JP2000109598A - Polyolefin resin film - Google Patents
Polyolefin resin filmInfo
- Publication number
- JP2000109598A JP2000109598A JP10294648A JP29464898A JP2000109598A JP 2000109598 A JP2000109598 A JP 2000109598A JP 10294648 A JP10294648 A JP 10294648A JP 29464898 A JP29464898 A JP 29464898A JP 2000109598 A JP2000109598 A JP 2000109598A
- Authority
- JP
- Japan
- Prior art keywords
- organic polymer
- porous spherical
- film
- polyolefin resin
- resin film
- 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
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、透明性、滑り性、
耐ブロッキング性、耐スクラッチ性に優れ、更に製膜時
ダイスリップに発生する「目脂」と称される樹脂滴の発
生が少なく、膜生産性に優れたポリオレフィン樹脂フィ
ルムに関する。[0001] The present invention relates to transparency, slipperiness,
The present invention relates to a polyolefin resin film which is excellent in blocking resistance and scratch resistance, has less occurrence of resin droplets called "eye oil" generated in die slip during film formation, and is excellent in film productivity.
【0002】[0002]
【従来の技術】従来、ポリオレフィン樹脂フィルムの滑
り性、耐ブロッキング性を改良する方法として、樹脂に
微粉末のシリカ、タルク等の無機微粒子を添加したもの
や、有機高分子架橋粒子を添加する方法が知られてい
る。これらの方法の中で有機高分子架橋粒子を添加する
方法は、無機微粒子を添加する方法に比べて、透明性、
耐スクラッチ性に優れたポリオレフィン樹脂フィルムが
得られる(特開平5−214120)。しかし、有機高
分子架橋粒子を添加する方法は、無機微粒子を添加する
方法に比べて、製膜時の「目脂」の発生率が高く、その
「目脂」がフィルム上に付着するとフィルムに傷を作る
のでそれを除去する必要があり、ダイスリップの掃除の
回数が多くなって、膜生産性が低下するという問題があ
った。2. Description of the Related Art Conventionally, as a method for improving the slipperiness and blocking resistance of a polyolefin resin film, a method in which fine inorganic particles such as silica or talc are added to a resin, and a method in which organic polymer crosslinked particles are added. It has been known. Among these methods, the method of adding the organic polymer crosslinked particles is more transparent than the method of adding the inorganic fine particles,
A polyolefin resin film having excellent scratch resistance can be obtained (JP-A-5-214120). However, the method of adding the organic polymer cross-linked particles has a higher incidence of "eye oil" during film formation than the method of adding the inorganic fine particles, and when the "eye oil" adheres to the film, the film becomes Since a scratch is formed, it is necessary to remove it, and there is a problem that the frequency of cleaning the die slip increases, and the film productivity decreases.
【0003】[0003]
【発明が解決しようとする課題】本発明は、透明性、滑
り性、耐ブロッキング性、耐スクラッチ性に優れ、更に
製膜時の「目脂」と呼ばれるダイスの汚染が少なく、膜
生産性に優れたポリオレフィン樹脂フィルムを提供する
ことにある。DISCLOSURE OF THE INVENTION The present invention is excellent in transparency, slipperiness, blocking resistance, and scratch resistance, has less contamination of dies called "eye oil" at the time of film formation, and has improved film productivity. It is to provide an excellent polyolefin resin film.
【0004】[0004]
【課題を解決するための手段】本発明者らは種々検討の
結果、ポリオレフィン樹脂100重量部に対して平均粒
子径1〜20μmの多孔質球状有機高分子架橋粒子を
0.01〜3重量部配合することにより前述のすべての
課題が解決されることをつきとめ本発明を完成した。す
なわち、本発明は、(1)平均粒子径1〜20μmの多
孔質球状有機高分子架橋粒子を0.01〜1重量%含有
するポリオレフィン樹脂フィルム、(2)多孔質球状有
機高分子架橋粒子が、空隙率5〜50%で、孔の直径が
5〜5,000nmのものである前記(1)記載のポリ
オレフィン樹脂フィルム、および(3)多孔質球状有機
高分子架橋粒子が、アルキル(メタ)アクリレート50
〜99.9重量%、分子内に2個以上のビニル基を有す
る多官能性モノマー0.1〜30重量%及びその他の共
重合性モノマー0〜49.9重量%からなるモノマー混
合物を多孔質化剤の存在下に共重合して得られた物であ
る前記(1)記載のポリオレフィン樹脂フィルム、であ
る。As a result of various studies, the present inventors have found that, based on 100 parts by weight of a polyolefin resin, 0.01 to 3 parts by weight of a porous spherical organic polymer crosslinked particle having an average particle diameter of 1 to 20 μm. The inventors of the present invention have found that all the above-mentioned problems can be solved by blending, and have completed the present invention. That is, the present invention relates to (1) a polyolefin resin film containing 0.01 to 1% by weight of porous spherical organic polymer crosslinked particles having an average particle diameter of 1 to 20 μm, and (2) a porous spherical organic polymer crosslinked particle. The polyolefin resin film according to (1), wherein the porosity is 5 to 50% and the pore diameter is 5 to 5,000 nm; and (3) the porous spherical organic polymer crosslinked particles are alkyl (meth) Acrylate 50
A monomer mixture comprising 0.1 to 30% by weight of a polyfunctional monomer having two or more vinyl groups in the molecule and 0 to 49.9% by weight of another copolymerizable monomer. The polyolefin resin film according to the above (1), which is obtained by copolymerization in the presence of an agent.
