JPH01282278A - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPH01282278A JPH01282278A JP11152688A JP11152688A JPH01282278A JP H01282278 A JPH01282278 A JP H01282278A JP 11152688 A JP11152688 A JP 11152688A JP 11152688 A JP11152688 A JP 11152688A JP H01282278 A JPH01282278 A JP H01282278A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- weight
- density polyethylene
- linear low
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000000853 adhesive Substances 0.000 title claims description 24
- 230000001070 adhesive effect Effects 0.000 title claims description 24
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 30
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 30
- 229920005604 random copolymer Polymers 0.000 claims abstract description 11
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 abstract description 2
- -1 polyethylene Polymers 0.000 description 58
- 239000010410 layer Substances 0.000 description 40
- 239000010408 film Substances 0.000 description 32
- 239000004698 Polyethylene Substances 0.000 description 29
- 229920000573 polyethylene Polymers 0.000 description 29
- 229920001155 polypropylene Polymers 0.000 description 29
- 239000004743 Polypropylene Substances 0.000 description 28
- 229910000831 Steel Inorganic materials 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 11
- 239000010959 steel Substances 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野］
本発明は、ポリオレフィン、極性樹脂、金属などを相互
に実用的に充分な強度で接着するための接着剤組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive composition for adhering polyolefins, polar resins, metals, etc. to each other with practically sufficient strength.
〔従来の技術及び解決されるべき課題〕ポリエチレンと
ポリプロピレンとは同じポリオレフィンではあるが、殆
ど相溶１１がみられず、積層フィルムにした場合、相互
の接着性は極めて劣るものであり、フィ、ルム外観も不
良である。又、ポリエチレン或いはポリプロピレンとポ
リアミド、ポリビニルアルコールなどの極性樹脂或いは
金属などとの接着性も極めて低い、そのためポリエチレ
ン或いはポリプロピレンを含む積層フィルム及びポリエ
チレン或いはポリプロピレンを金属と積層させた製品の
用途は大幅に制限されている。そこで、上記積層フィル
ム或いは金属との積層品などの各材料間に各種の接着剤
層を介在させて、接着性を改良することが試みられてき
た。しかし、充分な接着力が得られ、且つ、製品外観が
良好な積層フィルム或いは金−との積層品を製造し得る
接着剤組成物は未だ開発されていない。[Prior Art and Problems to Be Solved] Although polyethylene and polypropylene are the same polyolefins, there is almost no compatibility with each other, and when they are made into a laminated film, their mutual adhesion is extremely poor. The appearance of the lumen is also poor. In addition, the adhesion between polyethylene or polypropylene and polar resins such as polyamide or polyvinyl alcohol, or metals is extremely low.Therefore, the applications of laminated films containing polyethylene or polypropylene and products in which polyethylene or polypropylene is laminated with metal are greatly limited. has been done. Therefore, attempts have been made to improve adhesiveness by interposing various adhesive layers between materials such as the above-mentioned laminated films or laminated products with metals. However, an adhesive composition that can produce a laminated film or a laminated product with gold that provides sufficient adhesive strength and has a good product appearance has not yet been developed.
〔課題を解決するための手段］
本発明は、ポリエチレンとポリプロピレンとの積層、ポ
リエチレン、ポリプロピレンとポリアミド、ポリビニル
アルコールなどの極性樹脂或いは金属などとの積層に用
いられる接着剤組成物に関する。[Means for Solving the Problems] The present invention relates to an adhesive composition used for laminating polyethylene and polypropylene, and for laminating polyethylene, polypropylene and polar resins such as polyamide, polyvinyl alcohol, or metals.
