JPH01244847A - Laminate of polyamide film or sheet - Google Patents
Laminate of polyamide film or sheetInfo
- Publication number
- JPH01244847A JPH01244847A JP7385088A JP7385088A JPH01244847A JP H01244847 A JPH01244847 A JP H01244847A JP 7385088 A JP7385088 A JP 7385088A JP 7385088 A JP7385088 A JP 7385088A JP H01244847 A JPH01244847 A JP H01244847A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- adhesive
- polyamide film
- film
- adhesion
- 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
- 229920002647 polyamide Polymers 0.000 title claims description 40
- 239000004952 Polyamide Substances 0.000 title claims description 39
- 239000010410 layer Substances 0.000 claims abstract description 69
- 239000000565 sealant Substances 0.000 claims abstract description 22
- 239000012790 adhesive layer Substances 0.000 claims abstract description 17
- 229920006233 biaxially oriented polyamide Polymers 0.000 claims abstract description 6
- 238000007639 printing Methods 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 abstract description 28
- 230000001070 adhesive effect Effects 0.000 abstract description 28
- 229920000728 polyester Polymers 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 6
- 229920002635 polyurethane Polymers 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 5
- 239000004814 polyurethane Substances 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 3
- 150000002513 isocyanates Chemical class 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 229920003002 synthetic resin Polymers 0.000 abstract description 3
- 239000000057 synthetic resin Substances 0.000 abstract description 3
- -1 acryl group Chemical group 0.000 abstract description 2
- 239000004840 adhesive resin Substances 0.000 abstract description 2
- 229920006223 adhesive resin Polymers 0.000 abstract description 2
- 229920002678 cellulose Polymers 0.000 abstract description 2
- 239000001913 cellulose Substances 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 20
- 238000011282 treatment Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 238000003475 lamination Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- FQLAJSQGBDYBAL-UHFFFAOYSA-N 3-(azepane-1-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2CCCCCC2)=C1 FQLAJSQGBDYBAL-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009820 dry lamination Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 2
- PGGROMGHWHXWJL-UHFFFAOYSA-N 4-(azepane-1-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1CCCCCC1 PGGROMGHWHXWJL-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 235000015429 Mirabilis expansa Nutrition 0.000 description 1
- 244000294411 Mirabilis expansa Species 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 239000004839 Moisture curing adhesive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はポリアミドフィルムまたはシートの積層体に関
するものであり、該ポリアミド積層体を形成する各層間
の接着力が定常状態において良好であるとともに、たと
えば水分含有食品や薬品等の包装袋などとして使用し、
或は更に清水処理やレトルト処理などの過酷な処理を加
えても水分等の層間浸入による眉間剥離等を生じない様
なポリアミドフィルムまたはシートの積層体に関するも
のである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a laminate of polyamide films or sheets, which has good adhesion between the layers forming the polyamide laminate in a steady state, and For example, it can be used as packaging bags for water-containing foods, medicines, etc.
Furthermore, the present invention relates to a laminate of polyamide films or sheets that does not cause peeling between the eyebrows due to interlayer penetration of moisture, etc. even when subjected to severe treatments such as fresh water treatment and retort treatment.
［従来の技術］
二軸延伸ポリアミドフィルムまたはシート（以下フィル
ムで代表する）は強靭性、耐ピンホール性、耐屈曲性お
よび耐熱性等に優れており、各種用途に汎用されている
。そのうち例えばポリアミドフィルムを包装袋として使
用する際には、−膜内には二軸延伸ポリアミドフィルム
の少なくとも片面に必要により印刷を施し、更に接着剤
層を設けた上へドライラミネート法によってシーラント
層を設けるか、あるいはＡＣ剤層を設けた上に押出ラミ
ネート法によりシーラント層を設けるなどしてポリアミ
ドフィルム積層体とし、該積層体を用いて袋を作成し内
容物を充填後間口部をヒートシールしてたとえば味噌や
醤油などの調味料、スープやレトルト食品等の水分含有
食品あるいは薬品などを包装して一般消費者に提供して
いる。[Prior Art] Biaxially stretched polyamide films or sheets (hereinafter referred to as films) have excellent toughness, pinhole resistance, bending resistance, heat resistance, etc., and are widely used for various purposes. For example, when polyamide film is used as a packaging bag, printing is performed on at least one side of the biaxially stretched polyamide film inside the membrane, and an adhesive layer is further provided on top of which a sealant layer is applied by dry lamination. Alternatively, a polyamide film laminate can be obtained by forming a sealant layer on top of the AC agent layer using an extrusion lamination method, making a bag using the laminate, filling it with contents, and then heat-sealing the opening. For example, seasonings such as miso and soy sauce, water-containing foods such as soup and retort foods, and medicines are packaged and provided to general consumers.
