JPS6250373A - Adhesive composition - Google Patents
Adhesive compositionInfo
- Publication number
- JPS6250373A JPS6250373A JP60189689A JP18968985A JPS6250373A JP S6250373 A JPS6250373 A JP S6250373A JP 60189689 A JP60189689 A JP 60189689A JP 18968985 A JP18968985 A JP 18968985A JP S6250373 A JPS6250373 A JP S6250373A
- Authority
- JP
- Japan
- Prior art keywords
- water
- prepolymer
- self
- aqueous
- 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
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- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は耐水性、耐熱性、安定性に優れてす・るのはも
とより、経時黄変性をも改善された水性接着剤組成物に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous adhesive composition that not only has excellent water resistance, heat resistance, and stability, but also has improved yellowing over time.
従来、木質材料、プラスチック、金属材料等の加工用接
着剤として尿素樹脂、尿素−メラミン共縮合樹脂、フェ
ノール樹脂等のホルマリン系＋！Ｉｉ脂、アクリル樹脂
、エポキシ樹脂等がその用途に応じて使用されているが
、ホルムアルデヒドの放出、樹脂価格、作業性、耐水性
、耐熱性、耐薬品性等Ｐこ回らかの欠点を有している。Traditionally, formalin-based adhesives such as urea resin, urea-melamine cocondensation resin, and phenolic resin have been used as adhesives for processing wood materials, plastics, metal materials, etc. Ii resins, acrylic resins, epoxy resins, etc. are used depending on the purpose, but they have drawbacks such as formaldehyde emission, resin price, workability, water resistance, heat resistance, chemical resistance, etc. ing.
又、低価格で非ホルマリン系の蛋白質系、酢酸ビニル系
、ゴムラテックス系、ポリビニルアルコール系等の接着
剤もあるが、耐水性に乏しく実用的でない。In addition, there are low-cost non-formalin-based adhesives such as protein-based, vinyl acetate-based, rubber latex-based, and polyvinyl alcohol-based adhesives, but they lack water resistance and are not practical.
ただし、耐水性向上の目的で上記物質の単独或いは混合
物をインシアネートとの混合系に於て使用する接着剤組
成向は公知の事実であるが、一般的にはインシアネート
使用の系は混合後の可使時間が比較的垣かく、作業性、
接着特性に悪影響を及ばずことがあると同時に、芳香族
インシアネートが使用されることが多く、その化学構造
上、ζ′丘時により接着層が黄変することを避けること
が出来ない。脂肪族インシアネート、水添化インシアネ
ート等が難黄変性であることは公知の事実であるが、水
系での使用では分散性が悪く、又毒性の面で問題が生じ
る。However, although it is a well-known fact that the above substances or a mixture thereof is used in a mixed system with incyanate for the purpose of improving water resistance, in general, systems using incyanate are used after mixing. The pot life is relatively short, the workability is
At the same time, aromatic incyanates are often used without adversely affecting the adhesive properties, and due to their chemical structure, it is impossible to avoid yellowing of the adhesive layer over time. It is a well-known fact that aliphatic incyanates, hydrogenated incyanates, etc. are resistant to yellowing, but when used in aqueous systems, they have poor dispersibility and also pose problems in terms of toxicity.
本発明者等は、鋭意研究の結果水性高分子の水散液への
インシアネート導入によって耐水性力向上するという公
知の事実を踏まえて、その状態で生じる種々の欠点をイ
ンシアヌレート環を含有するヘキサメチレンジイソシア
ネート重合体を使用することにより解決することを見出
し本発明に到達したものである。Based on the well-known fact that water resistance is improved by introducing incyanate into an aqueous dispersion of an aqueous polymer as a result of intensive research, the present inventors have determined that the various drawbacks that occur in this state can be solved by incorporating incyanurate rings. The inventors have discovered that the problem can be solved by using a hexamethylene diisocyanate polymer, and have arrived at the present invention.
即ち本発明は、
ド記１及び２の成分を混合して成る接着剤組成物
１、水溶性高分子体及び水性エマルジョンならびＰこ安
定化剤及び／又は増粘剤及び／又は充填剤を含む水分散
液
２イソノアヌレート環を含有するヘキサメチレンジイン
シアネート重合体と分子［２５０〜４０００のアルコキ
シポリフルキレングリコールを反応させて得られる末端
がイソシアネート基である自己乳化型プレポリマー
に関するものである。That is, the present invention comprises an adhesive composition 1 formed by mixing the components 1 and 2, a water-soluble polymer and an aqueous emulsion, and a stabilizer and/or thickener and/or filler. Aqueous Dispersion 2 This invention relates to a self-emulsifying prepolymer whose terminal end is an isocyanate group obtained by reacting a hexamethylene diinocyanate polymer containing an isonanurate ring with an alkoxypolyfulkylene glycol having a molecular weight of 250 to 4,000.
