JPH08134306A - Vinylidene chloride resin wrapping film and its production - Google Patents
Vinylidene chloride resin wrapping film and its productionInfo
- Publication number
- JPH08134306A JPH08134306A JP27786994A JP27786994A JPH08134306A JP H08134306 A JPH08134306 A JP H08134306A JP 27786994 A JP27786994 A JP 27786994A JP 27786994 A JP27786994 A JP 27786994A JP H08134306 A JPH08134306 A JP H08134306A
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene chloride
- chloride resin
- weight
- film
- liquid plasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Wrappers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、一般家庭の多くで皿な
どの容器に入れた食品や、あるいは食品それ自体を直接
包む場合に用いるラップフィルムに関し、弾性率が高く
て、ハリ・コシ感があり、かつ、ラップフィルム相互の
密着性に優れた塩化ビニリデン系樹脂ラップフィルムお
よびその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wrap film used in many households for directly wrapping food in a container such as a plate or the food itself, and has a high elastic modulus and a firm and elastic feeling. And a vinylidene chloride-based resin wrap film having excellent adhesiveness to each other and a method for producing the same.
【０００２】[0002]
【従来の技術】サランラップ等の商品名で市販されてい
る塩化ビニリデン系樹脂ラップフィルムは、食生活上の
様々な食品の簡易的包装材として一般家庭の多くで使用
されている。それは、塩化ビニリデン系樹脂ラップフィ
ルム特有の高弾性率、密着性、匂いバリア性、電子レン
ジによる調理が可能等の性質が食品の簡易的包装材とし
て適しているからである。2. Description of the Related Art Vinylidene chloride resin wrap films marketed under the trade name of Saran wrap and the like are used in many households as a simple packaging material for various foods in the diet. This is because the unique properties of vinylidene chloride resin wrap film such as high elastic modulus, adhesiveness, odor barrier property, and ability to be cooked in a microwave oven are suitable as a simple packaging material for foods.
【０００３】特に、他のポリエチレン等の素材からなる
ラップと比較すると塩化ビニリデン系樹脂ラップフィル
ムは、まず弾性率が高く、ハリ・コシ感があり、フィル
ム同士の密着性が良いこと、匂いバリア性が良好である
こと、耐熱性の良いことが利点であって、サランラップ
（商品名、旭化成（株）社製）、クレラップ（商品名、
呉羽化学（株）社製）の名称で広く使用されている。In particular, vinylidene chloride resin wrap films have a high elastic modulus, a firm and firm feeling, good adhesion between the films, and an odor barrier property as compared with other wraps made of materials such as polyethylene. Is good and has good heat resistance. Saran wrap (trade name, manufactured by Asahi Kasei Co., Ltd.), crerap (trade name,
It is widely used under the name of Kureha Chemical Co., Ltd.).
【０００４】近年、一般家庭での、この塩化ビニリデン
系ラップフィルム使用の普及にともなって、ラップフィ
ルムに対する性能要求はさらに厳しいものになってきて
いる。一方、生産の立場からは押出機を大型化し押出速
度を高めて製造コストを下げ製品を安価に提供する事も
満たす必要があり、より優れた成膜加工性に対する要求
も強いものである。市場からのフィルム物性に対する要
求と生産の立場からの要求をまとめると、成膜加工性に
優れ、かつ弾性率が高くしゃっきりとしたハリコシ感が
あって、従来品より使い勝手が良く、それでいてフィル
ム同士の密着性が保たれているものが求められている。In recent years, with the widespread use of vinylidene chloride wrap films in general households, performance requirements for wrap films have become even more severe. On the other hand, from the standpoint of production, it is necessary to satisfy the requirements for higher film forming processability, since it is necessary to satisfy the requirements of increasing the size of the extruder and increasing the extrusion speed to reduce the manufacturing cost and provide the product at a low cost. Summarizing the demands from the market for film physical properties and the demands from the standpoint of production, it has excellent film-forming processability, high elastic modulus and a crisp elasticity, and is easier to use than conventional products, yet it is a film-to-film product. There is a demand for materials that maintain close contact.
【０００５】塩化ビニリデン系樹脂ラップフィルムにお
いて、弾性率を向上させることの困難さは、成膜加工性
と弾性率の向上及び密着性の維持という三者を並立させ
ることの困難さにある。まず、塩化ビニリデン系樹脂
は、押出加工温度と樹脂の熱分解温度とが近くて、成膜
加工性に乏しいので液状可塑剤を添加することにより成
膜加工性を付与してやる必要がある。また、その液状可
塑剤の添加は、成膜されたラップフィルムの密着性を高
める役割も同時に果たしている。ただし、液状可塑剤は
室温の状態でも可塑剤として作用するために、フィルム
の弾性率を低下させてしまう作用もある。したがって、
フィルムの弾性率を高めようとして液状可塑剤添加量を
減量すると成膜加工性が悪化すると同時に、フィルム同
士の密着性も低くなってしまう事になり、成膜加工性と
弾性率、密着性三者の調和をとることの困難性が存在す
るのである。In the vinylidene chloride resin wrap film, the difficulty in improving the elastic modulus lies in the difficulty in arranging the three aspects of film-forming processability, improving the elastic modulus and maintaining adhesion. First, since vinylidene chloride-based resin has a low extrusion process temperature and a thermal decomposition temperature of the resin and is poor in film forming processability, it is necessary to add film forming processability by adding a liquid plasticizer. Further, the addition of the liquid plasticizer also plays a role of enhancing the adhesiveness of the formed wrap film. However, since the liquid plasticizer acts as a plasticizer even at room temperature, it also reduces the elastic modulus of the film. Therefore,
When the amount of the liquid plasticizer added is reduced in order to increase the elastic modulus of the film, the film forming processability deteriorates, and at the same time, the adhesion between the films also decreases. There is a difficulty in harmonizing the people.
【０００６】特にラップフィルムのように、厚み２０μ
以下の極薄成膜を行う際には、狭いダイリップから高剪
断下で溶融押出するので分解物の形成が促進され、また
微少な分解物の流出によってもインフレーション工程で
のパンクが頻発したりするので、成膜加工性の確保は極
薄フィルムを工業的に得る上での前提条件となる。A thickness of 20 μm, especially for a wrap film.
When performing the following ultra-thin film formation, since melt extrusion is performed from a narrow die lip under high shear, the formation of decomposition products is promoted, and even the outflow of minute decomposition products often causes puncture in the inflation process. Therefore, securing the film forming processability is a prerequisite for industrially obtaining an ultrathin film.
【０００７】そこで、従来より有効な液状可塑剤種を選
びこれの添加量を調節する方法が検討されているが（例
えば、特公昭５７−２７４１号）、成膜加工性を確保す
るという観点から、液状可塑剤の添加量としては通常７
重量部以上が添加されているのが実状である。また、特
公平５−６２１３５には、成膜加工性を犠牲にせずにフ
ィルムの弾性率を向上させる方法として塩化ビニリデン
とメチルアクリレートとの共重合体を用いて、成膜後の
液状可塑剤の逸散性が向上する性質を利用しフィルム内
に含まれる可塑剤量が３重量％以下の塩化ビニリデン系
共重合樹脂製ラップフィルムが開示され、この方法によ
れば高弾性率のラップフィルムが得られるとしている。
また、特公平４−１０２６号には、液状可塑剤の添加量
を減らす代替に、エチレンと酢酸ビニルとの共重合体グ
リースを添加する樹脂組成物が開示され、この樹脂組成
物で作られる塩化ビニリデン系樹脂ラップフィルムは弾
性率が高まり、かつラップフィルム同士の密着性を保つ
ことが出来るとしている。Therefore, a method of selecting a more effective liquid plasticizer species and adjusting the addition amount thereof has been studied (for example, Japanese Patent Publication No. 57-2741), but from the viewpoint of ensuring film forming processability. The amount of liquid plasticizer added is usually 7
The actual situation is that more than one part by weight is added. Further, Japanese Patent Publication No. 62135/1993 discloses a liquid plasticizer after film formation using a copolymer of vinylidene chloride and methyl acrylate as a method for improving the elastic modulus of the film without sacrificing film forming processability. A wrap film made of vinylidene chloride-based copolymer resin containing 3% by weight or less of a plasticizer contained in the film is disclosed by utilizing the property of improving the escape property. According to this method, a wrap film having a high elastic modulus can be obtained. It is supposed to be.
Further, Japanese Patent Publication No. 1026/1992 discloses a resin composition in which a copolymer grease of ethylene and vinyl acetate is added as an alternative to reduce the amount of the liquid plasticizer added. It is said that the vinylidene resin wrap film has an increased elastic modulus and can maintain the adhesion between the wrap films.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、上記の
特公昭５７−２７４１号に記載の方法の如く可塑剤の種
類を適宜選択するだけでは、液状可塑剤の添加量を弾性
率が向上するまでに減らすことは成膜加工性、密着性を
並立させるという観点から限界があり困難なものであ
る。However, if the kind of the plasticizer is appropriately selected as in the method described in Japanese Patent Publication No. 57-2741, the amount of the liquid plasticizer to be added will not be increased until the elastic modulus is improved. It is difficult to reduce the film forming workability and the adhesiveness because there is a limit from the viewpoint of parallelization.
【０００９】また、上記の特公平５−６２１３５に記載
の方法では、まず得られたフィルムの密着性は現状の市
場要求を満たせない問題点がある。液状可塑剤量を高め
て密着性を高めようとしても、液状可塑剤の逸散率が液
状可塑剤の添加量約３重量％を超えた時点で急激に上昇
するために、液状可塑剤量が３重量％以上のものに調節
することが極めて困難となり、密着性が不十分なものし
か得ることができないという欠点がある。つまり、この
方法はフィルム内の液状可塑剤の含有量の調節に際し
て、その逸散率が急激に変化するという事は、一定した
品質の製品の製造には不適切であることを意味してい
る。Further, in the method described in Japanese Patent Publication No. 5-62135, there is a problem that the adhesiveness of the obtained film cannot satisfy the current market demand. Even if the amount of the liquid plasticizer is increased to improve the adhesion, the amount of the liquid plasticizer rapidly increases when the dissipation rate of the liquid plasticizer exceeds about 3% by weight of the liquid plasticizer. It is extremely difficult to adjust the content to 3% by weight or more, and there is a drawback that only adhesives having insufficient adhesion can be obtained. In other words, in this method, when the content of the liquid plasticizer in the film is adjusted, its extinction rate changes abruptly, which means that it is not suitable for producing a product of constant quality. .
【００１０】また、特公平４−１０２６号に記載の樹脂
組成物では、エチレンと酢酸ビニルとの共重合体グリー
スは溶融加工時の可塑化効果が不十分であり、成膜加工
性を犠牲にせざるを得ないものである。また、成膜加工
性を高めようとして共重合体グリースの添加量を増やす
と、得られたラップフィルムにベタツキ感が生じてしま
い好ましくないものである。Further, in the resin composition described in Japanese Examined Patent Publication No. 4-1026, the copolymer grease of ethylene and vinyl acetate has an insufficient plasticizing effect during melt processing and sacrifices film forming processability. It is inevitable. Further, if the amount of the copolymer grease added is increased in order to improve the film-forming processability, the resulting wrap film will be sticky, which is not preferable.
【００１１】本発明の第一の目的は、高められた市場品
質要求、すなわち弾性率が高くてハリ・コシ感に優れ、
かつラップフィルム相互の密着性に優れた塩化ビニリデ
ン系樹脂ラップフィルムを提供するものであり、また第
二の目的は、高められた生産条件における成膜加工性に
優れ、かつ上記第一の目的を達成するラップフィルムの
製造方法を提供するものである。The first object of the present invention is to have an increased market quality requirement, that is, high elastic modulus and excellent elasticity and elasticity.
And to provide a vinylidene chloride resin wrap film having excellent adhesiveness between the wrap films, and a second object is excellent film forming processability under increased production conditions, and the first object described above. It is intended to provide a method of manufacturing a wrap film to be achieved.