皿ち、本発明は、α、β−不飽和カルボン酸で変性され
た線状低密度ポリエチレンを１０重量％以上含む線状低
密度ポリエチレン２０〜８０重量％とエチレン含有量が
２〜１０重量％の範囲のエチレン−プロピレンブロック
或いはランダム共重合体８０〜２０重１％とからなる接
着剤組成物に関する。The present invention uses linear low-density polyethylene of 20 to 80% by weight containing 10% by weight or more of linear low-density polyethylene modified with α,β-unsaturated carboxylic acid and 2 to 10% by weight of ethylene. The present invention relates to an adhesive composition comprising 80 to 20 1% by weight of an ethylene-propylene block or random copolymer in the range of
本発明の接着剤組成物を、ポリエチレンとポリエチレン
との積層或いはポリエチレン、ポリプロピレンとポリア
ミド、ポリビニルアルコールなどの極性樹脂又は金属と
の積層に用いた場合、得られる積層品は、眉間が強固に
接着されているばかりではなく、外観及び積層フィルム
であれば透明性などが極めて優れている。When the adhesive composition of the present invention is used for laminating polyethylene and polyethylene, or for laminating polyethylene, polypropylene and a polar resin such as polyamide or polyvinyl alcohol, or a metal, the resulting laminate will have strong adhesion between the eyebrows. Not only does it have excellent appearance, but also the transparency of the laminated film.
線状低密度ポリエチレンとしては、遷移金属触媒を用い
て、中低圧の圧力で、５０モル％以上のエチレンとα−
オレフィンとを溶液重合、気相重合或いはスラリー重合
などの公知の方法で共重合させた、比較的密度の低いエ
チレン−α−オレフィン共重合体を使用し得る。共重合
のコモノマーとして使用されるα−オレフィンとしては
、プロピレン、ブテン、ペンテン、４−メチルペンテン
−１、オクテンなどが挙げられる。As linear low density polyethylene, 50 mol% or more of ethylene and α-
An ethylene-α-olefin copolymer having a relatively low density, which is copolymerized with an olefin by a known method such as solution polymerization, gas phase polymerization, or slurry polymerization, can be used. Examples of the α-olefin used as a comonomer for copolymerization include propylene, butene, pentene, 4-methylpentene-1, octene, and the like.
線状低密度ポリエチレンはその優れた透明性、耐熱性、
機械的強度などのため、本発明に用いられる極薄の接着
剤層用の原料として好適である。Linear low-density polyethylene has excellent transparency, heat resistance,
Due to its mechanical strength, etc., it is suitable as a raw material for the ultra-thin adhesive layer used in the present invention.
線状低密度ポリエチレンのメルトインデックスは０．５
〜２０ｇ／１０分、特に１〜１０ｇ／１０分の範囲が、
フィルム成形性及び得られたフィルムの機械的強度が良
好であって好ましい。The melt index of linear low density polyethylene is 0.5
~20g/10min, especially in the range of 1~10g/10min,
It is preferable because the film formability and the mechanical strength of the obtained film are good.
尚、線状低密度ポリエチレンには酸化防止剤、スリップ
剤、アンチブロック剤などの添力Ｕ剤が含まれていても
よい。Note that the linear low density polyethylene may contain additives such as antioxidants, slip agents, and antiblock agents.
本発明に於ける線状低密度ポリエチレンに代えて、低密
度ポリエチレン、高密度ポリエチレン、エチレン−酢酸
ビニル共重合体或いはそれらをα。In place of the linear low-density polyethylene in the present invention, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, or α.
β−不飽和カルボン酸によって変性したものなどを使用
すると、エチレン−プロピレンブロック或いはランダム
共重合体との配合比が適切であっても、充分な接着力が
得られない。又、製造された積層フィルム或いは積層物
品の這明性或いは外観などが不良となる。If a material modified with β-unsaturated carboxylic acid is used, sufficient adhesive strength cannot be obtained even if the blending ratio with the ethylene-propylene block or random copolymer is appropriate. Moreover, the visibility or appearance of the manufactured laminated film or laminated article becomes poor.
エチレン−プロピレンブロック或いはランダム共重合体
としては、結晶性であって、共重合体中のエチレン含有
量が２〜１０重量％、好ましくは４〜８重量％の範囲の
ものが使用される。エチレン−プロピレンブロック或い
はランダム共重合体のエチレン含有量が２重量％未満で
は、ポリエチレン層との接着力が不充分であり、エチレ
ン含有量が１０重世％を越える場合は、共重合体の製造
そのものが困難となるばかりではなく、シェルの発生に
より積層フィルムの場合、その外観が悪化するため好ま
しくない。As the ethylene-propylene block or random copolymer, one that is crystalline and has an ethylene content in the range of 2 to 10% by weight, preferably 4 to 8% by weight is used. If the ethylene content of the ethylene-propylene block or random copolymer is less than 2% by weight, the adhesive strength with the polyethylene layer will be insufficient, and if the ethylene content exceeds 10% by weight, the production of the copolymer will be Not only is this difficult, but the appearance of a laminated film deteriorates due to the occurrence of shells, which is not preferable.
