ratio of calcium and zinc is 1: 2 to 1: 3 by mass ratio. If the ratio of zinc is less than 2, the redness peculiar to calcium salts will appear. If the ratio of zinc is more than 3, the zinc chloride produced during molding will be vinyl chloride resin. As a decomposition catalyst, rapid blackening and decomposition called “zinc burn” occur.
その他にも、防曇剤、界面活性剤、帯電防止剤、紫外線吸収剤、酸化防止剤、抗菌・抗カビ剤、加工助剤、滑剤、着色剤、充填剤等、上記作用を損なわない範囲で、かつ塩ビ食品衛生協議会（ＪＨＰＡ）発行のポジティブリスト記載の添加剤を添加しても良い。
本発明における塩化ビニル系樹脂組成物は、上記の塩化ビニル系樹脂と、添加剤とをスーパーミキサー等の通常用いられる混合装置に投入し、加熱、撹拌、冷却する事により得られる。加熱温度や撹拌時間は、監視窓等から混合状態を見ながら決めれば良い。
本発明におけるストレッチフィルムの成形は、得られたコンパウンドを、単軸、２軸、または多軸押出機等を用いてＴダイ法、またはインフレーション法にて製膜して得られる。
In addition, antifogging agents, surfactants, antistatic agents, ultraviolet absorbers, antioxidants, antibacterial / antifungal agents, processing aids, lubricants, coloring agents, fillers, etc. In addition, additives described in the positive list issued by the PVC Food Sanitation Council (JHPA) may be added.
The vinyl chloride resin composition in the present invention can be obtained by charging the above vinyl chloride resin and additives into a commonly used mixing apparatus such as a super mixer, and heating, stirring and cooling. What is necessary is just to determine heating temperature and stirring time, seeing a mixing state from a monitoring window.
The formation of the stretch film in the present invention is obtained by forming the obtained compound into a film by a T-die method or an inflation method using a single-screw, twin-screw, or multi-screw extruder.
以下、本発明の効果を実施例に基づいて詳細に説明するが、本発明は以下の実施例に限定されるものではない。
表１に示す配合比率で各配合剤を撹拌しながらスーパーミキサーに投入し、材料温度１３０℃まで昇温し、６５℃まで冷却して取り出して、塩化ビニル系樹脂組成物を得た。
使用した原料は下記の通りである。
Hereinafter, although the effect of the present invention is explained in detail based on an example, the present invention is not limited to the following examples.
Each compounding agent was added to the supermixer while stirring at the blending ratio shown in Table 1, and the temperature was raised to 130 ° C., cooled to 65 ° C., and taken out to obtain a vinyl chloride resin composition.
The raw materials used are as follows.
・塩化ビニル系樹脂：「ＴＫ−１０００」（信越化学工業（株）社製）平均重合度１０５０の塩化ビニルホモポリマー
（Ａ）アジピン酸エステル系可塑剤：ジイソノニルアジペート：「サンソサイザーＤＩＮＡ」（新日本理化（株）社製）
（Ｂ）アジピン酸ポリエステル系可塑剤：「ＢＡＡ−１５」（大八化学工業（株）社製） 重量平均分子量約２，５００
（Ｃ−１）エポキシ基含有アクリル系化合物：「マープルーフＧ−１００５Ｓ」（日本油脂（株）社製）エポキシ当量３，３００、平均分子量１００，０００
（Ｃ−２）エポキシ基含有アクリル系化合物：「ブレンマーＣＰ−１５」（日本油脂（株）社製）エポキシ当量１，０００、平均分子量１１，４００
-Vinyl chloride resin: "TK-1000" (manufactured by Shin-Etsu Chemical Co., Ltd.) Vinyl chloride homopolymer with an average polymerization degree of 1050 (A) Adipate plasticizer: Diisononyl adipate: "Sunsosizer DINA" (New (Made by Nippon Rika Co., Ltd.)
