JPS6229469B2 - - Google Patents
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- Publication number
- JPS6229469B2 JPS6229469B2 JP54126349A JP12634979A JPS6229469B2 JP S6229469 B2 JPS6229469 B2 JP S6229469B2 JP 54126349 A JP54126349 A JP 54126349A JP 12634979 A JP12634979 A JP 12634979A JP S6229469 B2 JPS6229469 B2 JP S6229469B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- adhesive
- resin
- parts
- 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.)
- Expired
Links
- 229920001400 block copolymer Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000004840 adhesive resin Substances 0.000 claims description 17
- 229920006223 adhesive resin Polymers 0.000 claims description 17
- 239000000853 adhesive Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000004831 Hot glue Substances 0.000 claims description 11
- 150000003097 polyterpenes Chemical class 0.000 claims description 10
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920001195 polyisoprene Polymers 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- 239000002390 adhesive tape Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000000123 paper Substances 0.000 description 7
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 239000005060 rubber Substances 0.000 description 4
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 239000011111 cardboard Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- -1 phthalate ester Chemical class 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】
本発明は、ポリブタジエンまたはポリイソプレ
ンブロツクとポリスチレンブロツクとからなるブ
ロツク共重合体を使用したホツトメルト粘着剤に
おいて、特に紙等に対する粘着性の改良されたホ
ツトメルト粘着剤組成物を提供するものである。
従来、粘着剤は粘着テープ・ラベル等種々の用
途に使用されてきている。テープ類への粘着剤の
塗布は、粘着剤を溶剤に溶かした粘着剤溶液をロ
ール、スプレー等の手段によつて基材へ塗布する
方法がとられている。しかしながら、かかる溶剤
の使用は、公害、火災、労働衛生等の面から粘着
テープ類の感圧製品製造上の問題点であり、近年
ますます社会問題として重大視されるに至つてい
る。そこで、かかる不都合を解決する手段とし
て、最近非溶剤型のホツトメルト粘着剤が注目さ
れてきているが、一般に紙に対する粘着性が悪
く、段ボールの包装等に問題があつた。
本発明者はポリブタジエンまたはポリイソプレ
ンブロツクとポリスチレンブロツクとからなるブ
ロツク共重合体を粘着剤のベースポリマーとして
使用し、特定の粘着性樹脂混合物を配合すること
により、特に紙に対する粘着性の優れたホツトメ
ルト粘着剤が得られることを見い出し、本発明に
到達した。
本発明は、(1)一般式Ａ―Ｂ―Ａ、（Ａ−Ｂ）o、
Ｂ（―Ａ−Ｂ）o、（Ａ−Ｂ））―oＡ、（Ａ−Ｂ）nＸ
〔ここでＢは実質的にポリブタジエンまたはポリ