［発明が解決しようとする課題］
ところが二軸延伸ポリアミドフィルム積層体を形成する
各層の界面に水分が浸入すると、層間の接着力が著しく
低下し、包装袋として使用した場合破袋の原因となる。[Problems to be Solved by the Invention] However, when moisture enters the interface between each layer forming a biaxially stretched polyamide film laminate, the adhesive strength between the layers decreases significantly, causing the bag to break when used as a packaging bag. .
たとえばレトルト食品を清水処理あるいはレトルト処理
する際は一層破袋しやすくなる。また包装製品の高級化
につれて全面且つ多色刷り印刷が普及し、印刷インキ層
の存在に基く色々な問題も発生している。For example, when retort food is subjected to fresh water treatment or retort treatment, the bag becomes more likely to break. Further, as packaging products become more sophisticated, full-page and multi-color printing has become widespread, and various problems have arisen due to the presence of the printing ink layer.
また二軸延伸ポリアミドフィルム層とシーラント層の間
に接着剤層を介在する場合、接着剤の種類によっては湿
度によってその接着力に影響を受けやすいものがあり、
特に湿分硬化型の接着剤ではその影響が顕著に表われ、
冬季のような乾燥時においては十分な接着力が得られず
、夏季のような多湿時には湿気が接着剤層に浸入して接
着力を低下させる。Furthermore, when an adhesive layer is interposed between the biaxially oriented polyamide film layer and the sealant layer, the adhesive strength of some types of adhesive may be easily affected by humidity.
This effect is particularly noticeable with moisture-curing adhesives.
Sufficient adhesive strength cannot be obtained in dry times such as winter, and moisture infiltrates the adhesive layer during humid times such as summer, reducing adhesive strength.
そこで本発明においてはポリアミドフィルム積層体にお
ける各層間の接着性が良好であるとともに湿潤時におい
ても高い接着性が保たれるポリアミドフィルム積層体に
ついて検討した。Therefore, in the present invention, we investigated a polyamide film laminate that has good adhesion between each layer and maintains high adhesion even when wet.
［課題を解決するための手段］
上記課題を解決することのできた本発明とは表面張力が
３５〜４９ Ｄｙｎｅ−ｃｍである二軸延伸ポリアミド
フィルムの少なくとも片面に接着改質層／印刷インキ層
／接着剤層／シーラント層を順次設けたものであること
を構成要旨とするものである。[Means for Solving the Problems] The present invention, which has solved the above problems, includes an adhesion-modifying layer/printing ink layer/ The gist of the structure is that an adhesive layer/sealant layer is sequentially provided.
［作用コ
ところで二軸延伸ポリアミドフィルムに印刷インキ層あ
るいはシーラント層を設ける場合、フィルム表面をコロ
ナ放電あるいはその他の方法で表面活性化処理して接着
力の向上を図ることが行なわれている。表面が活性化さ
れている場合は、第１表に示すように確かにポリアミド
層と印刷インキ層との接着力は表面張力が高くなるほど
高くなっている。[Operations] When a printing ink layer or a sealant layer is provided on a biaxially stretched polyamide film, the surface of the film is surface activated by corona discharge or other methods to improve adhesive strength. When the surface is activated, as shown in Table 1, the adhesive force between the polyamide layer and the printing ink layer increases as the surface tension increases.
第 １ 表
○ ：インキ剥れなし
△○：わずかに剥れる
△ ：半分程度剥れる
△×：はとんど剥れる
× ：全て剥れる
またシーラント層との接着力も第１図に示すように表面
張力が高いほど高くなる傾向にある。尚第１表は二軸延
伸ポリアミドフィルムとして東洋紡績社製Ｎｌ１００（
厚さ１５μｍ）を用い、該フィルムに東洋インキ社製マ
ルチセット口を印刷し、二軸延伸ポリアミドフィルムの
表面張力とセロテープ剥離テスト、爪によるひっかきテ
スト。Table 1 ○: Ink does not peel off △○: Slightly peels △: Approximately half peels △×: Slightly peels ×: Completely peels Also, the adhesive strength with the sealant layer is as shown in Figure 1. The higher the surface tension, the higher it tends to be. Table 1 shows Nl100 (manufactured by Toyobo Co., Ltd.) as a biaxially stretched polyamide film.
A multi-set mouth manufactured by Toyo Ink Co., Ltd. was printed on the film (thickness: 15 μm), and the surface tension of the biaxially stretched polyamide film, cellophane tape peeling test, and nail scratch test were conducted.
