JPH0641509A - Fast-curing adhesive and method for bonding - Google Patents
Fast-curing adhesive and method for bondingInfo
- Publication number
- JPH0641509A JPH0641509A JP18436792A JP18436792A JPH0641509A JP H0641509 A JPH0641509 A JP H0641509A JP 18436792 A JP18436792 A JP 18436792A JP 18436792 A JP18436792 A JP 18436792A JP H0641509 A JPH0641509 A JP H0641509A
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- Japan
- Prior art keywords
- liquid
- aqueous solution
- compound
- adhesive
- maleic anhydride
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は二液分別塗布型の速硬化
接着剤とその接着方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-liquid fractional coating type quick-setting adhesive and a bonding method thereof.
【０００２】[0002]
【従来の技術】最近木材工業等では、生産工程をコンベ
アーシステムで連続的に量産する試みがあり、接着速度
の早い接着剤が要望されている。この目的にシアノアク
リレート系瞬間接着剤が考えられるが、価格が高く実用
的でない。また二液分別塗布型の速硬化接着剤として
は、ユリア樹脂系接着剤をＡ成分とし、ポリビニルアル
コール（ＰＶＡ）などの高分子化合物の水溶液に燐酸な
どの強酸を混合してＢ成分とした製品が、かなり以前か
ら市販されている。しかしこの強酸は、ユリア樹脂系の
老化性を助長し、木材自身の強度を劣化させる欠点があ
り、広く普及していない。2. Description of the Related Art Recently, in the wood industry and the like, there has been an attempt to continuously mass-produce a production process by a conveyor system, and an adhesive having a high adhesion speed has been demanded. A cyanoacrylate instant adhesive is considered for this purpose, but it is not practical because of its high price. Further, as a two-component differential coating type quick-setting adhesive, a urea resin adhesive is used as the component A, and a strong acid such as phosphoric acid is mixed with an aqueous solution of a polymer compound such as polyvinyl alcohol (PVA) to be the component B. However, it has been on the market for quite some time. However, this strong acid has a drawback that it accelerates the aging property of the urea resin system and deteriorates the strength of the wood itself, and is not widely used.
【０００３】また、分子内にアミド結合を有する可溶性
蛋白質の水溶液、あるいはイミド基を有する合成高分子
化合物の水溶液と水性エマルジョンからなる第１液と水
溶性ジアルデヒド化合物の水溶液の第２液からなる速硬
化接着剤組成物（特公昭６３−１７８７１号公報）も開
示されている。Further, it consists of an aqueous solution of a soluble protein having an amide bond in the molecule, or an aqueous solution of a synthetic polymer compound having an imide group and a first solution comprising an aqueous emulsion and a second solution comprising an aqueous solution of a water-soluble dialdehyde compound. A fast-curing adhesive composition (Japanese Patent Publication No. 63-17871) is also disclosed.
【０００４】また、分子内にアセトアセチル基を有する
高分子化合物の水性溶液および／または水性エマルジョ
ンからなる第１液と、アルデヒド化合物の水性溶液から
なる第２液からなる急硬化水性接着剤と接着方法（特公
平１−６０１９０号公報）も開示されている。Further, a first liquid consisting of an aqueous solution and / or an aqueous emulsion of a polymer compound having an acetoacetyl group in the molecule and a fast-curing aqueous adhesive consisting of a second liquid consisting of an aqueous solution of an aldehyde compound are bonded. A method (Japanese Patent Publication No. 1-60190) is also disclosed.
【０００５】また、分子内にアセトアセチル基を有する
高分子化合物との水性溶液および／または水性エマルジ
ョンからなる第１液と、ヒドラジン化合物の水性溶液か
らなる第２液からなる瞬硬化水性接着剤と接着方法（特
公平１−６０１９２号公報）も開示されている。Further, a first liquid consisting of an aqueous solution and / or an aqueous emulsion with a polymer compound having an acetoacetyl group in the molecule, and an instantaneous curing aqueous adhesive consisting of a second liquid consisting of an aqueous solution of a hydrazine compound. A bonding method (Japanese Patent Publication No. 1-60192) is also disclosed.
