JP3529819B2 - Vertically oriented film, sheet or container and method for producing the same - Google Patents
Vertically oriented film, sheet or container and method for producing the sameInfo
- Publication number
- JP3529819B2 JP3529819B2 JP35335393A JP35335393A JP3529819B2 JP 3529819 B2 JP3529819 B2 JP 3529819B2 JP 35335393 A JP35335393 A JP 35335393A JP 35335393 A JP35335393 A JP 35335393A JP 3529819 B2 JP3529819 B2 JP 3529819B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- sheet
- film
- container
- melt
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 17
- 229920005992 thermoplastic resin Polymers 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 9
- 239000010410 layer Substances 0.000 description 76
- 238000000034 method Methods 0.000 description 17
- 239000004840 adhesive resin Substances 0.000 description 14
- 229920006223 adhesive resin Polymers 0.000 description 14
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 13
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 8
- 238000004898 kneading Methods 0.000 description 7
- -1 propylene, butylene Chemical group 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、熱可塑性物質（Ａ）お
よび（Ｂ）からなり、とくにエチレン−ビニルアルコー
ル（Ａ）および熱可塑性樹脂（Ｂ）からなり、（Ａ）お
よび／または（Ｂ）がフィルム、シートまたは容器の表
面に垂直に対し層状に配向したフィルム、シートまたは
容器およびその製法に関する。The present invention comprises thermoplastics (A) and (B), in particular ethylene-vinyl alcohol (A) and a thermoplastic resin (B), (A) and / or (B). ) Relates to a film, sheet or container oriented in a layered manner with respect to the surface of the film, sheet or container and a method for producing the same.
【０００２】[0002]
【従来の技術】エチレン−ビニルアルコール共重合体Ｅ
ＶＯＨ（Ａ）はガスバリアー性、保香性、耐油性の優れ
た熱可塑性樹脂であるが、親水性であるため高湿度の雰
囲気にさらされたり、水、アルコール等の極性溶剤に接
触すると上記の特性が失われる欠点を有する。そこでＥ
ＶＯＨ（Ａ）と熱可塑性樹脂との少なくとも２層あるい
はそれ以上からなる積層成形物として使用されるのが一
般的である。この場合、ＥＶＯＨ層の耐ピンホール性、
耐熱水性（耐レトルト性）、耐衝撃性、ガスバリアー性
の改善あるいは多層積層体成形時のスクラップ回収性を
改善するため、ＥＶＯＨ（Ａ）と熱可塑性樹脂（Ｂ）と
のブレンド組成物を用いる場合が益々増大する傾向にあ
り、これらのブレンド組成物をより均一に分散させる
為、各種の添加剤等の検討が成されてはいるが、分散を
改善しても、溶融成形加工時の本質的特性として、樹脂
の流れ方向（剪断方向）に平行な面状、線状、楕円状に
配向し、かつフィルム、シート表面に対し深さ方向に濃
度分布を持ち、深さ中央部を基準に、両表面に向かって
およそ対称的な濃度分布が生じる傾向にある。その結
果、フィルム、シートまたは容器の縦方向、横方向の各
種強度は優れているが、フィルム、シート、容器の厚み
方向の各種強度が充分でないという欠点があった。2. Description of the Related Art Ethylene-vinyl alcohol copolymer E
VOH (A) is a thermoplastic resin having excellent gas barrier properties, fragrance retaining properties, and oil resistance, but since it is hydrophilic, it is exposed to a high-humidity atmosphere or comes into contact with polar solvents such as water and alcohol as described above. Has the drawback that the properties of are lost. So E
It is generally used as a laminated molded product composed of at least two layers of VOH (A) and a thermoplastic resin or more. In this case, the pinhole resistance of the EVOH layer,
A blend composition of EVOH (A) and a thermoplastic resin (B) is used in order to improve hot water resistance (retort resistance), impact resistance, gas barrier property, or scrap recovery at the time of molding a multilayer laminate. However, in order to disperse these blend compositions more uniformly, various additives have been studied, but even if the dispersion is improved, the essence of the melt molding As a characteristic property, it is oriented in a plane, linear or elliptical shape parallel to the flow direction (shear direction) of the resin, and has a concentration distribution in the depth direction with respect to the film or sheet surface. , There is a tendency that an approximately symmetrical concentration distribution is generated toward both surfaces. As a result, the various strengths of the film, sheet or container in the longitudinal and transverse directions are excellent, but there is a drawback that the various strengths of the film, sheet or container in the thickness direction are not sufficient.
【０００３】[0003]
【発明が解決しようとする課題】しかして、本発明の目
的は、熱可塑性物質（Ａ）および（Ｂ）、とくにＥＶＯ
Ｈ（Ａ）および熱可塑性樹脂（Ｂ）からなる、厚さ方向
の各種強度の優れたフィルム、シートまたは容器を得る
ことにある。The object of the present invention is therefore to obtain thermoplastics (A) and (B), in particular EVO.