【００１２】[0012]
【課題を解決するための手段】本発明のラップフィルム
としての構成は、塩化ビニリデン系樹脂Ａと塩化ビニリ
デン系樹脂Ｂと液状可塑剤とからなる混合樹脂組成物で
あって、上記混合樹脂組成物内における塩化ビニリデン
系樹脂Ｂと液状可塑剤の含有量の割合は、液状可塑剤の
含有量（重量％）を横軸に、塩化ビニリデン系樹脂Ｂの
含有量（重量％）を縦軸にとった図において、座標点
イ．（３，１４）、ロ．（３、１０）、ハ．（６、
４）、ニ．（６、１４）を結んでなる四辺形の範囲内に
あることを特徴とする。The composition as a wrap film of the present invention is a mixed resin composition comprising a vinylidene chloride resin A, a vinylidene chloride resin B and a liquid plasticizer. The ratio of the content of the vinylidene chloride resin B to the content of the liquid plasticizer is shown in the horizontal axis of the content of the liquid plasticizer (% by weight) and the content of the vinylidene chloride resin B (% of weight) in the vertical axis. The coordinate points a. (3, 14), b. (3, 10), c. (6,
4), d. It is characterized by being in the range of a quadrangle formed by connecting (6, 14).
【００１３】またラップフィルムの製造方法としての構
成は、液状可塑剤を含有する塩化ビニリデン系樹脂組成
物を溶融押出しし、押出された溶融物を過冷却し、冷却
した押出物を２軸延伸成膜してフィルムとなし、このフ
ィルムを加熱して含有する液状可塑剤の一部を逸散せし
めて、液状可塑剤の含有量の小さいフィルムを得る塩化
ビニリデン系樹脂ラップフィルムの製造方法において、
上記塩化ビニリデン系樹脂組成物を、塩化ビニリデン系
樹脂Ａと、塩化ビニリデン系樹脂Ｂと液状可塑剤とから
なる混合樹脂組成物となし、上記液状可塑剤の一部を逸
散させる工程は、塩化ビニリデン系樹脂Ｂの割合が３．
９重量％から１３．９重量％である成膜されたフィルム
の状態下で行わしめ、得られるフィルム内に含有する塩
化ビニリデン系樹脂Ｂと液状可塑剤の含有量の割合を、
液状可塑剤の含有量（重量％）を横軸に、塩化ビニリデ
ン系樹脂Ｂの含有量（重量％）を縦軸にとった図におい
て、座標点イ．（３，１４）、ロ．（３、１０）、ハ．
（６、４）、ニ．（６、１４）を結んでなる四辺形の範
囲内のものにすることを特徴とする。The wrap film is manufactured by melt extruding a vinylidene chloride resin composition containing a liquid plasticizer, supercooling the extruded melt, and biaxially stretching the cooled extrudate. A film is formed into a film, a part of the liquid plasticizer contained in the film is heated to dissipate, and in the method for producing a vinylidene chloride resin wrap film, a film having a small content of the liquid plasticizer is obtained.
The vinylidene chloride resin composition is a mixed resin composition comprising vinylidene chloride resin A, vinylidene chloride resin B and a liquid plasticizer, and the step of dissipating a part of the liquid plasticizer is The ratio of vinylidene resin B is 3.
It was carried out under the condition of the film formed of 9 wt% to 13.9 wt%, and the ratio of the content of the vinylidene chloride resin B and the liquid plasticizer contained in the obtained film was
In the figure in which the content (wt%) of the liquid plasticizer is plotted on the horizontal axis and the content (wt%) of the vinylidene chloride resin B is plotted on the vertical axis, coordinate points a. (3, 14), b. (3, 10), c.
(6, 4), d. It is characterized in that it is within the range of a quadrangle formed by connecting (6, 14).
【００１４】上記ラップフィルム及びラップフィルムの
製造方法における塩化ビニリデン系樹脂Ａは、塩化ビニ
リデン含有量が８５重量％以上９５重量％以下であっ
て、ゲルパーミエーションクロマトグラフィー法による
重量平均分子量が８万以上１３万以下である塩化ビニリ
デン系樹脂である。また、塩化ビニリデン系樹脂Ｂは塩
化ビニリデン含有量が８０重量％以上９５重量％以下で
あって、ゲルパーミエーションクロマトグラフィー法に
よる重量平均分子量が２万以上６万以下である塩化ビニ
リデン系樹脂である。The vinylidene chloride resin A used in the wrap film and the method for producing the wrap film has a vinylidene chloride content of 85% by weight or more and 95% by weight or less, and a weight average molecular weight by gel permeation chromatography of 80,000. It is a vinylidene chloride resin having a content of 130,000 or less. The vinylidene chloride resin B is a vinylidene chloride resin having a vinylidene chloride content of 80% by weight or more and 95% by weight or less and a weight average molecular weight by gel permeation chromatography of 20,000 or more and 60,000 or less. .
【００１５】まず、本発明の内容を製造方法の観点から
説明する。First, the contents of the present invention will be described from the viewpoint of the manufacturing method.
【００１６】本発明の製造方法の従来技術との相違点
は、 （１）塩化ビニリデン系樹脂組成物を、塩化ビニリデン
系樹脂Ａと、塩化ビニリデン系樹脂Ｂと液状可塑剤の混
合組成物とすること。The difference between the production method of the present invention and the prior art is as follows: (1) The vinylidene chloride resin composition is a mixed composition of vinylidene chloride resin A, vinylidene chloride resin B and a liquid plasticizer. thing.
【００１７】（２）液状可塑剤の一部を逸散させる工程
を、ある特定割合の塩化ビニリデン系樹脂Ｂが含有され
ている成膜されたフィルムの状態下で行わしめること。 （３）液状可塑剤を逸散させて得られるフィルム内に含
有する塩化ビニリデン系樹脂Ｂと液状可塑剤の含有量の
割合を、ある特定範囲に調節すること。(2) The step of dissipating a part of the liquid plasticizer is carried out under the condition of a film formed containing a certain specific proportion of vinylidene chloride resin B. (3) The ratio of the content of the vinylidene chloride resin B and the content of the liquid plasticizer contained in the film obtained by allowing the liquid plasticizer to dissipate is adjusted to a certain range.
【００１８】の上記（１），（２），（３）の組み合わ
せにある。A combination of (1), (2) and (3) above.
【００１９】（１），（２），（３）の役割についてま
とめると次のようになる。すなわち、上記（１）の役割
は塩化ビニリデン系樹脂Ｂは、塩化ビニリデン系樹脂Ａ
との相溶性が優れており、可塑化効果が非常に高いので
溶融押出時に成膜加工性を向上させることができ、
（２）の役割は従来不可能であった液状可塑剤の逸散率
の上昇と安定化が達成され、（３）の役割はフィルム内
に含有する塩化ビニリデン系樹脂Ｂと液状可塑剤の含有
量の割合をある特定範囲に調節するので、成膜加工性と
弾性率の向上及び密着性の維持という三者を並立させる
ことが可能になったことにある。The roles of (1), (2) and (3) can be summarized as follows. That is, the role of the above (1) is that the vinylidene chloride resin B is the vinylidene chloride resin A.
It has excellent compatibility with and has a very high plasticizing effect, so it can improve film forming processability during melt extrusion,
The role of (2) achieves the increase and stabilization of the escape rate of the liquid plasticizer, which was not possible in the past, and the role of (3), contains vinylidene chloride resin B and the liquid plasticizer contained in the film. Since the ratio of the amounts is adjusted to a certain specific range, it is possible to make the three aspects of film-forming workability and elastic modulus improved and adhesion maintained in parallel.
【００２０】図１は、実施例１、比較例１、比較例２に
対応する実験結果図で、本発明の製造方法における上記
（２）の特長を示す図である。FIG. 1 is an experimental result diagram corresponding to Example 1, Comparative Example 1 and Comparative Example 2, and shows the feature (2) in the manufacturing method of the present invention.
【００２１】図１の横軸は樹脂内に当初含有していた可
塑剤の添加量（単位重量％）、縦軸は含有可塑剤の逸散
率（単位重量％）を目盛っている。×印は、従来の塩化
ビニリデン系樹脂、即ち市販のサランラップ（商品名、
旭化成工業製）用樹脂の場合、○は本発明に用いる特定
分子量の塩化ビニリデン系樹脂を含んでなる樹脂の場
合、△は特公平５−６２１３５に記載の、メチルアクリ
レート成分を含む塩化ビニリデン系共重合樹脂の場合で
ある。The abscissa of FIG. 1 is the amount of the plasticizer initially contained in the resin (unit weight%), and the ordinate is the escape rate of the contained plasticizer (unit weight%). A cross mark indicates a conventional vinylidene chloride resin, that is, a commercially available Saran wrap (trade name,
In the case of a resin for Asahi Kasei), ◯ is a resin containing a vinylidene chloride resin of a specific molecular weight used in the present invention, and Δ is a vinylidene chloride resin containing a methyl acrylate component described in JP-B-5-62135. This is the case of polymerized resin.
【００２２】上記図１において、本発明の樹脂組成は、
従来の塩化ビニリデン系樹脂に比較し液状可塑剤の逸散
率が大きく、かつ逸散率が液状可塑剤の添加量に対して
安定しているという特性を有する事が示されている。本
発明の製造方法における上記（２）の特長は、従来の塩
化ビニリデン系樹脂では、可塑剤の逸散率が低すぎるた
めに弾性率が向上する領域まで液状可塑剤を減量させる
ことは不可能であったこと、またメチルアクリレート成
分を含んでなる塩化ビニリデン系樹脂を用いた場合で
は、液状可塑剤の添加量に対して逸散率の変化が大きす
ぎ、液状可塑剤量が３重量％以上のもの（密着性を満た
すもの）に調節することが極めて困難であったこと、の
双方を克服しフィルムに含有される液状可塑剤の量を所
定の範囲に減量させることに成功したものである。また
本発明に用いる塩化ビニリデン系樹脂組成物は、液状可
塑剤の逸散率の変化が安定しているために、一定した品
質の製品を製造するという点においても極めて優れたも
のである。In FIG. 1 above, the resin composition of the present invention is
It has been shown that the liquid plasticizer has a large dissipation factor as compared with a conventional vinylidene chloride resin and that the dissipation ratio is stable with respect to the amount of the liquid plasticizer added. The feature of the above (2) in the production method of the present invention is that in the conventional vinylidene chloride-based resin, it is impossible to reduce the amount of the liquid plasticizer to the region where the elastic modulus is improved because the dissipation rate of the plasticizer is too low. In addition, when the vinylidene chloride resin containing a methyl acrylate component was used, the change in the escape rate was too large with respect to the amount of the liquid plasticizer added, and the amount of the liquid plasticizer was 3% by weight or more. It was extremely difficult to adjust the amount of the liquid plasticizer (which satisfies the adhesiveness), and succeeded in reducing the amount of the liquid plasticizer contained in the film to a predetermined range. . The vinylidene chloride resin composition used in the present invention is also extremely excellent in that it produces a product of constant quality because the change in the dissipation rate of the liquid plasticizer is stable.
【００２３】この時の、塩化ビニリデン系樹脂Ｂの添加
量の割合は、３重量％から１５重量％の範囲である。塩
化ビニリデン系樹脂Ｂの添加量が少なすぎると液状可塑
剤の逸散性が不十分となり、また溶融押出時の可塑化効
果も不十分となるので、液状可塑剤の添加量を減量する
と成膜加工性が低下する。また、塩化ビニリデン系樹脂
Ｂの添加量が多すぎると、ラップフィルムの引裂トラブ
ル性が悪化するので好ましくない。上記と同じ観点で厳
選すると、塩化ビニリデン系樹脂Ｂの添加量の割合は
３．９重量％から１３．９重量％の範囲にするのが望ま
しい。The proportion of the vinylidene chloride resin B added at this time is in the range of 3% by weight to 15% by weight. If the amount of the vinylidene chloride resin B added is too small, the liquid plasticizer will have insufficient dissipative properties, and the plasticizing effect during melt extrusion will also be insufficient. Therefore, if the amount of the liquid plasticizer added is reduced, film formation Workability is reduced. Further, if the amount of the vinylidene chloride resin B added is too large, the tear trouble of the wrap film is deteriorated, which is not preferable. If carefully selected from the same viewpoint as above, it is desirable that the proportion of the vinylidene chloride resin B to be added be in the range of 3.9% by weight to 13.9% by weight.