イソプレンブロツク、Ａは実質的にポリスチレン
ブロツクであり、ｎは２〜10の整数を表わす。Ｘ
はｍ個の重合体鎖が結合している多官能性化合物
であり、ｍは３〜７の整数を表わす。〕で表わさ
れるフローレイト（ASTM―1238、Ｇ条件）が
0.1〜40ｇ／10分の範囲であり、スチレン含有量
が５〜50重量％の範囲であるブロツク共重合体ま
たはこれらの混合物と、該ブロツク共重合体100
重量部に基づいて、少なくとも20重量％以上のポ
リテルペン系樹脂を含む軟化点60℃以上の粘着性
樹脂Ｓと軟化点30℃以下の粘着性樹脂Ｌとの比が
Ｓ／Ｌ＝9/1〜4/6の範囲である粘着性樹脂混合物
50〜200重量部とからなることを特徴とするホツ
トメルト粘着剤組成物に関するものである。
本発明で用いられるブロツク共重合体は、一般
式Ａ―Ｂ―Ａ、（Ａ−Ｂ）o、Ｂ（―Ａ−Ｂ）o、（Ａ−
Ｂ）―oＡ、（Ａ−Ｂ）nＸ〔式中のＡ，Ｂ，Ｘ，ｎお
よびｍは前記と同じ意味をもつ〕で表わされるも
ので、アルカリ金属を基材として開始剤によりリ
ビングアニオン重合法により得ることができる。
このようなブロツク共重合体は、前記開始剤の存
在下に、単量体をブロツクごとに順次重合させる
方法、または共重合反応性比の異なる２種の単量
体を同時に装入して重合させブロツク共重合体を
得る方法、あるいは前記開始剤によるリビングブ
ロツク共重合体をカツプリングする方法により得
ることができる。前記（Ａ−Ｂ）nＸで表わされる
ブロツク共重合体はＡ−Ｂなるリビングブロツ
ク共重合体を多官能性カツプリング剤によりカツ
プリングさせることにより得ることができる。例
えば、四塩化スズ、四塩化ケイ素などの四官能性
カツプリング剤を使用することができる。ブロツ
ク共重合体のフローレイト（ASTM―D1238、Ｇ
条件）は0.1〜40ｇ／10分であり、好ましくは１
〜20ｇ／10分である。0.1ｇ／10分未満では得ら
れるホツトメルト粘着剤組成物の溶融粘度が高
く、実用性に乏しく、40ｇ／10分を越えると保持
力が低く好ましくない。ブロツク共重合体中のス
チレン含有量は全重合体に対して５〜50重量％、
好ましくは10〜45重量％の範囲で選択することが
できる。該範囲外では得られたホツトメルト粘着
剤を用いた粘着テープ類の粘着特性が悪く好まし
くない。また、ブロツク共重合体は前記一般式で
示されるものであればいずれのものでも良いが、
特に（Ａ−Ｂ）nＸで示されるブロツク共重合体
は、該ブロツク共重合体を使用したホツトメルト
粘着剤の溶融粘度が他の一般式で示されるブロツ
ク共重合体のものより低く、加工性の面から有利
であり好ましい。
本発明で重要な構成成分である粘着性樹脂は、
少なくとも20重量％以上のポリテルペン系樹脂を
含む軟化点60℃以上の粘着性樹脂Ｓと軟化点30℃
以下の粘着性樹脂Ｌとの比がＳ／Ｌ＝9/1〜4/6の
範囲であり、Ｓ＋Ｌがブロツク共重合体100重量
部を基準にして50〜200重量部の範囲で使用され
る。ここでいう軟化点とは、JIS K2531による環
球法軟化点である。粘着性樹脂Ｓは20〜100重量
％のポリテルペン系樹脂と80〜０重量％のポリテ
ルペン系樹脂以外の粘着性樹脂とからなり、その
軟化点が60℃以上でなければならない。ポリテル
ペン系樹脂が20重量％以上含まれないと、得られ
る粘着剤紙に対する粘着性および保持力が劣り、
実用性に乏しい。ポリテルペン系樹脂としては、
α―ピネン重合体、β―ピネン重合体、ジペンテ
ン重合体、α―ピネン―フエノール共重合体、β
―ピネン―フエノール共重合体等があり、いずれ
のものでも使用できるが、特にα―ピネン重合体
が好ましい。粘着性樹脂Ｓに80〜０重量％含まれ
るポリテルペン系樹脂以外の粘着性樹脂として
は、ロジン系樹脂（例えば、ロジン、水添ロジ
ン、水添ロジンのエステル化物など）、石油系樹
脂の水添物（例えば、ナフサ分解油中のC4，
C5，C9留分やシクロペンタジエンを主成分とす
る分解油を重合し、水添したもの）等がある。粘
着性樹脂Ｓの軟化点が60℃以上でないと、得られ
る粘着剤の保持力が劣り、実用性に乏しい。粘着
性樹脂Ｌは、その軟化点が30℃以下でなければな
らず、30℃以下でなければタツクを改良する効果
が乏しい。粘着性樹脂Ｌとしては、その軟化点が
30℃以下であればポリテルペン系樹脂、ロジン系
樹脂、石油系樹脂の水添物等いかなるものでも良
いが、特にポリテルペン系樹脂が好ましく、α―
ピネン重合体がさらに好ましい。粘着性樹脂Ｓと
Ｌは、その比Ｓ／Ｌが9/1〜4/6の範囲で使用され
る9/1よりＬが少ないと、タツクが悪くなり好ま
しくない。また、4/6よりＬが多いと、粘着剤の
保持力が低下し好ましくない。配合量Ｓ＋Ｌが50
〜200重量部の範囲外では、得られる粘着剤を用
いた粘着テープ類の粘着特性が悪く好ましくな
い。軟化剤は必要に応じてブロツク共重合体100
