JP2005125530A - Biaxially oriented moistureproof polypropylene film - Google Patents
Biaxially oriented moistureproof polypropylene film Download PDFInfo
- Publication number
- JP2005125530A JP2005125530A JP2003361493A JP2003361493A JP2005125530A JP 2005125530 A JP2005125530 A JP 2005125530A JP 2003361493 A JP2003361493 A JP 2003361493A JP 2003361493 A JP2003361493 A JP 2003361493A JP 2005125530 A JP2005125530 A JP 2005125530A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene film
- propylene
- biaxially stretched
- moisture
- layer
- 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
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 110
- -1 polypropylene Polymers 0.000 title claims abstract description 87
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 82
- 239000010410 layer Substances 0.000 claims abstract description 57
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 50
- 239000004711 α-olefin Substances 0.000 claims abstract description 40
- 239000011247 coating layer Substances 0.000 claims abstract description 39
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 29
- 230000008018 melting Effects 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 239000012793 heat-sealing layer Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 14
- 238000010030 laminating Methods 0.000 abstract description 5
- 229920006378 biaxially oriented polypropylene Polymers 0.000 abstract description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 abstract description 4
- 238000003475 lamination Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 25
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- 239000005977 Ethylene Substances 0.000 description 20
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- 238000011156 evaluation Methods 0.000 description 10
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
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Landscapes
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Abstract
Description
本発明は防湿性、ラミネート強度及びガスバリア性に優れた二軸延伸防湿ポリプロピレンフィルムに関する。 The present invention relates to a biaxially stretched moisture-proof polypropylene film having excellent moisture resistance, laminate strength and gas barrier properties.
二軸延伸ポリプロピレンフィルム（以下ＯＰＰフィルムと呼ぶことがある）は、その優れた透明性、機械的強度、防湿性、剛性等を活かして包装材料をはじめ広い分野で使用されている。しかし、ＯＰＰフイルムは単層ではヒートシール可能温度が高くしかもヒートシールの適正な温度範囲が狭いという欠点がある。そこで、ＯＰＰフイルムのヒートシール性を改善するために、ＯＰＰフイルムの片面又は両面に低融点のプロピレン・エチレン共重合体層を積層した二軸延伸複合フィルム（特許文献１）、特定の三元ランダム共重合体層をヒートシール層としたフィルム（特許文献２）、特定のプロピレン・１−ブテンランダム共重合体と結晶性プロピレン・α―オレフィンランダム共重合体との組成物を積層したポリプロピレン複合フィルム（特許文献３）等、ポリプロピレンに比べて低融点の樹脂を積層させる方法が多数提案され、且つ、幅広く使用されている。
また、ＯＰＰフイルムの防湿性を更に改良するために、石油樹脂、テルペン樹脂等の粘着付与剤を添加する方法も多々提案されている（例えば、特許文献４〜５）。
Biaxially stretched polypropylene films (hereinafter sometimes referred to as OPP films) are used in a wide range of fields including packaging materials, taking advantage of their excellent transparency, mechanical strength, moisture resistance, rigidity, and the like. However, the OPP film has a drawback that a single layer has a high heat-sealable temperature and a narrow temperature range for heat-seal. Therefore, in order to improve the heat sealability of the OPP film, a biaxially stretched composite film (Patent Document 1) in which a low melting point propylene / ethylene copolymer layer is laminated on one side or both sides of an OPP film, a specific ternary random A film having a copolymer layer as a heat seal layer (Patent Document 2), a polypropylene composite film in which a composition of a specific propylene / 1-butene random copolymer and a crystalline propylene / α-olefin random copolymer is laminated A number of methods for laminating a resin having a lower melting point than polypropylene such as (Patent Document 3) have been proposed and widely used.
In order to further improve the moisture resistance of the OPP film, many methods for adding a tackifier such as petroleum resin and terpene resin have been proposed (for example, Patent Documents 4 to 5).
しかしながら、かかる方法で得られる複合フィルムは、低温ヒートシール強度は改良されるものの、ヒートシール層にプロピレン共重合体を用いることから、用途によっては、耐ブロッキング性、密封性がしばしば問題となり、耐ブロッキング性、密封性の改良が望まれている。また、無延伸のポリプロピレンフィルム（ＣＰＰ）やポリエチレンフィルムを複合フィルムにラミネートした場合に、ラミネート強度が不足するため、用途によっては、しばしば問題となりラミネート強度の向上も望まれている。 However, although the composite film obtained by such a method has improved low-temperature heat seal strength, a propylene copolymer is used for the heat seal layer. Improvements in blocking properties and sealing properties are desired. In addition, when unstretched polypropylene film (CPP) or polyethylene film is laminated on a composite film, the laminate strength is insufficient. Therefore, depending on the application, it often becomes a problem, and improvement of the laminate strength is also desired.
本発明の目的は、防湿性及びラミネート強度に優れた二軸延伸防湿ポリプロピレンフィルムの開発することにある。 An object of the present invention is to develop a biaxially stretched moisture-proof polypropylene film excellent in moisture resistance and laminate strength.
本発明は、粘着付与剤（Ｃ）３〜２５重量％を含むプロピレン系重合体（Ａ−１）組成物層から得られる二軸延伸ポリプロピレンフィルム基材層の片面に、ＤＳＣに基づく結晶融解曲線から求められたピーク温度（Ｔｐ）が１１０〜１４０℃及び融解開始温度（Ｔｓ）と融解終了温度（Ｔｅ）との差（Ｔｅ−Ｔｓ）が４５℃未満のプロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）が積層されてなることを特徴とする二軸延伸防湿ポリプロピレンフィルムに関する。 The present invention provides a crystal melting curve based on DSC on one side of a biaxially oriented polypropylene film substrate layer obtained from a propylene-based polymer (A-1) composition layer containing 3 to 25% by weight of a tackifier (C). A propylene / α-olefin copolymer having a peak temperature (Tp) determined from 110 to 140 ° C. and a difference (Te-Ts) between the melting start temperature (Ts) and the melting end temperature (Te) of less than 45 ° C. ( The coating layer (I) obtained from B) is laminated | stacked, It is related with the biaxial stretching moisture-proof polypropylene film characterized by the above-mentioned.
本発明は、また前記二軸延伸ポリプロピレンフィルム基材層の他の片面に、プロピレン系重合体（Ａ―２）から得られる被覆層（ＩＩ）、好ましくはブロッキング防止剤を含んでなる被覆層（ＩＩ）が積層されてなる二軸延伸防湿ポリプロピレンフィルムに関する。 The present invention also provides a coating layer (II) obtained from the propylene polymer (A-2) on the other surface of the biaxially oriented polypropylene film substrate layer, preferably a coating layer comprising an antiblocking agent ( II) relates to a biaxially stretched moisture-proof polypropylene film laminated.
本発明の他の態様はプロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）にビニルアルコール系重合体（Ｄ）層が積層されてなる二軸延伸防湿ポリプロピレンフィルムに関する。 Another embodiment of the present invention relates to a biaxially stretched moisture-proof polypropylene film in which a vinyl alcohol polymer (D) layer is laminated on a coating layer (I) obtained from a propylene / α-olefin copolymer (B).
本発明の二軸延伸防湿ポリプロピレンフィルムは被覆層（Ｉ）として特定の熱融解特性を有するプロピレン・α―オレフィン共重合体（Ｂ）を有し、二軸延伸ポリプロピレンフィルム基材層に粘着付与剤（Ｃ）３〜２５重量％を含むので、ラミネート強度及び防湿性に優れている。 The biaxially stretched moisture-proof polypropylene film of the present invention has, as the coating layer (I), a propylene / α-olefin copolymer (B) having specific heat melting characteristics, and a tackifier for the biaxially stretched polypropylene film substrate layer. (C) Since 3 to 25% by weight is contained, the laminate strength and moisture resistance are excellent.
本発明の二軸延伸防湿ポリプロピレンフィルムは被覆層（Ｉ）として特定の熱融解特性を有するプロピレン・α―オレフィン共重合体（Ｂ）を有し、被覆層（Ｉ）面にガスバリア性に優れたビニルアルコール系重合体が積層されてなるので、二軸延伸ポリプロピレンフィルム基材層に粘着付与剤（Ｃ）３〜２５重量％を含むのでガスバリア性、防湿性に優れ、且つビニルアルコール系重合体（Ｄ）層と被覆層（Ｉ）延いては二軸延伸ポリプロピレンフィルム基材層とのラミネート強度にも優れている。 The biaxially stretched moisture-proof polypropylene film of the present invention has a propylene / α-olefin copolymer (B) having specific heat melting characteristics as the coating layer (I), and has excellent gas barrier properties on the surface of the coating layer (I). Since the vinyl alcohol polymer is laminated, the biaxially stretched polypropylene film base layer contains 3 to 25% by weight of the tackifier (C), so that it has excellent gas barrier properties and moisture resistance, and is a vinyl alcohol polymer ( The laminate strength between the D) layer and the coating layer (I), that is, the biaxially oriented polypropylene film substrate layer is also excellent.