エチレン−ブロビレンフ゛ロック或いはランダム共重合
体のメルトフローレイショハ、０．５〜１５ｇ／１０分
のものが、極薄の接着剤層に成形する場合の成形性が良
好であって好ましい。A melt flow rate of 0.5 to 15 g/10 min of ethylene-brobylene block or random copolymer is preferred because it has good moldability when molded into an extremely thin adhesive layer.
尚、これらのエチレン−プロピレンブロック或いはラン
ダム共重合体には酸化防止剤、スリ・ノブ剤、アンチブ
ロック剤などの添加剤が含まれていてもよい。Incidentally, these ethylene-propylene block or random copolymers may contain additives such as antioxidants, pickpocketing agents, and antiblocking agents.
エチレンーブロビレンフ゛ロンク或いはランダム共重合
体に代えてプロピレンホモポリマーを使用すると、ポリ
エチレン層との接着力が不充分であるか、或いは充分な
接着力が得られる場合であっても、積層フィルムの場合
、その透明性及び外観が不良となる。If a propylene homopolymer is used instead of an ethylene-propylene carbon or random copolymer, the adhesion to the polyethylene layer may be insufficient, or even if sufficient adhesion is obtained, the laminated film In this case, the transparency and appearance are poor.
本発明に於ける接着剤組成物の組成は、α、β−不飽和
カルボン酸で変成された線状低密度ポリエチレンを１０
重量％以上含む線状低密度ポリエチレンが２０〜８０重
量％であって、エチレン−プロピレンランダム或いはブ
ロック共重合体が８０〜２０重量％である。特に、線状
低密度ポリエチレンが５０〜７０重量％であって、エチ
レン−プロピレンランダム或いはブロック共重合体が５
０〜３０重量％であることが好ましい。The composition of the adhesive composition in the present invention consists of 10% linear low density polyethylene modified with α,β-unsaturated carboxylic acid.
The linear low density polyethylene containing at least 20 to 80 weight % is 20 to 80 weight %, and the ethylene-propylene random or block copolymer is 80 to 20 weight %. In particular, the linear low density polyethylene is 50 to 70% by weight, and the ethylene-propylene random or block copolymer is 50% to 70% by weight.
It is preferably 0 to 30% by weight.
線状低密度ポリエチレンが８０重量％を越える場合は、
ポリプロピレン層と接着剤層とが殆ど接着されない。又
、エチレン−プロピレンランダム或いはブロック共重合
体が８０重量％を越える場合は、透明性及びフィルム外
観が不良となる。更に、線状低密度ポリエチレン中の変
成線状低密度ポリエチレンの含有量が１０重量％未満の
場合は、ポリエチレン層との接着性が不良となる。If linear low density polyethylene exceeds 80% by weight,
The polypropylene layer and adhesive layer are hardly bonded together. Furthermore, if the content of the ethylene-propylene random or block copolymer exceeds 80% by weight, the transparency and appearance of the film will be poor. Furthermore, if the content of modified linear low-density polyethylene in the linear low-density polyethylene is less than 10% by weight, the adhesion to the polyethylene layer will be poor.
この発明に於いては、線状低密度ポリエチレン２０〜８
０重１％とエチレン−プロピレンランダム或いはブロッ
ク共重合体８０〜２０重量％とを配合し、そのまま、又
は事前に溶融混練したものを押出機により極薄に成形し
たフィルムを、溶融状態のポリエチレン層とポリプロピ
レン層との間或いはポリエチレン、ポリプロピレンから
なるフィルムとポリアミド、ポリビリビニルアルコール
などの極性樹脂からなるフィルム或いは金属物品との間
にに介在させて積層し、冷却固化することによって積層
物品を製造する。In this invention, linear low density polyethylene 20 to 8
A polyethylene layer in a molten state is formed by blending 0% by weight and 80 to 20% by weight of an ethylene-propylene random or block copolymer, and forming an extremely thin film using an extruder as it is or by melt-kneading it in advance. and a polypropylene layer, or between a film made of polyethylene or polypropylene and a film made of a polar resin such as polyamide or polybilibinyl alcohol, or a metal article, and then cooled and solidified to produce a laminated article. do.
