JP3807844B2 - Strong water-resistant cardboard adhesive - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、段ボールの製造に用いられる耐水段ボール用接着剤に関する。さらに詳しくは、ステインホール方式、プレミックス方式、ノーキャリア方式、ワンタンクキャリア方式などの製糊方法によって調製される耐水段ボール用接着剤においてラテックスと澱粉と熱硬化性樹脂と架橋剤を含むことを特徴とする強耐水段ボール用接着剤に関する。
【０００２】
【従来の技術】
従来、段ボールの製造に使用される接着剤には、天然物で安全性が高く、取り扱いが容易で、安価に入手できるところから澱粉系接着剤が使われてきた。しかし、澱粉の一番の弱点は耐水性に乏しいところであり、澱粉系接着剤で貼合した段ボールシートを水に浸しておくと自然に剥がれてしまう。この欠点を補うべく、従来よりホルムアルデヒド系樹脂を澱粉系接着剤に加え耐水性を付与してきた。すなわち、尿素・ホルムアルデヒド樹脂、フェノール・ホルムアルデヒド樹脂、レゾルシノール・ホルムアルデヒド樹脂、ケトン・ホルムアルデヒド樹脂などのホルムアルデヒド系樹脂を澱粉系接着剤に加える方法が取られてきた。しかし、これらの樹脂を加える方法では、未だ冷凍食品、青果物等で求められている耐水接着強度を十分満足させるに至っていない。特に近年高度化した流通システムに幅広く対応できる強耐水段ボール用接着剤の開発が強く求められている。また、昨今エコロジーの観点から木箱や合成系包装容器が段ボール箱へ変換されており、より一層段ボール接着剤の耐水性に対する要求度が強くなってきている。これまで強耐水段ボール用接着剤として米国特許第4,018,959号明細書などに見られる酢ビエマルジョンを用いたものがあるが、糊剤pHが低く腐食性の問題を起こすこと、硼砂を含む一般段ボール用澱粉接着剤と混ぜ合わせるとゲル化を起こす問題があることなどから使われていない。耐水段ボール用接着剤の実用化に当たっては、一般段ボール用澱粉接着剤と混ぜ合わせたとき、ゲル化等の現象を起こさないことも求められる物性である。
【０００３】
上述のように、従来の耐水段ボール用接着剤よりも優れた耐水性能を有し、しかも一般段ボール用澱粉接着剤と混ぜ合わせてもゲル化を起こさない強耐水段ボール用接着剤の開発が待たれていた。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、従来から使われている耐水段ボール用接着剤よりも耐水性能が優れ、しかも一般段ボール用澱粉接着剤とも任意に混合可能な強耐水段ボール用接着剤を提供することである。
【０００５】
【課題を解決するための手段】
本発明者らは上記課題を解決するために種々検討した結果、カルボキシル基を有するラテックスと澱粉と熱硬化性樹脂及び架橋剤とを含む耐水段ボール用接着剤を採用することにより、上記課題を解決できることを見い出し、本発明を完成するに至った。
すなわち、本発明は、通常の段ボール用澱粉接着剤の製造過程で、段ボール用澱粉接着剤にカルボキシル基を有するラテックスを加え、さらに熱硬化性樹脂、架橋剤を加えることを特徴とする優れた耐水性を有する強耐水段ボール用接着剤を提供する。
【０００６】
【発明の実施の形態】
以下、本発明の優れた耐水性を有する強耐水段ボール用接着剤について詳細に説明する。
本発明の強耐水段ボール用接着剤は、好適実施態様において、ラテックスと澱粉が固形分比で５対９５〜８５対１５の範囲の割合からなり、ラテックスと澱粉の合わせた固形分に対し１重量%〜２０重量%の熱硬化性樹脂、及び１重量%〜１０重量%の架橋剤を加え調製される。
【０００７】
本発明において使用されるカルボキシル基を有するラテックスは、段ボール用接着剤において強耐水性を達成し得るものであれば天然または合成を問わずいずれの高分子物質も使用できるが、たとえばスチレン−ブタジエン系共重合体（ＳＢＲ）、アクリロニトリル−ブタジエン系共重合体（ＮＢＲ）、メチルメタアクリレート−ブタジエン系共重合体（ＭＢＲ）等のラテックスが使用でき、市販品としてたとえばＳＢＲラテックス：ＸＡ-7711(旭化成工業(株))、ＮＢＲラテックス：ニッポール１５７１（日本ゼオン(株)）およびＭＢＲラテックス：ポリラック５２５−８(三井東圧化学(株))が知られている。また、これらの内から二種以上のラテックスを選び使用してよい。これらのラテックスは、Ｔｇ（ガラス転移温度）が−４５℃〜＋６０℃の間、好ましくは−４５℃〜＋５５℃の間にあり、カルボキシル化されたものを使用する。Ｔｇが−４５℃より下がると調製した接着剤の皮膜が形成されやすくなり接着剤のハンドリング困難となる他、接着剤使用後の糊バットの掃除も面倒になる。Ｔｇが＋６０℃以上になるとＭＦＴ（最低造膜温度）が高くなるため、エマルジョン粒子の融着が起こりずらくなるため、接着が悪くなる現象が見られ好ましくない。また、カルボキシル基の含有率は０．５重量％〜６重量％、好ましくは１重量％〜６重量％が良く、カルボキシル化したラテックスには機械的安定性、化学的安定性、貯蔵安定性、凍結安定性があるが、カルボキシル基含有率が０．５重量％以下のラテックスを使うと接着剤の粘度安定性が悪く、耐水性能も低下させる傾向となり好ましくない。カルボキシル基含有率が６重量％以上のラテックスを使うと接着層が硬く脆くなり、常態接着強度が低下する傾向を示し好ましくない。
【０００８】
本発明において使用する澱粉は、段ボール用の接着剤調製方式として通常用いるステインホール方式、プレミックス方式、ノーキャリア方式、ワンタンクキャリア方式等に使用する澱粉で良く、特に限定されるものではない。すなわち、コーンスターチ（ハイアミロースコーンスターチ、ワキシーコーンスターチも含む）、馬鈴薯、タピオカ、小麦、甘藷等の澱粉、また、これらを常法に従って酸化、酸処理、エーテル化、エステル化、グラフト化した加工澱粉、これら澱粉を組み合わせたもの、上記澱粉をα化した澱粉が使用できる。