プロピレン系重合体（Ａ−１）、（Ａ−２）
本発明に係るプロピレン系重合体（Ａ−１）及び（Ａ−２）は、一般にポリプロピレンの名称で製造・販売されているプロピレンを主体とした重合体で、通常、密度が０．８９０〜０．９３０ｇ／ｃｍ３、ＭＦＲ（ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度２３０℃）が０．５〜６０ｇ／１０分、好ましくは０．５〜１０ｇ／１０分、更に好ましくは１〜５ｇ／１０分のプロピレンの単独重合体若しくはプロピレンと他の少量例えば、１重量％以下のα−オレフィン、例えばエチレン、ブテン、ヘキセン−１等との共重合体である。これらの中でも、プロピレンの単独重合体、若しくは１重量％以下のランダム共重合体でアイソタクテシティの高い重合体が得られる二軸延伸防湿ポリプロピレンフィルムの透明性、剛性が優れるので好ましい。
本発明に係るプロピレン系重合体（Ａ−１）は二軸延伸防湿ポリプロピレンフィルムの基材層、プロピレン系重合体（Ａ−２）は二軸延伸防湿ポリプロピレンフィルムの被覆層（ＩＩ）の原料となる。本発明に係るプロピレン系重合体（Ａ−１）及び（Ａ−２）は上記範囲にある限り、同一の重合体であっても、異なる重合体であってもよい。
本発明に係るプロピレン系重合体（Ａ−１）及び（Ａ−２）には耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、帯電防止剤、防曇剤、顔料、染料、無機または有機の充填剤等の通常ポリオレフィンに用いる各種添加剤を本発明の目的を損なわない範囲で添加しておいてもよい。
Propylene polymer (A-1), (A-2)
The propylene polymers (A-1) and (A-2) according to the present invention are polymers mainly composed of propylene which are generally produced and sold under the name of polypropylene, and usually have a density of 0.890-0. .930 g / cm 3 , MFR (ASTM D1238 load 2160 g, temperature 230 ° C.) of 0.5 to 60 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes, more preferably 1 to 5 g / 10 minutes. A homopolymer or a copolymer of propylene and another small amount, for example, 1% by weight or less of an α-olefin such as ethylene, butene, hexene-1, and the like. Among these, a biaxially stretched moisture-proof polypropylene film from which a homopolymer of propylene or a random copolymer of 1% by weight or less can obtain a polymer having high isotacticity is preferable because of excellent transparency and rigidity.
The propylene polymer (A-1) according to the present invention is a base material layer of a biaxially stretched moisture-proof polypropylene film, and the propylene polymer (A-2) is a raw material of the coating layer (II) of the biaxially stretched moistureproof polypropylene film. Become. The propylene polymers (A-1) and (A-2) according to the present invention may be the same polymer or different polymers as long as they are within the above range.
The propylene polymers (A-1) and (A-2) according to the present invention include heat stabilizers, weather stabilizers, ultraviolet absorbers, lubricants, slip agents, nucleating agents, antistatic agents, antifogging agents, and pigments. Various additives usually used in polyolefins such as dyes, inorganic or organic fillers, etc. may be added within the range not impairing the object of the present invention.
本発明の二軸延伸防湿ポリプロピレンフィルムの被覆層（ＩＩ）を形成するプロピレン系重合体（Ａ−２）には、ブロッキング防止剤を０．０１〜３．０重量％、好ましくは０．０５〜１．０重量％を添加しておくと、透明性に優れ、且つブロッキング防止性を有する二軸延伸防湿ポリプロピレンフィルムとすることができる。ブロッキング防止剤の量が０．０１重量％未満では、得られる二軸延伸防湿ポリプロピレンフィルムのブロッキング防止効果が充分でなく、一方、３．０重量％を越えると、得られる二軸延伸防湿ポリプロピレンフィルムの透明性が劣る傾向にある。かかるブロッキング防止剤としては、種々公知のもの、例えば、シリカ、タルク、雲母、ゼオライトや更には金属アルコキシドを焼成して得た金属酸化物等の無機化合物粒子、ポリメタクリル酸メチル、メラミンホルマリン樹脂、メラミン尿素樹脂、ポリエステル樹脂等の有機化合物粒子等を用い得る。これらの中でも、シリカ、ポリメタクリル酸メチルがアンチブロッキング性、透明性の面から特に好ましい。 The propylene-based polymer (A-2) that forms the coating layer (II) of the biaxially stretched moisture-proof polypropylene film of the present invention has an anti-blocking agent content of 0.01 to 3.0% by weight, preferably 0.05 to When 1.0% by weight is added, a biaxially stretched moisture-proof polypropylene film having excellent transparency and antiblocking properties can be obtained. When the amount of the anti-blocking agent is less than 0.01% by weight, the resulting biaxially stretched moisture-proof polypropylene film is not sufficiently effective in blocking, while when it exceeds 3.0% by weight, the resulting biaxially stretched moisture-proof polypropylene film is obtained. Tends to be inferior in transparency. As such an antiblocking agent, various known compounds such as silica, talc, mica, zeolite, and further inorganic compound particles such as metal oxide obtained by firing metal alkoxide, polymethyl methacrylate, melamine formalin resin, Organic compound particles such as melamine urea resin and polyester resin can be used. Among these, silica and polymethyl methacrylate are particularly preferable in terms of antiblocking properties and transparency.
プロピレン・α―オレフィン共重合体（Ｂ）
本発明に係わるプロピレン・α−オレフィン共重合体（Ｂ）は、ＤＳＣに基づく結晶融解曲線から求められたピーク温度（Ｔｐ）が１１０〜１４０℃、好ましくは１１５〜１３０℃、融解開始温度（Ｔｓ）と融解終了温度（Ｔｅ）との差（Ｔｅ−Ｔｓ）が４５℃未満、好ましくは３０〜４０℃の範囲にあり、好ましくは融解開始温度（Ｔｓ）とピーク温度（Ｔｐ）との差（Ｔｐ−Ｔｓ）が３５℃未満、より好ましくは２５〜３４℃の範囲にある。プロピレン・α−オレフィン共重合体（Ｂ）のα―オレフィンの含有量は上記熱融解特性を有する限りとくに制限はされないが、通常はα―オレフィンの含有量は１．０〜２０重量％、より好ましくは１．５〜１５重量％の範囲にある。α―オレフィンとしては、エチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等が例示できる。これらの中では、エチレン及び／又は１−ブテンとのランダム共重合体が好ましい。又、ＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）はフィルムとすることができる限り特に限定はされないが、通常０．５〜２０ｇ／１０分、好ましくは２〜１０ｇ／１０分の範囲にある。本発明に係わるプロピレン・α−オレフィン共重合体（Ｂ）は通常、分子量分布（重量平均分子量Ｍｗと数平均分子量Ｍｎとの比で表される）が１．５〜３の範囲にある。本発明に係わるプロピレン・α―オレフィン共重合体（Ｂ）は被覆層（Ｉ）の原料となる。
本発明に係わるプロピレン・α−オレフィン共重合体（Ｂ）の上記ピーク温度（Ｔｐ）、融解開始温度（Ｔｓ）及び融解終了温度（Ｔｅ）は以下の方法で測定した。プロピレン・α−オレフィン共重合体（Ｂ）約５ｍｇを秤量し、セイコ−電子工業株式会社製の示差走査熱量計（ＤＳＣ２２０モジュ−ル）を用いて、昇温速度；１０℃／分で２００℃まで昇温し、２００℃で５分間保持した後、降温速度；１００℃／分で０℃まで冷却し、再度、昇温速度；１０℃／分で０℃〜２００℃まで昇温したときの融解曲線を測定し、かかる融解曲線から、ＡＳＴＭ Ｄ３４１９の方法に習い、融解曲線からピ−ク温度（Ｔｐ）、融解開始温度（Ｔｓ）、融解終了温度（Ｔｅ）を求めた。尚、本発明では、ＡＳＴＭ Ｄ３４１９に記載の（Ｔｐｍ１）を（Ｔｐ）、（Ｔｅｉｍ）を（Ｔｓ）及び（Ｔｅｆｍ）を（Ｔｅ）とした。
Propylene / α-olefin copolymer (B)
The propylene / α-olefin copolymer (B) according to the present invention has a peak temperature (Tp) determined from a crystal melting curve based on DSC of 110 to 140 ° C., preferably 115 to 130 ° C., and a melting start temperature (Ts). ) And the melting end temperature (Te) (Te−Ts) is less than 45 ° C., preferably in the range of 30-40 ° C., preferably the difference between the melting start temperature (Ts) and the peak temperature (Tp) ( Tp−Ts) is less than 35 ° C., more preferably in the range of 25 to 34 ° C. The α-olefin content of the propylene / α-olefin copolymer (B) is not particularly limited as long as the propylene / α-olefin copolymer (B) has the above-mentioned heat melting characteristics, but usually the α-olefin content is 1.0 to 20% by weight, more Preferably it exists in the range of 1.5 to 15 weight%. Examples of the α-olefin include ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene and the like. In these, the random copolymer with ethylene and / or 1-butene is preferable. The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) is not particularly limited as long as it can be made into a film, but is usually 0.5 to 20 g / 10 minutes, preferably 2 to 10 g / 10. In the range of minutes. The propylene / α-olefin copolymer (B) according to the present invention usually has a molecular weight distribution (expressed by a ratio of the weight average molecular weight Mw and the number average molecular weight Mn) in the range of 1.5 to 3. The propylene / α-olefin copolymer (B) according to the present invention is a raw material for the coating layer (I).
The peak temperature (Tp), melting start temperature (Ts) and melting end temperature (Te) of the propylene / α-olefin copolymer (B) according to the present invention were measured by the following methods. About 5 mg of propylene / α-olefin copolymer (B) is weighed, and using a differential scanning calorimeter (DSC220 module) manufactured by Seiko Denshi Kogyo Co., Ltd., the heating rate is 200 ° C. at 10 ° C./min. The temperature was raised to 200 ° C., held at 200 ° C. for 5 minutes, and then cooled down to 0 ° C. at 100 ° C./min, and again raised to 0 ° C. to 200 ° C. at 10 ° C./min. A melting curve was measured, and the peak temperature (Tp), melting start temperature (Ts), and melting end temperature (Te) were determined from the melting curve according to the method of ASTM D3419. In the present invention, (Tpm1) described in ASTM D3419 is (Tp), (Tim) is (Ts), and (Tefm) is (Te).
本発明に係るプロピレン・α−オレフィン共重合体（Ｂ）には耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、ブロッキング防止剤、帯電防止剤、防曇剤、顔料、染料、無機または有機の充填剤等の通常ポリオレフィンに用いる各種添加剤を本発明の目的を損なわない範囲で添加しておいてもよい。 The propylene / α-olefin copolymer (B) according to the present invention includes a heat resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, a lubricant, a slip agent, a nucleating agent, an antiblocking agent, an antistatic agent, an antifogging agent, and a pigment. Various additives usually used in polyolefins such as dyes, inorganic or organic fillers, etc. may be added within the range not impairing the object of the present invention.