本発明に使用される水溶性高分子体は、ポリビニルアル
コール、水溶性エチレン酢ビ共重合体、ポリエチレンオ
ギサイド、水溶性アクリル樹脂、水溶性エポキシ樹脂、
水溶性セルロース誘導体、水溶性ポリエステル及び水溶
性リグニン誘導体等が挙げられる。The water-soluble polymers used in the present invention include polyvinyl alcohol, water-soluble ethylene vinyl acetate copolymer, polyethylene ogicide, water-soluble acrylic resin, water-soluble epoxy resin,
Examples include water-soluble cellulose derivatives, water-soluble polyesters, and water-soluble lignin derivatives.
又、本発明に使用されうる水性エマルジョンとは、いわ
ゆるラテックス、エマルジョンと表現すれるもの全てを
包含する。例えば、スチレンブタジェン共重合体ラテッ
クス、アクリルニトリル−ブタジェン共重合体ラテック
ス、メチルメタアクリレート−ブタジェン共重合体ラテ
ックス、りｐ−ブレンラテックス、ポリブタジェンラテ
ックス等のゴム系ラテックス、ポリアクリル酸エステル
ラテックス、ポリ塩化ビニリデンラテックス、ポリブタ
ジェンラテックス、或いはこれらのラテックスをカルボ
キシル変性したものなどが挙げられ、史にはポリ塩化ビ
ニルエマルジョン、ウレタンアクリルエマルジョン、シ
リコンアクリルエマルジ３ン、酢酸ビニルアクリルエマ
ルジョン、ウレタンエマルジョン、アクリルエマルジョ
ン等力列挙される。Furthermore, the aqueous emulsion that can be used in the present invention includes all so-called latexes and emulsions. For example, rubber latex such as styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, p-brene latex, polybutadiene latex, and polyacrylic acid ester latex. , polyvinylidene chloride latex, polybutadiene latex, or carboxyl-modified versions of these latexes. History includes polyvinyl chloride emulsion, urethane acrylic emulsion, silicone acrylic emulsion, vinyl acetate acrylic emulsion, and urethane. Emulsions, acrylic emulsions, etc. are enumerated.
上記組成物に耐水性を付与する目的でインシアネート化
合物を使用することは公知の事実であるが、本発明ｒこ
おいては耐水性のみならず、接着剤組成物の可使時間の
延長、耐熱性の向上、黄変性の改良等現在までこの系の
接着剤組成物として残されていた問題点を解決したこと
に大きな特徴がある。It is a well-known fact that an incyanate compound is used for the purpose of imparting water resistance to the above composition, but in the present invention, not only water resistance but also extension of pot life of the adhesive composition, A major feature of this product is that it solves the problems that remained with adhesive compositions of this type until now, such as improved heat resistance and yellowing.
インシアヌレート環を含有するヘキサメチレンジイソシ
アネートの重合体は、ヘキサメチレンジイソ／７ネート
に触媒として第３級アミン類、フルキル置換エチレンイ
ミン類、第３級アルキルホスフィン類、ア七チルアセト
ン金属塩類、各ｍ有機酸の金属塩類等を単独使用又は併
用し、必要に応じて助触媒を用い、１００℃以下でイン
シアヌレート化反応を行うことにより得ることが出来る
。The polymer of hexamethylene diisocyanate containing an incyanurate ring is prepared by adding tertiary amines, furkyl-substituted ethyleneimines, tertiary alkyl phosphines, acetyl acetone metal salts to hexamethylene diiso/septinate as a catalyst, It can be obtained by carrying out an incyanurate reaction at 100° C. or lower, using metal salts of each organic acid alone or in combination, and using a co-catalyst if necessary.
助触媒としては、フェノール性ヒト−キシ化合物、アル
コール性ヒドロキシ化合物、第３級アミン類等を必要に
応じて用いることによって反応を更に容易に進めること
が出来る。触媒は、停止剤として公知の強酸、例えばリ
ン酸、硫酸等を使用することにより不活性にすることが
出来る。The reaction can proceed more easily by using a phenolic hydroxy compound, an alcoholic hydroxy compound, a tertiary amine, or the like as a cocatalyst, if necessary. The catalyst can be made inactive by using known strong acids such as phosphoric acid, sulfuric acid, etc. as terminators.
インシアヌレート環ヲ含有するヘキサメチレンジインシ
アネート重合体と本発明で使用されるプレポリマーを構
成するアルコキシポリフルキレングリコールの分子量は
２５０〜４０００の範囲のものが使用され、特に好まし
くは６００〜２０００の範囲のものである。このプレポ
リマーは水分散後、プレポリマー粒子表面にポリウレア
保護皮膜を形成し、プレポリマーのインシアネート基と
水との反応を抑制しうる状態を保ち、安定化したインシ
アネートエマルジョンを得ることが出来る。The molecular weight of the hexamethylene diincyanate polymer containing an incyanurate ring and the alkoxypolyfulkylene glycol constituting the prepolymer used in the present invention is in the range of 250 to 4,000, particularly preferably 600 to 2,000. It's a range of things. After dispersion in water, this prepolymer forms a polyurea protective film on the surface of the prepolymer particles, maintaining a state that can inhibit the reaction between the incyanate groups of the prepolymer and water, making it possible to obtain a stabilized incyanate emulsion. .