It is to obtain a film, sheet or container which is made of H (A) and a thermoplastic resin (B) and has various strengths in the thickness direction.
【０００４】[0004]
【課題を解決するための手段】上記目的は、少なくとも
エチレン−ビニルアルコール共重合体（Ａ）および
（Ａ）以外の熱可塑性樹脂（Ｂ）からなり、（Ａ）と
（Ｂ）のうち量の少ない方がフィルム、シートまたは容
器の表面に対し垂直に層状に配向したフィルム、シート
または容器を提供することによって解決される。The above-mentioned objects are at least as follows.
Ethylene-vinyl alcohol copolymer (A) and
Made of a thermoplastic resin (B ) other than (A), and (A)
The lesser of (B) is solved by providing a film, sheet or container oriented in layers in a direction perpendicular to the surface of the film, sheet or container.
【０００５】本発明の垂直配向構造体の製法を、図面
（模式図）により説明する。最良の製法を示す図１につ
いてまず説明する。まず第１ステップとして、（Ａ）お
よび（Ｂ）二種類あるいはそれ以上の溶融混練物１を横
方向に、さらに必要に応じ流れ方向、縦方向に延伸して
溶融混練体２を得る。次に第２ステップとして前記溶融
混練体２を、縦方向（上下方向）から剪断作用を与えて
混練し、すなわち縦方向にモーター１０により回転する
回転混練機（例えば二重円筒状回転混練機）９により混
練し、溶融混練体３を得る。次に第３ステップとして前
記混練体３を横方向から圧縮し、第１ステップに近い形
状に回復した混練体４を得るとともに流れ方向を軸にし
て、９０±２０度、好ましくは９０±１０度、ねじれ回
転をかけ、溶融混練体５を得る。その後ねじれ回転を加
えた混練体５を通常のダイス６に導き（すなわち、前記
の混練体の縦方向が横方向になり、横方向が縦方向にな
る）、成形することにより、成形物の表面に対し垂直に
層状（ここで層状とは層状のみならず、面状、線状、ま
たは楕円状を意味する。）に配向した単層あるいは多層
のフィルム、シートまたは容器７（厚さ方向の断面構造
８）を得る。A method of manufacturing the vertically aligned structure of the present invention will be described with reference to the drawings (schematic diagrams). First, FIG. 1 showing the best manufacturing method will be described. First, as a first step, two or more kinds of (A) and (B) melt-kneaded products 1 are stretched in the transverse direction and, if necessary, in the flow direction and the longitudinal direction to obtain a melt-kneaded product 2. Next, as a second step, the melt-kneaded body 2 is kneaded by applying a shearing action in the vertical direction (vertical direction), that is, a rotary kneader that rotates by a motor 10 in the vertical direction (for example, a double cylindrical rotary kneader). The mixture is kneaded with 9 to obtain a melt-kneaded body 3. Next, as a third step, the kneading body 3 is compressed from the lateral direction to obtain a kneading body 4 that has recovered to a shape close to that of the first step, and 90 ± 20 degrees, preferably 90 ± 10 degrees with the flow direction as an axis. Then, a twisted rotation is applied to obtain a melt-kneaded body 5. After that, the kneaded body 5 to which the twist rotation is applied is guided to a normal die 6 (that is, the longitudinal direction of the kneaded body becomes the horizontal direction and the horizontal direction becomes the vertical direction), and the surface of the molded product is obtained. A single-layer or multi-layer film, sheet or container 7 (cross-section in the thickness direction) oriented vertically in a layered manner (here, layered means not only layered but also planar, linear or elliptical). Structure 8) is obtained.
【０００６】図１において重要な工程は第３ステップの
９０度±２０度回転をかけることであり、この工程によ
りフィルムまたはシートの表面に対し垂直に（Ａ）およ
び／または（Ｂ）を層状に配向させることができる。図
５は第２ステップの溶融混練体２を縦方向に回転する回
転体により混練する方法の一例｛（ａ）〜（ｄ）｝であ
り、溶融混練体２を二重円筒状回転混練機９による混練
する方法を示している。第２ステップは省略することも
可能であり、この第２ステップとを省略した工程の模式
図を図３に示す。図３において１５は溶融混練体、１６
は圧縮後の溶融混練体、１７は９０±２０度ねじれ回転
をかけた溶融混練体である。また第３ステップにおける
圧縮一形状回復工程も省略することができるが、設ける
ことが好ましい。In FIG. 1, an important step is to apply a 90 ° ± 20 ° rotation in the third step, and by this step, (A) and / or (B) are layered perpendicularly to the surface of the film or sheet. It can be oriented. FIG. 5 shows an example {(a) to (d)} of the second step of kneading the melt-kneaded body 2 with a rotating body that rotates in the longitudinal direction. The melt-kneaded body 2 is a double cylindrical rotary kneader 9 The method of kneading is shown. The second step can be omitted, and a schematic view of the process omitting the second step is shown in FIG. In FIG. 3, 15 is a melt-kneaded product, 16
Is a melt-kneaded body after compression, and 17 is a melt-kneaded body that is twisted and rotated by 90 ± 20 degrees. Although the compression-one-shape recovery step in the third step can be omitted, it is preferable to provide it.
