JPS61271366A - Waterproof emulsion adhesive - Google Patents

Abstract

PURPOSE:To improve initial bond performance, waterproofing bond performance and shelf stability, by blending a previously emulsified amino resin and an org. amine and/or a basic salt with a resin emulsion mainly composed of vinyl acetate and adjusting the pH to a value within a specified range. CONSTITUTION:A previously emulsified amino resin is mixed with a resin emulsion mainly composed of vinyl acetate. An org. amine and/or a basic salt are/is blended with the mixture to adjust the ph to 7.0 or above, thus obtaining the titled adhesive. The pH of the mixture is adjusted by the org. amine in place of conventional alkaline substance (e.g., NaOH) to thereby improve shelf stability. Examples of the org. amines are ethylenediamine and diethylenetriamine. Examples of the basic salts are sodium carbonate, ammonium carbonate, disodium hydrogen-phosphate and sodium phosphate.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、耐水性を有する酢酸ビニルを主成分とする樹
脂エマルジョンに関するもので１％に木材、紙などの接
着に好適なエマルジ璽ンを提供する仁とにある。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a water-resistant resin emulsion mainly composed of vinyl acetate, and contains 1% of an emulsion seal suitable for bonding wood, paper, etc. It is in the interest of providing.

〔従来の技術〕[Conventional technology]

従来、酢酸ビニル樹脂エマルジ曹ンは接着強度の発現性
（初期接着性）がよく、使いやすいなどの優れた特徴が
あるために、木材や紙などの接着剤として広く使用され
て−る。しかし、耐水性に劣るなどの欠点が６抄、その
欠点を補うためにエリア樹脂やメラミン四指などのアミ
ノ系樹脂液状接着剤を配合して使用することが一般に行
われて−る。Conventionally, vinyl acetate resin emulsion carbon has been widely used as an adhesive for wood, paper, etc. because it has excellent characteristics such as good adhesive strength development (initial adhesion) and ease of use. However, they have drawbacks such as poor water resistance, and to compensate for these drawbacks, it is common practice to mix and use amino resin liquid adhesives such as area resins and melamine resins.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

しかしながら、かかる方法は糊液と製糊する手数がわず
られしく、また、アミノ圀脂液状接着剤ｔ−混合するこ
とによりて酢酸ビニル樹脂工マルジＭノの特色で必る優
れた初期接着性能を低下させるなどの間ｍを生じていた
。However, such a method requires a lot of work for preparing the size liquid and the size, and the excellent initial adhesion performance required by the characteristics of the vinyl acetate resin resin Maruji M is achieved by mixing the amino resin liquid adhesive T-. During the process of lowering the

〔問題を解決するための手段と作用〕[Means and actions to solve the problem]

このような問題を解決するために、本発明者らは鋭意研
究を菖ねた結果、ユリア嘲脂やメラくン樹脂などのアミ
ノ系樹脂をあらかじめエマルジ璽ン化して酢酸ビニル樹
脂エマルジ盲ンに混合することによって、初期接着性能
を低下させることなく、酢酸ビニル樹脂エマルジョンの
欠点である耐水接着性能を改善することができ、さらに
、興味あることには、アミノ系樹脂乳濁液と６１ｉ殴ビ
ニル樹脂エマルジ目ンとの混合物に有機アミンおよび／
または塩基性塩ｔ−加えて該混合液のＰｋｌを７．ｌＪ
以上にｉ、ｔｉｎすることにより、アミノ糸樹脂乳濁液
ト酢酸ビニル樹脂エマルジ胃ンの混合比率をいかなる割
合にしても分離することなく、極めて保存安定性に優れ
九混合液が得られ、Ｍ混合液は長期間の貯蔵に耐えるこ
とを見出し、本発明を完成し虎。In order to solve these problems, the inventors of the present invention have conducted extensive research and have developed an emulsion bottle of vinyl acetate resin by emulsifying amino resins such as urea resin and Melacin resin in advance. By mixing, the water-resistant adhesion performance, which is a drawback of vinyl acetate resin emulsions, can be improved without reducing the initial adhesion performance.Moreover, interestingly, it is possible to improve the water-resistant adhesion performance, which is a drawback of vinyl acetate resin emulsions. Organic amine and/or
Or add a basic salt t- to adjust the Pkl of the mixture to 7. lJ
By carrying out the above steps, a mixture of amino thread resin emulsion to vinyl acetate resin emulsion can be obtained without separation regardless of the mixing ratio, and has excellent storage stability. He discovered that the mixed liquid could withstand long-term storage, and completed the invention.

