JPS6020980A - Aqueous dispersion type adhesive - Google Patents

Abstract

PURPOSE:To provide an aqueous dispersion type adhesive having bonding power at normal temp. and exhibiting excellent boiling resistant adhesive strength, etc., prepd. by adding a compd, having two or more epoxy groups in the molecule to a mixt. of a specified normal-temp. crosslinking acrylic emulsion and an aqueous soln. of PVA. CONSTITUTION:An emulsion of a normal-temp. crosslinking acrylic resin having a carbonyl or also group and two or more residues of hydrazine is prepd. by copolymerization of a hydrazine deriv. having at least two hydrazine residues, a vinyl monomer having a carbonyl or also group and a monomer selected from among methyl methacrylate, acrylonitrile, etc. The acrylic emulsion is mixed with polyvinyl alcohol and a compd. having at least two epoxy groups in the molecule (e.g. ethylene glycol diglycidyl ether) is added to the mixt. to obtain the aimed aqueous dispersion type adhesive.

Description

【発明の詳細な説明】 本発明は可使時間が長く、常温接着で耐煮沸接着力にも
優れている２液型の水分散型接着剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a two-component water-dispersed adhesive that has a long pot life, adhesives at room temperature, and has excellent boiling-resistant adhesive strength.

従来より、水分散型接着剤としては酢酸ビニル系エマル
ジョンまたはクロロプレン系やスチレンブクジエン系の
ラテックスなどがあり、耐水性を向上させる方法として
尿素樹脂やフェノール樹脂などの水溶性熱硬化性樹脂を
混入したシ、ポリビニルアルコール水溶液を含む水系エ
マルジョンにイソンアナートを分散させたシしているが
、いずれも２液型であり経時増粘が著しく作業性が悪い
のみか硬化後の耐水接着力も充分でなかった。また、エ
ポキシ基と反応しうる活性水素を含む重合体と各種ラテ
ックスおよびエポキシ基を分子中に２個以上含む化合物
の混合物からなる接着剤も開示されているが、２液型の
欠点の他に耐水接着力、殊に耐煮沸接着力の点で劣って
いた。Conventionally, water-dispersible adhesives include vinyl acetate emulsions, chloroprene-based and styrene-buccadiene-based latexes, and water-soluble thermosetting resins such as urea resins and phenolic resins are mixed in to improve water resistance. Isonanate was dispersed in an aqueous emulsion containing an aqueous polyvinyl alcohol solution, but both were two-component types, and their viscosity increased significantly over time, resulting in poor workability and insufficient water-resistant adhesive strength after curing. . In addition, adhesives made of a mixture of a polymer containing active hydrogen that can react with an epoxy group, various latexes, and a compound containing two or more epoxy groups in the molecule have also been disclosed, but in addition to the drawbacks of the two-component type, It was inferior in terms of water-resistant adhesive strength, especially boiling-resistant adhesive strength.

本発明は、前記欠点を改良した可使時間が長くて常温接
着で耐煮沸接着力にも優れている２液型の水分散型接着
剤に関する。The present invention relates to a two-component water-dispersed adhesive that overcomes the above-mentioned drawbacks, has a long pot life, has excellent room-temperature adhesion, and has excellent boiling-resistant adhesive strength.

本発明は、力μボニル基又はアルド基を有するビニルモ
ノマーを共重合し、少なくとも２個のヒドラジン残基を
有するヒドラジン誘導体を含有する常温架橋型アクリル
系エマルジョンとポリビニルアルコール水溶液との混合
物に、エポキシ基を分子中に２個以上含む化合物を添加
する２液型の水分散型接着剤である。The present invention involves copolymerizing a vinyl monomer having a μbonyl group or an aldo group, and adding an epoxy resin to a mixture of a cold crosslinkable acrylic emulsion containing a hydrazine derivative having at least two hydrazine residues and an aqueous polyvinyl alcohol solution. It is a two-component water-dispersed adhesive to which a compound containing two or more groups in the molecule is added.

