JP3577597B2 - Water resistant adhesive composition for cardboard - Google Patents
Water resistant adhesive composition for cardboard Download PDFInfo
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- JP3577597B2 JP3577597B2 JP35847991A JP35847991A JP3577597B2 JP 3577597 B2 JP3577597 B2 JP 3577597B2 JP 35847991 A JP35847991 A JP 35847991A JP 35847991 A JP35847991 A JP 35847991A JP 3577597 B2 JP3577597 B2 JP 3577597B2
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- Japan
- Prior art keywords
- water
- starch
- cardboard
- resin
- polyamide 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.)
- Expired - Fee Related
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Description
【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。
【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。
【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。
【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。
【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。
【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。
【０００７】
すなわち本発明の段ボール用耐水性接着剤組成物は、澱粉と無限大希釈可能なカチオン系水溶性ポリアミド樹脂とからなり、澱粉１００重量部に対する該ポリアミド樹脂の含有量は、仮に固形分５０％の濃度の該ポリアミド樹脂水溶液としたときの量で表すと０．１ 〜１５重量部であることを特徴とするものである。
【０００８】
本発明におけるカチオン化水溶性ポリアミド樹脂は、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で得られる。
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。
【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。
【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。
【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。
【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％の該ポリアミド樹脂水溶液とした場合には 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。
【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。
【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。
【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。
【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。
【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。
【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。
【００１９】
【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。
【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。[0001]
[Industrial applications]
The present invention relates to a starch-based water-resistant cardboard adhesive composition comprising a starch and a specific amount of a cationic water-soluble polyamide resin.
[0002]
[Prior art]
Adhesives for corrugated cardboard in Japan are mainly made of starch in terms of economy and workability.However, starch-based adhesives have poor water resistance and swell and soften when wet or wet. And loses its adhesive strength.
Conventionally, as a method of making a starch-based cardboard adhesive water-resistant, a method of adding a formalin-based thermosetting resin such as a water-soluble urea resin, a melamine resin, a phenol resin, a resorcinol resin, and a ketone resin to starch is known. Have been.
[0003]
[Problems to be solved by the invention]
However, the addition of these water-soluble resins has drawbacks such as a poor water resistance imparting effect, poor workability, and a high temperature or a long time for curing. Not been.
An object of the present invention is to provide a water-resistant adhesive composition which improves the above-mentioned drawbacks at the time of laminating water-resistant cardboard, has good workability, and exhibits excellent water resistance.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-mentioned object, and as a result, by adding a cationic water-soluble polyamide resin to starch, significantly improve the water resistance of corrugated cardboard while maintaining good workability. I found that I got it.
[0005]
Although the mechanism of the performance improvement is not clear, the cationic water-soluble polyamide resin coats the starch granules in the adhesive composition, and at the same time, due to its cationic property, quickly fixes and crosslinks to the cardboard base paper, and has a strong property. It is presumed to express binding.
As a result, the productized cardboard retains its adhesive strength even if it gets wet due to the weather such as rain or snow, receives water from the package contents, or is exposed to high humidity. Therefore, it can be applied to applications requiring a high degree of water resistance, such as cardboard boxes for fish, vegetables and fruits.
[0006]
Furthermore, since the cationic water-soluble polyamide resin according to the present invention is obtained as an aqueous solution that can be diluted to infinity, it exhibits good affinity with the base paper of the corrugated cardboard as the adherend in an aqueous paste liquid mainly composed of starch. Does not adversely affect lamination.
[0007]
That is, the water-resistant adhesive composition for cardboard according to the present invention comprises starch and a cationic water-soluble polyamide resin which can be infinitely diluted , and the content of the polyamide resin with respect to 100 parts by weight of the starch is supposed to be 50% solids. The amount is 0.1 to 15 parts by weight in terms of the concentration of the polyamide resin aqueous solution .
[0008]
Cationized water-soluble polyamide resins in the present invention, dehydrated and polyalkylene down polyamine and dibasic carboxylic acid or a dehydration condensation polyamides polyamines and derivatives thereof or polyalkylene urea and dibasic carboxylic acid or its derivatives, It is obtained by a method in which epihalohydrin is added to the condensed polyamide urea to cationize it.
Formaldehyde may be co-condensed during the synthesis of the polyamide resin.
[0009]
Examples of the polyalkylene polyamine include polyethylene polyamine, polypropylene polyamine, and polybutylene polyamine. Among them, polyethylene polyamine is preferable, and among them, diethylene triamine, triethylene tetramine or tetraethylene pentamine is most preferable.
[0010]
A typical example of the polyalkylene polyurea is a deammonification reaction product from the above-described polyalkylene polyamine and urea.
These polyalkylene polyamines or polyalkylene polyureas may be used alone or in combination of two or more, or may be used in combination with each other. An aliphatic diamine such as ethylenediamine, propylenediamine or hexamethylenediamine may be used in combination with the polyalkylene polyamine and / or polyalkylene polyurea in an amount of 50 mol% or less.
