JPS6135938B2 - - Google Patents
Info
- Publication number
- JPS6135938B2 JPS6135938B2 JP55177897A JP17789780A JPS6135938B2 JP S6135938 B2 JPS6135938 B2 JP S6135938B2 JP 55177897 A JP55177897 A JP 55177897A JP 17789780 A JP17789780 A JP 17789780A JP S6135938 B2 JPS6135938 B2 JP S6135938B2
- Authority
- JP
- Japan
- Prior art keywords
- low
- polyethylene resin
- density polyethylene
- base sheet
- resin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 229920001684 low density polyethylene Polymers 0.000 claims description 41
- 239000004702 low-density polyethylene Substances 0.000 claims description 41
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 22
- 238000001125 extrusion Methods 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 230000001070 adhesive effect Effects 0.000 description 12
- -1 polyethylene Polymers 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000007664 blowing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Description
本発明は表面に低密度ポリエチレン系樹脂層が
被覆されている積層体の製造方法に関するもの
で、熱接着強度が大きく、且つこの強度の経時変
化が小さな低密度ポリエチレン系樹脂層を有し、
良好なるホツトタツク性を具備し、しかも低密度
ポリエチレン系樹脂層に起因するポリエチレン臭
の少ない積層体を容易、且つ確実に得られる積層
体の製造方法を提供するものである。
アルミニウム箔等の金属箔、各種合成樹脂製フ
イルム、及びこれらに塩化ビニリデンを被覆した
もの或は紙等の基材シートに低密度ポリエチレン
系樹脂の溶融押出しフイルムを密接、押圧し接着
させることにより、熱接着性を具備する積層シー
トを得ることは、諸種の包装材料等の製造方法と
して広く知られていることである。
ところで、この押出しラミネート加工を利用し
て低密度ポリエチレン系樹脂層を有する積層体を
得る方法においては、基材シートに積層される際
の低密度ポリエチレン系樹脂の溶融押出しフイル
ムが300℃以下の低温度になると基材シートに対
する低密度ポリエチレン系樹脂フイルムの接着強
度が急激に低下することから、押出し成形温度
300℃以上の高温度で押出し成形された直後の低
密度ポリエチレン系樹脂フイルムを基材シートと
密接させて積層体を得るのが一般的な方法であ
る。しかしながらこの方法で得られた積層体は、
該積層体における低密度ポリエチレン系樹脂が
300℃以上の高温加熱を受けたものであり、この
高温加熱でポリエチレンが分解して低分子量物が
生成しているものであるため、基材シート表面に
設けられているポリエチレン系樹脂層自体の熱接
着強度が低下しているばかりでなく、この熱接着
強度が時間とともに更に低下するし、しかも前記
ポリエチレン系樹脂層にはポリエチレン臭が発生
するために食品、医薬品等を充填するための包装
材としては利用しにくく、更にはホツトタツク性
に対しても十分な性能が得られない等の欠点を有
している。
このため、基材シートに密接される側即ち内面
層の押出し機の押出し温度を300℃以上にし、外
面層の押出し機の押出し温度を低温に設定した多
層押出し機を使用して低密度ポリエチレン系樹脂
を押出しこれを別製の基材シート表面にラミネー
ト加工したり、あるいは基材シートに密接される
側の反対側に窒素ガスや燃焼ガス等の不活性ガス
を吹き付けながら溶融押出しされた低密度ポリエ
チレン系樹脂フイルムを基材シート表面に密接
し、ラミネート加工する等の方法も提案されてい
るが、多層押出し機を使用する方法は、得られる
低密度ポリエチレン系樹脂フイルムの内層面と外
層面との間の温度差が、押出し機の設定温度のよ
うにはならないこと、また不活性ガスを吹き付け
る方法は大量のガスを必要とするので、製造経費
が高価格となる等、いずれも満足される方法では
ない。
本発明は特許請求の範囲の通りの構成、即ち、
290℃以下の押出し温度で押出し成形した直後
の、少なくとも表面部分が溶融状態にある低密度
ポリエチレン系樹脂フイルムの片面に、１ｇ/m3
以上のオゾンを含有する気体を50ml/m2以上の割
合で吹き付け、しかる後にこの低密度ポリエチレ
ン系樹脂フイルムと、表面にアンカーコート剤に
よるアンカーコート層を有する別製の基材シート
とを、前記低密度ポリエチレン系樹脂フイルムに
おけるオゾン処理面と基材シートにおけるアンカ
ーコート層面とが密接するようにして積層、押圧
し、接着させることにより低密度ポリエチレン系
樹脂層の熱接着強度が大きく、この熱接着強度に
経時変化がなく、しかも低密度ポリエチレン系樹
脂層に起因するポリエチレン臭の少ない積層体を
容易、且つ確実に得られる積層体の製造方法を提
供するものである。
さらに本発明においては、前記したような特質
に加え、ホツトタツク性、即ち積層体からなる包
装材料の熱接着（シール）部におけるシーラント
樹脂が十分に冷却、固化する以前に該シール部に
充填物の重量等による剥離力が作用した場合の接
着（シール）強度に優れた性質を有する積層体を