【0005】[0005]
【発明の実施の形態】本発明における多孔質球状有機高
分子架橋性粒子を配合するポリオレフィン樹脂フィルム
には、たとえば、エチレン、プロピレン、ブテン、4−
メチルペンテン−1等主鎖の炭素数が2〜6のオレフィ
ン系炭化水素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あげられる。本発明における多
孔質球状有機高分子架橋粒子とは、アルキル(メタ)ア
クリレート50〜99.9重量%、分子内に2個以上の
ビニル基を有する多官能性モノマー0.1〜30重量%
およびその他の共重合性モノマー0〜49.9重量%か
らなるモノマー混合物を多孔質化剤の存在下に共重合す
ることにより得られる。前記のアルキル(メタ)アクリ
レートとしては、メチル(メタ)アクリレート、エチル
(メタ)アクリレート、プロピル(メタ)アクリレー
ト、ブチル(メタ)アクリレート、シクロヘキシル(メ
タ)アクリレート、2−エチルヘキシル(メタ)アクリ
レート、イソノニル(メタ)アクリレート等アルキル基
の炭素数が1〜10の物が挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin resin film containing the porous spherical organic polymer crosslinkable particles according to the present invention includes, for example, ethylene, propylene, butene, 4-
Examples thereof include homopolymers or copolymers of olefinic hydrocarbons having 2 to 6 carbon atoms in the main chain such as methylpentene-1, or a mixture of these polymers. The porous spherical organic polymer crosslinked particles in the present invention are defined as 50 to 99.9% by weight of an alkyl (meth) acrylate and 0.1 to 30% by weight of a polyfunctional monomer having two or more vinyl groups in a molecule.
And a monomer mixture consisting of 0 to 49.9% by weight of other copolymerizable monomers in the presence of a porosifying agent. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isononyl ( An alkyl group such as meth) acrylate having 1 to 10 carbon atoms is exemplified.
【0006】分子内に2個以上のビニル基を有する多官
能性モノマーとしては、ジビニルベンゼン等の芳香族ジ
ビニルモノマー、エチレングリコールジ(メタ)アクリ
レート、ブチレングリコールジ(メタ)アクリレート、
ヘキサンジオールジ(メタ)アクリレート、トリメチロ
ールプロパンジ(メタ)アクリレート、トリメチロール
プロパントリ(メタ)アクリレート等のアルカンポリオ
ールポリ(メタ)アクリレート、アリル(メタ)アクリ
レート、ジアリルイタコネート等の異なる反応性のビニ
ル基を有するモノマー、その他ウレタンジ(メタ)アク
リレート、エポキシ(メタ)アクリレート等が挙げられ
る。その他の共重合性モノマーとしては、スチレン、ビ
ニルトルエン、α−メチルスチレン等の芳香族ビニル、
芳香族ビニリデン、アクリロニトリル、メタクリロニト
リル等のシアン化ビニル、シアン化ビニリデン、ウレタ
ン(メタ)アクリレート等が挙げられる。また、官能基
を持ったモノマーを共重合させることもできる。たとえ
ば、グリシジルメタクリレート等のエポキシ基を持つモ
ノマー、アクリル酸、メタクリル酸、マレイン酸、イタ
コン酸等のカルボキシル基を持つモノマー、2−ヒドロ
キシエチル(メタ)アクリレート等の水酸基を持つモノ
マー、ジエチルアミノエチル(メタ)アクリレート等の
アミノ基を持つモノマー等が挙げられる。本発明におけ
る多孔質球状有機高分子架橋粒子の合成方法は、乳化重
合、懸濁重合、分散重合等の方法が用いられ、好ましく
は、懸濁重合を行う。懸濁重合は、先に述べたモノマー
混合物、分散安定剤、界面活性剤、油溶性ラジカル重合
開始剤、多孔質化剤等を用いて行われる。油溶性のラジ
カル重合開始剤及び多孔質化剤は、先に述べたモノマー
混合物に予め溶解または、分散させておくことが望まし
い。Examples of polyfunctional monomers having two or more vinyl groups in the molecule include aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and the like.