２０回もみテストとの関係を調べた結果であり、第１図
は同フィルムに接着剤層（ＡＣ剤；イソシアネート系樹
脂）を用いＬＤＰＥをラミネートした積層フィルムにお
ける二軸延伸ポリアミドフィルムの表面張力とシーラン
ト層接着強度との関係を示す図である。The results are the results of examining the relationship with the 20-time kneading test. Figure 1 shows the surface tension of a biaxially stretched polyamide film in a laminated film in which LDPE is laminated using an adhesive layer (AC agent; isocyanate resin) on the same film. It is a figure showing the relationship with sealant layer adhesion strength.
一方、前述と同様にして得た（第１図の説明参照）二軸
延伸ポリアミド層とシーラント層の間に水分が浸入した
場合の接着力を湿潤時接着力として調べてみると第２図
に示すようになる。第２図から明らかな様に表面張力が
高いほど湿潤時接着力は低下している。また検討の結果
この傾向が清水処理時の破袋に大きく影響し、表面張力
が高いほど破袋率が大きいことも確認された。On the other hand, when we investigated the adhesive strength when moisture entered between the biaxially oriented polyamide layer obtained in the same manner as above (see explanation of Figure 1) and the sealant layer, we found Figure 2. It comes to show. As is clear from FIG. 2, the higher the surface tension, the lower the wet adhesive strength. As a result of the study, it was also confirmed that this tendency has a large effect on bag breakage during fresh water treatment, and that the higher the surface tension, the greater the bag breakage rate.
そこで本発明者等が鋭意検討した結果、優れた湿潤時シ
ーラント層接着強度を示す表面張力３５〜４９ Ｄｙｎ
ｅ −ｃｍ、好ましくは３５〜４３ Ｄｙｎｅ −ｃｍ
の二軸延伸フィルムを使用し、該フィルムに接着改質層
を設けて該接着改質層上に印刷インキ層を施し、さらに
印刷インキ層上に接着剤層を形成させたところ、二軸延
伸ポリアミドフィルムと印刷インキ層との接着力および
更にシーラント層との接着力にも優れるとともに、湿潤
時シーラント層接着強度においても優れた性質を示すポ
リアミド積層体を得ることができた。Therefore, as a result of intensive study by the present inventors, a surface tension of 35 to 49 Dyn, which shows excellent adhesive strength of the sealant layer when wet, was found.
e-cm, preferably 35-43 Dyne-cm
When a biaxially stretched film was used, an adhesive modification layer was provided on the film, a printing ink layer was applied on the adhesive modification layer, and an adhesive layer was further formed on the printing ink layer. It was possible to obtain a polyamide laminate that exhibits excellent adhesive strength between the polyamide film and the printing ink layer, as well as excellent adhesive strength between the sealant layer and the adhesive strength of the sealant layer when wet.
本発明で用いる二軸延伸ポリアミドフィルムの原料とな
るポリアミドはアミド結合を有する高分子化合物であり
脂肪族ポリアミドでも芳香族ポリアミドであってもよく
、代表的なポリアミドとしてはナイロン６、ナイロン６
−６、ナイロン６−１０、ナイロン１１．ナイロン１２
．ポリエチレンイソフタラミド、ポリメタキシリレンア
ジパミド、ポリ（ヘキサメチレンイソフタラミド／テレ
フタラミド）、ポリ（ヘキサメチレンイソフタラミド／
モノメチルテレフタラミド）、ヘキサメチレンイソフタ
ラミド／テレフタラミドとイプシロンカプロラクタムと
の共重合体、ヘキサメチレンテレフタラミドとヘキサメ
チレンアジパミドとの共重合体などが非限定的に例示さ
れる。The polyamide that is the raw material for the biaxially stretched polyamide film used in the present invention is a polymer compound having amide bonds, and may be an aliphatic polyamide or an aromatic polyamide. Typical polyamides include nylon 6 and nylon 6.
-6, nylon 6-10, nylon 11. nylon 12
．． Polyethylene isophthalamide, polymethaxylylene adipamide, poly(hexamethylene isophthalamide/terephthalamide), poly(hexamethylene isophthalamide/
Non-limiting examples include copolymers of hexamethylene isophthalamide/terephthalamide and epsilon caprolactam, and copolymers of hexamethylene terephthalamide and hexamethylene adipamide.
尚目的性能を損なわない限り前記ポリアミドに対して酸
化防止剤、耐光剤、ゲル化防止剤、滑剤、ブロッキング
防止剤、顔料、帯電防止剤、界面活性剤等を配合するこ
とができる。In addition, antioxidants, light-resistant agents, anti-gelling agents, lubricants, anti-blocking agents, pigments, antistatic agents, surfactants, etc. may be added to the polyamide as long as the desired performance is not impaired.