本発明のカルボニμ基又はアルド基を有するビニルモノ
マーを共重合し、少なくとも２個のヒドラジン残基を有
するヒドラジン誘導体を含有する常温架橋型アクリル系
エマルジョンとは、例えば特開昭５７−３８５０号に開
示されている如く、（Ａ）成分：少なくとも２個のヒド
ラジン残基を有するヒドラジン誘導体、Ｂ成分：（ａ）
メタクリル酸メチル、アクリル酸第３ブチル、ビニル芳
香族化合物、ハロゲン化ビニル、エチレン、アクリロニ
トリル、メタクリルニトリル 単量体１０〜７５重量％と、（ｂ）２〜８個の炭素原子
を有するアルコールのアクリル酸またはメタクリル酸の
エステル、アクリル酸メチル、ビニルエステル、１．３
−ジエンより選ばれた単量体９０〜２５重量％と、（Ｃ
）少なくとも分子中に個のアルド基またはケト基と１個
の重合可能な二重結合を有するカルボ二〜基含有単量体
０〜２０重量％と、（ｄ）３〜５個の炭素原子ケ有する
モノまたは１およびジカルボン酸または１および窒素原
子において１〜４個の炭素原子を仔するアルキル基−ま
たは１およびアルキロール基により置換されたこれらの
酸のアミド０．５〜１０重量％とを乳化重合して得られ
る共重合物［’ｌ］１．００重量部を核とし、これに、
更に上記（ａ）及竹（ｄ）の単量体を、次の開会で混合
した単駄滓５〜２５０重量部を加え乳化重合してｉ４：
Ｊ記核の外（則に共重合体の殻を形成させた複層ＩＩ′
＋７造のカルボニル基含有共重合物［ＩＩ，］粒子の水
性分１■１ｋ、（　ａ　’）の単量体１０へ一７５重ｒ
ｊｋ％、（ｂ）の中ノ」上体９０〜２５重量％、（ｃ）
の（１１■体０．　１〜２０重量％、（ｄ）の単量体０
．５〜１０重量％、上記（Ｂ）成分の複層構造のカルボ
ニル基８自共屯合物のカルボニ）ｖ基１モルに対し、（
Ａ）成分が０．０２〜１モルの割合で配合されているカ
ルボニル 体粒子の水性分散τイｉ組成物であり、具体的にｄ、油
化パーディツシュ（株）製の部品名「アクロナール」の
ことを言う。また、ポリビニルアルコールとは、ポリ酢
酸ビニルのようなポリビニルエステルの加水分解によっ
て製造することができる公知のポリビニルアルコ−／し
、及びアクリル酸、メタクリル酸やアクリルアミド、メ
タクリルアミド等で変性したもの、更に部分的にアセト
酢酸エステル化したものをも含み、ケン化度８０〜９９
モル％、平均重合度３００〜２５００のもので、このう
ちでも高重合度物が耐水性の点で適しており、水溶液の
濃度は任意であるが３〜３０重量％が適当である。次に
エポキシ基を分子中に２個以上含む化合物としては、エ
チレングリコ−７レジグリシジルエーテ／し、ポリエチ
レングリコールジグリシジルエーテル、クグリセリンジ
グリシシ／レエーテ７Ｈグリセリントリグリシジルエー
テル、プロピレジジグリシジルエーテル、ポリプロピレ
ンジグリンジμエーテ／Ｉ／等の多価アルコール類のポ
リグリシジルエーテルやカルボキシル基を分子中に２個
以上含む化合物のポリグリシジルエーテルなどがあり、
これらのうちでも完全まだは部分的に水溶性のものが好
ましいが、水に対する溶解性が低くても本接着剤中で均
一に分散できるものでちるなら使用でき、例えば、ビス
フェノ−／Ｌ／Ａのジリシジルエーテル、脂環式エポキ
シ樹脂、含窒素エポキシ樹脂、ポリブタジェン型エポキ
シ樹脂、ウレクン変性エポキシ樹脂、含金属エポキシ樹
脂等があげられる。まだ接着性改良や過度の吸い込み防
止のため無機、有機の充填材の添加、及びエポキシ化合
物の硬化促進剤となるアミン類、金属化合物等を添加し
てもよい。次に、配合比率であるが、固型分重量換算値
で、前記常温架橋型アクリル系エマルジョン１００部に
対して、固形のポリビニルアルコール ００部が良い。エポキシ化合物についてはアクリル系エ
マルジョンとポリビニルアルコールの合計１００部に対
して０．１〜１５０部、好ましくは１本発明の水分散型
接着剤は、常温架橋型アクリル系エマルジョン粒子が多
段階重合による複層構造を形成しており、粒子表面に多
く偏在するカルボニル基またはアルド基とジヒドヮジン
化合物とが脱水架橋反応し、そして、やはり粒子表面上
に存在するアミド基と、エポキシ基の重付加反応による
架橋がともに高度に進行するために強肇刃な接着層を形
成し、煮沸試験にも耐え得る接着力を発揮するものと考
えられる。また、水溶性のポリビニルアルコールが保水
作用をして粘着保持時間を延長して、乾燥液ゼによる接
着不良を防止しながら上記の脱水架橋反応及び重付加反
応の均一化を図り、木材等の被着体へのぬれや密着性及
び初期接着力の向上などの作用効果をなしている。更に
、ポリビニルアルコール及びエポキシ化合物ハ、アクリ
ル系エマルジョンの最低造膜温度の低温化の作用効果も
あり、接着作業幅の拡大にも寄与している。The room-temperature crosslinkable acrylic emulsion containing a hydrazine derivative having at least two hydrazine residues obtained by copolymerizing a vinyl monomer having a carbonyl μ group or an aldo group according to the present invention is described in, for example, JP-A No. 57-3850. As disclosed, component (A): a hydrazine derivative having at least two hydrazine residues, component B: (a)
Methyl methacrylate, tert-butyl acrylate, vinyl aromatics, vinyl halides, ethylene, acrylonitrile, 10 to 75% by weight of methacrylonitrile monomer and (b) acrylic alcohols having 2 to 8 carbon atoms. Acids or esters of methacrylic acid, methyl acrylate, vinyl esters, 1.3
-90 to 25% by weight of a monomer selected from dienes, and (C
) 0 to 20% by weight of a carbon di-group-containing monomer having at least 1 aldo or keto group and 1 polymerizable double bond in the molecule; and (d) 3 to 5 carbon atoms. 0.5 to 10% by weight of mono- or dicarboxylic acids or amides of these acids substituted at the nitrogen atom by an alkyl group having 1 to 4 carbon atoms or 1 and an alkylol group; Using 1.00 parts by weight of the copolymer ['l] obtained by emulsion polymerization as a core,
Further, 5 to 250 parts by weight of the monomers of (a) and bamboo (d) above were mixed in the next opening, and emulsion polymerization was carried out to obtain i4:
A multilayer II' in which a copolymer shell is formed outside the J core (in accordance with the rule)