粘着付与剤（Ｃ）
本発明に係わる粘着付与剤（Ｃ）は、一般に粘着付与剤として製造・販売されている樹脂状物質で、具体的には、クマロン・インデン樹脂等のクマロン樹脂、フェノール・ホルムアルデヒド樹脂、テルペン・フェノール樹脂、ポリテルペン樹脂及びキシレン・ホルムアルデヒド樹脂等のフェノール，テルペン樹脂、合成ポリテルペン樹脂、芳香族系炭化水素樹脂、脂肪族系炭化水素樹脂、脂肪族系環状炭化水素樹脂、脂肪族・脂環族系石油樹脂、脂肪族・芳香族系石油樹脂、不飽和炭化水素重合体、水素添加炭化水素樹脂及び炭化水素系粘着化樹脂等の石油系炭化水素樹脂、ロジンのペンタエリスリトール・エステル、ロジンのグリセロール・エステル、水素添加ロジン、水素添加ロジン・エステル、特殊ロジンエステル及びロジン系粘着付与剤等のロジン誘導体及びテルペン系粘着付与剤等を例示できる。
これらの中では、軟化点が１１０℃以上、好ましくは１２５〜１４５℃の範囲にある水素添加率が９５％以上、更には９９％以上の水素添加炭化水素樹脂、水素添加脂肪族系環状炭化水素樹脂、水素添加脂肪族・脂環族系石油樹脂、水素添加テルペン樹脂、水素添加合成ポリテルペン樹脂等の水素添加樹脂が、プロピレン系重合体（Ａ−１）組成物との相溶性に優れるので好ましい。軟化点が１１０℃未満のものは成形時に発煙の問題が発生し、成形機を汚ごす虞が生ずる場合があり、一方、１４５℃を超えるものはプロピレン系重合体（Ａ−１）組成物と相溶しづらくなるため得られる二軸延伸防湿ポリプロピレンフィルムの外観が悪くなる虞がある。
Tackifier (C)
The tackifier (C) according to the present invention is a resinous substance that is generally produced and sold as a tackifier. Specifically, it is a coumarone resin such as coumarone / indene resin, phenol / formaldehyde resin, terpene / phenol. Resins, polyterpene resins and phenols such as xylene / formaldehyde resins, terpene resins, synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic and alicyclic petroleum Resins, aliphatic / aromatic petroleum resins, unsaturated hydrocarbon polymers, petroleum hydrocarbon resins such as hydrogenated hydrocarbon resins and hydrocarbon tackifying resins, rosin pentaerythritol ester, rosin glycerol ester , Hydrogenated rosin, hydrogenated rosin ester, special rosin ester and rosin adhesive Agent rosin derivatives and terpene tackifier such like may be exemplified.
Among these, a hydrogenated hydrocarbon resin, a hydrogenated aliphatic cyclic hydrocarbon having a softening point of 110 ° C. or higher, preferably a hydrogenation rate in the range of 125 to 145 ° C. of 95% or higher, more preferably 99% or higher. Hydrogenated resins such as resins, hydrogenated aliphatic / alicyclic petroleum resins, hydrogenated terpene resins, hydrogenated synthetic polyterpene resins and the like are preferable because they are excellent in compatibility with the propylene polymer (A-1) composition. . When the softening point is less than 110 ° C., a problem of smoke generation may occur at the time of molding, and the molding machine may be contaminated. On the other hand, when the softening point exceeds 145 ° C., the propylene polymer (A-1) composition The biaxially stretched moisture-proof polypropylene film obtained may be poor in appearance because it is difficult to be compatible with.
ビニルアルコール系重合体（Ｄ）
本発明に係わるビニルアルコール系重合体（Ｄ）は、酢酸ビニル系重合体をケン化して得られる分子内に水酸基を持つ、好ましくは水に可溶の重合体である。原料である酢酸ビニル系重合体は酢酸ビニルの単独重合体であってもよいし、他の共重合可能なモノマー、例えばエチレン、プロピレンまたは１−ブテン等のα―オレフィン等が３０モル％まで共重合されたものであってもよい。共重合のモノマーが３０モル％を越えると、ガスバリアー性が低下して、バリアー材としての性能が不十分になる。
ビニルアルコール系重合体（Ｄ）のケン化度は通常９０％以上、好ましくは９９％以上であり、この範囲にあると高湿度下でのバリア性が維持される。重合度は特に制限されないが３００〜５０００、より好ましくは５００〜２０００の範囲が望ましい。重合度が３００以下ではガスバリア性が不充分な虞があり、５０００以上ではかかるビニルアルコール系重合体（Ｅ）を塗布する際の分散液の粘度が高くなりすぎて塗布加工が難しくなる。
Vinyl alcohol polymer (D)
The vinyl alcohol polymer (D) according to the present invention is a polymer having a hydroxyl group in a molecule obtained by saponifying a vinyl acetate polymer, preferably soluble in water. The raw material vinyl acetate polymer may be a homopolymer of vinyl acetate, or other copolymerizable monomers such as ethylene, propylene or α-olefins such as 1-butene may be added up to 30 mol%. It may be polymerized. When the copolymerization monomer exceeds 30 mol%, the gas barrier property is lowered and the performance as a barrier material becomes insufficient.
The degree of saponification of the vinyl alcohol polymer (D) is usually 90% or more, preferably 99% or more. When it is within this range, the barrier property under high humidity is maintained. The degree of polymerization is not particularly limited, but is preferably in the range of 300 to 5000, more preferably 500 to 2000. When the degree of polymerization is 300 or less, the gas barrier property may be insufficient. When the degree of polymerization is 5000 or more, the viscosity of the dispersion when applying the vinyl alcohol polymer (E) becomes too high, and the coating process becomes difficult.
無機層状化合物（Ｅ）
本発明に係わる無機層状化合物（Ｅ）は、極薄の単位結晶層が１枚または数枚重なった多層構造をもって板状の粒子を形成している無機化合物のことであり、粘土鉱物が好ましく用いられる。本発明における粘土鉱物とは極薄の単位結晶層間に水を配位、吸収する性質、特には水分子が配位することにより浸漬前より体積が増加する化合物を持つ粘土化合物であり、一般にはＳｉ４＋がＯ２−対して配位し４面体構造を構成する層とＡｌ３＋、Ｍｇ２＋、Ｆｅ２＋、Ｆｅ３＋、Ｌｉ＋等がＯ２−およびＯＨ−に対して配位し８面体構造を構成する層とが１対１あるいは２対１で結合し積み重なって層状構造を構成しており、天然のものであっても合成されたものでも良い。代表的なものとしては、モンモリロナイト、バイデライト、サポナイト、ヘクトライト、カオリナイト、ハロイサイト、バーミキュライト、ディッカイト、ナクライト、アンチゴライト、パイロフィライト、マーガライト、タルク、テトラシリリックマイカ、白雲母、金雲母、緑泥石等が挙げられる。中でも、スメクタイト群と呼ばれているモンモリロナイト、バイデライト、ヘクトライトやサポナイトが好ましく用いられ、更には不純物の少ない合成品が好ましく、その中でも結晶構造が成長し、アスペクト比を大きくできる溶融法で生成したナトリウム型テトラシリシックマイカが特に好ましい。
上記層状化合物の層と層との間には通常陽イオンが保持されている。このような層間イオンとしては、Ｋ＋、Ｎａ＋、Ｌｉ＋等のアルカリ金属イオンを例示することが出来る。特に陽イオンが膨潤性を向上させるためにＮａ＋で置換されていることが好ましい。
Inorganic layered compound (E)
The inorganic layered compound (E) according to the present invention is an inorganic compound in which plate-like particles are formed with a multilayer structure in which one or several ultrathin unit crystal layers overlap each other, and a clay mineral is preferably used. It is done. The clay mineral in the present invention is a clay compound having a property of coordinating and absorbing water between ultra-thin unit crystal layers, in particular, a compound whose volume increases from before immersion due to coordination of water molecules. Si 4+ is coordinated to O 2− to form a tetrahedral structure, and Al 3+ , Mg 2+ , Fe 2+ , Fe 3+ , Li + and the like are coordinated to O 2− and OH − to form an octahedral structure. The layers constituting the layer are combined in a one-to-one or two-to-one manner and stacked to form a layered structure, which may be natural or synthesized. Typical examples include montmorillonite, beidellite, saponite, hectorite, kaolinite, halloysite, vermiculite, dickite, nacrite, antigolite, pyrophyllite, margarite, talc, tetrasilic mica, muscovite, phlogopite. Chlorite and the like. Among them, montmorillonite, beidellite, hectorite, and saponite, which are called smectite groups, are preferably used, and synthetic products with less impurities are preferable. Among them, the crystal structure grows and is produced by a melting method that can increase the aspect ratio. Sodium tetralithic mica is particularly preferred.
Cations are usually held between the layers of the layered compound. Examples of such interlayer ions include alkali metal ions such as K + , Na + , and Li + . In particular, the cation is preferably substituted with Na + in order to improve the swelling property.
無機層状化合物（Ｅ）の平均粒子径は特に限定されないが、長さ方向が通常３００Å以上、５μｍ以下のものが好ましく用いられる。５μｍ以上では透明性が損なわれ、また劈開が不充分だと高湿度下でのバリア性が著しく低下する。また、アスペクト比（長さ径と厚みの比）は大きいほど透明性、バリア性が良好であるが、プロピレン・α―オレフィン共重合体（Ｂ）層との密着性が低下することから２０〜２０００が好ましく用いられる。
又、かかる無機層状化合物（Ｅ）をビニルアルコール系重合体（Ｄ）に添加する場合は、ビニルアルコール系重合体（Ｄ）と無機層状化合物（Ｅ）との混合比は重量比で（Ｄ）／（Ｅ）が３／７以下、更には５／５以下が好ましい。無機層状化合物（Ｅ）の添加量が３／７より大きいと透明性が低下し、プロピレン・α−オレフィン共重合体（Ｂ）層との密着性も低下する傾向にある。
The average particle size of the inorganic layered compound (E) is not particularly limited, but those having a length direction of usually 300 to 5 μm are preferably used. If it is 5 μm or more, the transparency is impaired, and if the cleavage is insufficient, the barrier property under high humidity is remarkably lowered. Further, the larger the aspect ratio (ratio of length and thickness) is, the better the transparency and barrier properties are, but the adhesiveness with the propylene / α-olefin copolymer (B) layer is lowered. 2000 is preferably used.