[0011]
The dibasic carboxylic acid or a derivative thereof includes a compound having two carboxyl groups in a molecule, an ester thereof, and an acid anhydride thereof.
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 acids 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 or epibromohydrin is used.
[0012]
The blending amount of the cationic water-soluble polyamide resin with respect to the starch is 0.1 to 15 parts by weight when the polyamide resin aqueous solution having a solid content of 50% with respect to 100 parts by weight of starch is used in consideration of the blending effect and economy. And preferably 1 to 10 parts by weight. That is, the effect of imparting water resistance is weak at 0.1 parts by weight or less, and even at 15 parts by weight or more, no remarkable improvement in water resistance is observed, conversely, the cost increases, the disadvantage of increasing the viscosity of the size liquid appears, However, it is not realistic.
[0013]
【Example】
Examples of the present invention will be described below, but the gist of the invention is not limited to this.
[0014]
Example (1) In a 500 mL four-necked flask equipped with a thermometer, a reflux condenser, and a stirring rod, 113.4 g (1.1 mol) of diethylenetriamine, 50 g of water, and 146.1 g (1.0 mol) of adipic acid. , And the mixture was heated while draining water, and 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 aqueous polyamide solution and 110 g of water were charged into another flask, and 13.9 g (0.15 mol) of epichlorohydrin was added dropwise at 50 ° C. over 30 minutes. After reacting for 2 hours, cooling to room temperature, 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 was designated as waterproofing agent A.
[0015]
(2) A commercially available waterproofing agent was used for performance comparison of the waterproofing agent according to the present invention.
Non-cationic ketone resin: Epinox P-468L (manufactured by Dick Hercules KK) (solid content adjusted to 50%) was used as a water-proofing agent B
[0016]
(3) 120 kg of Carrier starch for water-resistant cardboard adhesive [HR-160, manufactured by Honen Corporation] is suspended in 550 L (liter) of 60 ° C. hot water, and 13.8 kg of caustic soda is added thereto for gelatinization. The mixture was further stirred at this temperature for 15 minutes to obtain a carrier size liquid.
On the other hand, to a solution in which 9 kg of borax was previously dissolved in 1080 L of water at 35 ° C., 500 kg of a water-resistant cardboard adhesive main starch [HR-202, manufactured by Honen Corporation] and 31 kg of the above-mentioned water-resistant agent were added, and the mixture was thoroughly stirred and mixed. To prepare the main part.
The above-mentioned carrier size liquid was gradually added to the main part, and after the addition, stirring was continued for 15 minutes to obtain a finished size liquid.
[0017]
In order to clarify the effect of the method of the present invention, a water-resistant corrugated cardboard adhesive paste liquid prepared by blending a cationic water-soluble resin synthesized by the method described above and a commercially available water-resistant resin as a control was used. Using a corrugator (lamination speed: 200 m / min, lamination width: 2200 mm) manufactured by Mitsubishi Langston Co., Ltd., a liner (manufactured by Daishowa Paper, water-resistant liner, KT-280) and a core (manufactured by Daishowa Paper, water-resistant) Core, SCPT-180), and the bonding speed was observed.
[0018]
The obtained corrugated cardboard sheet was cut into a size of 8 cm × 5 cm to prepare a test piece, and the adhesive strength in a normal state and the adhesive strength in a wet state of each test piece after immersion in water at 20 ° C. for 3 minutes and 60 minutes were measured. It was measured with a pin tester according to JIS-Z-0402.
Further, the viscosity was measured by the Ford cup method immediately after the above-mentioned adhesive paste liquid was formed and after standing at 40 ° C. for 24 hours.
The results are shown in the table below.
[0019]
【The invention's effect】
As can be clearly seen from the above results, when using the water-resistant adhesive composition using the cationic water-soluble polyamide resin of the present invention as a water-proofing agent, it has excellent water-resistant performance without lowering the bonding speed. Corrugated products can be obtained.
[0021]
The adhesive obtained in the present invention has been described as a corrugated cardboard adhesive because it is most suitable for use in the production of corrugated cardboard, but the cationic water-soluble polyamide resin used in the present invention reduces the adhesive strength of the starch-based adhesive. Since it acts as a water-proofing agent without lowering, it can be used as a water-proofing agent for starch-based compositions without being limited to adhesives. Can also be used as a starch-based adhesive.
Claims (1)
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 JPH05209159A (en) | 1993-08-20 |
| JP3577597B2 true 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 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3577597B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19829757A1 (en) * | 1998-07-03 | 2000-01-05 | Stockhausen Chem Fab Gmbh | Aqueous adhesive dispersions and their use in the production of multilayer papers |
-
1991
- 1991-12-30 JP JP35847991A patent/JP3577597B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05209159A (en) | 1993-08-20 |
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