JPH0726074A - Polyolefin resin film - Google Patents
Polyolefin resin filmInfo
- Publication number
- JPH0726074A JPH0726074A JP5192871A JP19287193A JPH0726074A JP H0726074 A JPH0726074 A JP H0726074A JP 5192871 A JP5192871 A JP 5192871A JP 19287193 A JP19287193 A JP 19287193A JP H0726074 A JPH0726074 A JP H0726074A
- Authority
- JP
- Japan
- Prior art keywords
- film
- weight
- particles
- polyolefin resin
- crosslinked
- 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.)
- Pending
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は透明性に優れ、かつ滑り
性、耐スクラッチ性が良く、更に製膜時のダイスの汚染
が少なく、製膜操業性に優れたポリオレフィン樹脂フイ
ルムに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin film which is excellent in transparency, has good slipperiness and scratch resistance, has less die contamination during film formation, and has excellent film forming operability. .
【０００２】[0002]
【従来の技術】従来、ポリオレフィン樹脂フイルムの滑
り性、耐ブロッキング性を改良する方法として、無機の
微粒子を添加したもの（例えば特公昭５２−１６１３４
号公報、特公昭４２−２４５２３号公報、特開平３−９
９３８号公報）や有機重合体の微粒子の添加したもの
（特開昭４９−１１９４５号公報、特開昭５７−６４５
２２号公報、特開昭６２−３９２１９号公報）などが知
られている。2. Description of the Related Art Conventionally, as a method for improving the slipperiness and blocking resistance of a polyolefin resin film, one containing inorganic fine particles (for example, Japanese Examined Patent Publication No. 52-16134).
Japanese Patent Publication No. 42-24523 and Japanese Patent Laid-Open No. 3-9
938) and organic polymer fine particles (JP-A-49-11945 and JP-A-57-645).
No. 22, JP-A-62-39219) and the like are known.
【０００３】これらの方法の中で有機重合体の微粒子を
用いる方法は、無機微粒子を用いる方法に比べ透明性や
耐スクラッチ性に優れたフイルムが得られることより有
用な方法である。しかしながら、有機重合体の微粒子を
用いる方法は、無機の微粒子に比べ耐熱性が劣るため
に、例えば、製膜時にダイス出口の劣化物による汚染が
大きく、ダイリップの掃除の回数を多くする必要があ
り、製膜の操業性が低下するなどの問題があった。Of these methods, the method of using fine particles of an organic polymer is more useful than the method of using inorganic fine particles because a film having excellent transparency and scratch resistance can be obtained. However, the method using the fine particles of the organic polymer is inferior in heat resistance as compared with the inorganic fine particles, and therefore, for example, the contamination by the deteriorated material at the die outlet during film formation is large, and the number of times of cleaning the die lip needs to be increased. However, there is a problem that the operability of film formation is reduced.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記従来の
問題点を解決するものであり、その目的は、透明性に優
れ、かつ耐ブロッキング性、耐スクラッチ性、滑り性が
良く、更に製膜時のダイスの汚染が少なく製膜操業性に
優れたポリオレフィン樹脂フイルムを提供することにあ
る。SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned conventional problems, and its object is to provide excellent transparency, good blocking resistance, scratch resistance, and slipperiness. An object of the present invention is to provide a polyolefin resin film which is less likely to contaminate the die during film formation and has excellent film forming operability.
【０００５】[0005]
【課題を解決するための手段】本発明のポリオレフィン
樹脂フイルムは、ポリオレフィン樹脂１００重量部に対
して平均粒径０．４〜７μｍの３価以上の多価アルコー
ルのアクリル酸および／またはメタアクリル酸のエステ
ルで架橋したポリアクリル酸系重合体の架橋粒子を０．
００５〜２重量部配合した組成物からなることを特徴と
するポリオレフィン樹脂フイルムである。The polyolefin resin film of the present invention comprises acrylic acid and / or methacrylic acid of a polyhydric alcohol having a valence of 3 or more and an average particle diameter of 0.4 to 7 μm with respect to 100 parts by weight of the polyolefin resin. The crosslinked particles of the polyacrylic acid polymer crosslinked with the ester of 0.
A polyolefin resin film comprising a composition in which 005 to 2 parts by weight is blended.
【０００６】本発明におけるポリオレフィン樹脂として
は、プロピレン、エチレン、ブテン、４−メチルペンテ
ン−１などの単独重合体もしくは共重合体またはこれら
の重合体の混合物が挙げられる。Examples of the polyolefin resin in the present invention include homopolymers or copolymers of propylene, ethylene, butene, 4-methylpentene-1, and the like, or a mixture of these polymers.
【０００７】本発明におけるポリアクリル酸系重合体の
架橋粒子は、３価以上の多価アルコールのアクリル酸お
よび／またはメタアクリル酸のエステルで架橋したもの
である必要がある。なぜならば、非架橋粒子、２価アル
コールのアクリル酸および／またはメタアクリル酸のエ
ステルやジビニルベンゼンなどの２価の架橋剤で架橋し
た粒子の場合は、粒子の耐熱性が低いため、たとえば、
製膜時のダイス出口に劣化物が蓄積し、フイルムにすじ
状の傷が発生するので蓄積した劣化物を取除くためのダ
イリップの掃除の回数を多くする必要があり、製膜の操
業性（以下、単に製膜の操業性と称する）が低下するの
で好ましくないからである。The crosslinked particles of the polyacrylic acid type polymer in the present invention must be crosslinked with an ester of acrylic acid and / or methacrylic acid of a polyhydric alcohol having a valence of 3 or more. This is because, in the case of non-crosslinked particles, particles crosslinked with a divalent crosslinking agent such as an ester of acrylic acid and / or methacrylic acid of a dihydric alcohol or divinylbenzene, the heat resistance of the particle is low.
