JP2018127533A - Master batch - Google Patents
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Abstract
Description
本発明は、食品包装フィルムおよびシート用の防曇剤マスターバッチに関する。具体的には、水分を含んだ食品を包装した後の冷蔵保存で、フィルム内面に結露した水が、水膜となって中身の視認性を損なうことがない防曇性を発揮する食品包装フィルム用の高濃度防曇剤マスターバッチに関する。 The present invention relates to an antifogging agent masterbatch for food packaging films and sheets. Specifically, a food packaging film that exhibits anti-fogging properties so that the water condensing on the inner surface of the film becomes a water film and does not impair the visibility of the contents in refrigerated storage after packaging foods that contain moisture The present invention relates to a high concentration antifogging agent master batch.
食品包装用フィルムにはそれぞれの目的に応じて、グリセリン脂肪酸エステルを始めとした界面活性剤を添加することで、水に対し親和性が低いプラスチック表面の濡れ性を改善し、防曇性を発現させる。
かかる食品包装用フィルムへの防曇剤の添加方法としては、予めベースとなる樹脂に防曇剤を高濃度に配合させた防曇剤マスターバッチを押出機内で溶融混練して、防曇剤を希釈してフィルムを成型するマスターバッチ添加法等がある。
Depending on the purpose of the food packaging film, surfactants such as glycerin fatty acid esters are added to improve the wettability of plastic surfaces with low affinity for water and to exhibit antifogging properties. Let
As a method for adding an antifogging agent to such a food packaging film, an antifogging agent master batch in which an antifogging agent is blended in a high concentration with a base resin in advance is melt-kneaded in an extruder, and the antifogging agent is added. There is a master batch addition method for diluting and forming a film.
ところで、食品包装用フィルムの食品接触層には低温ヒートシール性等に優れるエチレン−酢酸ビニル共重合体が広く使われてきたが、輸送時の振動、衝撃によるシール部の剥離（シールパンク）等のトラブルに対して、ヒートシール強度やホットタック強度に優れるエチレン−α−オレフィン共重合体が使用される場合がある。
エチレン−αオレフィン共重合体は極性が低く、グリセリン脂肪酸エステルを始めとする防曇剤との親和性が乏しいため、防曇剤を多量に混練させようとすると、分散不良を起こして、防曇性を発揮しづらい場合がある。
By the way, ethylene-vinyl acetate copolymers with excellent low-temperature heat-sealing properties have been widely used for food contact layers of food packaging films, but the seals are peeled off (sealed punctures) due to vibration during transportation and impact. In some cases, an ethylene-α-olefin copolymer having excellent heat seal strength and hot tack strength is used.
The ethylene-α olefin copolymer has low polarity and poor affinity with anti-fogging agents such as glycerin fatty acid esters. Therefore, when a large amount of the anti-fogging agent is kneaded, poor dispersion occurs and anti-fogging occurs. There are cases where it is difficult to exert sex.
特許文献１には、樹脂が、ポリエチレン、エチレン−酢酸ビニル共重合体等と防曇剤を用いた樹脂組成物が開示されている。 Patent Document 1 discloses a resin composition in which a resin uses polyethylene, an ethylene-vinyl acetate copolymer, and the like and an antifogging agent.
しかしながら、特許文献１に記載のポリエチレン樹脂組成物の場合は前述したように樹脂の極性が低く、防曇剤の混練性が劣るため、高濃度マスターバッチ化が困難であり、エチレン−酢酸ビニル共重合体の場合はポリエチレンよりも極性が高いため、高濃度マスターバッチ化は容易であるが、マスターバッチ化した後にブリードアウトしやすいため、表面がべたつき、フィルムおよびシート成型時の押出変動の原因となりやすい。またエチレン−酢酸ビニル共重合体をベース樹脂としたマスターバッチをポリエチレンに添加して使用すると、相溶性が悪いため、フィルムやシートに成型した後の透明性が低下する場合がある。
従って、食品接触層と同じ樹脂をベースとして、マスターバッチ化し、フィルムおよびシートに成型した後、透明性を損なわず、防曇性に優れたフィルムが求められている。
However, in the case of the polyethylene resin composition described in Patent Document 1, since the polarity of the resin is low and the kneading property of the antifogging agent is inferior as described above, it is difficult to make a high-concentration masterbatch. In the case of polymer, since it is more polar than polyethylene, it is easy to make a high-concentration masterbatch, but since it tends to bleed out after it is masterbatched, it causes stickiness on the surface and causes fluctuations in extrusion during film and sheet molding. Cheap. Moreover, when a master batch using an ethylene-vinyl acetate copolymer as a base resin is added to polyethylene and used, the compatibility after molding into a film or sheet may be lowered due to poor compatibility.