線状低密度ポリエチレンとエチレン−プロピレンランダ
ム或いはブロック共重合体とを配合する方法は、公知の
あらゆる方法が適用でき、各種ブレンダー、−軸又は二
軸押出機又は積層フィルム製造装置の押出機で行うこと
ができる。All known methods can be used to blend linear low-density polyethylene and ethylene-propylene random or block copolymer, and it can be carried out using various blenders, screw or twin screw extruders, or extruders of laminated film manufacturing equipment. be able to.
上記の積層フィルム製造装置とは、押出機を３台以上組
み合わせて、１個のダイスから多層フィルムを押し出す
ものであればよく、インフレーションフィルム製造装置
でもＴ−ダイフィルム製造装置でもよい。The above-mentioned laminated film manufacturing apparatus may be one that combines three or more extruders and extrudes a multilayer film from one die, and may be a blown film manufacturing apparatus or a T-die film manufacturing apparatus.
前記のポリエチレン層を形成するポリエチレン及びポリ
プロピレン層を形成するポリプロピレンとしては、従来
フィルム用に使用されているポリエチレン及びポリプロ
ピレンがそれぞれ使用される。又、ポリアミド、ポリビ
ニルアルコールなどの極性樹脂或いは金属なども特に限
定されるものではない。As the polyethylene forming the polyethylene layer and the polypropylene forming the polypropylene layer, polyethylene and polypropylene, which are conventionally used for films, are used, respectively. Further, polar resins such as polyamide and polyvinyl alcohol, metals, and the like are not particularly limited.
この発明の方法によって得られる積層フィルムは、好ま
しくはポリエチレン、ポリプロピレン、極性樹脂からな
るフィルム層の厚さが５〜１００μ、接着剤組成物層の
厚さが３〜１００μであるものが好ましい。The laminated film obtained by the method of the present invention preferably has a film layer made of polyethylene, polypropylene, or a polar resin having a thickness of 5 to 100 μm, and an adhesive composition layer having a thickness of 3 to 100 μm.
以下に実施例及び比較例によって本発明を更に詳しく説
明する。The present invention will be explained in more detail below using Examples and Comparative Examples.
実施例１
線状低密度ポリエチレン（Ｍｌ：２．０ｇ／１０分、密
度： ０．９１９ ｇ／ｃｍ！、ブテン−１含量：４重
量％）４０重量％、エチレン−プロピレンブロック共重
合体（ＭＦＲ： ２．０ ｇ／ｌ ０分、ｘ−ｙ−レン
含ｔニア重量％）３０重量％、前記線状低密度ポリエチ
レンに無水マレイン酸１重量％と、反応開始剤としての
ジクミル０．２４重量％とを添加して、ヘンシェルミキ
サー中で混合後、Ｌ／Ｄ−２４、スクリュー径６５１φ
の単軸押出機を使用して、反応温度２６０℃で押出変成
したもの（無水マレイン酸付加ｆ ： ０．９５重１％
）３００重量をタンブラ−によって混合後、前記押出機
によって樹脂温度２２０°Ｃの条件で押出し、接着剤組
成物を得た。Example 1 Linear low density polyethylene (Ml: 2.0 g/10 min, density: 0.919 g/cm!, butene-1 content: 4 wt%) 40 wt%, ethylene-propylene block copolymer (MFR : 2.0 g/l 0 min, x-y-lene containing tnia weight%) 30% by weight, 1% by weight of maleic anhydride in the linear low density polyethylene, and 0.24% by weight of dicumyl as a reaction initiator. % and mixed in a Henschel mixer, L/D-24, screw diameter 651φ
Extrusion modification was carried out at a reaction temperature of 260°C using a single-screw extruder (maleic anhydride addition f: 0.95 wt. 1%).
) were mixed in a tumbler and extruded using the extruder at a resin temperature of 220°C to obtain an adhesive composition.