本発明に使用されるアルコキシポリフルキレングリコー
ルの一般式はＲＩＯ＋Ｒ，ＯｉＨで示され、ここでＲ１
はアルキル基、鳥はフルキレン基であり、このアルコキ
シ基全体が非イオン性界面活性剤的な働きをするため、
自己乳化性の特徴を発揮すると考えられる。分子量が４
０００以上になると水乳化性は良好であるが、水中安定
性が悪くなると同時に、分子量４０００以上の化合物は
結晶性が高いため、得られるプレポリマー自体の低温で
の貯蔵安定性が低下し、１１等が発生する。プレポリマ
ーの製造は公知の方法で一般的には溶剤の不存在下で行
なわれ、残存ＮＧＯ含有量は１５〜２４％となる様ンこ
１傳節することが望ましい。１５％以下であると乳化時
、乳化粒子の界面層において親水性が必要以上に強くな
るため安定性が悪くなり、又高粘度となるため分散性が
劣る。２４％以上では界面層における現水性が不足する
ため、安定な乳化液が形成され難い。The general formula of the alkoxypolyfulkylene glycol used in the present invention is RIO+R, OiH, where R1
is an alkyl group, and bird is a fullylene group, and this alkoxy group as a whole acts like a nonionic surfactant, so
It is thought that it exhibits self-emulsifying characteristics. molecular weight is 4
When the molecular weight exceeds 000, the water emulsifying property is good, but the stability in water deteriorates, and at the same time, since compounds with a molecular weight of 4000 or more have high crystallinity, the storage stability of the obtained prepolymer itself at low temperatures decreases. etc. occur. Prepolymers are produced by known methods, generally in the absence of solvents, and preferably have a residual NGO content of 15 to 24%. If it is less than 15%, during emulsification, the interfacial layer of the emulsified particles will have stronger hydrophilicity than necessary, resulting in poor stability, and high viscosity, resulting in poor dispersibility. If it exceeds 24%, the water resistance in the interface layer is insufficient, making it difficult to form a stable emulsion.
本発明に使用されうる安定化剤としては、塩素化パラフ
ィンの如き・・ロゲン化炭化水素類、エチレングリコー
ルモノブチルエーテルの如きエーテル類、フタル酸エス
テル類、オレイン酸エステル類、アジピン酸エステル類
、アゼライン酸エステル・頃、ステアリン酸エステル類
、安息ａ５１ｔニスｆル類、リン酸エステル類、トリメ
リット酸エステル項、フレイン酸エステル類、フマル酸
エステル類等の如きエステル類、環式アルキレンカーボ
ネート須、第３級アミン類、非イオン性界面活性剤類等
が挙げられる。Stabilizers that can be used in the present invention include chlorogenated hydrocarbons such as chlorinated paraffins, ethers such as ethylene glycol monobutyl ether, phthalates, oleates, adipic esters, and azelain. Acid esters, stearates, benzene a51t esters, phosphoric esters, trimellitic esters, furyates, fumaric esters, etc., cyclic alkylene carbonates, etc. Examples include tertiary amines and nonionic surfactants.
増粘剤としては、小麦粉、カルホキ／メチルセルロース
、ヒドロキシエチルセルロース、ヒドロキシプロピルメ
チルセルロース等のセルロース類等が挙げられる。Examples of the thickening agent include celluloses such as wheat flour, kalhoki/methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl methyl cellulose.
充填剤としては、シリカ、タルク、木粉、クレー、ベン
トナイト、スターチ等が挙ケられ、接着剤層における樹
脂分の硬さを調整することが可能である。Examples of the filler include silica, talc, wood flour, clay, bentonite, starch, etc., and it is possible to adjust the hardness of the resin component in the adhesive layer.
ｌ１ｉＪ述の各成分の添加順序はインシアネート成分を
除いて全く自由に添加すればよい。そのことにより粘度
や接着力にはほとんど影響を与えない。The order of addition of each of the components described in 11iJ may be completely arbitrary except for the incyanate component. This has almost no effect on viscosity or adhesive strength.
インシアネート成分は水エマルジョンとして添加するが
、場合によって）１直接添加しても差つかえない。The incyanate component is added as a water emulsion, but in some cases it may also be added directly.
又、本接着剤組成物は常温接着でも充分な接着力を発現
するが、作業性、接着性及び耐水、耐熱性向上のため、
適当な加熱処理を行うことも有意義なことである。In addition, although this adhesive composition exhibits sufficient adhesive strength even when bonded at room temperature, in order to improve workability, adhesion, water resistance, and heat resistance,
It is also significant to perform appropriate heat treatment.
本発明によれば、
（ａ）へキサメチレンジイソシアネートをインシアヌレ
ート化し、遊離のへキサメチレンジイソシアネートを除
去することでその毒性を極めて減少させることが出来る
と共に、イソシアヌレート環の導入ｒこよって接着剤と
しての耐熱性を向上させることが可能になった。According to the present invention, (a) By converting hexamethylene diisocyanate into incyanurate and removing free hexamethylene diisocyanate, its toxicity can be extremely reduced, and at the same time, the isocyanurate ring is introduced. It has become possible to improve the heat resistance of the agent.