得ることが出来るということもまた１つの特質で
ある。このホツトタツク性の良、否が問題にされ
るのは就中、錠剤などのストリツプ包装、砂糖等
を１スプーン宛包装する多連ダイロール包装、重
量物を包装する縦ピロー包装等においてであり、
ホツトタツク性の悪い包装材を用いた場合には、
シール部は剥離やピンホールが発生する原因とな
つており、横ピロー包装においても、高速充填、
包装化に伴い袋底部のシール部に充填物の慣性に
よる剥離力が作用するために該シール部に剥離が
発生する等のためである。本発明で得られる良好
なるホツトタツク性は低密度ポリエチレン系樹脂
を290℃以下の低温度にて押出しラミネートする
ことによるものであり、この押出し温度を低くす
る程優れたホツトタツク性を有する積層体を得る
ことができる。
本発明において、得られる積層体に良好なる熱
接着性能（ヒートシール特性）を具備せしめる目
的で基材シートに押出しラミネートされる低密度
ポリエチレン系樹脂としては、従来から良好なる
熱接着性等を具備せしめる目的で基材シート表面
に低密度ポリエチレン系樹脂層を形成する際に使
用されていた樹脂、即ち密度0.900〜0.940、溶融
指数〔MI〕0.4〜40のエチレン単独重合体、エチ
レンとプロピレン、ブテン、ペンテン、ヘキセ
ン、オクテン、ノネン、デセン、４−メチルペン
テン−１、酢酸ビニル、アクリル酸、アクリル酸
エステル等のα−オレフイン類との共重合体、あ
るいはこれらに無水マレイン酸等の不飽和カルボ
ン酸類をグラフト重合させた共重合体、またはカ
ルボキシル基を含むものを金属イオン化させたも
の等が使用出来る。
本発明においては、後述する表面にアンカーコ
ート剤によるアンカーコート層を有する基材シー
トと積層される少なくとも表面部分が溶融状態に
ある低密度ポリエチレン系樹脂フイルムは、前記
低密度ポリエチレン系樹脂を290℃以下の押出し
温度で押出し成形することによつて得られるもの
であるが、この押出し成形の際の下限温度は、通
常成形、加工速度、エヤーギヤツプの大小、押出
し成形された低密度ポリエチレン系樹脂フイルム
に吹き付ける気体中のオゾン含有量の大小、該気
体の吹付け量、押出し成形原料として使用される
合成樹脂の加工適性等によつて制限を受けるもの
であるが、約200℃程度が利用され得る下限温度
である。
本発明においては前述の通り、経時変化に伴う
熱接着強度の低下やポリエチレン臭の原因となる
ポリエチレンの分解生成物たる低分子量物の生成
を起すことの無い低温度、即ち290℃以下の押出
し温度で押出し成形した直後の少なくとも表面部
分が溶融状態にある低密度ポリエチレン系樹脂フ
イルムの片面にオゾンを含有する気体を吹き付
け、該面を酸化することにより、別製の、表面に
アンカーコート剤によるアンカーコート層を有す
る基材シートとの接着性を改良するものである。
この表面部分が溶融状態にある低密度ポリエチレ
ン系樹脂フイルムの接着面となる片面に吹き付け
るオゾンを含有する気体は通常のオゾン発生機に
空気あるいは酸素を供給することによつて得られ
るが、本発明においては少なくとも表面部分が溶
融状態にある低密度ポリエチレン系樹脂フイルム
の片面に、オゾン濃度１ｇ/m3以上の気体を50ml/
m2以上の割合で吹き付けることが必要である。こ
れは、低密度ポリエチレン系樹脂フイルム面に吹
き付けられる気体のオゾン濃度が１ｇ/m3未満だ
つたり或るいは吹き付けられる気体の量が50ml/
m2未満だつたりした場合には、この気体の吹き付
け工程において、低密度ポリエチレン系樹脂フイ
ルムの表面酸化の度合が十分ではなく、表面にア
ンカーコート剤によるアンカーコート層を有する
別製の基材シートとの間の強大なる接着強度が得
られなくなり、本発明の目的を達成することがで
きなくなるためである。
低密度ポリエチレン系樹脂フイルムによる低密
度ポリエチレン系樹脂層が形成される基材シート
としては、従来のこの種の積層体の製造方法にお
いて使用されている基材シート、例えばアルミニ
ウム箔などの金属箔、セロフアン、ポリプロピレ
ン、ナイロン、ポリエステル、ポリスチレン、ポ
リカーボネート等の各種プラスチツクの未延伸又
は延伸フイルム、及びこれらのフイルムに塩化ビ
ニリデン等の被覆用樹脂をコーテイングした積層
フイルム、更にはこれらの二種以上を貼り合わせ
た、あるいは紙との貼り合わせ積層シート等が利
用できる。この各種基材シートは、前述の少なく
とも表面部分が溶融状態にある低密度ポリエチレ
ン系樹脂フイルムと接着される面に、アンカーコ
ート剤、例えば有機チタネート、ポリエチレンイ
ミン、イソシアネート基を有する化合物等からな
るアンカーコート剤によるアンカーコート層を有
していることが必要であり、アンカーコート層の
表面には、コロナ放電処理、火炎処理等の一般の
接着性改良処理が施されていても良い。
以下、本発明の積層体の製造方法の具体的な構
成を図示実施例に基いて説明する。
図面に示す工程の説明
オゾン発生器１に、ブローワーあるいはコンプ
レツサーを使用して空気または酸素ボンベからの
気体２を給気する。
押出しダイス３から低密度ポリエチレン系樹脂
をフイルム状に押出し成形し、得られる少なくと
も表面部分が溶融状態にある低密度ポリエチレン
系樹脂フイルム４の片面に、前記オゾン発生機１
に連結させてある気体吹き付け管５に設けられて
いる細孔によるノズルからオゾンを含有する気体
を吹き付け、低密度ポリエチレン系樹脂フイルム
４′とする。
別製のアンカーコート剤によるアンカーコート
層６を有する基材シート７に、前記オゾンを含有
する気体を吹き付けた低密度ポリエチレン系樹脂
フイルム４′を、該フイルム４′におけるオゾン処
理面と、基材シート７におけるアンカーコート層
６面とが密接するようにしてキヤストし、同時に
ニツプロール８と温度約15℃のチルロール９とに
より押圧、冷却と同時に熱接着することにより積
層体１０を得る。
実施例
前記図面に示す工程に従つて、押出しダイス３
の低密度ポリエチレン系樹脂フイルムの押出し成
形温度を290℃、280℃、260℃に変えて３種の積
層体Ａ，Ｂ，Ｃを得た。
尚、積層体Ａ，Ｂ，Ｃは各々押出しダイス３か
