JPH03258844A - Adhesive for laminate - Google Patents
Adhesive for laminateInfo
- Publication number
- JPH03258844A JPH03258844A JP5506890A JP5506890A JPH03258844A JP H03258844 A JPH03258844 A JP H03258844A JP 5506890 A JP5506890 A JP 5506890A JP 5506890 A JP5506890 A JP 5506890A JP H03258844 A JPH03258844 A JP H03258844A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- resin
- styrene
- copolymer
- block copolymer
- 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
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 75
- 239000000853 adhesive Substances 0.000 title claims abstract description 74
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000004743 Polypropylene Substances 0.000 claims abstract description 37
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 polypropylene Polymers 0.000 claims abstract description 19
- 229920001155 polypropylene Polymers 0.000 claims abstract description 10
- 229920001400 block copolymer Polymers 0.000 claims abstract description 9
- 150000001993 dienes Chemical class 0.000 claims abstract description 7
- 229920005990 polystyrene resin Polymers 0.000 claims 1
- 229920005604 random copolymer Polymers 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 239000004793 Polystyrene Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 229920006132 styrene block copolymer Polymers 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007666 vacuum forming Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- 102100034492 Serine/threonine-protein phosphatase 4 catalytic subunit Human genes 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 101150009837 ppp4c gene Proteins 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポリスチレン（以下ＰＳと略す）系樹脂とポリ
プロピレン樹脂（以下ＰＰと略す）の積層物用接着剤に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive for a laminate of polystyrene (hereinafter abbreviated as PS) based resin and polypropylene resin (hereinafter abbreviated as PP).
シートやブロー及びフィルム等の、主として包装用に使
用される成形材料は、成形性、食品衛生の点、耐熱性、
耐油性等が要求されている、現在、これらの分野におい
ては、ＰＳ系樹脂が生産性、とりわけ成形性に優れてい
るので最も多く用いられている。しかし、ＰＳ系樹脂は
耐熱性、耐油性に問題がある。一方、ＰＰ樹脂は耐熱性
、耐油性は優れているが、生産性に問題がある。この両
者の特徴を生かす為に、ＰＳ系樹脂とＰＰ樹脂を積層し
た材料は、成形性が良く、耐熱性、耐油性が良好で、包
装材料及び成形材料として大変好ましいと考えられるが
、ＰＳ系樹脂はＰＰ樹脂とは親和性、接着性に乏しく、
積層には接着剤を使用する必要がある。Molding materials used mainly for packaging, such as sheets, blown sheets, and films, are characterized by moldability, food hygiene, heat resistance,
Currently, in these fields where oil resistance and the like are required, PS resins are most often used because they are excellent in productivity, especially moldability. However, PS resins have problems in heat resistance and oil resistance. On the other hand, PP resin has excellent heat resistance and oil resistance, but has a problem with productivity. In order to take advantage of the characteristics of both, materials made by laminating PS resin and PP resin have good moldability, heat resistance, and oil resistance, and are considered to be very preferable as packaging materials and molding materials. Resin has poor affinity and adhesiveness with PP resin,
It is necessary to use adhesive for lamination.
この積層用の接着剤としては種々の接着剤を使用する方
法が提案されている０例えば特開昭５４−１１０２８５
号にスチレン−ブタジェン共重合体とポリオレフィンを
特定の割合で混合して使用する方法、特開昭６２−５７
４４０号にビニル芳香族化合物と共役ジエンのブロック
共重合体、エチレン−酢酸ビニル共重合体とポリオレフ
ィンの混合物を使用する方法などが知られているが、こ
れらの方法では何れも接着 性が充分ではなく、更に後
者は熱安定性が不充分で焼は焦げが発生したり、酢酸臭
があり食品包装には使用が困難である。Methods of using various adhesives as adhesives for lamination have been proposed.
No. 62-57, a method of mixing styrene-butadiene copolymer and polyolefin in a specific ratio,
440 using a block copolymer of a vinyl aromatic compound and a conjugated diene, or a mixture of an ethylene-vinyl acetate copolymer and a polyolefin, but none of these methods have sufficient adhesive properties. Moreover, the latter has insufficient thermal stability, causes charring when baked, and has an acetic acid odor, making it difficult to use for food packaging.