の）上記重合体を分子ｆｉ２５０〜４０００のフルコキ
ンポリアルキレングリコールで変性することで自己乳化
性を有するプレポリマーとなり極めて水系での分散性を
向上させることが可能になった。By modifying the above polymer with flucoquine polyalkylene glycol having a molecular fi of 250 to 4000, it becomes a prepolymer with self-emulsifying properties, making it possible to significantly improve the dispersibility in an aqueous system.
（Ｃ）へキサメチレンジイソシアネートはその化学構造
上、紫外線による経時黄変に対して極めてすぐれた性能
を有するため、接着剤としての黄変性を改良することが
可能になった３゜
（社）本発明に使用される自己乳化性プレポリマーの水
乳化液はプレポリマー：水＝１＝１で液温２゜℃の場合
、その可使時間は１０時間以上を有するため、接着剤の
架橋剤として使用された場合においても極めて安定性に
優れた糊液な得ることが可能になった。(C) Due to its chemical structure, hexamethylene diisocyanate has extremely excellent performance against yellowing over time due to ultraviolet rays, so it has become possible to improve yellowing as an adhesive. The water emulsion of the self-emulsifying prepolymer used in the invention has a pot life of 10 hours or more when the prepolymer:water = 1 and the liquid temperature is 2°C, so it can be used as a crosslinking agent for adhesives. It has now become possible to obtain a thickening liquid that is extremely stable even when used.
（ｅ）ホルマリン系樹脂を全く使用せず、水系であるこ
とから環境を汚染する放出物は何んら存在しない。(e) No formalin-based resin is used, and since it is water-based, there are no emissions that pollute the environment.
即ち、環境を汚染する放出物もなく、可使時間が長いこ
とから、安−ゼした状態での使用かり能になり、結果と
して基材への塗布性に優れ、且つ充分な接着力が得られ
、成形品は耐水性、耐熱性、耐黄変性及び接着強度に優
れたものとなる。That is, there are no emissions that pollute the environment, and the pot life is long, so it can be used in a frozen state, and as a result, it has excellent applicability to substrates and has sufficient adhesive strength. As a result, the molded product has excellent water resistance, heat resistance, yellowing resistance, and adhesive strength.
本接着剤組成物は殊に木質材料、プラスチック、金属材
料等の加工用接着剤として好適なものであるが、段ポー
ル用、紙用、繊維加工用としても有効なものである。This adhesive composition is particularly suitable as an adhesive for processing wood materials, plastics, metal materials, etc., but is also effective for corrugated poles, paper, and fiber processing.
次に本発明を実施例によって詳細に説明するが、本発明
はこれら実施例に限定されるものではない。EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例及び比較例ンこおける部及び％はそれぞれ重量部
及び重量％を示すものである。Parts and percentages in Examples and Comparative Examples refer to parts by weight and percentages by weight, respectively.
自己乳化型プレポリマーの製造
合成例１
コフネー）Ｅ）ｌ（インシアヌレート環を有スるヘキサ
メチレンジインシアネート重合体、日本ポリウレタン工
業製、ＮＣＯ含有ｉ ２１．０％以下同じ）この液の赤
外吸収スペクトルは、１６８０ｃｎｔ−’にインシアヌ
レート環特有の強い吸収がみられ、又２量体特有の１７
８００１１−’の吸収はまったく認められなかった。Production of self-emulsifying prepolymer Synthesis Example 1 Kohne)E)l (hexamethylene diincyanate polymer with incyanurate ring, manufactured by Nippon Polyurethane Industries, NCO content 21.0% or less) The red color of this liquid The external absorption spectrum shows a strong absorption characteristic of the incyanurate ring at 1680 cnt-', and a strong absorption characteristic of the incyanurate ring at 17 cnt-', which is characteristic of the dimer.
No absorption of 80011-' was observed.
コロネートＥＨ１００部を温度計、攪拌機、窒素シール
管を備えた５０〇−容慴合わせ直付ガラス裂４つロフラ
スコに仕込み、次いでメトキシポリエチレングリコール
（ＭＰＧ−０８１、日本乳化剤工業部）２部を加え、昇
温し、７０℃を保持しながら３時間反応させた所ｓ Ｎ
ＣＯ含有ｆｆｉ １９．８％、粘度３２００ Ｃ９８
７２５℃の淡黄色透明のインシアネート基末端プレポリ
マーを得た。このプレポリマーは自己乳化性を有してい
た。100 parts of Coronate EH was charged into a 500-capacity, direct-attached glass-slit four-glass flask equipped with a thermometer, a stirrer, and a nitrogen-sealed tube, and then 2 parts of methoxypolyethylene glycol (MPG-081, Nippon Nyukazai Kogyo Department) was added. The temperature was raised and the reaction was carried out for 3 hours while maintaining the temperature at 70°C.