【００２４】次に、本発明の内容をラップフィルムの面
から説明する。本発明のラップフィルムの従来技術との
相違点は、 （ａ）塩化ビニリデン系樹脂Ａと塩化ビニリデン系樹脂
Ｂと液状可塑剤とからなる混合樹脂組成物であること。Next, the contents of the present invention will be described in terms of the wrap film. The difference between the wrap film of the present invention and the prior art is that (a) a mixed resin composition comprising a vinylidene chloride resin A, a vinylidene chloride resin B and a liquid plasticizer.
【００２５】（ｂ）上記樹脂組成物内における塩化ビニ
リデン系樹脂Ｂと液状可塑剤の含有量の割合は、液状可
塑剤の含有量（重量％）を横軸に、塩化ビニリデン系樹
脂Ｂの含有量（重量％）を縦軸にとった図において、座
標点イ．（３，１４）、ロ．（３、１０）、ハ．（６、
４）、ニ．（６、１４）を結んでなる四辺形の範囲内で
あること。(B) The content ratio of the vinylidene chloride resin B and the liquid plasticizer in the resin composition is such that the content (wt%) of the liquid plasticizer is the horizontal axis and the content of the vinylidene chloride resin B is In the figure in which the vertical axis represents the amount (% by weight), the coordinate points a. (3, 14), b. (3, 10), c. (6,
4), d. It must be within the range of a quadrangle formed by connecting (6, 14).
【００２６】にある。It is in.
【００２７】すなわち従来よりも液状可塑剤含有量が減
量されてなるラップフィルムであって、ラップフィルム
の弾性率が向上し、さらにその減量された液状可塑剤含
有量においても、フィルム同士の密着性が維持されてい
るとういう２つの特性が両立されていることである。ラ
ップフィルム中に含有する塩化ビニリデン系樹脂Ｂと液
状可塑剤の含有量の割合は、フィルムの弾性率と密着
性、さらに成膜加工性をも加えた３者の調和の観点から
選ばれる。That is, the wrap film has a liquid plasticizer content reduced as compared with the conventional one, and the elastic modulus of the wrap film is improved. Further, even at the reduced liquid plasticizer content, the adhesion between films is improved. That is, the two characteristics that "is maintained" are compatible with each other. The content ratio of the vinylidene chloride resin B and the liquid plasticizer contained in the wrap film is selected from the viewpoint of harmony among the three factors including the elastic modulus of the film, the adhesiveness, and the film forming processability.
【００２８】図２は実施例５、比較例６に対応する本発
明フィルムの実験解析図で、フィルム中の液状可塑剤の
含有量（重量％）を横軸に、塩化ビニリデン系樹脂Ｂの
含有量（重量％）を縦軸にとったものである。図中の番
号はそれぞれのラップＮｏ．を表している。図中の記号
はラップとしての総合評価を表すもので、◎は非常に優
れる、○は優れる、△は劣る、×は非常に劣るものであ
る。実施例５、比較例６のラップを分析した結果、成膜
加工性が優れ、弾性率が高く、密着性が高いという条件
を満たし、さらに引裂トラブル性においても問題のない
ものは、図２において、座標点イ．（３，１４）、ロ．
（３、１０）、ハ．（６、４）、ニ．（６、１４）を結
んでなる四辺形の範囲内であることがわかった。液状可
塑剤の含有量が３重量％に満たないものでは、ラップフ
ィルムとしての密着性が不十分なものであり、また成膜
加工性に対しても不利なものとなるので好ましくなかっ
た。また液状可塑剤量が６重量％を超えるものでは、弾
性率の向上効果が不足であり好ましくないものであっ
た。また塩化ビニリデン系樹脂Ｂの含有量が４重量％を
下回るものでは、成膜加工時における液状可塑剤の逸散
性が不十分なことと、塩化ビニリデン系樹脂Ｂ自体の溶
融押出加工時における可塑化効果も不足であるため弾性
率の向上が十分なされるまで液状可塑剤の減量を達成す
ることが出来なかったものである。塩化ビニリデン系樹
脂のＢの割合が１４重量％を超えると、フィルムが脆い
ような感じのものとなって、化粧箱から引き出す際に途
中で切れてしまったり、ラップフィルムをカットする際
にフィルムが横方向にきれいに切れず、縦方向に切れて
しまったりという引裂トラブルが起きるようになり好ま
しくない。座標点ロ．ハ．間の関係は、主として成膜加
工性の観点から、塩化ビニリデン系樹脂Ｂの含有量が少
なくなると溶融押出時に必要な液状可塑剤の必要量が増
加する関係から定まるものである。FIG. 2 is an experimental analysis diagram of the film of the present invention corresponding to Example 5 and Comparative Example 6, in which the content (% by weight) of the liquid plasticizer in the film is plotted on the horizontal axis and the content of the vinylidene chloride resin B is contained. The amount (% by weight) is plotted on the vertical axis. The numbers in the figure indicate the respective lap numbers. Is represented. The symbols in the figure represent the overall evaluation as a lap, and ⊚ is extremely excellent, ◯ is excellent, Δ is inferior, and x is extremely inferior. As a result of analyzing the laps of Example 5 and Comparative Example 6, the ones satisfying the conditions of excellent film forming processability, high elastic modulus and high adhesion, and having no problem in tearing trouble are shown in FIG. , Coordinate point a. (3, 14), b.
(3, 10), c. (6, 4), d. It was found to be within the range of a quadrangle formed by connecting (6, 14). When the content of the liquid plasticizer is less than 3% by weight, the adhesiveness as a wrap film is insufficient and it is also disadvantageous to the film forming processability, which is not preferable. On the other hand, when the amount of the liquid plasticizer exceeds 6% by weight, the effect of improving the elastic modulus is insufficient, which is not preferable. Further, when the content of the vinylidene chloride resin B is less than 4% by weight, the dissipative property of the liquid plasticizer during the film forming process is insufficient, and the plasticity during the melt extrusion process of the vinylidene chloride resin B itself is insufficient. Since the chemical effect is also insufficient, the reduction of the liquid plasticizer could not be achieved until the elastic modulus was sufficiently improved. If the proportion of B in the vinylidene chloride resin exceeds 14% by weight, the film feels brittle and may be cut off when it is pulled out from the box or cut off when the wrap film is cut. It is not preferable because tearing troubles such as not being cut cleanly in the horizontal direction and being cut in the vertical direction will occur. Coordinate point b. C. The relationship between the two is determined mainly from the viewpoint of film-forming processability, as the content of the vinylidene chloride resin B decreases, the required amount of the liquid plasticizer required during melt extrusion increases.
【００２９】すなわち、本発明は塩化ビニリデン系樹脂
Ｂを添加することにより、液状可塑剤逸散率を従来不可
能であった領域に調節することができて、かつ塩化ビニ
リデン系樹脂Ｂの含有量と液状可塑剤の含有量との割合
を、ある特定の範囲内に調整することによって、ラップ
フィルムの高弾性率と良好なる密着性というものが両立
することを見い出し、成膜加工性に優れた、弾性率が高
くてハリ・コシ感に優れ、かつラップフィルム相互の密
着性が良好な塩化ビニリデン系樹脂ラップフィルムの製
造方法とラップフィルムを提供するに至ったものであ
る。That is, according to the present invention, by adding the vinylidene chloride resin B, the liquid plasticizer escape rate can be adjusted to a range which has hitherto been impossible, and the content of the vinylidene chloride resin B is increased. By adjusting the ratio between the content of the liquid plasticizer and the content of the liquid plasticizer within a certain range, it was found that the high elastic modulus of the wrap film and good adhesion are compatible, and film forming processability was excellent. The present invention provides a method for producing a vinylidene chloride-based resin wrap film and a wrap film, which have a high elastic modulus, are excellent in elasticity and stiffness, and have good adhesiveness to each other.
【００３０】包装材としての強度、包装時の取り扱いの
容易性、フィルムとしての経済性を兼備させる観点から
フィルム厚みとしては、５ミクロン以上１５ミクロン以
下のものが好ましい。From the viewpoints of strength as a packaging material, ease of handling during packaging, and economy as a film, the film thickness is preferably 5 μm or more and 15 μm or less.
【００３１】上記のラップフィルム及び製造方法におけ
る作用効果が期待できる塩化ビニリデン系樹脂Ｂは、塩
化ビニリデン含有量が８０重量％以上９５重量％以下で
あって、ゲルパーミエーションクロマトグラフィー法に
よる重量平均分子量が２万以上６万以下、好ましくは３
万以上５万以下のものである。２万未満の分子量もの
は、弾性率を向上させる効果が少なく、６万を超える分
子量のものは成膜加工性を改良する効果が少ないので不
都合である。The vinylidene chloride resin B, which can be expected to have the effects of the wrap film and the production method, has a vinylidene chloride content of 80% by weight or more and 95% by weight or less, and has a weight average molecular weight by gel permeation chromatography. Is 20,000 or more and 60,000 or less, preferably 3
It is more than 10,000 and less than 50,000. Those having a molecular weight of less than 20,000 have a small effect of improving the elastic modulus, and those having a molecular weight of more than 60,000 have a small effect of improving the film forming processability, which are disadvantageous.
【００３２】塩化ビニリデン系樹脂Ａはラップフィルム
用として通常公知のもので、塩化ビニリデンと共重合可
能なモノマーとしては、例えば塩化ビニル、２−エチル
ヘキシルアクリレート等のアクリル酸エステル、メチル
メタアクリレート、ブチルメタアクリレート、２−エチ
ルヘキシルメタアクリレート等のメタアクリル酸エステ
ル、酢酸ビニル、プロピオン酸ビニル等の脂肪族カルボ
ン酸のビニルエステルなどの単量体を挙げることがで
き、その重量平均分子量が８万以上１３万以下である塩
化ビニリデン系樹脂である。８万未満の分子量のもので
は、ラップフィルムの引裂強度が低すぎ実用的でなく、
１３万を超えるものでは、塩化ビニリデン系樹脂Ｂや、
液状可塑剤を添加しても、極薄成膜加工性を実用的範囲
に保つことが出来ず不都合である。The vinylidene chloride resin A is generally known for wrap films, and examples of the monomer copolymerizable with vinylidene chloride include acrylic acid esters such as vinyl chloride and 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate. Examples thereof include monomers such as acrylates, methacrylic acid esters such as 2-ethylhexyl methacrylate, vinyl acetate, vinyl esters of aliphatic carboxylic acids such as vinyl propionate, and the like, and the weight average molecular weight thereof is 80,000 or more and 130,000. The following is a vinylidene chloride resin. If the molecular weight is less than 80,000, the tear strength of the wrap film is too low to be practical,
If it exceeds 130,000, vinylidene chloride resin B or
Even if a liquid plasticizer is added, it is not possible to keep the ultrathin film-forming processability within a practical range.