ら低密度ポリエチレン〔密度0.923、溶融指数
3.7：三井ポリケミカル(株)製（ミラソン−16）〕を
厚さ30μに押出し成形し、得られた表面部分が溶
融状態にある低密度ポリエチレンフイルム４の片
面に、オゾン発生機〔日本オゾン(株)製〕に連結さ
せてあるノズルを有するステンレススチール製の
気体吹き付け管から、オゾン濃度10ｇ/m3の酸素
ガスを、160ml/m2の割合で均一に吹き付け、しか
る後にこの低密度ポリエチレンフイルムに別製の
厚さ12μの二軸延伸ポリエチレンテレフタレート
フイルムに、アンカーコート剤〔タケラツクＡ−
315：タケネートＡ−50（配合比８／１）〕（武田
薬品工業(株)製〕を0.5ｇ/m2の割合に塗布したアン
カーコート層を有する基材シートを密接、押圧し
て得たものである。
以上の実施例によつて得られた積層体Ａ，Ｂ，
Ｃを、比較のために低密度ポリエチレン系樹脂フ
イルムの押出し成形温度を310℃、300℃とし、オ
ゾンを含有する気体の吹き付けを行わないで得た
積層シートＤ，Ｅの各物性と比較し第１表に示
す。
The present invention relates to a method for manufacturing a laminate whose surface is coated with a low-density polyethylene resin layer, which has a low-density polyethylene resin layer that has high thermal bonding strength and whose strength changes little over time.
The present invention provides a method for producing a laminate that can easily and reliably produce a laminate that has good hot-tack properties and has little polyethylene odor caused by a low-density polyethylene resin layer. By closely pressing and adhering a melt-extruded film of low-density polyethylene resin to metal foil such as aluminum foil, various synthetic resin films, coated with vinylidene chloride, or base material sheets such as paper, Obtaining a laminated sheet having thermal adhesive properties is a widely known method for producing various packaging materials. By the way, in the method of obtaining a laminate having a low-density polyethylene resin layer using this extrusion lamination process, the melt-extruded film of the low-density polyethylene resin when laminated on the base sheet is heated at a low temperature of 300°C or less. Since the adhesive strength of low-density polyethylene resin film to the base sheet decreases rapidly at
A common method is to obtain a laminate by bringing a low-density polyethylene resin film that has just been extruded at a high temperature of 300° C. or higher into close contact with a base sheet. However, the laminate obtained by this method is
The low density polyethylene resin in the laminate is
It has been subjected to high-temperature heating of 300℃ or more, and as the polyethylene decomposes and produces low-molecular-weight substances due to this high-temperature heating, the polyethylene resin layer itself provided on the surface of the base sheet may deteriorate. Not only does the thermal adhesive strength decrease, but the thermal adhesive strength further decreases over time, and the polyethylene resin layer generates a polyethylene odor, making it difficult to use as a packaging material for filling foods, medicines, etc. It is difficult to use as a material, and furthermore, it has drawbacks such as insufficient hot-tack performance. For this reason, a