すなわち、本発明は酢酸とニＡ−を生成分とする樹指孔
濁液に、６らかじめエマルジヨン化し九アミノ樹脂と、
有機アミンおよび／ｆたは塩基性塩とを配合し、ＰＨｔ
−７，０以上にＩＡ贅してなる耐水性エマルジｗｙｉ着
剤である。That is, in the present invention, a resin pore suspension containing acetic acid and di-A- is pre-emulsionized with a nine-amino resin,
By blending an organic amine and/f or a basic salt, PHt
This is a water-resistant emulsion adhesive with an IA rating of -7.0 or higher.

アぐノ系樹脂水習液を酢酸ビニル樹脂エマルジ冒ンＩｌ
１合したときは、混合液のｐｎを１０以上に＃Ｉ４整し
てお−ても、アンノ樹脂水醪液の混合比率が５Ω％以下
の低比率になると、保存中に分離を生ずる。Adding aguno-based resin water study fluid to vinyl acetate resin emulsion.
Even if the pn of the mixed liquid is adjusted to #I4 to be 10 or more when the mixture is mixed, if the mixing ratio of the anno-resin water mortar is as low as 5 Ω% or less, separation will occur during storage.

これに対し、本発明にお−で使用するアミノ系樹脂工マ
ルジ冒ンは、いかなる比率で混合することも可能となり
、この相違はまりなく予想することができない新知見で
ある。On the other hand, the amino resin resin used in the present invention can be mixed in any ratio, and this difference is a new finding that cannot be predicted.

また、混合液のｐｕｔ−７，０以上にする際に通常のア
ルカリ物質、例えばカセイソーダのごときものを用いる
と、酢酸ビニル樹脂から遊離する酸の影響を受けてＰＨ
がすぐに低下し、保存安定性が低下してしまう。しかし
、有機アミンおよび／または塩基性塩のとききアルカリ
性物質ｔ−使用すると混合液のＰＨの経日的変化を抑え
ることが可能になる。In addition, if a normal alkaline substance such as caustic soda is used to make the mixed solution put-7.0 or higher, the PH will be affected by the acid liberated from the vinyl acetate resin.
quickly decreases, resulting in decreased storage stability. However, if an alkaline substance is used when an organic amine and/or a basic salt is used, it becomes possible to suppress changes in the pH of the mixture over time.

ここでいう有機アずンとは、エチレンシアイン、ジエチ
Ｖントリアばン、ヘキテメチレンテトラぐン、トリエタ
ノ−ルアはン、アンモニアなどが例示さｎる。また、塩
基性塩には、炭酸カリウム、嶽酸ンーダ、災酸アンモニ
ワム、第２および纂３リン酸ンーダなどがある。Examples of the organic azole herein include ethylenecyane, diethyltriabane, hextemethylenetetraban, triethanolamine, and ammonia. Further, basic salts include potassium carbonate, sodium sulfate, ammonium dibasic acid, dibasic and triphosphate, and the like.