CO content ffi 19.8%, viscosity 3200 C98
A pale yellow transparent incyanate group-terminated prepolymer was obtained at 725°C. This prepolymer had self-emulsifying properties.
合成例２
コロ＊ −） Ｅ Ｈ１００部を合成（Ｍｌと同様の器
具を備えた反応器に仕込み、次いでメトキシポリエチレ
ングリコール（ＭＰＧ−ｏ ：ｉ ｓ、日本乳化剤工業
部）２部を加え昇温し、７０℃を保持しながら３時間反
応させた所、ＮＧＯ含有量１９．５％、粘度３０００
Ｃｐ’８７２５℃の淡黄色透明のインシアネート基末端
プレポリマーを得た。Synthesis Example 2 100 parts of E H were charged into a reactor equipped with the same equipment as for synthesis (Ml), and then 2 parts of methoxypolyethylene glycol (MPG-O: IS, Nippon Nyukazai Kogyo Department) was added and the temperature was raised. , when reacted for 3 hours while maintaining 70°C, NGO content was 19.5% and viscosity was 3000.
A pale yellow transparent incyanate group-terminated prepolymer having a Cp' of 8725° C. was obtained.
このプレポリマーは自己乳化性を有していた。This prepolymer had self-emulsifying properties.
合成例３
温度計、攪拌機、窒素シール管を備えたＩＪ容摺合わせ
蓋付ガラス製４つロフラスコにヘキサメチレンジイソシ
アネート（ＨＤｌ、日本ポリウレタン工業製）５００部
を仕込み、次いで４０℃まで昇温した所で１．３ブタン
ジオール３８．５部を加え、更に８０℃まで昇温しで３
時間反応させた。Synthesis Example 3 500 parts of hexamethylene diisocyanate (HDl, manufactured by Nippon Polyurethane Industries) was charged into a four-bottle glass flask equipped with a thermometer, a stirrer, and a nitrogen-sealed tube with a sliding lid, and the temperature was then raised to 40°C. Add 38.5 parts of 1.3-butanediol and further raise the temperature to 80°C.
Allowed time to react.
得られた無色透明の反応液のＮＣＯ含有量を測定した所
、３９．８％であった。分子蒸溜装置により遊離のへキ
サメチレンジイソシアネートを除去した。得られた液は
淡黄色液体でＮＧＯ含有量１７．５％、粘度２７００
Ｃ１）Ｓ／２５℃、遊離のへキサメチレンジイソシアネ
ート０．４％の性状を有していた。この液の赤外吸収ス
ペクトルはインシアヌレート環特有の１６８０ ｅｘ−
”（ｒ） 強い吸収はまったく認められなかった。The NCO content of the resulting colorless and transparent reaction solution was measured and found to be 39.8%. Free hexamethylene diisocyanate was removed using a molecular distillation apparatus. The resulting liquid was a pale yellow liquid with an NGO content of 17.5% and a viscosity of 2700.
C1) S/25° C., free hexamethylene diisocyanate 0.4%. The infrared absorption spectrum of this liquid is 1680 ex-
”(r) No strong absorption was observed at all.
コノ様にして得られたヘキサメチレンジイソンアネート
変性体１００部を合成例１と同様の器具を備えた反応器
に仕込み、次いでメトキシポリエチレングリコール（Ｍ
ＰＧ−０８１，日本乳化剤工業！１４）２部を加え、昇
温し、７０℃を保持しながら３時間反応させた所、ＮＧ
Ｏ含有量１６．３％、粘度３５００ Ｃ１）８７２５℃
の淡黄色透明のインシアネート基末端プレポリマーを得
た。コノフレホナマーは自己乳化性を有していた。100 parts of the modified hexamethylene diisonanate obtained in the same manner as above was charged into a reactor equipped with the same equipment as in Synthesis Example 1, and then methoxypolyethylene glycol (M
PG-081, Japan Emulsifier Industry! 14) Added 2 parts, raised the temperature, and reacted for 3 hours while maintaining the temperature at 70°C.
O content 16.3%, viscosity 3500 C1) 8725°C
A pale yellow transparent incyanate group-terminated prepolymer was obtained. Conofrefonamer had self-emulsifying properties.
実施例１
２８％アンモニア水でＰＨ５，０に調整されたビニルア
クリル、！［合体ラテックス（ハーフレックス２０８、
ＩＣＩ社製）４０部、ポリビニルアルコール１０％水溶
液（ＰＡ−１ｓ、信ｍ化学工業製）１００部、スチレン
ブタジェン共重合体ラテックスにボール
本ゼオン製）４０部、及びタルク２５部をよく況合し、
水分散液を得た。Example 1 Vinyl acrylic whose pH was adjusted to 5.0 with 28% ammonia water! [Combined latex (Halflex 208,
(manufactured by ICI), 100 parts of a 10% polyvinyl alcohol aqueous solution (PA-1s, manufactured by Shinm Chemical Industry Co., Ltd.), 40 parts of styrene-butadiene copolymer latex (manufactured by Zeon), and 25 parts of talc were mixed in a well-balanced manner. death,
An aqueous dispersion was obtained.