The aqueous content of the carbonyl group-containing copolymer [II,] particles of +7 structure is 1 x 1 k, and the monomer 10 of (a') is 175 parts by weight.
jk%, (b) middle body 90-25% by weight, (c)
(11-isomer 0.1-20% by weight, (d) monomer 0
．． 5 to 10% by weight, per mole of the carbonyl)v group of the carbonyl group 8-carbonyl group of the multilayer structure of component (B), (
A) This is an aqueous dispersion of carbonyl particles in which the component is blended in a proportion of 0.02 to 1 mole. say something In addition, polyvinyl alcohol refers to known polyvinyl alcohols that can be produced by hydrolysis of polyvinyl esters such as polyvinyl acetate, and those modified with acrylic acid, methacrylic acid, acrylamide, methacrylamide, etc. Saponification degree is 80 to 99, including partially acetoacetic acid ester.
% by mole and average degree of polymerization of 300 to 2,500. Among these, those with a high degree of polymerization are suitable in terms of water resistance, and the concentration of the aqueous solution is arbitrary, but 3 to 30% by weight is suitable. Next, as compounds containing two or more epoxy groups in the molecule, ethylene glycol diglycidyl ether/reglycidyl ether, polyethylene glycol diglycidyl ether, gulycerin diglycidyl ether/reate 7H glycerin triglycidyl ether, propylene glycidyl ether, There are polyglycidyl ethers of polyhydric alcohols such as polypropylene digrin diμether/I/, and polyglycidyl ethers of compounds containing two or more carboxyl groups in the molecule.
Among these, completely or partially water-soluble ones are preferred, but even if the solubility in water is low, it can be used as long as it can be uniformly dispersed in this adhesive. For example, bispheno-/L/A Examples include dilycidyl ether, alicyclic epoxy resin, nitrogen-containing epoxy resin, polybutadiene-type epoxy resin, urekune-modified epoxy resin, metal-containing epoxy resin, and the like. In order to improve adhesion and prevent excessive suction, inorganic or organic fillers may be added, and amines, metal compounds, etc. that act as curing accelerators for epoxy compounds may be added. Next, regarding the blending ratio, in terms of solid content weight, it is preferable to use 00 parts of solid polyvinyl alcohol to 100 parts of the room-temperature crosslinkable acrylic emulsion. The epoxy compound is 0.1 to 150 parts, preferably 1, based on the total of 100 parts of the acrylic emulsion and polyvinyl alcohol. Forming a layered structure, carbonyl groups or aldo groups, which are abundant and unevenly distributed on the particle surface, undergo a dehydration crosslinking reaction with the dihydrodine compound, and then crosslinking occurs due to a polyaddition reaction between the amide group, which also exists on the particle surface, and the epoxy group. It is thought that this progresses to a high degree, forming a strong adhesive layer that exhibits adhesive strength that can withstand boiling tests. In addition, water-soluble polyvinyl alcohol has a water-retaining effect and extends the adhesion retention time, preventing adhesion failure due to drying liquid and making the above-mentioned dehydration crosslinking reaction and polyaddition reaction uniform. It has effects such as improving wettability and adhesion to the adherend and initial adhesive strength. Furthermore, polyvinyl alcohol and epoxy compounds also have the effect of lowering the minimum film forming temperature of acrylic emulsions, contributing to the expansion of the range of bonding operations.