【０００６】しかし、上記の如き、二液分別塗布型接着
剤には次の様な欠点があった。However, the above-mentioned two-liquid fractional coating type adhesive has the following drawbacks.
【０００７】[0007]
【発明が解決しようとする課題】シアノアクリレート系
瞬間接着剤は価格が高く現実的でなく、ユリア樹脂系接
着剤をＡ成分とし、高分子化合物の水溶液に燐酸などの
強酸を混合してＢ成分とした製品においては、強酸が、
ユリア樹脂系の老化性を助長し、木材自身の強度を劣化
させる欠点があり、広く普及していない。また、分子内
にイミド基を有した高分子とジアルデヒドとの架橋反応
を利用した２液分別塗布型の接着剤組成物においては、
その架橋反応が熱による可逆反応のため耐久性に問題が
ある。また、分子内にアセトアセチル基を有した高分子
化合物は水溶液としての保存安定性やＰＨによる架橋反
応の依存性が高いことに問題がある。A cyanoacrylate-based instant adhesive is expensive and unrealistic. A urea resin-based adhesive is used as the component A, and an aqueous solution of a polymer compound is mixed with a strong acid such as phosphoric acid to be used as the component B. In the product,
It is not widely used because it has the drawback of promoting the aging properties of the urea resin system and deteriorating the strength of the wood itself. Further, in a two-liquid fractional coating type adhesive composition utilizing a crosslinking reaction between a polymer having an imide group in the molecule and a dialdehyde,
Since the crosslinking reaction is a reversible reaction due to heat, there is a problem in durability. Further, a polymer compound having an acetoacetyl group in the molecule has a problem that it has a high storage stability as an aqueous solution and a high dependency of a crosslinking reaction by PH.
【０００８】[0008]
【課題を解決するための手段】本発明は、分子内にヒド
ラジト基および／またはヒドラジン基を有する高分子化
合物の水溶液および／または水性エマルジョンからなる
Ａ液と、カルボキシル化合物の水性溶液又は分散液から
なるＢ液との二液からなる速硬化接着剤であり、また、
このＡ液とＢ液との二液を分別塗布して被着体を貼合わ
せる接着方法である。DISCLOSURE OF THE INVENTION The present invention comprises a solution A comprising an aqueous solution and / or an aqueous emulsion of a polymer compound having a hydrazito group and / or a hydrazine group in the molecule, and an aqueous solution or dispersion solution of a carboxyl compound. It is a fast-curing adhesive consisting of two liquids, B liquid, and
This is a bonding method in which the two liquids of the A liquid and the B liquid are separately applied and the adherends are stuck together.
【０００９】本発明での分子内にヒドラジド基および／
またはヒドラジン基を有する高分子化合物とは、重合性
のα、β−不飽和化合物類と無水マレイン酸との多元共
重合体にヒドラジンを反応せしめて、分子内の無水マレ
イン酸の一部をヒドラジド化および／またはヒドラジン
化することによって得ることができる高分子化合物であ
り、そのまま水に溶解せしめるか、または塩基性物質
（アルカリ金属の炭酸塩、炭酸アンモニウム、燐酸アン
モニウム、硼砂の如きアルカリ性の弱酸塩、アルカリ土
類金属の水酸化物、あるいはアンモニア、エタノールア
ミン類、モルホリン等の水溶性の塩基性の有機化合物な
ど）を添加して水可溶化して水溶液とする。もしくは、
上記多元共重合体を水可溶化して水溶液としたのちに、
ヒドラジド化および／またはヒドラジン化することによ
っても得ることができる。In the present invention, a hydrazide group and / or
Alternatively, a polymer compound having a hydrazine group means that a multicomponent copolymer of polymerizable α, β-unsaturated compounds and maleic anhydride is reacted with hydrazine, and a part of maleic anhydride in the molecule is hydrazide. It is a polymer compound that can be obtained by hydrating and / or hydrazinizing it, and can be dissolved in water as it is, or a basic substance (alkali metal carbonate, ammonium carbonate, ammonium phosphate, alkaline weak acid salt such as borax). , A hydroxide of an alkaline earth metal, or a water-soluble basic organic compound such as ammonia, ethanolamines, morpholine, etc.) is added to solubilize the solution into an aqueous solution. Or
After solubilizing the above multicomponent copolymer into an aqueous solution,
It can also be obtained by hydrazidation and / or hydrazination.