Deteriorated material accumulates at the die exit during film formation, causing streak-like scratches on the film.Therefore, it is necessary to increase the number of times of cleaning the die lip to remove the accumulated deteriorated material. This is because this is not preferable since the operability of film formation will be reduced).
【０００８】本発明におけるポリアクリル酸系重合体と
しては、アクリル酸、アクリル酸メチル、アクリル酸エ
チル、アクリル酸ブチル等のアクリル酸またはアクリル
酸のエステル誘導体、メタアクリル酸、メタアクリル酸
メチル、メタアクリル酸ブチル等のメタアクリル酸また
はメタアクリル酸のエステル誘導体を５０重量％以上含
む重合体が挙げられ、前記アクリル系モノマーは、単体
として用いてもよいし、２種以上を併用して用いてもよ
い。また、少量であれば、アクリル酸やメタアクリル酸
の金属塩、アミド誘導体、ヒドロキシエステルやジメチ
ルアミノエチルエステル等の特殊な構造のエステル誘導
体を用いてもかまわない。Examples of the polyacrylic acid-based polymer in the present invention include acrylic acid, acrylic acid such as methyl acrylate, ethyl acrylate, and butyl acrylate, or ester derivatives of acrylic acid, methacrylic acid, methyl methacrylate, and meta. Examples of the polymer include 50% by weight or more of methacrylic acid or an ester derivative of methacrylic acid such as butyl acrylate. The acrylic monomer may be used alone or in combination of two or more. Good. Further, as long as it is a small amount, a metal salt of acrylic acid or methacrylic acid, an amide derivative, an ester derivative having a special structure such as a hydroxy ester or dimethylaminoethyl ester may be used.
【０００９】他のビニル系単量体としては、スチレン、
メチルスチレン、αメチルスチレン等のスチレンまたは
その誘導体、酢酸ビニル、塩化ビニル、塩化ビニリデ
ン、アクリルニトリル等の重合性のビニル単量体が挙げ
られる。Other vinyl monomers include styrene,
Examples thereof include styrene such as methylstyrene and α-methylstyrene, or a derivative thereof, and a polymerizable vinyl monomer such as vinyl acetate, vinyl chloride, vinylidene chloride, and acrylonitrile.
【００１０】本発明における３価以上の多価アルコール
のアクリル酸および／またはメタアクリル酸エステルと
しては、たとえば、トリメチロールプロパントリアクリ
レート、トリメチロールプロパントリメタアクリレー
ト、ペンタエリスリトールテトラアクリレート、ペンタ
エリスリトールテトラメタアクリレート等が挙げられる
が、これらに限定はされない。このうち、２種類以上を
併用してもかまわない。また、ジビニルベンゼンや２価
アルコールのアクリル酸および／またはメタアクリル酸
のエステル等の２価の架橋剤をこれらに併用してもかま
わない。Examples of the acrylic acid and / or methacrylic acid ester of a polyhydric alcohol having 3 or more valences in the present invention include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate and pentaerythritol tetrameta. Examples thereof include, but are not limited to, acrylates and the like. Of these, two or more types may be used in combination. Further, a divalent cross-linking agent such as divinylbenzene or an ester of acrylic acid and / or methacrylic acid of a dihydric alcohol may be used in combination therewith.
【００１１】該３価以上の多価アルコールのアクリル酸
および／またはメタアクリル酸のエステルは、架橋重合
体粒子中に０．０１〜０．５重量％の範囲で含まれるよ
う添加するのが好ましい。０．０１重量％未満の添加量
では粒子の耐熱性が悪化し製膜操業性が低下するので好
ましくない。逆に１０重量％の添加量を越えると耐熱性
向上効果が飽和し、かつ粒子が硬くなるためフイルムの
耐スクラッチ性が悪くなるので好ましくない。The acrylic acid and / or methacrylic acid ester of a polyhydric alcohol having a valence of 3 or more is preferably added so as to be contained in the crosslinked polymer particles in an amount of 0.01 to 0.5% by weight. . If the addition amount is less than 0.01% by weight, the heat resistance of the particles is deteriorated and the film forming operability is deteriorated, which is not preferable. On the other hand, if the amount added exceeds 10% by weight, the heat resistance improving effect is saturated and the particles become hard, so that the scratch resistance of the film deteriorates, which is not preferable.
【００１２】該重合体を微粒子化する方法も限定はされ
ないが、エマルジョン重合や懸濁重合等の方法を用い、
重合時に直接微粒子化する方法が好適である。該方法を
採用する場合は、重合体に自己乳化性を付与するために
特殊な構造の極性モノマーを共重合する手段がとられる
が、これらの手段をとることは何ら制限を受けず、むし
ろ好ましい実施態様である。該重合体微粒子の形状も特
に限定はされないが、実質的に球状のものが好ましい。The method for making the polymer into fine particles is not limited, but a method such as emulsion polymerization or suspension polymerization is used.