multilayer extruder is used in which the extrusion temperature of the extruder for the side that is in close contact with the base sheet, that is, the inner layer, is set to 300°C or higher, and the extrusion temperature of the extruder for the outer layer is set to a low temperature. Low-density resin extruded and laminated onto the surface of a separate base sheet, or melt-extruded while blowing an inert gas such as nitrogen gas or combustion gas on the side opposite to the side that is in close contact with the base sheet. Methods such as laminating the polyethylene resin film in close contact with the surface of the base sheet have been proposed, but the method using a multilayer extruder is difficult because the inner and outer layer surfaces of the resulting low-density polyethylene resin film The difference in temperature between the two is not as high as the set temperature of the extruder, and the method of blowing inert gas requires a large amount of gas, which results in high manufacturing costs. Not the method. The present invention has the constitution as claimed in the claims, that is,
Immediately after extrusion molding at an extrusion temperature of 290°C or less, 1 g/m 3
The above ozone-containing gas is sprayed at a rate of 50 ml/m 2 or more, and then this low density polyethylene resin film and a separate base sheet having an anchor coat layer made of an anchor coat agent on the surface are coated with the above ozone-containing gas. By laminating, pressing, and bonding the ozone-treated surface of the low-density polyethylene resin film and the anchor coat layer surface of the base sheet in close contact with each other, the thermal bonding strength of the low-density polyethylene resin layer is high, and this thermal bonding The present invention provides a method for producing a laminate that can easily and reliably produce a laminate that does not change in strength over time and has little polyethylene odor caused by a low-density polyethylene resin layer. Furthermore, in the present invention, in addition to the above-mentioned characteristics, the hot-tack property, that is, the sealant resin in the thermally bonded (sealed) part of the packaging material made of the laminate is sufficiently cooled and solidified, before the sealant resin is sufficiently cooled and solidified. Another characteristic is that it is possible to obtain a laminate having excellent adhesive (seal) strength when subjected to peeling force due to weight or the like. The quality of hot tack is particularly important in strip packaging for tablets, multiple die-roll packaging for packaging sugar etc. per spoon, and vertical pillow packaging for heavy items.