重量部に基づいて、５重量部未満の範囲で使用さ
れる。５重量部以上では得られるホツトメルト粘
着剤の保持力が低下し、実用性に乏しい。軟化剤
としては、ゴム展開油、可塑剤（例えばフタル酸
エステル等）等が使用できる。
上記組成物は所望ならば酸化防止剤等の物質を
添加してもよく、またホツトメルト粘着剤の特徴
を失なわさせない限り、普通のエラストマー（例
えば、天然ゴム、ポリイソプレンゴム、ポリブタ
ジエンゴム、スチレン―ブタジエン共重合ゴム
等）や充てん剤等を混合してもよい。
本発明のホツトメルト粘着剤組成物の製造は、
種々の方法が使用できる。例えば、溶融がま、ニ
ーダー、ミキシングロール、押出機、インターナ
ルミキサーなどを用いることができる。
本発明のホツトメルト粘着剤組成物は、特に紙
に対しての粘着力に優れると同時に、他の被着
体、例えばプラスチツクフイルム、金属、ガラス
等に対しては、従来のホツトメルト粘着剤と同等
の粘着力を有するため、汎用の各種粘着テープ・
ラベル、などに有効である。
以下に実施例を示す。実施例は本発明を代表す
るものであるが、本発明の範囲を制限するもので
はない。
実施例 １
窒素ガス雰囲気下において、スチレンを含むト
ルエン溶液にノルマル―ブチルリチウムを加え、
スチレンの重合を開始させ、スチレンの99％以上
が重合した後、更に、１，３―ブタジエンを含む
トルエン溶液を添加し、加えた１，３―ブタジエ
ンの99％以上が重合した後に、活性を失わせるこ
となく四塩化ケイ素を添加し、カツプリング反応
を行なつた。得られた重合体は（ポリスチレン―
ポリブタンジエン）４ケイ素型のブロツク共重合
体であり、メルトフロー（Ｇ条件）８ｇ／10分、
スチレン含有量30重量％のものであつた。
得られたブロツク共重合体100重量部を基準に
して、撹拌機容器中にYSレジンＡ―1150（α―
ピネン重合体、軟化点115℃、安原油脂製）80重
量部、YSオイルＤ（テルペン低重合体、軟化点
０℃以下安原油脂製）20重量部、ノクラツクNS
―７（２，５―ジ―第三―ブチルハイドロキノ
ン、大内新興化学製）３重量部を仕込み、約180
℃で加熱溶融した。溶融後、上記記載のブロツク
共重合体100重量部を添加し、約１時間溶融混合
を続けて透明で滑らかに流れる均質な組成物を得
た。この組成物を型に流し込み冷却し、粘着性を
有するブロツクとした。このようにして製造した
ホツトメルト粘着剤の一部を溶融し、約170℃で
背面処理したクラフト原紙（坪量75ｇ／m2）上に
約50μの厚さとなるように塗布し、クラフト粘着
テープを作製した。このクラフト粘着テープにつ
いて、タツクと紙に対する粘着性（フラツプ保持
力）を測定し、その結果を表―１に示す。各測定
は以下に示す方法によつた。タツクは角度30゜の
傾斜を有する板上に粘着テープを固定し、J.Dow
の球ころがし法により、粘着テープの表面に止つ
たボールNo.を測定する。ボールNo.が大きい程タツ
クが大である。タツクの測定は20℃で行なつた。
フラツプ保持力は第１図に示すように、２mmの
間隔で、タテ方向に相対した２枚の段ボール紙
（タテ75mm、ヨコ50mm、厚さ５mm）２に、幅20
mm、長さ27mmの粘着テープ３を、重さ200ｇのロ
ーラーを用いて２回圧着させ、その段ボール紙の
両端支点１に固定するとともに、中央部のスキ間
に１Kgの荷重４をかけ、40℃の温度条件下で、粘
着テープがはがれるまでの時間を測定した。
実施例 ２〜６
実施例１と同様の方法を用いて、表１に示した
配合を用いた場合の結果も表１に示す。
比較例 １〜５
実施例１と同様の方法を用いて、表１に示した
配合を用いた場合の結果も表１に示す。
表１より明らかなように、本発明の粘着剤は、
紙に対する粘着性が極めて優れており、しかもタ
ツクの良好な粘着剤である。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention provides a hot melt adhesive composition that uses a block copolymer consisting of a polybutadiene or polyisoprene block and a polystyrene block, and has particularly improved adhesiveness to paper, etc. This is what we provide. Conventionally, adhesives have been used for various purposes such as adhesive tapes and labels. Adhesives are applied to tapes by applying an