When such an inorganic layered compound (E) is added to the vinyl alcohol polymer (D), the mixing ratio of the vinyl alcohol polymer (D) and the inorganic layered compound (E) is (D) by weight. / (E) is preferably 3/7 or less, more preferably 5/5 or less. When the addition amount of the inorganic layered compound (E) is larger than 3/7, the transparency is lowered and the adhesion with the propylene / α-olefin copolymer (B) layer tends to be lowered.
プロピレン系重合体（Ａ−１）組成物
本発明に係わるプロピレン系重合体（Ａ−１）組成物は、プロピレン系重合体（Ａ−１）９７〜７５重量％、好ましくは９６〜８５重量％と、粘着付与剤（Ｃ）３〜２５重量％、好ましくは４〜１５重量％を含む組成物である。粘着付与剤（Ｃ）の量が３重量％未満では、防湿性に優れた二軸延伸フィルムが得られず、一方、２５重量％を超えると防湿性の改良効果は飽和するとともに、押出し成形がし難い傾向にある。
Propylene Polymer (A-1) Composition The propylene polymer (A-1) composition according to the present invention is 97 to 75% by weight, preferably 96 to 85% by weight, of the propylene polymer (A-1). And 3 to 25 wt%, preferably 4 to 15 wt% of the tackifier (C). If the amount of the tackifier (C) is less than 3% by weight, a biaxially stretched film excellent in moisture resistance cannot be obtained. On the other hand, if it exceeds 25% by weight, the moisture-proof improvement effect is saturated and extrusion molding is not possible. It tends to be difficult.
プロピレン系重合体の製造方法
本発明に係わるプロピレン系重合体（Ａ−１）、（Ａ−２）及びプロピレン・α−オレフィン共重合体（Ｂ）は種々公知の方法、例えば、典型的には固体状チタン触媒成分と有機金属化合物触媒成分から形成される触媒、あるいはこれら両成分および電子供与体から形成される触媒を用いて製造することができる。
Propylene Polymer Production Method The propylene polymers (A-1) and (A-2) and the propylene / α-olefin copolymer (B) according to the present invention may be produced by various known methods such as typically It can be produced using a catalyst formed from a solid titanium catalyst component and an organometallic compound catalyst component, or a catalyst formed from both components and an electron donor.
固体状チタン触媒成分としては、各種方法で製造された三塩化チタンまたは三塩化チタン組成物、あるいはマグネシウム、ハロゲン、電子供与体、好ましくは芳香族カルボン酸エステルまたはアルキル基含有エーテルおよびチタンを必須成分とする、比表面積が好適には１００ｍ２／ｇ以上の担体付チタン触媒成分が挙げられる。特に後者の担体付触媒成分を用いて製造された重合体が好適である。
有機金属化合物触媒成分としては、有機アルミニウム化合物が好適であり、具体的には、トリアルキルアルミニウム、ジアルキルアルミニウムハライド、アルキルアルミニウムセスキハライド、アルキルアルミニウムジハライドなどが挙げられる。これらの化合物のうち、好適な有機金属化合物触媒成分は、使用する上記チタン触媒成分の種類によって異なる。
電子供与体は、窒素、リン、イオウ、酸素、ケイ素、ホウ素などを含む有機化合物であり、好適な具体例としては、これらの元素を有する有機エステル、有機エーテルなどを挙げることができる。
担体付触媒成分を用いた重合体の製造方法に関しては、たとえば特開昭５０−１０８３８５号、特開昭５０−１２６５９０号、特開昭５１−２０２９７号、特開昭５１−２８１８９号、特開昭５２−１５１６９１号などの各公報に開示されている。
As a solid titanium catalyst component, titanium trichloride or a titanium trichloride composition produced by various methods, or magnesium, halogen, an electron donor, preferably an aromatic carboxylic acid ester or an alkyl group-containing ether and titanium are essential components. And a supported titanium catalyst component having a specific surface area of preferably 100 m 2 / g or more. In particular, a polymer produced using the latter supported catalyst component is preferred.
The organometallic compound catalyst component is preferably an organoaluminum compound, and specific examples include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, and the like. Among these compounds, a suitable organometallic compound catalyst component varies depending on the type of the titanium catalyst component used.
The electron donor is an organic compound containing nitrogen, phosphorus, sulfur, oxygen, silicon, boron, and the like. Suitable specific examples include organic esters and organic ethers having these elements.
With respect to the method for producing a polymer using a catalyst component with a carrier, for example, JP-A-50-108385, JP-A-50-126590, JP-A-51-20297, JP-A-51-28189, JP It is disclosed in each publication such as Sho 52-151691.
本発明に係わるプロピレン・α−オレフィン共重合体（Ｂ）は、特にはシングルサイト触媒を用いて製造することができる。シングルサイト触媒は、活性点が均一（シングルサイト）である触媒であり、例えばメタロセン触媒（いわゆるカミンスキー触媒）やブルックハート触媒などがあげられる。例えばメタロセン触媒は、メタロセン系遷移金属化合物と、有機アルミニウム化合物および上記メタロセン系遷移金属化合物と反応してイオン対を形成する化合物からなる群から選ばれる少なくとも一種の化合物とからなる触媒であり、無機物に担持されていてもよい。
前記メタロセン系遷移金属化合物としては、例えば特開平５−２０９０１４号、特開平６−１００５７９号、特開平１−３０１７０４号、特開平３−１９３７９６号、特開平５−１４８２８４号、特開２０００−２０４３１号等に記載された化合物などがあげられる。
有機アルミニウム化合物としては、アルキルアルミニウム、または鎖状あるいは環状アルミノキサン等があげられる。上記鎖状あるいは環状アルミノキサンは、アルキルアルミニウムと水とを接触させることにより生成される。例えば重合時にアルキルアルミニウムを加えておいて、後で水を添加するか、あるいは錯塩の結晶水または有機、無機化合物の吸着水とアルキルアルミニウムとを反応させることにより得られる。
前記メタロセン系遷移金属化合物と反応してイオン対を形成する化合物は、例えば特表平１−５０１９５０号、特開平３−２０７７０４号、特開２００２−２０４３１号等に記載された化合物などがあげられる。シングルサイト触媒を担持させる前記無機物としては、シリカゲル、ゼオライト、珪藻土等があげられる。
重合方法としては、塊状重合、溶液重合、懸濁重合、気相重合等があげられる。これらの重合はバッチ法であっても連続法であっても良い。重合条件は通常、重合温度；−１００〜＋２５０℃、重合時間；５分〜１０時間、反応圧力；常圧〜３００Ｋｇ／ｃｍ２（ゲージ圧）である。
The propylene / α-olefin copolymer (B) according to the present invention can be produced particularly using a single site catalyst. The single site catalyst is a catalyst having a uniform active site (single site), and examples thereof include a metallocene catalyst (so-called Kaminsky catalyst) and a Brookhart catalyst. For example, a metallocene catalyst is a catalyst comprising a metallocene transition metal compound, at least one compound selected from the group consisting of an organoaluminum compound and a compound that forms an ion pair by reacting with the metallocene transition metal compound, and an inorganic substance. It may be carried on.
Examples of the metallocene transition metal compound include JP-A-5-209014, JP-A-6-1005209, JP-A-1-301704, JP-A-3-193966, JP-A-5-148284, and JP-A-2000-20431. And the like, and the like.
Examples of the organoaluminum compound include alkylaluminum, chain or cyclic aluminoxane, and the like. The chain or cyclic aluminoxane is produced by bringing alkylaluminum into contact with water. For example, it can be obtained by adding alkylaluminum at the time of polymerization and adding water later, or by reacting crystallization water of a complex salt or adsorbed water of an organic or inorganic compound with alkylaluminum.
Examples of the compound that reacts with the metallocene transition metal compound to form an ion pair include compounds described in JP-A-1-501950, JP-A-3-207704, JP-A-2002-20431, and the like. . Examples of the inorganic substance that supports the single-site catalyst include silica gel, zeolite, diatomaceous earth, and the like.
Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, gas phase polymerization and the like. These polymerizations may be batch processes or continuous processes. The polymerization conditions are usually a polymerization temperature: −100 to + 250 ° C., a polymerization time: 5 minutes to 10 hours, a reaction pressure; a normal pressure to 300 Kg / cm 2 (gauge pressure).
二軸延伸防湿ポリプロピレンフィルム
本発明の二軸延伸防湿ポリプロピレンフィルムは、粘着付与剤（Ｃ）３〜２５重量％を含むプロピレン系重合体（Ａ−１）組成物層から得られる二軸延伸ポリプロピレンフィルム基材層の片面に、ＤＳＣに基づく結晶融解曲線から求められたピーク温度（Ｔｐ）が１１０〜１４０℃及び融解開始温度（Ｔｓ）と融解終了温度（Ｔｅ）との差（Ｔｅ−Ｔｓ）が４５℃未満のプロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）が積層されてなる層から構成される。かかる構成からなる二軸延伸防湿ポリプロピレンフィルムの各層の厚さは、用途により種々決められるものであり、特に限定はされないが、通常、二軸延伸ポリプロピレンフィルム基材層が１０〜１００μｍ、好ましくは１５〜５０μｍ、プロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）が０．５〜１５μｍ、好ましくは１〜１０μｍの範囲にある。
Biaxially stretched moisture-proof polypropylene film The biaxially stretched moisture-proof polypropylene film of the present invention is a biaxially stretched polypropylene film obtained from a propylene-based polymer (A-1) composition layer containing 3 to 25% by weight of a tackifier (C). On one side of the base material layer, the peak temperature (Tp) obtained from the crystal melting curve based on DSC is 110 to 140 ° C., and the difference (Te−Ts) between the melting start temperature (Ts) and the melting end temperature (Te) is The coating layer (I) obtained from the propylene / α-olefin copolymer (B) having a temperature of less than 45 ° C. is composed of a laminated layer. The thickness of each layer of the biaxially stretched moisture-proof polypropylene film having such a configuration can be variously determined depending on the application, and is not particularly limited. Usually, the biaxially stretched polypropylene film base layer is 10 to 100 μm, preferably 15 The coating layer (I) obtained from ˜50 μm and the propylene / α-olefin copolymer (B) is in the range of 0.5 to 15 μm, preferably 1 to 10 μm.