【０００９】
本発明の接着剤は、ステインホール方式、プレミックス方式、ノーキャリア方式、ワンタンクキャリア方式等で調製する澱粉系段ボール用接着剤とラテックスを混ぜ合わせることを基本とし、これに熱硬化性樹脂、架橋剤を加え調製する。澱粉系段ボール用接着剤とラテックスの混合方法は、各製糊方式で調製した澱粉系段ボール用接着剤とラテックスとを所定の固形分比により直接混合する方法と、ラテックスを澱粉系段ボール用接着剤調製時の澱粉溶解水と一緒に予め混合しておく方法がある。どちらの方法を選択しても良く、混合方法は作業性を考慮して決められる。
【００１０】
本発明のラテックスと澱粉の固形分比は、８５/１５〜５/９５の範囲で使用できる。好ましくは、７０/３０〜１５/８５の範囲が良い。ラテックス固形分が極端に低下すると、耐水性は従来の耐水段ボール用接着剤と変わらなくなり本接着剤の特色がなくなる。また、ラテックス固形分を多くしても耐水性能がそれに従って極端に良くなるわけでなく頭打ちとなり、これを考慮すると不経済となる。
【００１１】
この様に調製した接着剤中の水と澱粉の重量比（倍水率）は、1.８〜５が好ましい。倍水率が高すぎると初期接着力が劣り生産が落ち実用的でない。倍水率が低すぎると、澱粉の糊化に必要な水分が不足し未糊化澱粉が発生し接着力に影響を与え好ましくない。また、接着剤の糊化温度を調節するためにアルカリ、たとえば通常使用されている苛性ソーダーが使われる。使用量は、接着剤の全重量に対し通常０.３０％〜１.０％、好ましくは０. ４５％〜０. ７５％が良く、目標糊化温度になるように使用量を調整する。接着剤には、糊化した澱粉にタック（粘着性）を与えるため硼砂、硼酸等の硼素化合物を加える。使用量は、澱粉に対し１.０％〜２. ５％が好ましい。
【００１２】
この様に調製した接着剤に熱硬化性樹脂と架橋剤を加え、強耐水段ボール用接着剤が出来上がる。本発明で使用される熱硬化性樹脂は、段ボール用接着剤において強耐水性を達成し得るものであればいずれの樹脂も使用可能であるが、たとえば尿素樹脂、フェノール樹脂、レゾルシノール樹脂、ケトン樹脂、メラミン樹脂などのホルムアルデヒド系樹脂が挙げられる。例示したこれらの樹脂は従来より澱粉の耐水化剤として使われているが、本発明では澱粉の耐水化の他にラテックスの架橋剤としての作用も有している。熱硬化性樹脂の添加率は澱粉とラテックスの固形分合計に対し１重量％〜２０重量%を加える。1重量％を下回ると耐水性への効果が低下する。また、２０重量%を超えると耐水性への効果も頭打ちとなり、経済的にも好ましくない。架橋剤は、ラテックスのカルボキシル基と架橋反応を起こし耐水性を付与する。ここで使用する架橋剤は、エポキシ基を持つ化合物であるポリアミドエポキシ、ポリエチレングリコールジエポキサイド、ビスフェノールAグリシジルエーテルなど；イソシアネート基を持つ化合物であるジフェニルメタンジイソシアネート、トリレンジイソシアネートなど；エチレンイミン基を持つ化合物であるジエチレンイミン化合物類など；アルコキシメチル基を持つ化合物であるヘキサメチレンテトラミン、メトキシメチロールユリアなど；金属塩として酸化亜鉛、酢酸亜鉛アンモニウム、炭酸アンモニウムジルコニウムなどが使用できる。架橋剤の添加率は澱粉とラテックスの固形分合計に対し１重量％〜１０重量%を加える。添加率が１重量%以下であると架橋効果がなく、１０重量%を超えると頭打ちとなり経済的にも好ましくない。また、架橋剤の多くは澱粉の水酸基とも架橋反応を起こし得るためさらに耐水性を得ることが可能となった。また、本発明の強耐水段ボール用接着剤には必要に応じて消泡剤や増粘剤等の添加剤を加えてもよい。
【００１３】
この様にして得られる強耐水段ボール用接着剤を用いると、従来の耐水段ボール用接着剤では得られなかった耐水強度が得られるようになる。
以下に、実施例を挙げて本発明を更に具体的に説明するが、本発明の範囲は、これらの実施例に限定されるものではない。
【００１４】
【実施例】
実施例中の▲１▼アルカリブラベンダーアミログラム法による測定、および▲２▼耐水接着強度の測定は以下の方法によった。
▲１▼アルカリブラベンダーアミログラム法：乾燥重量で４５ｇのα化澱粉をビーカーに取り、同量のエチルアルコールを分散剤として該α化澱粉に均一に含浸させる。次いで純水３５０ｇを加え、素早く攪拌してα化澱粉を溶解させる。直ちにブラベンダーアミログラムの容器（ピンタイプ）に移し、さらに純水を加え全量を４８３ｇに調整してブラベンダーアミログラムを始動させる。温度を４０℃に保持するようにセットして、４０℃になったら２０重量％の水酸化ナトリウム溶液１７ｇを添加する。添加３０分後のブラベンダー粘度（BU）をα化澱粉粘度とする。このアルカリブラベンダーアミログラム法ではカートリッジ３５０ｃｍ-gを使用し、回転数７５ｒｐｍの条件で測定した。
【００１５】
▲２▼耐水接着強度：５０ｍｍ×８５ｍｍの大きさの片面段ボール（原紙構成：北陽ＨＰＷ２９０ｇ／ＨＰ２００ｇ）に、絶乾１０ｇ／ｍ2−片面に調製後０ｈと２４ｈ経過した強耐水段ボール用接着剤をロールコーターで塗布した。１８５℃のプレートヒーター上にライナー（原紙：王子ＳＳＫ２８０ｇ）を置き、強耐水段ボール用接着剤を塗布した上記片面段ボールをこのライナーの上に重ね、２ｋｇ ｆ／４２．５ｃｍ2の荷重をかけて５秒間加熱圧着した。加熱圧着後、温度２０℃、相対湿度６５％の状態に２４時間放置し、次いで２０℃の水に１時間浸した後リングクラッシュテスター（日本ＴＭＣ（株）製）でその強度を測定した。