従って、ＰＳ系樹脂／ＰＰ樹脂の積層物としては満足す
るものが無く、良好な接着剤が求められているのが現状
である。Therefore, there is no satisfactory laminate of PS resin/PP resin, and there is currently a need for a good adhesive.
本発明の目的はＰＳ系樹脂とＰＰ樹脂の積層において、
熱安定性と充分な強度を有する接着剤を提供することに
ある。The purpose of the present invention is to laminate PS resin and PP resin,
The object of the present invention is to provide an adhesive having thermal stability and sufficient strength.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた
結果、ＰＳ系樹脂とＰＰ樹脂とを積層して包装用又は成
形用材料を製造するにあたり、接着剤として、スチレン
系ブロック共重合体とポリプロピレンを用い、とくに限
定された量の樹脂配合により課題を解決するに充分に高
い接着強度が得られることさらに、積層物のスクラップ
が問題なく再利用でき、また積層物の熱成形など二次加
工時の成形サイクルとドローダウン性に関しても良好な
ことを見出し、本発明に到達した。As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when producing packaging or molding materials by laminating PS resin and PP resin, a styrene block copolymer is used as an adhesive. By using polypropylene and polypropylene, a bond strength high enough to solve the problem can be obtained, especially with a limited amount of resin formulation.Furthermore, the scraps of the laminate can be reused without problems, and it is possible to It was also found that the molding cycle and drawdown properties during subsequent processing were good, and the present invention was achieved.
即ち、本発明は、スチレンと共役ジエンとのブロック共
重合体及び／又はその水添物１００重量部に対し、ポリ
プロピレン樹脂２５〜２００重量部を添加してなること
を特徴とするＰＳ系樹脂とＰＰ樹脂の積層物用接着剤で
ある。That is, the present invention provides a PS resin characterized in that 25 to 200 parts by weight of a polypropylene resin is added to 100 parts by weight of a block copolymer of styrene and conjugated diene and/or its hydrogenated product. This is an adhesive for PP resin laminates.
本発明で用いるスチレンと共役ジエンとのブロック共重
合体又はその水添物は、スチレン−ブタジェン−ブロッ
ク共重合体、スチレン−イソプレン−ブロック共重合体
、スチレン−エチレン−ブチレン−スチレンブロック共
重合体等が知られており、ブロックの構造は、グイブロ
ック構造、トリブロック構造、ラジアルブロック構造、
マルチブロック構造などが知られており、これら何れの
構造の共重合体又はその水添物を用いることができ、水
添物を用いると接着強度が高く特に好ましい。ブロック
共重合体中のスチレンの割合としては、１０〜５ｏｉ１
％が適当であり、目的やブロックの構造に応じて選定さ
れる。このスチレン系ブロック共重合体のメルトインデ
ックス（ＪＩＳ Ｋ ７２１０に従って測定し、１９０
℃・２．１６ｋｇ条件）は通常、０．１未満であると得
られる接着剤の、流動性が低下し薄肉化が困難になるが
、その他については特に制限は受けない。The block copolymer of styrene and conjugated diene used in the present invention or its hydrogenated product is a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a styrene-ethylene-butylene-styrene block copolymer. etc. are known, and the block structures include Gui block structure, triblock structure, radial block structure,
A multi-block structure is known, and a copolymer having any of these structures or a hydrogenated product thereof can be used, and hydrogenated products are particularly preferred because of their high adhesive strength. The proportion of styrene in the block copolymer is 10 to 5 oi1
% is appropriate and is selected depending on the purpose and block structure. The melt index of this styrenic block copolymer (measured according to JIS K 7210, 190
℃・2.16kg condition) is usually less than 0.1, the fluidity of the obtained adhesive will decrease and it will be difficult to make it thin, but other than that, there are no particular restrictions.