【００１０】また、これらの多元共重合体としては、酢
酸ビニル−無水マレイン酸、スチレン−無水マレイン
酸、イソブチレン−無水マレイン酸、アクリル酸エステ
ル類−無水マレイン酸、メタクリル酸エステル類−無水
マレイン酸などが挙げられる。Examples of these multi-component copolymers are vinyl acetate-maleic anhydride, styrene-maleic anhydride, isobutylene-maleic anhydride, acrylic acid esters-maleic anhydride, methacrylic acid esters-maleic anhydride. And so on.
【００１１】また、水性エマルジョンとしては、酢酸ビ
ニル、アクリル酸エステル、メタクリル酸エステルなど
のビニル系単量体を主体に単独乳化重合したエマルジョ
ンや、エチレン−酢酸ビニルまたはアクリル酸エステル
類などの乳化重合した共重合体エマルジョン、などの合
成樹脂エマルジョン及び天然ゴム、イソプレンゴム、ス
チレン−ブタジエンゴム、ブタジエンゴム、ブチルゴ
ム、クロロプレンゴム、ニトリルゴムなどのゴム乳化重
合物であるゴムラテックスやこれらのカルボキシル基な
どの官能基を導入した変性ゴムラテックスなどがあり、
これら合成樹脂エマルジョンやゴムラテックスを単独な
いしは２種類以上を混合して用いることもできる。As the aqueous emulsion, an emulsion obtained by homoemulsifying mainly vinyl monomers such as vinyl acetate, acrylic acid ester and methacrylic acid ester, and emulsion polymerization of ethylene-vinyl acetate or acrylic acid ester. Such as synthetic resin emulsions such as copolymer emulsions and natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, chloroprene rubber, nitrile rubber, and other rubber emulsion polymers such as rubber latex and carboxyl groups thereof. There is a modified rubber latex with a functional group introduced,
These synthetic resin emulsions and rubber latices may be used alone or in admixture of two or more.
【００１２】本発明におけるＡ液の調整に当っては、前
記の如くして得られた分子内にヒドラジド基および／ま
たはヒドラジン基を有する高分子化合物の１〜６０重量
％の水溶液、通常は１０〜５０％濃度で、水性エマルジ
ョンに混入してＡ液とする。In the preparation of the solution A in the present invention, a 1-60% by weight aqueous solution of the polymer compound having a hydrazide group and / or a hydrazine group in the molecule obtained as described above, usually 10 Mix to an aqueous emulsion at a concentration of 50% to prepare a liquid A.
【００１３】次に、本発明におけるＢ液となるカルボキ
シル化合物の水性溶液又は分散液としては、シュウ酸、
マロン酸、メンシュウ酸、オキサロ酢酸、コハク酸、リ
ンゴ酸、フマル酸、マレイン酸の水性溶液又は分散液が
好適である。水性溶液の濃度としては通常１〜５０％が
適当である。Next, as the aqueous solution or dispersion of the carboxyl compound, which is the liquid B in the present invention, oxalic acid,
Aqueous solutions or dispersions of malonic acid, menoxalic acid, oxaloacetic acid, succinic acid, malic acid, fumaric acid, maleic acid are preferred. The suitable concentration of the aqueous solution is usually 1 to 50%.
【００１４】本発明の接着剤は、上記の如き必須成分の
外に、必要に応じて充填剤（炭酸カルシウム、カオリ
ン、クレーなど）、可塑剤、防腐剤、着色剤、界面活性
剤、粘度調整剤、などを適宜添加することができる。The adhesive of the present invention contains, in addition to the above-mentioned essential components, a filler (calcium carbonate, kaolin, clay, etc.), a plasticizer, a preservative, a coloring agent, a surfactant, and a viscosity adjusting agent, if necessary. Agents and the like can be added as appropriate.