【００３３】上述した公知の重量平均分子量が８万以上
１３万以下である塩化ビニリデン系樹脂Ａは、次の製造
方法で作成できる。まず、重合機の中にイオン交換水と
懸濁剤としてメチルセルロース等のセルロース誘導体、
重合開始剤としてジイソプロピルパーオキシジカーボネ
ート等の有機過酸化物を入れ、その中に塩化ビニリデン
モノマーが７０から９５重量％と塩化ビニリデンと共重
合するモノマーが５から３０重量％であるモノマー混合
物をイオン交換水と同重量入れて撹拌する。撹拌される
混合液の温度を４０から８０℃の温度に加熱しながら、
約４０から７０時間かけて重合を行う。重合が終了した
後、未反応モノマーを回収してスラリーを取り出し脱水
する。この重合体を熱風乾燥機で乾燥し、完全に水分を
除去した。The known vinylidene chloride resin A having a weight average molecular weight of 80,000 or more and 130,000 or less can be prepared by the following production method. First, in a polymerization machine, ion-exchanged water and a cellulose derivative such as methylcellulose as a suspending agent,
An organic peroxide such as diisopropyl peroxydicarbonate was added as a polymerization initiator, and a monomer mixture containing 70 to 95% by weight of vinylidene chloride monomer and 5 to 30% by weight of a monomer copolymerizable with vinylidene chloride was ionized. Add the same weight as the exchanged water and stir. While heating the temperature of the stirred liquid mixture to a temperature of 40 to 80 ° C,
Polymerization is carried out for about 40 to 70 hours. After the polymerization is completed, the unreacted monomer is recovered and the slurry is taken out and dehydrated. This polymer was dried with a hot air dryer to completely remove water.
【００３４】一方、上述した重量平均分子量が２万以上
６万以下の塩化ビニリデン系樹脂Ｂでは、分子量を小さ
くして作成するために、上述の塩化ビニリデン系樹脂Ａ
とは異なる作成方法となる。主な相違点は、重合開始剤
としてｔ−ブチルパーオキシ−ピバレートのような高温
分解型の開始剤を多量に使用し、高温で重合することで
ある。これにより重合開始点を多くして分子量を低く
し、また重合熱の除熱を容易にできて、重合を約５から
２０時間の短時間で行うことができる様になる。この作
成方法をとることにより、従来工業的生産が困難であっ
た分子量が２万から６万の塩化ビニリデン系樹脂の重合
が可能となった。On the other hand, in the above-mentioned vinylidene chloride resin B having a weight average molecular weight of 20,000 or more and 60,000 or less, in order to make it with a small molecular weight, the above-mentioned vinylidene chloride resin A is used.
The creation method is different from. The main difference is that a large amount of a high temperature decomposition type initiator such as t-butylperoxy-pivalate is used as a polymerization initiator and the polymerization is carried out at a high temperature. As a result, the number of polymerization initiation points is increased to lower the molecular weight, and the heat of polymerization can be easily removed, so that the polymerization can be carried out in a short time of about 5 to 20 hours. By adopting this production method, it has become possible to polymerize a vinylidene chloride resin having a molecular weight of 20,000 to 60,000, which has been difficult to produce industrially in the past.
【００３５】塩化ビニリデン系樹脂Ｂを得るための塩化
ビニリデンと共重合可能なモノマーとしては、例えば塩
化ビニル、メチルアクリレート、ブチルアクリレート、
２−エチルヘキシルアクリレート等のアクリル酸エステ
ル、メチルメタアクリレート、ブチルメタアクリレー
ト、２−エチルヘキシルメタアクリレート等のメタアク
リル酸エステル、酢酸ビニル、プロピオン酸ビニル等の
脂肪族カルボン酸のビニルエステルなどの単量体を挙げ
ることができる。Examples of the monomer copolymerizable with vinylidene chloride for obtaining vinylidene chloride resin B include vinyl chloride, methyl acrylate, butyl acrylate,
Monomers such as acrylic acid ester such as 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, methacrylic acid ester such as 2-ethylhexyl methacrylate, vinyl ester of aliphatic carboxylic acid such as vinyl acetate and vinyl propionate Can be mentioned.
【００３６】塩化ビニリデン含有量については、本発明
の塩化ビニリデン系樹脂Ａはビニリデン含有量が８５重
量％未満の時は、ラップフィルムの耐熱性が十分でな
く、塩化ビニリデン含有量が９５重量％を超えるとき
は、成膜加工性が不十分なものとなり不都合である。Regarding the vinylidene chloride content, when the vinylidene chloride resin A of the present invention has a vinylidene content of less than 85% by weight, the heat resistance of the wrap film is insufficient and the vinylidene chloride content is 95% by weight. If it exceeds, the film-forming processability becomes insufficient, which is inconvenient.
【００３７】本発明の塩化ビニリデン樹脂Ｂはビニリデ
ン含有量が８０重量％未満の時は、ラップフィルムの弾
性率向上効果が十分なものではなく、また塩化ビニリデ
ン含有量が９５重量％を超えるときは、成膜加工性を大
きく阻害してしまうので不満足なものである。In the vinylidene chloride resin B of the present invention, when the vinylidene content is less than 80% by weight, the effect of improving the elastic modulus of the wrap film is not sufficient, and when the vinylidene chloride content exceeds 95% by weight. However, it is unsatisfactory because it greatly impairs film forming processability.
【００３８】本発明に用いられる液状可塑剤としては、
ジブチルセバケート（ＤＢＳ），ジオクチルアジペート
（ＤＯＡ）、ジ−２−エチルヘキシルアジペート（２Ｅ
ＨＡ）、アセチルトリブチルシトレート（ＡＴＢＣ）、
アジピン酸ジイソブチル（ＡＩＢ）等の可塑剤、エポキ
シ化大豆油（ＥＳＯ）、エポキシ化アマニ油（ＥＬ
Ｏ）、エポキシ化ステアリン酸オクチル（ＥＳＯＴ）、
ビスフェノールＡジグリシジルエーテル（ＢＰＧＥ）、
メタクリル酸グリシジル（ＧＭＡ）等のエポキシ化合物
可塑剤等を挙げることが出来る。The liquid plasticizer used in the present invention includes:
Dibutyl sebacate (DBS), dioctyl adipate (DOA), di-2-ethylhexyl adipate (2E
HA), acetyltributyl citrate (ATBC),
Plasticizers such as diisobutyl adipate (AIB), epoxidized soybean oil (ESO), epoxidized linseed oil (EL
O), epoxidized octyl stearate (ESOT),
Bisphenol A diglycidyl ether (BPGE),
Examples thereof include epoxy compound plasticizers such as glycidyl methacrylate (GMA).
【００３９】次に、本発明に用いる評価方法について以
下に示す。Next, the evaluation method used in the present invention will be described below.
【００４０】＜重量平均分子量＞本発明でいう塩化ビニ
リデン系樹脂Ａ及び塩化ビニリデン系樹脂Ｂの重量平均
分子量は、ポリスチレンを標準としたゲルパーミエーシ
ョンクロマトグラフィー法により求めたものである。使
用機器類は以下の通りである。<Weight Average Molecular Weight> The weight average molecular weights of the vinylidene chloride resin A and the vinylidene chloride resin B in the present invention are determined by gel permeation chromatography using polystyrene as a standard. The equipment used is as follows.
【００４１】機種 高速液体クロマトグラフィー（東ソ
ー社製） カラム ＧＭＨ６（東ソー社製） 溶媒 テトラヒドロフラン（和光純薬社製、液体クロマ
トグラフィー用） 測定方法は以下の通りである。Model High performance liquid chromatography (manufactured by Tosoh Corporation) Column GMH6 (manufactured by Tosoh Corporation) Solvent Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, for liquid chromatography) The measuring method is as follows.
【００４２】テトラヒドロフランに０．５重量％濃度に
溶解させた測定対象試料を、溶媒と共に２０℃に保温し
たカラムに注入し、試料注入後からの示差屈折計の出力
電流値の時間経過に伴う変化を、記録計のチャートに描
かせる。A sample to be measured, which was dissolved in tetrahydrofuran at a concentration of 0.5% by weight, was injected together with a solvent into a column kept at 20 ° C., and the change in output current value of the differential refractometer with time after injection of the sample. To be drawn on the chart of the recorder.
【００４３】分子量の較正は以下の通りである。The molecular weight calibration is as follows.
【００４４】分子量が３６００、３５０００、１１００
００、６５００００、１４６００００である５種の単分
散ポリスチレンの各々について、本測定機による測定を
前もって完了させておき、このデータを検量線として塩
化ビニリデン系樹脂の計算基礎とする。即ち、分子量既
知の単分散ポリスチレンが示す示差屈折計の出力電流の
ピーク値が生じるまでのゲルパーミエーションクロマト
グラフィーカウント数（試料注入時を起点０とする秒
数）とそのものの分子量の対数値との関係を座標点と
し、この５種の座標点を結ぶグラフを作り、これを分子
量算定の検量線とする。Molecular weights of 3600, 35000, 1100
For each of the five types of monodisperse polystyrenes of 00, 650000, and 146000, the measurement by this measuring machine is completed in advance, and this data is used as a calibration curve to calculate the vinylidene chloride resin. That is, the gel permeation chromatography count number until the peak value of the output current of the differential refractometer indicated by monodisperse polystyrene having a known molecular weight (the number of seconds starting from sample injection 0) and the logarithmic value of the molecular weight of the gel permeation chromatography. Is used as a coordinate point, and a graph connecting these five types of coordinate points is prepared and used as a calibration curve for calculating the molecular weight.
【００４５】測定と計算は以下の通りである。The measurement and calculation are as follows.
【００４６】対象とする樹脂試料で描かれたゲルパーミ
エーションクロマトグラフィーカウント数と示差屈折計
の出力電流値との関係チャートから、ゲルパーミエーシ
ョンクロマトグラフィーカウント数９００から１４４０
の間を２０カウント毎に区切った位置に示されている出
力電流値（Ｐｉ）を、ゲルパーミエーションクロマトグ
ラフィーカウント数に対応する分子量（検量線による）
Ｍｉの度数として求め各々次のように計算する。From the relationship chart between the gel permeation chromatography count number drawn on the target resin sample and the output current value of the differential refractometer, from the gel permeation chromatography count number 900 to 1440.
The output current value (Pi) shown in the position divided by every 20 counts is the molecular weight corresponding to the gel permeation chromatography count number (according to the calibration curve).
It is calculated as the frequency of Mi and calculated as follows.
【００４７】分子量Ｍｉの重量分率Ｗｉ＝Ｐｉ／ΣＰｉ 本発明でいう塩化ビニリデン系樹脂の重量平均分子量
は、このようにして計算した分子量Ｍｉの重量分率Ｗｉ
と分子量Ｍｉとを使って、次のように計算する。 重量平均分子量＝Σ（Ｗｉ×Ｍｉ） ＜可塑剤の逸散率＞可塑剤の逸散率とは、押出−成膜工
程中に逸散する可塑剤量（Ｙ）の当初含有量に対する割
合であり、次の関係で示す。Weight fraction of molecular weight Mi Wi = Pi / ΣPi The weight average molecular weight of the vinylidene chloride resin referred to in the present invention is the weight fraction Wi of the molecular weight Mi thus calculated.
And the molecular weight Mi are calculated as follows. Weight average molecular weight = Σ (Wi × Mi) <Plasticizer escape rate> The plasticizer escape rate is the ratio of the plasticizer amount (Y) that escapes during the extrusion-film formation process to the initial content. Yes, with the following relationship:
【００４８】可塑剤の逸散率（％）＝Ｙ／Ｘ×１００ Ｙ＝原料樹脂組成物中の可塑剤量（重量％）−フィルム
中の可塑剤量（重量％） Ｘ＝原料樹脂組成物中の可塑剤量（重量％） 可塑剤量の定性、定量は例えば「高分子ハンドブック」
（日本分析化学会編 １９８５年）に記載の溶剤抽出法
により、ガスクロマトグラフ及び質量分析計を用いる方
法で行うことができる。Emission rate of plasticizer (%) = Y / X × 100 Y = amount of plasticizer in raw resin composition (wt%)-amount of plasticizer in film (wt%) X = raw resin composition Amount of plasticizer (% by weight) Qualitative and quantitative amount of plasticizer, for example, "Polymer Handbook"
It can be carried out by a method using a gas chromatograph and a mass spectrometer by the solvent extraction method described in (Japan Society for Analytical Chemistry, 1985).