Different reactivity of alkane polyols such as hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, poly (meth) acrylate, allyl (meth) acrylate, diallyl itaconate Examples of the monomer include a vinyl group-containing monomer, urethane di (meth) acrylate, and epoxy (meth) acrylate. As other copolymerizable monomers, styrene, vinyl toluene, aromatic vinyl such as α-methylstyrene,
Examples thereof include vinyl cyanide such as aromatic vinylidene, acrylonitrile, and methacrylonitrile, vinylidene cyanide, and urethane (meth) acrylate. Further, a monomer having a functional group can be copolymerized. For example, a monomer having an epoxy group such as glycidyl methacrylate, a monomer having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid; a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; ) Monomers having an amino group such as acrylate. As a method for synthesizing the porous spherical organic polymer crosslinked particles in the present invention, methods such as emulsion polymerization, suspension polymerization, and dispersion polymerization are used, and preferably, suspension polymerization is performed. The suspension polymerization is carried out using the above-mentioned monomer mixture, dispersion stabilizer, surfactant, oil-soluble radical polymerization initiator, porogen, and the like. It is desirable that the oil-soluble radical polymerization initiator and the porogen are previously dissolved or dispersed in the monomer mixture described above.
【0007】分散安定剤としては、ゼラチン、メチルセ
ルロース、ヒドロキシエチルセルロース、ヒドロキシプ
ロピルセルロース、カルボキシメチルセルロース、ポリ
エチレングリコール、ポリアクリルアミド、ポリアクリ
ル酸、ポリアクリル酸塩、アルギン酸ナトリウム、ポリ
ビニルアルコールの部分ケン化物等の水溶性高分子、リ
ン酸三カルシウム、酸化チタン、炭酸カルシウム、二酸
化珪素等の無機物などが用いられる。また、これらの分
散安定剤は、一種類または二種類以上使用できる。界面
活性剤としては、ドデシルベンゼンスルホン酸ナトリウ
ム、ジアルキルスルホコハク酸エステルナトリウム、ラ
ウリル硫酸ナトリウム等のアニオン界面活性剤、ポリエ
チレングリコールノニルフェニルエーテル等のノニオン
界面活性剤等が用いられる。また、これらの界面活性剤
は、一種類または二種類以上使用できる。油溶性ラジカ
ル重合開始剤としては、ベンゾイルパーオキサイド、o
−メトキシベンゾイルパーオキサイド、o−クロロベン
ゾイルパーオキサイド、ラウロイルパーオキサイド、ク
メンハイドロパーオキサイド等の有機過酸化物、2,
2′−アゾビスイソブチロニトリル、2,2′−アゾビ
ス−2,4−ジメチルバレロニトリル等のアゾ系化合物
等が用いられる。また、これらの油溶性ラジカル重合開
始剤は、一種類または二種類以上使用できる。Examples of the dispersion stabilizer include aqueous solutions of gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, polyethylene glycol, polyacrylamide, polyacrylic acid, polyacrylate, sodium alginate and partially saponified polyvinyl alcohol. Inorganic substances such as conductive polymers, tricalcium phosphate, titanium oxide, calcium carbonate, and silicon dioxide are used. One or more of these dispersion stabilizers can be used. Examples of the surfactant include anionic surfactants such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, and sodium lauryl sulfate, and nonionic surfactants such as polyethylene glycol nonylphenyl ether. One or more of these surfactants can be used. Examples of oil-soluble radical polymerization initiators include benzoyl peroxide, o
Organic peroxides such as -methoxybenzoyl peroxide, o-chlorobenzoyl peroxide, lauroyl peroxide, cumene hydroperoxide,
Azo compounds such as 2'-azobisisobutyronitrile and 2,2'-azobis-2,4-dimethylvaleronitrile are used. One or more of these oil-soluble radical polymerization initiators can be used.
【0008】多孔質化剤は有機高分子架橋粒子を多孔質
化する物質であり、いくつかの種類のものがあげられ
る。そのうちの1つとして、たとえばトルエン、イソオ
クタン、メチルイソブチルケトン等のように、先に述べ
たモノマー混合物には溶解するが、その重合後のポリマ
ーには溶解しない溶剤があげられる。この場合、溶剤の
使用量はモノマー混合物100重量部に対し20〜20
0重量部程度であり、用いた多孔質化剤は、粒子の乾燥
工程で除去され、該溶剤が除去された部分が細孔とな
る。また、別の多孔質化剤として、たとえば炭酸カルシ
ウム、リン酸三カルシウム等のように強酸によって溶解
する無機物を用いることができる。この場合、無機物の
使用量はモノマー混合物100重量部に対し20〜20
0重量部程度であり、用いた多孔質化剤は、重合終了後
の粒子を精製する工程で強酸によって溶解させる事によ
って取り除かれ、その溶解して取り除かれた部分が細孔
となる。さらに別の多孔質化剤として、たとえばポリ
(メタ)アクリル酸アルキル等のように、先に述べたモ
ノマー混合物に溶解する直鎖状のポリマーが用いられ
る。この場合の直鎖状ポリマーの使用量はモノマー混合
物100重量部に対し1〜10重量部程度であり、先に
述べたモノマー混合物が重合を進めて行く過程におい
て、溶解させておいた直鎖状のポリマーと相分離を起こ
し、粒子が多孔質化する。用いられる直鎖状のポリマー
の種類は特に制限はないが、ポリマーの種類により、細
孔の形や大きさが異なってくる。これらの多孔質球状高
分子架橋粒子を得る多孔質化剤は、一種類または二種類
以上を併用してもかまわない。[0008] Porous agents are substances that make organic polymer crosslinked particles porous, and include several types. One of them is a solvent such as toluene, isooctane, methyl isobutyl ketone, which is soluble in the above-mentioned monomer mixture but is insoluble in the polymer after polymerization. In this case, the amount of the solvent used is 20 to 20 parts by weight per 100 parts by weight of the monomer mixture.