次いで、多層インフレーション押出機を使用して、ダイ
ス温度２１０°Ｃ１引取速度１０ｍ／分の条件で下記構
成の多層フィルム（４種５層）＠成形した。Next, using a multilayer inflation extruder, a multilayer film (4 types, 5 layers) with the following configuration was molded under the conditions of a die temperature of 210° C. and a take-up speed of 10 m/min.
内層：
低苫度ポリエチレン（ＦＯ２２（宇部興産■＝）Ｍｘ
：０．８ｇ／１０分、密度：０．９２２ｇ／ｄ〕厚さ二
６５μｍ
第１接着剤層
接着剤組成物、厚さ＝５μｍ
中間層
部分ケン化エチレン酢酸ビニル共重合体〔ソアノールＥ
Ｔ（日本合成化学工業■ｆｉ） Ｍ Ｆ Ｉ ： ２゜
Ｏｇ／１０分、エチレン含有量：３８モル％、融点：１
７３°Ｃ〕厚さ：１０μｌ
第２接着剤層
接着剤組成物、厚さ：５μ鴎
外層
ポリプロピレン（ＲＦ３５５Ｂ（宇部興産■製）ＭＦｒ
：２．７ｇ／１０分、密度：０．９１０ｇ／１０分］厚
さ二６５μｍ
このようにして得られた多層フィルムの各Ｎ間のＴＭ０
１離強度を、ＪＩＳ Ｋ６８５４に準拠し、インスト
ロン社製万能引張試験機によって、５０ｒｍ／分の引張
速度で評価した。結果は下記の通りであった。Inner layer: Low-stiffness polyethylene (FO22 (Ube Industries ■=) Mx
: 0.8 g/10 min, density: 0.922 g/d] Thickness 2 65 μm First adhesive layer Adhesive composition, thickness = 5 μm Intermediate layer partially saponified ethylene vinyl acetate copolymer [Soarnol E
T (Nippon Synthetic Chemical Industry fi) MFI: 2°Og/10min, ethylene content: 38 mol%, melting point: 1
73°C] Thickness: 10μl Second adhesive layer adhesive composition, thickness: 5μ Ogai layer polypropylene (RF355B (manufactured by Ube Industries) MFr
: 2.7 g/10 minutes, density: 0.910 g/10 minutes] Thickness: 265 μm TM0 between each N of the multilayer film thus obtained
The 1-separation strength was evaluated in accordance with JIS K6854 using a universal tensile tester manufactured by Instron at a tensile speed of 50 rm/min. The results were as follows.
内層−中間層間： ｌ Ｏ９０ｇ／２．５ｃｍ幅中間層
−外層間： １００ Ｑ ｇ／２．５ｃｍ幅何れの眉間
も接着剤層が破壊する凝集剥離であった。Inner layer-intermediate layer: 1 O90 g/2.5 cm width Intermediate layer-outer layer: 100 Q g/2.5 cm width There was cohesive peeling in which the adhesive layer was destroyed at both glabella intervals.
次に金属との接着性を評価した。先ず、トリクロロエチ
レンによって脱脂した５Ｓ４１１Ｗき鋼板（６Ｘ５０Ｘ
１５０ｍｍサイズ）を加熱プレート上で２００°Ｃに予
熱し、その上に上記接着剤組成物を０．１５Ｘ５０Ｘ１
００ｍｎ＋のシートに成形したものを静置し、更にその
接着剤シートの上に、２×５０Ｘ１５０ｍｍの低密度ポ
リエチレン（Ｍｌ：Ｏ。Next, adhesion to metal was evaluated. First, a 5S411W steel plate (6X50X
150mm size) on a heating plate to 200°C, and apply the above adhesive composition 0.15X50X1 on it.
00mm+ sheet was left standing, and then a 2 x 50 x 150 mm low density polyethylene (Ml:O) sheet was placed on top of the adhesive sheet.