A method of directly forming fine particles during polymerization is suitable. When this method is adopted, a means of copolymerizing a polar monomer having a special structure is used in order to impart self-emulsifying property to the polymer, but there is no limitation to use these means, and it is rather preferable. It is an embodiment. The shape of the polymer fine particles is not particularly limited, but is preferably substantially spherical.
【００１３】該架橋粒子の平均粒径は０．４〜７μｍの
範囲であることが必要である。平均粒径が０．４μｍ未
満では滑り性の改良効果が小さくなり、逆に７μｍを越
えると滑り性の改良効果が飽和し、透明性が悪化するの
で、好ましくない。また、該架橋粒子の粒度分布は、シ
ャープであることが、透明性、滑り性、耐ブロッキング
性を満足するうえで好ましい。なお、該重合体微粒子の
平均粒径は、走査型電子顕微鏡で写真撮影し、イメージ
アナライザー装置を用いて水平方向のフェレ径を測定
し、その平均値で表示したものである。The average particle size of the crosslinked particles must be in the range of 0.4 to 7 μm. If the average particle size is less than 0.4 μm, the effect of improving the slipperiness is reduced, and if it exceeds 7 μm, the effect of improving the slipperiness is saturated and the transparency is deteriorated, which is not preferable. The particle size distribution of the crosslinked particles is preferably sharp in order to satisfy transparency, slipperiness and blocking resistance. The average particle size of the polymer fine particles is obtained by taking a photograph with a scanning electron microscope, measuring the Feret diameter in the horizontal direction using an image analyzer, and displaying the average value.
【００１４】本発明で用いるポリオレフィン樹脂と該架
橋粒子の配合割合は、ポリオレフィン樹脂１００重量部
に対して架橋粒子を０．００５〜２重量部、好ましくは
０．０１〜１重量部である。架橋粒子の配合量が０．０
０５重量部未満ではフイルムに滑り性および耐ブロッキ
ング性を付与することが不可能であり、一方、２重量部
を越えると、滑り性、耐ブロッキング性は十分与えられ
るものの、フイルムの透明性が著しく阻害されるので好
ましくない。The blending ratio of the polyolefin resin used in the present invention and the crosslinked particles is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, of the crosslinked particles to 100 parts by weight of the polyolefin resin. The amount of crosslinked particles blended is 0.0
If it is less than 05 parts by weight, it is impossible to impart slipperiness and blocking resistance to the film. On the other hand, if it exceeds 2 parts by weight, the slipperiness and blocking resistance are sufficiently provided, but the transparency of the film is remarkably high. It is not preferable because it is inhibited.
【００１５】該架橋粒子の平均粒子径や配合割合の最適
値は、ポリオレフィン樹脂の種類、フイルムの厚みや構
成、延伸の有無等により大きく変化するので、目的とす
るフイルム特性に合わせて前記した範囲で適宜任意に設
定するのがよい。The optimum values of the average particle diameter and the blending ratio of the crosslinked particles greatly vary depending on the type of polyolefin resin, the thickness and composition of the film, the presence or absence of stretching, etc. Therefore, it is preferable to arbitrarily set it.
【００１６】本発明では、本発明の効果を損なわない範
囲であれば、該架橋粒子以外の有機や無機の微粒子を併
用することができる。更に、本発明では、高級脂肪酸ア
マイド、高級脂肪酸エステル、ワックス、金属石ケン等
の潤滑剤を併用し、滑り性を向上させる等の手段をとる
こともでき、むしろ、これらの潤滑剤の併用は好まし
い。In the present invention, organic or inorganic fine particles other than the crosslinked particles can be used in combination as long as the effects of the present invention are not impaired. Further, in the present invention, a lubricant such as higher fatty acid amide, higher fatty acid ester, wax, and metallic soap may be used in combination to take measures such as improving the slipperiness. Rather, these lubricants should not be used in combination. preferable.
【００１７】また、一般にポリオレフィン樹脂用に使用
される安定剤、帯電防止剤、紫外線吸収剤、加工助剤、
可塑剤等の併用も何ら制限を受けない。Further, stabilizers, antistatic agents, ultraviolet absorbers, processing aids, which are generally used for polyolefin resins,
There is no restriction on the combined use of plasticizers.
【００１８】前述の架橋粒子や添加剤等の混合方法とし
ては、Ｖ型ブレンダ、スクリュー型ブレンダ、ドライブ
レンダ、リボンブレンダ、ヘンシェルミキサーなどの混
合機にて均一混合した後、混練ペレット化するのが一般
的であるが、特にこれらに限定されるものではない。As a method for mixing the above-mentioned crosslinked particles, additives, etc., a mixer such as a V type blender, a screw type blender, a dry blender, a ribbon blender or a Henschel mixer is used to uniformly mix them, and then kneaded into pellets. It is general, but not limited to these.