It is about 0 parts by weight, and the used porogen is removed in the step of drying the particles, and the portion from which the solvent has been removed becomes pores. Further, as another porous agent, an inorganic substance which can be dissolved by a strong acid such as calcium carbonate and tricalcium phosphate can be used. In this case, the amount of the inorganic substance used is 20 to 20 parts by weight per 100 parts by weight of the monomer mixture.
It is about 0 parts by weight, and the used porosifying agent is removed by dissolving with a strong acid in the step of purifying the particles after the polymerization, and the dissolved and removed portions become pores. As another porogen, for example, a linear polymer soluble in the above-mentioned monomer mixture, such as poly (alkyl methacrylate), is used. In this case, the amount of the linear polymer used is about 1 to 10 parts by weight based on 100 parts by weight of the monomer mixture. Causes phase separation with the polymer, and the particles become porous. The type of linear polymer used is not particularly limited, but the shape and size of the pores differ depending on the type of polymer. These porous spherical polymer crosslinked particles may be used alone or in combination of two or more.
【0009】本発明に用いられる多孔質球状有機高分子
架橋粒子の平均粒子径は通常1〜20μm、好ましくは
2〜15μmの範囲である。平均粒子径が上記範囲より
小さい場合には、耐ブロッキング性の効果が小さくな
り、多量の添加量を必要とし、ポリオレフィン樹脂フィ
ルムの透明性が損なわれる。一方、平均粒子径が上記範
囲より大きい場合はフィルムにザラつき感が生じ、透明
性も損なわれる。本発明の粒子における「球状」とは必
ずしも真球状のものでなくてもよく、大きな突起のない
粒子状という意味である。上記の方法で得られた多孔質
球状有機高分子架橋粒子は、空隙率5〜50%で、孔の
直径が5〜5,000nmの範囲であることが好まし
く、この範囲からはずれると十分なアンカー効果が得ら
れず、「目脂」の発生を軽減することはできない。上記
の方法で得られた多孔質球状有機高分子架橋粒子のポリ
オレフィン樹脂に対する配合割合は、ポリオレフィン樹
脂100重量部に対して通常0.01〜3重量部、好ま
しくは0.1〜1重量部である。配合割合が上記範囲よ
り小さい場合には、十分な滑り性、耐ブロッキング性を
付与することができない。一方、配合割合が上記範囲よ
り大きい場合には、十分な滑り性、耐ブロッキング性は
付与されるが、著しく透明性が阻害される。The average particle size of the porous spherical organic polymer crosslinked particles used in the present invention is usually in the range of 1 to 20 μm, preferably 2 to 15 μm. When the average particle size is smaller than the above range, the effect of blocking resistance is reduced, a large amount is required, and the transparency of the polyolefin resin film is impaired. On the other hand, when the average particle size is larger than the above range, the film has a grainy feeling and transparency is impaired. “Spherical” in the particles of the present invention does not necessarily have to be a true sphere, but means a particle without large projections. The porous spherical organic polymer cross-linked particles obtained by the above method preferably have a porosity of 5 to 50% and a pore diameter of 5 to 5,000 nm. No effect is obtained, and the generation of "eye oil" cannot be reduced. The compounding ratio of the porous spherical organic polymer crosslinked particles obtained by the above method to the polyolefin resin is usually from 0.01 to 3 parts by weight, preferably from 0.1 to 1 part by weight, per 100 parts by weight of the polyolefin resin. is there. If the compounding ratio is smaller than the above range, sufficient sliding properties and blocking resistance cannot be imparted. On the other hand, when the mixing ratio is larger than the above range, sufficient slipperiness and blocking resistance are imparted, but transparency is significantly impaired.
