JPS6020980A - Aqueous dispersion type adhesive - Google Patents
Aqueous dispersion type adhesiveInfo
- Publication number
- JPS6020980A JPS6020980A JP12848183A JP12848183A JPS6020980A JP S6020980 A JPS6020980 A JP S6020980A JP 12848183 A JP12848183 A JP 12848183A JP 12848183 A JP12848183 A JP 12848183A JP S6020980 A JPS6020980 A JP S6020980A
- Authority
- JP
- Japan
- Prior art keywords
- group
- hydrazine
- aqueous dispersion
- dispersion type
- parts
- 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
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
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)
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12848183A JPS6020980A (en) | 1983-07-14 | 1983-07-14 | Aqueous dispersion type adhesive |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12848183A JPS6020980A (en) | 1983-07-14 | 1983-07-14 | Aqueous dispersion type adhesive |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6020980A true JPS6020980A (en) | 1985-02-02 |
JPS643916B2 JPS643916B2 (en) | 1989-01-24 |
Family
ID=14985801
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12848183A Granted JPS6020980A (en) | 1983-07-14 | 1983-07-14 | Aqueous dispersion type adhesive |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6020980A (en) |
-
1983
- 1983-07-14 JP JP12848183A patent/JPS6020980A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS643916B2 (en) | 1989-01-24 |
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