adhesive solution prepared by dissolving the adhesive in a solvent onto a base material by means of a roll, spray, or the like. However, the use of such solvents is a problem in the production of pressure-sensitive products such as adhesive tapes in terms of pollution, fire, occupational health, etc., and has become increasingly regarded as a social problem in recent years. Therefore, non-solvent type hot melt adhesives have recently been attracting attention as a means to solve these problems, but they generally have poor adhesion to paper and have caused problems when packaging corrugated cardboard, etc. The present inventor has developed a hot melt product that has excellent adhesion to paper by using polybutadiene or a block copolymer consisting of a polyisoprene block and a polystyrene block as the base polymer of an adhesive, and by blending a specific adhesive resin mixture. The present invention was achieved by discovering that an adhesive can be obtained. The present invention provides (1) general formula A-B-A, (A-B) o ,
B(-A-B) o , (A-B))- o A, (A-B) n X
[Here, B is substantially a polybutadiene or polyisoprene block, A is substantially a polystyrene block, and n represents an integer from 2 to 10. X
is a polyfunctional compound in which m polymer chains are bonded, and m represents an integer of 3 to 7. ] The flow rate (ASTM-1238, G conditions) is
A block copolymer or a mixture thereof having a styrene content ranging from 0.1 to 40 g/10 minutes and a styrene content ranging from 5 to 50% by weight, and the block copolymer 100% by weight.
Based on parts by weight, the ratio of adhesive resin S with a softening point of 60°C or higher and adhesive resin L with a softening point of 30°C or lower containing at least 20% by weight or more of polyterpene resin is S/L = 9/1 ~ Sticky resin mixture that is in the range of 4/6
50 to 200 parts by weight of the hot melt adhesive composition. The block copolymers used in the present invention have general formulas A-B-A, (A-B) o , B(-A-B) o , (A-
B) - o A, (A-B) n It can be obtained by an anionic polymerization method.