【０００７】また他の製法として、図１の第３ステップ
のねじれ回転の工程を省略する方法もある。この工程の
模式図を図４に示すが、この方法によれば、押出しシー
ト８の構造は（Ａ）および／または（Ｂ）が、シート表
面に対し垂直に配向した構造（ただし流れ方向と平行な
断面からみて）となる。なお流れ方向と直角な断面から
みた構造は（Ａ）および／または（Ｂ）の１部はシート
表面に対し平行に配向した構造となる。As another manufacturing method, there is a method in which the twisting and rotating step of the third step in FIG. 1 is omitted. A schematic diagram of this step is shown in FIG. 4. According to this method, the structure of the extruded sheet 8 is such that (A) and / or (B) is oriented perpendicularly to the sheet surface (however, it is parallel to the flow direction). Seen from the cross section). In the structure viewed from the cross section perpendicular to the flow direction, a part of (A) and / or (B) is oriented parallel to the sheet surface.
【０００８】また他の製法として、図２に示すように溶
融混練体１をダイス６に導入し、ダイス内に設けられた
縦方向にモーター１２により回転する回転混練機１１
（図１の９の構造と同じ）により混練したあと成形し
て、シート１３を得る方法もある。この方法によれば図
２の押出しシート１４の厚さ方向の断面から明らかなよ
うに（Ａ）および／または（Ｂ）がシート表面に対し垂
直に配向した構造（ただし流れ方向と平行な断面からみ
て）となる。As another manufacturing method, as shown in FIG. 2, the melt-kneading body 1 is introduced into a die 6, and a rotary kneader 11 is installed in the die and is rotated by a motor 12 in a vertical direction.
There is also a method in which the sheet 13 is obtained by kneading (the same structure as 9 in FIG. 1) and then molding. According to this method, as is apparent from the cross section in the thickness direction of the extruded sheet 14 in FIG. 2, a structure in which (A) and / or (B) is oriented perpendicular to the sheet surface (however, from the cross section parallel to the flow direction) See).
【０００９】このようにして得られた成形物は、（Ａ）
および（Ｂ）がフィルム、シートまたは容器の表面に垂
直に配向した櫛形構造となっているため、厚み方向に対
する各種強度が優れている。The molded product thus obtained is (A)
Since (B) and (B) have a comb-like structure that is oriented perpendicular to the surface of the film, sheet or container, various strengths in the thickness direction are excellent.
【００１０】本発明において熱可塑性物質（Ａ）および
（Ｂ）としては、各種熱可塑性樹脂が代表例としてあげ
られるが、（Ａ）および（Ｂ）はそれぞれの欠点を相補
う樹脂同士の組合せが好ましい。In the present invention, as the thermoplastic substances (A) and (B), various thermoplastic resins can be mentioned as typical examples. However, in (A) and (B), a combination of resins which complement each other's drawbacks is used. preferable.
【００１１】（Ａ）としては、たとえばガスバリヤー性
の優れたＥＶＯＨがあげられ、ＥＶＯＨ（Ａ）としては
エチレン含量１０〜７０モル％、好適には１５〜６５モ
ル％の範囲のものがあげられる。 エチレン含量が１０
モル％未満では溶融成形性が悪く、一方７０モル％で
は、ガスバリアー性が不足する。また、鹸化度は９０％
以上が好ましく、９０％未満では、ガスバリアー性およ
び熱安定性が悪くなる。本発明においては、ＥＶＯＨ製
造時に用いるビニルエステルとしては酢酸ビニルが代表
的なものとしてあげらるが、本発明の目的が阻害されな
い範囲で、他の共重合体［例えば、プロピレン、ブチレ
ン、不飽和カルボン酸又はそのエステル｛（メタ）アク
リル酸、（メタ）アクリル酸エステルメチル、エチル）
など｝、ビニルピロリドン（Ｎ−ビニルピロリドンな
ど）ビニルシラン化合物を共重合体することも出来る
し、さらに、熱安定剤、紫外線吸収剤、酸化防止剤、着
色剤、他の樹脂（ポリアミド、部分けん化エチレン−酢
酸ビニル共重合体など）をブレンドすることも自由であ
る。また、本発明に用いるＥＶＯＨの好適なメルトイン
デックス（ＭＩ）１９０℃、２１６０ｇ荷重下：ただ
し、融点が１９０℃付近あるいは１９０℃を越えるもの
は２１６０ｇ荷重下、融点以上の複数の温度で測定し、
片対数グラフで絶対温度の逆数を横軸、メルトインデッ
クスを縦軸としてプロットし、１９０℃に外押して求め
た値）は０．１〜５０ｇ／１０ｍｉｎ．、最適には０．
５〜２０ｇ／１０ｍｉｎ．である。Examples of (A) include EVOH having an excellent gas barrier property, and examples of EVOH (A) include those having an ethylene content of 10 to 70 mol%, preferably 15 to 65 mol%. . Ethylene content 10
If it is less than mol%, the melt moldability will be poor, while if it is 70 mol%, the gas barrier property will be insufficient. The degree of saponification is 90%
The above is preferable, and if it is less than 90%, gas barrier properties and thermal stability are deteriorated. In the present invention, vinyl acetate is mentioned as a typical vinyl ester used in the production of EVOH, but other copolymers such as propylene, butylene and unsaturated may be used as long as the object of the present invention is not impaired. Carboxylic acid or its ester {(meth) acrylic acid, (meth) acrylic acid ester methyl, ethyl)
}, Vinylpyrrolidone (N-vinylpyrrolidone, etc.) vinylsilane compound can be copolymerized, and further, heat stabilizer, ultraviolet absorber, antioxidant, colorant, other resin (polyamide, partially saponified ethylene) -Vinyl acetate copolymer etc.) is also free to blend. In addition, a suitable melt index (MI) of EVOH used in the present invention is 190 ° C. under a load of 2160 g: However, if the melting point is around 190 ° C. or exceeds 190 ° C., it is measured under a load of 2160 g at a plurality of temperatures above the melting point.