Accordingly, there is a demand for a film excellent in anti-fogging property without deteriorating transparency after being formed into a master batch based on the same resin as the food contact layer and molded into a film and a sheet.
本発明は、ペレット表面がべたつくことなく、マスターバッチ中に、高濃度に防曇剤を保持することができ、フィルム成型後には表面に防曇剤を持続的に保持することが可能な高濃度防曇剤マスターバッチの提供を目的とする。 The present invention is capable of holding the antifogging agent at a high concentration in the master batch without stickiness of the pellet surface, and capable of continuously holding the antifogging agent on the surface after film formation. The purpose is to provide an antifogging agent masterbatch.
すなわち、本発明は下記の通りである。
１）エチレン−α−オレフィン共重合体４０〜９０質量％、エチレン系共重合体１〜４０質量％、及び防曇剤５〜４０質量％を含み、かつ該エチレン系共重合体と該防曇剤の質量比が１：１〜１：５である、食品包装フィルムまたはシート用のマスターバッチ。
２）前記エチレン−α−オレフィン共重合体の密度が、０．８８０〜０．９３０ｇ／ｃｍ３である１）に記載の食品包装フィルムまたはシート用のマスターバッチ。
That is, the present invention is as follows.
1) It contains 40 to 90% by mass of an ethylene-α-olefin copolymer, 1 to 40% by mass of an ethylene copolymer, and 5 to 40% by mass of an antifogging agent, and the ethylene copolymer and the antifogging agent. A master batch for a food packaging film or sheet, wherein the mass ratio of the agent is 1: 1 to 1: 5.
2) The food batch film or sheet masterbatch according to 1), wherein the density of the ethylene-α-olefin copolymer is 0.880 to 0.930 g / cm 3 .
３）前記エチレン系共重合体が、エチレン−脂肪族不飽和カルボン酸共重合体、エチレン−脂肪族不飽和カルボン酸エステル共重合体、変性ポリエチレン、及びアイオノマー樹脂から選ばれる少なくとも１種である、１）または２）に記載の食品包装フィルムまたはシート用のマスターバッチ。
４）前記アイオノマーの金属イオンが、カリウム、ナトリウム、亜鉛、マグネシウム、及びリチウムから選ばれる少なくとも１種である、３）に記載の食品包装フィルムまたはシート用のマスターバッチ。
3) The ethylene copolymer is at least one selected from an ethylene-aliphatic unsaturated carboxylic acid copolymer, an ethylene-aliphatic unsaturated carboxylic acid ester copolymer, a modified polyethylene, and an ionomer resin. A master batch for a food packaging film or sheet according to 1) or 2).
4) The master batch for a food packaging film or sheet according to 3), wherein the metal ion of the ionomer is at least one selected from potassium, sodium, zinc, magnesium, and lithium.
５）前記防曇剤が、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、及びポリオキシエチレングリセリン脂肪酸エステルから選ばれる少なくとも1種である、１）〜４）のいずれか１つに記載の食品包装フィルムまたはシート用のマスターバッチ。
６）１）〜５）のいずれか１つに記載のマスターバッチが、食品接触層に１〜４０質量％含まれ、前記食品接触層がエチレン−α−オレフィン共重合体を９０〜９８％含む食品包装フィルムまたはシート。
5) The antifogging agent is at least one selected from glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene glycerin fatty acid ester. A masterbatch for a food packaging film or sheet according to any one of 1) to 4).
6) The masterbatch according to any one of 1) to 5) is contained in a food contact layer in an amount of 1 to 40% by mass, and the food contact layer contains an ethylene-α-olefin copolymer in an amount of 90 to 98%. Food packaging film or sheet.
ペレット表面がべたつくことなく、マスターバッチ中に、高濃度に防曇剤を保持することができ、フィルム成型後には表面に防曇剤を持続的に保持することが可能である。 The antifogging agent can be held at a high concentration in the master batch without stickiness of the pellet surface, and the antifogging agent can be continuously held on the surface after film formation.