Such block copolymers can be produced by sequentially polymerizing monomers block by block in the presence of the initiator, or by simultaneously charging two types of monomers with different copolymerization reactivity ratios. It can be obtained by a method of obtaining a living block copolymer or a method of coupling a living block copolymer using the above-mentioned initiator. The block copolymer represented by (A-B) n X can be obtained by coupling the living block copolymer A-B with a polyfunctional coupling agent. For example, tetrafunctional coupling agents such as tin tetrachloride, silicon tetrachloride, etc. can be used. Flow rate of block copolymer (ASTM-D1238, G
condition) is 0.1 to 40g/10 minutes, preferably 1
~20g/10min. If it is less than 0.1 g/10 minutes, the resulting hot melt pressure-sensitive adhesive composition will have a high melt viscosity, making it impractical, and if it exceeds 40 g/10 minutes, the holding power will be low, which is not preferred. The styrene content in the block copolymer is 5 to 50% by weight based on the total polymer,
Preferably, it can be selected within the range of 10 to 45% by weight. Outside this range, the resulting adhesive tapes using the hot melt adhesive will have poor adhesive properties, which is not preferable. Further, the block copolymer may be any one as long as it is represented by the above general formula, but
In particular, the block copolymer represented by (A-B) n This is advantageous and preferable from the point of view. The adhesive resin, which is an important component in the present invention, is
Adhesive resin S with a softening point of 60℃ or higher containing at least 20% by weight of polyterpene resin and a softening point of 30℃
The ratio with the adhesive resin L below is S/L = 9/1 to 4/6, and S+L is used in the range of 50 to 200 parts by weight based on 100 parts by weight of the block copolymer. . The softening point here is the ring and ball softening point according to JIS K2531. The adhesive resin S consists of 20 to 100% by weight of a polyterpene resin and 80 to 0% by weight of an adhesive resin other than the polyterpene resin, and its softening point must be 60°C or higher. If the polyterpene resin does not contain 20% by weight or more, the resulting adhesive paper will have poor adhesion and holding power.
Poor practicality. As a polyterpene resin,
α-pinene polymer, β-pinene polymer, dipentene polymer, α-pinene-phenol copolymer, β
-pinene-phenol copolymers, etc., and any of them can be used, but α-pinene polymers are particularly preferred. Adhesive resins other than polyterpene resins contained in the adhesive resin S at 80 to 0% by weight include rosin resins (for example, rosin, hydrogenated rosin, esterified products of hydrogenated rosin, etc.), hydrogenated petroleum resins, etc. substances (e.g. C 4 in naphtha cracked oil,
C 5 and C 9 fractions and cracked oil containing cyclopentadiene as the main components are polymerized and hydrogenated). If the softening point of the adhesive resin S is not 60° C. or higher, the resulting adhesive will have poor holding power and will be impractical. The adhesive resin L must have a softening point of 30°C or less, and if it is not 30°C or less, the effect of improving tack is poor. As adhesive resin L, its softening point is
Any resin such as polyterpene resin, rosin resin, or hydrogenated petroleum resin may be used as long as it is below 30°C, but polyterpene resin is particularly preferred.
More preferred are pinene polymers. The ratio S/L of the adhesive resins S and L is in the range of 9/1 to 4/6, and if L is less than 9/1, the tack will be poor, which is not preferable. Moreover, if L is more than 4/6, the holding power of the adhesive will decrease, which is not preferable. Blend amount S+L is 50
If the amount is outside the range of 200 parts by weight, the adhesive properties of adhesive tapes using the resulting adhesive will be poor, which is not preferable. Softener is block copolymer 100 as required.