【００１９】本発明の架橋粒子や添加剤等は、単に押出
成形した未延伸のキャスティングフイルムにも、同キャ
スティングフイルムを１軸または２軸方向に延伸した延
伸フイルムのどちらにも適用できる。また、単層構成お
よび２層以上よりなる多層構成のいずれにも適用でき
る。多層構成の場合は、上記した架橋粒子は表面層に添
加するのが一般的であるが、これに限定はされない。The crosslinked particles, additives and the like of the present invention can be applied to either an unstretched casting film which is simply extruded or a stretched film which is obtained by stretching the casting film uniaxially or biaxially. Further, it can be applied to both a single layer structure and a multilayer structure composed of two or more layers. In the case of a multi-layer structure, the above-mentioned crosslinked particles are generally added to the surface layer, but the present invention is not limited to this.
【００２０】さらに、本発明ではフイルムにコロナ放電
処理、プラズマ処理、紫外線照射処理等の表面活性化処
理を行うことにより表面の接着性を向上させることが好
ましい。Further, in the present invention, it is preferable to improve the adhesiveness of the surface by subjecting the film to surface activation treatment such as corona discharge treatment, plasma treatment and ultraviolet irradiation treatment.
【００２１】[0021]
【実施例】以下に本発明を実施例に基づき説明するが、
本発明はこれらに限定されるものではない。なお実施例
で用いた測定方法は次の通りである。EXAMPLES The present invention will be described below based on examples.
The present invention is not limited to these. The measuring method used in the examples is as follows.
【００２２】(1) 曇価 ＪＩＳＥ−Ｋ６７１４に従い、東洋精機ヘーズデスター
Ｊで測定した。(1) Haze value: Measured by Toyo Seiki Haze Destar J according to JIS-K6714.
【００２３】(2) 摩擦係数 ２０℃×６５％ＲＨにおいてＡＳＴＭ−Ｄ１８９４によ
り測定した。(2) Coefficient of friction Measured by ASTM-D1894 at 20 ° C. × 65% RH.
【００２４】(3) 耐スクラッチ性 ＪＩＳ−Ｌ０８２３−１９７１に準じ、東洋精機製染色
堅牢度摩擦試験機により、２００ｇｆの荷重下の下、５
０回摩擦試験を行い、試験前後の曇価の測定により摩擦
試験による曇価の増加度を測定した。増加度が小さい方
が耐スクラッチ性は良好である。(3) Scratch resistance According to JIS-L0823-1971, under a load of 200 gf, with a dyeing fastness friction tester manufactured by Toyo Seiki Co., Ltd., 5
The friction test was performed 0 times, and the degree of increase in the haze value by the friction test was measured by measuring the haze value before and after the test. The smaller the degree of increase, the better the scratch resistance.
【００２５】(4) 製膜操業指数 ４ｍｍφのノズルを装着した２軸押出機を用い、ポリマ
ー組成物（多層フイルムの場合は表層に用いるポリマー
組成物を用いる）を２７０℃の温度、１２ｋｇ／ｈｒの
吐出量で８時間溶融押出しし、ノズル表面に析出する熱
劣化物の成長度（長さ：ｍｍ）で表示した。成長度が低
いものほど製膜操業性は良好である。(4) Film-forming operation index Using a twin-screw extruder equipped with a nozzle having a diameter of 4 mm, the polymer composition (in the case of a multi-layer film, the polymer composition used for the surface layer) is used at a temperature of 270 ° C. and 12 kg / hr. It was melt-extruded at a discharge amount of 8 hours, and the growth degree (length: mm) of the thermally deteriorated substance deposited on the nozzle surface was displayed. The lower the growth rate, the better the film forming operability.
【００２６】実施例 １ 基層（Ａ）として、エチレン含有量０．５重量％のプロ
ピレンエチレン共重合体９０重量％と石油樹脂（商品名
アルコンＰ−１１５）１０重量％からなる混合物１００
重量部に対してグリセリン樹脂酸エステルを０．３重量
部、エルカ酸アミドを０．３重量部混合した組成物を用
いた。Example 1 As a base layer (A), a mixture 100 consisting of 90% by weight of a propylene-ethylene copolymer having an ethylene content of 0.5% by weight and 10% by weight of a petroleum resin (trade name Alcon P-115).
A composition obtained by mixing 0.3 part by weight of glycerin resin acid ester and 0.3 part by weight of erucic acid amide with respect to parts by weight was used.
【００２７】一方、表面層（Ｂ）としてブテン含有率２
３重量％のプロピレン／ブテン−１共重合体（メルトイ
ンデックス６．０ｇ／１０分）１００重量部に、平均粒
径２．０μｍの球状でほぼ単分散の粒径分布よりなる架
橋アクリル系重合体粒子〔組成：メチルメタアクリレー
ト／トリメチロールプロパントリメタクリレート＝９９
／１（重量比）〕０．１５重量部、グリセリン脂肪酸エ
ステル０．５重量部、ヒドロキシステアロアミド０．５
重量部を混合し１８０℃で溶融押出ししたものをペレッ
ト化した組成物を用いた。該Ａ層およびＢ層の組成物を
２台の押出機から溶融押出しし、Ｂ／Ａ／Ｂの３層未延
伸フイルムを得た。該未延伸フイルムを１３０℃で縦方
向に４．５倍、横方向に８倍延伸し、両表面にコロナ放
電処理を施し、厚さ２５μｍ（厚み比５：９０：５）の
２軸延伸フイルムを得た。得られたフイルムの特性値を
表１に示す。本実施例で得られたフイルムは、透明性、
滑り性、耐スクラッチ性に優れており、かつ製膜時の操
業指数も良好である。On the other hand, the butene content of the surface layer (B) is 2
Cross-linked acrylic polymer having a spherical and nearly monodisperse particle size distribution with an average particle size of 2.0 μm in 100 parts by weight of a 3% by weight propylene / butene-1 copolymer (melt index 6.0 g / 10 min). Particles [Composition: methyl methacrylate / trimethylolpropane trimethacrylate = 99
/ 1 (weight ratio)] 0.15 part by weight, glycerin fatty acid ester 0.5 part by weight, hydroxystearoamide 0.5
A composition in which parts by weight were mixed and melt-extruded at 180 ° C. was pelletized was used. The composition of the A layer and the B layer was melt extruded from two extruders to obtain a B / A / B three-layer unstretched film. The unstretched film was stretched 4.5 times in the longitudinal direction and 8 times in the transverse direction at 130 ° C., both surfaces were subjected to corona discharge treatment, and a biaxially stretched film having a thickness of 25 μm (thickness ratio 5: 90: 5). Got The characteristic values of the obtained film are shown in Table 1. The film obtained in this example has transparency,
It has excellent slipperiness and scratch resistance, and also has a good operation index during film formation.