【００４９】＜成膜加工性＞各成分組成の塩化ビニリデ
ン系樹脂組成物を通常での押出成膜方法、すなはち溶融
押出機に供給して溶融し、押出機の先端に取り付けられ
た環状ダイでのスリット部出口での溶融樹脂温度が１８
５℃になるように押出機の加熱冷却条件を調節しなが
ら、５０ｋｇ／ｈｒの製造能力で管状に押出し、過冷却
したのち、インフレーションして管状フィルムとし、厚
み１０ミクロンのラップフィルムを得た。<Film forming workability> A vinylidene chloride resin composition of each component composition is supplied to an ordinary extrusion film forming method, that is, a melt extruder and melted, and attached to the tip of the extruder. The molten resin temperature at the exit of the slit in the die is 18
While controlling the heating and cooling conditions of the extruder so as to be 5 ° C., it was extruded into a tubular shape with a production capacity of 50 kg / hr, supercooled, and then inflation was performed into a tubular film to obtain a wrap film having a thickness of 10 μm.
【００５０】押出条件安定後、１０時間以内に発生した
インフレーション時の破裂（パンク）回数を測定した。
（単位 回／５００ｋｇ） 評価尺度 評価記号 水準値 備考 ◎ ； ０ 生産性の良い安定な連続生産が可能 ○ ； １以上３未満 安定な連続生産が可能 △ ； ３以上５未満 生産性は悪いが連続生産可能 × ； ５以上 連続生産は不可能 ＜耐熱性＞木枠に緊張状態で張ったフィルムを、温度調
節可能な半径４０ｍｍの熱板に１分間接触させ、フィル
ムに穴開きが発生しない最高熱板温度を１０℃刻みで測
定した。After stabilizing the extrusion conditions, the number of bursts (punctures) during inflation generated within 10 hours was measured.
(Units / 500 kg) Evaluation scale Evaluation symbol Level value Remark ◎ ； 0 Stable continuous production with good productivity ○ ； 1 or more and less than 3 Stable continuous production possible △ ； 3 or more and less than 5 Continuous but poor productivity Producable ×: 5 or more Continuous production is not possible <Heat resistance> A film stretched under tension on a wooden frame is brought into contact with a temperature-controllable hot plate with a radius of 40 mm for 1 minute, and the film does not puncture. The plate temperature was measured in steps of 10 ° C.
【００５１】 評価尺度 評価記号 水準値 備考 ○ ； １５０℃以上 耐熱性が非常に優れる △ ； １３０℃以上１５０℃未満 耐熱性が劣る × ； １３０℃未満 耐熱性が非常に劣る ＜引張弾性率＞ＡＳＴＭ−Ｄ８８２準拠。（２％伸張時
の見掛けの弾性率） （単位 Ｋｇ／ｃｍ2 ）ラップフィルムのタテ方向（Ｍ
Ｄ）の値とヨコ方向（ＴＤ）の値の平均値で表した。Evaluation scale Evaluation symbol Level value Remark ○: 150 ° C or higher, very good heat resistance △: 130 ° C or higher but lower than 150 ° C Poor heat resistance ×: Less than 130 ° C, very poor heat resistance <Tensile modulus> ASTM -Based on D882. (Apparent elastic modulus at 2% elongation) (Unit: Kg / cm2) Vertical direction of wrap film (M
It is represented by the average value of the value of D) and the value of the horizontal direction (TD).
【００５２】 評価尺度 評価記号 水準値 備考 ◎ ；5800Kg/cm2以上 ハリ・コシ感が極めて優れている ○ ；5000Kg/cm2以上〜5800Kg/cm2未満ハリ・コシ感が優れている × ；5000Kg/cm2未満 ハリ・コシ感が従来品とあまり変 わらない ＜密着性＞２３℃の恒温室で、面積が２５ｃｍ2の円柱
のそれぞれの底面側に、しわの入らないようにラップフ
ィルムを緊張させて固定し、そのラップフィルム面の相
互が重なり合うように２本の円柱を合わせ、加重５００
ｇで１分間圧着した後、インストロン引張試験機にてラ
ップフィルムを相互に垂直な方向に引き剥がすときに必
要な仕事量を測定する。（単位 ｇ・ｃｍ／２５ｃ
ｍ2） 評価尺度 評価記号 水準値（単位 ｇ・ｃｍ／２５ｃｍ2） 備考 ◎ ； １５以上 密着性が非常に良い ○ ； １２以上１５未満 密着性が良い △ ； １０以上１２未満 密着性が劣る × ； １０未満 密着性が非常に劣る ＜引裂トラブル性＞熟練したパネリスト２０人を用意し
て、各人について、厚み１０ミクロン、巾３０ｃｍ、巻
き長２０ｍののラップフィルムを化粧箱に入れたラップ
を３０本づつ用意した。そして、約１ｍづつラップフィ
ルムを引き出し、ノコ刃で切るという作業を各ラップに
ついて１５回づつ、計４５０回行った。そして、その時
の、ラップのタテ裂けトラブル、途中切れトラブルの回
数を数えて引裂トラブル性を定量化した。Evaluation scale Evaluation symbol Standard value Remark ◎: 5800Kg / cm 2 or more Very good elasticity and elasticity ○: 5000Kg / cm 2 or more to less than 5800Kg / cm 2 Excellent elasticity and elasticity ×; 5000Kg / Less than cm 2 Elasticity and elasticity are not much different from conventional products <Adhesion> In a constant temperature room at 23 ° C, tension the wrap film on the bottom side of each cylinder with an area of 25 cm 2 to prevent wrinkles. The two cylinders so that the wrap film surfaces overlap each other, and apply a weight of 500
After pressure bonding for 1 minute at g, the work required for peeling the wrap films in mutually perpendicular directions is measured by an Instron tensile tester. (Unit: g · cm / 25c
m 2 ) Evaluation scale Evaluation symbol Level value (unit: g · cm / 25 cm 2 ) Remark ◎: 15 or more and very good adhesion ○: 12 or more and less than 15 Adhesiveness good △: 10 or more and less than 12 Adhesion poor × Less than 10 Adhesion is very poor <Tearing Trouble> 20 skilled panelists are prepared, and for each person, a wrap film with a wrap film having a thickness of 10 microns, a width of 30 cm, and a winding length of 20 m is put in a cosmetic box. I prepared 30 bottles each. The work of pulling out the wrap film about 1 m each and cutting it with a saw blade was performed 15 times for each lap, for a total of 450 times. Then, at that time, the number of times of lap vertical tear troubles and halfway troubles was counted to quantify the tear trouble property.
【００５３】 評価尺度 評価記号 水準値 備考 ◎ ； ３回未満 引裂トラブル少なく良好 ○ ； ３回以上１０回未満 引裂トラブル実用上問題なし △ ； １０回以上２０回未満 引裂トラブル多く問題 × ； ２０回以上 引裂トラブル多く実用不可 ＜総合評価＞ 評価記号 ◎ ； 非常に優れる ○ ； 優れる △ ； やや劣る × ； 劣るEvaluation scale Evaluation symbol Level value Remark ◎: Less than 3 times Tearing trouble is small and good ○ ； 3 times or more and less than 10 times Tearing trouble No practical problem △ ； 10 times or more and less than 20 times Tearing trouble many problem × ； 20 times or more Tear troubles Not practically applicable <Comprehensive evaluation> Evaluation symbol ◎: Very good ○: Excellent △: Slightly inferior ×; Inferior
【００５４】[0054]
【実施例】以下に本発明を実施例に基づき、さらに詳し
く説明する。EXAMPLES The present invention will be described in more detail based on the following examples.
【００５５】（実施例１）本文記載の方法で測定した重
量平均分子量が１２万である塩化ビニリデン系樹脂Ａ
（塩化ビニリデン含有量が９０重量％、塩化ビニル含有
量が１０重量％）に、重量平均分子量が４万である塩化
ビニリデン系樹脂Ｂ（塩化ビニリデン含有量が９０重量
％、塩化ビニル含有量が１０重量％）とジブチルセバケ
ート（ＤＢＳ）とエポキシ化大豆油（ＥＳＯ）をそれぞ
れ８７．０重量％、９．０重量％、３．０重量％、１．
０重量％の割合で混ぜ、コニカルブレンダーにて３０分
間混合した後、４０℃で２４時間熟成し混合樹脂組成物
を得た。Example 1 Vinylidene chloride resin A having a weight average molecular weight of 120,000 measured by the method described in the text.
(Vinylidene chloride content 90% by weight, vinyl chloride content 10% by weight), vinylidene chloride resin B having a weight average molecular weight of 40,000 (vinylidene chloride content 90% by weight, vinyl chloride content 10%). %), Dibutyl sebacate (DBS) and epoxidized soybean oil (ESO), respectively, 87.0%, 9.0%, 3.0%, 1.
The mixture was mixed at a ratio of 0% by weight, mixed with a conical blender for 30 minutes, and then aged at 40 ° C. for 24 hours to obtain a mixed resin composition.
【００５６】上記の塩化ビニリデン系混合樹脂組成物を
通常での押出成膜方法、すなわち溶融押出機に供給して
溶融し、押出機の先端に取り付けられた環状ダイでのス
リット部出口での溶融樹脂温度が１８５℃になるように
押出機の加熱冷却条件を調節しながら、管状に５０Ｋｇ
／ｈｒのレートで押出し、過冷却したのち、インフレー
ションして管状フィルムとし、この管状フィルムをピン
チして偏平に押し潰して、熱風で１２０℃に温調された
加熱炉内に導き、加熱処理（炉長約５ｍ）を施した後、
冷却ローラーで冷却し折り巾７００ｍｍの肉厚み１０ミ
クロンの２枚重ね（計２０ミクロン）のフィルムを巻速
３６ｍ／分にて巻き取った。このフィルムを、３００ｍ
ｍ巾に２列取りにしてスリットし、１枚のフィルムにな
るように剥がしながら巻き取り、厚み１０ミクロンのラ
ップフィルムを得た。このものをラップＮｏ．１とし
た。The above-mentioned vinylidene chloride-based mixed resin composition is subjected to a usual extrusion film-forming method, that is, it is supplied to a melt extruder to be melted, and melted at an exit of a slit portion of an annular die attached to the tip of the extruder. While controlling the heating and cooling conditions of the extruder so that the resin temperature becomes 185 ° C, 50 kg in a tubular shape
After extruding at a rate of / hr and supercooling, it is inflationed into a tubular film, which is pinched and flattened, and then introduced into a heating furnace whose temperature is controlled at 120 ° C. by hot air, and a heat treatment ( After applying the furnace length of about 5 m),
The film was cooled with a cooling roller, and a film having a folding width of 700 mm and a thickness of 10 μm and a two-layer film (total 20 μm) was wound at a winding speed of 36 m / min. This film is 300m
The film was taken in two rows with a width of m, slit, and wound while peeling it off to form a single film, to obtain a wrap film having a thickness of 10 μm. This is the lap number. It was set to 1.
【００５７】次に塩化ビニリデン系樹脂Ｂの割合を９．
０重量％と固定し、塩化ビニリデン系樹脂Ａと液状可塑
剤の混合割合を表．１に示すように変更したことの他は
ラップＮｏ．１と同じ実験を繰り返し３種類のラップＮ
ｏ．２、３、４を得た。Next, the ratio of the vinylidene chloride resin B was set to 9.
Fixing at 0% by weight, the mixing ratio of vinylidene chloride resin A and liquid plasticizer is shown in Table. Lap No. other than the change as shown in FIG. Repeated the same experiment as 1 and 3 types of lap N
o. 2, 3 and 4 were obtained.