In a semi-logarithmic graph, the reciprocal of absolute temperature is plotted on the abscissa and the melt index is plotted on the ordinate, and the value obtained by pushing to 190 ° C.) is 0.1 to 50 g / 10 min. , Optimally 0.
5 to 20 g / 10 min. Is.
【００１２】熱可塑性樹脂（Ｂ）としては特に限定され
るものではなく、溶融押出成形出来る熱可塑性樹脂、液
晶樹脂、無機物、金属があげられ、例えばポリエチレ
ン、ポリプロピレン、ポリアミド、ポリエステル、ポリ
カーボネート、ポリアクリロニトリル、ポリアクリル酸
エステル、ポリメタアクリル酸エステル、ポリスチレ
ン、エチレン−ビニルエステル共重合体、エチレン−ア
クリル酸共重合体、エチレン−メタアクリル酸共重合
体、エチレン−アクリル酸エステル共重合体、エチレン
−メタアクリル酸エステル共重合体、ポリ塩化ビニル、
ポリ塩化ビニリデン、ポリフッ化ビニル、シリコン樹
脂、低融点ガラス等が挙げられる。The thermoplastic resin (B) is not particularly limited, and examples thereof include melt-extrudable thermoplastic resins, liquid crystal resins, inorganic substances, and metals. For example, polyethylene, polypropylene, polyamide, polyester, polycarbonate, polyacrylonitrile. , Polyacrylic acid ester, polymethacrylic acid ester, polystyrene, ethylene-vinyl ester copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene- Methacrylic acid ester copolymer, polyvinyl chloride,
Examples thereof include polyvinylidene chloride, polyvinyl fluoride, silicone resin and low melting point glass.
【００１３】ここで、熱可塑性樹脂（Ｂ）の特性とし
て、より好適な条件としては、成形温度における溶融粘
性指数（メルトインデックス：ＭＩ）が（Ａ）と類似し
ていることであり、具体的には（Ａ）の５０〜１／５０
倍の範囲、より好適には２０〜１／２０倍、更に好適に
は１０〜１／１０倍である。５０〜１／５０倍の範囲を
越えると均一、微細な分散が出来ず不透明化など外観不
良が生じやすくなる。As a characteristic of the thermoplastic resin (B), a more preferable condition is that the melt viscosity index (melt index: MI) at the molding temperature is similar to that of (A). 50 to 1/50 of (A)
The range is twice, more preferably 20 to 1/20 times, and further preferably 10 to 1/10 times. If it exceeds 50 to 1/50 times, uniform and fine dispersion cannot be achieved and appearance defects such as opacity are likely to occur.
【００１４】（Ａ）と（Ｂ）の配合割合は、（Ａ）：
（Ｂ）＝５：９５〜９５：５が好ましく、さらに好適に
は１０：９０〜９０：１０である。このうち量の少ない
方が垂直に層状に配向することが多い。The mixing ratio of (A) and (B) is (A):
(B) = 5: 95 to 95: 5 is preferable, and 10:90 to 90:10 is more preferable. Of these, the smaller amount often aligns vertically in a layered manner.
【００１５】さらに（Ａ）と（Ｂ）との分散性および界
面接着性を改善するため、（Ａ）と（Ｂ）との相溶性を
向上を目的に相溶化剤を０．５〜２０重量％添加する事
があり、相溶化剤としては、例えば、無水マレイン酸、
カルボン酸、シリル化合物など、（Ａ）たとえばＥＶＯ
Ｈと反応あるいは相互作用がある官能基を有する熱可塑
性樹脂が有効である。Further, in order to improve the dispersibility of (A) and (B) and the interfacial adhesion, 0.5 to 20 parts by weight of a compatibilizer is added for the purpose of improving the compatibility of (A) and (B). % May be added, and as the compatibilizing agent, for example, maleic anhydride,
Carboxylic acid, silyl compound, etc. (A) For example, EVO
A thermoplastic resin having a functional group that reacts or interacts with H is effective.