Ｉｇ／１０分、密度： ０．９２２ ｇ／ｃｆｆｌ）の
シートを静置し、その上に５ｋｇの荷重を載せて３分間
加圧し、融着した。次いで、この貼合体を水中に投入し
て冷却し、接着強度評価用のポリエチレン被覆鋼板とし
た。同様にしてポリエチレンシートに代えてポリプロピ
レンシート（ポリプロピレンのＭ Ｆ Ｒ： ９ ｇ
／ １０分）を用い、接着強度評価用のポリプロピレン
被覆鋼板を用意した。Ig/10 minutes, density: 0.922 g/cffl) sheet was left standing, a load of 5 kg was placed thereon, and pressure was applied for 3 minutes to fuse the sheet. Next, this bonded body was put into water and cooled to obtain a polyethylene-coated steel plate for evaluation of adhesive strength. Similarly, instead of the polyethylene sheet, a polypropylene sheet (MFR of polypropylene: 9 g
/ 10 minutes) to prepare a polypropylene-coated steel plate for adhesive strength evaluation.
これら被覆鋼板を用いて、９０°剥離強度を、ＪＩＳ
Ｋ６８５４に準拠し、インストロン社製万能引張試験
機によって、５０鵡／分の引張速度で評価したところ、
結果はポリエチレン被覆鋼板の場合が８ｋｇ／ｃｍ、ポ
リプロピレン被覆鋼板の場合が５ｋｇ／Ｃｌ１１であっ
た。Using these coated steel plates, the 90° peel strength was determined according to JIS
Based on K6854, it was evaluated using a universal tensile tester manufactured by Instron at a tensile rate of 50 min/min.
The results were 8 kg/cm for the polyethylene coated steel plate and 5 kg/Cl11 for the polypropylene coated steel plate.
実施例２
実施例１の線状低密度ポリエチレン、エチレン−プロピ
レンブロック共重合体及び変性線状低密度ポリエチレン
の配合割合を、それぞれ７０重量％、２０重量％及び１
０重量％とじた以外は実施例１と同様にして多層フィル
ムを成形した。この多層フィルムを用いて実施例１と同
様にして各層間のＴ剥離強度を測定した。結果は下記の
通りであった。Example 2 The blending ratios of linear low density polyethylene, ethylene-propylene block copolymer and modified linear low density polyethylene of Example 1 were 70% by weight, 20% by weight and 1% by weight, respectively.
A multilayer film was molded in the same manner as in Example 1 except that it was bound at 0% by weight. Using this multilayer film, the T peel strength between each layer was measured in the same manner as in Example 1. The results were as follows.
内層−中間層間： ７００ ｇ ／ ２．５ ｃｍｍ幅
間間層外層間：５５０ｇ／２．５ｃｍ幅何れの眉間も接
着剤層が破壊する凝集剥離であった。Inner layer-intermediate layer: 700 g/2.5 cm width Interlayer outer layer: 550 g/2.5 cm Both glabella widths showed cohesive peeling in which the adhesive layer was destroyed.
又、実施例１の鋼板に代えて銅板を使用した他は、実施
例１と同様にしてポリエチレン被覆銅板及びポリプロピ
レン被覆ｆｌ＋Ｉｉを用意し、実施例１と同様にして９
０°剥離強度を測定したところ、ポリエチレン被覆銅板
の場合が９ ｋｇ ／ Ｃ１１ｌ、ポリプロピレン被Ｉ
Ｘ板の場合が３ ｋｇ ／ Ｃ１１であった。Further, a polyethylene-coated copper plate and a polypropylene-coated fl+Ii were prepared in the same manner as in Example 1, except that a copper plate was used in place of the steel plate in Example 1.
When the 0° peel strength was measured, it was 9 kg/C11l for the polyethylene-coated copper plate, and 9 kg/C11l for the polypropylene-coated copper plate.
In the case of the X plate, it was 3 kg/C11.
実施例３
実施例１の線状低密度ポリエチレン、エチレン−プロピ
レンブロック共重合体及び変性線状低密度ポリエチレン
の配合割合を、それぞれ１０重量％、６０重１％及び３
（１１％とした以外は実施例１と同様にして多層フィル
ムを成形した。この多層フィルムを用いて実施例１と同
様にして各層間のＴ剥離強度を測定した。結果は下記の
通りであった。Example 3 The blending proportions of the linear low density polyethylene, ethylene-propylene block copolymer and modified linear low density polyethylene of Example 1 were 10% by weight, 1% by weight by 60% and 3% by weight, respectively.