【0010】多孔質球状有機高分子架橋粒子の平均粒子
径や樹脂の配合の最適値は、ポリオレフィン樹脂の種
類、ポリオレフィン樹脂フィルムの厚みや構成、延伸の
有無等により大きく変化するので、目的とするポリオレ
フィン樹脂フィルムの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。本発明では、本発明の効果
を阻害しない範囲であれば、多孔質球状有機高分子架橋
粒子以外の添加剤を配合してもかまわない。添加剤とし
ては、酸化防止剤、紫外線吸収剤等の各種安定剤、滑
剤、帯電防止剤など、場合によっては無機質の充填剤等
も挙げられる。上記した多孔質球状有機高分子架橋粒子
や添加剤などの混合方法としては、特に限定されるもの
ではないが、ヘンシルミキサー、タンブラー等で混合
し、単軸もしくは二軸押し出し機で溶融混練し、ペレッ
ト化するのが一般的である。本発明では、単に押し出し
成型した未延伸のキャスティングフィルムにも、同キャ
スティングフィルムを1軸または2軸方向に延伸した延
伸フィルムの何れについても適用できる。また、単層構
成及び多層構成の何れについても適用できる。多層構成
の場合は、上記した多孔質球状有機高分子架橋粒子は、
表面層に添加するのが一般的であるが、これに限定しな
い。The average particle size of the porous spherical organic polymer cross-linked particles and the optimum value of the resin composition greatly vary depending on the type of polyolefin resin, the thickness and configuration of the polyolefin resin film, the presence or absence of stretching, and the like. It is preferable to appropriately set the above range appropriately in accordance with the characteristics of the polyolefin resin film. In the present invention, additives other than the porous spherical organic polymer crosslinked particles may be blended as long as the effects of the present invention are not impaired. Examples of the additive include various stabilizers such as an antioxidant and an ultraviolet absorber, a lubricant, an antistatic agent, and in some cases, an inorganic filler. The method of mixing the above-mentioned porous spherical organic polymer crosslinked particles and additives is not particularly limited, but is mixed with a Hensyl mixer, a tumbler or the like, and melt-kneaded with a single or twin screw extruder. In general, pelletization is performed. In the present invention, the present invention can be applied to an unstretched casting film simply extruded or a stretched film obtained by stretching the casting film in a uniaxial or biaxial direction. Further, the present invention can be applied to both a single-layer configuration and a multilayer configuration. In the case of a multilayer structure, the porous spherical organic polymer crosslinked particles described above are:
It is generally added to the surface layer, but is not limited to this.
【0011】[0011]
【実施例】以下に本発明を参考例、実施例および比較例
に基づきさらに具体的に説明するが、本発明はこれらに
より限定されるものではない。 参考例1 多孔質球状有機高分子架橋粒子の調製 水555gにポリビニルアルコール(クラレポバール2
05、(株)クラレ製)5gを溶解させた水溶液に、メ
チルメタクリレート190g、トリメチロールプロパン
トリメタクリレート10g、ラウロイルパーオキサイド
1g、メチルイソブチルケトン100gからなる混合液
を加え、これをホモミキサーを用いて撹拌し、モノマー
混合液の分散液を調製した。この際ホモミキサーの撹拌
翼の回転数をそれぞれ5,000rpm、3,200rp
mおよび2,100rpmとして撹拌し、3種類の粒子
径の異なる分散溶液を調製した。このそれぞれの分散溶
液を撹拌機、還流冷却器、温度計、窒素吹き込み口を備
えた4つ口フラスコに移し、窒素気流下で撹拌しなが
ら、60℃に昇温し、そのまま3時間反応した。得られ
た懸濁液を室温まで冷却後、濾別水洗し、フィルターケ
ーキを110℃で24時間乾燥させて、多孔質球状有機
高分子架橋粒子を得た。得られた多孔質球状有機高分子
架橋粒子を粒子径の小さい方からそれぞれA−1、A−
2、A−3とした。その粒子の性状を〔表1〕に示す。EXAMPLES The present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these. Reference Example 1 Preparation of Porous Spherical Organic Polymer Cross-Linked Particles To 555 g of water was added polyvinyl alcohol (Kuraray Povar 2).
05, manufactured by Kuraray Co., Ltd.), a mixed solution consisting of 190 g of methyl methacrylate, 10 g of trimethylolpropane trimethacrylate, 1 g of lauroyl peroxide, and 100 g of methyl isobutyl ketone was added to an aqueous solution in which 5 g was dissolved. The mixture was stirred to prepare a dispersion of the monomer mixture. At this time, the rotation speed of the stirring blade of the homomixer was set to 5,000 rpm and 3,200 rpm, respectively.
The mixture was stirred at m and 2,100 rpm to prepare three types of dispersion solutions having different particle diameters. Each of the dispersion solutions was transferred to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet. The temperature was raised to 60 ° C. while stirring under a nitrogen stream, and the reaction was allowed to proceed for 3 hours. The obtained suspension was cooled to room temperature, filtered and washed with water, and the filter cake was dried at 110 ° C. for 24 hours to obtain porous spherical organic polymer crosslinked particles. The obtained porous spherical organic polymer cross-linked particles were A-1 and A-
2, A-3. The properties of the particles are shown in [Table 1].
【0012】参考例2 非多孔質球状有機高分子架橋粒子の調製 水555gにポリビニルアルコール(クラレポバール2
05(株)クラレ製)5gを溶解させた水溶液に、メチ
ルメタクリレート190g、トリメチロールプロパント
リメタクリレート10g、ラウロイルパーオキサイド1
gの混合液を加えた。これをホモミキサーを用いて撹拌
し、モノマー混合液の分散溶液を調製した。この際ホモ
ミキサーの撹拌の強さを参考例1と同様に3段階に変
え、3種類の粒子径の異なる分散溶液を調製した。この
それぞれの分散溶液を撹拌機、還流冷却器、温度計、窒
素吹き込み口を備えた4つ口フラスコに移し、窒素気流
下で撹拌しながら、60℃に昇温し、そのまま3時間反
応した。得られた懸濁液を室温まで冷却後、濾別水洗
し、フィルターケーキを110℃で24時間乾燥させ
て、非多孔質球状有機高分子架橋粒子を得た。得られた
非多孔質球状有機高分子架橋粒子を粒子径の小さい方か
らそれぞれB−1、B−2、B−3とした。その性状を
〔表1〕に示す。Reference Example 2 Preparation of Nonporous Spherical Organic Polymer Cross-Linked Particles 555 g of water was mixed with polyvinyl alcohol (Kuraray Povar 2).