本発明について、好ましい実施態様を中心に、以下詳細に説明する。
［マスターバッチ］
本発明のマスターバッチは、エチレン−α−オレフィン共重合体４０〜９０質量％、エチレン系共重合体１〜４０質量％、及び防曇剤５〜４０質量％を含む。
上記エチレン−α−オレフィン共重合体とは、エチレンと、炭素数が３〜１８のα−オレフィンから選ばれる少なくとも１種の単量体との共重合体をいう。
上記炭素数が３〜１８のα−オレフィンとしては、プロピレン、ブテン−１、ペンテン−１、４−メチル−ペンテン−１、ヘキセン−１、オクテン−１、デセン−１、ドデセン−１等が挙げられる。
The present invention will be described in detail below with a focus on preferred embodiments.
[Master Badge]
The masterbatch of the present invention contains 40 to 90% by mass of an ethylene-α-olefin copolymer, 1 to 40% by mass of an ethylene copolymer, and 5 to 40% by mass of an antifogging agent.
The ethylene-α-olefin copolymer refers to a copolymer of ethylene and at least one monomer selected from α-olefins having 3 to 18 carbon atoms.
Examples of the α-olefin having 3 to 18 carbon atoms include propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, decene-1, dodecene-1, and the like. It is done.
上記エチレン−α−オレフィン共重合体を製造する際に用いられる重合触媒は、特に限定されないが、例えば、マルチサイト触媒やシングルサイト触媒等が挙げられる。
上記エチレン−α−オレフィン共重合体は、１種を単独で又は２種以上の密度やコモノマー種の異なるものを混ぜて用いてもよい。
エチレン−α−オレフィン共重合体の密度は好ましくは０．８８０〜０．９３０ｇ／ｃｍ３の範囲であり、フィルム成型後のヒートシール強度やホットタック強度を付与する点で、より好ましくは０．８８５〜０．９２５ｇ／ｃ３、更に好ましくは０．９００〜０．９２０ｇ／ｃｍ３である。
Although the polymerization catalyst used when manufacturing the said ethylene-alpha-olefin copolymer is not specifically limited, For example, a multi-site catalyst, a single site catalyst, etc. are mentioned.
The ethylene-α-olefin copolymers may be used singly or as a mixture of two or more densities or different comonomer types.
The density of the ethylene-α-olefin copolymer is preferably in the range of 0.880 to 0.930 g / cm 3 , and more preferably from the viewpoint of imparting heat seal strength and hot tack strength after film molding. 885 to 0.925 g / c 3 , more preferably 0.900 to 0.920 g / cm 3 .
エチレン系共重合体は、エチレン−脂肪族不飽和カルボン酸共重合体、エチレン−脂肪族不飽和カルボン酸エステル共重合体、変性ポリエチレン、及びアイオノマー樹脂から選ばれる少なくとも１種が好ましく、中でも極性が高く、防曇剤の保持力が高いアイオノマーがより好ましい。
アイオノマーの金属イオンとしては、カリウム、ナトリウム、亜鉛、マグネシウム、及びリチウムから選ばれる少なくとも１種が好ましく、フィルム化した後の透明性の点でカリウム、ナトリウムがより好ましい。
The ethylene copolymer is preferably at least one selected from an ethylene-aliphatic unsaturated carboxylic acid copolymer, an ethylene-aliphatic unsaturated carboxylic acid ester copolymer, a modified polyethylene, and an ionomer resin. An ionomer that is high and has high antifogging agent retention power is more preferable.
The ionomer metal ion is preferably at least one selected from potassium, sodium, zinc, magnesium and lithium, and more preferably potassium and sodium from the viewpoint of transparency after film formation.
防曇剤は熱安定性や加工性の観点から、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、及びポリオキシエチレングリセリン脂肪酸エステルから選ばれる少なくとも１種が好ましい。 The antifogging agent is selected from glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene glycerin fatty acid ester from the viewpoint of thermal stability and processability. At least one is preferred.