本発明で用いるＰＰ樹脂は、ポリプロピレンホモポリマ
ー又は、プロピレンとのα−オレフィン（プロピレンを
除く）との共重合体であり、共重合体の構造はランダム
共重合体でも、ブロック共重合体でも何れの共重合体を
用いてもよいが、エチレン含有率が０．５〜８重Ｈｚの
プロピレン−エチレンランダム共重合体が特に接着強度
の点で好ましい、α−オレフィンとは、エチレン、１−
ブテン、１−ペンテン、ｌ−ヘキセン等であり、これら
の１種又は２種以上を用いることができる。このポリプ
ロピレン樹脂のメルトインデックス（ＪＩＳ Ｋ ７２
１０に従って測定し、２３０℃、２．１６ｋｇ条件）は
通常、０．３〜３０の範囲が一般的であるが、やはり流
動性の良いものを用いることが望ましい。The PP resin used in the present invention is a polypropylene homopolymer or a copolymer of propylene and an α-olefin (excluding propylene), and the structure of the copolymer may be either a random copolymer or a block copolymer. Although a propylene-ethylene random copolymer having an ethylene content of 0.5 to 8 FHz may be used, a propylene-ethylene random copolymer having an ethylene content of 0.5 to 8 FHz is particularly preferable from the viewpoint of adhesive strength.
These include butene, 1-pentene, 1-hexene, etc., and one or more of these can be used. Melt index (JIS K 72) of this polypropylene resin
10, 230° C., 2.16 kg conditions) is generally in the range of 0.3 to 30, but it is still desirable to use a material with good fluidity.
本発明のそれぞれの配合割合は、スチレンと共役ジエン
とのブロック共重合体及び／又はその水添物１００重量
部に対し、ＰＰＰ４脂２５〜２００重量部を添加するこ
とが好ましい、さらに好ましくは、スチレン系ブロック
共重合体１００重量部に対し、ＰＰ樹脂３０〜１２０重
量部の範囲である。The blending ratio of each of the present invention is preferably such that 25 to 200 parts by weight of PPP4 fat is added to 100 parts by weight of the block copolymer of styrene and conjugated diene and/or its hydrogenated product, and more preferably, The amount is in the range of 30 to 120 parts by weight of the PP resin per 100 parts by weight of the styrene block copolymer.
ＰＰ樹脂が２５重量部未満であるとＰＰ樹脂層との接着
性が低下し、さらに接着剤の流動性が低下し好ましくな
い、２００重量部を越えるとＰＳ樹脂層との接着性が低
下し、好ましくない。If the amount of PP resin is less than 25 parts by weight, the adhesiveness with the PP resin layer will decrease, and the fluidity of the adhesive will also decrease, which is undesirable. If it exceeds 200 parts by weight, the adhesiveness with the PS resin layer will decrease, Undesirable.
本発明の接着剤には、接着性を低下させない範囲におい
て、必要に応じ他の樹脂、又は石油樹脂、ワックス等の
粘着性付与剤を添加しても良い、樹脂の他に必要な添加
剤、例えば、酸化防止剤、紫外線吸収剤、顔料、染料、
充填剤、核剤、ブロッキング防止剤、スリップ剤、帯電
防止剤、難燃剤などを適量加えても良い。To the adhesive of the present invention, other resins or tackifiers such as petroleum resins and wax may be added as necessary within a range that does not reduce the adhesiveness. Necessary additives in addition to the resin, For example, antioxidants, ultraviolet absorbers, pigments, dyes,
Appropriate amounts of fillers, nucleating agents, antiblocking agents, slip agents, antistatic agents, flame retardants, etc. may be added.
本発明で使用する接着剤を調製する方法としては、公知
の種々の方法、例えば、各成分をリボンブレンダー、Ｖ
型ブレンダー、タンブラ−ヘンシェルミキサー、などで
混合し、押出機、バンバリーミキサ−１二本ロール、ニ
ーダ−などで溶融混練する方法、あるいは各成分を溶媒
で溶解し、良く撹拌した後、貧溶媒を添加して析出させ
る方法などが挙げられる。The adhesive used in the present invention can be prepared by various known methods, for example, by mixing each component in a ribbon blender, V
Mixing with a mold blender, tumbler-Henschel mixer, etc., followed by melt-kneading with an extruder, Banbury mixer (1/2 rolls), kneader, etc. Alternatively, dissolve each component in a solvent, stir well, and then remove the poor solvent. Examples include a method of adding and precipitating.
本発明の接着剤を適用するＰＳ系樹脂とは、ポリスチレ
ン、ハイインパクトポリスチレン、スチレン−アクリル
ニトリル共重合体、ＡＢＳ樹脂などスチレンを主体とし
た樹脂であり、その他の制限は特にない。The PS resin to which the adhesive of the present invention is applied is a resin mainly composed of styrene, such as polystyrene, high-impact polystyrene, styrene-acrylonitrile copolymer, and ABS resin, and there are no other limitations.