【００５８】（比較例１）重量平均分子量が１２万であ
る塩化ビニリデン系樹脂Ａ（塩化ビニリデン含有量が９
０重量％、塩化ビニル含有量が１０重量％）に、塩化ビ
ニリデン系樹脂Ｂを添加することなく液状可塑剤とし
て、ジブチルセバケート（ＤＢＳ）とエポキシ化大豆油
（ＥＳＯ）を表．１に示す割合で添加したことの他は、
ラップＮｏ．１と同じ実験を繰り返しラップＮｏ．５、
６、７を得た。(Comparative Example 1) Vinylidene chloride resin A having a weight average molecular weight of 120,000 (having a vinylidene chloride content of 9).
0% by weight, vinyl chloride content 10% by weight), dibutyl sebacate (DBS) and epoxidized soybean oil (ESO) were used as liquid plasticizers without adding vinylidene chloride resin B. In addition to the addition in the ratio shown in 1,
Wrap No. The same experiment as in 1 was repeated and the lap No. 5,
6 and 7 were obtained.
【００５９】（比較例２）塩化ビニリデン系樹脂Ａを、
重量平均分子量が１２万で塩化ビニリデン含有量が９３
重量％、メチルアクリレート含有量が７重量％であるも
のに変更し、塩化ビニリデン系樹脂Ｂを添加することな
く、液状可塑剤を表．１に示す割合量添加したことの他
は、ラップＮｏ．１と同じ実験を繰り返しラップＮｏ．
８、９、１０を得た。Comparative Example 2 Vinylidene chloride resin A was
Weight average molecular weight of 120,000 and vinylidene chloride content of 93
% By weight, methyl acrylate content was changed to 7% by weight, and the liquid plasticizer was prepared without adding vinylidene chloride resin B. Lap No. 1 except that the ratio amount shown in FIG. The same experiment as in 1 was repeated and the lap No.
8, 9, 10 were obtained.
【００６０】ラップフィルムＮｏ．１〜Ｎｏ．１０につ
いて、液状可塑剤含有量、極薄成膜時の成膜加工性、得
られたラップフィルムの弾性率、密着性、引裂トラブル
性について評価した結果を表．２に示す。ラップフィル
ムの物性は成膜後２８℃にて３０日間保管して後測定を
行った。Wrap film No. 1 to No. Table 10 shows the results of evaluating the content of the liquid plasticizer, the film-forming processability during ultra-thin film formation, the elastic modulus of the obtained wrap film, the adhesiveness, and the tearing trouble property. It is shown in FIG. The physical properties of the wrap film were measured after being stored at 28 ° C. for 30 days after the film formation.
【００６１】[0061]
【表１】 [Table 1]
【００６２】[0062]
【表２】 [Table 2]
【００６３】表．２の結果によれば、ラップＮｏ．１、
２、３、４は成膜加工性に優れ、フィルム弾性率が高
く、同時に密着性も高く、さらに引裂トラブルも少なく
良好な物であることがわかる。Table. According to the result of No. 2, the lap No. 1,
It can be seen that Nos. 2, 3 and 4 are excellent in film forming processability, high in film elastic modulus, high in adhesiveness at the same time, and have few tearing troubles.
【００６４】塩化ビニリデン系樹脂Ｂを含まない組成物
は、液状可塑剤６重量部以下では、極薄成膜加工性が悪
く、不都合なことがわかる。（ラップＮｏ．５、Ｎｏ．
６） また、成膜加工性が良好になるまで液状可塑剤を添加し
たものでは、引張弾性率が低く不良なことがわかる。
（ラップＮｏ．７） 塩化ビニリデン系樹脂Ａに塩化ビニリデンとメチルアク
リレートとの共重合体を用いて、かつ塩化ビニリデン系
樹脂Ｂを含まない組成物は、液状可塑剤量が比較的に低
含有量の条件で成膜加工性は良好であるが、得られたラ
ップフィルムに含有される液状可塑剤量が低くなりす
ぎ、密着性がいずれも低く不満足なことがわかる。（ラ
ップＮｏ．８、９、１０） ラップＮｏ．１からＮｏ．１０について、表．２に示さ
れる液状可塑剤含有量の測定結果と、表．１に示された
液状可塑剤添加量とから求めた可塑剤の逸散率を、液状
可塑剤の添加量を横軸にし、液状可塑剤の逸散率を縦軸
にしてプロットしたものが図１である。ラップＮｏ．１
からＮｏ．４は○、ラップＮｏ．５からＮｏ．７は×、
ラップＮｏ．８からＮｏ．１０は△で示した。図１から
本発明の塩化ビニリデン系樹脂Ｂを含んでなる混合樹脂
組成物は、従来の塩化ビニリデン系樹脂に比較し液状可
塑剤の逸散率が大きく、かつ逸散率が液状可塑剤の添加
量に対して安定しているという特性を有する事がわか
る。It can be seen that the composition containing no vinylidene chloride resin B is inferior in the workability of extremely thin film formation when the amount of the liquid plasticizer is 6 parts by weight or less. (Lap No. 5, No. 5)
6) Further, it can be seen that in the case where the liquid plasticizer is added until the film forming processability becomes good, the tensile elastic modulus is low and it is unsatisfactory.
(Wrap No. 7) A composition using a vinylidene chloride resin A with a copolymer of vinylidene chloride and methyl acrylate and containing no vinylidene chloride resin B has a relatively low liquid plasticizer content. It is understood that the film forming processability is good under the conditions of 1), but the amount of the liquid plasticizer contained in the obtained wrap film becomes too low, and the adhesion is low and unsatisfactory. (Lap No. 8, 9, 10) Lap No. 1 to No. Table 10 for. Table 2 shows the measurement results of the liquid plasticizer content shown in Table 2. Figure 1 plots the plasticizer escape rate obtained from the liquid plasticizer addition amount shown in 1 with the liquid plasticizer addition amount on the horizontal axis and the liquid plasticizer escape rate on the vertical axis. It is 1. Wrap No. 1
To No. No. 4 is ○, lap No. 5 to No. 7 is ×,
Wrap No. 8 to No. 10 is indicated by Δ. As shown in FIG. 1, the mixed resin composition containing the vinylidene chloride resin B of the present invention has a larger liquid plasticizer escape rate than the conventional vinylidene chloride resin, and the addition rate of the liquid plasticizer is higher than that of the conventional vinylidene chloride resin. It can be seen that it has the property of being stable with respect to the amount.
【００６５】（実施例２及び比較例３）塩化ビニリデン
系樹脂Ａ（塩化ビニリデン含有量が９０重量％、塩化ビ
ニル含有量が１０重量％）の重量平均分子量を、７万、
８万、１０万、１３万、１４万と変更したものと、塩化
ビニリデン系樹脂Ｂとして、重量平均分子量が３万（塩
化ビニリデン含有量が９０重量％、塩化ビニル含有量が
１０重量％）のものと、液状可塑剤としてアセチルトリ
ブチルシトレート（ＡＴＢＣ）と、エポキシ化大豆油
（ＥＳＯ）を表．３に示すような割合で混合し、ラップ
フィルムの厚みを８ミクロンとしたことの他は、ラップ
Ｎｏ．１と同じ実験を繰り返してラップＮｏ．１１、１
２、１３、１４、１５を得た。(Example 2 and Comparative Example 3) The vinylidene chloride resin A (having a vinylidene chloride content of 90% by weight and a vinyl chloride content of 10% by weight) had a weight average molecular weight of 70,000,
The vinylidene chloride resin B having a weight average molecular weight of 30,000 (vinylidene chloride content of 90% by weight, vinyl chloride content of 10% by weight) was changed to 80,000, 100,000, 130,000, 140,000. And acetyl tributyl citrate (ATBC) as liquid plasticizer and epoxidized soybean oil (ESO). Lap No. 3 except that the wrap film was mixed at a ratio as shown in FIG. The same experiment as in 1 was repeated and the lap No. 11, 1
2, 13, 14, and 15 were obtained.
【００６６】これらの混合樹脂組成物について、極薄成
膜時の成膜加工性、得られたラップフィルムの弾性率、
密着性、引裂トラブル性について評価した結果を表．４
に示す。ラップフィルムの物性は成膜後２８℃にて３０
日間保管して後測定を行った。With regard to these mixed resin compositions, film-forming processability during ultra-thin film formation, elastic modulus of the obtained wrap film,
The table below shows the results of evaluation of adhesion and tearing trouble. Four
Shown in The physical properties of the wrap film are 30 at 28 ℃ after film formation.
It was stored for a day and then measured.
【００６７】[0067]
【表３】 [Table 3]
【００６８】[0068]
【表４】 [Table 4]
【００６９】表．４の結果によれば、塩化ビニリデン系
樹脂Ａの重量平均分子量が８万〜１３万のものは、極薄
成膜時の成膜加工性が良好で、また、ラップフィルムの
弾性率、密着性、引裂トラブル性も良好であることがわ
かる。（ラップＮｏ．１２、１３、１４） これに比べ、塩化ビニリデン系樹脂Ａの重量平均分子量
が８万に満たないものでは、引裂トラブルが多く実用に
適さないことがわかる。（ラップＮｏ．１１） 一方、塩化ビニリデン系樹脂Ｂの重量平均分子量が１４
万を超えるものでは、成膜加工性が不良であり、安定し
て延伸を行う事が出来ず、連続生産不可能なものである
ことがわかる。（ラップＮｏ．１５） （実施例３及び比較例４）実施例１で用いた塩化ビニリ
デン系樹脂Ａに、塩化ビニリデン含有量が９０重量％、
塩化ビニル含有量が１０重量％である塩化ビニリデン系
樹脂Ｂの重量平均分子量を１万、２万、３万、５万、６
万、７万に変更したものと、液状可塑剤として、ジオク
チルアジペート（ＤＯＡ）４．５重量％とエポキシ化ス
テアリンオクチル（ＥＳＯＴ）１．５重量％を、表．５
に示すような割合で混合し、ラップフィルム厚みを１２
ミクロンとしたことの他は、ラップＮｏ．１と同じ実験
を繰り返しラップＮｏ．１６、１７、１８、１９、２
０、２１を得た。Table. According to the result of 4, the vinylidene chloride resin A having a weight average molecular weight of 80,000 to 130,000 has good film-forming processability during ultra-thin film formation, and also has an elastic modulus and adhesiveness of the wrap film. It can be seen that the tearing trouble property is also good. (Lap Nos. 12, 13, 14) On the other hand, it can be seen that the vinylidene chloride resin A having a weight average molecular weight of less than 80,000 has many tearing problems and is not suitable for practical use. (Wrap No. 11) On the other hand, the vinylidene chloride resin B has a weight average molecular weight of 14
It can be seen that if it exceeds 10,000, the film forming processability is poor, stable stretching cannot be performed, and continuous production is impossible. (Wrap No. 15) (Example 3 and Comparative Example 4) The vinylidene chloride resin A used in Example 1 has a vinylidene chloride content of 90% by weight,
The vinylidene chloride resin B having a vinyl chloride content of 10% by weight has a weight average molecular weight of 10,000, 20,000, 30,000, 50,000, 6
Table 4 shows the amount of dioctyl adipate (DOA) 4.5% by weight and epoxidized stearyl octyl (ESOT) 1.5% by weight as liquid plasticizers. 5
Mix in the proportions shown in to make the wrap film thickness 12
Lap No. except that it was set to micron. The same experiment as in 1 was repeated and the lap No. 16, 17, 18, 19, 2
0 and 21 were obtained.
【００７０】これらの樹脂組成物について、極薄成膜時
の成膜加工性、得られたラップフィルムの弾性率、密着
性、引裂トラブル性について評価した結果を表．６に示
す。ラップフィルムの物性は成膜後２８℃にて３０日間
保管して後測定を行った。With respect to these resin compositions, the results of evaluation of film forming processability during ultrathin film formation, elastic modulus of the obtained wrap film, adhesion, and tearing trouble are shown in Table. 6 is shown. The physical properties of the wrap film were measured after being stored at 28 ° C. for 30 days after the film formation.