【００１５】次に、本発明の速硬化接着剤を使用して被
着体を貼合わせる接着方法としては、被接着物の接着面
にＡ液とＢ液とを夫々別々に塗布し接着面を接触させ圧
締する方法、例えば、Ａ液を木材などの表面に塗布し、
Ｂ液をスレート板などの表面に塗布し、直ちにこの両面
を合わせて接触させ圧締し接着する方法がある。Next, as a bonding method for adhering adherends using the fast-curing adhesive of the present invention, the liquid A and the liquid B are separately applied to the adhesive surfaces of the adherends and the adhesive surfaces are adhered. A method of contacting and pressing, for example, applying liquid A to the surface of wood,
There is a method in which the liquid B is applied to the surface of a slate plate or the like and immediately both surfaces are brought into contact with each other and pressed to bond them.
【００１６】また、Ａ液とＢ液を、各々同時に噴霧域が
重なる様にして被着体へ噴霧する方法としては、例えば
エアスプレー、エアレススプレーのいずれでもよいが、
２個のスプレーガンを用いたり、双頭スプレーガンを用
いることができる。As a method of spraying the liquid A and the liquid B onto the adherend at the same time so that the spraying areas overlap each other, for example, either air spray or airless spray may be used.
Two spray guns or a double-headed spray gun can be used.
【００１７】また、一方の被着体にＡ液とＢ液を分別重
ね塗布した面に、他方の被着体を貼り付ける方法、例え
ば、木材、合板、パーチクルボード、スレート板などの
多孔質板体にスプレーまたは刷毛などの塗布具でＡ液と
Ｂ液を塗布した面に、発泡体や紙などの多孔質被着体を
貼り付ける方法がある。接着剤の塗布量は、Ａ液１０〜
３００ｇ／ｍ2（固形分）、Ｂ液１〜５０ｇ／ｍ2（カル
ボキシル化合物として）が適当である。Further, a method of sticking the other adherend to the surface of one adherend on which the liquid A and the liquid B are applied separately, for example, a porous plate such as wood, plywood, particle board, slate plate, etc. There is a method of attaching a porous adherend such as foam or paper to the surface coated with the liquid A and the liquid B with an application tool such as a spray or a brush. The amount of adhesive to be applied is 10 to A liquid.
300 g / m 2 (solid content), (a carboxyl compound) B solution 1 to 50 g / m 2 are suitable.
【００１８】[0018]
【発明の効果】一般に水系の接着剤は室温ではかなり長
時間圧締を行わないと十分な最終接着強度が得られない
が、本発明の速硬化接着剤は短時間圧締するだけで、放
置養生後十分な最終接着強度が得られる。この場合大切
なことは２液を混合することなく別々に塗布することで
ある。In general, a water-based adhesive cannot obtain a sufficient final adhesive strength at room temperature unless it is pressed for a considerably long time. However, the fast-curing adhesive of the present invention is left alone after being pressed for a short time. Sufficient final adhesive strength is obtained after curing. In this case, what is important is to apply the two solutions separately without mixing them.
【００１９】ヒドラジド基またはヒドラジン基とカルボ
キシル化合物との反応は非常に速いので、混合して塗布
すると、混合中にゲル化してしまい、ゲル化物は接着性
を示さないからである。次に本発明を実施例により説明
する。This is because the reaction between the hydrazide group or hydrazine group and the carboxyl compound is so fast that when mixed and applied, gelation occurs during mixing and the gelled product does not exhibit adhesiveness. Next, the present invention will be described with reference to examples.