この水分散液１００部に合成例１で得た自己乳化型プレ
ポリマー１５部を加え、ガラス棒で攪拌混合した所、容
易に分散した。この糊液の２５℃に於ける可使時間は１
２時間以上であった。更にこの糊液を挽板用接着剤とし
て使用し、下記の条件で接着試験（ ＪＩＳＫ６８５２
による以下同じ）を行なった。15 parts of the self-emulsifying prepolymer obtained in Synthesis Example 1 was added to 100 parts of this aqueous dispersion, and the mixture was stirred and mixed with a glass rod, resulting in easy dispersion. The pot life of this paste at 25℃ is 1
It was over 2 hours. Furthermore, this paste liquid was used as an adhesive for sawing boards, and an adhesion test (JISK6852) was conducted under the following conditions.
(hereinafter the same) was carried out.
被着材：カバ／カバ（ｔｏｅ） 圧締： １ ０ Ｋ
ｇ／ａＡＸ ２時間塗布量： ３ ０ ０ ？Ａｔ？
養生：３日以上常態接着カニ１６５４，匂
水波率 ８６％煮沸くり返し接着カニ ６ ６ Ｋｐ／
ｃｄ 水波率 ９５％耐熱接着力（ １２０ｔｌ：
ｘ ２４時間）：１７５整匈 木破率９５％実施例２
アクリルエマルジョン（ＡＥ−９４２，Ｅ本合成ゴムｆ
ｉ）６部部、ポリビニルアルコール１０％水溶液（ＰＡ
−１５、信越化学工業層） ｉｏ。Adherent material: Cover/cover (toe) Pressure: 10K
g/aAX 2 hour application amount: 3 0 0? At?
Curing: 3 days or more normally adhered crab 1654, odor
Water wave rate 86% boiling repeated adhesive crab 6 6 Kp/
cd water wave rate 95% heat resistant adhesive strength (120tl:
x 24 hours): 175 level Wood breakage rate 95% Example 2 Acrylic emulsion (AE-942, E main synthetic rubber f
i) 6 parts, 10% aqueous solution of polyvinyl alcohol (PA
-15, Shin-Etsu Chemical Layer) io.
部、スチレンブタジェン共重合体ラテックス（二ボール
２５７０Ｘ５、日本上オン４）２０部、ヒドロキシプロ
ピルメチルセルロース３％水溶液（ハイメトローズ９０
ＳＩ４−４０００．信越化学工業製）２０部、及びタル
ク２５部をよく混合し、水分散液を得た。1 part, 20 parts of styrene-butadiene copolymer latex (2-ball 2570
SI4-4000. (manufactured by Shin-Etsu Chemical Co., Ltd.) and 25 parts of talc were thoroughly mixed to obtain an aqueous dispersion.
この水分散液１００部に合成例２で得た自己乳化型フレ
ポリマー１５部を加え、ガラス棒で攪拌混合した所、容
易に分散した。この糊液の２５℃に於ける可使時間は１
２時間以上であった。更にこの糊液を挽板用接着剤とし
て使用し、実施例１と同様の条件で接着試験を行なった
。To 100 parts of this aqueous dispersion, 15 parts of the self-emulsifying Flepolymer obtained in Synthesis Example 2 was added and mixed by stirring with a glass rod, resulting in easy dispersion. The pot life of this paste at 25℃ is 1
It was over 2 hours. Furthermore, this paste liquid was used as an adhesive for sawing boards, and an adhesion test was conducted under the same conditions as in Example 1.
常態接着カニ１５８勢輸 水波率 ９０％煮沸くり返
し接着カニ６５に９／ａＪ木破率 １００％耐熱接着力
（１２０℃Ｘ２４時間）：１７０々２を水波率９８％比
較例１
実施例１の水分散液１００部に合成例３で得た自己乳化
型プレポリマー１５部を加え、ガラス棒で攪拌混合した
所容易に分散した。この糊液の２５℃に於ける可使時間
は１２時間以上であった。更にこの糊液を挽板用接着剤
として使用し、実施例１と同様の条件で接着試験を行な
った。Normal adhesive crab 158 force water wave rate 90% boiling repeated adhesion crab 65 to 9/aJ wood breakage rate 100% Heat resistant adhesive strength (120°C x 24 hours): 170 2 to water wave rate 98% Comparative example 1 Water of Example 1 15 parts of the self-emulsifying prepolymer obtained in Synthesis Example 3 was added to 100 parts of the dispersion, and the mixture was stirred and mixed with a glass rod, resulting in easy dispersion. The pot life of this size liquid at 25° C. was 12 hours or more. Furthermore, this paste liquid was used as an adhesive for sawing boards, and an adhesion test was conducted under the same conditions as in Example 1.