【００１６】
（実施例１）
アルカリブラベンダーアミログラム法による粘度が４００BUのα澱粉を７重量％、硼砂２重量％、コーンスターチ９１重量％からなる一般段ボール用接着剤原料のプレミックス澱粉を調製した。４０℃に加温した水を８Ｌ容のバケツに２２６５ｇ、ＳＢＲラテックス（旭化成工業（株）製ＸＡ−７７１１：固形分５０％、カルボキシル基含有率２％、Ｔｇ−１２℃）７５０ｇを取り、これにプレミックス澱粉１１２５ｇを加え特殊機化工業（株）製の撹拌機ロボミックス（４７００ｒｐｍ）で分散させ澱粉スラリーを調製した。撹拌しながらこの澱粉スラリーに１５％濃度の苛性ソーダ溶液２０４ｇを定量ポンプで１５分かけて添加した。さらに、これに熱硬化性樹脂のケトン樹脂（王子コーンスターチ（株）製：商品名耐水化剤A）を全固形分に対し３重量％、架橋剤のエポキシ化合物（三井東圧化学（株）製：商品名ユーラミンＰ−５６００（ポリアミドエポキシ））を全固形分に対し４重量％添加し１５分撹拌を続け、澱粉/ラテックス固形分比７５/２５の強耐水段ボール用接着剤とした。
【００１７】
得られた接着剤の耐水接着強度を以下のようにして測定した。５０ｍｍ×８５ｍｍの大きさの片面段ボール（原紙構成：北陽ＨＰＷ２９０ｇ／ＨＰ２００ｇ）に、絶乾１０ｇ／ｍ2−片面の上記強耐水段ボール用接着剤をロールコーターで塗布した。１８５℃のプレートヒーター上にライナー（原紙：王子ＳＳＫ２８０ｇ）を置き、強耐水段ボール用接着剤を塗布した上記片面段ボールをこのライナーの上に重ね、２ｋｇ ｆ／４２．５ｃｍ2の荷重をかけて５秒間加熱圧着した。加熱圧着後、温度２０℃、相対湿度６５％の状態に２４時間放置し、次いで２０℃の水に１時間浸した後、リングクラッシュテスター（日本ＴＭＣ（株）製）でその強度を測定した。測定結果を表１に示す。
【００１８】
（比較例１）
市販の耐水段ボール用接着剤ＯＰＭ―Ｗ１００システム（プレミックス方式）（王子コーンスターチ（株）製）を用いて実施例１と同様の測定を行った。すなわち、４０℃に加温した水を８Ｌ容のバケツに３３３０ｇを取り、これにプレミックス澱粉ＯＰＭ−Ｗ１００を１４００ｇ加え特殊機化工業（株）製の撹拌機ロボミックス（４７００ｒｐｍ）で分散させ澱粉スラリーを調製した。撹拌しながらこの澱粉スラリーに１５％濃度の苛性ソーダ溶液１９７ｇを定量ポンプで１５分かけて添加した。さらに、これに熱硬化性樹脂の耐水化剤Ａ、耐水化剤Ｂ（王子コーンスターチ（株）製：フェノール樹脂）を澱粉に対し各々３重量％加え、１５分撹拌を続け耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表１に示す。
【００１９】
（比較例２）
市販の耐水段ボール用接着剤オプタミルＡシステム（ステインホール方式）（日本エヌエスシー（株）製）を用いて実施例１と同様の測定を行った。すなわち、６０℃に加温した水を３Ｌ容のバケツに７００ｇを取り、これにキャリア澱粉オプタミルＡを２７０ｇ加え特殊機化工業（株）製の撹拌機ロボミックス（４７００ｒｐｍ）で分散させ調製した澱粉スラリーに２５％濃度の苛性ソーダ溶液１２０ｇを加え１５分撹拌し、水２５０ｇを加え５分撹拌してキャリアパートを調製した。一方３５℃に加温した水を８Ｌ容のバケツに２４６０ｇを取り、これに硼砂２５．５ｇ、メイン澱粉ＯＨＰ−ＭＷ−８００（王子コーンスターチ（株）製）を１２３０ｇ加え特殊機化工業（株）製の撹拌機ロボミックス（４７００ｒｐｍ）で分散させメインパートを調製した。次いで、メインパートにキャリアパートを１５分かけて添加混合し、これに熱硬化性樹脂ＢＯＮＲＥＺ−３０（日本エヌエスシー（株）製：ケトン樹脂）を澱粉に対し６重量％加え５分撹拌を続け、耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表１に示す。
【００２０】
（実施例２）
６０℃に加温した水を３Ｌ容のバケツに９９０ｇを取り、これにキャリア澱粉ＯＨＰ−Ｃ−１５３（王子コーンスターチ（株）製）１３５ｇ加え撹拌機ロボミックス（４７００ｒｐｍ）で分散させ調製した澱粉スラリーに苛性ソーダ２７.０ｇを加え１５分撹拌しキャリアパートを調製した。一方３０℃に加温した水を８Ｌ容のバケツに１４５０ｇ、ＳＢＲラテックス（ＸＡ７７１１）７５０ｇを取り、これに硼砂２２．５ｇ、コーンスターチ（王子コーンスターチ（株）製）９９０ｇを加え撹拌機ロボミックス（４７００ｒｐｍ）で分散させメインパートを調製した。次いで、メインパートにキャリアパートを１５分かけて添加混合し、これに耐水化剤Ａを全固形分に対し３重量％、ユーラミンＰ−５６００を全固形分に対し４重量％添加し１５分撹拌を続けステインホール方式で調製した澱粉/ラテックス固形分比７５/２５の強耐水段ボール用接着剤とした。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表２に示す。
【００２１】
（実施例３）
４０℃に加温した水を８Ｌ容のバケツに２２７５ｇを取り、更に実施例１のＳＢＲラテックス７５０ｇを取り、コーンスターチ１１２５ｇを撹拌機ロボミックス（４７００ｒｐｍ）で分散させ調製した澱粉スラリーに１５％濃度の苛性ソーダ溶液１９１ｇを加え、ノークロス粘度計で粘度管理を行い、スラリー粘度が５秒になったところで硼酸１４.６ｇを加え、これに実施例１の熱硬化性樹脂、架橋剤を各々全固形分に対し３重量％及び４重量％加え、ノーキャリア方式で調製した澱粉/ラテックス固形分比７５/２５の強耐水段ボール用接着剤とした。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表２に示す。
【００２２】
（実施例４）