【００２０】[0020]
実施例１ 還流冷却器つき四つ口フラスコに、イソブチレン−無水
マレイン酸共重合体（商品名「イソバン０６」、クラレ
イソプレンケミカル株式会社製）５４重量部（以下、部
と記す）、可溶化剤としての工業用２５％アンモニア水
６部、水２４６部の配合で仕込み、撹拌下で９０℃、５
時間反応して、水溶性のイソブチレン−無水マレイン酸
共重合体とし、さらに適下ロートにより、ヒドラジン水
和物（８０％水加ヒドラジン、日本ヒドラジン工業株式
会社製）６．７部を適下して１時間反応させることによ
り、ヒドラジド基および／またはヒドラジン基を有する
共重合体の２０％水溶液を得た。この水溶液１００部
に、樹脂分５８％アクリルエマルジョン接着剤（商品名
「アイカアイボンＲＡＸ−７０」、アイカ工業株式会社
製）１５０部と充填剤として炭酸カルシウム５０部を加
え、撹拌混合してＡ液とした。また、シュウ酸の２０％
水溶液をＢ液とした。上記のＡ液とＢ液との二液を実施
例１の接着剤とした。Example 1 In a four-necked flask equipped with a reflux condenser, isobutylene-maleic anhydride copolymer (trade name "Isoban 06", manufactured by Kuraray Isoprene Chemical Co., Ltd.) 54 parts by weight (hereinafter referred to as "part"), a solubilizer 25% ammonia water for industrial use as a mixture of 6 parts and 246 parts of water were added, and the mixture was stirred at 90 ° C. for 5
After reacting for a time to obtain a water-soluble isobutylene-maleic anhydride copolymer, and further using a suitable funnel, 6.7 parts of hydrazine hydrate (80% hydrated hydrazine, manufactured by Nippon Hydrazine Industry Co., Ltd.) was applied. By reacting for 1 hour, a 20% aqueous solution of a copolymer having a hydrazide group and / or a hydrazine group was obtained. To 100 parts of this aqueous solution, 150 parts of a 58% resin content acrylic emulsion adhesive (trade name "Aika Aibon RAX-70", manufactured by Aika Kogyo Co., Ltd.) and 50 parts of calcium carbonate as a filler are added, stirred and mixed, and liquid A is added. And Also, 20% of oxalic acid
The aqueous solution was designated as solution B. The two liquids of the above liquids A and B were used as the adhesive of Example 1.
【００２１】実施例２ Ａ液としては実施例１と同一のＡ液を使用した。Ｂ液と
して、シュウ酸の２０％水溶液５０部とグリセリンジグ
リシジルエーテル２．５部との混合物を使用した。上記
のＡ液とＢ液との二液を実施例２の接着剤とした。Example 2 As the solution A, the same solution A as in Example 1 was used. As the solution B, a mixture of 50 parts of a 20% aqueous solution of oxalic acid and 2.5 parts of glycerin diglycidyl ether was used. The above-mentioned two liquids, A liquid and B liquid, were used as the adhesive of Example 2.
【００２２】比較例１ 実施例１のＡ液のみを用いて比較例１の接着剤とした。Comparative Example 1 The adhesive of Comparative Example 1 was prepared by using only the liquid A of Example 1.
【００２３】比較試験 実施例１と２及び比較例１の接着剤を用い、ＪＩＳ Ｋ
６８５３「接着剤の割裂接着強さ試験方法」に示された
方法に準じて、接着強さを測定した結果を表１に示す。Comparative Test Using the adhesives of Examples 1 and 2 and Comparative Example 1, JIS K
Table 1 shows the results of measuring the adhesive strength according to the method shown in "Testing method for split adhesive strength of adhesive".
【００２４】試験方法の概略は次の如くである。パーチ
クルボード（８０mm×８０mm×１０mm）と中比重繊維板
（ＭＤＦ）（８５mm×８０mm×２mm）の２片の被着体
で、パーチクルボード側にＡ液を塗布量約１５０ｇ／ｍ
2塗布し、ＭＤＦ側にＢ液を塗布量約３０ｇ／ｍ2塗布
し、両面を密着貼合わせて、直ちに約２Kg／cm2で５秒
間圧締し、解圧直後、および２４時間後（経時）の割裂
強度を測定した。なお、試験における雰囲気温度は２０
℃であった。The outline of the test method is as follows. Particle board (80 mm × 80 mm × 10 mm) and medium specific gravity fiber board (MDF) (85 mm × 80 mm × 2 mm), two pieces of adherends. Liquid A is applied to the particle board side of about 150 g / m
Apply 2 times, apply the amount of solution B to the MDF side of about 30 g / m 2 , adhere both sides closely, and immediately press at about 2 kg / cm 2 for 5 seconds, immediately after decompressing, and after 24 hours (aging). ) Was measured. The ambient temperature in the test is 20
It was ℃.