本発明の接着剤を適用するＰＰはポリプロピレンホモポ
リマー又は、プロピレンとα−オレフィン（プロピレン
を除く）との共重合体である以外は特に制限は受けず、
一般に公知のものを用いることができる。The PP to which the adhesive of the present invention is applied is not particularly limited, except that it is a polypropylene homopolymer or a copolymer of propylene and α-olefin (excluding propylene).
Generally known ones can be used.
本発明の接着剤を用い積層物を製造する方法としては、
予め、ＰＳ系樹脂、ＰＰおよび接着剤の各々のフィルム
、シートを製造しておき、接着剤を他の樹脂のフィルム
、シートで挾んで熱圧着する方法、ＰＳ系樹脂とＰＰの
何れかのフィルム、シートの上に溶融した接着剤を押出
し、さらに他方の樹脂のフィルム、シートを重ね合わせ
る方法、ＰＳ系樹脂、ＰＰ、接着剤を別個の押出機で溶
融し、多層構造のＴダイやサーキュラ−ダイにより共押
出し、フィルム、シート、発泡シート、パイプなどを得
る方法が採用できる。また、多層パリソンを形威し、ブ
ロー底形によりボトルを得ることも可能である。A method for producing a laminate using the adhesive of the present invention includes:
A method in which films or sheets of PS resin, PP, and adhesive are manufactured in advance, and the adhesive is sandwiched between films or sheets of other resins and bonded by thermocompression, or a film of either PS resin or PP. , a method in which molten adhesive is extruded onto a sheet and then the other resin film and sheet are superimposed, a method in which PS resin, PP, and adhesive are melted in separate extruders, and a multilayer structure T-die or circular Methods such as coextrusion using a die to obtain films, sheets, foam sheets, pipes, etc. can be adopted. It is also possible to obtain a bottle with a blown bottom shape using a multilayer parison.
Ｔダイ法には、フィードブロック及びＴダイを使用する
方法とマルチマニホールドダイによる方法とがあり、何
れの方法を用いても良い。The T-die method includes a method using a feed block and a T-die and a method using a multi-manifold die, and either method may be used.
ＰＳ系樹脂やＰＰを押出す時の温度は、従来の押出温度
で良く、接着剤の押出温度は通常、１６０〜３００℃、
好ましくは１７０〜２４０°Ｃが適当である。The temperature when extruding PS resin or PP may be the conventional extrusion temperature, and the extrusion temperature of the adhesive is usually 160 to 300 ° C.
Preferably, 170 to 240°C is appropriate.
本発明の接着剤を適用し得る積層物の形状としては種々
の物があり、例えば、フィルム、シート、発泡シート、
パイプ、ボトルなどが挙げられ、積層シートを予め製造
しておき、真空成形、圧空成形などの方法により種々の
容器を製造することも可能である。There are various shapes of laminates to which the adhesive of the present invention can be applied, such as films, sheets, foam sheets,
Examples include pipes and bottles, and it is also possible to manufacture various containers by manufacturing laminated sheets in advance and using methods such as vacuum forming and pressure forming.
以下、実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
接着強度はＪＩＳ Ｋ−６８５４（Ｔ型剥離試験に従っ
て測定した。メルトインデックス（Ｍｌ）はＪＩＳ Ｋ
−７２１Ｏに従って測定し、以下、（１９０°Ｃ・２．
１６ｋｇ）の条件をＭ Ｉ （ａ）、（２００°Ｃ・５
．０ｋｇ）の条件をＭｌ（ｂ）、（２３０°Ｃ・２．１
６ｋｇ）の条件をＭ Ｉ （Ｃ）と略す。Adhesive strength was measured according to JIS K-6854 (T-type peel test. Melt index (Ml) was measured according to JIS K-6854 (T-type peel test).
-721O, and below (190°C・2.
M I (a), (200°C・5
．． Ml(b), (230°C・2.1
6 kg) is abbreviated as M I (C).