05 (manufactured by Kuraray Co., Ltd.) in an aqueous solution having 5 g dissolved therein, 190 g of methyl methacrylate, 10 g of trimethylolpropane trimethacrylate, lauroyl peroxide 1
g of the mixture was added. This was stirred using a homomixer to prepare a dispersion of the monomer mixture. At this time, the intensity of stirring of the homomixer was changed to three stages as in Reference Example 1, and three types of dispersion solutions having different particle diameters were prepared. Each of the dispersion solutions was transferred to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet, and heated to 60 ° C. while stirring under a nitrogen stream, and reacted for 3 hours as it was. The obtained suspension was cooled to room temperature, filtered and washed with water, and the filter cake was dried at 110 ° C. for 24 hours to obtain nonporous spherical organic polymer crosslinked particles. The obtained non-porous spherical organic polymer crosslinked particles were designated as B-1, B-2, and B-3, respectively, from the smaller particle diameter. The properties are shown in [Table 1].
【0013】なお、前記各参考例において得られた粒子
の各種物性試験は、次の方法によって行った。 〔平均粒子径(μm)〕コールターマルチサイダーII
(コールター(株)製)により測定し、重量分布の算術
径の値を採用した。 〔空隙率(%)〕水銀圧入法より求めた。 〔孔の直径(nm)〕SEMにより孔の大きさを確認し
た。The physical properties of the particles obtained in each of the above Reference Examples were tested by the following methods. [Average particle size (μm)] Coulter Multisider II
(Manufactured by Coulter KK), and the value of the arithmetic diameter of the weight distribution was adopted. [Porosity (%)] It was determined by a mercury intrusion method. [Diameter of hole (nm)] The size of the hole was confirmed by SEM.
【0014】[0014]
【表1】 [Table 1]
【0015】実施例1 多孔質球状有機高分子架橋粒子A−1を0.3重量%を
含むポリプロピレンを樹脂温度270℃でTダイより押
し出し、厚さ30μmのフィルムを得た。得られたフィ
ルムは、透明性、滑り性、耐スクラッチ性に優れたフィ
ルムであり、更に製膜時の「目脂」の発生が少なかっ
た。得られたフィルムの性状を〔表2〕に示す。 比較例1 多孔質球状有機高分子架橋粒子A−1に替え、非多孔質
球状有機高分子架橋粒子B−1を用いたこと以外は実施
例1と同様の方法でフィルムを得た。得られたフィルム
は、透明性、滑り性、耐スクラッチ性に優れたフィルム
であったが、製膜時の「目脂」の発生が多かった。得ら
れたフィルムの性状を〔表2〕に示す。 比較例2 多孔質球状有機高分子架橋粒子A−1に替え、平均粒子
径の大きい多孔質球状有機高分子架橋粒子A−3を用い
た以外は、実施例1と同様の方法でフィルムを得た。得
られたフィルムは、滑り性、耐スクラッチ性に優れたフ
ィルムであるが、透明性が劣っていた。しかし製膜時の
「目脂」の発生は少なかった。得られたフィルムの性状
を〔表2〕に示す。 比較例3 多孔質球状有機高分子架橋粒子A−1に替え、微粉末の
シリカ(平均粒子径2.5μm)を用いた以外は、実施
例1と同様の方法でフィルムを得た。得られたフィルム
は、透明性、滑り性、耐スクラッチ性に劣っていたが、
製膜時の「目脂」の発生が少なかった。得られたフィル
ムの性状を〔表2〕に示す。Example 1 A polypropylene containing 0.3% by weight of porous spherical organic polymer crosslinked particles A-1 was extruded from a T-die at a resin temperature of 270 ° C. to obtain a film having a thickness of 30 μm. The obtained film was a film excellent in transparency, slipperiness and scratch resistance, and further, the generation of "eye oil" during film formation was small. The properties of the obtained film are shown in [Table 2]. Comparative Example 1 A film was obtained in the same manner as in Example 1 except that the porous spherical organic polymer crosslinked particles B-1 were used instead of the porous spherical organic polymer crosslinked particles A-1. The obtained film was excellent in transparency, slipperiness and scratch resistance, but generated much "eye oil" during film formation. The properties of the obtained film are shown in [Table 2]. Comparative Example 2 A film was obtained in the same manner as in Example 1, except that the porous spherical organic polymer crosslinked particles A-3 having a large average particle diameter were used instead of the porous spherical organic polymer crosslinked particles A-1. Was. The obtained film was excellent in slipperiness and scratch resistance, but was inferior in transparency. However, the generation of "eye oil" during film formation was small. The properties of the obtained film are shown in [Table 2]. Comparative Example 3 A film was obtained in the same manner as in Example 1, except that fine powdered silica (average particle diameter of 2.5 μm) was used instead of the porous spherical organic polymer crosslinked particles A-1. The resulting film was inferior in transparency, slipperiness and scratch resistance,
The generation of "eye oil" during film formation was small. The properties of the obtained film are shown in [Table 2].