【００１６】また、ブレンドする際、他の添加剤（可塑
剤、熱安定剤、紫外線吸収剤、酸化防止剤、着色剤、フ
ィラー、他の樹脂など）を本発明の目的が阻害されない
範囲で使用する事は自由である。特に、ゲル発生防止対
策として、ハイドロタルサイト系化合物、ヒンダードフ
ェノール系、ヒンダードアミン系熱安定剤、高級脂肪族
カルボン酸の金属塩（たとえば、ステアリン酸カルシウ
ム、ステアリン酸マグネシウムなど）の一種または二種
以上を０．０１〜１重量％添加する事は好適である。When blending, other additives (plasticizer, heat stabilizer, UV absorber, antioxidant, colorant, filler, other resin, etc.) are used within a range not impairing the object of the present invention. You are free to do anything. In particular, one or more of hydrotalcite-based compounds, hindered phenol-based, hindered amine-based heat stabilizers, metal salts of higher aliphatic carboxylic acids (for example, calcium stearate, magnesium stearate, etc.) are used as a measure for preventing gel formation. Is preferably added in an amount of 0.01 to 1% by weight.
【００１７】本発明の（Ａ）と（Ｂ）との垂直配向構造
体（Ｃ）の厚みとしては１〜３０００μ、好適には３〜
２０００μ、より好適には５〜１０００μである。ま
た、フィルム、シートまたは容器の表面に対し垂直に層
状に配向した（Ａ）、（Ｂ）の濃度分布としては測定が
困難であるが、フィルム流れ方向に垂直な面の断面を電
子顕微鏡で観察して、フィルム厚み方向に層状に配向し
た物の面積より濃度分布を求めた場合、全体の面積に対
し１０面積％以上、好適には２０％以上である。ここで
表面に対し垂直とは９０±６０度、好ましくは９０±４
５度を意味する。The thickness of the vertically aligned structure (C) of (A) and (B) of the present invention is 1 to 3000 μ, preferably 3 to.
It is 2000μ, and more preferably 5 to 1000μ. Further, it is difficult to measure the concentration distribution of (A) and (B) oriented in a layer shape perpendicular to the surface of the film, sheet or container, but the cross section of the plane perpendicular to the film flow direction is observed with an electron microscope. Then, when the concentration distribution is obtained from the area of the product oriented in the film thickness direction in a layered manner, it is 10% by area or more, preferably 20% or more with respect to the entire area. Here, perpendicular to the surface is 90 ± 60 degrees, preferably 90 ± 4
Means 5 degrees.
【００１８】垂直配向構造体（Ｃ）は、周知の溶融成形
法、圧縮成形法によりフィルム、シート、容器（ボト
ル、カップ）に成形する事が出来る。本発明の垂直配向
構造体を多層構造体の一層として使用するとき、顕著な
特徴が発揮されるので、以下この点について説明を加え
る。まず、多層構造体を得る方法としては、前記垂直配
向構造体（Ｃ）は（Ａ）、（Ｂ）あるいは接着性樹脂を
介して（Ｂ）以外の熱可塑性樹脂（Ｄ）とを押出ラミネ
ート法、ドライラミネート法、共押出ラミネート法、共
押出シート成形法、共押出パイプ成形法、共射出成形
法、溶液コート法などにより多層構造体を得、次いで、
多層構造体を真空圧空深絞り成形、延伸ブロー成形する
方法、さらには（Ａ）、たとえばＥＶＯＨの溶融以下の
範囲で再加熱し延伸操作を行う方法、あるいは、該積層
体（フィルム又はシート）を二軸延伸機に供し、加熱延
伸する方法などがあげられる。The vertically aligned structure (C) can be formed into a film, a sheet or a container (bottle, cup) by a well-known melt molding method or compression molding method. When the vertically aligned structure of the present invention is used as one layer of a multi-layer structure, remarkable features are exhibited, and therefore, this point will be described below. First, as a method for obtaining a multilayer structure, the vertical alignment structure (C) is extrusion laminated with (A), (B) or a thermoplastic resin (D) other than (B) via an adhesive resin. , A dry lamination method, a co-extrusion lamination method, a co-extrusion sheet molding method, a co-extrusion pipe molding method, a co-injection molding method, a solution coating method, etc. to obtain a multilayer structure, and then,
A method of vacuum-pneumatic deep drawing, stretch blow molding of a multilayer structure, and further (A), for example, a method of reheating in a range of not more than melting of EVOH and performing a stretching operation, or the laminate (film or sheet) Examples include a method of subjecting to a biaxial stretching machine and heating and stretching.