二軸延伸ポリアミドフィルム上に形成される接着改質層
に用いる接着性樹脂としては、ポリエステル、ポリウレ
タン、エポキシ系樹脂、アクリル系等の樹脂およびこれ
らの共重合物あるいは混合物を使用することができる。As the adhesive resin used for the adhesion-modifying layer formed on the biaxially stretched polyamide film, resins such as polyester, polyurethane, epoxy resin, acrylic resin, and copolymers or mixtures thereof can be used.
例えばポリエステルとポリイソシアネートの混合物を用
いる場合は、ポリエステルを構成する酸成分の８０〜２
０モル％がテレフタル酸で残りの２０〜８０％がアジピ
ン酸、セバシン酸等の脂肪族二塩基酸やイソフタル酸、
オルソフタル酸、ジフェニルジカルボン酸等の芳香族二
塩基酸よりなり、アルコール成分の２０〜７０％がエチ
レングリコールで残りの８０〜３０モル％が１．２−プ
ロピレングリコール、１．３−プロピレングリコール、
１．４−ブタンジオール、１．３−ブタンジオール、ジ
エチレングリコール、トリエチレングリコール、ネオペ
ンチルグリコール等からなるポリエステル、特に酸成分
の２０モル％以上がテレフタル酸やイソフタル酸で残り
がセバシン酸やアジピン酸から選ばれた１種以上からな
り、アルコール成分の２０〜７９モル％がグリコールか
らなり、有機溶媒に可溶な線状ポリエステルを用いる。For example, when using a mixture of polyester and polyisocyanate, 80 to 2
0 mol% is terephthalic acid and the remaining 20-80% is aliphatic dibasic acids such as adipic acid and sebacic acid, isophthalic acid,
Consisting of aromatic dibasic acids such as orthophthalic acid and diphenyldicarboxylic acid, 20-70% of the alcohol component is ethylene glycol and the remaining 80-30 mol% is 1.2-propylene glycol, 1.3-propylene glycol,
Polyester consisting of 1.4-butanediol, 1.3-butanediol, diethylene glycol, triethylene glycol, neopentyl glycol, etc., especially 20 mol% or more of the acid component is terephthalic acid or isophthalic acid, and the remainder is sebacic acid or adipic acid. The linear polyester is composed of one or more selected from the following, 20 to 79 mol% of the alcohol component is glycol, and is soluble in an organic solvent.
またポリイソシアネートとしては少なくとも２個以上の
イソシアネート基を含有するもので、２．４−および２
゜６−ドリレンジイソシアネート、４．４’ −ジフェ
ニルメタンジイソシアネート、メタキシリレンジイソシ
アネート、トリレンジイソシアネート３モルとトリメチ
ロールプロパン１モルの反応生成物、ヘキサメチレンジ
イソシアネート等の脂肪族ならびに芳香族のポリイソシ
アネートが一般的に用いられる。前記ポリエステルとポ
リウレタンの混合比は固形分比で１００：５〜１０：１
００となるように配合するのが好ましく、酢酸エチル、
メチルエチルケトン、トルエン等の有機溶媒に溶解して
二軸延伸ポリアミドに塗布する。Furthermore, polyisocyanates include those containing at least two or more isocyanate groups, such as 2,4- and 2-
゜Aliphatic and aromatic polyisocyanates such as 6-tolylene diisocyanate, 4.4'-diphenylmethane diisocyanate, metaxylylene diisocyanate, the reaction product of 3 moles of tolylene diisocyanate and 1 mole of trimethylolpropane, and hexamethylene diisocyanate. Commonly used. The mixing ratio of the polyester and polyurethane is 100:5 to 10:1 in solid content ratio.
It is preferable to mix it so that it becomes 00, and ethyl acetate,
It is dissolved in an organic solvent such as methyl ethyl ketone or toluene and applied to biaxially stretched polyamide.
塗布方法としてはグラビアロール法、リバースロール法
、ロッド法、デイツプ法等通常の塗布方法を採用し、固
形分として０．０１〜０．５ｇ／ｍ’になるように塗布
する。又接着改質層の塗布後４０℃程度で熟成すること
によって、その効果は一段と向上する。As a coating method, a conventional coating method such as a gravure roll method, a reverse roll method, a rod method, or a dip method is adopted, and the coating is applied so that the solid content is 0.01 to 0.5 g/m'. Further, by aging the adhesion-modifying layer at about 40° C. after coating, the effect is further improved.