(B) Adipic acid polyester plasticizer: “BAA-15” (manufactured by Daihachi Chemical Industry Co., Ltd.) Weight average molecular weight of about 2,500
(C-1) Epoxy group-containing acrylic compound: “Marproof G-1005S” (manufactured by NOF Corporation), epoxy equivalent 3,300, average molecular weight 100,000
(C-2) Epoxy group-containing acrylic compound: “Blemmer CP-15” (manufactured by NOF Corporation), epoxy equivalent 1,000, average molecular weight 11,400
その他添加剤
・エポキシ化植物油：エポキシ化大豆油：「カポックスＳ−６」（花王（株）社製）
・Ｃａ−Ｚｎ安定剤：「アデカスタブＳＰ−７６」（旭電化工業（株）社製）
・防曇剤：「リケマールＸＯ−１００」（理研ビタミン（株）社製）グリセリンモノオレート
Other additives, Epoxidized vegetable oil: Epoxidized soybean oil: "Capox S-6" (manufactured by Kao Corporation)
Ca-Zn stabilizer: “ADK STAB SP-76” (Asahi Denka Kogyo Co., Ltd.)
Antifogging agent: “Riquemar XO-100” (manufactured by Riken Vitamin Co., Ltd.) Glycerol monooleate
得られた樹脂組成物を、Ｔダイ（幅３５０ｍｍ、ギャップ０．５ｍｍ）を装着したφ４０ｍｍの単軸押出機（Ｌ／Ｄ＝２０）にて樹脂温度２００℃で押出成形してフィルムを得た。得られたフィルムにつき以下の評価を行ない、その結果を表１に示した。 The obtained resin composition was extrusion molded at a resin temperature of 200 ° C. with a φ40 mm single screw extruder (L / D = 20) equipped with a T die (width 350 mm, gap 0.5 mm) to obtain a film. . The obtained film was evaluated as follows, and the results are shown in Table 1.
[成形加工性]
・押出フィルムの外観を目視により観察し、以下の基準にて判断した。
○：着色、分解による炭化物等の発生が無くフィルムの採取ができた。
△：着色が見られるが、炭化物等の発生までは至らず、フィルムの採取ができた。
×：着色が見られ、炭化物が流出し、フィルムの採取が困難であった。
[Molding processability]
-The appearance of the extruded film was visually observed and judged according to the following criteria.
○: The film could be collected without generation of carbides due to coloring and decomposition.
(Triangle | delta): Although coloring was seen, it did not reach generation | occurrence | production of a carbide | carbonized_material etc. but the film | membrane was able to be extract | collected.
X: Coloring was observed, carbides flowed out, and film collection was difficult.
[食品衛生試験]
・ｎ−ヘプタン抽出試験：昭和５７年厚生省告示２０号に定める蒸発残留物試験法で抽出量を測定し、ｎ−ヘプタン抽出量（ｐｐｍ）として示した。
○：５０質量ｐｐｍ以下
×：５０質量ｐｐｍ超
[Food hygiene test]
-N-Heptane extraction test: The extraction amount was measured by the evaporation residue test method stipulated in Ministry of Health and Welfare Notification No. 20 in 1982, and indicated as n-heptane extraction amount (ppm).
○: 50 mass ppm or less ×: more than 50 mass ppm
[包装適性]
・自動包装機適性：ＰＰ製のトレーにシシャモ８尾を盛りつけ、フジキカイ社製自動包装機「Ａ−１８Ｋ」により包装速度４０パック／分で自動包装し、包装適性を下記の基準で評価した。
○：しわや破れがなく包装できたもの
△：やや滑り不足、シワ等見られるが包装できたもの
×：しわ、破れまたは張り不足で包装不適なもの
-Suitability of automatic packaging machine: Eight shishamo were put on a PP tray, and automatic packaging was carried out at a packaging speed of 40 packs / minute by an automatic packaging machine "A-18K" manufactured by Fujikikai, and packaging suitability was evaluated according to the following criteria.
○: Wrapped without tearing or tearing △: Slightly lacking in slipping, wrinkles, etc. but could be packaged x: Wrinkled, torn or insufficiently stretched
表１から、実施例１〜４は外観（成形加工性）、ｎ−ヘプタン抽出性、包装適性に優れることが分かる。
これに対して比較例１は、エポキシ基含有アクリル系化合物の添加量が少なく、外観が悪化する。比較例２は、エポキシ基含有アクリル系化合物の添加量が多く、柔軟性が損なわれることから包装適性が悪化する。比較例３は、エポキシ基含有アクリル系化合物に替えてエポキシ化大豆油を用いると外観や包装適性は優れるものの、ｎ−ヘプタン抽出量が多いことが分かる。
From Table 1, it can be seen that Examples 1 to 4 are excellent in appearance (molding processability), n-heptane extractability, and packaging suitability.