実施例１
スチレン−ブタジェンブロック共重合体′り７プＬ／７
Ａ’ （旭化戒■製、ＭＨａ）＝２．６ 、スチレン
量−４０重量％）１００重量部、プロピレン−エチレン
ランダム共重合体“三井ノーブレンＭＪＳ−Ｇ″ （三
井東圧化学■製、Ｍｌ（Ｃ）＝１．５ 、エチレン−４
，０重量％）７０重量部をタンブラ−で混合し、３０鵬
押出機で押出し、接着剤のベレットを得た。上記接着剤
とハイインパクトＰＳ （旧ＰＳ）＃トーボレックス８
３０−０５’ （三井東圧化学■製、旧（ｂ）＝２．
５）とＰＰホモポリマー“三井ノーブレンＪＳ−Ｇ’
（三井東圧化学■製、Ｍｌ（Ｃ）＝１．５）を用い、
計３台の押出機とフィードブロック及びＴダイにより、
以下の構成からなる多層押出シートを製造した。樹脂の
構成はＰＳ／接着剤／ＰＰの３種３Ｊ！であり、各層の
厚さは０．５ ／ ０．０３ ／ ０．１ｍに調整した
。各樹脂層の押出しはそれぞれ、ＰＳ（上側）：６５ｍ
１ｌ、接着剤： ３０ｍｍ機、Ｐ Ｐ ： ６５ｍｍ機
で行った。また、押出温度は各樹脂層ともに２１０°Ｃ
とした。接着剤はＰＳ、ＰＰの何れの層にも充分な接着
強度を有・していた、接着剤の臭い、焼は焦げについて
も特に問題はなかった。（接着剤の組成、接着強度を表
−１に示す）
本実施例で得られた多層押出シート、ＰＰシート及びＰ
Ｓシートを用いて真空成形試験を行ない比較した。ＰＰ
シート及びＰＳシートは本実施例で用いた原料を使用し
、評価の方法は大型真空成形機に９００ Ｘ ９００ｍ
５のシートをセットし、ヒーターで加熱し真空成形に適
正な時間及びその時のシート中央部のドローダウン距離
を測定した。この結果多層シートはＰＰシートに比べ成
形時間が短く、ドローダウンが小さい等の良好な特徴が
認められた。測定結果を次の表に示す。Example 1 Styrene-butadiene block copolymer 7pL/7
A' (manufactured by Asahi Kakai ■, MHa) = 2.6, styrene content - 40% by weight) 100 parts by weight, propylene-ethylene random copolymer "Mitsui Noblen MJS-G" (manufactured by Mitsui Toatsu Chemical ■, Ml (C)=1.5, ethylene-4
, 0% by weight) were mixed in a tumbler and extruded in a 30-Peng extruder to obtain an adhesive pellet. The above adhesive and High Impact PS (formerly PS) #Tobolex 8
30-05' (Mitsui Toatsu Chemical ■, old (b) = 2.
5) and PP homopolymer “Mitsui Noblen JS-G’
(manufactured by Mitsui Toatsu Chemical ■, Ml (C) = 1.5),
With a total of 3 extruders, feed blocks and T-dies,
A multilayer extruded sheet having the following configuration was manufactured. The resin composition is 3J: PS/adhesive/PP! The thickness of each layer was adjusted to 0.5/0.03/0.1 m. The extrusion of each resin layer is PS (upper side): 65 m
1l, adhesive: 30mm machine, PP: 65mm machine. In addition, the extrusion temperature is 210°C for each resin layer.
And so. The adhesive had sufficient adhesive strength for both the PS and PP layers, and there were no particular problems with the adhesive's odor or burning. (The composition and adhesive strength of the adhesive are shown in Table 1) The multilayer extruded sheet, PP sheet and P
A vacuum forming test was conducted using S sheet and compared. PP
The raw materials used in this example were used for the sheet and PS sheet, and the evaluation method was as follows: 900 x 900 m in a large vacuum forming machine.
The sheet No. 5 was set, heated with a heater, and the appropriate time for vacuum forming and the drawdown distance at the center of the sheet at that time were measured. As a result, the multilayer sheet was found to have favorable characteristics such as shorter molding time and smaller drawdown compared to the PP sheet. The measurement results are shown in the table below.
またこの時、φ９０ｓｎ、深さ４３■−の−船釣な真空
成形用金型で丸カップを成形し、成形品の外観と接着性
の変化について観察した。成形品の外観はＰＳシートと
同様に良好で、接着性についてはもとのシートと何ら変
わらなかった。Also, at this time, a round cup was molded using a vacuum molding mold having a diameter of 90 mm and a depth of 43 mm, and changes in the appearance and adhesion of the molded product were observed. The appearance of the molded product was as good as the PS sheet, and the adhesiveness was no different from the original sheet.