【００１９】さらに、多層構造体の厚み構成に関して
は、特に限定されるものではないが、成形性およびコス
ト等を考慮した場合、全厚みに対するＥＶＯＨなどの
（Ａ）層の厚み比率は２〜２０％である。また、多層構
造体の構成としては垂直配向構造体（Ｃ）層／接着性樹
脂層／（Ａ）層、（Ａ）層／接着性樹脂層／垂直配向構
造体（Ｃ）層／接着性樹脂層／（Ｂ）層、（Ａ）層／垂
直配向構造体（Ｃ）層／接着性樹脂層／（Ｂ）層、
（Ａ）層／接着性樹脂層／（Ａ）層／垂直配向構造体
（Ｃ）層／接着性樹脂層／（Ｂ）層、（Ａ）層／接着性
樹脂層／（Ａ）層／接着性樹脂層／垂直配向構造体
（Ｃ）層／（Ｂ）層が代表的なものとしてあげられる。
両外層に熱可塑性樹脂層を設ける場合は、該樹脂が異な
っていてもよいし、また同じものでもよい。また、成形
時発生するトリムなどのスクラップを熱可塑性樹脂層に
ブレンドしたり、別途、回収層をもうけて再使用される
場合も多い。Further, the thickness constitution of the multilayer structure is not particularly limited, but in consideration of moldability and cost, the thickness ratio of the (A) layer such as EVOH to the total thickness is 2 to 20. %. Further, the structure of the multi-layer structure includes vertical alignment structure (C) layer / adhesive resin layer / (A) layer, (A) layer / adhesive resin layer / vertical alignment structure (C) layer / adhesive resin Layer / (B) layer, (A) layer / vertical alignment structure (C) layer / adhesive resin layer / (B) layer,
(A) layer / adhesive resin layer / (A) layer / vertical alignment structure (C) layer / adhesive resin layer / (B) layer, (A) layer / adhesive resin layer / (A) layer / adhesion A typical example is a resin layer / vertical alignment structure (C) layer / (B) layer.
When thermoplastic resin layers are provided on both outer layers, the resins may be different or the same. Further, in many cases, scrap such as trim generated at the time of molding is blended with the thermoplastic resin layer, or a recovery layer is separately provided for reuse.
【００２０】この様にして得られた垂直配向構造体
（Ｃ）により本発明の目的である、厚さ方向に対する各
種強度が優れたフィルムまたはシートを得ることができ
る。以下、実施例により本発明をさらに説明するが、こ
れによりなんら限定されるものではない。The vertically aligned structure (C) thus obtained can provide a film or sheet excellent in various strengths in the thickness direction, which is the object of the present invention. Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto.
【００２１】[0021]
実施例１
エチレン含有量３２モル％、けん化度９９．６％、メル
トインデックス（ＭＩ１９０℃，２１６０ｇ荷重）１．
５ｇ／１０ｍｉｎ．のＥＶＯＨ（Ａ）７０重量部にＭＩ
が１．５のエチレン−酢酸ビニル共重合体（ＥＶＡ）樹
脂（Ｂ）３０重量部をブレンドした樹脂を、図１および
図５の（ａ）を用いて押出し成形するとともに、３種５
層共押出装置にかけ、直鎖状低密度ポリエチレン層／接
着性樹脂層／垂直配向構造層／接着性樹脂層／直鎖状低
密度ポリエチレン層の多層フィルムを得た。各層の厚み
は４０／１０／２０／１０／４０μであり、垂直配向構
造体の断面（押出し方向）を観察したところ、ＥＶＡが
シートの表面に対しほぼ垂直に層状に配向していること
が認められた。また垂直配向構造層の断面を熱キシレン
（１３０℃）に浸漬し、ポリエチレン層を僅かに溶解し
電子顕微鏡で垂直配向構造を示すＥＶＡの濃度を算出し
た結果、２５面積％の垂直配向構造を示している事を確
認した。得られた垂直配向構造層を含む多層フィルムの
接着性を評価しようとしたが、各層の剥離が出来ず、測
定不可能なほど強固な接着を示した。また垂直配向構造
層の層内剥離も認められなかった。Example 1 Ethylene content 32 mol%, saponification degree 99.6%, melt index (MI190 ° C., 2160 g load) 1.
5 g / 10 min. MI in 70 parts by weight of EVOH (A)
A resin obtained by blending 30 parts by weight of an ethylene-vinyl acetate copolymer (EVA) resin (B) having a ratio of 1.5 is extruded using FIG. 1 and FIG.