If packaging materials with poor hot-tack properties are used,
The seal part is the cause of peeling and pinholes, and even in horizontal pillow packaging, high-speed filling,
This is because peeling force due to the inertia of the filling acts on the seal at the bottom of the bag during packaging, causing peeling at the seal. The good hot-tack properties obtained in the present invention are due to extrusion lamination of the low-density polyethylene resin at a low temperature of 290°C or lower, and the lower the extrusion temperature, the better the hot-tack properties obtained. be able to. In the present invention, the low-density polyethylene resin that is extruded and laminated onto the base sheet for the purpose of providing the resulting laminate with good thermal adhesive properties (heat sealing properties) has conventionally had good thermal adhesive properties. Resins used to form a low-density polyethylene resin layer on the surface of the base sheet for the purpose of tightening, i.e., ethylene homopolymer, ethylene, propylene, and butene with a density of 0.900 to 0.940 and a melting index [MI] of 0.4 to 40. , pentene, hexene, octene, nonene, decene, 4-methylpentene-1, vinyl acetate, acrylic acid, copolymers with α-olefins such as acrylic esters, or copolymers of these with unsaturated carboxylic acids such as maleic anhydride. Copolymers obtained by graft polymerization of acids, or copolymers obtained by ionizing metals containing carboxyl groups, etc. can be used. In the present invention, a low-density polyethylene resin film, at least a surface portion of which is in a molten state, is laminated with a base sheet having an anchor coat layer formed of an anchor coat agent on its surface, which will be described later. It is obtained by extrusion molding at the following extrusion temperature, but the lower limit temperature during extrusion molding depends on the normal molding, processing speed, air gap size, and extruded low density polyethylene resin film. There are restrictions depending on the ozone content in the gas to be blown, the amount of the gas to be blown, the processing suitability of the synthetic resin used as the raw material for extrusion molding, etc., but the lower limit that can be used is about 200°C. It's temperature. As mentioned above, in the present invention, the extrusion temperature is low, that is, 290°C or less, which does not cause the generation of low molecular weight products that are decomposition products of polyethylene, which cause a decrease in thermal bonding strength due to changes over time and the cause of polyethylene odor. By spraying ozone-containing gas onto one side of a low-density polyethylene resin film, at least the surface of which is in a molten state, immediately after extrusion molding to oxidize the surface, an anchor coated with a separate anchor coating agent is applied to the surface. This improves the adhesion to the base sheet having a coat layer.
The ozone-containing gas that is sprayed onto one side of the low-density polyethylene resin film that is in a molten state, which will be the adhesive surface, can be obtained by supplying air or oxygen to an ordinary ozone generator, but the present invention In this case, 50 ml of gas with an ozone concentration of 1 g/m 3 or more is applied to one side of a low-density polyethylene resin film whose surface portion is in a molten state.