フィルムまたはシートの食品接触層にはヒートシール性やホットタックシール強度に優れるエチレン−α−オレフィン共重合体が広く使用される。同じエチレン−α−オレフィン共重合体をマスターバッチのベース樹脂として使用することで、フィルム化する際に分散性が向上し、透明性が良好となるため、マスターバッチ中のエチレン−α−オレフィン共重合体は４０〜９０質量％であり、好ましくは３０〜８０質量％である。 An ethylene-α-olefin copolymer excellent in heat sealability and hot tack seal strength is widely used in the food contact layer of the film or sheet. By using the same ethylene-α-olefin copolymer as the base resin of the masterbatch, dispersibility is improved when forming a film, and transparency is improved. Therefore, the ethylene-α-olefin copolymer in the masterbatch is improved. A polymer is 40-90 mass%, Preferably it is 30-80 mass%.
エチレン系共重合樹脂はマスターバッチ中に適量配合することで、防曇剤の保持力を高めて、高濃度の防曇剤を配合したマスターバッチとすることができる。
エチレン系共重合体の極性が高く、添加量が多いほど、フィルム化した後の防曇剤の保持力は高まるが同時に防曇剤を強く引き寄せる効果があるため、ブリードアウトを強く抑制し、防曇性が低下したり、フィルムの透明性が低下する場合がる。
フィルム化した後の透明性と防曇性を両立する上で、マスターバッチ中のエチレン系共重合体は１〜４０質量％であり、好ましくは３〜３５質量％、より好ましくは５〜３０質量％である。
By blending an appropriate amount of the ethylene copolymer resin in the master batch, the retention strength of the anti-fogging agent can be increased and a master batch containing a high concentration of the anti-fogging agent can be obtained.
The higher the polarity of the ethylene-based copolymer and the greater the amount added, the higher the retention of the antifogging agent after filming, but at the same time, it has the effect of strongly attracting the antifogging agent. The haze may decrease or the transparency of the film may decrease.
In order to achieve both transparency and antifogging properties after film formation, the ethylene copolymer in the masterbatch is 1 to 40% by mass, preferably 3 to 35% by mass, more preferably 5 to 30% by mass. %.
防曇剤はマスターバッチ作成時の混練性と、フィルム化した後の防曇性を両立する点で５〜４０質量％であり、好ましくは１０〜３５質量％である。
エチレン系共重合体と防曇剤の質量比は１：１〜１：５の範囲である。エチレン系共重合体が１に対して、防曇剤が１未満ではフィルム化した後に防曇剤のブリードアウトを抑制するため、防曇性が発揮しづらく、５を超えるとマスターバッチ作成時にストランドが安定しづらくなる。
The antifogging agent is 5 to 40% by mass, preferably 10 to 35% by mass in terms of achieving both kneadability at the time of preparing the master batch and antifogging after forming into a film.
The mass ratio of the ethylene copolymer and the antifogging agent is in the range of 1: 1 to 1: 5. When the ethylene copolymer is less than 1 and the antifogging agent is less than 1, the antifogging agent bleed-out is suppressed after film formation. Becomes difficult to stabilize.
［マスターバッチの製造方法］
本発明における、マスターバッチの製造方法は特に限定されないが、異方向二軸押出機や同方向二軸押出機で溶融混練する方法が望ましい。
押出温度は防曇剤の劣化を防止するため、２３０℃以下とするのが望ましい。
防曇剤は予め樹脂と混ぜてから、押出機に供給しても良いが押出機のスクリューへの供給を安定させるため、樹脂が溶融し始めた後に押出機シリンダー内に防曇剤を注入して混練する方法が好ましい。
[Manufacturing method of master batch]
The production method of the masterbatch in the present invention is not particularly limited, but a melt kneading method using a different direction twin screw extruder or the same direction twin screw extruder is desirable.
The extrusion temperature is desirably 230 ° C. or lower in order to prevent the antifogging agent from deteriorating.
The antifogging agent may be mixed with the resin in advance and then supplied to the extruder. However, in order to stabilize the supply to the screw of the extruder, the antifogging agent is injected into the extruder cylinder after the resin starts to melt. The kneading method is preferable.