以上の如く、本発明の水分散型接着剤は２液型ではある
が、可使時間が長くて作業性が良く、初期接着力及び耐
熱水接着力にも優れており、主に木材用接着剤として有
用である。As described above, although the water-dispersible adhesive of the present invention is a two-component type, it has a long pot life, good workability, excellent initial adhesive strength and hot water-resistant adhesive strength, and is mainly used for adhesives for wood. It is useful as a drug.

次に本発明を実施例により説明するが、部とあるは重量
部を示す。Next, the present invention will be explained with reference to Examples, where parts and parts indicate parts by weight.

実施例１゜ 固形分４８％の常温架橋型アクリル・スチレン共重合体
エマルジョン（アクロナーｗＹＪ−２７１５Ｄ、油化パ
デイシュＫ　Ｋ製）１００部に、固形分１５％の重合度
２３００の部分ケン化ポリビニルアルコ−μ水溶液１０
０部と炭酸カルシウム１００部を添加混合し、粘度２７
，０００　ｃｐｓ／２５℃、不揮発分５３．６％の主剤
エマルジョンを得九主剤１００部に、エポキシ化合物と
してグリセリンジグリシジルエーテ／Ｉ１５部を加え実
施例１の接着剤とした。Example 1 Partially saponified polyvinyl alcohol with a degree of polymerization of 2300 and a solid content of 15% is added to 100 parts of a room-temperature crosslinking type acrylic-styrene copolymer emulsion (Acroner wYJ-2715D, manufactured by Yuka Padeish K K) with a solid content of 48%. -μ aqueous solution 10
0 parts and 100 parts of calcium carbonate were added and mixed, and the viscosity was 27.
,000 cps/25° C., a base resin emulsion with a non-volatile content of 53.6% was obtained.To 100 parts of the base resin, 15 parts of glycerin diglycidyl ether/I as an epoxy compound was added to prepare the adhesive of Example 1.

実施例２゜ 固形分４７．４％の常温架橋型アクリル系重合体ｘ　マ
Ａ／　シａ　７　（７クロナ／１／　Ｙ　Ｊ　２７３０
　Ｄ　）１００部に、固形分２０％の重合度１７００の
部分ケン化ポリビニルアルコール水溶液１００部を添加
混合し、粘度１６０００　ｃｐｓ／２５℃、不揮発分３
３％の主剤エマルジョンを体だ。Example 2゜Cross-linked acrylic polymer at room temperature with a solid content of 47.4%
D) Add and mix 100 parts of a partially saponified polyvinyl alcohol aqueous solution with a solid content of 20% and a degree of polymerization of 1700 to 100 parts, and the resulting mixture has a viscosity of 16000 cps/25°C and a non-volatile content of 3.
Use a 3% base emulsion.