It is necessary to spray at a rate of at least m2 . This applies if the ozone concentration of the gas sprayed onto the surface of the low-density polyethylene resin film is less than 1 g/ m3 , or if the amount of gas sprayed is 50 ml/m3.
If the amount is less than m2 , the degree of surface oxidation of the low-density polyethylene resin film is not sufficient during this gas spraying process, and a separate base material with an anchor coat layer made of an anchor coat agent on the surface may be used. This is because it becomes impossible to obtain strong adhesive strength with the sheet, making it impossible to achieve the object of the present invention. The base sheet on which the low-density polyethylene resin layer is formed by a low-density polyethylene resin film may be a base sheet used in the conventional manufacturing method of this type of laminate, such as a metal foil such as aluminum foil, Unstretched or stretched films of various plastics such as cellophane, polypropylene, nylon, polyester, polystyrene, and polycarbonate, laminated films made by coating these films with coating resins such as vinylidene chloride, and lamination of two or more of these films. Alternatively, a laminated sheet pasted with paper can be used. These various base material sheets are coated with an anchor coating agent, such as an organic titanate, polyethyleneimine, or an isocyanate group-containing compound, on the surface to be adhered to the low-density polyethylene resin film, at least the surface of which is in a molten state. It is necessary to have an anchor coat layer made of a coating agent, and the surface of the anchor coat layer may be subjected to general adhesion improvement treatment such as corona discharge treatment or flame treatment. Hereinafter, a specific configuration of the method for manufacturing a laminate of the present invention will be explained based on illustrated embodiments. Description of the process shown in the drawings The ozone generator 1 is supplied with air or gas 2 from an oxygen cylinder using a blower or compressor. A low density polyethylene resin is extruded into a film form from an extrusion die 3, and the ozone generator 1 is placed on one side of the obtained low density polyethylene resin film 4, which has at least the surface portion in a molten state.
Ozone-containing gas is blown from a nozzle formed in a pore provided in a gas blowing tube 5 connected to the wafer to form a low-density polyethylene resin film 4'. A low-density polyethylene resin film 4' onto which the ozone-containing gas has been sprayed is applied to a base sheet 7 having an anchor coat layer 6 made of a separate anchor coat agent, and the ozone-treated surface of the film 4' and the base material A laminate 10 is obtained by casting the sheet 7 so that the surface of the anchor coat layer 6 is in close contact with the sheet 7, and simultaneously pressing, cooling, and thermally bonding the sheet 7 with a nip roll 8 and a chill roll 9 at a temperature of about 15°C. Example According to the process shown in the drawings, extrusion die 3
Three types of laminates A, B, and C were obtained by changing the extrusion temperature of the low-density polyethylene resin film to 290°C, 280°C, and 260°C. In addition, the laminates A, B, and C are each made of low-density polyethylene [density 0.923, melting index
3.7: Mitsui Polychemical Co., Ltd. (Mirason-16)] was extruded to a thickness of 30 μm, and an ozone generator [Japan Ozone ( Oxygen gas with an ozone concentration of 10 g/m 3 is uniformly sprayed at a rate of 160 ml/m 2 from a stainless steel gas blowing tube with a nozzle connected to Anchor coating agent [Takerak A-
315: Obtained by closely pressing a base sheet having an anchor coat layer coated with Takenate A-50 (mixing ratio 8/1) (manufactured by Takeda Pharmaceutical Co., Ltd.) at a ratio of 0.5 g/m 2 The laminates A, B, and B obtained in the above examples
For comparison, C was compared with the physical properties of laminated sheets D and E obtained by extruding a low-density polyethylene resin film at 310°C and 300°C without spraying ozone-containing gas. It is shown in Table 1.