It was subjected to a layer coextrusion device to obtain a multilayer film of linear low-density polyethylene layer / adhesive resin layer / vertical alignment structure layer / adhesive resin layer / linear low-density polyethylene layer. The thickness of each layer was 40/10/20/10 / 40μ, and when the cross section (extrusion direction) of the vertically oriented structure was observed, it was confirmed that EVA was oriented in a layer shape almost perpendicular to the surface of the sheet. Was given. Further, the cross section of the vertically aligned structure layer was immersed in hot xylene (130 ° C.), the polyethylene layer was slightly dissolved, and the concentration of EVA showing the vertically aligned structure was calculated by an electron microscope. I confirmed that. An attempt was made to evaluate the adhesiveness of the obtained multi-layered film including the vertically aligned structure layer, but the layers could not be peeled off, and the adhesion was so strong that it could not be measured. In addition, no peeling of the vertically aligned structure layer was observed.
【００２２】比較例１
実施例１においてブレンドを押出しダイ６に直接導入
し、それ以外は実施例１と同様に多層フィルムを得た。
多層フィルムは引取速度２５０ｍｍ／ｍｉｎでの接着強
度は１５０ｇ／１５ｍｍ巾と非常に低い値を示し、ブレ
ンド物層内が剥離している事より、層内剥離により接着
強度の低下と予想される。Comparative Example 1 A multilayer film was obtained in the same manner as in Example 1 except that the blend in Example 1 was directly introduced into the extrusion die 6.
The adhesive strength of the multilayer film at a take-up speed of 250 mm / min was a very low value of 150 g / 15 mm width, and since the inside of the blended product layer was peeled off, it is expected that the adhesive strength would be reduced due to peeling within the layer.
【００２３】実施例２
エチレン含有量３２モル％、けん化度９９．６％、メル
トインデックス（ＭＩ１９０℃、２１６０ｇ荷重）１．
５ｇ／１０ｍｉｎ．のＥＶＯＨ（Ａ）８０重量％と６−
１２ナイロン（Ｂ）２０重量％をブレンドした樹脂を図
１および図５の（ａ）を用い、厚さ２０μの単層フィル
ムを得た。該フィルムの両面の延伸ナイロンフィルムお
よびポリプロピレンフィルムを接着剤をはさんでドライ
ラミネートし、更に該多層フィルムをヒートシーラーを
用いて水充填パウチ作成した後１２０℃３０分間加熱熱
水レトルト殺菌を行った。その結果、得られたパウチは
白化もなく外観が非常に良好であった。またブレンドフ
ィルムの層内剥離も認められなかった。Example 2 Ethylene content 32 mol%, saponification degree 99.6%, melt index (MI 190 ° C., 2160 g load) 1.
5 g / 10 min. EVOH (A) of 80% by weight and 6-
A resin blended with 20% by weight of 12 nylon (B) was used in FIGS. 1 and 5 (a) to obtain a single-layer film having a thickness of 20 μm. A stretched nylon film and a polypropylene film on both sides of the film were dry-laminated with an adhesive, and the multi-layer film was made into a water-filled pouch using a heat sealer, and then hot water retort sterilization was performed at 120 ° C. for 30 minutes. . As a result, the obtained pouch had no whitening and had a very good appearance. Further, peeling within the layer of the blend film was not observed.
【００２４】比較例２
実施例２においてブレンドを押出しダイ６に直接導入
し、それ以外は実施例２と同様に行った。得られたパウ
チは折れ目部分、シール部分等に白化、ブレンドフィル
ムが認められた。Comparative Example 2 The same procedure as in Example 2 was carried out except that the blend was directly introduced into the extrusion die 6 in Example 2. In the obtained pouch, whitening and a blend film were observed in the folds and seals.
【００２５】実施例３
ポリスチレン層／接着性樹脂層／ＥＶＯＨ層／接着性樹
脂層／ポリスチレン層の３種５層シートで熱成形を行
い、容器を打抜いた後、不要になった部分（スクラップ
部分）を回収再使用するため、粉砕し、ポリスチレン層
／回収層／接着性樹脂層／ＥＶＯＨ層／接着性樹脂層／
回収層／ポリスチレン層の４種７層の共押出しシートを
作成した。その場合回収層については回収物（ブレン
ド）を図１および図５の（ａ）を用いて押出し成形し
た。得られたシートで熱成形容器を作成し、水を充填し
落下衝撃を評価した結果、最大落下高さは１．２ｍｍで
あった。Example 3 Thermoforming was performed using a three-layer five-layer sheet of polystyrene layer / adhesive resin layer / EVOH layer / adhesive resin layer / polystyrene layer, and after punching out the container, the unnecessary portion (scrap) (Part) for recovery and reuse, pulverized and polystyrene layer / recovery layer / adhesive resin layer / EVOH layer / adhesive resin layer /
A coextrusion sheet of 4 layers and 7 layers of recovery layer / polystyrene layer was prepared. In that case, for the recovery layer, the recovered product (blend) was extruded using (a) of FIGS. 1 and 5. A thermoformed container was prepared from the obtained sheet, filled with water, and the drop impact was evaluated. As a result, the maximum drop height was 1.2 mm.