On the other hand, in Comparative Example 1, the amount of the epoxy group-containing acrylic compound added is small, and the appearance is deteriorated. In Comparative Example 2, since the amount of the epoxy group-containing acrylic compound added is large and flexibility is impaired, packaging suitability is deteriorated. In Comparative Example 3, it can be seen that when epoxidized soybean oil is used instead of the epoxy group-containing acrylic compound, the appearance and packaging suitability are excellent, but the amount of n-heptane extracted is large.
塩化ビニル系樹脂組成物及びそれを用いた食品包装用ストレッチフィルムに関し、特に熱安定性に優れ、なおかつ塩化ビニル系樹脂組成物を製膜してなるフィルムが、昭和５７年厚生省告示２０号に定める蒸発残留物試験法にて測定したｎ−ヘプタン抽出量が極めて少ない食品包装用ストレッチフィルムとしての利用性が大きい。
Regarding a vinyl chloride resin composition and a stretch film for food packaging using the same, a film which is particularly excellent in thermal stability and is formed from a vinyl chloride resin composition is stipulated in Notification No. 20 of the Ministry of Health and Welfare in 1982. The utility as a stretch film for food packaging with a very small n-heptane extract amount measured by the evaporation residue test method is great.
Claims (2)
A film obtained by forming the vinyl chloride resin composition according to claim 1, having a film thickness of 5 to 10 μm, and measured by an evaporation residue test method stipulated in Ministry of Health and Welfare Notification No. 20 of 1982. A stretch film for food packaging, wherein the n-heptane extraction amount is 50 ppm or less.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094731A1 (en) * | 2015-11-30 | 2017-06-08 | 日立化成株式会社 | Food packaging film, and gift-boxed small roll of food packaging film |
| JP2019038164A (en) * | 2017-08-24 | 2019-03-14 | 信越ポリマー株式会社 | Polyvinyl chloride resin-made wrapping film and method for producing the same |
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| JPS604543A (en) * | 1983-06-22 | 1985-01-11 | Nippon Carbide Ind Co Ltd | Semirigid vinyl chloride molding resin |
| JPS62138546A (en) * | 1985-12-12 | 1987-06-22 | Sekisui Chem Co Ltd | Vinyl chloride based resin composition |
| JP2001106990A (en) * | 1999-10-01 | 2001-04-17 | Bando Chem Ind Ltd | Substrate film for adhesive sheet and its production |
| JP2001214018A (en) * | 2000-01-31 | 2001-08-07 | Achilles Corp | Synthetic resin film for agricultural use |
| JP2006104242A (en) * | 2004-10-01 | 2006-04-20 | Mitsubishi Plastics Ind Ltd | Polyvinyl chloride-based resin composition and stretch film using the same |
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2006
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS604543A (en) * | 1983-06-22 | 1985-01-11 | Nippon Carbide Ind Co Ltd | Semirigid vinyl chloride molding resin |
| JPS62138546A (en) * | 1985-12-12 | 1987-06-22 | Sekisui Chem Co Ltd | Vinyl chloride based resin composition |
| JP2001106990A (en) * | 1999-10-01 | 2001-04-17 | Bando Chem Ind Ltd | Substrate film for adhesive sheet and its production |
| JP2001214018A (en) * | 2000-01-31 | 2001-08-07 | Achilles Corp | Synthetic resin film for agricultural use |
| JP2006104242A (en) * | 2004-10-01 | 2006-04-20 | Mitsubishi Plastics Ind Ltd | Polyvinyl chloride-based resin composition and stretch film using the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017094731A1 (en) * | 2015-11-30 | 2017-06-08 | 日立化成株式会社 | Food packaging film, and gift-boxed small roll of food packaging film |
| WO2017094076A1 (en) * | 2015-11-30 | 2017-06-08 | 日立化成株式会社 | Food packaging film |
| JP6202660B1 (en) * | 2015-11-30 | 2017-09-27 | 日立化成株式会社 | Food packaging film |
| CN108291039A (en) * | 2015-11-30 | 2018-07-17 | 日立化成株式会社 | Food packaging film and food packaging wound membrane with packing box |
| JPWO2017094731A1 (en) * | 2015-11-30 | 2018-09-13 | 日立化成株式会社 | Food packaging film and small roll film for food packaging with cosmetic box |
| CN108291039B (en) * | 2015-11-30 | 2021-08-06 | 昭和电工材料株式会社 | Film for food packaging and roll film for food packaging with package box |
| JP2019038164A (en) * | 2017-08-24 | 2019-03-14 | 信越ポリマー株式会社 | Polyvinyl chloride resin-made wrapping film and method for producing the same |
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