【表】
熱接着強度（ｇ／15mm）：
得られた各積層体を低密度ポリエチレン系樹脂
層同士が密接するようにして重ね合わせ、これを
センチネルヒートシーラーにより、熱接着条件
140℃、1.5Kg/cm2、0.5秒で熱接着し、しかる後に
得られた試験片を幅15mmに切り取り、50mm/min
で剥離角度90度で剥離する際の強度を測定した。
60日後の熱接着強度は前記熱接着した試験片を40
℃、相対湿度80％にて60日間保管したものを測定
した値である。
ホツトタツク性：
得られた各積層体を巾30mmに切り取り低密度ポ
リエチレン系樹脂層同士が密接するようにして重
ね合わせ、フイルムの端面に50ｇの荷重をつけこ
れを熱接着条件120℃、1.0Kg/cm2、0.5秒にて熱接
着し、熱接着盤が離れる瞬間に荷重により剥離す
る長さを測定した。
本発明の積層体の製造方法は叙上の通りの構成
から成るものであり、熱接着性を具備せしめるた
めの低密度ポリエチレン系樹脂層を、290℃を越
える高温度加工を経ることなく、しかもオゾン処
理による接着性改良面を利用して設けるものであ
るから、高温度加工によるポリエチレンの分解に
起因する低分子量物の生成を伴うことなく積層体
を得ることができるので、熱接着強度に経時変化
の少ない低密度ポリエチレン系樹脂層を有し、且
つポリエチレン臭の無い、しかも基材シートとの
間の接着強度の大きな積層体を容易に、確実に得
ることが出来るという作用、効果を有する。[Table] Thermal bonding strength (g/15mm): The obtained laminates were stacked so that the low-density polyethylene resin layers were in close contact with each other, and this was bonded using a sentinel heat sealer under thermal bonding conditions.
Heat bonded at 140℃, 1.5Kg/cm 2 for 0.5 seconds, then cut the obtained test piece to a width of 15mm, and heated at 50mm/min.
The strength was measured when peeling at a peel angle of 90 degrees.
The heat bonding strength after 60 days was 40
The values were measured after storage for 60 days at ℃ and 80% relative humidity. Hot-tackiness: Each of the obtained laminates was cut to a width of 30 mm and stacked so that the low-density polyethylene resin layers were in close contact with each other. A load of 50 g was applied to the end face of the film, and this was thermally bonded at 120°C and 1.0 kg/ cm 2 , was thermally bonded for 0.5 seconds, and the length of peeling due to load was measured at the moment the thermal bonding disc was separated. The method for producing a laminate of the present invention is constructed as described above, and the low-density polyethylene resin layer for providing thermal adhesiveness is formed without undergoing high-temperature processing exceeding 290°C. Since the adhesive is improved by ozone treatment, the laminate can be obtained without the generation of low molecular weight substances caused by the decomposition of polyethylene due to high temperature processing, so the thermal adhesive strength will change over time. It has the effect of easily and reliably obtaining a laminate that has a low density polyethylene resin layer with little change, has no polyethylene odor, and has high adhesive strength with the base sheet.
図は本発明の積層体の製造方法例を工程順に従
つて示した模型的説明図である。
１……オゾン発生機、２……空気または酸素ボ
ンベからの気体、３……押出しダイス、４……少
なくとも表面部分が溶融状態にある低密度ポリエ
チレン系樹脂フイルム、５……気体吹き付け管、
６……アンカーコート層、７……基材シート、１
０……積層体。
The figure is a schematic explanatory view showing an example of the method for manufacturing a laminate according to the present invention in the order of steps. 1...Ozone generator, 2...Gas from air or an oxygen cylinder, 3...Extrusion die, 4...Low density polyethylene resin film whose surface portion is in a molten state, 5...Gas blowing tube,
6... Anchor coat layer, 7... Base sheet, 1
0...Laminated body.