七トゲアナイン、ベンゾグアナミ７などのうちから選ば
れた１棟もしくは２樵以上とホルムアルデヒドとを反応
させて４た樹脂であり、これらに必４に応じてフェノー
ル、レゾルシノール、ｙｖｙ−ル、デフ／リン、アルキ
ルレゾルシノール、キシレノール、バラトルエンスルホ
ンアイド、アセトン、メチルエチルクトン、シクロヘキ
テノ７などから選ばれた１樵もしくは２棟以上を共縮さ
せても本発明の効果は変らなめ。It is a resin made by reacting formaldehyde with one or more selected from the group consisting of seven togeanain, benzoguanami, etc., and depending on these, phenol, resorcinol, yvyl, def/phosphorus, The effect of the present invention remains unchanged even when one or more woodcutter selected from alkylresorcinol, xylenol, baratoluene sulfonide, acetone, methyl ethyl lactone, cyclohexteno7, etc. are co-condensed.

まな、酢酸ビニル樹脂エマルジ冒ンには、そのホモポリ
！−のみならず、酢酸ビニルとアクリル酸およびその誘
導体、メタクリルｅＩＲおよびその誘導体、エチレン、
塩化ビニル、塩化ビニリデン、マレイン！！、　Ｎ−メ
チロールアクリルアミド、アリルアルコール、アリルグ
リシジルエーテル、アリルアルデヒド、クロトン酸、イ
タ；７置なとのごとき共重合可能物よ＃）辿ばれた１樵
もしくは２ａ１以上との共縮合樹脂エマルジ曹ンが用い
られる。Mana, vinyl acetate resin emulsion is a homopoly! - as well as vinyl acetate and acrylic acid and its derivatives, methacrylic eIR and its derivatives, ethylene,
Vinyl chloride, vinylidene chloride, malein! ! , N-methylol acrylamide, allyl alcohol, allyl glycidyl ether, allyl aldehyde, crotonic acid, and copolymerizable materials such as is used.

〔発明の効果〕〔Effect of the invention〕

本発明方法によって得られた接着剤は、初期接着性能、
耐水接着性能、保存安定性などが優れているためプリン
ト紙や化粧突板を合板に接着するために好適であり、ま
九、フラッシュパネル、集成材、フィンガーシラインド
、家具の組立てなどの接着、板紙、紙管、段ボールなど
の接着などにも好適である。The adhesive obtained by the method of the present invention has initial adhesion performance,
Due to its excellent water-resistant adhesion performance and storage stability, it is suitable for adhering printed paper and decorative veneer to plywood, and is suitable for adhesion of wall panels, flush panels, laminated wood, finger sillboard, furniture assembly, etc., and paperboard. It is also suitable for adhering paper tubes, cardboard, etc.

〔実施例〕〔Example〕

以下に実施例によって本発明の詳細な説明する。 The present invention will be explained in detail below by way of examples.

実施例１゜ ３７％ｔＩｋ度のホルマリン２１０？、尿素５０？、メ
ラミン４８１を容量５００−の三ツロフラスコに蓋り取
り、第５リン酸ンーダ１に７１ｇえてＰＨ９，６とし、
攪拌しながら９０℃まで昇温した。９０℃で５０分間反
応させてから２０％ギ酸水浴液金加えて反応液のＰＨを
５．０とし、縮合反応を続は九。反応液ｔ２０℃まで冷
却して白濁する時点で第３りン醒ノーダを加えて反応液
のＰＨｔ−９，０にすると同時に反応液１ｌｔｌＩを５
０℃まで冷却した。次いで、アセトン１０？およびポリ
ビニルアルコール（鎮りラレ製◆２０５　）Ｌｏｔとノ
ニオン系界面活性剤（ライオンＫＫＩａ、＋）　ボ、ｔ
　ｔｙｘ　）０．７ｆｔｍ１．２０分間反応させ九款８
０℃に昇温して、さらに３０分間反応さエマルジ嘗ン化
巳な時点で第６リン酸ンーダを加えてＰＨを７．５とし
て冷却した。Example 1 37% tIk degree formalin 210? , Urea 50? , put a lid on melamine 481 in a 500-capacity Mitsuro flask, add 71 g to 5th phosphate powder 1, and adjust the pH to 9.6.
The temperature was raised to 90°C while stirring. After reacting at 90°C for 50 minutes, 20% formic acid water bath liquid gold was added to adjust the pH of the reaction solution to 5.0, and the condensation reaction was continued. When the reaction solution is cooled to 20°C and becomes cloudy, add a third phosphorus agent to bring the PHt of the reaction solution to -9.0.At the same time, 1ltlI of the reaction solution is
Cooled to 0°C. Next, acetone 10? and polyvinyl alcohol (Chidari Rare ◆205) Lot and nonionic surfactant (Lion KKIa, +) Bo, t
tyx) 0.7ftm1.React for 20 minutes
The temperature was raised to 0° C., and the mixture was reacted for another 30 minutes, and when the emulsion was complete, 6th phosphate was added to adjust the pH to 7.5, and the mixture was cooled.