【００２５】[0025]
【表１】 [Table 1]
Claims (5)
ドラジン基を有する高分子化合物の水溶液および／また
は水性エマルジョンからなるＡ液と、カルボキシル化合
物の水性溶液又は分散液からなるＢ液との二液からなる
ことを特徴とする速硬化接着剤。1. A liquid A comprising an aqueous solution and / or an aqueous emulsion of a polymer compound having a hydrazide group and / or a hydrazine group in the molecule and a liquid B comprising an aqueous solution or dispersion of a carboxyl compound. A fast-curing adhesive characterized in that
ドラジン基を有する高分子化合物の水溶液および／また
は水性エマルジョンからなるＡ液と、カルボキシル化合
物の水性溶液又は分散液からなるＢ液との二液を分別塗
布して被着体を貼合わせることを特徴とする接着方法。2. A liquid A comprising an aqueous solution and / or an aqueous emulsion of a polymer compound having a hydrazide group and / or a hydrazine group in a molecule, and a liquid B comprising an aqueous solution or dispersion of a carboxyl compound. A bonding method characterized by separately applying and adhering adherends.
が、被接着物の接着面にＡ液とＢ液を夫々別々に塗布
し、ついで接着面を接触させる請求項２記載の接着方
法。3. The bonding method according to claim 2, wherein the method of separately applying and adhering the adherends is to separately apply the liquid A and the liquid B to the adhesive surface of the adherend and then to contact the adhesive surfaces. .
々、同時に噴霧し、霧滴状態で混合して被着体に塗布す
る請求項２記載の接着方法。4. The bonding method according to claim 2, wherein the separately applying method is to spray the solutions A and B at the same time, mix them in the form of mist droplets, and apply the mixture to the adherend.
が、一方の被着体にＡ液とＢ液を分別重ね塗布した面
に、他方の被着体を貼付ける請求項２記載の接着方法。5. The method of separately applying and adhering an adherend, according to claim 2, wherein one of the adherends is separately superposed with the solution A and the solution B, and the other adherend is applied. Bonding method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18436792A JP2509847B2 (en) | 1992-06-17 | 1992-06-17 | Fast curing adhesive and bonding method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18436792A JP2509847B2 (en) | 1992-06-17 | 1992-06-17 | Fast curing adhesive and bonding method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0641509A true JPH0641509A (en) | 1994-02-15 |
| JP2509847B2 JP2509847B2 (en) | 1996-06-26 |
Family
ID=16151989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18436792A Expired - Fee Related JP2509847B2 (en) | 1992-06-17 | 1992-06-17 | Fast curing adhesive and bonding method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2509847B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010534268A (en) * | 2007-07-23 | 2010-11-04 | ヘンケル コーポレイション | Novel adducts useful as curing components for anaerobic curable compositions |
| US10273317B2 (en) | 2016-08-29 | 2019-04-30 | Ppg Industries Ohio, Inc. | Polymers with functional imide groups and pigment dispersions and coatings formed therefrom |
-
1992
- 1992-06-17 JP JP18436792A patent/JP2509847B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010534268A (en) * | 2007-07-23 | 2010-11-04 | ヘンケル コーポレイション | Novel adducts useful as curing components for anaerobic curable compositions |
| US8598279B2 (en) | 2007-07-23 | 2013-12-03 | Henkel IP US LLC | Adducts useful as cure components for anaerobic curable compositions |
| US10273317B2 (en) | 2016-08-29 | 2019-04-30 | Ppg Industries Ohio, Inc. | Polymers with functional imide groups and pigment dispersions and coatings formed therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2509847B2 (en) | 1996-06-26 |
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