【００２８】比較例 １ 実施例１の架橋アクリル系重合体粒子の架橋剤をトリメ
チロールプロパントリメタアクリレートに替えて、エチ
レングリコールジメタアクリレートとする以外、実施例
１と同じ方法でフイルムを得た。得られたフイルムの特
性を表１に示す。本比較例で得たフイルムは、透明性、
滑り性、耐スクラッチ性に優れているが製膜時の操業指
数が劣る。Comparative Example 1 A film was obtained in the same manner as in Example 1 except that ethylene glycol dimethacrylate was used instead of trimethylolpropane trimethacrylate as the crosslinking agent for the crosslinked acrylic polymer particles of Example 1. . The properties of the obtained film are shown in Table 1. The film obtained in this comparative example has transparency,
Excellent in slipperiness and scratch resistance, but inferior in operation index during film formation.
【００２９】比較例 ２ 実施例１の架橋アクリル系重合体粒子に替えて、架橋ポ
リスチレン系重合体粒子〔組成：スチレン／トリメチロ
ールプロパントリメタアクリレート＝９９／１（重量
比）〕を用いる以外、実施例１と同じ方法でフイルムを
得た。得られたフイルムの特性を表１に示す。本比較例
で得たフイルムは、製膜時の操業指数や耐スクラッチ性
は良好であるが、透明性が劣る。Comparative Example 2 In place of the crosslinked acrylic polymer particles of Example 1, crosslinked polystyrene polymer particles [composition: styrene / trimethylolpropane trimethacrylate = 99/1 (weight ratio)] were used. A film was obtained in the same manner as in Example 1. The properties of the obtained film are shown in Table 1. The film obtained in this comparative example has a good operation index and scratch resistance during film formation, but is inferior in transparency.
【００３０】比較例 ３ 実施例１の架橋アクリル系重合体粒子に替えて、平均粒
径２．５μｍのほぼ単分散の粒径分布よりなる球状シリ
カを用いる以外、実施例１と同じ方法でフイルムを得
た。得られたフイルムの特性を表１に示す。本比較例で
得たフイルムは、製膜時の操業指数は良好であるが透明
性や耐スクラッチ性が劣る。Comparative Example 3 A film was prepared in the same manner as in Example 1 except that spherical silica having an average particle size of 2.5 μm and having a substantially monodispersed particle size distribution was used in place of the crosslinked acrylic polymer particles of Example 1. Got The properties of the obtained film are shown in Table 1. The film obtained in this comparative example has a good operation index during film formation, but is inferior in transparency and scratch resistance.
【００３１】実施例 ２ 平均粒径が２．２μｍの架橋アクリル系重合体〔組成：
メチルメタアクリレート／ｎ−ブチルアクリレート／ス
チレン／トリメチロールプロパントリメタアクリレート
＝７９／１０／１０／１（重量比）〕０．１重量％を含
む、メルトインデックス２．５ｇ／１０分のポリプロピ
レンを樹脂温度２７０℃で溶融押出しを行い、３０℃の
冷却ロールで急冷することにより、厚さ０．７２ｍｍの
シートとした。得られたシートを、縦延伸機のロール周
速差を利用して延伸温度、４０℃で縦方向に４．５倍延
伸し、引き続きテンター式延伸機により延伸温度１５５
℃で横方向に８倍延伸した。次いで１６０℃で熱処理を
行い、厚さ約２０μｍの２軸延伸フイルムとした後、片
面にコロナ処理を施した。得られたフイルムの特性を表
１に示す。本実施例で得たフイルムは、透明性、滑り
性、耐スクラッチ性に優れており、かつ製膜時の操業指
数も良好である。Example 2 Cross-linked acrylic polymer having an average particle size of 2.2 μm [composition:
Methyl methacrylate / n-butyl acrylate / styrene / trimethylolpropane trimethacrylate = 79/10/10/1 (weight ratio)] 0.1 wt% of polypropylene having a melt index of 2.5 g / 10 min. Melt extrusion was performed at a temperature of 270 ° C., and rapid cooling was performed with a cooling roll at 30 ° C. to obtain a sheet having a thickness of 0.72 mm. The obtained sheet is stretched at a stretching temperature of 40 ° C. by a factor of 4.5 in the machine direction using the roll peripheral speed difference of the longitudinal stretching machine, and subsequently stretched at a stretching temperature of 155 by a tenter type stretching machine.