次に印刷に用いる印刷インキとしては、セルロール誘導
体をバインダーとしたインキあるいは合成樹脂をバイン
ダーとしたグラビアインキが主として用いられ、特に耐
沸水性が要求される場合には、水酸基等の末端官能基を
有する塩化ビニル、ポリエステル、ポリエーテル、ポリ
オール等をバインダーとしたインキを、硬化剤を添加し
て用い、前記接着改質層上へ全面的または部分的にある
いは任意の図柄として印刷インキ層を形成する。Next, as printing inks used for printing, inks with a cellulose derivative as a binder or gravure inks with a synthetic resin as a binder are mainly used, and when particularly boiling water resistance is required, terminal functional groups such as hydroxyl groups are used. Using an ink containing vinyl chloride, polyester, polyether, polyol, etc. as a binder, with the addition of a curing agent, a printing ink layer is formed entirely or partially or as an arbitrary pattern on the adhesion-modifying layer. .
また印刷インキ層上に設けられる接着剤層を形成する接
着剤は、該接着剤層上に設けるシーラント層が押出ラミ
ネートによって設けられる場合には、イソシアネート系
接着剤が好ましく、例えば−波型としてジイソシアネー
トと多価アルコールとの反応物でＮＧＯ基を末端に有す
るポリウレタン又はＮＧＯ基を末端に有するプレポリマ
ーなどがある。二液型としてはポリイソシアネートとポ
リオールあるいはＯＨ基を末端に有するポリウレタンプ
レポリマーとを使用前に混合して用いる。In addition, the adhesive forming the adhesive layer provided on the printing ink layer is preferably an isocyanate adhesive when the sealant layer provided on the adhesive layer is provided by extrusion lamination. and a polyhydric alcohol, such as polyurethane having an NGO group at its end or a prepolymer having an NGO group at its end. As a two-component type, a polyisocyanate and a polyol or a polyurethane prepolymer having an OH group at the end are mixed before use.
シーラント層がドライラミネートによって積層される場
合に用いられる接着剤としては、ビニル系、アクリル系
、ポリアミド系、エポキシ系、ウレタン系などが挙げら
れるが、主としてポリイソシアネートとポリオールを使
用直前に混合して用いるポリウレタン系接着剤が好まし
い。接着剤層はこれらの樹脂の溶液あるいはエマルジョ
ンを常法に従って塗布して形成する。Adhesives used when the sealant layer is laminated by dry lamination include vinyl-based, acrylic-based, polyamide-based, epoxy-based, urethane-based, etc., but mainly polyisocyanate and polyol are mixed immediately before use. It is preferable to use a polyurethane adhesive. The adhesive layer is formed by applying a solution or emulsion of these resins according to a conventional method.
前記のようにして接着剤層が形成されたならば接着剤層
上にシーラント層を設ける。シーラント層はＬＤＰＥ、
ＥＶＡ、フイオ／マー、ＰＰ等の合成樹脂を押出ラミネ
ートあるいはドライラミネートにより設ける。Once the adhesive layer is formed as described above, a sealant layer is provided on the adhesive layer. The sealant layer is LDPE,
A synthetic resin such as EVA, Fio/mer, PP, etc. is provided by extrusion lamination or dry lamination.
このようにして得られたポリアミド積層体は、二軸延伸
ポリアミドフィルム表面の表面張力が低く、水に対する
親和性が乏しいため、接着改質層と該フィルム表面との
間に水分が浸入し難く、被包装物の水分あるいは導水処
理やレトルト処理時の水分等の影晋に対して優れた耐水
性が得られる。また印刷インキ層に対する接着性は接着
改質層によって十分な接着力が得られ、従来両立が困難
であった耐水性と印刷インキ層に対する接着力共に優れ
た積層体が得られる。In the polyamide laminate thus obtained, the surface tension of the biaxially stretched polyamide film is low and the affinity for water is poor, so water is difficult to enter between the adhesion-modifying layer and the film surface. Excellent water resistance can be obtained against the influence of moisture in the packaged object or moisture during water conveyance treatment or retort treatment. In addition, sufficient adhesion to the printing ink layer can be obtained by the adhesion-modifying layer, and a laminate can be obtained that is excellent in both water resistance and adhesion to the printing ink layer, which have been difficult to achieve in the past.