On a parts by weight basis, amounts of less than 5 parts by weight are used. If the amount is more than 5 parts by weight, the holding power of the obtained hot melt pressure-sensitive adhesive will be reduced and it will be impractical. As the softener, rubber developing oil, plasticizer (for example, phthalate ester, etc.), etc. can be used. The above compositions may contain substances such as antioxidants, if desired, and may be made of common elastomers (e.g., natural rubber, polyisoprene rubber, polybutadiene rubber, styrene rubber, butadiene copolymer rubber, etc.), fillers, etc. may be mixed. The production of the hot melt adhesive composition of the present invention includes:
Various methods can be used. For example, a melting kettle, kneader, mixing roll, extruder, internal mixer, etc. can be used. The hot-melt adhesive composition of the present invention has excellent adhesive strength particularly to paper, and at the same time has the same adhesive strength as conventional hot-melt adhesives to other adherends such as plastic films, metals, glass, etc. Due to its adhesive strength, various general-purpose adhesive tapes and
Effective for labels, etc. Examples are shown below. The examples are representative of the invention but are not intended to limit the scope of the invention. Example 1 In a nitrogen gas atmosphere, n-butyllithium was added to a toluene solution containing styrene,
After styrene polymerization has started and more than 99% of the styrene has polymerized, a toluene solution containing 1,3-butadiene is further added, and after 99% or more of the added 1,3-butadiene has polymerized, the activity is activated. Silicon tetrachloride was added without loss, and a coupling reaction was performed. The obtained polymer is (polystyrene-
Polybutane diene) is a 4- silicon type block copolymer, with a melt flow (G condition) of 8 g/10 minutes,
The styrene content was 30% by weight. Based on 100 parts by weight of the obtained block copolymer, add YS resin A-1150 (α-
Pinene polymer, softening point 115℃, manufactured by Cheap Oil) 80 parts by weight, YS Oil D (terpene low polymer, softening point below 0℃, manufactured by Cheap Oil) 20 parts by weight, Nokrac NS
-7 (2,5-di-tert-butylhydroquinone, manufactured by Ouchi Shinko Chemical), 3 parts by weight, approximately 180
It was heated and melted at ℃. After melting, 100 parts by weight of the block copolymer described above was added and melt mixing was continued for about 1 hour to obtain a transparent, smoothly flowing, homogeneous composition. This composition was poured into a mold and cooled to form a sticky block. A portion of the hot melt adhesive produced in this way was melted and applied to a thickness of approximately 50μ on back-treated kraft paper (basis weight 75 g/m 2 ) at approximately 170°C, followed by kraft adhesive tape. Created. The adhesion (flap retention force) of this kraft adhesive tape to tack and paper was measured, and the results are shown in Table 1. Each measurement was carried out by the method shown below. Tatsuku fixes adhesive tape on a board with an angle of 30°, and uses J.Dow
Measure the ball number that stopped on the surface of the adhesive tape using the ball rolling method. The higher the ball number, the greater the tack. Tack measurements were carried out at 20°C. As shown in Figure 1, the flap retention force is determined by placing two sheets of corrugated paper (vertical 75 mm, horizontal 50 mm, thickness 5 mm) 2 facing each other vertically with a width of 20 mm, as shown in Figure 1.
Adhesive tape 3 with a length of 27 mm and a weight of 200 g is pressed twice using a roller weighing 200 g, and is fixed to the supporting points 1 at both ends of the corrugated paperboard, and a load 4 of 1 kg is applied between the gap in the center. The time required for the adhesive tape to peel off was measured at a temperature of .degree. Examples 2 to 6 Table 1 also shows the results when the same method as in Example 1 was used and the formulations shown in Table 1 were used. Comparative Examples 1 to 5 Table 1 also shows the results when the same method as in Example 1 was used and the formulations shown in Table 1 were used. As is clear from Table 1, the adhesive of the present invention is
This adhesive has extremely good adhesion to paper and has good tack. 【table】
第１図はフラツプ保持力の測定法を示す側面図
である。
１は支点、２は段ボール紙、３は粘着テープ、
４はおもり。
FIG. 1 is a side view showing a method for measuring flap retention force. 1 is the fulcrum, 2 is the cardboard, 3 is the adhesive tape,
4 is a weight.