Claims (1)
後の、少なくとも表面部分が溶融状態にある低密
度ポリエチレン系樹脂フイルムの片面に、１ｇ/
m3以上のオゾンを含有する気体を50ml/m2以上の
割合で吹き付け、しかる後にこの低密度ポリエチ
レン系樹脂フイルムと、表面にアンカーコート剤
によるアンカーコート層を有する別製の基材シー
トとを、低密度ポリエチレン系樹脂フイルムにお
けるオゾン処理面と基材シートにおけるアンカー
コート層面とが密接するようにして積層し、押圧
することを特徴とする積層体の製造方法。1. Immediately after extrusion molding at an extrusion temperature of 290°C or less, 1 g/g of
A gas containing ozone of 3 m or more is sprayed at a rate of 50 ml/m 2 or more, and then this low-density polyethylene resin film and a separately manufactured base sheet having an anchor coat layer made of an anchor coat agent on the surface are coated. A method for producing a laminate, which comprises stacking and pressing so that the ozone-treated surface of the low-density polyethylene resin film and the anchor coat layer surface of the base sheet come into close contact with each other.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55177897A JPS57102318A (en) | 1980-12-16 | 1980-12-16 | Production of laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55177897A JPS57102318A (en) | 1980-12-16 | 1980-12-16 | Production of laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57102318A JPS57102318A (en) | 1982-06-25 |
| JPS6135938B2 true JPS6135938B2 (en) | 1986-08-15 |
Family
ID=16038967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55177897A Granted JPS57102318A (en) | 1980-12-16 | 1980-12-16 | Production of laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57102318A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5962107A (en) * | 1982-10-01 | 1984-04-09 | Mitsubishi Petrochem Co Ltd | Extrusion laminating method of ethylene family resin |
| JPS60219036A (en) * | 1984-04-16 | 1985-11-01 | エービー テトラパック | Manufacture of laminated sheet material for packaging food |
| CN109454845B (en) * | 2018-11-06 | 2020-09-01 | 江门市辉隆塑料机械有限公司 | Extrusion compounding device and process for high-peel-strength glue-free composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB738474A (en) * | 1952-11-29 | 1955-10-12 | Du Pont | Improvements relating to the treatment of polyethylene surfaces |
| US3227605A (en) * | 1952-11-29 | 1966-01-04 | Du Pont | Method of treating polyethylene with ozone to render it adherent to coatings and lamina and resultant articles |
| JPS5232079A (en) * | 1975-09-05 | 1977-03-10 | Dainippon Printing Co Ltd | Low-odor packaging film |
| JPS55161620A (en) * | 1979-06-04 | 1980-12-16 | Mitsubishi Plastics Ind Ltd | Manufacture of coextruded composite film |
| JPS5689515A (en) * | 1979-12-21 | 1981-07-20 | Du Pont Mitsui Polychem Co Ltd | Production of laminate and extrusion die used therefor |
| JPS6051438A (en) * | 1983-06-21 | 1985-03-22 | ゼネラル・エレクトリツク・カンパニイ | Rotary electric machine and assembling method and device |
-
1980
- 1980-12-16 JP JP55177897A patent/JPS57102318A/en active Granted
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB738474A (en) * | 1952-11-29 | 1955-10-12 | Du Pont | Improvements relating to the treatment of polyethylene surfaces |
| GB758461A (en) * | 1952-11-29 | 1956-10-03 | Du Pont | Improvements relating to the surface treatment of polyethylene-containing structures |
| US3227605A (en) * | 1952-11-29 | 1966-01-04 | Du Pont | Method of treating polyethylene with ozone to render it adherent to coatings and lamina and resultant articles |
| JPS5232079A (en) * | 1975-09-05 | 1977-03-10 | Dainippon Printing Co Ltd | Low-odor packaging film |
| JPS55161620A (en) * | 1979-06-04 | 1980-12-16 | Mitsubishi Plastics Ind Ltd | Manufacture of coextruded composite film |
| JPS5689515A (en) * | 1979-12-21 | 1981-07-20 | Du Pont Mitsui Polychem Co Ltd | Production of laminate and extrusion die used therefor |
| JPS6051438A (en) * | 1983-06-21 | 1985-03-22 | ゼネラル・エレクトリツク・カンパニイ | Rotary electric machine and assembling method and device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57102318A (en) | 1982-06-25 |
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