又、本実施例で得られた多層押出シートを粉砕機で粉砕
し、ＰＳ樹脂中に３０％ブレンドして、ＰＰ層及び接着
層はそのまま同様にして多層シートを得た。得られたシ
ートの外観、接着強度、熱成形性などはスクラップを添
加しないもとのシートと何ら変わらなかった。Further, the multilayer extruded sheet obtained in this example was pulverized with a pulverizer, and 30% blended into PS resin, and the PP layer and adhesive layer were left in the same manner to obtain a multilayer sheet. The appearance, adhesive strength, thermoformability, etc. of the obtained sheet were no different from the original sheet without the addition of scrap.
表 成形特性の測定結果
実施例２．３
実施例１と同様の成分で、スチレン系プロ・ンク共重合
体１００重量部に対し、プロピレン−エチレン共重合体
の添加量を各々、実施例２では３０重量部に、実施例３
では１５０重量部に変えた以外は実施例１と同様にして
多層シートを得た、これらの接着剤も充分な接着強度を
有していた。接着剤の組成、接着強度を表−１に示す。Table Measurement results of molding properties Example 2.3 Using the same ingredients as in Example 1, the amount of propylene-ethylene copolymer added to 100 parts by weight of the styrene-based Pro-Nc copolymer was Example 3 to 30 parts by weight
A multilayer sheet was obtained in the same manner as in Example 1 except that the amount was changed to 150 parts by weight. These adhesives also had sufficient adhesive strength. Table 1 shows the composition and adhesive strength of the adhesive.
実施例４
実施例１においてスチレン系ブロック共重合体をスチレ
ン−イソプレン−スチレンブロック共重合体′カリフレ
ックスＴ Ｒ１１０７″ （シェル化学■製、Ｍｌ（ｂ
）＝９．スチレン量・１４重量％）に変えた以外は実施
例１と同様にして多層シートを得た。この接着剤も充分
な接着強度を有していた。接着剤の組成、接着強度を表
−１に示す。Example 4 In Example 1, the styrenic block copolymer was replaced with styrene-isoprene-styrene block copolymer 'Califlex TR1107'' (manufactured by Shell Chemical ■, Ml(b
)=9. A multilayer sheet was obtained in the same manner as in Example 1 except that the amount of styrene was changed to 14% by weight. This adhesive also had sufficient adhesive strength. Table 1 shows the composition and adhesive strength of the adhesive.
実施例５
実施例１において用いたスチレン系ブロック共重合体を
水添されたスチレン系ブロック共重合体であるスチレン
−エチレン−ブチレン−スチレンブロック共重合体１ク
レイトンＧ−１６５０（シェル化学■製、スチレン量＝
３０重量％）に変えた以外は実施例１と同様にして多層
シートを得た。この接着剤も充分な接着強度を有してい
た。接着剤の総酸、接着強度を表−１に示す。Example 5 Styrene-ethylene-butylene-styrene block copolymer 1, which is a styrenic block copolymer obtained by hydrogenating the styrenic block copolymer used in Example 1, Kraton G-1650 (manufactured by Shell Chemical Co., Ltd., Amount of styrene =
A multilayer sheet was obtained in the same manner as in Example 1 except that the amount was changed to 30% by weight). This adhesive also had sufficient adhesive strength. Table 1 shows the total acid content and adhesive strength of the adhesive.
実施例６
実施例１において、接着層の厚みを薄くするため、厚み
構成をＰＳ／接着剤／ＰＰ−０，５１０，００８／ ０
．１ ｍに調整した以外は実施例１と同様にして多層シ
ートを得た。この多層シートも充分な接着強度を有して
いた。接着剤の組成、接着強度を表−１に示す。Example 6 In Example 1, in order to reduce the thickness of the adhesive layer, the thickness composition was changed to PS/adhesive/PP-0,510,008/0
．． A multilayer sheet was obtained in the same manner as in Example 1 except that the thickness was adjusted to 1 m. This multilayer sheet also had sufficient adhesive strength. Table 1 shows the composition and adhesive strength of the adhesive.
実施例７
実施例１において、厚み構成は変えずに引取速度のみを
早くして、合計厚み０．３間の多層シートを得た。この
接着剤も充分な接着強度を有していた。接着剤の組成、
接着強度を表−１に示す。Example 7 In Example 1, only the take-up speed was increased without changing the thickness structure to obtain a multilayer sheet with a total thickness of 0.3. This adhesive also had sufficient adhesive strength. Adhesive composition,
The adhesive strength is shown in Table-1.