前記押出機の先端に５〜８ｍｍ程度の紡口を数カ所設け、溶融混練した樹脂を紐状（以下、ストランドと称する）に押し出し、水中で２秒以上冷却固化し、カッターにて長さ５ｍｍ程度にカットして、マスターバッチを得る。
得られたマスターバッチは良く水を切り、除湿乾燥機等で含水率０．１％未満まで、十分乾燥させてからフィルムやシート成型に用いる。
Several spouts of about 5 to 8 mm are provided at the tip of the extruder, and the melt-kneaded resin is extruded into a string (hereinafter referred to as a strand), cooled and solidified for 2 seconds or more in water, and about 5 mm in length with a cutter. Cut into a master batch.
The obtained master batch is well drained and dried sufficiently to a moisture content of less than 0.1% using a dehumidifying dryer or the like, and then used for film or sheet molding.
［フィルムの製造方法］
本発明のフィルム製造方法は特に限定されないが、ダイレクトインフレーション法、ダブルバブルインフレーション法等の環状ダイスよりフィルムをチューブ状に押出して延伸する方法やＴダイより押し出したシートを、加熱ロールを用いて縦方向にのみ延伸する方法や縦方向に延伸した後にテンターを用いて、横方向に延伸して二軸延伸する方法、テンター内で同時二軸延伸を行う方法等が挙げられる。
中でもダブルバブルインフレーション法によって得られる多層フィルムまたは多層シートは収縮性や機械的強度に優れるため、食品包装用フィルムとして好適である。
[Film Production Method]
The film production method of the present invention is not particularly limited, but a method of extruding and stretching a film from a circular die such as a direct inflation method or a double bubble inflation method, or a sheet extruded from a T die is longitudinally heated using a heating roll. Examples thereof include a method of stretching only in the direction, a method of stretching in the longitudinal direction and then using a tenter, stretching in the transverse direction and biaxial stretching, and a method of performing simultaneous biaxial stretching in the tenter.
Among these, a multilayer film or a multilayer sheet obtained by the double bubble inflation method is suitable as a food packaging film because it is excellent in shrinkability and mechanical strength.
具体的な製造方法の例としては、押出機を用いて各層を構成する樹脂組成物を溶融押出して、１層ずつ環状ダイス内で順次合流させるか、環状ダイス内で１度に合流させて、多層のチューブ状未延伸原反を得る。このとき、１層につき１台の押出機を使用してもよいし、１台の押出機から環状ダイスに樹脂組成物が流入するまでに２つ以上に分割して、複数の層としてもよい。 As an example of a specific manufacturing method, the resin composition constituting each layer is melt-extruded using an extruder, and the layers are sequentially joined together in an annular die, or joined at once in an annular die, A multilayer tubular unstretched raw material is obtained. At this time, one extruder may be used per layer, or it may be divided into two or more by the time the resin composition flows from one extruder into the annular die. .
食品接触層に本発明のマスターバッチを１〜４０質量％、事前に配合することで、防曇剤を高濃度に均一に含有させることが出来る。食品接触層にはヒートシール強度やホットタック強度を向上させるためにエチレン−α−オレフィン共重合体を９０〜９８％含むことが好ましい。これを急冷固化したものを延伸機内に誘導し、目的に応じて、延伸開始点の加熱温度を調整し、速度差を設けたニップロール間でエアー注入を行い、流れ方向、幅方向に、それぞれ３．０倍以上の延伸を行う。 By adding 1 to 40% by mass of the master batch of the present invention in advance in the food contact layer, the antifogging agent can be uniformly contained in a high concentration. The food contact layer preferably contains 90 to 98% of an ethylene-α-olefin copolymer in order to improve heat seal strength and hot tack strength. This is rapidly cooled and solidified, guided into the stretching machine, the heating temperature at the stretching start point is adjusted according to the purpose, and air is injected between the nip rolls provided with a speed difference, and the flow direction and the width direction are 3 respectively. Stretching by 0 times or more.
延伸倍率の上限として、延伸安定性の観点から１２．０倍以下が好ましく、表面層を構成する樹脂組成物の融点以下で延伸することで、透明性が優れるフィルムが得やすい。より高倍率延伸を行いたい場合、表面層の融点以上で延伸したい場合は架橋処理を行うことで表面層の透明性を維持することも可能である。
さらに、本発明の目的を損なわない範囲で、マスターバッチ中に可塑剤として、アルコン（商標）、クリアロン（登録商標）、アイマーブ（登録商標）等の粘着付与樹脂や石油系樹脂を含んでもよい。上記可塑剤の含有量としては、各層を構成する樹脂組成物に対して０．１〜１０質量％とすると収縮性や透明性が向上する場合がある。
The upper limit of the stretching ratio is preferably 12.0 times or less from the viewpoint of stretching stability, and a film having excellent transparency can be easily obtained by stretching at a melting point or less of the resin composition constituting the surface layer. When it is desired to perform stretching at a higher magnification, or when stretching at a melting point or higher of the surface layer, it is possible to maintain the transparency of the surface layer by performing a crosslinking treatment.
