JPH08218053A - One-pack urethane-based adhesive for tile - Google Patents
One-pack urethane-based adhesive for tileInfo
- Publication number
- JPH08218053A JPH08218053A JP2176695A JP2176695A JPH08218053A JP H08218053 A JPH08218053 A JP H08218053A JP 2176695 A JP2176695 A JP 2176695A JP 2176695 A JP2176695 A JP 2176695A JP H08218053 A JPH08218053 A JP H08218053A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- pack
- urethane
- weight
- tiles
- 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.)
- Pending
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はタイル用一液型ウレタン
系接着剤に関する。更に詳しくは貯蔵安定性（粘度上
昇）に優れ、且つ低温湿潤状態のモルタル、窯業系サイ
ディング材等の下地材面への塗布性に優れ、低温時にタ
イルを張り合わせても充分な接着力立ち上がりを示し、
標準強度、温水中浸漬強度、アルカリ水中浸漬強度等の
接着諸物性に優れたタイル用一液ウレタン系接着剤に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-pack type urethane adhesive for tiles. More specifically, it has excellent storage stability (increased viscosity) and excellent coatability on the surface of base materials such as mortar and ceramic siding that are in a low temperature wet state, and shows sufficient adhesive force rise even when tiles are laminated at low temperatures. ,
The present invention relates to a one-component urethane adhesive for tiles having excellent adhesive properties such as standard strength, immersion strength in warm water, and immersion strength in alkaline water.
【０００２】[0002]
【従来の技術】タイル用接着剤はＪＩＳ Ａ−５５４８
に規格されており、その中でタイプＩグレードは、湿っ
た下地材に適用される接着剤として用途区分されてい
る。更に詳しくは、１週間水中浸浸した高含水率の下地
材とタイルの接着について規格化している。従来よりこ
のタイプＩ用接着剤としては例えば、二液型のエポキシ
系接着剤が用いられてきたが、二液混合の作業の煩雑さ
と計量ミスによる硬化不良トラブル、ポットライフが短
かい（二液配合物の使用可能時間）、低温硬化性不備、
可撓性不足や通常用いられるアミン系硬化剤による臭気
及び皮膚障害、等々の問題があった。2. Description of the Related Art An adhesive for tiles is JIS A-5548.
The Type I grade is classified as an adhesive applied to a wet base material. More specifically, the standardization is made on the adhesion between the tile and the high water content base material that has been immersed in water for one week. Conventionally, for example, a two-pack type epoxy adhesive has been used as this type I adhesive, but the complexity of the work of mixing the two liquids, the curing failure trouble due to a measurement error, and the short pot life (two liquids). Usable time of the compound), insufficient low temperature curability,
There are problems such as lack of flexibility, odor and skin damage due to commonly used amine-based curing agents.
【０００３】[0003]
【発明が解決しようとする課題】これらの問題を解決す
べく接着剤として、特開平４−１６８１８５号の明細書
に記載のごとく活性イソシアネート基含有ウレタンプレ
ポリマー（以下ＮＣＯ含有プレポリマーと略称する）に
セメントを配合したタイル用一液型ウレタン系接着剤が
提案されているが、低温湿潤面下地材との接着性には優
れるものの貯蔵時の粘度安定性、タイルとの密着性に問
題があった。また、月刊誌「接着」（１９９４年、３８
巻１２号）に記載のごとく、変性シリコーン系接着剤に
更にエポキシ樹脂で変性した接着剤の提案がなされてい
るが、接着諸物性的には満足されるものの、汎用の建築
資材用接着剤と比較した場合極めて高価のため、経済性
面の問題を抱えている。To solve these problems, as an adhesive, an active isocyanate group-containing urethane prepolymer (hereinafter abbreviated as NCO-containing prepolymer) as described in the specification of JP-A-4-168185. Although a one-component urethane adhesive for tiles has been proposed that contains cement as a cement, it has excellent adhesiveness with low temperature wet surface base materials, but it has problems in viscosity stability during storage and adhesion with tiles. It was In addition, the monthly magazine “Adhesion” (1994, 38
As described in Vol. 12), there has been proposed an adhesive obtained by further modifying a modified silicone adhesive with an epoxy resin. However, although it is satisfactory in various adhesive properties, it is a general-purpose adhesive for building materials. It is extremely expensive when compared, and has economic problems.