本発明の二軸延伸防湿ポリプロピレンフィルムは、二軸延伸ポリプロピレンフィルム基材層の他の片面に、プロピレン系重合体（Ａ―２）、好ましくはブロッキング防止剤を０．０１〜３．０重量％、更には０．０５〜１．０重量％をから得られる被覆層（ＩＩ）が積層されてなる構成を取り得る。かかる被覆層（ＩＩ）の厚さも用途により種々決められるものであり、特に限定はされないが、通常、０．５〜１５μｍ、好ましくは１〜１０μｍの範囲にある。 In the biaxially stretched moisture-proof polypropylene film of the present invention, 0.01 to 3.0% by weight of a propylene-based polymer (A-2), preferably an antiblocking agent, is formed on the other surface of the biaxially stretched polypropylene film substrate layer. Furthermore, the structure formed by laminating the coating layer (II) obtained from 0.05 to 1.0% by weight can be taken. The thickness of the coating layer (II) is also variously determined depending on the application and is not particularly limited, but is usually in the range of 0.5 to 15 μm, preferably 1 to 10 μm.
本発明の二軸延伸防湿ポリプロピレンフィルムは、プロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）面に、ビニルアルコール系重合体（Ｄ）層が積層されてなる構成を取り得る。かかるビニルアルコール系重合体（Ｄ）層の厚さも用途により種々決められるものであり、特に限定はされないが、通常、０．１〜１０μｍ、好ましくは０．２〜３μｍの範囲にある。 The biaxially stretched moisture-proof polypropylene film of the present invention has a configuration in which a vinyl alcohol polymer (D) layer is laminated on the coating layer (I) surface obtained from the propylene / α-olefin copolymer (B). obtain. The thickness of the vinyl alcohol polymer (D) layer is also variously determined depending on the application and is not particularly limited, but is usually in the range of 0.1 to 10 μm, preferably 0.2 to 3 μm.
本発明の二軸延伸防湿ポリプロピレンフィルムは、プロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）面に、無機層状化合物（Ｅ）を含むビニルアルコール系重合体（Ｄ）組成物層が積層されてなる構成を取り得る。かかるビニルアルコール系重合体（Ｄ）組成物層の厚さも用途により種々決められるものであり、特に限定はされないが、通常、０．１〜１０μｍ、好ましくは０．２〜３μｍの範囲にある。 The biaxially stretched moisture-proof polypropylene film of the present invention comprises a vinyl alcohol polymer (D) composition containing an inorganic layered compound (E) on the surface of the coating layer (I) obtained from the propylene / α-olefin copolymer (B). A structure in which physical layers are laminated can be employed. The thickness of the vinyl alcohol polymer (D) composition layer is also variously determined depending on the use and is not particularly limited, but is usually in the range of 0.1 to 10 μm, preferably 0.2 to 3 μm.
本発明の二軸延伸防湿ポリプロピレンフィルムは必要に応じて片面あるいは両面をコロナ処理、火炎処理等の表面処理をしてもよい。また、本発明の二軸延伸防湿ポリプロピレンフィルムは更に用途により、低温ヒートシール性を付与するために、高圧法低密度ポリエチレン、線状低密度ポリエチレン、結晶性あるいは低結晶性のエチレンと炭素数３〜１０のα−オレフィンとのランダム共重合体あるいはプロピレンとエチレンもしくは炭素数４以上のα−オレフィンとのランダム共重合体、ポリブテン、エチレン・酢酸ビニル共重合体等の低融点のポリマーを単独あるいはそれらの組成物を、プロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）、ビニルアルコール系重合体（Ｄ）層若しくは無機層状化合物（Ｅ）を含むビニルアルコール系重合体組成物（Ｄ）層あるいはプロピレン系重合体（Ａ―２）層からなる被覆層（ＩＩ）面に積層してもよい。また、更にガスバリア性を強化するために、エチレン・ビニルアルコール共重合体、ポリアミド、ポリエステル、塩化ビニリデン系重合体等を押出しコーティング、フィルムラミネート等で積層してもよいし、金属あるいはその酸化物、シリカ等を蒸着してもよい。勿論、他の物質との接着性を増すために、二軸延伸防湿ポリプロピレンフィルムの表面をイミン、ウレタン等の接着剤でアンカー処理してもよいし、無水マレイン酸変性ポリオレフィンを積層してもよい。 The biaxially stretched moisture-proof polypropylene film of the present invention may be subjected to surface treatment such as corona treatment or flame treatment on one side or both sides as necessary. In addition, the biaxially stretched moisture-proof polypropylene film of the present invention is further subjected to high-pressure method low-density polyethylene, linear low-density polyethylene, crystalline or low-crystalline ethylene, and carbon number 3 in order to impart low-temperature heat sealability depending on applications. A random copolymer of 10 to α-olefin or a low-melting polymer such as a random copolymer of propylene and ethylene or an α-olefin having 4 or more carbon atoms, polybutene, ethylene / vinyl acetate copolymer, or the like A vinyl alcohol polymer composition comprising a coating layer (I), a vinyl alcohol polymer (D) layer or an inorganic layered compound (E) obtained from the propylene / α-olefin copolymer (B). You may laminate | stack on the coating layer (II) surface which consists of a product (D) layer or a propylene-type polymer (A-2) layer. Further, in order to further enhance the gas barrier property, an ethylene / vinyl alcohol copolymer, polyamide, polyester, vinylidene chloride polymer, etc. may be laminated by extrusion coating, film lamination, etc., or a metal or its oxide, Silica or the like may be deposited. Of course, in order to increase the adhesion to other substances, the surface of the biaxially stretched moisture-proof polypropylene film may be anchored with an adhesive such as imine or urethane, or maleic anhydride-modified polyolefin may be laminated. .
二軸延伸防湿ポリプロピレンフィルムの製造方法
本発明の二軸延伸防湿ポリプロピレンフィルムは、種々公知の製造方法、例えば、基材層の原料として粘着付与剤（Ｃ）３〜２５重量％を含むプロピレン系重合体（Ａ−１）組成物を、被覆層（Ｉ）の原料として必要に応じてブロッキング防止剤を所定量添加したプロピレン・α−オレフィン共重合体（Ｂ）を、被覆層（ＩＩ）を有する二軸延伸防湿ポリプロピレンフィルムを得る場合は、原料として必要に応じてブロッキング防止剤を所定量添加したプロピレン系重合体（Ａ―２）を夫々別個の押出し機で溶融した後、多層ダイから共押出し成形して得た多層シートを、公知の同時二軸延伸法あるいは逐次二軸延伸法等の二軸延伸フィルム製造方法、例えば、逐次二軸延伸法では、縦延伸温度を１２５℃〜１４５℃、延伸倍率を４．５〜６倍の範囲、横延伸温度を１６５〜１９０℃、延伸倍率を９〜１１倍の範囲で延伸することにより得られる。
ビニルアルコール系重合体（Ｄ）層を有する二軸延伸防湿ポリプロピレンフィルムを製造する場合は、上記方法で得られた二軸延伸防湿ポリプロピレンフィルムの被覆層（Ｉ）面にビニルアルコール系重合体（Ｄ）若しくは無機層状化合物（Ｅ）を含むビニルアルコール系重合体（Ｄ）分散液を塗布・乾燥する方法、あるいは共押出し成形して得た多層シートに分散液を塗布した後、ニ軸延伸してもよいし、共押出し成形して得た多層シートを縦方向に延伸したシートに分散液を塗布した後、横方向に延伸して二軸延伸防湿ポリプロピレンフィルムとしてもよい。
Method for Producing Biaxially Stretched Moisture-Proof Polypropylene Film The biaxially stretched moisture-proof polypropylene film of the present invention is produced by various known production methods, for example, a propylene-based polymer containing 3 to 25% by weight of a tackifier (C) as a raw material for a substrate layer. A coating layer (II) having a propylene / α-olefin copolymer (B) in which a predetermined amount of an antiblocking agent is added as a raw material of the coalescence (A-1) composition as a raw material of the coating layer (I) When obtaining a biaxially stretched moisture-proof polypropylene film, the propylene polymer (A-2) to which a predetermined amount of an antiblocking agent is added as a raw material is melted with a separate extruder and then coextruded from a multilayer die. The multilayer sheet obtained by molding is formed into a biaxially stretched film production method such as a known simultaneous biaxial stretching method or a sequential biaxial stretching method, for example, a sequential biaxial stretching method. The 125 ° C. to 145 ° C., the range of 4.5 to 6 times the draw ratio, the transverse stretching temperature one hundred sixty-five to one hundred and ninety ° C., obtained by stretching in the range of 9-11 times the draw ratio.
In the case of producing a biaxially stretched moisture-proof polypropylene film having a vinyl alcohol polymer (D) layer, the vinyl alcohol polymer (D) is formed on the coating layer (I) surface of the biaxially stretched moisture-proof polypropylene film obtained by the above method. ) Or a method of applying and drying a vinyl alcohol polymer (D) dispersion containing an inorganic layered compound (E), or applying a dispersion to a multilayer sheet obtained by coextrusion molding, and then biaxially stretching. Alternatively, a biaxially stretched moisture-proof polypropylene film may be obtained by applying a dispersion liquid to a sheet obtained by stretching a multilayer sheet obtained by coextrusion molding in the longitudinal direction and then stretching it in the transverse direction.