実施例１のプレミックス澱粉組成をα澱粉１２重量％、硼砂２重量％、コーンスターチ８６重量％に、プレミックス澱粉量を１４２５ｇに、４０℃に加温した水を８Ｌ容のバケツに３３１４ｇに、ＳＢＲラテックスを１５０ｇに代え澱粉/ラテックス固形分比を９５／５にした以外は実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表３に示した。
【００２３】
（実施例５）
４０℃に加温した水を８Ｌ容のバケツに５６２ｇを取り、それに組成α澱粉８重量％、硼砂２重量％、コーンスターチ９０重量％のプレミックス澱粉３００ｇを分散させて、さらに１５％濃度の苛性ソーダ溶液４５ｇを添加して段ボール用接着剤を調製した。この接着剤に実施例１のＳＢＲラテックス２４００ｇ加え、実施例１同様に熱硬化性樹脂、架橋剤を加え澱粉/ラテックス固形分比を２０／８０にした以外は実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表３に示した。
【００２４】
（実施例６）
実施例１のケトン樹脂の添加率を１重量％にした以外は、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表４に示した。
（実施例７）
実施例１の架橋剤の添加率を１重量％にした以外は、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表４に示した。
【００２５】
（実施例８）
実施例１のケトン樹脂の添加率を１０重量％にした以外は、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表４に示した。
（実施例９）
実施例１の架橋剤の添加率を１０重量％にした以外は、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表４に示した。
【００２６】
（比較例３）
実施例１のケトン樹脂、架橋剤を加えない以外は、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表４に示した。
（比較例４）
実施例１のケトン樹脂を０.５重量％、架橋剤を０.５重量％加えた以外は、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表４に示した。
【００２７】
（実施例１０）
実施例１のＳＢＲラテックスのカルボキシル含有率を６重量％にした以外、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表５に示した。
（比較例５）
実施例１ののＳＢＲラテックスのカルボキシル含有率を０重量％にした以外、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表５に示した。
【００２８】
（実施例１１）
実施例１のＳＢＲラテックスのＴｇ６０℃のものを使用した以外、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表６に示した。
（実施例１２）
実施例１のＳＢＲラテックスのＴｇ−４４℃のものを使用した以外、実施例１と同様の手順で強耐水段ボール用接着剤を調製した。得られた接着剤の耐水接着強度を実施例１と同様に測定し測定結果を表６に示した。
【００２９】
（実施例１３）
実施例１の強耐水段ボール用接着剤と下記条件で調製した一般段ボール用接着剤を容量率で混合しゲル化の発生状況を調べた。結果を表7に示した。
６０℃に加温した水を３Ｌ容のバケツに９９０ｇを取り、これにキャリア澱粉ＯＨＰ−Ｃ−１５３（王子コーンスターチ（株）製）１３５ｇ加え撹拌機ロボミックス（４７００ｒｐｍ）で分散させ調製した澱粉スラリーに苛性ソーダ２７.０ｇを加え１５分撹拌しキャリアパートを調製した。一方３０℃に加温した水を８Ｌ容のバケツに１８２５ｇ、これに硼砂２２．５ｇ、コーンスターチ（王子コーンスターチ（株）製）９９０ｇを加え撹拌機ロボミックス（４７００ｒｐｍ）で分散させメインパートを調製した。次いで、メインパートにキャリアパートを１５分かけて添加混合し、一般段ボール用接着剤を調製した。
【００３０】
【表１】
【表２】
【表３】
【表４】
【表５】
【表６】
【表７】
表１〜表６より、本発明の強耐水段ボール用接着剤は、従来の耐水段ボール用接着剤と比べて耐水接着強度が格別優れていることがわかる。また、表７から一般段ボール用接着剤ともゲル化せずに任意に混合できることがわかる。
【００３８】
【発明の効果】
本発明によるラテックスと澱粉と熱硬化性樹脂及び架橋剤とを含む強耐水段ボール用接着剤は、従来の耐水段ボール用接着剤と比べ優れた耐水性能を付与する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a water-resistant corrugated adhesive used in the production of corrugated cardboard. More specifically, the adhesive for water-resistant cardboard prepared by a paste making method such as a stain hole method, a premix method, a no-carrier method, a one-tank carrier method, etc. includes latex, starch, a thermosetting resin, and a crosslinking agent. The present invention relates to an adhesive for strong water-resistant cardboard.