【０００４】[0004]
【課題を解決するための手段】本発明者らはかかる問題
を解決するべく、ＪＩＳ Ａ−５５４８規格に適合する
タイプ１の新規なタイル用接着剤を開発するために鋭意
検討した結果、ＮＣＯ含有プレポリマーに含水率が０．
１重量％未満の充填剤及び揺変剤、可塑剤、硬化促進
剤、並びにアミノ系及びグリシジル系シランカップリン
グ剤を配合することで、前記二液型のポキシ系接着剤
や、タイル用一液型ウレタン系接着剤、エポキシ樹脂を
配合した変性シリコーン系接着剤見られる前記諸問題を
解決し、低温湿潤下地面への塗布性に優れ、低温時にタ
イルを張り合わせても充分な接着力立ち上がりを示し、
前記の接着諸物性にも優れる事を見い出し本発明を完成
させるに至った。The inventors of the present invention have conducted extensive studies to develop a new type 1 tile adhesive that conforms to JIS A-5548 standard in order to solve such a problem. The prepolymer has a water content of 0.
By blending less than 1% by weight of a filler and a thixotropic agent, a plasticizer, a curing accelerator, and an amino-based and glycidyl-based silane coupling agent, the two-pack type poxy-based adhesive and one liquid for tiles. -Type urethane adhesives, modified silicone adhesives containing epoxy resin solved the above-mentioned problems, excellent in coating properties on low temperature wet base surface, and shows sufficient adhesive force rise even when tiles are stuck at low temperature ,
The inventors have found that the above-mentioned various adhesive properties are also excellent, and have completed the present invention.
【０００５】即ち本発明は １．ポリオールと過剰のポリイソシアネート化合物を反
応させて得られるＮＣＯ含有プレポリマーに、含水率
０．１重量％未満の充填剤及び揺変剤、可塑剤、硬化促
進剤、並びにアミノ系及びグリシジル系シランカップリ
ング剤を配合して成ることを特徴とするタイル用一液型
ウレタン系接着剤 ２．ＮＣＯ含有プレポリマー１００重量部に対して、ア
ミノ系及びグリシジル系シランカップリング剤を各々
０．０５〜３．０重量部配合して成ることを特徴とする
請求項第１項記載のタイル用一液型ウレタン系接着剤 である。That is, the present invention is: A NCO-containing prepolymer obtained by reacting a polyol with an excess of a polyisocyanate compound, a filler and a thixotropic agent having a water content of less than 0.1% by weight, a plasticizer, a curing accelerator, and an amino-based and glycidyl-based silane cup. A one-component urethane adhesive for tiles, which is characterized by being mixed with a ring agent. The tile composition according to claim 1, wherein the amino-based and glycidyl-based silane coupling agents are each mixed in an amount of 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the NCO-containing prepolymer. It is a liquid urethane adhesive.
【０００６】本発明に用いるポリオールとしては、ポリ
エーテルポリオール例えばエチレングリコール、プロピ
レングリコール、ブチレングリコール等のジオール類、
グリセリン、トリメチロールプロパン等のトリオール
類、アンモニア、エチレンジアミン等のアミン類の１種
または２種以上の存在下にプロピレンオキサイド及び、
又はエチレンオキサイドを開環重合させて得られるラン
ダムまたはブロック共重合体、ポリエステルポリオール
としてはエチレングリコール、プロピレングリコール、
１，４ブタンジオール、オオペンチルグリコールの存在
下にアジピン酸、セバチン酸、テレフタル酸等を重縮合
させて得られる共重合体、ε−カプロラクトン、パレロ
ラクトンの開環重合で得られるもの、ビスフェノール
Ａ、ヒマシ油等の活性水素基２個以上を有する低分子活
性水素化合物が挙げられ、通常分子量１００〜７００
０、１分子中のヒドロキシル基（０Ｈ）２〜４のものが
使用できる。これらの内分子量５００〜５０００のポリ
オキシプロピレンジオール及びポリオキシプロピレント
リオールの単独もしくは併用が経済性、アルカリ水中浸
漬強度面から好ましい。As the polyol used in the present invention, polyether polyols such as diols such as ethylene glycol, propylene glycol and butylene glycol,
Propylene oxide in the presence of one or more triols such as glycerin and trimethylolpropane, amines such as ammonia and ethylenediamine, and
Or random or block copolymer obtained by ring-opening polymerization of ethylene oxide, as the polyester polyol, ethylene glycol, propylene glycol,
Copolymers obtained by polycondensation of adipic acid, sebacic acid, terephthalic acid and the like in the presence of 1,4 butanediol and opentyl glycol, ε-caprolactone, those obtained by ring-opening polymerization of parerolactone, bisphenol A, Examples include low molecular weight active hydrogen compounds having two or more active hydrogen groups such as castor oil, and usually have a molecular weight of 100 to 700.