It was stretched 8 times in the transverse direction at 0 ° C. Next, heat treatment was performed at 160 ° C. to obtain a biaxially stretched film having a thickness of about 20 μm, and then one surface was subjected to corona treatment. The properties of the obtained film are shown in Table 1. The film obtained in this example is excellent in transparency, slipperiness, and scratch resistance, and also has a good operation index during film formation.
【００３２】比較例 ４ 実施例２の架橋アクリル系重合体粒子の架橋剤をトリメ
チロールプロパントリメタアクリレートに替えて、エチ
レングリコールジメタアクリレートとする以外、実施例
２と同じ方法でフイルムを得た。得られたフイルムの特
性を表１に示す。本比較例で得たフイルムは、透明性、
滑り性、耐スクラッチ性等のフイルム特性は良好である
が、製膜時の操業指数が劣る。Comparative Example 4 A film was obtained in the same manner as in Example 2 except that ethylene glycol dimethacrylate was used instead of trimethylolpropane trimethacrylate as the crosslinking agent for the crosslinked acrylic polymer particles of Example 2. . The properties of the obtained film are shown in Table 1. The film obtained in this comparative example has transparency,
Film properties such as slipperiness and scratch resistance are good, but the operation index during film formation is poor.
【００３３】比較例 ５ 実施例２の架橋アクリル系共重合体粒子に替えて、平均
粒径が５μｍのナイロン６および平均粒径が３μｍの不
定形シリカをそれぞれ０．０５重量％配合する以外、実
施例２と同じ方法でフイルムを得た。得られたフイルム
の特性を表１に示す。本比較例で得たフイルムは、透明
性、滑り性、耐スクラッチ性等のフイルム特性は良好で
あるが、製膜時の操業指数が著しく劣る。Comparative Example 5 In place of the crosslinked acrylic copolymer particles of Example 2, 0.05% by weight of nylon 6 having an average particle size of 5 μm and amorphous silica having an average particle size of 3 μm were added, respectively. A film was obtained in the same manner as in Example 2. The properties of the obtained film are shown in Table 1. The film obtained in this Comparative Example has good film properties such as transparency, slipperiness, and scratch resistance, but the operation index during film formation is extremely poor.
【００３４】実施例 ３ 基層用フイルム素材（Ａ）としては、アイソタクチック
ポリブテン−１−エチレン共重合体（エチレン含有量：
３．５重量％）８０重量％とプロピレン−ブテン１共重
合体１０重量％及びプロピレン−エチレン共重合体１０
重量％からなる混合組成物に、帯電防止剤としてアルキ
ルアミンのエチレンオキサイド付加物１重量％を混合し
たものを使用した。また、被覆用フイルム素材（Ｂ）と
しては、プロピレン−ブテン１共重合体（ブテン含有量
１２重量％）とプロピレン−エチレン共重合体（エチレ
ン含有量４．５重量％）をそれぞれ５０重量％ずつ混合
し、この混合物に平均粒径３．５μｍの架橋アクリル系
重合体粒子〔組成は実施例１と同じ〕０．２重量％を混
合したものを使用した。上記素材（Ａ），（Ｂ）をそれ
ぞれ溶融押出しした後、溶融状態で積層した後２５℃の
冷却ロールで冷却し、（Ｂ）層／（Ａ）層／（Ｂ）層の
厚みの比率が１５／７５／１５である７２０μｍの積層
未延伸フイルムを得た。該未延伸フイルムを１２５℃で
縦方向へ４．０倍、横方向へ４．５倍に２軸延伸し、４
０μｍの２軸延伸フイルムを得た。得られたフイルムの
特性を表１に示す。本実施例で得たフイルムは、透明
性、滑り性、耐スクラッチ性等のフイルム特性が優れて
おり、かつ製膜時の操業指数も良好である。Example 3 As the base film material (A), an isotactic polybutene-1-ethylene copolymer (ethylene content:
3.5 wt%) 80 wt%, propylene-butene 1 copolymer 10 wt% and propylene-ethylene copolymer 10
A mixed composition of 1% by weight of an ethylene oxide adduct of alkylamine as an antistatic agent was used in a mixed composition of 1% by weight. As the coating film material (B), 50% by weight of propylene-butene 1 copolymer (butene content 12% by weight) and 50% by weight of propylene-ethylene copolymer (ethylene content 4.5% by weight) are used. The mixture was mixed, and 0.2% by weight of cross-linked acrylic polymer particles having the average particle diameter of 3.5 μm (the composition is the same as in Example 1) was used. The materials (A) and (B) are melt-extruded, laminated in a molten state, and then cooled by a cooling roll at 25 ° C., and the thickness ratio of (B) layer / (A) layer / (B) layer is A laminated unstretched film having a thickness of 15/75/15 and a thickness of 720 μm was obtained. The unstretched film was biaxially stretched at 125 ° C. 4.0 times in the longitudinal direction and 4.5 times in the transverse direction, and 4
A 0 μm biaxially stretched film was obtained. The properties of the obtained film are shown in Table 1. The film obtained in this example has excellent film characteristics such as transparency, slipperiness, and scratch resistance, and also has a good operation index during film formation.