常態後６゛カニ】６２り殉 水波率 ８４％煮ｄＩ
８＜９返し接着カニ ４２ Ｋｐ／ａＡ 水波率 ４
０％耐熱接岩力（１２０℃Ｘ２４時間）ニア５陣４ 水
波率４８％実施例：１
アクリルエマルシ運ン（ＡＥ−９４２、日本＆ Ｆｌ−
コム＠） １００ 部、ポリビニルアルコール５％水溶
液（ＰＡ−１８、信越化学工業裏）３０部及ヒヒドロキ
シプロビルメチルセルロース１．５％水溶液（／〜イメ
トｐ−ズ９０ＳＨ−４０００、信越化学工業製）２０部
をよく混合し、水分散液を得た。この水分散液１００部
に合成例１で得た自己乳化型プレポリマー２０部を加え
、ガラス棒で攪拌混合したところ容易ンこ分散した。6゛ crab after normal state] 62 years of death water wave rate 84% boiled dI
8<9 Return adhesive crab 42 Kp/aA Water wave coefficient 4
0% heat resistant rock contact strength (120℃ x 24 hours) Near 5 groups 4 Water wave rate 48% Example: 1 Acrylic emulsion transport (AE-942, Japan & Fl-
Com@) 100 parts, 30 parts of 5% polyvinyl alcohol aqueous solution (PA-18, Shin-Etsu Chemical Co., Ltd.) and 1.5% aqueous solution of hydoxypropyl methyl cellulose (/~Imetop-Z 90SH-4000, Shin-Etsu Chemical Co., Ltd.) 20 parts were mixed well to obtain an aqueous dispersion. When 20 parts of the self-emulsifying prepolymer obtained in Synthesis Example 1 was added to 100 parts of this aqueous dispersion and mixed by stirring with a glass rod, the mixture was easily dispersed.
この糊液の２５℃に於る可使時間は１２時間以上であっ
た。更にこの糊液な白色の不織布に含浸せしめ、８０℃
で３時間乾燥させた後屋外に暴露した。９０日経過後も
何ら変色はみられなかった。The pot life of this paste at 25° C. was 12 hours or more. Furthermore, impregnate this starch liquid into a white non-woven fabric and heat it at 80°C.
After drying for 3 hours, it was exposed outdoors. No discoloration was observed even after 90 days.
比較例２
実施例３と同様の処方で糊液を調製した。但し実施例３
の自己乳化型プレポリマーの代りにトリレンジイソシア
ネートのトリメチロールプロパンアダクト体（コロネー
トし１日本ポリウレタン工業製）を２０部使用した。こ
の糊液の可使時間は２時間２０分であった。実施例３と
同様の試験を実施したところ、９０日経過後は茶褐色に
変色していた。Comparative Example 2 A glue solution was prepared using the same recipe as in Example 3. However, Example 3
Instead of the self-emulsifying prepolymer, 20 parts of a trimethylolpropane adduct of tolylene diisocyanate (Coronate 1, manufactured by Nippon Polyurethane Industries) was used. The pot life of this paste was 2 hours and 20 minutes. When the same test as in Example 3 was conducted, the color changed to brown after 90 days.
Claims (1)
化剤及び／又は増粘剤及び／又は充填剤を含む水分散液 ２、イソシアヌレート環を含有するヘキサメチレンジイ
ソシアネート重合体と分子量２５０〜４０００のアルコ
キシポリアルキレングリコールを反応させて得られる末
端がイソシアネート基である自己乳化型プレポリマー。[Claims] Adhesive composition 1 formed by mixing the following components 1 and 2, an aqueous dispersion containing a water-soluble polymer, an aqueous emulsion, and a stabilizer and/or thickener and/or filler. Liquid 2, a self-emulsifying prepolymer whose terminal end is an isocyanate group obtained by reacting a hexamethylene diisocyanate polymer containing an isocyanurate ring with an alkoxypolyalkylene glycol having a molecular weight of 250 to 4,000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60189689A JPS6250373A (en) | 1985-08-30 | 1985-08-30 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60189689A JPS6250373A (en) | 1985-08-30 | 1985-08-30 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6250373A true JPS6250373A (en) | 1987-03-05 |
| JPH0415270B2 JPH0415270B2 (en) | 1992-03-17 |
Family
ID=16245533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60189689A Granted JPS6250373A (en) | 1985-08-30 | 1985-08-30 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6250373A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0501348A2 (en) * | 1991-02-22 | 1992-09-02 | Dainippon Ink And Chemicals, Inc. | Isocyanurate ring-containing crosslinked polyurethane polyurea particulate polymer and process for producing the same |
| US5631341A (en) * | 1994-06-13 | 1997-05-20 | Nippon Polyurethane Industry Co., Ltd. | Self-emulsifiable polyisocyanate mixture and aqueous coating or adhesive composition comprising the mixture |
| US5652300A (en) * | 1995-12-11 | 1997-07-29 | Nippon Polyurethane Industry Co., Ltd. | Self-emulsifiable polyisocyanate mixture and aqueous coating or adhesive compostion comprising the mixture |
| WO2004078819A1 (en) * | 2003-03-06 | 2004-09-16 | Kyowa Hakko Chemical Co., Ltd. | Polyisocyanate composition and aqueous curing composition using same |