[0002]
[Prior art]
Conventionally, starch-based adhesives have been used as adhesives used in the manufacture of corrugated cardboard because they are natural products, high in safety, easy to handle, and available at low cost. However, the most weak point of starch is that it has poor water resistance. If a corrugated cardboard sheet bonded with a starch adhesive is immersed in water, it will peel off naturally. In order to compensate for this drawback, a formaldehyde resin has been conventionally added to a starch adhesive to provide water resistance. That is, a method of adding a formaldehyde resin such as urea / formaldehyde resin, phenol / formaldehyde resin, resorcinol / formaldehyde resin, ketone / formaldehyde resin to the starch adhesive has been taken. However, the method of adding these resins has not yet fully satisfied the water-resistant adhesive strength required for frozen foods, fruits and vegetables. In particular, there is a strong demand for the development of strong water-resistant corrugated adhesives that can be used in a wide range of distribution systems that have become more sophisticated in recent years. In recent years, wooden boxes and synthetic packaging containers have been converted to cardboard boxes from the viewpoint of ecology, and the degree of demand for water resistance of corrugated cardboard adhesives has become stronger. Up to now, there has been used a vinyl acetate emulsion found in US Pat. No. 4,018,959 as a strong water-resistant corrugated adhesive, but it has a low pH adhesive and causes corrosive problems. For general corrugated board containing borax It is not used because it causes gelation when mixed with starch adhesive. In the practical application of a water-resistant corrugated cardboard adhesive, it is a physical property that is not required to cause a phenomenon such as gelation when mixed with a general corrugated starch adhesive.
[0003]
As mentioned above, the development of a strong water-resistant corrugated cardboard adhesive that has water resistance superior to conventional water-resistant corrugated cardboard adhesives and does not cause gelation even when mixed with general starch cardboard adhesives is awaited. It was.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a strong water-resistant corrugated cardboard adhesive which is superior in water-resistant performance to conventional water-resistant corrugated cardboard adhesives and can be arbitrarily mixed with a general corrugated starch adhesive.
[0005]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventors have solved the above problems by adopting a water-resistant corrugated adhesive containing a carboxyl group-containing latex, starch, a thermosetting resin, and a crosslinking agent. The present inventors have found what can be done and have completed the present invention.
That is, the present invention is an excellent water resistance characterized by adding a latex having a carboxyl group to a starch adhesive for corrugated cardboard, and further adding a thermosetting resin and a crosslinking agent in the process of producing a normal starch adhesive for corrugated cardboard. Provided is a strong water-resistant adhesive for corrugated cardboard.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the strong water-resistant cardboard adhesive having excellent water resistance according to the present invention will be described in detail.
In a preferred embodiment, the strong water-resistant corrugated cardboard adhesive of the present invention has a ratio of latex to starch in the range of 5 to 95 to 85 to 15 in terms of solid content, and 1 weight to the combined solid content of latex and starch. % To 20% by weight of thermosetting resin and 1% to 10% by weight of crosslinker.
[0007]
As the latex having a carboxyl group used in the present invention, any polymer material can be used regardless of natural or synthetic as long as it can achieve strong water resistance in an adhesive for corrugated cardboard. Latex such as copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), methyl methacrylate-butadiene copolymer (MBR) can be used, and commercially available products such as SBR latex: XA-7711 (Asahi Kasei Kogyo) NBR latex: Nippon 1571 (Nippon Zeon Corporation) and MBR latex: Polylac 525-8 (Mitsui Toatsu Chemicals) are known. Moreover, you may select and use 2 or more types of latex from these. These latexes have a Tg (glass transition temperature) between −45 ° C. and + 60 ° C., preferably between −45 ° C. and + 55 ° C., and are carboxylated. When Tg falls below −45 ° C., a film of the prepared adhesive is easily formed and the handling of the adhesive becomes difficult, and cleaning of the glue bat after using the adhesive becomes troublesome. When Tg is + 60 ° C. or higher, MFT (minimum film-forming temperature) is increased, and it is difficult to fuse emulsion particles. Further, the carboxyl group content is preferably 0.5% to 6% by weight, and preferably 1% to 6% by weight. The carboxylated latex has mechanical stability, chemical stability, storage stability, Although there is freezing stability, it is not preferable to use a latex having a carboxyl group content of 0.5% by weight or less because the viscosity stability of the adhesive is poor and the water resistance performance tends to be lowered. If latex having a carboxyl group content of 6% by weight or more is used, the adhesive layer becomes hard and brittle, and the normal adhesive strength tends to decrease, such being undesirable.
[0008]
The starch used in the present invention may be starch used in a stain hole method, a premix method, a no-carrier method, a one-tank carrier method or the like that is usually used as an adhesive preparation method for corrugated cardboard, and is not particularly limited. That is, starches such as corn starch (including high amylose corn starch and waxy corn starch), potato, tapioca, wheat, sweet potato, etc., and oxidized, acid-treated, etherified, esterified, and grafted processed starch according to conventional methods, these A combination of starches, or starch obtained by pregelatinizing the above starches can be used.
[0009]
The adhesive of the present invention is based on mixing a starch-based corrugated cardboard adhesive prepared with a stain hole method, a premix method, a no carrier method, a one-tank carrier method, etc., with a thermosetting resin, a crosslink Add to the preparation. The method for mixing starch-based corrugated cardboard adhesive and latex is a method of directly mixing starch-based corrugated cardboard adhesive and latex prepared by each paste making method at a predetermined solid content ratio, and latex is used for starch-based corrugated cardboard adhesive. There is a method of premixing together with starch-dissolving water at the time of preparation. Either method may be selected, and the mixing method is determined in consideration of workability.
[0010]
The solid content ratio of the latex of the present invention and starch can be used in the range of 85/15 to 5/95. The range of 70/30 to 15/85 is preferable. When the latex solids are extremely reduced, the water resistance is no different from that of conventional water-resistant corrugated cardboard adhesives and the characteristics of the present adhesive are lost. Further, even if the latex solid content is increased, the water resistance performance does not become extremely good in accordance with it, and reaches a peak, and this is uneconomical.