Those having hydroxyl groups (0H) 2 to 4 in 0, 1 molecule can be used. These polyoxypropylene diols and polyoxypropylene triols having an internal molecular weight of 500 to 5,000 are preferably used alone or in combination from the viewpoint of economic efficiency and immersion strength in alkaline water.
【０００７】本発明に用いるポリイソシアネート化合物
としては、例えばヘキサメチレンジイソシアネート（Ｈ
ＤＩ）、リジンメチルエステルジイソシアネート等の脂
肪族ポリイソシアネート類、水添ジフェニルメタンジイ
ソシアネート、イソホロンジイソシアネート、水添トリ
レンジイソシアネート等の脂環式ポリイソシアネート
類、ジフェニルメタンジイソシアネート（ＭＤＩ）、ト
リレンジイソシアネート（ＴＤＩ）、ナフタレンジイソ
シアネート等の芳香族イソシアネート類、及びこれらの
混合物が挙げられる。これらのうち毒性や価格面よりＭ
ＤＩの使用が好ましい。Examples of the polyisocyanate compound used in the present invention include hexamethylene diisocyanate (H
DI), aliphatic polyisocyanates such as lysine methyl ester diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, alicyclic polyisocyanates such as hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), Aromatic isocyanates such as naphthalene diisocyanate, and mixtures thereof. Of these, M
The use of DI is preferred.
【０００８】前記ポリオールと過剰のポリイソシアネー
ト化合物を反応させてＮＣＯ含有プレポリマーが得られ
る。具体的にはＮＣＯ含有プレポリマーは、ＯＨを２個
以上を有するポリオールとイソシアネート基（ＮＣＯ）
を２個以上有するポリイソシアネート化合物をイソシア
ネート基が過剰となるように、即ちＮＣＯ／ＯＨ等量比
が１より大となるようにする。例えば２．０≦ＮＣＯ／
ＯＨ≦１５．０の割合にて、窒素又はドライエアー気流
中で７０〜１００℃の温度条件下で数時間反応させるこ
とにより製造され、通常のＮＣＯ含有量は２〜２５％
（重量％、以下同様）の範囲であり、好ましくは５〜１
５％の範囲である。同一分子量ポリオールを用いてＮＣ
Ｏ含有量を低く設定すると、ＮＣＯ含有プレポリマーの
硬化物は柔軟性を呈し、逆に多く設定すると硬質で脆く
なる。An NCO-containing prepolymer is obtained by reacting the above-mentioned polyol with an excess polyisocyanate compound. Specifically, the NCO-containing prepolymer includes a polyol having two or more OH and an isocyanate group (NCO).
The polyisocyanate compound having two or more of is adjusted so that the isocyanate group becomes excessive, that is, the NCO / OH equivalent ratio is greater than 1. For example 2.0 ≦ NCO /
Produced by reacting at a ratio of OH ≦ 15.0 in a nitrogen or dry air stream under a temperature condition of 70 to 100 ° C. for several hours, and a normal NCO content is 2 to 25%.
(% By weight, the same applies hereinafter), preferably 5 to 1
It is in the range of 5%. NC using same molecular weight polyol
If the O content is set low, the cured product of the NCO-containing prepolymer exhibits flexibility, and conversely, if it is set high, it becomes hard and brittle.