このようにして得たアずノｍ指エマルジＷ／と市販の静
置ビニル樹脂エマルジｗ　ｙ　（豊年製油鉢良：ｖｗ−
４１５）とを種々の比率で混合したのち。The thus obtained Azuno m finger emulsion W/ and the commercially available stationary vinyl resin emulsion w y (Hounen oil pot good: vw-
415) in various ratios.

これらの混合樹脂にトリエタノールアミンを加えてＰＨ
ｔ−ａ５に＃Ｉ４盛し、本発明の耐水性エマルジョン接
着剤を得た。Add triethanolamine to these mixed resins and adjust the pH.
#I4 was plated on t-a5 to obtain a water-resistant emulsion adhesive of the present invention.

この接着剤の特性を明らかにするなめに、該接着剤を５
０℃に保持した恒温器中に保存し、経日的な粘度変化を
測定することによって貯蔵安定性を調べた。In order to clarify the properties of this adhesive,
Storage stability was investigated by storing in a constant temperature chamber maintained at 0° C. and measuring changes in viscosity over time.

ま虎、この接着剤１００重量部に５３％一度のパラトル
エンスルホン＃！７に浴１％［ｔ−６ｍ菫部加えて糊液
ｔ−調製したのち、厚さ２．０〜のラワン単板の両面に
５５０９／１ｒｌ（両面）の割合で塗付し、同じ厚さの
ラワン単板をその繊維方向が直交するように上下に重ね
合わせ、８穆／−の圧力を加えて１時間圧締した。Well, 100 parts by weight of this adhesive contains 53% paratoluene sulfone #! 7 to 1% [t-6m violet] to prepare a paste solution T-, then apply it to both sides of a lauan veneer with a thickness of 2.0~ at a ratio of 5509/1rl (both sides) to the same thickness. The lauan veneers were stacked one on top of the other so that their fiber directions were perpendicular to each other, and a pressure of 8 m/- was applied for 1 hour.

その後１週間放置し次のち、ＪＡＳ普適合板２類試験法
によ＃）Ｉ！着彌さを測定した。避らに、同じｍｆｆ１
ｔ用いてＪｌさ２．５Ｘ、１ｍ２５％、　長さ７５％’
）ラワン合板の片面に、長さ２５Ｘの部分に、１６０？
／イの割合になるよう金付し、長さ２５％の部分にオー
バーラツプするよう同じ形状のラワン合板を重ね合わせ
て、圧力１０Ｋｇ／−で圧締した。After that, it was left for one week and then tested according to the JAS General Compatibility Board Class 2 Test Method #)I! The firmness was measured. Avoid the same mff1
Jl length 2.5X, 1m 25%, length 75%'
) On one side of the lauan plywood, add 160mm to the 25x length part.
/A, and lauan plywood of the same shape was stacked so as to overlap 25% of the length, and pressed together with a pressure of 10 kg/-.

このようにして得た試験片を室温下、所定時間ごとに取
り出し、直ちに引張り接着強さを測定することによって
接着強さ発現性を調べた。The test piece thus obtained was taken out at predetermined time intervals at room temperature, and the tensile adhesive strength was immediately measured to examine adhesive strength development.