[0011]
The weight ratio (water ratio) of water and starch in the adhesive prepared as described above is preferably 1.8 to 5. If the double water ratio is too high, the initial adhesive strength is inferior and the production falls, which is not practical. If the water doubling rate is too low, water necessary for gelatinization of starch is insufficient, and ungelatinized starch is generated, which affects the adhesive force and is not preferable. In order to adjust the gelatinization temperature of the adhesive, an alkali such as a commonly used caustic soda is used. The amount used is usually 0.30% to 1.0%, preferably 0.45% to 0.75%, based on the total weight of the adhesive, and the amount used is adjusted so that the target gelatinization temperature is reached. Boron compounds such as borax and boric acid are added to the adhesive to give tack to the gelatinized starch. The amount used is preferably 1.0% to 2.5% with respect to the starch.
[0012]
A thermosetting resin and a cross-linking agent are added to the adhesive prepared in this way, and a strong water-resistant cardboard adhesive is completed. As the thermosetting resin used in the present invention, any resin can be used as long as it can achieve strong water resistance in an adhesive for corrugated cardboard. For example, urea resin, phenol resin, resorcinol resin, ketone resin can be used. And formaldehyde resins such as melamine resin. These exemplified resins are conventionally used as a water-resistant agent for starch, but in the present invention, in addition to making water resistant to starch, the resin also has an action as a crosslinking agent for latex. The addition rate of the thermosetting resin is 1 to 20% by weight based on the total solid content of starch and latex. If it is less than 1% by weight, the effect on water resistance is lowered. On the other hand, if it exceeds 20% by weight, the effect on water resistance will reach its peak, which is not preferable economically. The crosslinking agent causes a crosslinking reaction with the carboxyl group of the latex and imparts water resistance. The crosslinking agent used here is a compound having an epoxy group such as polyamide epoxy, polyethylene glycol diepoxide, bisphenol A glycidyl ether; a compound having an isocyanate group such as diphenylmethane diisocyanate or tolylene diisocyanate; a compound having an ethyleneimine group Diethyleneimine compounds such as: hexamethylenetetramine, methoxymethylol urea, etc., which are compounds having an alkoxymethyl group; zinc oxide, zinc ammonium acetate, ammonium zirconium carbonate, etc. can be used as metal salts. The addition ratio of the crosslinking agent is 1 to 10% by weight based on the total solid content of starch and latex. When the addition ratio is 1% by weight or less, there is no crosslinking effect, and when it exceeds 10% by weight, it becomes a peak and is not economically preferable. In addition, since many of the crosslinking agents can cause a crosslinking reaction with the hydroxyl groups of starch, it has become possible to obtain further water resistance. Moreover, you may add additives, such as an antifoamer and a thickener, to the adhesive for strong water-resistant cardboards of this invention as needed.
[0013]
When the strong water-resistant corrugated cardboard adhesive obtained in this way is used, the water-resistant strength that cannot be obtained with the conventional water-resistant corrugated cardboard adhesive can be obtained.
Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.
[0014]
【Example】
In the examples, (1) measurement by the alkali Brabender amylogram method and (2) measurement of water-resistant adhesive strength were carried out by the following methods.
(1) Alkaline Brabender amylogram method: 45 g of pregelatinized starch by dry weight is placed in a beaker, and the pregelatinized starch is uniformly impregnated with the same amount of ethyl alcohol as a dispersant. Next, 350 g of pure water is added and stirred rapidly to dissolve the pregelatinized starch. Immediately transfer to a Brabender amylogram container (pin type), add pure water to adjust the total amount to 483 g, and start the Brabender amylogram. The temperature is set to be kept at 40 ° C., and when it reaches 40 ° C., 17 g of 20 wt% sodium hydroxide solution is added. The Brabender viscosity (BU) 30 minutes after the addition is defined as pregelatinized starch viscosity. In this alkali Brabender amylogram method, a cartridge of 350 cm-g was used, and measurement was performed under the condition of a rotational speed of 75 rpm.
[0015]
(2) Water-resistant adhesive strength: 50 mm × 85 mm single-sided corrugated cardboard (base paper composition: Hokuyo HPW 290 g / HP 200 g), absolutely dry 10 g / m 2 -on one side, an adhesive for strong water-resistant corrugated board that has been prepared for 0 h and 24 h It applied with the roll coater. A liner (base paper: Oji SSK 280 g) was placed on a plate heater at 185 ° C., and the above single-sided cardboard coated with a strong water-resistant cardboard adhesive was stacked on this liner and applied with a load of 2 kg f / 42.5 cm 2. Heat-bonded for 2 seconds. After thermocompression bonding, it was left for 24 hours at a temperature of 20 ° C. and a relative humidity of 65%, and then immersed in water at 20 ° C. for 1 hour, and then its strength was measured with a ring crush tester (manufactured by Nippon TMC Co., Ltd.).
[0016]
Example 1
A premix starch of an adhesive raw material for general corrugated board consisting of 7% by weight of α starch having a viscosity of 400 BU according to the alkali Brabender amylogram method, 2% by weight of borax, and 91% by weight of corn starch was prepared. Take 2265g of water heated to 40 ° C in an 8L bucket, 750g of SBR latex (Asahi Kasei Kogyo XA-7711: solid content 50%, carboxyl group content 2%, Tg-12 ° C) 1125 g of premix starch was added to and dispersed with a stirrer robot mix (4700 rpm) manufactured by Tokushu Kika Kogyo Co., Ltd. to prepare a starch slurry. With stirring, 204 g of a 15% strength caustic soda solution was added to the starch slurry with a metering pump over 15 minutes. Furthermore, a thermosetting resin ketone resin (made by Oji Cornstarch Co., Ltd .: trade name waterproofing agent A) is 3% by weight with respect to the total solid content, and an epoxy compound as a crosslinking agent (Mitsui Toatsu Chemical Co., Ltd.). : 4% by weight of Euramin P-5600 (polyamide epoxy) was added to the total solid content, and stirring was continued for 15 minutes to obtain a strong water-resistant cardboard adhesive having a starch / latex solid content ratio of 75/25.