【０００９】本発明で用いる含水率が０．１重量％の充
填剤は、原石を焼成後直ちに防湿袋に包装したもので含
水率が０．１％未満のもの、もしくは別途１００〜１５
０℃乾燥機等で含水率を０．１％未満に調整された、例
えばクレー、タルク、炭酸カルシウム、ケイ砂、スレー
ト粉、マイカ、生石灰等の平均粒径１〜３００μの無機
充填剤を意味する。含水率が０．１％を超えるものを用
いた場合、製造時の粘度が高粘度化し、且つ経時による
粘度上昇が顕しく、更にはアミノ系及びグリシジル系シ
ランカップリング剤が加水分解を起こし、接着力を著し
く低下させる。これらの内ち経済性面より重質炭酸カル
シウムが好ましい。本炭酸カルシウムは接着剤としての
適正粘度面から比較的平均粒子径の大きなもの１種、も
しくは粒径の異なるものを二種以上の配合が好ましい。The filler having a water content of 0.1% by weight used in the present invention is a raw stone packed in a moisture-proof bag immediately after firing and having a water content of less than 0.1%, or separately 100 to 15
An inorganic filler having an average particle size of 1 to 300 μ, such as clay, talc, calcium carbonate, silica sand, slate powder, mica, quicklime, etc., whose water content is adjusted to less than 0.1% by a 0 ° C. dryer or the like. To do. When a water content of more than 0.1% is used, the viscosity at the time of production becomes high, and the viscosity increases with time, and further, the amino-based and glycidyl-based silane coupling agents cause hydrolysis, Remarkably reduces the adhesive strength. Of these, ground calcium carbonate is preferred from the economical aspect. From the viewpoint of proper viscosity as an adhesive, it is preferable to use one kind of calcium carbonate having a relatively large average particle diameter or two or more kinds of calcium carbonate having different particle diameters.
【００１０】充填剤の配合量はＮＣＯ含有プレポリマー
１００重量部に対して、３０〜２５０重量％、好ましく
は５０〜２００重量％の範囲である。３０重量％未満で
あると揺変性付与及び接着力向上効果に欠け経済性にも
欠ける。２５０重量％を超えると製造時の粘度上昇が著
しく、接着剤取扱時の作業性に支障をきたし、接着力も
低下の傾向にある。充填剤は通常予め製造したＮＣＯ含
有プレポリマーにプラネタリーミキサー等を用い撹拌混
合するが、乾燥により含水率０．１％未満の調整が困難
の場合は、充填剤と共に水分見合い分のイソシアネート
化合物を過剰に仕込み、ポリオールと反応させてＮＣＯ
含有プレポリマーを製造しても良い。The content of the filler is 30 to 250% by weight, preferably 50 to 200% by weight, based on 100 parts by weight of the NCO-containing prepolymer. If it is less than 30% by weight, the effects of imparting thixotropy and improving the adhesive strength are lacking, and the economical efficiency is also poor. If it exceeds 250% by weight, the viscosity at the time of production will remarkably increase, which will hinder the workability during handling of the adhesive and tend to lower the adhesive strength. The filler is usually agitated and mixed with a pre-produced NCO-containing prepolymer using a planetary mixer or the like. However, when it is difficult to adjust the water content to less than 0.1% by drying, an isocyanate compound of a moisture proportion is used together with the filler. Excessly charged and reacted with polyol to produce NCO
The containing prepolymer may be prepared.
【００１１】本発明で配合する揺変剤は、含水率０．１
％未満に調整されたシリカ粉、石綿粉等の無機揺変剤を
始め、含水率が０、１重量％未満である有機ベントナイ
ト、変性ポリエステルポリオール、ポリ塩化ビニル粉
末、ヒマシ油脂肪酸系等の有機揺変剤が挙げられる。中
でも少量で揺変性付与効果の大きいシリカ粉が好まし
い。揺変剤の配合量はＮＣＯ含有プレポリマー１００重
量部に対して０〜２５重量％の範囲であり、好ましくは
０．１〜１５重量％の範囲で用いれば良い。２５重量％
を超えると製造時の粘度が高粘度化し、塗布時の作業性
に支障をきたしまた、シリカ粉は高価なため経済性にも
欠ける。揺変剤の含水率が０．１重量％を超える場合は
前記充填剤同様の粘度安定性の低下及び、シランカップ
リング剤の加水分解による接着力低下を起こし問題とな
る。The thixotropic agent compounded in the present invention has a water content of 0.1.