Claims (1)
Ｂ）ｎ、（Ａ−Ｂ）―nA、（Ａ−Ｂ）mX〔ここでＢ
は実質的にポリブタジエンまたはポリイソプレン
ブロツク、Ａは実質的にポリスチレンブロツクで
あり、ｎは２〜10の整数を表わす。Ｘはｍ個の重
合体鎖が結合している多官能性化合物であり、ｍ
は３〜７の整数を表わす。〕で表わされるフロー
レイト（ASTM―D1238、Ｇ条件）が0.1〜40
ｇ／10分の範囲であり、スチレン含有量が５〜50
重量％の範囲であるブロツク共重合体またはこれ
らの混合物と、該ブロツク共重合体100重量部に
基づいて、少なくとも20重量％以上のポリテルペ
ン系樹脂を含む軟化点60℃以上の粘着性樹脂Ｓと
軟化点30℃以下の粘着性樹脂Ｌとの比がＳ／Ｌ＝
9/1〜4/6の範囲である粘着性樹脂混合物50〜200
重量部とからなることを特徴とするホツトメルト
粘着剤組成物。 ２ 粘着性樹脂Ｌがテルペン低重合体である特許
請求の範囲第１項記載のホツトメルト粘着剤組成
物。 ３ 粘着剤組成物が、５重量部未満の軟化剤を添
加含有させたものである特許請求の範囲第１項又
は第２項記載のホツトメルト粘着剤組成物。[Claims] 1 General formula A-B-A, (A-B)n, B(-A-
B) n, (A-B) - nA, (A-B) mX [where B
is substantially a polybutadiene or polyisoprene block, A is substantially a polystyrene block, and n represents an integer from 2 to 10. X is a polyfunctional compound to which m polymer chains are bonded, m
represents an integer from 3 to 7. ] Flow rate (ASTM-D1238, G conditions) is 0.1 to 40
g/10 minutes, and the styrene content is 5 to 50
% by weight of a block copolymer or a mixture thereof, and an adhesive resin S having a softening point of 60° C. or higher and containing at least 20% by weight or more of a polyterpene resin based on 100 parts by weight of the block copolymer. The ratio of adhesive resin L with a softening point of 30℃ or less is S/L=
Sticky resin mixture ranging from 9/1 to 4/6 50 to 200
A hot melt adhesive composition comprising parts by weight. 2. The hot melt adhesive composition according to claim 1, wherein the adhesive resin L is a terpene low polymer. 3. The hot melt adhesive composition according to claim 1 or 2, wherein the adhesive composition contains less than 5 parts by weight of a softener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12634979A JPS5650978A (en) | 1979-10-02 | 1979-10-02 | Hot-melt sticking composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12634979A JPS5650978A (en) | 1979-10-02 | 1979-10-02 | Hot-melt sticking composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5650978A JPS5650978A (en) | 1981-05-08 |
| JPS6229469B2 true JPS6229469B2 (en) | 1987-06-26 |
Family
ID=14932965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12634979A Granted JPS5650978A (en) | 1979-10-02 | 1979-10-02 | Hot-melt sticking composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5650978A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4526577A (en) * | 1984-01-09 | 1985-07-02 | National Starch And Chemical Corporation | Disposable article constructions |
| JPS6144966A (en) * | 1984-08-10 | 1986-03-04 | Asahi Chem Ind Co Ltd | Bondable elastomer for acrylonitrile resin |
| JPS6270472A (en) * | 1985-09-24 | 1987-03-31 | Sunstar Giken Kk | Tackifier composition |
| JPH0645780B2 (en) * | 1985-10-11 | 1994-06-15 | 旭化成工業株式会社 | Adhesive composition |
| US4704110A (en) * | 1986-06-20 | 1987-11-03 | National Starch And Chemical Corporation | Hot melt pressure sensitive positioning adhesives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS528429A (en) * | 1975-07-04 | 1977-01-22 | Siemens Ag | Electric converting valve |
| JPS5314743A (en) * | 1976-07-27 | 1978-02-09 | Kuraray Co Ltd | Pressure-sensitive adhesive composition |
-
1979
- 1979-10-02 JP JP12634979A patent/JPS5650978A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS528429A (en) * | 1975-07-04 | 1977-01-22 | Siemens Ag | Electric converting valve |
| JPS5314743A (en) * | 1976-07-27 | 1978-02-09 | Kuraray Co Ltd | Pressure-sensitive adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5650978A (en) | 1981-05-08 |
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