主剤１００部に、エポキシ゛化合物としてエチレングリ
コ−μジグリシジルエーテ）Ｖ　３　皿’に−加え実施
例２の接着剤とした。The adhesive of Example 2 was prepared by adding ethylene glyco-μ diglycidyl ether (V 3 ) as an epoxy compound to 100 parts of the base resin.

比較例′１； 実施例１．にて、エポキシ化合物を加えない主剤エマル
ジョンのみを比較例１．の接着剤とした。Comparative example '1; Example 1. In Comparative Example 1., only the base emulsion without adding an epoxy compound was used. It was used as an adhesive.

比較例２、 実施例２．にて、ポリビニルアルコール加えないアクロ
ナールＹＪー２７３０Ｄ１００部にエポキシ化合物を３
部加え比較例２．の４ｉｊ：ｆｉｔ剤とした。Comparative Example 2, Example 2. 3 epoxy compounds were added to 100 parts of Acronal YJ-2730D without adding polyvinyl alcohol.
Part addition comparative example 2. 4ij: Used as a fit agent.

比較例３。Comparative example 3.

市販のカルボキシル基導入スチレンブタジェンヲテック
ス１００部に、エポキシ化合物（グリセリンジグリンジ
ルエーテ／Ｌ’）５部を加え比較例３。Comparative Example 3 was prepared by adding 5 parts of an epoxy compound (glycerin diglyrindyl ether/L') to 100 parts of commercially available styrene butadiene wotex introduced with a carboxyl group.

の接着剤とした。It was used as an adhesive.

各種）、主剤の２０〜２５′ｃにおける可使時間（　ｈ
　ｒ　）ｔよ第１表の如し。various types), pot life at 20-25'c of the main agent (h
r) t as shown in Table 1.

次に厚さｌＯ’＃Ｍ＊巾２５ツのカバ柾目利からなる被
５ａ体に、上記各接着剤を蹴布量２００ｇΔ？ｌ塗布し
、５公庫に塗布面にポリエチレンフ／／７レムを当て粘
着保持１＋．′ｊ間（分）を測定した。また、塗布及び
養生ＨＦｙ間５日間後の常ｒＭ接着カ、更にＪＡＳ集成
月規格に準じた６　０　’ｃの温水中に３時間浸漬後の
ぬれた状態での耐温水接着力、及び煮沸繰り返し処理後
の耐煮沸接着力を、それぞれＪＩＳＫ−６　８　５　２
に準じて圧縮せん断接着力（ｋＱ・ｆＡゎを測定した結
果を第１表に示す。Next, apply each of the above-mentioned adhesives in an amount of 200g∆∆ to the cover body 5a, which is made of square cross-section with a thickness of lO'#M*width of 25cm. Apply polyethylene film to the coated surface and hold adhesive 1+. 'j interval (minutes) was measured. In addition, the normal rM adhesion strength after 5 days of application and curing with HFy, the hot water resistant adhesive strength in a wet state after immersion in 60'C hot water for 3 hours according to the JAS Assemblage Standard, and the repeated boiling. The boiling resistant adhesive strength after treatment was determined by JISK-6 8 5 2, respectively.
Table 1 shows the results of measuring the compressive shear adhesive strength (kQ·fAゎ) according to the following.

第１表　測定結果Table 1 Measurement results

Claims (1)

【特許請求の範囲】[Claims] を有するヒドラジン誘導体を含有する常温架橋型アクリ
ル系エマルジョンとポリビニルアルコール水溶液との混
合物に、エポキシ基を分子中に２個以上含む化合物を添
加してなることを特徴とする水分散型接着剤。A water-dispersed adhesive characterized in that a compound containing two or more epoxy groups in the molecule is added to a mixture of a room-temperature crosslinkable acrylic emulsion containing a hydrazine derivative having the following formula and an aqueous polyvinyl alcohol solution.