Inorganic thixotropic agents such as silica powder and asbestos powder adjusted to less than 10%, organic bentonite with a water content of 0, less than 1% by weight, modified polyester polyol, polyvinyl chloride powder, castor oil fatty acid-based organic Examples include thixotropic agents. Among them, silica powder having a small thixotropic effect is large is preferable. The blending amount of the thixotropic agent is 0 to 25% by weight, preferably 0.1 to 15% by weight, based on 100 parts by weight of the NCO-containing prepolymer. 25% by weight
When it exceeds, the viscosity at the time of production becomes high, and the workability at the time of coating is hindered, and the silica powder is expensive, so that it is not economical. If the water content of the thixotropic agent exceeds 0.1% by weight, the viscosity stability is lowered as in the above-mentioned filler and the adhesive strength is lowered due to hydrolysis of the silane coupling agent, which causes a problem.
【００１２】本発明に用いる可塑剤としてはジメチルフ
タレート、ジエチルフタレート、ジブチルフタレート、
ジオクチルフタレート、ジ−ｎ−オクチルフタレート等
のフタル酸誘導体、ジ−ｎ−ブチルアジペート、ジオク
チルアジペートジイソデシルアジペート等のアジピン酸
誘導体、ジオクチルアゼレート、ジイソオクチルアゼレ
ート、等のアゼライン酸誘導体の他、イソフタル酸誘導
体、セバシン酸誘導体、マレイン酸誘導体、フマル酸誘
導体、オレイン酸誘導体、リシノール酸誘導体、ステア
リン酸誘導体、エポキシ誘導体、ポリエステル重合型可
塑剤、石油炭化水素系可塑剤等が挙げられる。これらの
中ＮＣＯ含有プレポリマーとの相溶性、接着剤の低粘度
高揺変性付与、低臭気、更には経済性面からジオクチル
フタレート、ジオクチルアジペート、石油炭化水素系可
塑剤から選ばれた１種もしくは２種以上の配合が好まし
い。本可塑剤の配合量は、接着剤として塗布に支障のな
い粘度及び揺変性付与を目的として用いるため特に限定
するものではない。Examples of the plasticizer used in the present invention include dimethyl phthalate, diethyl phthalate, dibutyl phthalate,
In addition to phthalic acid derivatives such as dioctyl phthalate and di-n-octyl phthalate, adipic acid derivatives such as di-n-butyl adipate and dioctyl adipate diisodecyl adipate, and azelaic acid derivatives such as dioctyl azelate and diisooctyl azelate. Examples thereof include isophthalic acid derivative, sebacic acid derivative, maleic acid derivative, fumaric acid derivative, oleic acid derivative, ricinoleic acid derivative, stearic acid derivative, epoxy derivative, polyester polymerization type plasticizer and petroleum hydrocarbon type plasticizer. Among these, one selected from dioctyl phthalate, dioctyl adipate, and petroleum hydrocarbon-based plasticizers in view of compatibility with NCO-containing prepolymers, low viscosity and high thixotropic impartation of adhesives, low odor, and economical efficiency, or A combination of two or more kinds is preferable. The blending amount of the present plasticizer is not particularly limited because it is used as an adhesive for the purpose of imparting viscosity and thixotropy that do not hinder application.
【００１３】本発明に用いる硬化促進剤は、一般にウレ
タン樹脂の硬化剤として用いられているジブチル錫ジラ
ウレート（ＤＢＴＤＬ）、オクチル酸鉛等の有機金属塩
や、アミン系硬化促進剤が挙げられる。これらの内貯蔵
時の粘度安定性からＤＢＴＤＬが最も好ましい。硬化促
進剤の量は特に限定するものではないが、四季を通じい
ずれの気象条件下でも支障なく使用可能な配合量は、Ｎ
ＣＯ含有プレポリマー１００重量部に対して０．０５〜
０．２０重量％の範囲であり、好ましくは０．０８〜
０．１２重量％の範囲である。０．０５重量％未満の場
合は冬季の接着力立ち上がりが遅くなり、０．２０重量
％を超えると夏期の可使時間、即ちタイル張り付け可能
時間が極端に短くなり、作業性に支障をきたす。Examples of the curing accelerator used in the present invention include organic metal salts such as dibutyltin dilaurate (DBTDL) and lead octylate which are generally used as curing agents for urethane resins, and amine curing accelerators. Of these, DBTDL is most preferable because of its viscosity stability during storage. The amount of the curing accelerator is not particularly limited, but the compounding amount that can be used without any problem under any weather condition throughout the four seasons is N
0.05 to 100 parts by weight of the CO-containing prepolymer
It is in the range of 0.20% by weight, preferably 0.08-
It is in the range of 0.12% by weight. If it is less than 0.05% by weight, the adhesive strength rises slowly in winter, and if it exceeds 0.20% by weight, the pot life in summer, that is, the tileable time becomes extremely short, and workability is impaired.