【0016】実施例2 多孔質球状有機高分子架橋粒子A−2を0.3重量%含
むポリエチレンを樹脂温度240℃でTダイより押し出
し、厚さ20μmのフィルムを得た。得られたフィルム
は、透明性、滑り性、耐スクラッチ性に優れたフィルム
であり、さらに製膜時の「目脂」の発生が少なかった。
得られたフィルムの性状を〔表2〕に示す。 比較例4 多孔質球状有機高分子架橋粒子A−2に替え、非多孔質
球状有機高分子架橋粒子B−2を用いた以外は、実施例
2と同様の方法でフィルムを得た。得られたフィルム
は、透明性、滑り性、耐スクラッチ性に優れたフィルム
であるが、製膜時の「目脂」の発生が多かった。得られ
たフィルムの性状を〔表2〕に示す。 比較例5 多孔質球状有機高分子架橋粒子A−2に替え、平均粒子
径の大きい非多孔質球状有機高分子架橋粒子B−3を用
いた以外は、実施例2と同様の方法でフィルムを得た。
得られたフィルムは、滑り性、耐スクラッチ性に優れた
フィルムであるが、透明性が劣っていた。しかし製膜時
の「目脂」の発生は多かった。得られたフィルムの性状
を〔表2〕に示す。Example 2 A polyethylene containing 0.3% by weight of porous spherical organic polymer crosslinked particles A-2 was extruded from a T-die at a resin temperature of 240 ° C. to obtain a film having a thickness of 20 μm. The obtained film was a film excellent in transparency, slipperiness and scratch resistance, and further, the generation of "eye oil" during film formation was small.
The properties of the obtained film are shown in [Table 2]. Comparative Example 4 A film was obtained in the same manner as in Example 2, except that the porous spherical organic polymer crosslinked particles B-2 were used instead of the porous spherical organic polymer crosslinked particles A-2. The resulting film was excellent in transparency, slipperiness, and scratch resistance, but generated much "eye oil" during film formation. The properties of the obtained film are shown in [Table 2]. Comparative Example 5 A film was formed in the same manner as in Example 2 except that the non-porous spherical organic polymer crosslinked particles B-3 having a large average particle diameter were used instead of the porous spherical organic polymer crosslinked particles A-2. Obtained.
The obtained film was excellent in slipperiness and scratch resistance, but was inferior in transparency. However, "eye oil" was frequently generated during film formation. The properties of the obtained film are shown in [Table 2].
【0017】比較例6 多孔質球状有機高分子架橋粒子A−2に替え、微粉末の
シリカ(平均粒子径2.5μm)を用いた以外は、実施
例2と同様の方法でフィルムを得た。得られたフィルム
は、透明性、滑り性、耐スクラッチ性に劣っていたが、
製膜時の「目脂」の発生は少なかった。得られたフィル
ムの性状を〔表2〕に示す。なお、前記実施例および比
較例で得られた各フィルムの試験は次の方法によって行
った。 〔ヘイズ(%)〕JIS−K6714に準じ東洋精機ヘ
イズテスターJで測定した。 〔耐スクラッチ性〕JIS−LO823−1971に準
じ測定した。すなわち、東洋精機製染色堅牢度摩擦試験
機により200gfの荷重下、50回摩擦試験を行い、
試験前後の曇価の測定を行って曇価の増加度を測定し
た。 〔目脂の発生度合い〕2軸押し出し機(池貝鉄鋼(株)
製:PCM−30)を用い、ポリオレフィン樹脂と粒子
や添加剤などを溶融混練し、4kg/hrの吐出量で1
時間押し出し、ペレット化する際にダイスに発生する
「目脂」の発生量と、ペレットをTダイ(中外貿易製:
EXTRUDER(Type:MK−B4))によりフィルム化する
際の「目脂」の発生量を目視により観察し、その総合評
価を5段階の「目脂」発生度合いとして表示した(数字
の大きい方が「目脂」の発生量が多いことを表す)。Comparative Example 6 A film was obtained in the same manner as in Example 2 except that fine powdered silica (average particle diameter of 2.5 μm) was used instead of the porous spherical organic polymer crosslinked particles A-2. . The resulting film was inferior in transparency, slipperiness and scratch resistance,
The generation of "eye oil" during film formation was small. The properties of the obtained film are shown in [Table 2]. In addition, the test of each film obtained by the said Example and the comparative example was performed by the following method. [Haze (%)] The haze was measured using a haze tester J according to JIS-K6714. [Scratch resistance] Measured according to JIS-LO823-1971. That is, a 50 times friction test was performed under a load of 200 gf using a dyeing fastness friction tester manufactured by Toyo Seiki Co., Ltd.