【００７１】[0071]
【表５】 [Table 5]
【００７２】[0072]
【表６】 [Table 6]
【００７３】表．６の結果によれば、塩化ビニリデン系
樹脂Ｂの重量平均分子量が２万〜６万のものは極薄成膜
時の成膜加工性は良好であり、またラップフィルムの弾
性率、密着性、引裂トラブル性も良好であり、特に重量
平均分子量が３万から６万のものが良好であることがわ
かる。（ラップＮｏ．１７、１８、１９、２０） これに比べ、塩化ビニリデン系樹脂Ｂの重量平均分子量
が２万に満たないものでは、引裂トラブルが多く実用に
適さないものであることがわかる。（ラップＮｏ．１
６）一方、塩化ビニリデン系樹脂Ｂの重量平均分子量が
６万を超えるものでは、成膜加工性が不良であり、イン
フレーション成膜が安定せず、連続生産不可能なもの
で、また液状可塑剤の逸散も不十分なものとなり、引張
弾性率の向上も不十分であることがわかる。（ラップＮ
ｏ．２１） （実施例４及び比較例５）重量平均分子量１０万の塩化
ビニリデン系樹脂Ａの、塩化ビニリデン含有量を８０、
８５、８８、９５、９７重量％に変更し（塩化ビニリデ
ンと共重合可能なモノマーは塩化ビニルとした。）、重
量平均分子量４万の塩化ビニリデン系樹脂Ｂの塩化ビニ
リデン含有量を７０、８０、９０、９５、９８重量％に
変更し（塩化ビニリデンと共重合可能なモノマーは塩化
ビニルとした。）、液状可塑剤として、アジピン酸ジイ
ソブチル（ＡＩＢ）とビスフェノールＡジグリシジルエ
ーテル（ＢＰＧＥ）を下記表．７に示すように混合した
ことの他は、ラップＮｏ．１と同じ実験を繰り返し、厚
み１０ミクロンのラップＮｏ．２２、２３、２４、２
５、２６、２７、２８、２９を得た。Table. According to the result of 6, the vinylidene chloride resin B having a weight average molecular weight of 20,000 to 60,000 has good film-forming processability during ultra-thin film formation, and the elastic modulus, adhesion, and It can be seen that the tearing property is also good, and that the weight average molecular weight of 30,000 to 60,000 is particularly good. (Lap Nos. 17, 18, 19, 20) In comparison, when the vinylidene chloride resin B has a weight average molecular weight of less than 20,000, it is found that the vinylidene chloride resin B has many tearing problems and is not suitable for practical use. (Lap No. 1
6) On the other hand, when the weight average molecular weight of the vinylidene chloride resin B exceeds 60,000, the film forming processability is poor, the inflation film formation is not stable, and continuous production is impossible, and the liquid plasticizer is also used. It can be seen that the dissipation of γ is also insufficient and the tensile modulus is not sufficiently improved. (Rap N
o. 21) (Example 4 and Comparative Example 5) The vinylidene chloride resin A having a weight average molecular weight of 100,000 has a vinylidene chloride content of 80,
85, 88, 95, 97% by weight (the vinylidene chloride copolymerizable monomer was vinyl chloride), the vinylidene chloride resin B having a weight average molecular weight of 40,000 has a vinylidene chloride content of 70, 80, The content was changed to 90, 95, 98% by weight (the vinylidene chloride-copolymerizable monomer was vinyl chloride), and diisobutyl adipate (AIB) and bisphenol A diglycidyl ether (BPGE) were used as liquid plasticizers in the table below. ． In addition to mixing as shown in FIG. The same experiment as in Example 1 was repeated to obtain a lap No. 22, 23, 24, 2
5, 26, 27, 28, 29 were obtained.
【００７４】これらの樹脂組成物について、極薄成膜時
の成膜加工性、得られたラップフィルムの耐熱性、弾性
率、密着性、引裂トラブル性について評価した結果を
表．７に示す。The results of evaluation of these resin compositions for film-forming processability during ultra-thin film formation, heat resistance of the obtained wrap film, elastic modulus, adhesion, and tear trouble are shown in Table. 7 shows.
【００７５】ラップフィルムの物性は成膜後２８℃にて
３０日間保管して後測定を行った。The physical properties of the wrap film were measured after being stored at 28 ° C. for 30 days after the film formation.
【００７６】[0076]
【表７】 [Table 7]
【００７７】[0077]
【表８】 [Table 8]
【００７８】表．８の結果によれば、塩化ビニリデン系
樹脂Ａの塩化ビニリデン含有量が８５、８８、９５重量
％であり、塩化ビニリデン系樹脂Ｂの塩化ビニリデン含
有量が８０、９０、９５重量％のものは、極薄成膜時の
成膜加工性が良好で、また、ラップフィルムの耐熱性、
弾性率、密着性、引裂トラブル性も良好なことがわか
る。（ラップＮｏ．２３、２４、２７、２８）一方、塩
化ビニリデン系樹脂Ａの塩化ビニリデン含有量が８０重
量％のものは、耐熱性に劣っていることがわかる。（ラ
ップＮｏ．２２）また、塩化ビニリデン含有量が９８重
量％のものは、成膜加工性が非常に劣り、また密着性も
低下していることがわかる。（ラップＮｏ．２９） また一方、塩化ビニリデン系樹脂Ｂの塩化ビニリデン含
有量が７０重量％のものは引張弾性率の向上が殆ど見ら
れず不満足なことがわかる。（ラップＮｏ．２６）塩化
ビニリデン含有量が９８重量％のものは、成膜加工性が
劣り、さらに引裂トラブル性も不良で、密着性にも劣っ
ていることがわかる。（ラップＮｏ．２９） （実施例５及び比較例６）塩化ビニリデン系樹脂Ａ、塩
化ビニリデン系樹脂Ｂ、及び液状可塑剤の種類と混合割
合を表．９に記載の如く変更したことの他は、ラップＮ
ｏ．１と同じ実験を繰り返してラップＮｏ．３０〜４９
を得た。Table. According to the result of 8, the vinylidene chloride resin A has a vinylidene chloride content of 85, 88, and 95% by weight, and the vinylidene chloride resin B has a vinylidene chloride content of 80, 90, and 95% by weight. Good film forming workability during ultra-thin film formation, heat resistance of wrap film,
It can be seen that the elastic modulus, adhesiveness, and tearing resistance are also good. (Lap Nos. 23, 24, 27, 28) On the other hand, it can be seen that the vinylidene chloride resin A having a vinylidene chloride content of 80% by weight is inferior in heat resistance. (Wrap No. 22) Further, it can be seen that the film having a vinylidene chloride content of 98% by weight has very poor film-forming processability and also has poor adhesion. (Lap No. 29) On the other hand, it can be seen that the vinylidene chloride resin B having a vinylidene chloride content of 70% by weight shows an unsatisfactory improvement in tensile modulus. (Lap No. 26) It can be seen that when the vinylidene chloride content is 98% by weight, the film forming processability is poor, the tearing trouble is also poor, and the adhesion is also poor. (Lap No. 29) (Example 5 and Comparative Example 6) Tables showing the types and mixing ratios of the vinylidene chloride resin A, the vinylidene chloride resin B, and the liquid plasticizer. Lap N except for changes as described in 9
o. The same experiment as in 1 was repeated and the lap No. 30-49
I got
【００７９】これらの樹脂組成物について、極薄成膜時
の成膜加工性、得られたラップフィルムの弾性率、密着
性、引裂トラブル性について評価した結果を表．１０に
示す。ラップフィルムの物性は成膜後２８℃にて３０日
間保管して後測定を行った。With respect to these resin compositions, the results of evaluation of film forming processability during ultra-thin film formation, elastic modulus of the obtained wrap film, adhesiveness, and tearing trouble are shown in Table. Shown in 10. The physical properties of the wrap film were measured after being stored at 28 ° C. for 30 days after the film formation.
【００８０】[0080]
【表９】 [Table 9]
【００８１】[0081]
【表１０】 [Table 10]
【００８２】[0082]
【表１１】 [Table 11]
【００８３】[0083]
【表１２】 [Table 12]
【００８４】表．１０からラップＮｏ．３０〜４１はい
ずれも成膜加工性に優れ、得られたラップフィルムは、
引張弾性率が高く、ハリ・コシがあり、密着性、引裂ト
ラブル性にも優れていることがわかる。Table. Lap No. 10 to 30 to 41 are all excellent in film-forming processability, and the obtained wrap film is
It can be seen that the tensile elastic modulus is high, it has elasticity and elasticity, and it has excellent adhesion and tear trouble resistance.
【００８５】比較例６、ラップＮｏ．４２、４３はいず
れも、塩化ビニリデン系樹脂Ｂの含有量が１７重量％以
上と多すぎ、引裂トラブル性が不良なことがわかる。Comparative Example 6, Lap No. It can be seen that in both 42 and 43, the content of the vinylidene chloride-based resin B is 17% by weight or more, which is too large, and the tearing trouble property is poor.
【００８６】比較例６、ラップＮｏ．４４は、塩化ビニ
リデン系樹脂Ｂの添加量に対して、液状可塑剤の添加量
が少ないために成膜加工性が劣り、またラップフィルム
中の液状可塑剤含有量も低くて密着性に劣っていること
がわかる。Comparative Example 6, Lap No. No. 44 was inferior in film forming processability because the amount of the liquid plasticizer added was small relative to the amount of the vinylidene chloride resin B added, and the content of the liquid plasticizer in the wrap film was low and the adhesiveness was inferior. You can see that
【００８７】比較例６、ラップＮｏ．４５、４７は塩化
ビニリデン系樹脂Ｂの添加量が比較的に低めであって、
またそれに対する液状可塑剤の添加量も少ないために成
膜加工性が劣っていることがわかる。Comparative Example 6, Lap No. 45 and 47, the amount of vinylidene chloride resin B added was relatively low,
Further, it can be seen that the film forming processability is inferior because the amount of the liquid plasticizer added is small.
【００８８】比較例６、ラップＮｏ．４６、４８、４９
は液状可塑剤の添加量が多すぎるので、液状可塑剤の逸
散がなされた後であってもラップ中の液状可塑剤の量が
７重量％以上を超え引張弾性率の向上効果がみられない
ことがわかる。Comparative Example 6, Lap No. 46, 48, 49
Since the amount of the liquid plasticizer added is too large, the amount of the liquid plasticizer in the wrap exceeds 7% by weight or more and the effect of improving the tensile elastic modulus is observed even after the liquid plasticizer is dispersed. I know there isn't.
【００８９】ラップＮｏ．３０からＮｏ．４９につい
て、液状可塑剤の含有量（重量％）を横軸にし、塩化ビ
ニリデン系樹脂Ｂの含有量を縦軸にしてプロットした実
験解析結果が図２である。図中のＮｏ．はラップＮｏ．
を表し、◎、○、△、×は総合評価の結果を表す。優れ
た成膜加工性と弾性率の向上及び密着性の維持という三
者の特質が並立され、さらに引裂トラブルも少なく実用
上問題のないラップは図２において、座標点イ．（３，
１４）、ロ．（３、１０）、ハ．（６、４）、ニ．
（６、１４）を結んでなる四辺形の範囲内であることが
わかる。そして当該範囲の塩化ビニリデン系樹脂Ｂと液
状可塑剤の含有量の割合であるラップフィルムを得る方
法は、液状可塑剤を含有する塩化ビニリデン系樹脂組成
物を溶融押出し、押出された溶融物を過冷却し、冷却し
た押出物を２軸延伸成膜してフィルムとなし、このフィ
ルムを加熱して含有する液状可塑剤の一部を逸散せしめ
て液状可塑剤の含有量の小さいフィルムを得る塩化ビニ
リデン系樹脂ラップフィルムの製造方法において、上記
塩化ビニリデン系樹脂組成物を、塩化ビニリデン系樹脂
Ａと、塩化ビニリデン系樹脂Ｂと液状可塑剤の混合樹脂
組成物となし、上記液状可塑剤の一部を逸散させる工程
は、塩化ビニリデン系樹脂Ｂの割合が３．９重量％以
上、１３．９重量％以下である成膜されたフィルムの状
態下で行わしめたものであることがわかる。。Lap No. 30 to No. FIG. 2 shows the experimental analysis result of No. 49 in which the content (% by weight) of the liquid plasticizer is plotted on the horizontal axis and the content of the vinylidene chloride resin B is plotted on the vertical axis. No. in the figure. Is the lap number.
