JPH05209159A - Water-resistant adhesive composition for corrugated fiberboard - Google Patents

Water-resistant adhesive composition for corrugated fiberboard

Info

Publication number
JPH05209159A
JPH05209159A JP35847991A JP35847991A JPH05209159A JP H05209159 A JPH05209159 A JP H05209159A JP 35847991 A JP35847991 A JP 35847991A JP 35847991 A JP35847991 A JP 35847991A JP H05209159 A JPH05209159 A JP H05209159A
Authority
JP
Japan
Prior art keywords
water
starch
adhesive composition
polyamide resin
resin
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.)
Granted
Application number
JP35847991A
Other languages
Japanese (ja)
Other versions
JP3577597B2 (en
Inventor
Katsuaki Tanaka
克明 田中
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honen Corp
Original Assignee
Honen Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Honen Corp filed Critical Honen Corp
Priority to JP35847991A priority Critical patent/JP3577597B2/en
Publication of JPH05209159A publication Critical patent/JPH05209159A/en
Application granted granted Critical
Publication of JP3577597B2 publication Critical patent/JP3577597B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Abstract

PURPOSE:To provide the subject composition excellent in workability, quick laminating suitability and economy, comprising starch and a cationic water-soluble polyamide resin at specified proportion. CONSTITUTION:The objective composition comprises 100 pts.wt. of starch and 0.1-15 pts.wt. of a cationic water-soluble polyamide resin.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は澱粉にカチオン系水溶性
ポリアミド樹脂を特定量添加して成る澱粉系耐水段ボー
ル用接着剤組成物に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a starch-based adhesive composition for water-resistant corrugated board, which is obtained by adding a specific amount of a cationic water-soluble polyamide resin to starch.

【0002】[0002]

【従来の技術】わが国における段ボール用接着剤は、経
済性、作業性の点からそのほとんどが澱粉を主体とする
ものであるが、この澱粉主体の接着剤は耐水性能が乏し
く、湿ったり濡れたりした時に膨潤軟化してその接着力
を失うという問題点を有している。従来、澱粉主体の段
ボール用接着剤を耐水化する方法として、澱粉に水溶性
のユリア樹脂、メラミン樹脂、フェノール樹脂、レゾル
シノール樹脂、ケトン樹脂の如きホルマリン系の熱硬化
性樹脂を添加する方法が知られている。
2. Description of the Related Art Most of the adhesives for corrugated board in Japan are mainly composed of starch from the viewpoint of economical efficiency and workability. However, these starch-based adhesives have poor water resistance and are not wet or wet. However, there is a problem in that it swells and softens and loses its adhesive strength. Conventionally, as a method for making starch-based cardboard adhesives water-resistant, a method of adding a formalin-based thermosetting resin such as water-soluble urea resin, melamine resin, phenol resin, resorcinol resin, or ketone resin to starch is known. Has been.

【0003】[0003]

【発明が解決しようとする課題】しかしながら、これら
水溶性の樹脂の添加は、耐水性付与効果が弱い、作業性
が悪い、キュアリングに高温または長時間を要する等の
欠点を有し、いまだ充分満足し得る段ボール用接着剤は
得られていない。本発明の目的は、耐水段ボールの貼合
に際しての上記の欠点を改良し、作業性が良く、優れた
耐水性能を示す耐水性接着剤組成物を提供することにあ
る。
However, the addition of these water-soluble resins has drawbacks such as a weak effect of imparting water resistance, poor workability, and high temperature or long time required for curing. No satisfactory corrugated board adhesive has been obtained. An object of the present invention is to provide a water-resistant adhesive composition that improves the above-mentioned drawbacks in bonding water-resistant corrugated board, has good workability, and exhibits excellent water resistance.

【0004】[0004]

【課題を解決するための手段】本発明者らは、上記目的
を解決するために鋭意検討を重ねた結果、澱粉にカチオ
ン系水溶性ポリアミド樹脂を添加することにより、良好
な作業性を維持しつつ段ボールの耐水性を著しく向上さ
せ得ることを見出した。
Means for Solving the Problems As a result of intensive studies for solving the above-mentioned object, the inventors of the present invention have maintained good workability by adding a cationic water-soluble polyamide resin to starch. Meanwhile, they have found that the water resistance of corrugated board can be significantly improved.