対照Ｍ　１゜ 実施ｆ１１で使用し九アずノ樹脂エマルジ冒／の代わり
に市販のエリア樹脂接着剤（豊年製油誌製二ｌ７Ｗ−０
６２）を用いたほかは実施例１と同様にして対照の接着
剤を得た◎ この接着剤について、実権例１と同じ方法で貯蔵安定性
、耐水接着性、接Ｎ強さ発現性を調べた。Control M 1゜In place of the 9Azuno resin emulsion used in the F11 test, a commercially available area resin adhesive (Honen Oil Press 217W-0) was used.
A control adhesive was obtained in the same manner as in Example 1 except that 62) was used.◎ This adhesive was examined for storage stability, water resistant adhesion, and N contact strength development in the same manner as in Actual Example 1. Ta.

これら実施例１と対照例１の試験結果２よび酢酸ビニル
樹脂エマルジョン（豊年製油ＫＫｍ：　ｖｗ−４１５）
単独を用い次場合の試験結果を比較して次表に記した。These test results 2 of Example 1 and Control Example 1 and vinyl acetate resin emulsion (Honen Oil KKm: vw-415)
The following table shows the comparison of the test results for the following cases using only one of these.

冥捲ｆ１２゜ ３７％濃度のホルマリン１２０Ｃ１、尿素２５０２、メ
ラξン４００Ｆ、水４５０２、へ−？チメチレンテトラ
イン２ｆ、アクリルアミドとアクリル酸との水浴性共重
合体５０２を三ツロフラスコに鷺抄とり、攪拌しながら
８０℃まで昇温した。８０℃で２５０分間反応させ喪後
、２５Ｘカセイ　ンーグ５ｆｔ−加え、５０℃まで冷却
しアずノ樹脂エマルジ薯ン′Ｉｒ侍た。Formalin 120C1 at 37% concentration, urea 2502, Melan 400F, water 4502, h-? Thimethylenetetrain 2f and water-bathable copolymer of acrylamide and acrylic acid 502 were placed in a Mitsuro flask and heated to 80° C. with stirring. After reacting at 80°C for 250 minutes, 5ft of 25X caustic solution was added, the mixture was cooled to 50°C, and the azuno resin emulsion was added.

このアミノ樹脂工マルジ目ンを用いて実権例１と同様な
方法により酢酸ビニル樹脂エマルジョン（豊年製油Ｉｃ
Ｋ製：ＶＷ−４１５）と混合し次のち、これらの混合衝
折に＠３りンばンーダを加えてＰＨ７，５に、ｍ！ｉＬ
、本発明の耐水性エマルジョン接着剤を得た。Using this amino resin emulsion, a vinyl acetate resin emulsion (Honen Oil Ic
(manufactured by K: VW-415), and then @3 Rinbanda was added to the mixed mixture to make the pH 7.5, m! iL
, a water-resistant emulsion adhesive of the present invention was obtained.

この接着剤の特性を明らかにするために、実７１！ｉｉ
肉１と同様に貯蔵安定性、耐水接着性、擾層強さ発現性
を調べた。In order to clarify the characteristics of this adhesive, we will use 71! ii
In the same way as Meat 1, storage stability, water resistance and adhesion, and strength development of the membrane layer were examined.

その結果を次表に記した。The results are shown in the table below.

以上の５Ａ施例によって、不発明の方法が優れた効果ｔ
−有することが明らかでろる。The above 5A examples show that the uninvented method has excellent effects.
-It is obvious that it has.

特許出績人：豊年製油株式会社Patent author: Hoenen Oil Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] 酢酸ビニルを主成分とする樹脂乳濁液にあらかじめエマ
ルジョン化したアミノ樹脂と有機アミンおよび／または
塩基性塩とを配合し、ＰＨを７．０以上に調整してなる
耐水性エマルジョン接着剤。A water-resistant emulsion adhesive prepared by blending a pre-emulsified amino resin with an organic amine and/or a basic salt into a resin emulsion containing vinyl acetate as a main component, and adjusting the pH to 7.0 or higher.