[0017]
The water-resistant adhesive strength of the obtained adhesive was measured as follows. The above-mentioned strong water-resistant corrugated cardboard adhesive of 10 g / m 2 -single side was applied to a single-sided cardboard (base paper configuration: Hokuyo HPW 290 g / HP 200 g) having a size of 50 mm × 85 mm with a roll coater. A liner (base paper: Oji SSK 280 g) was placed on a plate heater at 185 ° C., and the above single-sided cardboard coated with a strong water-resistant cardboard adhesive was stacked on this liner and applied with a load of 2 kg f / 42.5 cm 2. Heat-bonded for 2 seconds. After thermocompression bonding, it was allowed to stand for 24 hours at a temperature of 20 ° C. and a relative humidity of 65%, and then immersed in water at 20 ° C. for 1 hour, and its strength was measured with a ring crush tester (manufactured by Nippon TMC Co., Ltd.). The measurement results are shown in Table 1.
[0018]
(Comparative Example 1)
The same measurement as in Example 1 was performed using a commercially available adhesive OPM-W100 for water-resistant cardboard (premix method) (manufactured by Oji Cornstarch Co., Ltd.). That is, 3330 g of water heated to 40 ° C. is taken in an 8 L bucket, 1400 g of premix starch OPM-W100 is added thereto, and the mixture is dispersed with a stirrer robot mix (4700 rpm) manufactured by Tokushu Kika Kogyo Co., Ltd. A slurry was prepared. While stirring, 197 g of a 15% strength sodium hydroxide solution was added to the starch slurry with a metering pump over 15 minutes. Further, 3% by weight of each of water-resistant agent A and water-resistant agent B (produced by Oji Corn Starch Co., Ltd .: phenol resin) of thermosetting resin is added to the starch, and stirring is continued for 15 minutes to provide an adhesive for water-resistant cardboard. Prepared. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 1.
[0019]
(Comparative Example 2)
The same measurement as in Example 1 was performed using a commercially available water resistant corrugated adhesive OPTAMILL A system (stain hole method) (manufactured by Nippon SC Co., Ltd.). In other words, 700 g of water heated to 60 ° C. was taken up in a 3 L bucket, 270 g of carrier starch Optamil A was added thereto, and the starch was prepared by dispersing with a stirrer robot mix (4700 rpm) manufactured by Tokushu Kika Kogyo Co., Ltd. A carrier part was prepared by adding 120 g of 25% strength caustic soda solution to the slurry and stirring for 15 minutes, adding 250 g of water and stirring for 5 minutes. On the other hand, 2460 g of water heated to 35 ° C. is taken in an 8 L bucket, 25.5 g of borax, and 1230 g of main starch OHP-MW-800 (manufactured by Oji Cornstarch Co., Ltd.) are added thereto. The main part was prepared by dispersing with an agitator robot mix (4700 rpm). Next, the carrier part is added to the main part over 15 minutes, and 6% by weight of thermosetting resin BONREZ-30 (manufactured by Nippon SC Co., Ltd .: ketone resin) is added to the starch and stirring is continued for 5 minutes. Then, an adhesive for water-resistant cardboard was prepared. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 1.
[0020]
(Example 2)
990 g of water heated to 60 ° C. was taken up in a 3 L bucket, and 135 g of carrier starch OHP-C-153 (manufactured by Oji Cornstarch Co., Ltd.) was added thereto and dispersed with a stirrer robot mix (4700 rpm). To this was added 27.0 g of caustic soda and stirred for 15 minutes to prepare a carrier part. On the other hand, 1450 g of water heated to 30 ° C. and 750 g of SBR latex (XA7711) are taken in an 8 L bucket, 22.5 g of borax and 990 g of corn starch (manufactured by Oji Cornstarch Co., Ltd.) are added to this, and an agitator robot mix (4700 rpm) ) To prepare a main part. Next, the carrier part is added to and mixed with the main part over 15 minutes, to which water resistance agent A is added at 3% by weight with respect to the total solids, and Euramin P-5600 is added at 4% by weight with respect to the total solids, and stirred for 15 minutes. Then, a strong water-resistant corrugated cardboard adhesive having a starch / latex solid content ratio of 75/25 prepared by a stain hole method was obtained. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 2.
[0021]
Example 3
Take 2275 g of water heated to 40 ° C. in an 8 L bucket, further take 750 g of SBR latex of Example 1 and disperse 1125 g of corn starch with a stirrer robotics (4700 rpm) to a starch slurry of 15% concentration. 191 g of caustic soda solution was added, and the viscosity was controlled with a no-cross viscometer. When the slurry viscosity reached 5 seconds, 14.6 g of boric acid was added, and the thermosetting resin and crosslinking agent of Example 1 were added to the total solid content. 3% by weight and 4% by weight were added, and a strong water-resistant corrugated cardboard adhesive having a starch / latex solid content ratio of 75/25 prepared by a no carrier method was obtained. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 2.
[0022]
Example 4
The premix starch composition of Example 1 was 12% by weight α starch, 2% by weight borax, 86% by weight corn starch, the amount of premix starch was 1425 g, and the water heated to 40 ° C. was 3314 g in an 8 L bucket. A strong water-resistant corrugated cardboard adhesive was prepared in the same manner as in Example 1 except that the SBR latex was replaced with 150 g and the starch / latex solid content ratio was 95/5. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 3.
[0023]
(Example 5)
Take 562 g of water heated to 40 ° C. in a 8 L bucket, and disperse 300 g of premix starch of 8% by weight of alpha starch, 2% by weight of borax and 90% by weight of corn starch, and then add 15% caustic soda. An adhesive for corrugated board was prepared by adding 45 g of the solution. To this adhesive, 2400 g of the SBR latex of Example 1 was added, and a thermosetting resin and a crosslinking agent were added as in Example 1 to make the starch / latex solid content ratio 20/80. A water-resistant cardboard adhesive was prepared. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 3.