ビニルアルコール系重合体（Ｄ）等の分散液には、プロピレン・α−オレフィン共重合体（Ｂ）層との密着性向上、及び／または皮膜の強度向上のためにビニルアルコール系重合体（Ｄ）に架橋剤成分を添加しても良い。かかる架橋剤成分としては、シランカップリング剤、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、アミン系化合物などがあるが、高湿度下でも密着性低下しないことからイソシアネート系架橋剤が好ましく、特に水性の自己乳化タイプが水溶液中で安定であるので好ましい。その添加量はビニルアルコール系重合体（Ｄ）に対し重量比で１〜１０％の範囲にあることが好ましい。
又、ビニルアルコール系重合体（Ｄ）等の分散液に架橋剤成分を添加する代りに、プロピレン・α−オレフィン共重合体（Ｂ）層の表面を種々公知のアンカー（ＡＣ）剤、例えば有機チタン系ＡＣ剤、ポリウレタン系ＡＣ剤、ポリエチレンイミン系ＡＣ剤、ポリブタジエン系ＡＣ剤等で処理しておいてもよい。
本発明に係わるビニルアルコール系重合体（Ｄ）には、本発明の目的を阻害しない範囲で濡れ性向上剤、帯電防止剤、その他各種添加剤を加えることが可能である。特に、アンチブロッキング剤として粒径が０．１〜１０μｍ程度の酸化珪素、カオリン等の無機系微粒子やポリメチルメタクリレート、メラミン等の有機系微粒子を好ましく用いることが出来る。
ビニルアルコール系重合体（Ｄ）の分散媒としては、コスト、作業環境面から水が好ましく用いられるが、水以外の溶媒、例えばメタノール、エタノール、イソプロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、或いはその他ジエチルエーテル、テトラヒドロフラン等を必要に応じて、１種または２種以上を組み合わせて加えることも可能である。
In order to improve adhesion to the propylene / α-olefin copolymer (B) layer and / or to improve the strength of the film, a dispersion of vinyl alcohol polymer (D) or the like is used. ) May contain a crosslinking agent component. Such crosslinker components include silane coupling agents, isocyanate crosslinkers, epoxy crosslinkers, melamine crosslinkers, amine compounds, etc., but isocyanate crosslinkers do not deteriorate adhesion even under high humidity. The aqueous self-emulsifying type is particularly preferable because it is stable in an aqueous solution. The addition amount is preferably in the range of 1 to 10% by weight with respect to the vinyl alcohol polymer (D).
In addition, instead of adding a crosslinking agent component to a dispersion of vinyl alcohol polymer (D) or the like, the surface of the propylene / α-olefin copolymer (B) layer is coated with various known anchor (AC) agents such as organic You may process by titanium AC agent, polyurethane AC agent, polyethyleneimine AC agent, polybutadiene AC agent, etc.
It is possible to add a wettability improver, an antistatic agent, and other various additives to the vinyl alcohol polymer (D) according to the present invention as long as the object of the present invention is not impaired. In particular, as the antiblocking agent, inorganic fine particles such as silicon oxide and kaolin having a particle diameter of about 0.1 to 10 μm, and organic fine particles such as polymethyl methacrylate and melamine can be preferably used.
As a dispersion medium for the vinyl alcohol polymer (D), water is preferably used from the viewpoint of cost and working environment, but solvents other than water, for example, alcohols such as methanol, ethanol and isopropanol, and ketones such as acetone and methyl ethyl ketone. Alternatively, diethyl ether, tetrahydrofuran or the like can be added alone or in combination of two or more as required.
次に実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を越えない限りこれらの実施例に制約されるものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited to these Examples, unless the summary is exceeded.
実施例及び比較例における物性値等は、以下の評価方法により求めた。
（１）防湿性（水蒸気透過度）：ＪＩＳ Ｚ ０２０８に準じ、条件Ａ；温度４０℃、湿度９０％ＲＨで測定した。
（２）ガスバリア性（酸素透過度）：モコン社製酸素透過度計ＯＸ−ＴＲＡＮ２／２０を用いて、ＪＩＳ Ｋ ７１２６に準じ、温度２０℃で湿度５０％ＲＨ及び８０％ＲＨで測定した。
（３）ラミネート強度：二軸延伸防湿ポリプロピレンフィルムに３０μｍの無延伸ポリプロピレンフィルムを、接着剤（三井武田ケミカル社製 タケラックＡ−３１０）６０重量％、硬化剤（三井武田ケミカル社製 タケネートＡ−３）５重量％、酢酸エチル（関東化学社製1級）３５重量％で配合した液でドライラミした。作成したラミネートフィルムは、４０℃で２４時間オーブン中放置した後、１５ｍｍ幅に切り出し東洋精機社製テンシロンを用いて引っ張り速度３００ｍｍ／分で９０℃の剥離強度を測定しラミネート強度とした。
The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
(1) Moisture resistance (water vapor permeability): Measured according to JIS Z 0208, Condition A; temperature 40 ° C., humidity 90% RH.
(2) Gas barrier property (oxygen permeability): Measured according to JIS K 7126 using a Mocon oxygen permeability meter OX-TRAN 2/20 at a temperature of 20 ° C. and a humidity of 50% RH and 80% RH.
(3) Laminate strength: 30 μm unstretched polypropylene film on biaxially stretched moisture-proof polypropylene film, 60% by weight of adhesive (Takelac A-310 manufactured by Mitsui Takeda Chemical Co., Ltd.), curing agent (Takenate A-3 manufactured by Mitsui Takeda Chemical Co., Ltd.) ) Dry laminating was conducted with a solution containing 5% by weight and 35% by weight of ethyl acetate (Kanto Chemical Co., Ltd. Grade 1). The prepared laminate film was left in an oven at 40 ° C. for 24 hours, then cut into a 15 mm width, and the peel strength at 90 ° C. was measured at a pulling rate of 300 mm / min using Tensilon manufactured by Toyo Seiki Co., Ltd., to obtain the laminate strength.
実施例１
＜基材層：プロピレン重合体組成物層＞
プロピレン単独重合体（ＭＦＲ：２．０ｇ／１０分（２３０℃））に耐熱安定剤としてテトラキス［メチレンー３−（３'、５’―ジーｔ―ブチルー４’ヒドロキシフェニル）プロピオネート］メタン（日本チバガイキー社製品 製品名イルガノックス１０１０）１０００ｐｐｍ及びステアリン酸カルシウム（日本油脂社製）１０００ｐｐｍを加えたプロピレン系重合体組成物を用意し、当該プロピレン重合体組成物９５重量％に対し、水素添加テルペン系石油樹脂（ヤスハラケミカル社製品 製品名クリアロンＰ−１２５、軟化点；１２５℃）５重量％添加しピロピレン重合体組成物を用意した。
＜被覆層（Ｉ）：プロピレン共重合体組成物層＞
被覆層（Ｉ）を構成する重合体組成物として、プロピレン・α―オレフィン共重合体（１）；エチレン含有量：３．１重量％、Ｔｓ：９４．０℃、Ｔｐ：１２６．６℃、Ｔｅ：１３１．４℃、Ｔｅ−Ｔｓ：３７．４℃、Ｔｐ−Ｔｓ：３２．６℃、Ｍｗ／Ｍｎ：２．７及びＭＦＲ：７ｇ／１０分（２３０℃）の組成物に、ポリメチルメタクリレート粒子からなるアンチ・ブロッキング剤を０．１０重量％、耐熱安定剤としてテトラキス［メチレンー３−（３’、５’―ジーｔ―ブチルー４’ヒドロキシフェニル）プロピオネート］メタン（日本チバガイキー社製 イルガノックス１０１０）１０００ｐｐｍ及びステアリン酸カルシウム（日本油脂社製）１０００ｐｐｍを加えたプロピレン共重合体組成物を用意した。
＜被覆層（ＩＩ）：プロピレン重合体層＞
被覆層（ＩＩ）を構成する重合体として、基材層に用いたプロピレン単独重合体（ＭＦＲ：２．０ｇ／１０分（２３０℃））に耐熱安定剤としてテトラキス［メチレンー３−（３’、５’―ジーｔ―ブチルー４’ヒドロキシフェニル）プロピオネート］メタン（日本チバガイキー社製 イルガノックス１０１０）１０００ｐｐｍ及びステアリン酸カルシウム（日本油脂社製）１０００ｐｐｍを加えたプロピレン系重合体組成物に、ポリメチルメタクリレート粒子からなるアンチ・ブロッキング剤を０．１０重量％、耐熱安定剤としてテトラキス［メチレンー３−（３’、５’―ジーｔ―ブチルー４’ヒドロキシフェニル）プロピオネート］メタン（日本チバガイキー社製 イルガノックス１０１０）１０００ｐｐｍ及びステアリン酸カルシウム（日本油脂社製）１０００ｐｐｍを加えたプロピレン系重合体組成物を用意した。
＜二軸延伸防湿ポリプロピレンフィルムの製造＞
前記、プロピレン重合体組成物、プロピレン共重合体組成物及びプロピレン重合体組成物を押出量比（１／１０／１）になるよう各々スクリュー押出機を用いて溶融押出しマルチマニホールドタイプＴ−ダイを用いて押出し、冷却ロール上にて急冷し厚さ約１．５ｍｍの多層シートを得た。このシートを１２０℃で加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１６０℃で加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して、基材層の厚さ：２５μｍ、熱融着層（ラミネート層）の厚さ：２．５μｍ及び被覆層の厚さ：２．５μｍ（合計厚さ：３０μｍ）の二軸延伸防湿ポリプロピレンフィルムを得た。
この二軸延伸防湿ポリプロピレンフィルムのラミネート層にコロナ処理を施した。かかる二軸延伸防湿ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表１に示す。
Example 1
<Base material layer: Propylene polymer composition layer>
Propylene homopolymer (MFR: 2.0 g / 10 min (230 ° C.)) tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′hydroxyphenyl) propionate] methane (Nippon Ciba-Gaiky) as a heat-resistant stabilizer Company product Product name Irganox 1010) Propylene polymer composition containing 1000 ppm and calcium stearate (manufactured by NOF Corporation) 1000 ppm was prepared, and hydrogenated terpene petroleum resin with respect to 95% by weight of the propylene polymer composition. (Yasuhara Chemical Co., Ltd., product name Clearon P-125, softening point: 125 ° C.) 5% by weight was added to prepare a pyropyrene polymer composition.
<Coating layer (I): Propylene copolymer composition layer>
As a polymer composition constituting the coating layer (I), propylene / α-olefin copolymer (1); ethylene content: 3.1 wt%, Ts: 94.0 ° C., Tp: 126.6 ° C., Te: 131.4 ° C., Te-Ts: 37.4 ° C., Tp-Ts: 32.6 ° C., Mw / Mn: 2.7 and MFR: 7 g / 10 min (230 ° C.) 0.10% by weight of an anti-blocking agent composed of methacrylate particles, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′hydroxyphenyl) propionate] methane as a heat stabilizer (Irganox, manufactured by Ciba-Gaykey, Japan) 1010) A propylene copolymer composition to which 1000 ppm and calcium stearate (manufactured by NOF Corporation) 1000 ppm were added was prepared.