【００３５】比較例 ６ 実施例３の架橋アクリル系重合体粒子に替えて、平均粒
径３．５μｍの不定形シリカを０．４重量％配合する以
外、実施例３と同じ方法でフイルムを得た。得られたフ
イルムの特性を表１に示す。本比較例で得たフイルム
は、滑り性が劣る。Comparative Example 6 A film was obtained in the same manner as in Example 3 except that 0.4% by weight of amorphous silica having an average particle size of 3.5 μm was blended in place of the crosslinked acrylic polymer particles of Example 3. It was The properties of the obtained film are shown in Table 1. The film obtained in this comparative example is inferior in slipperiness.
【００３６】比較例 ７ 実施例３の架橋アクリル系重合体粒子の架橋剤をトリメ
チロールプロパントリメタアクリレートに替えて、エチ
レングリコールジメタアクリレートとするする以外、実
施例１と同じ方法でフイルムを得た。得られたフイルム
の特性を表１に示す。本比較例で得たフイルムは、透明
性、滑り性、耐スクラッチ性に優れているが、製膜時の
操業指数が劣る。Comparative Example 7 A film was obtained in the same manner as in Example 1 except that ethylene glycol dimethacrylate was used instead of trimethylolpropane trimethacrylate as the crosslinking agent for the crosslinked acrylic polymer particles of Example 3. It was The properties of the obtained film are shown in Table 1. The film obtained in this comparative example is excellent in transparency, slipperiness, and scratch resistance, but the operation index during film formation is inferior.
【００３７】実施例 ４ メルトインデックス５ｇ／１０分のプロピレン−エチレ
ンのランダム共重合体（エチレン含有量５重量％）１０
０重量部にステアリン酸アマイド０．２５重量部と平均
粒径が５μｍの架橋アクリル系重合体粒子〔組成は実施
例１と同じ〕０．３重量部を配合し樹脂温度２５０℃で
溶融押出しし、２５℃の冷却ロールで急冷することによ
り厚さ４０μｍのキャストフイルムを得た。得られたキ
ャストフイルムの特性を表１に示す。本実施例で得たフ
イルムは、透明性、滑り性、耐スクラッチ性に優れてお
り、かつ製膜時の操業指数も良好である。Example 4 Propylene-ethylene random copolymer having a melt index of 5 g / 10 min (ethylene content 5% by weight) 10
0 part by weight of 0.25 part by weight of stearic acid amide and 0.3 part by weight of crosslinked acrylic polymer particles having an average particle size of 5 μm (composition is the same as in Example 1) were mixed and melt extruded at a resin temperature of 250 ° C. A cast film having a thickness of 40 μm was obtained by quenching with a cooling roll at 25 ° C. Table 1 shows the properties of the obtained cast film. The film obtained in this example is excellent in transparency, slipperiness, and scratch resistance, and also has a good operation index during film formation.
【００３８】比較例 ８ 実施例４の架橋アクリル系重合体粒子に替えて、平均粒
径５．０μｍの球状ゼオライトを０．３重量部配合する
以外、実施例４と同じ方法でキャストフイルムを得た。
得られたキャストフイルムの特性を表１に示す。本比較
例で得たフイルムは、透明性および耐スクラッチ性が劣
る。Comparative Example 8 A cast film was obtained in the same manner as in Example 4, except that 0.3 part by weight of spherical zeolite having an average particle size of 5.0 μm was blended in place of the crosslinked acrylic polymer particles of Example 4. It was
Table 1 shows the properties of the obtained cast film. The film obtained in this comparative example is inferior in transparency and scratch resistance.
【００３９】実施例 ５ メルトインデックス２．０ｇ／１０分のオクテン共重合
の線状低密度ポリエチレン１００重量部にオレイン酸ア
マイド０．２５重量部と平均粒径が３．５μｍの架橋ア
クリル系重合体粒子０．４０重量部を配合し、実施例４
と同じ方法で６０μｍの厚さのキャストフイルムを得
た。得られたキャストフイルムの特性を表１に示す。本
実施例で得たフイルムは、透明性、滑り性および耐スク
ラッチ性に優れており、かつ製膜時の操業指数も良好で
ある。Example 5 100 parts by weight of linear low-density polyethylene copolymerized with octene having a melt index of 2.0 g / 10 min, 0.25 part by weight of amide oleate and a crosslinked acrylic polymer having an average particle size of 3.5 μm Example 4 was compounded with 0.40 part by weight of particles.
A cast film having a thickness of 60 μm was obtained by the same method as described above. Table 1 shows the properties of the obtained cast film. The film obtained in this example is excellent in transparency, slipperiness and scratch resistance, and also has a good operation index during film formation.
【００４０】比較例 ９ 実施例５の架橋アクリル系重合体粒子に替えて、平均粒
径３．５μｍの珪藻土よりなる粒子０．４０重量部を配
合する以外、実施例５と同じ方法でキャストフイルムを
得た。得られたキャストフイルムの特性を表１に示す。
本比較例で得られたフイルムは、製膜時の操業指数も良
好であるが、透明性、滑り性、耐スクラッチ性いずれも
が劣るものであった。Comparative Example 9 A cast film was prepared in the same manner as in Example 5 except that 0.40 parts by weight of particles of diatomaceous earth having an average particle size of 3.5 μm were used in place of the crosslinked acrylic polymer particles of Example 5. Got Table 1 shows the properties of the obtained cast film.