(A multilayer film was molded in the same manner as in Example 1 except that the ratio was 11%. Using this multilayer film, the T-peel strength between each layer was measured in the same manner as in Example 1. The results are as follows. Ta.
内層−中間層間： ５３０ ｇ／２．５ｃｍ幅中間層−
外層間：剥離不能（フィルム切断）何れの眉間も接着剤
層が破壊する凝集剥離であった。Between inner layer and middle layer: 530 g/2.5cm width middle layer
Between outer layers: Unable to peel (film cut) Cohesive peeling occurred in which the adhesive layer was destroyed in both glabella areas.
又、実施例１と同様にしてポリエチレン被ｙｉ鋼板及び
ポリプロピレン被覆鋼板を用意し、実施例１と同様にし
て９０°剥離強度を測定したところ、ポリエチレン被覆
銅板の場合が５ｋｇ／Ω、ポリプロピレン被覆銅板の場
合が剥離不能（シート切断）であった。In addition, a polyethylene-coated yi steel plate and a polypropylene-coated steel plate were prepared in the same manner as in Example 1, and the 90° peel strength was measured in the same manner as in Example 1. The peel strength was 5 kg/Ω for the polyethylene-coated copper plate, and 5 kg/Ω for the polypropylene-coated copper plate. In this case, peeling was impossible (sheet cutting).
比較例１
実施例１と同じ線状低密度ポリエチレンに、無水マレイ
ン酸０．３重量％、反応開始剤として１−ブチルハイド
ロパーオキサイド０．１２重世％を添加し、ヘンシェル
ミキサーで混合後、Ｌ／Ｄ＝２４、スクリュー径６５ｍ
！１＋φの単軸押出機を使用して、反応温度２２０°Ｃ
で押出変成したもの（無水マレイン酸付加１： ０．２
７重１％）４０重１％と、低密度ポリエチレン（Ｍｌ：
２ｇ／１０分、密度： ０．９２２ ｇ／ｃｎｌ）に無
水マレイン酸を０．１重量％、反応開始剤としてｔ−ブ
チルハイドロパーオキサイドを０．０４！Ｉ％を添加し
て、上記と同様にして変成したもの（無水マレイン酸付
加量：０．０９重１％）４０重量％と、エチレン−プロ
ピレンゴム［ｔ ： ４．０ ｇ／ｌ ０分、タフマー
Ｐ○１８０（三片石油化学工業■製））２０重１％を混
合して実施例１と同様にして接着剤組成物を製造した。Comparative Example 1 To the same linear low density polyethylene as in Example 1, 0.3% by weight of maleic anhydride and 0.12% by weight of 1-butyl hydroperoxide as a reaction initiator were added, and after mixing with a Henschel mixer, L/D=24, screw diameter 65m
! Using a 1+φ single-screw extruder, the reaction temperature was 220°C.
(maleic anhydride addition 1: 0.2
7 weight 1%) 40 weight 1% and low density polyethylene (Ml:
2 g/10 min, density: 0.922 g/cnl), 0.1% by weight of maleic anhydride, and 0.04% of t-butyl hydroperoxide as a reaction initiator. I% was added and modified in the same manner as above (maleic anhydride addition amount: 0.09 wt. 1%) and 40 wt.% of ethylene-propylene rubber [t: 4.0 g/l 0 min. An adhesive composition was prepared in the same manner as in Example 1 by mixing 20% by weight of Tafmer P○180 (manufactured by Mikata Petrochemical Industry ■).
上記接着剤組成物を接着剤層として、実施倒１と同様に
してインフレーシコン成形法によって多層フィルムを成
形し、各層間のＴ剥離強度を実施例１と同様にして評価
した。結果は下記の通りである。Using the above adhesive composition as an adhesive layer, a multilayer film was molded by the inflatable molding method in the same manner as in Example 1, and the T-peel strength between each layer was evaluated in the same manner as in Example 1. The results are as follows.