[0024]
(Example 6)
A strong water-resistant corrugated cardboard adhesive was prepared in the same procedure as in Example 1 except that the addition rate of the ketone resin in Example 1 was changed to 1% by weight. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 4.
(Example 7)
A strong water-resistant cardboard adhesive was prepared in the same procedure as in Example 1 except that the addition ratio of the crosslinking agent in Example 1 was changed to 1% by weight. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 4.
[0025]
(Example 8)
A strong water-resistant cardboard adhesive was prepared in the same manner as in Example 1 except that the addition rate of the ketone resin in Example 1 was changed to 10% by weight. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 4.
Example 9
A strong water-resistant corrugated cardboard adhesive was prepared in the same procedure as in Example 1 except that the addition ratio of the crosslinking agent in Example 1 was changed to 10% by weight. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 4.
[0026]
(Comparative Example 3)
A strong water-resistant corrugated cardboard adhesive was prepared in the same procedure as in Example 1 except that the ketone resin and the crosslinking agent of Example 1 were not added. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 4.
(Comparative Example 4)
A strong water-resistant corrugated cardboard adhesive was prepared in the same procedure as in Example 1 except that 0.5% by weight of the ketone resin of Example 1 and 0.5% by weight of a crosslinking agent were added. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 4.
[0027]
(Example 10)
A strong water-resistant corrugated cardboard adhesive was prepared in the same procedure as in Example 1 except that the carboxyl content of the SBR latex of Example 1 was changed to 6% by weight. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 5.
(Comparative Example 5)
A strong water-resistant cardboard adhesive was prepared in the same procedure as in Example 1, except that the carboxyl content of the SBR latex of Example 1 was 0% by weight. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 5.
[0028]
(Example 11)
A strong water-resistant corrugated cardboard adhesive was prepared in the same procedure as in Example 1, except that the SBR latex of Example 1 having a Tg of 60 ° C. was used. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 6.
(Example 12)
A strong water-resistant corrugated cardboard adhesive was prepared in the same procedure as in Example 1, except that the SBR latex of Example 1 having a Tg of -44 ° C was used. The water-resistant adhesive strength of the obtained adhesive was measured in the same manner as in Example 1, and the measurement results are shown in Table 6.
[0029]
(Example 13)
The strong water-resistant corrugated cardboard adhesive of Example 1 and the general corrugated cardboard adhesive prepared under the following conditions were mixed at a volume ratio to examine the occurrence of gelation. The results are shown in Table 7.
990 g of water heated to 60 ° C. is taken in a 3 L bucket, 135 g of carrier starch OHP-C-153 (manufactured by Oji Cornstarch Co., Ltd.) is added thereto, and the starch slurry is prepared by dispersing with a stirrer robot mix (4700 rpm). To this was added 27.0 g of caustic soda and stirred for 15 minutes to prepare a carrier part. On the other hand, 1825g of water heated to 30 ° C was added to an 18L bucket, 22.5g of borax and 990g of corn starch (manufactured by Oji Corn Starch Co., Ltd.) were added thereto, and dispersed with a stirrer robot mix (4700rpm) to prepare a main part. . Next, the carrier part was added to and mixed with the main part over 15 minutes to prepare a general corrugated adhesive.
[0030]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[Table 7]
From Tables 1 to 6, it can be seen that the strong water-resistant corrugated cardboard adhesive of the present invention has a particularly excellent water-resistant adhesive strength compared to conventional water-resistant corrugated cardboard adhesives. Moreover, it can be seen from Table 7 that the adhesive for general cardboard can be arbitrarily mixed without gelation.
[0038]
【The invention's effect】
The strong water-resistant corrugated cardboard adhesive comprising latex, starch, thermosetting resin and crosslinking agent according to the present invention provides superior water resistance performance compared to conventional water-resistant corrugated cardboard adhesives.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07275398A JP3807844B2 (en) | 1998-03-20 | 1998-03-20 | Strong water-resistant cardboard adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07275398A JP3807844B2 (en) | 1998-03-20 | 1998-03-20 | Strong water-resistant cardboard adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11269444A JPH11269444A (en) | 1999-10-05 |
| JP3807844B2 true JP3807844B2 (en) | 2006-08-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07275398A Expired - Lifetime JP3807844B2 (en) | 1998-03-20 | 1998-03-20 | Strong water-resistant cardboard adhesive |
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| Country | Link |
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| JP (1) | JP3807844B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4644894B2 (en) * | 2000-01-20 | 2011-03-09 | 凸版印刷株式会社 | Waterproof paper |
| JP5046072B2 (en) * | 2001-04-25 | 2012-10-10 | 株式会社Ｊ−オイルミルズ | Strong water-resistant adhesive for cardboard |
| JP2003041124A (en) * | 2001-07-27 | 2003-02-13 | Sumitomo Chem Co Ltd | Resin composition for label bonding |
| JP4488689B2 (en) * | 2003-05-09 | 2010-06-23 | レンゴー株式会社 | Starch glue for corrugated cardboard |
| JP4601290B2 (en) * | 2003-12-25 | 2010-12-22 | 中央理化工業株式会社 | Adhesive composition |
| JP4592299B2 (en) * | 2004-02-13 | 2010-12-01 | 日本コーンスターチ株式会社 | Starch adhesive for corrugated board |
| KR101610815B1 (en) * | 2013-08-01 | 2016-04-08 | 요코하마 고무 가부시키가이샤 | Solidifying agent and tire puncture repair kit |
| JP7119777B2 (en) * | 2018-08-30 | 2022-08-17 | 王子ホールディングス株式会社 | Starch adhesive for cardboard |
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1998
- 1998-03-20 JP JP07275398A patent/JP3807844B2/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| JPH11269444A (en) | 1999-10-05 |
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