【0005】性能向上の発現機構については定かではな
いが、糊液中のカチオン系水溶性ポリアミド樹脂のエポ
キシ基が澱粉と反応して強固な結合を形成し、一方、ア
ミド基の部分が段ボール原紙と架橋して澱粉と段ボール
原紙の間の結合を促進するものと推定される。その結
果、製品化された段ボールが、雨、雪等の天候に基づく
水濡れや、包装内容物由来の水を被ったり、または高湿
度下に曝されたりしても、接着力を保持することがで
き、従って、魚、野菜、果物用の段ボール箱のような高
度な耐水性を必要とする用途に適用可能となる。
Although the mechanism by which the performance is improved is not clear, the epoxy group of the cationic water-soluble polyamide resin in the paste solution reacts with starch to form a strong bond, while the amide group part forms a corrugated cardboard base paper. It is presumed that it crosslinks with and promotes the bond between the starch and the corrugated board. As a result, the commercialized corrugated board should retain its adhesive strength even if it becomes wet due to the weather such as rain or snow, or if it is exposed to water derived from the package contents or exposed to high humidity. Therefore, it can be applied to applications requiring high water resistance such as cardboard boxes for fish, vegetables and fruits.

【0006】更に、本発明によるカチオン系水溶性ポリ
アミド樹脂は無限大希釈可能な水溶液として得られるた
め、澱粉を主体とする水系糊液中で被着体である段ボー
ル原紙と良好な親和性を示し、段ボールの貼合性に悪影
響を及ぼさない。
Further, since the cationic water-soluble polyamide resin according to the present invention is obtained as an infinitely dilutable aqueous solution, it shows a good affinity with the base paper for corrugated paper which is an adherend in an aqueous paste solution mainly composed of starch. , It does not have a bad influence on the bondability of corrugated board.

【0007】すなわち本発明の段ボール用耐水性接着剤
組成物は、澱粉 100重量部に対してカチオン化ポリアミ
ド樹脂を 0.1〜15重量部含むことを特徴とするものであ
る。
That is, the water resistant adhesive composition for corrugated board of the present invention is characterized by containing 0.1 to 15 parts by weight of a cationized polyamide resin with respect to 100 parts by weight of starch.

【0008】本発明におけるカチオン化水溶性ポリアミ
ド樹脂を製造する方法としては、例えば、ポリアルキレ
ンポリアミンと二塩基性カルボン酸あるいはその誘導体
とを脱水縮合したポリアミドポリアミン、またはポリア
ルキレンポリ尿素と二塩基性カルボン酸あるいはその誘
導体とを脱水縮合させたポリアミド尿素にエピハロヒド
リンを付加させてカチオン化する方法がある。なおこの
ポリアミド樹脂合成時にホルムアルデヒドを共縮合させ
ても良い。
The method for producing the cationized water-soluble polyamide resin in the present invention includes, for example, polyamide polyamine obtained by dehydration condensation of polyalkylene polyamine and dibasic carboxylic acid or its derivative, or polyalkylene polyurea and dibasic. There is a method in which epihalohydrin is added to polyamidourea obtained by dehydration condensation with carboxylic acid or its derivative to cationize. Formaldehyde may be co-condensed during the synthesis of the polyamide resin.

【0009】ポリアルキレンポリアミンとしては、ポリ
エチレンポリアミン、ポリプロピレンポリアミン、ポリ
ブチレンポリアミンなどがあるが、そのうちでもポリエ
チレンポリアミンが好ましく、就中ジエチレントリアミ
ン、トリエチレンテトラミンまたはテトラエチレンペン
タミンが最も好適である。
Examples of the polyalkylene polyamine include polyethylene polyamine, polypropylene polyamine and polybutylene polyamine. Among them, polyethylene polyamine is preferable, and diethylene triamine, triethylene tetramine or tetraethylene pentamine is most preferable.

【0010】ポリアルキレンポリ尿素としては、上述の
ポリアルキレンポリアミンと尿素とからの脱アンモニア
反応生成物が代表的なものである。これらポリアルキレ
ンポリアミンまたはポリアルキレンポリ尿素は共に、一
種類のみであっても二種以上の併用であってもよく、さ
らにはこれら相互の併用であってもよい。また、エチレ
ンジアミン、プロピレンジアミンまたはヘキサメチレン
ジアミンなどのごとき脂肪族ジアミン類を50モル%以下
の範囲でこれらポリアルキレンポリアミンおよび/また
はポリアルキレンポリ尿素と併用しても差し支えない。
As the polyalkylene polyurea, a deammonification reaction product from the above-mentioned polyalkylene polyamine and urea is typical. These polyalkylene polyamines or polyalkylene polyureas may be used alone or in combination of two or more, and may be used in combination with each other. In addition, aliphatic diamines such as ethylenediamine, propylenediamine or hexamethylenediamine may be used in combination with these polyalkylene polyamines and / or polyalkylene polyureas in the range of 50 mol% or less.