And ⊚, ○, Δ, and × represent the results of comprehensive evaluation. The three characteristics of excellent film-forming processability, improvement of elastic modulus, and maintenance of adhesion are put side by side. Furthermore, there are few tearing problems and there is practically no problem. (3,
14), b. (3, 10), c. (6, 4), d.
It can be seen that it is within the range of a quadrangle formed by connecting (6, 14). A method for obtaining a wrap film having a ratio of the content of the vinylidene chloride resin B to the content of the liquid plasticizer in the range is that the vinylidene chloride resin composition containing the liquid plasticizer is melt-extruded and the extruded melt is overheated. The cooled extrudate is biaxially stretched to form a film, which is then heated to dissipate a part of the liquid plasticizer contained in the film to obtain a film containing a small amount of the liquid plasticizer. In the method for producing a vinylidene-based resin wrap film, the vinylidene chloride-based resin composition is a mixed resin composition of vinylidene chloride-based resin A, vinylidene chloride-based resin B and a liquid plasticizer, and a part of the liquid plasticizer is used. The step of dissipating the resin is carried out under the condition of a film formed in which the proportion of vinylidene chloride resin B is 3.9% by weight or more and 13.9% by weight or less. Togawakaru. .
【００９０】[0090]
【発明の効果】以上説明したように、本発明の構成を満
たすことにより、弾性率が高くてハリ・コシ感に優れ、
またラップフィルム相互の密着性が良好で、かつ成膜加
工性にも優れた塩化ビニリデン系樹脂ラップフィルムを
得ることができる。As described above, by satisfying the constitution of the present invention, the elastic modulus is high and the elasticity and elasticity are excellent,
Further, it is possible to obtain a vinylidene chloride resin wrap film having good adhesion between the wrap films and excellent film forming processability.
【図１】図１は本発明のラップフィルムと従来のラップ
フィルムにおける液状可塑剤添加量と可塑剤逸散率との
関係を示す図である。FIG. 1 is a diagram showing a relationship between a liquid plasticizer addition amount and a plasticizer escape rate in a wrap film of the present invention and a conventional wrap film.
【図２】図２は本発明の塩化ビニリデン系樹脂ラップフ
ィルムの、塩化ビニリデン系樹脂Ｂと液状可塑剤の含有
量の割合を示す図である。FIG. 2 is a diagram showing the ratio of the content of vinylidene chloride resin B to the content of liquid plasticizer in the vinylidene chloride resin wrap film of the present invention.
Claims (3)
ビニリデン系樹脂Ｂと、液状可塑剤とからなる混合樹脂
組成物であって、上記混合樹脂組成物内における塩化ビ
ニリデン系樹脂Ｂと液状可塑剤の含有量の割合は、液状
可塑剤の含有量（重量％）を横軸に、塩化ビニリデン系
樹脂Ｂの含有量（重量％）を縦軸にとった図において、
座標点イ．（３，１４）、ロ．（３、１０）、ハ．
（６、４）、ニ．（６、１４）を結んでなる四辺形の範
囲内であることを特徴とする塩化ビニリデン系樹脂ラッ
プフィルム。 塩化ビニリデン系樹脂Ａ：塩化ビニリデン含有量が８５
重量％以上９５重量％以下であって、ゲルパーミエーシ
ョンクロマトグラフィー法による重量平均分子量が８万
以上１３万以下である塩化ビニリデン系樹脂。 塩化ビニリデン系樹脂Ｂ：塩化ビニリデン含有量が８０
重量％以上９５重量％以下であって、ゲルパーミエーシ
ョンクロマトグラフィー法による重量平均分子量が２万
以上６万以下である塩化ビニリデン系樹脂。1. A mixed resin composition comprising the following vinylidene chloride resin A, vinylidene chloride resin B, and a liquid plasticizer, wherein the vinylidene chloride resin B and the liquid plasticizer are contained in the mixed resin composition. The ratio of the content of the agent is shown in the figure in which the content (wt%) of the liquid plasticizer is plotted on the horizontal axis and the content (wt%) of the vinylidene chloride resin B is plotted on the vertical axis.
Coordinate point a. (3, 14), b. (3, 10), c.
(6, 4), d. A vinylidene chloride-based resin wrap film, which is in the range of a quadrangle formed by connecting (6, 14). Vinylidene chloride resin A: Vinylidene chloride content is 85
A vinylidene chloride resin having a weight average molecular weight of 80,000 or more and 95,000 or less and a weight average molecular weight of 80,000 or more and 130,000 or less as measured by gel permeation chromatography. Vinylidene chloride resin B: vinylidene chloride content of 80
A vinylidene chloride resin having a weight percentage of 95% by weight or more and a weight average molecular weight of 20,000 or more and 60,000 or less as determined by gel permeation chromatography.
ロン以上１５ミクロン以下、引張弾性率５０００ｋｇ／
ｃｍ2以上である請求項１に記載の塩化ビニリデン系樹
脂ラップフィルム。2. The film has a film thickness of 5 μm or more and 15 μm or less and a tensile elastic modulus of 5000 kg /
The vinylidene chloride resin wrap film according to claim 1, which has a cm 2 or more.
樹脂組成物を溶融押出しし、押出された溶融物を過冷却
し、冷却した押出物を２軸延伸成膜してフィルムとな
し、このフィルムを加熱して含有する液状可塑剤の一部
を逸散せしめて液状可塑剤の含有量の小さいフィルムを
得る塩化ビニリデン系樹脂ラップフィルムの製造方法に
おいて、上記塩化ビニリデン系樹脂組成物を、下記の塩
化ビニリデン系樹脂Ａと、塩化ビニリデン系樹脂Ｂと液
状可塑剤の混合樹脂組成物となし、上記液状可塑剤の一
部を逸散させる工程は、塩化ビニリデン系樹脂Ｂの割合
が３．９重量％以上、１３．９重量％以下である成膜さ
れたフィルムの状態下で行わしめ、得られるフィルム内
に含有する塩化ビニリデン系樹脂Ｂと液状可塑剤の含有
量の割合を、塩化ビニリデン系樹脂Ｂの含有量（重量
％）を縦軸に、液状可塑剤の含有量（重量％）を横軸に
とった図において、座標点イ．（３，１４）、ロ．
（３、１０）、ハ．（６、４）、ニ．（６、１４）を結
んでなる四辺形の範囲内のものにすることを特徴とする
塩化ビニリデン系樹脂ラップフィルムの製造方法。 塩化ビニリデン系樹脂Ａ：塩化ビニリデン含有量が８５
重量％以上９５重量％以下であって、ゲルパーミエーシ
ョンクロマトグラフィー法による重量平均分子量が８万
以上１３万以下である塩化ビニリデン系樹脂。 塩化ビニリデン系樹脂Ｂ：塩化ビニリデン含有量が８０
重量％以上９５重量％以下であって、ゲルパーミエーシ
ョンクロマトグラフィー法による重量平均分子量が２万
以上６万以下である塩化ビニリデン系樹脂。3. A vinylidene chloride resin composition containing a liquid plasticizer is melt-extruded, the extruded melt is supercooled, and the cooled extrudate is biaxially stretched to form a film. In the method for producing a vinylidene chloride-based resin wrap film, in which a part of the liquid plasticizer contained by heating is dispersed to obtain a film having a small content of the liquid plasticizer, the vinylidene chloride-based resin composition is In the step of forming a vinylidene chloride resin A, a mixed resin composition of vinylidene chloride resin B and a liquid plasticizer, and dissipating a part of the liquid plasticizer, the proportion of the vinylidene chloride resin B is 3.9% by weight. % Or more and 13.9% by weight or less, and the ratio of the content of the vinylidene chloride resin B to the content of the liquid plasticizer contained in the obtained film is vinyl chloride. In the figure in which the vertical axis represents the content (% by weight) of the lidene-based resin B and the horizontal axis represents the content (% by weight) of the liquid plasticizer, coordinate points a. (3, 14), b.
(3, 10), c. (6, 4), d. A method for producing a vinylidene chloride-based resin wrap film, characterized in that it is within the range of a quadrangle formed by connecting (6, 14). Vinylidene chloride resin A: Vinylidene chloride content is 85
A vinylidene chloride resin having a weight average molecular weight of 80,000 or more and 95,000 or less and a weight average molecular weight of 80,000 or more and 130,000 or less as measured by gel permeation chromatography. Vinylidene chloride resin B: vinylidene chloride content of 80
A vinylidene chloride resin having a weight percentage of 95% by weight or more and a weight average molecular weight of 20,000 or more and 60,000 or less as determined by gel permeation chromatography.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27786994A JP3471445B2 (en) | 1994-11-11 | 1994-11-11 | Vinylidene chloride resin wrap film and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27786994A JP3471445B2 (en) | 1994-11-11 | 1994-11-11 | Vinylidene chloride resin wrap film and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08134306A true JPH08134306A (en) | 1996-05-28 |
| JP3471445B2 JP3471445B2 (en) | 2003-12-02 |
Family
ID=17589422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27786994A Expired - Fee Related JP3471445B2 (en) | 1994-11-11 | 1994-11-11 | Vinylidene chloride resin wrap film and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3471445B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014054414A1 (en) * | 2012-10-01 | 2014-04-10 | 株式会社クレハ | Vinylidene chloride-based copolymer resin composition and wrap film |
| JP2014172312A (en) * | 2013-03-11 | 2014-09-22 | Asahi Kasei Chemicals Corp | Vinylidene chloride resin wrap film and production method thereof |
| JP2018096725A (en) * | 2016-12-08 | 2018-06-21 | 株式会社クラレ | Method for measuring content of plasticizer |
| KR20190099340A (en) | 2017-05-16 | 2019-08-26 | 가부시끼가이샤 구레하 | Vinylidene chloride-based resin film and vinylidene chloride-based resin composition |
| JPWO2020217362A1 (en) * | 2019-04-24 | 2020-10-29 |
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1994
- 1994-11-11 JP JP27786994A patent/JP3471445B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014054414A1 (en) * | 2012-10-01 | 2014-04-10 | 株式会社クレハ | Vinylidene chloride-based copolymer resin composition and wrap film |
| CN104704045A (en) * | 2012-10-01 | 2015-06-10 | 株式会社吴羽 | Vinylidene chloride-based copolymer resin composition and wrap film |
| TWI487718B (en) * | 2012-10-01 | 2015-06-11 | Kureha Corp | A vinyl chloride copolymer resin composition and a cling film |
| JPWO2014054414A1 (en) * | 2012-10-01 | 2016-08-25 | 株式会社クレハ | Vinylidene chloride copolymer resin composition and wrap film |
| JP2014172312A (en) * | 2013-03-11 | 2014-09-22 | Asahi Kasei Chemicals Corp | Vinylidene chloride resin wrap film and production method thereof |
| JP2018096725A (en) * | 2016-12-08 | 2018-06-21 | 株式会社クラレ | Method for measuring content of plasticizer |
| KR20190099340A (en) | 2017-05-16 | 2019-08-26 | 가부시끼가이샤 구레하 | Vinylidene chloride-based resin film and vinylidene chloride-based resin composition |
| JPWO2020217362A1 (en) * | 2019-04-24 | 2020-10-29 | ||
| WO2020217362A1 (en) * | 2019-04-24 | 2020-10-29 | 日立化成株式会社 | Resin composition, wrap film and wrap film-containing body |
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| Publication number | Publication date |
|---|---|
| JP3471445B2 (en) | 2003-12-02 |
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