<Coating layer (II): Propylene polymer layer>
As a polymer constituting the coating layer (II), a propylene homopolymer (MFR: 2.0 g / 10 min (230 ° C.)) used for the base material layer was added to a tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′hydroxyphenyl) propionate] methane (Irganox 1010 manufactured by Ciba-Gaiky Japan) 1000 ppm and calcium stearate (manufactured by Nippon Oil & Fats Co., Ltd.) 1000 ppm added to a propylene polymer composition, polymethyl methacrylate particles 0.10% by weight of an anti-blocking agent consisting of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′hydroxyphenyl) propionate] methane as a heat stabilizer (Irganox 1010 manufactured by Ciba-Gaykey, Japan) 1000 ppm and calcium stearate (Japanese oil It was prepared a propylene-based polymer composition obtained by adding a company Ltd.) 1000 ppm.
<Manufacture of biaxially stretched moisture-proof polypropylene film>
Each of the above-mentioned propylene polymer composition, propylene copolymer composition and propylene polymer composition was melt extruded using a screw extruder so as to have an extrusion ratio (1/10/1). The resultant was extruded and quenched on a cooling roll to obtain a multilayer sheet having a thickness of about 1.5 mm. This sheet was heated at 120 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times is heated at 160 ° C. and stretched 10 times in the direction orthogonal to the flow direction (lateral direction), the thickness of the base layer: 25 μm, the thickness of the heat-sealing layer (laminate layer) A biaxially stretched moisture-proof polypropylene film having a thickness of 2.5 μm and a coating layer thickness of 2.5 μm (total thickness: 30 μm) was obtained.
The laminate layer of this biaxially stretched moisture-proof polypropylene film was subjected to corona treatment. The evaluation of the biaxially stretched moisture-proof polypropylene film was measured by the method described above.
The results are shown in Table 1.
実施例２
実施例１の被覆層（Ｉ）で用いたプロピレン・エチレンランダム共重合体（１）に代えて、エチレン含有量：２．８重量％、Ｔｓ：９７．２℃、Ｔｐ：１２５．６℃、Ｔｅ：１３４．２℃、Ｔｅ−Ｔｓ：３７．０℃、Ｔｐ−Ｔｓ：２８．４℃、Ｍｗ／Ｍｎ：１．９及びＭＦＲ：７ｇ／１０分（２３０℃）のプロピレン・エチレンランダム共重合体（２）を用いる以外は実施例と同様に行い二軸延伸防湿ポリプロピレンフィルムを得た。かかる二軸延伸防湿ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表１に示す。
Example 2
In place of the propylene / ethylene random copolymer (1) used in the coating layer (I) of Example 1, ethylene content: 2.8 wt%, Ts: 97.2 ° C., Tp: 125.6 ° C., Te: 134.2 ° C, Te-Ts: 37.0 ° C, Tp-Ts: 28.4 ° C, Mw / Mn: 1.9 and MFR: 7 g / 10 min (230 ° C) A biaxially stretched moisture-proof polypropylene film was obtained in the same manner as in Example except that the coalesced (2) was used. The evaluation of the biaxially stretched moisture-proof polypropylene film was measured by the method described above.
The results are shown in Table 1.
比較例１
実施例１の被覆層（Ｉ）で用いたプロピレン・エチレンランダム共重合体（１）に代えて、エチレン含有量：２．２重量％、Ｔｓ：９５．４℃、Ｔｐ：１３９．４℃、Ｔｅ：１５０．３℃、Ｔｅ−Ｔｓ：５４．９℃、Ｔｐ−Ｔｓ：４３．９℃、Ｍｗ／Ｍｎ：３．９及びＭＦＲ：７ｇ／１０分（２３０℃）のプロピレン・エチレンランダム共重合体（３）を用いる以外は実施例と同様に行い二軸延伸防湿ポリプロピレンフィルムを得た。かかる二軸延伸防湿ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表１に示す。
Comparative Example 1
In place of the propylene / ethylene random copolymer (1) used in the coating layer (I) of Example 1, ethylene content: 2.2 wt%, Ts: 95.4 ° C., Tp: 139.4 ° C., Te: 150.3 ° C., Te-Ts: 54.9 ° C., Tp-Ts: 43.9 ° C., Mw / Mn: 3.9 and MFR: 7 g / 10 min (230 ° C.) A biaxially stretched moisture-proof polypropylene film was obtained in the same manner as in Example except that the coalesced (3) was used. The evaluation of the biaxially stretched moisture-proof polypropylene film was measured by the method described above.
The results are shown in Table 1.
表１の結果から明らかなように、本発明の二軸延伸防湿フィルム（実施例１及び２）は、比較例１に示したニ軸延伸防湿フィルムに比べ、ラミネート強度に優れ、且つ防湿性に優れていることが分かる。 As is clear from the results of Table 1, the biaxially stretched moisture-proof film of the present invention (Examples 1 and 2) is superior in laminate strength and moisture-proof to the biaxially stretched moisture-proof film shown in Comparative Example 1. It turns out that it is excellent.
実施例３
けん化度９９．９％、酢酸ナトリウム含有量０．２％、重合度１０００のポリビニルアルコールを熱水で溶解し、室温まで冷却して５％濃度の水溶液を得た。この水溶液に水性ウレタン（武田製品工業社製 ＷＤ７２６）を固形分比で３重量％、及び濡れ向上剤としてアニオン系界面活性剤（花王社製 ネオペレックスＦ２５）を０．５重量％添加し、これをビニルアルコール系重合体積層用のコート液とし、これを実施例１で得られた二軸延伸防湿ポリプロピレンフィルムの被覆層（Ｉ）上にメイヤバーを用いて塗布した後、８０℃のオーブン中で乾燥して二軸延伸防湿ポリプロピレンフィルムを得た。得られた二軸延伸防湿ポリプロピレンフィルムのビニルアルコール系重合体層の厚さは１μｍであった。かかる二軸延伸防湿ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表２に示す。
Example 3
Polyvinyl alcohol having a saponification degree of 99.9%, a sodium acetate content of 0.2% and a polymerization degree of 1000 was dissolved in hot water and cooled to room temperature to obtain a 5% strength aqueous solution. To this aqueous solution, 3% by weight of aqueous urethane (WD726 manufactured by Takeda Products Co., Ltd.) and 0.5% by weight of an anionic surfactant (Neopelex F25 manufactured by Kao) as a wetting improver were added. Was applied to the coating layer (I) of the biaxially stretched moisture-proof polypropylene film obtained in Example 1 using a Meyer bar, and then in an oven at 80 ° C. The biaxially stretched moisture-proof polypropylene film was obtained by drying. The thickness of the vinyl alcohol polymer layer of the obtained biaxially stretched moisture-proof polypropylene film was 1 μm. The evaluation of the biaxially stretched moisture-proof polypropylene film was measured by the method described above.
The results are shown in Table 2.
実施例４
実施例３の被覆層（Ｉ）で用いたプロピレン・エチレンランダム共重合体（１）に代えて、エチレン含有量：２．８重量％、Ｔｓ：９７．２℃、Ｔｐ：１２５．６℃、Ｔｅ：１３４．２℃、Ｔｅ−Ｔｓ：３７．０℃、Ｔｐ−Ｔｓ：２８．４℃、Ｍｗ／Ｍｎ：１．９及びＭＦＲ：７ｇ／１０分（２３０℃）のプロピレン・エチレンランダム共重合体（２）を用いる以外は実施例と同様に行い二軸延伸防湿ポリプロピレンフィルムを得た。かかる二軸延伸防湿ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表２に示す。
Example 4
Instead of the propylene / ethylene random copolymer (1) used in the coating layer (I) of Example 3, ethylene content: 2.8 wt%, Ts: 97.2 ° C., Tp: 125.6 ° C., Te: 134.2 ° C, Te-Ts: 37.0 ° C, Tp-Ts: 28.4 ° C, Mw / Mn: 1.9 and MFR: 7 g / 10 min (230 ° C) A biaxially stretched moisture-proof polypropylene film was obtained in the same manner as in Example except that the coalesced (2) was used. The evaluation of the biaxially stretched moisture-proof polypropylene film was measured by the method described above.
The results are shown in Table 2.
比較例２
実施例３の被覆層（Ｉ）で用いたプロピレン・エチレンランダム共重合体（１）に代えて、エチレン含有量：２．２重量％、Ｔｓ：９５．４℃、Ｔｐ：１３９．４℃、Ｔｅ：１５０．３℃、Ｔｅ−Ｔｓ：５４．９℃、Ｔｐ−Ｔｓ：４３．９℃、Ｍｗ／Ｍｎ：３．９及びＭＦＲ：７ｇ／１０分（２３０℃）のプロピレン・エチレンランダム共重合体（３）を用いる以外は実施例と同様に行い二軸延伸防湿ポリプロピレンフィルムを得た。かかる二軸延伸多層ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表２に示す。
Comparative Example 2
In place of the propylene / ethylene random copolymer (1) used in the coating layer (I) of Example 3, ethylene content: 2.2 wt%, Ts: 95.4 ° C., Tp: 139.4 ° C., Te: 150.3 ° C., Te-Ts: 54.9 ° C., Tp-Ts: 43.9 ° C., Mw / Mn: 3.9 and MFR: 7 g / 10 min (230 ° C.) A biaxially stretched moisture-proof polypropylene film was obtained in the same manner as in Example except that the coalesced (3) was used. Evaluation of such a biaxially stretched multilayer polypropylene film was measured by the method described above.
The results are shown in Table 2.