【0011】二塩基性カルボン酸あるいはその誘導体と
は、分子中に2個のカルボキシル基を有する化合物、あ
るいはそれらのエステル類、さらにはそれらの酸無水物
をも含む。具体的には、コハク酸、グルタル酸、アジピ
ン酸、セバシン酸、マレイン酸、フマル酸などの脂肪族
二塩基性カルボン酸とそれらのエステル類、あるいはフ
タル酸、イソフタル酸、テレフタル酸などの芳香族二塩
基性カルボン酸とそれらのエステル類、さらには無水コ
ハク酸、無水マレイン酸、無水フマル酸などの酸無水物
があるが、これらは一種類のみでも二種類以上の併用で
もよい。エピハロヒドリンとしてはエピクロルヒドリン
またはエピブロモヒドリンなどが用いられる。
The dibasic carboxylic acid or its derivative includes compounds having two carboxyl groups in the molecule, their esters, and their acid anhydrides. Specifically, aliphatic dibasic carboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid and fumaric acid and their esters, or aromatic compounds such as phthalic acid, isophthalic acid and terephthalic acid. There are dibasic carboxylic acids and their esters, and acid anhydrides such as succinic anhydride, maleic anhydride, and fumaric anhydride. These may be used alone or in combination of two or more. As epihalohydrin, epichlorohydrin, epibromohydrin or the like is used.

【0012】澱粉に対するカチオン系水溶性ポリアミド
樹脂の配合量は、配合効果と経済性との兼ね合いによ
り、澱粉 100重量部に対して固形分50%の本発明のカチ
オン系水溶性樹脂を 0.1〜15重量部、好ましくは1〜10
重量部配合することが望ましい。すなわち、 0.1重量部
以下ではその耐水性付与効果が弱く、15重量部以上にし
ても、耐水性に著しい向上は見られず、逆にコストの上
昇、糊液粘度の増大という欠点が現れ、いずれにしても
現実的ではない。
The amount of the cationic water-soluble polyamide resin to be added to the starch is 0.1 to 15% by weight of the cationic water-soluble resin of the present invention having a solid content of 50% relative to 100 parts by weight of the starch, in consideration of the effect of blending and the economical efficiency. Parts by weight, preferably 1-10
It is desirable to blend in parts by weight. That is, the effect of imparting water resistance is weak at 0.1 parts by weight or less, and even if it is 15 parts by weight or more, no remarkable improvement in water resistance is observed, and conversely, there is a drawback that the cost increases and the viscosity of the paste solution increases. However, it is not realistic.

【0013】[0013]

【実施例】以下に本発明の実施例を示すが、発明の主旨
はもとよりこれに限定されるものではない。
EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to the gist of the invention.

【0014】実施例 (1)温度計、還流冷却管、攪拌棒を備えた 500mL四ツ
口フラスコにジエチレントリアミン113.4 g(1.1 モ
ル)、水50g,アジピン酸146.1 g(1.0 モル)を仕込
み、水を抜きながら昇温し、 180−185 ℃で5時間反応
させた。60℃まで冷却後、水を加えて50%のポリアミド
水溶液とした。このポリアミド水溶液42.6g(0.1 モ
ル)と水 110gを別のフラスコに仕込み、これにエピク
ロルヒドリン13.9g(0.15モル)を50℃にて30分間かけ
て滴下し、その後60℃で2時間反応させ、室温に冷却
し、塩酸でpHを 4.0に調整した後、固形分50%のカチオ
ン系水溶性ポリアミド樹脂を得た。本樹脂を耐水化剤A
とした。
Example (1) A 500 mL four-necked flask equipped with a thermometer, a reflux condenser and a stir bar was charged with 113.4 g (1.1 mol) of diethylenetriamine, 50 g of water and 146.1 g (1.0 mol) of adipic acid, and water was added. The temperature was raised while pulling out, and the mixture was reacted at 180-185 ° C for 5 hours. After cooling to 60 ° C, water was added to obtain a 50% polyamide aqueous solution. 42.6 g (0.1 mol) of this polyamide aqueous solution and 110 g of water were charged into another flask, and 13.9 g (0.15 mol) of epichlorohydrin was added dropwise to this over 30 minutes at 50 ° C, and then reacted at 60 ° C for 2 hours and allowed to react at room temperature. After cooling to pH 4.0 and adjusting the pH to 4.0 with hydrochloric acid, a cationic water-soluble polyamide resin having a solid content of 50% was obtained. This resin is used as a water resistance agent A
And