| JP2022530928A (en) * | 2019-03-07 | 2022-07-05 | ダウ グローバル テクノロジーズ エルエルシー | Formaldehyde-free adhesive composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101426866B (en) | 2006-04-25 | 2012-06-13 | 旭硝子株式会社 | Composition for aqueous coating material, method for producing the same, and two-component curable aqueous coating material kit |
| JPWO2012039478A1 (en) | 2010-09-24 | 2014-02-03 | 旭硝子株式会社 | Aqueous paint composition and two-component curable aqueous paint kit |
| ES2726111T3 (en) | 2012-07-09 | 2019-10-01 | Covestro Deutschland Ag | Coating and hardener procedure for polyurethane paint |
| JP6432509B2 (en) | 2013-05-27 | 2018-12-05 | Ａｇｃ株式会社 | Aqueous paint composition, aqueous paint kit and article having a coating film |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930429A (en) * | 1972-07-04 | 1974-03-18 | ||
| JPS512734A (en) * | 1974-06-28 | 1976-01-10 | Toyo Ink Mfg Co | |
| JPS5350187A (en) * | 1976-10-18 | 1978-05-08 | Asahi Chem Ind Co Ltd | Preparation of plyisocyanates |
| JPS5615418A (en) * | 1979-04-25 | 1981-02-14 | Rhone Poulenc Textile | Method and apparatus for continuously opening fiber obtained by cutting tow |
| JPS579735A (en) * | 1978-04-19 | 1982-01-19 | Int Flavors & Fragrances Inc | Manufacture of compound useful for perfume |
| JPS5747321A (en) * | 1980-09-03 | 1982-03-18 | Nippon Polyurethan Kogyo Kk | Preparation of aliphatic isocyanurate compound |
| JPS5792075A (en) * | 1980-11-28 | 1982-06-08 | Nippon Urethane Service:Kk | Polyisocyanate modified adhesive of water emulsion type |
| JPS5887173A (en) * | 1981-11-18 | 1983-05-24 | Nippon Urethane Service:Kk | Self-emulsifiable polyisocyanate-modified water-resistant adhesive |
| JPS59217779A (en) * | 1983-05-26 | 1984-12-07 | Showa Highpolymer Co Ltd | Adhesive composition of aqueous contact type |
| JPS61291613A (en) * | 1985-06-15 | 1986-12-22 | バイエル・アクチエンゲゼルシヤフト | Polyisocyanate composition and aqueous adhesive composition |
-
1985
- 1985-08-30 JP JP60189689A patent/JPS6250373A/en active Granted
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930429A (en) * | 1972-07-04 | 1974-03-18 | ||
| JPS512734A (en) * | 1974-06-28 | 1976-01-10 | Toyo Ink Mfg Co | |
| JPS5350187A (en) * | 1976-10-18 | 1978-05-08 | Asahi Chem Ind Co Ltd | Preparation of plyisocyanates |
| JPS579735A (en) * | 1978-04-19 | 1982-01-19 | Int Flavors & Fragrances Inc | Manufacture of compound useful for perfume |
| JPS5615418A (en) * | 1979-04-25 | 1981-02-14 | Rhone Poulenc Textile | Method and apparatus for continuously opening fiber obtained by cutting tow |
| JPS5747321A (en) * | 1980-09-03 | 1982-03-18 | Nippon Polyurethan Kogyo Kk | Preparation of aliphatic isocyanurate compound |
| JPS5792075A (en) * | 1980-11-28 | 1982-06-08 | Nippon Urethane Service:Kk | Polyisocyanate modified adhesive of water emulsion type |
| JPS5887173A (en) * | 1981-11-18 | 1983-05-24 | Nippon Urethane Service:Kk | Self-emulsifiable polyisocyanate-modified water-resistant adhesive |
| JPS59217779A (en) * | 1983-05-26 | 1984-12-07 | Showa Highpolymer Co Ltd | Adhesive composition of aqueous contact type |
| JPS61291613A (en) * | 1985-06-15 | 1986-12-22 | バイエル・アクチエンゲゼルシヤフト | Polyisocyanate composition and aqueous adhesive composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0501348A2 (en) * | 1991-02-22 | 1992-09-02 | Dainippon Ink And Chemicals, Inc. | Isocyanurate ring-containing crosslinked polyurethane polyurea particulate polymer and process for producing the same |
| US5631341A (en) * | 1994-06-13 | 1997-05-20 | Nippon Polyurethane Industry Co., Ltd. | Self-emulsifiable polyisocyanate mixture and aqueous coating or adhesive composition comprising the mixture |
| US5652300A (en) * | 1995-12-11 | 1997-07-29 | Nippon Polyurethane Industry Co., Ltd. | Self-emulsifiable polyisocyanate mixture and aqueous coating or adhesive compostion comprising the mixture |
| WO2004078819A1 (en) * | 2003-03-06 | 2004-09-16 | Kyowa Hakko Chemical Co., Ltd. | Polyisocyanate composition and aqueous curing composition using same |
| JP2022530928A (en) * | 2019-03-07 | 2022-07-05 | ダウ グローバル テクノロジーズ エルエルシー | Formaldehyde-free adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0415270B2 (en) | 1992-03-17 |
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