実施例５
けん化度９９．９％、酢酸ナトリウム含有量０．２％、重合度１０００のポリビニルアルコールを熱水で溶解し、室温まで冷却して５％濃度の水溶液（１）を得た。ついで、無機膨潤性層状化合物のナトリウム型テトラシリシックマイカ（トピー工業社製 ＤＭＡ−３５０）を水で固形分が１0重量％になるよう分散させ、遠心分離機を用いて濃度調整し平均粒径２．５μｍの5重量％の濃度の無機膨潤性層状化合物の水分散液（２）を得た。この水溶液（１）と水分散液（２）とを重量比で７／３となるように混合し、さらに水性ウレタン（武田製品工業社製 ＷＤ７２６）を固形分比で３重量％、及び濡れ向上剤としてアニオン系界面活性剤（花王社製 ネオペレックスＦ２５）を０．５重量％添加し、これをビニルアルコール系重合体積層用のコート液とした。これを実施例１で得られた二軸延伸防湿ポリプロピレンフィルムの被覆層（Ｉ）上にメイヤバーを用いて塗布した後、８０℃のオーブン中で乾燥して二軸延伸防湿ポリプロピレンフィルムを得た。得られた二軸延伸防湿ポリプロピレンフィルムのビニルアルコール系重合体層の厚さは１μｍであった。かかる二軸延伸防湿ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表２に示す。
Example 5
Polyvinyl alcohol having a saponification degree of 99.9%, a sodium acetate content of 0.2% and a polymerization degree of 1000 was dissolved in hot water and cooled to room temperature to obtain a 5% aqueous solution (1). Next, sodium-type tetralithic mica (DMA-350 manufactured by Topy Industries Co., Ltd.), an inorganic swellable layered compound, is dispersed with water to a solid content of 10% by weight, the concentration is adjusted using a centrifuge, and the average particle size is adjusted. An aqueous dispersion (2) of an inorganic swellable layered compound having a concentration of 5% by weight of 2.5 μm was obtained. This aqueous solution (1) and aqueous dispersion (2) are mixed so that the weight ratio is 7/3, and further, aqueous urethane (WD726 manufactured by Takeda Products Co., Ltd.) is 3% by weight in solid content ratio, and wetting is improved. As an agent, 0.5% by weight of an anionic surfactant (Neopelex F25 manufactured by Kao Corporation) was added to obtain a coating solution for laminating a vinyl alcohol polymer. This was coated on the coating layer (I) of the biaxially stretched moisture-proof polypropylene film obtained in Example 1 using a Mayer bar, and then dried in an oven at 80 ° C. to obtain a biaxially stretched moisture-proof polypropylene film. The thickness of the vinyl alcohol polymer layer of the obtained biaxially stretched moisture-proof polypropylene film was 1 μm. The evaluation of the biaxially stretched moisture-proof polypropylene film was measured by the method described above.
The results are shown in Table 2.
実施例６
実施例５の被覆層（Ｉ）で用いたプロピレン・エチレンランダム共重合体（１）に代えて、エチレン含有量：２．８重量％、Ｔｓ：９７．２℃、Ｔｐ：１２５．６℃、Ｔｅ：１３４．２℃、Ｔｅ−Ｔｓ：３７．０℃、Ｔｐ−Ｔｓ：２８．４℃、Ｍｗ／Ｍｎ：１．９及びＭＦＲ：７ｇ／１０分（２３０℃）のプロピレン・エチレンランダム共重合体（２）を用いる以外は実施例と同様に行い二軸延伸防湿ポリプロピレンフィルムを得た。かかる二軸延伸防湿ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表２に示す。
Example 6
In place of the propylene / ethylene random copolymer (1) used in the coating layer (I) of Example 5, ethylene content: 2.8 wt%, Ts: 97.2 ° C., Tp: 125.6 ° C., Te: 134.2 ° C, Te-Ts: 37.0 ° C, Tp-Ts: 28.4 ° C, Mw / Mn: 1.9 and MFR: 7 g / 10 min (230 ° C) A biaxially stretched moisture-proof polypropylene film was obtained in the same manner as in Example except that the coalesced (2) was used. The evaluation of the biaxially stretched moisture-proof polypropylene film was measured by the method described above.
The results are shown in Table 2.
比較例３
実施例５の被覆層（Ｉ）で用いたプロピレン・エチレンランダム共重合体（１）に代えて、エチレン含有量：２．２重量％、Ｔｓ：９５．４℃、Ｔｐ：１３９．４℃、Ｔｅ：１５０．３℃、Ｔｅ−Ｔｓ：５４．９℃、Ｔｐ−Ｔｓ：４３．９℃、Ｍｗ／Ｍｎ：３．９及びＭＦＲ：７ｇ／１０分（２３０℃）のプロピレン・エチレンランダム共重合体（３）を用いる以外は実施例と同様に行い二軸延伸多層ポリプロピレンフィルムを得た。かかる二軸延伸多層ポリプロピレンフィルムの評価を前記記載の方法で測定した。
結果を表２に示す。
Comparative Example 3
In place of the propylene / ethylene random copolymer (1) used in the coating layer (I) of Example 5, ethylene content: 2.2 wt%, Ts: 95.4 ° C., Tp: 139.4 ° C., Te: 150.3 ° C., Te-Ts: 54.9 ° C., Tp-Ts: 43.9 ° C., Mw / Mn: 3.9 and MFR: 7 g / 10 min (230 ° C.) A biaxially stretched multilayer polypropylene film was obtained in the same manner as in Example except that the coalesced (3) was used. Evaluation of such a biaxially stretched multilayer polypropylene film was measured by the method described above.
The results are shown in Table 2.
表２の結果から、本発明の二軸延伸防湿ポリプロピレンフィルム（実施例３〜６）は、比較例２および３に示した二軸延伸防湿ポリプロピレンフィルムに比べ、ラミネート強度に優れ、且つ防湿性およびガスバリア性に優れていることが分かる。 From the results shown in Table 2, the biaxially stretched moisture-proof polypropylene films of the present invention (Examples 3 to 6) are superior in laminate strength and moisture-proof properties to the biaxially stretched moisture-proof polypropylene films shown in Comparative Examples 2 and 3. It turns out that it is excellent in gas barrier property.
本発明の二軸延伸防湿ポリプロピレンフィルムはプロピレン・α―オレフィン共重合体（Ｂ）から得られる被覆層（Ｉ）を有しているので、ラミネート強度に優れているので、被覆層（Ｉ）をラミネート層として、他のフィルムと貼り合せて、従来バリア性ＯＰＰフィルムが使用されている海苔類、米菓類等の乾燥食品、たばこ等の嗜好品等の包装用フィルムを始め、あらゆる被包装物の包装用フィルムに使用し得る。
また、ビニルアルコール系重合体層を有する二軸延伸防湿ポリプロピレンフィルムは、特に食品包装材料としてスナック菓子、米菓、ビスケット、ピーナッツ等の乾燥食品に使用し得るし、無機層状化合物を含んでなるビニルアルコール重合体組成物層を有する二軸延伸防湿ポリプロピレンフィルムは、さらに高いガスバリア性を有しているので前記乾燥菓子はもちろんのこと含水率の多い饅頭やカステラ、切り餅、鰹節、各種珍味等の広範囲な用途で使用し得る。
Since the biaxially stretched moisture-proof polypropylene film of the present invention has a coating layer (I) obtained from the propylene / α-olefin copolymer (B), it has excellent laminate strength. Laminate layers are laminated with other films, and traditionally used for barrier-wrapped OPP films such as laver, dried foods such as rice confectionery, and packaging films such as tobacco and other favorite products. It can be used for packaging films.
In addition, the biaxially stretched moisture-proof polypropylene film having a vinyl alcohol polymer layer can be used for dry foods such as snacks, rice cakes, biscuits, peanuts and the like, especially as food packaging materials, and vinyl alcohol comprising an inorganic layered compound Since the biaxially stretched moisture-proof polypropylene film having a polymer composition layer has a higher gas barrier property, it has a wide range of buns, castellas, chopped rice cakes, dried bonito, various delicacies as well as the dried confectionery. Can be used in applications.
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| JP (1) | JP4520721B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007061026A1 (en) * | 2005-11-25 | 2007-05-31 | Mitsui Chemicals, Inc. | Composite sheet and use thereof |
| JP2008073926A (en) * | 2006-09-20 | 2008-04-03 | Tohcello Co Ltd | Biaxially oriented multilayer polypropylene film |
| JP2020040256A (en) * | 2018-09-07 | 2020-03-19 | 大日本印刷株式会社 | Laminate substrate, laminate for packaging material and packaging material |
| JP2020040253A (en) * | 2018-09-07 | 2020-03-19 | 大日本印刷株式会社 | Laminate for packaging material and packaging material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151264A (en) * | 1999-11-26 | 2001-06-05 | Toppan Printing Co Ltd | Over-wrap film |
| JP2002363360A (en) * | 2001-06-01 | 2002-12-18 | Japan Polychem Corp | Polypropylenic unstretched film |
| JP2003103730A (en) * | 2001-09-28 | 2003-04-09 | Toray Ind Inc | Laminated film and metal vapor-deposited laminated film |
-
2003
- 2003-10-22 JP JP2003361493A patent/JP4520721B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001151264A (en) * | 1999-11-26 | 2001-06-05 | Toppan Printing Co Ltd | Over-wrap film |
| JP2002363360A (en) * | 2001-06-01 | 2002-12-18 | Japan Polychem Corp | Polypropylenic unstretched film |
| JP2003103730A (en) * | 2001-09-28 | 2003-04-09 | Toray Ind Inc | Laminated film and metal vapor-deposited laminated film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007061026A1 (en) * | 2005-11-25 | 2007-05-31 | Mitsui Chemicals, Inc. | Composite sheet and use thereof |
| JP4964782B2 (en) * | 2005-11-25 | 2012-07-04 | 三井化学東セロ株式会社 | Composite sheet and its use |
| JP2008073926A (en) * | 2006-09-20 | 2008-04-03 | Tohcello Co Ltd | Biaxially oriented multilayer polypropylene film |
| JP2020040256A (en) * | 2018-09-07 | 2020-03-19 | 大日本印刷株式会社 | Laminate substrate, laminate for packaging material and packaging material |
| JP2020040253A (en) * | 2018-09-07 | 2020-03-19 | 大日本印刷株式会社 | Laminate for packaging material and packaging material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4520721B2 (en) | 2010-08-11 |
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