Furthermore, the masterbatch may contain a tackifying resin such as Alcon (trademark), Clearon (registered trademark), and Imabe (registered trademark) or a petroleum resin as long as the object of the present invention is not impaired. As content of the said plasticizer, if it is 0.1-10 mass% with respect to the resin composition which comprises each layer, contractility and transparency may improve.
本発明を実施例に基づいて説明する。
以下に実施例、参考例、比較例において用いた測定方法を記す。
（１）押出機混練性
表１に記載の組成に混合した樹脂組成物を二軸押出機（東芝機械製 ＴＥＭ−１８ＳＳ）に投入し、５ｋｇ／ｈｒの押出量で、３箇所の直径８ｍｍの紡口から樹脂を押し出し、長さが２ｍの冷水槽内で冷却固化し、得られたストランドをカッターで裁断して、巾５ｍｍ×長さ５ｍｍのペレット状樹脂組成物とした。
押出時のストランドの外観を観察し、押出機混練性の評価とした。
○：ストランドに捩れや蛇行がなく、表面荒れの無いペレットを得ることができた。
△：表面に液泡が発生したがストランド切れは起こらなかった。
×：紡口から防曇剤が吹き出し、ストランドが得られなかった。
The present invention will be described based on examples.
The measurement methods used in Examples, Reference Examples, and Comparative Examples are described below.
(1) Extruder kneadability The resin composition mixed in the composition shown in Table 1 is put into a twin screw extruder (TEM-18SS manufactured by Toshiba Machine), and the extrusion rate is 5 kg / hr and the diameter is 3 mm and the diameter is 8 mm. The resin was extruded from the spinning nozzle, cooled and solidified in a cold water tank having a length of 2 m, and the obtained strand was cut with a cutter to obtain a pellet-shaped resin composition having a width of 5 mm and a length of 5 mm.
The appearance of the strands during extrusion was observed, and the kneadability of the extruder was evaluated.
○: The strands were not twisted or meandered, and pellets without surface roughness could be obtained.
(Triangle | delta): Although the liquid bubble generate | occur | produced on the surface, the strand breakage did not occur.
X: The antifogging agent was blown out from the spinning nozzle, and no strand was obtained.
（２）防曇性評価
ポリスチレン製容器（内寸法：１４５ｍｍ×９０ｍｍ×５５ｍｍ）に２０℃の水を２００ｍｌ入れ、各実施例に記載の方法により得られたフィルムで密封し、１２０℃に加熱したシュリンクトンネルで３秒間、熱処理を行った。このケースを５℃の冷蔵庫内に放置し、２時間経過後、１週間経過後に、容器を取り出し、フィルム内面の曇度を調べ、以下の判定基準により５段階で評価を行った。
◎：フィルム内面に均一水膜を生成し、完全に透明で曇りがない。
○：水膜に斑があるが、がほとんど透明である。
△：水膜に斑があり、１０ｍｍ以上の水滴が付着している。
×：１０ｍｍ以下の水滴が前面に付着し、中身が見えない。
(2) Evaluation of anti-fogging property 200 ml of 20 ° C. water was placed in a polystyrene container (inner dimensions: 145 mm × 90 mm × 55 mm), sealed with a film obtained by the method described in each example, and heated to 120 ° C. Heat treatment was performed for 3 seconds in the shrink tunnel. This case was left in a refrigerator at 5 ° C., 2 hours later, 1 week later, the container was taken out, the haze of the film inner surface was examined, and the evaluation was made in 5 stages according to the following criteria.
A: A uniform water film is formed on the inner surface of the film, and it is completely transparent and not cloudy.
○: There are spots on the water film, but it is almost transparent.
(Triangle | delta): The water film has spots and the water droplet of 10 mm or more has adhered.