【0015】(2)本発明による耐水化剤の性能比較に
は市販の耐水化剤を用いた。 非カチオン系ケトン樹脂:ディックハーキュレス(株)
製 エピノックスP−468L(固形分を50%に調製)
を耐水化剤Bとした。
(2) A commercially available waterproofing agent was used for the performance comparison of the waterproofing agent according to the present invention. Non-cationic ketone resin: Dick Hercules Co., Ltd.
Epinox P-468L (solid content adjusted to 50%)
Was used as a water resistance agent B.

【0016】(3)60℃の温水 550L(リットル)に耐
水段ボール接着剤用キャリャー澱粉[(株)ホーネンコ
ーポレーション社製、HR−160] 120Kgを懸濁さ
せ、これに苛性ソーダ13.8Kgを添加して糊化させ、さら
にこの温度で15分間攪拌を続けてキャリャー部糊液を得
た。一方、前もって35℃の水1080Lに硼砂9Kgを溶解し
た溶液に耐水段ボール接着剤メイン澱粉[(株)ホーネ
ンコーポレーション製、HR−202] 500Kgおよび上
述の耐水化剤31Kgを添加し、よく攪拌混合してメイン部
を調製した。このメイン部に前述のキャリャー部糊液を
徐々に添加し、添加後、15分間攪拌を続けでき上がり糊
液を得た。
(3) 120 kg of carrier starch for water-resistant corrugated adhesive [HR-160, manufactured by Honen Corporation, Co., Ltd.] was suspended in 550 liters of warm water at 60 ° C., and 13.8 kg of caustic soda was added thereto. The mixture was gelatinized, and stirring was continued for 15 minutes at this temperature to obtain a carrier paste solution. On the other hand, to a solution prepared by dissolving 9 kg of borax in 1080 L of water at 35 ° C. in advance, 500 kg of main starch for water-resistant corrugated board adhesive [HR-202, manufactured by Honen Corporation] and 31 kg of the above water-proofing agent were added, and mixed well by stirring. To prepare the main part. The above-mentioned carrier portion paste solution was gradually added to the main portion, and after the addition, stirring was continued for 15 minutes to obtain a paste solution.

【0017】本発明の方法による効果を明らかにするた
めに、前述の方法で合成したカチオン系水溶性樹脂およ
び比較対照としての市販の耐水化用樹脂を配合して調製
した耐水段ボール接着剤糊液を使用して、三菱ラングス
トン社製コルゲータ(貼合速度: 200m/min 、貼合
幅:2200mm)により、ライナー(大昭和製紙製、耐水ラ
イナー、KT−280)と中芯(大昭和製紙製、耐水中
芯、SCPT−180)を貼合し、その貼合速度を観察
した。
In order to clarify the effect of the method of the present invention, a water-resistant corrugated cardboard adhesive paste solution prepared by blending a cationic water-soluble resin synthesized by the above-mentioned method and a commercially available water-proofing resin as a comparative control. Using a corrugator manufactured by Mitsubishi Langston (laminating speed: 200 m / min, laminating width: 2200 mm), a liner (manufactured by Daishowa Paper Manufacturing, water resistant liner, KT-280) and a core (manufactured by Daishowa Paper Manufacturing) , Water resistant core, SCPT-180) were laminated, and the laminating speed was observed.

【0018】得られた段ボールシートを8cm×5cmの大
きさに切断して試験片とし、常態における接着力並び
に、20℃の水中に3分間および60分間浸漬した後の各試
験片の湿潤状態における接着力をJIS−Z−0402
に従ってピンテスターで測定した。また前記の接着剤糊
液の製糊直後と40℃に24時間放置した後の粘度をフォー
ドカップ法で測定した。その結果を下表に示す。
The obtained corrugated cardboard sheet was cut into a size of 8 cm × 5 cm to give a test piece, and the adhesive strength in the normal state and the wet state of each test piece after being immersed in water at 20 ° C. for 3 minutes and 60 minutes Adhesive strength according to JIS-Z-0402
It was measured with a pin tester in accordance with. Further, the viscosity of the above adhesive paste solution was measured by the Ford cup method immediately after the paste was made and after being left at 40 ° C. for 24 hours. The results are shown in the table below.