［実施例］
実施例１
表面張力が３７Ｄｙｎｅ−ｃｍの二軸延伸ポリアミドフ
ィルムをテンター法により製造して該フィルムの片面に
、線状ポリエステル樹脂（パイロン３００、東洋紡績社
製）およびポリイソシアネート（コロネートし、日本ポ
リウレタン社製）をｔｏｏ：１０（固形分比）となるよ
うに混合し、固形分濃度４％になるように酢酸エチルで
調製した混合液をグラビアコートにより０．１ｇ／Ｉ１
１”となるように塗布し乾燥後４０℃で２日間熟成を行
ない接着改質層を形成した。尚ブロッキング防止および
滑性付与の目的で無機滑剤（サイロイド１５０、富士デ
ビインソン社製）をポリアミド樹脂分に対し０．５％添
加した。[Examples] Example 1 A biaxially stretched polyamide film having a surface tension of 37 Dyne-cm was produced by a tenter method, and one side of the film was coated with a linear polyester resin (Pylon 300, manufactured by Toyobo Co., Ltd.) and a polyisocyanate (Coronate). (manufactured by Nippon Polyurethane Co., Ltd.) to a ratio of too:10 (solid content ratio), and prepared a mixed solution with ethyl acetate to give a solid content concentration of 4%.
1" and dried and aged at 40°C for 2 days to form an adhesion-modifying layer. In order to prevent blocking and impart lubricity, an inorganic lubricant (Syroid 150, manufactured by Fuji Devinson Co., Ltd.) was added to the polyamide resin. It was added at 0.5% per minute.
さらに接着改質層上にグラビアインキ（ラミエース６１
白二液タイプ、東洋インキ社製）をグラビア印刷して印
刷インキ層を形成し、次いで一液湿気硬化型ＡＣ剤（Ｔ
−１０４，日本ソーダ社製）を塗布してＡＣ剤層を形成
した後常法に従ってＬＤＰＥ押出ラミネートを行ないシ
ーラント層を設け、ポリアミドフィルム積層体を形成し
４０℃で熟成した。得られたポリアミドフィルム積層体
の常態保存（乾燥時および湿潤時）における接着力（剥
離強度）を測定した結果を第２表に示す。Furthermore, gravure ink (LamiAce 61
A printing ink layer was formed by gravure printing a white two-component type (manufactured by Toyo Ink Co., Ltd.), and then a one-component moisture-curing AC agent (T
-104, manufactured by Nippon Soda Co., Ltd.) to form an AC agent layer, LDPE extrusion lamination was performed according to a conventional method to provide a sealant layer, and a polyamide film laminate was formed and aged at 40°C. Table 2 shows the results of measuring the adhesive strength (peel strength) of the obtained polyamide film laminate under normal storage (dry and wet).
次にポリアミドフィルム積層体を内寸１０ｃｍｘ１０ｃ
ｍの三方袋に製袋し、内部に水２０ｍ１．空気１００ｍ
１を充填後間口部を密閉した。この密閉袋の導水（ボイ
ル）処理後の乾燥条件保存および湿潤条件保存における
剥離強度およびボイルパンクテストを行なった結果を第
２表に示す。Next, a polyamide film laminate with inner dimensions of 10 cm x 10 cm
The bag is made into a three-sided bag with a size of 2.5 m and 20 ml of water inside. air 100m
1 was filled, the frontage was sealed. Table 2 shows the peel strength and boil puncture test results of this airtight bag when stored under dry conditions and under wet conditions after water conduction (boiling) treatment.
比較例１
表面張力５３Ｄｙｎｅ−ｃｍの二軸延伸ポリアミドフィ
ルムをテンター法により製造し、該フィルムを用いた他
は実施例１と同様に処理した。結果を第２表に示す。Comparative Example 1 A biaxially stretched polyamide film having a surface tension of 53 Dyne-cm was produced by a tenter method, and the same treatment as in Example 1 was performed except that this film was used. The results are shown in Table 2.
比較例２
表面張力３７ Ｄｙｎｅ −ｃｍの二軸延伸ポリアミド
フィルムの片面に接着改質層を設けない他は実施例１と
同様に処理し試験した。結果を第２表に示す。Comparative Example 2 A biaxially stretched polyamide film having a surface tension of 37 Dyne -cm was treated and tested in the same manner as in Example 1, except that no adhesion-modifying layer was provided on one side. The results are shown in Table 2.
第２表から明らかなように本発明のポリアミドフィルム
積層体は常態およびボイル処理後のいずれの場合も湿潤
条件下に置いたときの剥離強度は比較例に比べてはるか
に優れており、バンクテスト率も良好な結果を示してい
る。As is clear from Table 2, the peel strength of the polyamide film laminate of the present invention when placed under wet conditions both in the normal state and after boiling treatment is far superior to that of the comparative example, and in the bank test The ratio also shows good results.