X: Water droplets of 10 mm or less adhere to the front surface and the contents cannot be seen.
実施例、参考例および比較例で用いた樹脂は以下のとおりである。
なお、分子内にＣ＝Ｏ基、ＯＨ基を有するもの、ＯＨ基を金属イオンで置換したものを極性樹脂、Ｃ，Ｈのみで構成されるものを非極性樹脂と表記した。
Resins used in Examples, Reference Examples and Comparative Examples are as follows.
In addition, what has C = O group and OH group in a molecule | numerator, what substituted OH group by the metal ion was described as polar resin, and what was comprised only by C and H was described as nonpolar resin.
・ＬＬ１（非極性）：エチレン−α−オレフィン共重合体（シングルサイト系触媒で重合されたもの）、密度：０．９１３ｇ／ｃｍ３、ＭＦＲ：２．０ｇ／１０分、融点：１１３℃
・ＥＭＡＡ（極性）：エチレン−メタクリル酸共重合体（酸含有量＝１１質量％）、ＭＦＲ＝８ｇ／１０分、融点＝９８℃
・ＥＡＡ（極性）：エチレン−アクリル酸共重合体（酸含量＝９．５質量％）、ＭＦＲ＝１．６ｇ／１０分、融点９８℃
・変性ポリエチレン１（極性）：ＭＦＲ＝６．２ｇ／１０分、融点１２０℃
・アイオノマー１（極性）：ＭＦＲ＝５ｇ／１０分、融点＝８６℃（イオン種：カリウム）
・アイオノマー２（極性）：ＭＦＲ＝３ｇ／１０分、融点＝９８℃（イオン種：ナトリウム）
・ＰＰ１（非極性）：エチレン−プロピレンコポリマー、ＭＦＲ＝５．３ｇ／１０分、融点＝１５０℃
・ポリオキシエチレンアルキルエーテル：ＨＬＢ＝１２
・ジグリセリンオレート：ＨＬＢ＝５．７
・ジグリセリンラウレート：ＨＬＢ＝６．３
・グリセリンモノオレート：ＨＬＢ＝４．７
LL1 (nonpolar): ethylene-α-olefin copolymer (polymerized with a single site catalyst), density: 0.913 g / cm 3 , MFR: 2.0 g / 10 min, melting point: 113 ° C.
EMAA (polar): ethylene-methacrylic acid copolymer (acid content = 11% by mass), MFR = 8 g / 10 min, melting point = 98 ° C.
EAA (polar): ethylene-acrylic acid copolymer (acid content = 9.5% by mass), MFR = 1.6 g / 10 min, melting point 98 ° C.
Modified polyethylene 1 (polar): MFR = 6.2 g / 10 min, melting point 120 ° C.
Ionomer 1 (polarity): MFR = 5 g / 10 min, melting point = 86 ° C. (ionic species: potassium)
Ionomer 2 (polarity): MFR = 3 g / 10 min, melting point = 98 ° C. (ionic species: sodium)
PP1 (nonpolar): ethylene-propylene copolymer, MFR = 5.3 g / 10 min, melting point = 150 ° C.
Polyoxyethylene alkyl ether: HLB = 12
Diglycerin oleate: HLB = 5.7
Diglycerin laurate: HLB = 6.3
-Glycerol monooleate: HLB = 4.7
［実施例１〜８］
表１に示す樹脂組成物を二軸押出機に投入した後に、防曇剤組成物を添加し、先端に設けた直径８ｍｍの紡口から溶融混練した樹脂を紐状（以下、ストランドと称する）に押し出して、水中で２秒以上冷却固化した。
得られたストランドに付着した水分を冷風で吹き飛ばした後、カッターにて長さ５ｍｍにカットして、マスターバッチを得た。
得られたマスターバッチを５０℃に設定した除湿乾燥機で含水率０．１％未満まで、十分乾燥させた。
[Examples 1 to 8]
After charging the resin composition shown in Table 1 into a twin screw extruder, the antifogging agent composition is added, and the resin melted and kneaded from the 8 mm diameter nozzle provided at the tip is a string (hereinafter referred to as a strand). And cooled and solidified in water for 2 seconds or longer.
After the moisture adhering to the obtained strand was blown off with cold air, it was cut into a length of 5 mm with a cutter to obtain a master batch.