内層−中間層間： １０３０ ｇ／２．５ｃｍ中間層−
外層間： ３０ ｇ／ ２．５ｃｒａ内層と中間層との
間は充分な接着力を有し、破壊形態も凝集破壊であった
が、中間層層と外層との間は実質的に接着されておらず
、又、その破壊形態は界面破壊であった。Between inner layer and middle layer: 1030 g/2.5cm middle layer
Between the outer layers: 30 g/2.5 cra There was sufficient adhesive force between the inner layer and the intermediate layer, and the failure mode was cohesive failure, but there was no substantial adhesion between the intermediate layer and the outer layer. However, the type of failure was interfacial failure.
又、実施例１と同様にして貼合体を用いて、ポリエチレ
ンシート及びポリプロピレンシートと鋼板との間の９０
°剥離強度を測定したところ、それぞれ７ ｋｇ ／
ｃｍ及び０．５ｋｇ／Ωであった。ポリプロピレンシー
トと鋼板との場合は、接着剤層とポリプロピレンシート
との間で界面剥離していた。In addition, using the bonded body in the same manner as in Example 1, the 90% bond between the polyethylene sheet, the polypropylene sheet, and the steel plate was
°When peel strength was measured, each was 7 kg/
cm and 0.5 kg/Ω. In the case of a polypropylene sheet and a steel plate, interfacial peeling occurred between the adhesive layer and the polypropylene sheet.
本発明による変成線状低密度ポリエチレンを含む線状低
密度ポリエチレンと特定のエチレンーブロビレンブロノ
ク或いはランダム共重合体とからなる接着剤組成物を中
間層として用いて、ポリエチレン層とポリプロピレン層
とを積層した場合或いはポリエチレン層、ポリプロピレ
ン層と極性樹脂層或いは金属とを積層した場合、その各
層間の接着力は充分であって、積層フィルム又は積層体
の透明性（ヘイズ）及びフィルム外観が非常に優れてい
る。特に、本発明によって得られる積層フィルムは、食
品等の包装用フィルムとして好適である。A polyethylene layer and a polypropylene layer are bonded to each other by using an adhesive composition consisting of a linear low-density polyethylene including modified linear low-density polyethylene according to the present invention and a specific ethylene-propylene polymer or random copolymer as an intermediate layer. When laminating a polyethylene layer, a polypropylene layer, and a polar resin layer or metal, the adhesive strength between each layer is sufficient, and the transparency (haze) and film appearance of the laminated film or laminate are extremely low. Excellent. In particular, the laminated film obtained by the present invention is suitable as a packaging film for foods and the like.
Claims (1)
エチレンを１０重量％以上含む線状低密度ポリエチレン
２０〜８０重量％と、エチレン含有量が２〜１０重量％
の範囲のエチレン−プロピレンブロック或いはランダム
共重合体８０〜２０重量％とからなる接着剤組成物。20-80% by weight of linear low-density polyethylene containing 10% by weight or more of linear low-density polyethylene modified with α,β-unsaturated carboxylic acid, and 2-10% by weight of ethylene.
An adhesive composition comprising 80 to 20% by weight of an ethylene-propylene block or random copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11152688A JPH01282278A (en) | 1988-05-10 | 1988-05-10 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11152688A JPH01282278A (en) | 1988-05-10 | 1988-05-10 | Adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01282278A true JPH01282278A (en) | 1989-11-14 |
Family
ID=14563568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11152688A Pending JPH01282278A (en) | 1988-05-10 | 1988-05-10 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01282278A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005047389A1 (en) | 2003-11-04 | 2005-05-26 | Kimberly-Clark Worldwide Inc. | Tackified amorphous-poly-alpha-olefin-bonded structures |
| JP2016507405A (en) * | 2012-12-28 | 2016-03-10 | ダウ グローバル テクノロジーズ エルエルシー | Multilayer film containing functional ethylene-based polymer composition |
-
1988
- 1988-05-10 JP JP11152688A patent/JPH01282278A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005047389A1 (en) | 2003-11-04 | 2005-05-26 | Kimberly-Clark Worldwide Inc. | Tackified amorphous-poly-alpha-olefin-bonded structures |
| JP2016507405A (en) * | 2012-12-28 | 2016-03-10 | ダウ グローバル テクノロジーズ エルエルシー | Multilayer film containing functional ethylene-based polymer composition |
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