実施例２
− 表面張力３７ Ｄｙｎｅ −ｃｍの二軸延伸ポリア
ミドフィルムをテンター法により製造し、該フィルムに
エポキシ樹脂（ＥｌｏｏＩ、油化シェル社製）およびポ
リアミド樹脂（Ｖａｒｓａｍｉｄｌ ２５ 、ヘンケル
日本社製）の混合物を７５：２５（固形分比）となるよ
うに混合し、固形分濃度５％になるようにメチルエチル
ケトン、イソプロピルアルコールで調製した混合物をグ
ラビアコートにより固形分で０．１ｇ／ｌ１１２となる
ように塗布し、４０℃で２日間熟成を行なった。さらに
グラビアインキ（マルチセット６１白二液タイプ、東洋
インキ社製）をグラビア印刷して印刷層を形成した後、
−液温気硬化型ＡＣ剤（ＥＬ２５０．東洋インキ社製）
を塗布し接着剤層を形成した後、常法により押出ラミネ
ートによりＬＤＰＥ層を設けた後４０℃で熟成した。こ
の様にして得たポリアミドフィルム積層体を実施例１と
同様にして剥離強度を測定した。結果を第３表に示す。Example 2 - A biaxially oriented polyamide film with a surface tension of 37 dyne-cm was produced by a tenter method, and the film was coated with an epoxy resin (ElooI, manufactured by Yuka Shell) and a polyamide resin (Varsamidl 25, manufactured by Henkel Nippon Co., Ltd.). The mixture was mixed at a ratio of 75:25 (solid content ratio), and the mixture prepared with methyl ethyl ketone and isopropyl alcohol to a solid content concentration of 5% was gravure coated to a solid content of 0.1 g/l112. It was applied and aged at 40°C for 2 days. Furthermore, after gravure printing with gravure ink (Multi Set 61 white two-component type, manufactured by Toyo Ink Co., Ltd.) to form a printing layer,
-Liquid temperature air curing type AC agent (EL250. Manufactured by Toyo Ink Co., Ltd.)
was applied to form an adhesive layer, and then an LDPE layer was provided by extrusion lamination according to a conventional method, followed by aging at 40°C. The peel strength of the polyamide film laminate thus obtained was measured in the same manner as in Example 1. The results are shown in Table 3.
比較例３
表面張力５３Ｄｙｎｅ−ｃｍの二軸延伸ポリアミドフィ
ルムを用いた他は実施例２と同様に処理し試験した。結
果を第３表に示す。Comparative Example 3 Processing and testing were carried out in the same manner as in Example 2, except that a biaxially stretched polyamide film having a surface tension of 53 Dyne-cm was used. The results are shown in Table 3.
第３表
第３表から明らかなように表面張力が３５〜４９ Ｄｙ
ｎｅ −ＣＩＯであるものは水分が付着した際の剥離強
度に優れていることがわかる。As is clear from Table 3, the surface tension is 35 to 49 Dy.
It can be seen that ne -CIO has excellent peel strength when moisture is attached.
［発明の効果コ
本発明は以上のように構成されているので本発明のポリ
アミドフィルム積層体は二軸延伸ポリアミドフィルム層
と印刷インキ層およびシーラント層との接着強度が良好
であるとともに湿潤時においてもこれらの層間の接着強
度が高く保たれる。[Effects of the Invention] Since the present invention is constructed as described above, the polyamide film laminate of the present invention has good adhesive strength between the biaxially oriented polyamide film layer and the printing ink layer and the sealant layer, and also has good adhesive strength when wet. Also, the adhesive strength between these layers is maintained high.