The obtained master batch was sufficiently dried to a moisture content of less than 0.1% with a dehumidifying dryer set at 50 ° C.
ストランドの状態を観察し、混練性と評価結果として、表１に記載した。
表面層１として、ＬＬ１と表１に示す防曇剤マスターバッチを９０：１０の比率で押し出し、第２層として、ＰＰ１を、表面層：第２層＝３０：７０の厚み比率で環状ダイスから２層の未延伸現反を押し出し、冷却固化して未延伸チューブ原反を作製した。これを延伸機内に誘導して再加熱を行い、２対の差動ニップロール間に通して、エアー注入によりバブルを形成し、流れ方向に４倍、幅方向に３倍の倍率でそれぞれ延伸を行い、平均厚みが１０μｍのシュリンクフィルムを得た。
このようにして得られたフィルムについて、防曇性評価を行った。
実施例１〜８で得られたマスターバッチは、いずれも安定した押出機混練性を示し、２時間後の初期防曇性に優れ、１週間後の持続防曇性にも優れる結果が得られた。
The state of the strand was observed, and the kneadability and evaluation results are shown in Table 1.
As surface layer 1, LL1 and an antifogging agent masterbatch shown in Table 1 are extruded at a ratio of 90:10, and PP1 is formed as a second layer from an annular die at a thickness ratio of surface layer: second layer = 30: 70. Two layers of unstretched fabric were extruded and cooled and solidified to produce an unstretched tube original fabric. This is induced in a stretching machine, reheated, passed between two pairs of differential nip rolls, bubbles are formed by air injection, and stretched at a magnification of 4 times in the flow direction and 3 times in the width direction. A shrink film having an average thickness of 10 μm was obtained.
The film thus obtained was evaluated for antifogging property.
The master batches obtained in Examples 1 to 8 all showed stable extruder kneading properties, excellent initial antifogging properties after 2 hours, and excellent antifogging properties after 1 week. It was.
比較例１はエチレン系共重合体を含まないため、混練性が不十分でストランドが途中で切れてしまい、マスターバッチが得られなかった。
比較例２はエチレン系共重合体に対し、防曇剤の量が多いため、押出機内での混練が不十分であったため、押出し時にストランドに液泡が発生し、マスターバッチを得ることはできたが、フィルム化した後の防曇性評価において、特に１週間後の持続防曇性が劣る結果となった。
比較例３はエチレン−α−オレフィン共重合体の量が少なく、防曇剤量も多かったため、ストランド切れにより、マスターバッチが得られなかった。
比較例４は実施例２と比較して防曇剤に対して、エチレン系共重合体の量が多く、優れた押出機混練性を示したが、エチレン系共重合体の防曇剤保持力が強いため、フィルム表面に防曇剤がブリードアウトせず、防曇性は発現されなかった。
Since Comparative Example 1 did not contain an ethylene-based copolymer, the kneadability was insufficient, the strands were cut off in the middle, and a master batch was not obtained.
In Comparative Example 2, since the amount of the antifogging agent was large with respect to the ethylene-based copolymer, kneading in the extruder was insufficient, so liquid bubbles were generated in the strand during extrusion, and a master batch could be obtained. However, in the evaluation of anti-fogging property after film formation, the result was inferior in the continuous anti-fogging property after one week.
In Comparative Example 3, since the amount of the ethylene-α-olefin copolymer was small and the amount of the antifogging agent was large, a master batch could not be obtained due to strand breakage.
In Comparative Example 4, the amount of the ethylene copolymer was large with respect to the antifogging agent compared to Example 2 and showed excellent extruder kneading properties. However, the antifogging agent holding power of the ethylene copolymer was shown. The antifogging agent did not bleed out on the film surface and the antifogging property was not exhibited.
本実施形態の高濃度防曇剤マスターバッチは防曇剤を高濃度に保持することができ、特にヒートシール性に優れるエチレン−α−オレフィン共重合体フィルムに優れた初期防曇性と持続防曇性を付与することが出来る。 The high-concentration antifogging agent masterbatch of the present embodiment can maintain the antifogging agent at a high concentration, and is particularly excellent in initial antifogging property and sustained prevention in an ethylene-α-olefin copolymer film excellent in heat sealability. Haze can be imparted.
Claims (6)
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