The film obtained in this comparative example had a good operation index at the time of film formation, but was poor in all of transparency, slipperiness and scratch resistance.
【００４１】[0041]
【表１】 [Table 1]
【００４２】[0042]
【発明の効果】本発明のフイルムは、上記のように特定
構造の架橋剤で架橋したポリアクリル酸系重合体の架橋
粒子を特定量ポリオレフィン樹脂に配合した組成物によ
り構成されているので、透明性に優れ、滑り性や耐スク
ラッチ性が良く、更に、製膜時のダイスの汚染が少なく
製膜操業性に優れた実用性の高いものである。The film of the present invention is composed of a composition in which a specific amount of cross-linked particles of a polyacrylic acid-based polymer cross-linked with a cross-linking agent having a specific structure as described above is blended with a polyolefin resin, so that it is transparent. It has excellent practicability, good slipperiness and scratch resistance, less contamination of the die during film formation, and excellent film forming operability, which is highly practical.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成５年７月１９日[Submission date] July 19, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１１】該３価以上の多価アルコールのアクリル酸
および／またはメタアクリル酸のエステルは、架橋重合
体粒子中に０．０１〜１０重量％の範囲で含まれるよう
添膜するのが好ましい。０．０１重量％未満の添加量で
は粒子の耐熱性が悪化し製膜操業性が低下するので好ま
しくない。逆に１０重量％の添加量を越えると耐熱性向
上効果が飽和し、かつ粒子が硬くなるためフイルムの耐
スクラッチ性が悪くなるので好ましくない。It is preferable that the ester of acrylic acid and / or methacrylic acid of a trihydric or higher polyhydric alcohol is added to the crosslinked polymer particles so as to be contained in the range of 0.01 to 10 % by weight. If the addition amount is less than 0.01% by weight, the heat resistance of the particles is deteriorated and the film forming operability is deteriorated, which is not preferable. On the other hand, if the amount added exceeds 10% by weight, the heat resistance improving effect is saturated and the particles become hard, so that the scratch resistance of the film deteriorates, which is not preferable.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２２[Name of item to be corrected] 0022
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２２】（１）曇価 ＪＩＳＥ−Ｋ６７１４に従い、東洋精機ヘーズテスター
Ｊで測定した。[0022] In accordance with (1) haze JISE-K6714, was measured by Toyo Seiki haze testers J.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井坂 勤 兵庫県西宮市小松北町１丁目６番Ｆ202 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Tsutomu Isaka 1-6-6 F202, Komatsukitamachi, Nishinomiya-shi, Hyogo
Claims (1)
て平均粒径０．４〜７μｍの３価以上の多価アルコール
のアクリル酸および／またはメタアクリル酸のエステル
で架橋したポリアクリル酸系重合体の架橋粒子を０．０
０５〜２重量部配合した組成物からなることを特徴とす
るポリオレフィン樹脂フイルム。1. A polyacrylic acid-based polymer crosslinked with an acrylic acid and / or methacrylic acid ester of a polyhydric alcohol having a valence of 3 or more and having an average particle diameter of 0.4 to 7 μm with respect to 100 parts by weight of a polyolefin resin. Crosslinked particles 0.0
A polyolefin resin film comprising a composition blended in an amount of 05 to 2 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5192871A JPH0726074A (en) | 1993-07-06 | 1993-07-06 | Polyolefin resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5192871A JPH0726074A (en) | 1993-07-06 | 1993-07-06 | Polyolefin resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0726074A true JPH0726074A (en) | 1995-01-27 |
Family
ID=16298364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5192871A Pending JPH0726074A (en) | 1993-07-06 | 1993-07-06 | Polyolefin resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0726074A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9692825B2 (en) | 2010-11-16 | 2017-06-27 | Intel Corporation | Endpoint caching for data storage systems |
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|---|---|---|---|---|
| JPS61181837A (en) * | 1985-02-06 | 1986-08-14 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin film |
| JPH04189837A (en) * | 1990-11-22 | 1992-07-08 | Kao Corp | Fine particle-containing polyolefin film |
| JPH05214120A (en) * | 1992-02-07 | 1993-08-24 | Toray Ind Inc | Biaxially oriented polypropylene film |
| JPH0673106A (en) * | 1992-06-16 | 1994-03-15 | Nippon Shokubai Co Ltd | Resin particle its production and use |
-
1993
- 1993-07-06 JP JP5192871A patent/JPH0726074A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61181837A (en) * | 1985-02-06 | 1986-08-14 | Japan Synthetic Rubber Co Ltd | Thermoplastic resin film |
| JPH04189837A (en) * | 1990-11-22 | 1992-07-08 | Kao Corp | Fine particle-containing polyolefin film |
| JPH05214120A (en) * | 1992-02-07 | 1993-08-24 | Toray Ind Inc | Biaxially oriented polypropylene film |
| JPH0673106A (en) * | 1992-06-16 | 1994-03-15 | Nippon Shokubai Co Ltd | Resin particle its production and use |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9692825B2 (en) | 2010-11-16 | 2017-06-27 | Intel Corporation | Endpoint caching for data storage systems |
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