第１図は二軸延伸ポリアミドフィルムの表面張力とシー
ラント層接着強度の関係を示す図、第２図は二軸延伸ポ
リアミドフィルムの表面張力と湿潤時シーラント層接着
強度の関係を示す図である。
第１図
表面張力［Ｄｙｎｅ−Ｃｍ ）
表面張力 （Ｄｙｎｅ−ｃｍ）
昭和６３年 ５月１を日
特許庁長官 小 川 邦 夫 殿
１ 事件の表示
昭和６３年特許願第７３８５０号
２、発明の名称
ポリアミドフィルムまたはシートの積層体３、補正をす
る者
事件との関係 特許出願人
４、代理人
住 所 大阪市北区堂島２丁目３番７号シシコー仁ゞル
４０７く自発）
６、補正の対象
明細書の「発明の詳細な説明」の欄
７ 補正の内容
別紙「正誤表」の通り訂正します、゛パ正 誤
表
第 ２ 表
ボイルバンクテスト：ｎ＝１０
９８〜１００℃ＸｔＯ分後のパンク率
ボイル処理条件：９５℃×３０分
Ｄｒｙの条件：空気中にて測定、ボイル処理後のものは
付着水分を拭きとって測定FIG. 1 is a diagram showing the relationship between the surface tension of a biaxially stretched polyamide film and the adhesive strength of the sealant layer, and FIG. 2 is a diagram showing the relationship between the surface tension of the biaxially stretched polyamide film and the adhesive strength of the sealant layer when wet. Figure 1 Surface tension [Dyne-cm) Surface tension (Dyne-cm) May 1, 1988 Director General of the Japan Patent Office Kunio Ogawa 1 Indication of the case Patent application No. 73850 of 1988 2, Title of the invention Polyamide film or sheet laminate 3, Relationship with the case of the person making the amendment Patent applicant 4, Agent address: 407 Shishiko Jin, 2-3-7 Dojima, Kita-ku, Osaka City (Voluntary initiative) 6. Subject of amendment Column 7 of "Detailed Description of the Invention" of the Specification Contents of the amendment The correction is made as per the attached "Errata" Table 2 Boil bank test: n=10 After 98-100℃XtO minutes Puncture rate Boil processing conditions: 95°C x 30 minutes Dry conditions: Measured in air, measured after boiling by wiping off adhering moisture
Claims (1)
リアミドフィルムまたはシートの少なくとも片面に接着
改質層／印刷インキ層／接着剤層／シーラント層を順次
設けたものであることを特徴とするポリアミドフィルム
またはシートの積層体。A polyamide film characterized in that it is a biaxially oriented polyamide film or sheet having a surface tension of 35 to 49 Dyne-cm, with an adhesion modifying layer/printing ink layer/adhesive layer/sealant layer sequentially provided on at least one side. or a laminate of sheets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073850A JPH06104356B2 (en) | 1988-03-28 | 1988-03-28 | Laminate excellent in peel resistance of polyamide film or sheet and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63073850A JPH06104356B2 (en) | 1988-03-28 | 1988-03-28 | Laminate excellent in peel resistance of polyamide film or sheet and method for producing the same |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8005127A Division JP2996164B2 (en) | 1996-01-16 | 1996-01-16 | Polyamide laminated bag excellent in bag breaking resistance and method for producing the same |
| JP25725397A Division JP2996220B2 (en) | 1997-09-22 | 1997-09-22 | Polyamide laminate for bag making with excellent bag breaking resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01244847A true JPH01244847A (en) | 1989-09-29 |
| JPH06104356B2 JPH06104356B2 (en) | 1994-12-21 |
Family
ID=13530037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63073850A Expired - Lifetime JPH06104356B2 (en) | 1988-03-28 | 1988-03-28 | Laminate excellent in peel resistance of polyamide film or sheet and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06104356B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0458378U (en) * | 1990-09-27 | 1992-05-19 | ||
| WO1996011108A1 (en) * | 1994-10-06 | 1996-04-18 | At Plastics Inc. | Articles formed of multilayered film having antifog properties |
| WO1998021268A1 (en) * | 1996-11-14 | 1998-05-22 | Alliedsignal Inc. | Coated nylon film |
| US6352762B1 (en) | 1997-07-07 | 2002-03-05 | Kohjin Co., Ltd. | Easily adhesive polyamide film |
| JP2007320580A (en) * | 2006-05-30 | 2007-12-13 | Kyodo Printing Co Ltd | Lid material capable of forming fluid passing-through hole and container using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4937584A (en) * | 1972-08-09 | 1974-04-08 | ||
| JPS5979732A (en) * | 1982-10-29 | 1984-05-09 | Unitika Ltd | Plastic film improved in adhesiveness |
-
1988
- 1988-03-28 JP JP63073850A patent/JPH06104356B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4937584A (en) * | 1972-08-09 | 1974-04-08 | ||
| JPS5979732A (en) * | 1982-10-29 | 1984-05-09 | Unitika Ltd | Plastic film improved in adhesiveness |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0458378U (en) * | 1990-09-27 | 1992-05-19 | ||
| WO1996011108A1 (en) * | 1994-10-06 | 1996-04-18 | At Plastics Inc. | Articles formed of multilayered film having antifog properties |
| WO1998021268A1 (en) * | 1996-11-14 | 1998-05-22 | Alliedsignal Inc. | Coated nylon film |
| US5952106A (en) * | 1996-11-14 | 1999-09-14 | Alliedsignal Inc. | Coated nylon film |
| US6352762B1 (en) | 1997-07-07 | 2002-03-05 | Kohjin Co., Ltd. | Easily adhesive polyamide film |
| JP2007320580A (en) * | 2006-05-30 | 2007-12-13 | Kyodo Printing Co Ltd | Lid material capable of forming fluid passing-through hole and container using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06104356B2 (en) | 1994-12-21 |
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