【００２６】比較例３
実施例３において、回収物を押出し６に直接導入し、そ
れ以外は実施例１と同様にして回収層を含む４種７層シ
ートを作成した。得られたシートで作成した熱成形容器
の落下衝撃高さは０．５ｍｍであった。Comparative Example 3 In Example 3, the recovered substance was directly introduced into the extrusion 6, and otherwise the same as in Example 1 to prepare a 4-kind 7-layer sheet including a recovered layer. The drop impact height of the thermoformed container made of the obtained sheet was 0.5 mm.
【００２７】[0027]
【発明の効果】熱可塑性物質（Ａ）および（Ｂ）のブレ
ンド組成物層の層内剥離による接着力の低下、衝撃強度
の悪化、層内ボイド発生による透明性の低下、白化を防
止、改善することができる。EFFECT OF THE INVENTION Adhesive strength of the blend composition layer of the thermoplastic substances (A) and (B) is reduced due to peeling within the layer, impact strength is deteriorated, transparency is reduced due to occurrence of voids in the layer, and whitening is prevented and improved. can do.
【図１】本発明の製造工程の模式図である。FIG. 1 is a schematic view of a manufacturing process of the present invention.
【図２】本発明の他の製造工程の模式図である。FIG. 2 is a schematic view of another manufacturing process of the present invention.
【図３】本発明の他の製造工程の模式図である。FIG. 3 is a schematic view of another manufacturing process of the present invention.
【図４】本発明の他の製造工程の模式図である。FIG. 4 is a schematic view of another manufacturing process of the present invention.
【図５】本発明の図１の第２ステップにおける混練の態
様を示す断面図である。5 is a cross-sectional view showing an aspect of kneading in the second step of FIG. 1 of the present invention.
１ 溶融混練体 ２ 延伸後の溶融混練体 ３ 回転体により混練された溶融混練体 ４ 圧縮後の溶融混練体 ５ ９０度の回転をかけた溶融混練体 ６ ダイス ７ 押出しシート ８ 押出しシート（厚さ方向の断面） ９ 二重円筒状の回転混練機 １０ モーター 1 Melt-kneaded product 2 Melt-kneaded product after drawing 3 Melt-kneaded body kneaded by a rotating body 4 Melt-kneaded product after compression 5 Melt-kneaded body rotated by 90 degrees 6 dice 7 Extruded sheet 8 Extruded sheet (cross section in the thickness direction) 9 Double cylindrical rotary kneader 10 motors
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ // Ｂ２９Ｋ 101:12 Ｂ２９Ｋ 101:12 Ｂ２９Ｌ 7:00 Ｂ２９Ｌ 7:00 22:00 22:00 Continuation of front page (51) Int.Cl. 7 Identification code FI // B29K 101: 12 B29K 101: 12 B29L 7:00 B29L 7:00 22:00 22:00
Claims (3)
共重合体（Ａ）および（Ａ）以外の熱可塑性樹脂（Ｂ）
からなり、（Ａ）と（Ｂ）のうち量の少ない方がフィル
ム、シートまたは容器の表面に対し垂直に層状に配向し
たフィルム、シートまたは容器。1. At least ethylene-vinyl alcohol
Copolymers (A) and thermoplastic resins (B) other than (A )
A film, sheet or container in which the smaller amount of (A) and (B) is oriented in a layered manner perpendicular to the surface of the film, sheet or container.
ルム、シートまたは容器。 2. The filter according to claim 1, which is composed of a multilayer structure.
Rum, sheet or container.
共重合体（Ａ）および（Ａ）以外の熱可塑性樹脂（Ｂ）
の溶融混練物を少なくとも一方向に延伸し、次に延伸し
た溶融混練物を、流れ方向を軸にして９０±２０度回転
させた後、成形することを特徴とする、請求項１または
２記載のフィルム、シートまたは容器の製法。3. At least ethylene-vinyl alcohol
Copolymers (A) and thermoplastic resins (B) other than (A )
The melt-kneaded product was stretched at least in one direction, then the melt-kneaded product was stretched, after to the flow direction by rotating it around 90 ± 20 degrees, characterized by molding, according to claim 1 or
2. The method for producing the film, sheet or container according to 2 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35335393A JP3529819B2 (en) | 1993-12-29 | 1993-12-29 | Vertically oriented film, sheet or container and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35335393A JP3529819B2 (en) | 1993-12-29 | 1993-12-29 | Vertically oriented film, sheet or container and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07195510A JPH07195510A (en) | 1995-08-01 |
| JP3529819B2 true JP3529819B2 (en) | 2004-05-24 |
Family
ID=18430267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35335393A Expired - Fee Related JP3529819B2 (en) | 1993-12-29 | 1993-12-29 | Vertically oriented film, sheet or container and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3529819B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3660337B2 (en) * | 2002-11-06 | 2005-06-15 | 株式会社コーハン | Manufacturing method of wooden synthetic resin board |
-
1993
- 1993-12-29 JP JP35335393A patent/JP3529819B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07195510A (en) | 1995-08-01 |
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