The haze was measured before and after the test to determine the degree of increase in haze. [Occurrence of eye oil] Twin screw extruder (Ikegai Iron and Steel Co., Ltd.)
Using PCM-30), melt-knead the polyolefin resin and particles, additives, etc., and mix at a discharge rate of 4 kg / hr.
The amount of "greasy oil" generated in the dies when extruded and pelletized for a time, and the pellets are converted to T dies (manufactured by Chugai Trading:
EXTRUDER (Type: MK-B4)) was used to visually observe the amount of "smear" generated when forming a film, and the overall evaluation was displayed as a five-step "smear" generation degree (the larger the number, the better). This indicates that the amount of "eye oil" generated is large).
【0018】[0018]
【表2】 [Table 2]
【0019】[0019]
【発明の効果】本発明多孔質球状有機高分子架橋粒子を
配合したポリオレフィン樹脂フィルムは、透明性、滑り
性、耐ブロッキング性、耐スクラッチ性に優れ、製膜時
ダイスリップに発生しがちな「目脂」と称される樹脂滴
の発生が少なく生産性が向上するうえ、フィルム延伸の
際にも粒子がフィルムから脱落しないのでボイドの発生
が抑制される。The polyolefin resin film blended with the porous spherical organic polymer crosslinked particles of the present invention is excellent in transparency, slipperiness, blocking resistance and scratch resistance, and tends to occur on a die slip during film formation. The productivity is improved with less generation of resin droplets called "eye oil", and the generation of voids is suppressed because the particles do not fall off the film even when the film is stretched.
フロントページの続き Fターム(参考) 4F071 AA15 AA20 AA32 AD06 BC01 4F074 AA48 BA35 BA74 BA84 BB02 BB10 BB28 BC02 BC04 CA33 CB03 CB14 CB17 CB37 CC06W DA02 DA03 DA59 4J002 AA002 BB011 BB021 BB111 BB151 BB171 BC012 BG032 BG042 BG052 BG053 BG072 CD192 CD202 CK022 DE236 DH046 EA016 EA056 EE036 FA092 FD323 FD326 Continued on the front page F term (reference) 4F071 AA15 AA20 AA32 AD06 BC01 4F074 AA48 BA35 BA74 BA84 BB02 BB10 BB28 BC02 BC04 CA33 CB03 CB14 CB17 CB37 CC06W DA02 DA03 DA59 4J002 AA002 BB011 BB023 BG111 BG111 BG111 BB111 BG151 BB151 BB151 DE236 DH046 EA016 EA056 EE036 FA092 FD323 FD326
Claims (3)
高分子架橋粒子を0.01〜3重量%含有するポリオレ
フィン樹脂フィルム。1. A polyolefin resin film containing 0.01 to 3% by weight of porous spherical organic polymer crosslinked particles having an average particle diameter of 1 to 20 μm.
5〜50%で、孔の直径が5〜5,000nmのもので
ある請求項1記載のポリオレフィン樹脂フィルム。2. The polyolefin resin film according to claim 1, wherein the porous spherical organic polymer crosslinked particles have a porosity of 5 to 50% and a pore diameter of 5 to 5,000 nm.
ル(メタ)アクリレート50〜99.9重量%、分子内
に2個以上のビニル基を有する多官能性モノマー0.1
〜30重量%及びその他の共重合性モノマー0〜49.
9重量%からなるモノマーを多孔質化剤の存在下に混合
物を共重合して得られた物である請求項1記載のポリオ
レフィン樹脂フィルム。3. A crosslinked porous spherical organic polymer particle comprising 50 to 99.9% by weight of an alkyl (meth) acrylate, and a polyfunctional monomer having at least two vinyl groups in a molecule of 0.1.
~ 30% by weight and other copolymerizable monomers.
The polyolefin resin film according to claim 1, which is obtained by copolymerizing a mixture comprising 9% by weight of a monomer in the presence of a porosifying agent.
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JP29464898A JP3428462B2 (en) | 1998-09-30 | 1998-09-30 | Manufacturing method of polyolefin resin film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29464898A JP3428462B2 (en) | 1998-09-30 | 1998-09-30 | Manufacturing method of polyolefin resin film |
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JP3428462B2 JP3428462B2 (en) | 2003-07-22 |
Family
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003081738A (en) * | 2001-09-05 | 2003-03-19 | Gantsu Kasei Kk | Skin cosmetic including spherical porous crosslinked polymer particle |
JP2020050847A (en) * | 2018-09-28 | 2020-04-02 | アイカ工業株式会社 | Production method of polyolefin resin film |
-
1998
- 1998-09-30 JP JP29464898A patent/JP3428462B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003081738A (en) * | 2001-09-05 | 2003-03-19 | Gantsu Kasei Kk | Skin cosmetic including spherical porous crosslinked polymer particle |
JP4651883B2 (en) * | 2001-09-05 | 2011-03-16 | ガンツ化成株式会社 | Skin cosmetics containing spherical porous crosslinked polymer particles |
JP2020050847A (en) * | 2018-09-28 | 2020-04-02 | アイカ工業株式会社 | Production method of polyolefin resin film |
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