【0019】 [0019]

【0020】[0020]

【発明の効果】以上の結果より明白に認められるよう
に、本発明のカチオン系水溶性ポリアミド樹脂を耐水化
剤として用いた耐水性接着剤組成物を使用すると、貼合
速度を落とすことなく優れた耐水性能を有する段ボール
製品を得ることができる。
As can be clearly seen from the above results, the use of the water-resistant adhesive composition using the cationic water-soluble polyamide resin of the present invention as the water-proofing agent is excellent without slowing down the laminating speed. A corrugated board product having excellent water resistance can be obtained.

【0021】本発明で得られる接着剤は、段ボールの製
造に使用して最適であることから段ボール用接着剤とし
て説明したが、本発明で使用するカチオン系水溶性ポリ
アミド樹脂は澱粉系接着剤の接着強度を低下させること
なく耐水化剤として作用することから、接着剤に限るこ
となく澱粉系組成物の耐水化剤として使用できるほか、
該耐水化剤を含む接着剤は段ボール用途以外の壁紙、合
紙などの澱粉系接着剤としても使用できる。
The adhesive obtained in the present invention has been described as an adhesive for corrugated board because it is most suitable for use in the production of corrugated board, but the cationic water-soluble polyamide resin used in the present invention is a starch-based adhesive. Since it acts as a waterproofing agent without lowering the adhesive strength, it can be used as a waterproofing agent for starch-based compositions without being limited to adhesives,
The adhesive containing the water-proofing agent can also be used as a starch-based adhesive for wallpaper, interleaving paper and the like other than cardboard applications.

─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───

【手続補正書】[Procedure amendment]

【提出日】平成5年3月24日[Submission date] March 24, 1993

【手続補正1】[Procedure Amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】0005[Correction target item name] 0005

【補正方法】変更[Correction method] Change

【補正内容】[Correction content]

【0005】性能向上の発現機構については定かではな
いが、カチオン系水溶性ポリアミド樹脂が、接着剤組成
物中の澱粉粒を被覆すると同時に、そのカチオン性によ
り、段ボール原紙へ迅速に定着、架橋し、強固な結合を
発現するものと推定される。その結果、製品化された段
ボールが、雨、雪等の天候に基づく水濡れや、包装内容
物由来の水を被ったり、または高湿度下に曝されたりし
ても、接着力を保持することができ、従って、魚、野
菜、果物用の段ボール箱のような高度の耐水性を必要と
する用途に適用可能となる。
Although the mechanism of manifestation of performance improvement is not clear, a cationic water-soluble polyamide resin is used as an adhesive composition.
At the same time as coating the starch granules in the product,
Fast fixing and cross-linking to corrugated cardboard for a strong bond.
It is presumed to occur. As a result, the commercialized corrugated board should retain its adhesive strength even if it gets wet due to the weather such as rain and snow, is exposed to water derived from the package contents, or is exposed to high humidity. Therefore, it can be applied to applications requiring high water resistance such as cardboard boxes for fish, vegetables and fruits.

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 澱粉 100重量部に対してカチオン系水溶
性ポリアミド樹脂を0.1 〜15重量部含むことを特徴とす
る段ボール用耐水性接着剤組成物。
1. A water-resistant adhesive composition for corrugated board, comprising 0.1 to 15 parts by weight of a cationic water-soluble polyamide resin with respect to 100 parts by weight of starch.
JP35847991A 1991-12-30 1991-12-30 Water resistant adhesive composition for cardboard Expired - Fee Related JP3577597B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP35847991A JP3577597B2 (en) 1991-12-30 1991-12-30 Water resistant adhesive composition for cardboard

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP35847991A JP3577597B2 (en) 1991-12-30 1991-12-30 Water resistant adhesive composition for cardboard

Publications (2)

Publication Number Publication Date
JPH05209159A true JPH05209159A (en) 1993-08-20
JP3577597B2 JP3577597B2 (en) 2004-10-13

Family

ID=18459527

Family Applications (1)

Application Number Title Priority Date Filing Date
JP35847991A Expired - Fee Related JP3577597B2 (en) 1991-12-30 1991-12-30 Water resistant adhesive composition for cardboard

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Publication number Priority date Publication date Assignee Title
WO2000001783A3 (en) * 1998-07-03 2001-06-07 Stockhausen Chem Fab Gmbh Aqueous adhesive dispersions and the use thereof in the production of multi-layered paper

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000001783A3 (en) * 1998-07-03 2001-06-07 Stockhausen Chem Fab Gmbh Aqueous adhesive dispersions and the use thereof in the production of multi-layered paper

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