比較例１
接着剤として、スチレン−ブタジェンブロック共重合体
“タフブレンＡ′を１００重１ｍ使用した以外は実施例
１と同様にして多層シートを得た。この接着剤の接着強
度は低かった。接着剤の組成、接着強度を表−２に示す
。Comparative Example 1 A multilayer sheet was obtained in the same manner as in Example 1 except that 100 weights and 1 m of styrene-butadiene block copolymer "Toughblen A'" was used as the adhesive.The adhesive strength of this adhesive was low. The composition and adhesive strength of the adhesive are shown in Table 2.
比較例２．３
実施例１と同様の取分て、スチレン系ブロック共重合体
１００重量部に対し、プロピレンーエチレン共重合体の
添加量を各々、比較例２では２０重量部に、比較例３で
は２５０重量部に変えた以外は実施例１と同様にして多
層シートを得た。Comparative Example 2.3 In the same manner as in Example 1, the amount of propylene-ethylene copolymer added to 100 parts by weight of the styrene block copolymer was 20 parts by weight in Comparative Example 2. In Example 3, a multilayer sheet was obtained in the same manner as in Example 1 except that the amount was changed to 250 parts by weight.
これらの接着剤の接着強度は低かった。接着剤の組成、
接着強度を表−２に示す。The adhesive strength of these adhesives was low. Adhesive composition,
The adhesive strength is shown in Table-2.
比較例４
接着剤原料として、スチレン−ブタジェンブロック共重
合体１タフプレンＡ′及びプロピレン−エチレンランダ
ム共重合体’ ＭＪＳ−Ｇ ’の他にエチレン−酢酸ビ
ニル共重合体” ＥＶＡ ＤＱＤＪ１８６Ｂ’ （日
本ユニカー−製、Ｍ ｌ （ａ）＝ ２ 、 ｓ、酢酸
ビニル含有率１８重ＩＸ ）を用い、３戒分の配合割合
を各々、１００重量部、１００重量部、３００重量部に
した以外は実施例１と同様にして多層シートを得た。こ
の接着剤の接着強度は低かった。Comparative Example 4 In addition to styrene-butadiene block copolymer 1-Tuffrene A' and propylene-ethylene random copolymer 'MJS-G', ethylene-vinyl acetate copolymer 'EVA DQDJ186B' (Nippon Unicar Co., Ltd.) was used as an adhesive raw material. Examples except that M l (a) = 2, s, vinyl acetate content 18x) was used, and the blending proportions of the three precepts were 100 parts by weight, 100 parts by weight, and 300 parts by weight, respectively. A multilayer sheet was obtained in the same manner as in Example 1. The adhesive strength of this adhesive was low.
又このシートは臭気が強く、若干の焼焦げが認められた
。接着剤の組成、接着強度を表−２に示す。Additionally, this sheet had a strong odor and was slightly burnt. The composition and adhesive strength of the adhesive are shown in Table 2.
本発明の接着剤はＰＳ系樹脂とＰＰの積層において、接
着剤層又は積層物全体の厚さが薄い場合においても充分
高い接着強度が得られるので、成形性がよく、耐熱性、
耐油性が良好な包装用及び成形用積層物を得ることがで
きる。The adhesive of the present invention can obtain sufficiently high adhesive strength even when the thickness of the adhesive layer or the entire laminate is thin in lamination of PS resin and PP, so it has good moldability, heat resistance,
Packaging and molding laminates with good oil resistance can be obtained.
表１ 表２Table 1 Table 2
Claims (1)
その水添物１００重量部に対し、ポリプロピレン樹脂２
５〜２００重量部を添加してなることを特徴とするポリ
スチレン系樹脂とポリプロピレン樹脂の積層物用接着剤For 100 parts by weight of a block copolymer of styrene and conjugated diene and/or its hydrogenated product, 2 parts by weight of polypropylene resin
Adhesive for laminates of polystyrene resin and polypropylene resin, characterized by adding 5 to 200 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5506890A JPH03258844A (en) | 1990-03-08 | 1990-03-08 | Adhesive for laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5506890A JPH03258844A (en) | 1990-03-08 | 1990-03-08 | Adhesive for laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03258844A true JPH03258844A (en) | 1991-11-19 |
Family
ID=12988380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5506890A Pending JPH03258844A (en) | 1990-03-08 | 1990-03-08 | Adhesive for laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03258844A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002225203A (en) * | 2001-02-02 | 2002-08-14 | Grand Polymer Co Ltd | Olefinic multilayer shrink film and packaging material |
| US6455627B1 (en) | 1999-06-25 | 2002-09-24 | Kraton Polymers Us Llc | Hot melt pressure sensitive positions adhesive (II) |
| US6465557B1 (en) | 1999-06-25 | 2002-10-15 | Kraton Polymers U.S. Llc | Hot melt pressure sensitive positioning adhesive |
| CN104559839A (en) * | 2015-01-09 | 2015-04-29 | 长园长通新材料有限公司 | Termite-resistant adhesive used for polyethylene pipeline, adhesive tape and preparation of adhesive tape |
| JP2019131722A (en) * | 2018-01-31 | 2019-08-08 | Ｍｃｐｐイノベーション合同会社 | Thermoplastic elastomer composition and joining member |
-
1990
- 1990-03-08 JP JP5506890A patent/JPH03258844A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6455627B1 (en) | 1999-06-25 | 2002-09-24 | Kraton Polymers Us Llc | Hot melt pressure sensitive positions adhesive (II) |
| US6465557B1 (en) | 1999-06-25 | 2002-10-15 | Kraton Polymers U.S. Llc | Hot melt pressure sensitive positioning adhesive |
| JP2002225203A (en) * | 2001-02-02 | 2002-08-14 | Grand Polymer Co Ltd | Olefinic multilayer shrink film and packaging material |
| JP4644946B2 (en) * | 2001-02-02 | 2011-03-09 | 株式会社プライムポリマー | Olefin-based multilayer shrink film and packaging material |
| CN104559839A (en) * | 2015-01-09 | 2015-04-29 | 长园长通新材料有限公司 | Termite-resistant adhesive used for polyethylene pipeline, adhesive tape and preparation of adhesive tape |
| JP2019131722A (en) * | 2018-01-31 | 2019-08-08 | Ｍｃｐｐイノベーション合同会社 | Thermoplastic elastomer composition and joining member |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5106696A (en) | Polyolefins compatibilized with styrene copolymers and/or polymer blends and articles produced therefrom | |
| EP0664327B1 (en) | Adhesive resin composition | |
| JP3154931B2 (en) | Embossed sheet, laminate using the same, and method of manufacturing the same | |
| US9708512B2 (en) | Tie-layer adhesives for styrene polymers and articles | |
| EP1973981B1 (en) | Tie-layer adhesive compositions for styrene polymers and articles | |
| JP2652507B2 (en) | Resin composition and biaxially stretched film, production method thereof, and food packaging material | |
| JPH03258844A (en) | Adhesive for laminate | |
| JP4780842B2 (en) | Polypropylene multilayer film | |
| CN112920743B (en) | Adhesive resin composition, sheet and lid using same, member set for sealed container, and container | |
| JP4059415B2 (en) | Polystyrene resin foam / polyolefin resin multilayer | |
| JP6832405B1 (en) | Multilayer film for laminating thermoformed sheets, laminated sheets for thermoforming, and thermoforming containers | |
| JP2019156484A (en) | Easily peelable film | |
| JP2000290620A (en) | Adhesive resin composition | |
| JP6502727B2 (en) | Multi-layer sheet for thermoforming, method for producing the same, and container for heating | |
| JPH03258843A (en) | Adhesive composition for laminate | |
| JPS62187779A (en) | Bondable resin composition | |
| JP3616717B2 (en) | Thermoplastic resin composition | |
| JP2020114889A (en) | Adhesive resin composition and laminate | |
| JP2009000984A (en) | Polyolefin multilayer sheet | |
| JP2548254B2 (en) | Adhesive for laminates | |
| JP4618824B2 (en) | Laminated container and manufacturing method thereof | |
| JP4510577B2 (en) | Laminated sheet for packaging body and packaging body formed from this sheet | |
| JPH0352980A (en) | Adhesive for laminated product | |
| JPH0673252A (en) | Resin composition for laminate | |
| JPS6291578A (en) | Adhesive resin composition |