【００１４】本発明のアミノ系シランカップリング剤と
しては、例えばビス（トリメトキシシリルプロピル）シ
ラン、γ−Ｎ−フェニルアミノプロピルトリメトキシシ
ラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリ
メトキシシラン、Ｎ−β（アミンエチル）γ−アミノプ
ロピルメチルジメトキシシラン、γ−アミノプロピルト
リエトキシシラン、γ−アミノプロピルトリメトキシシ
ラン、γ−アミノプロピル−メチルジエトキシシラン等
が挙げられ、これらの内低温接着時のタイルと密着性よ
りトリメトキシシラン系が優れ、具体的にはγ−アミノ
プロピルトリメトキシシランが好ましい。Examples of the amino silane coupling agent of the present invention include bis (trimethoxysilylpropyl) silane, γ-N-phenylaminopropyltrimethoxysilane and N-β (aminoethyl) γ-aminopropyltrimethoxysilane. , N-β (amine ethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-methyldiethoxysilane and the like, and low temperature adhesion among them A trimethoxysilane type is superior in adhesiveness to the tile at the time, and specifically, γ-aminopropyltrimethoxysilane is preferable.
【００１５】本発明のグリシジル系シランカップリング
剤としてはγ−（β、４エポキシシクロヘキシル）エチ
ルトリエトキシシラン、γ−グリシドキシプロピルトリ
メトキシシラン、γ−グリシドキシプロピルメチルジエ
トキシシラン等が挙げられ、これらの内、耐温水性、耐
熱性、アルカリ水中浸漬強度面よりγ−グリシドキシプ
ロピルトリメトキシシランが好ましい。Examples of the glycidyl silane coupling agent of the present invention include γ- (β, 4 epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like. Of these, γ-glycidoxypropyltrimethoxysilane is preferable from the viewpoint of hot water resistance, heat resistance, and immersion strength in alkaline water.
【００１６】本発明は、これらアミノ系及びグリシジル
系シランカップリング剤の併用が必須で、ちなみにアミ
ノ系のみを単独で用いた場合、低温接着時のタイルとの
密着性、即ち標準状態での接着力には優れるもの耐温水
性、耐熱性、アルカリ水中浸漬強度の低下が著しい。一
方、グリシジル系を単独で用いた場合、アミノ系とは全
く逆に耐温水性、耐熱性、アルカリ水中浸漬強度は優れ
るものの、低温接着時のタイルとの密着性に欠け、接着
力の値は得られるもののタイル界面から剥離する傾向が
増し問題となる。この相反する特性は両者の併用により
克服される。In the present invention, it is essential to use these amino-based and glycidyl-based silane coupling agents in combination. By the way, when only the amino-based silane coupling agent is used alone, the adhesion to the tile at low temperature bonding, that is, the bonding in the standard state It excels in strength, but its hot water resistance, heat resistance, and immersion strength in alkaline water are significantly reduced. On the other hand, when the glycidyl type is used alone, it is completely opposite to the amino type in hot water resistance, heat resistance, and is excellent in alkaline water immersion strength, but lacks in adhesion to tiles at low temperature adhesion, and the value of adhesive strength is The obtained product becomes more problematic because it tends to peel from the tile interface. This contradictory characteristic is overcome by using both in combination.
【００１７】これらアミノ系及びグリシジル系シランカ
ップリング剤の配合量は、ＮＣＯ含有プレポリマー１０
０重量部に対して各々０．０５〜３．０重量％の範囲で
等量用いると良い。更に好ましくは０．５〜１．０重量
％の範囲である。０、０５重量％未満の場合、低温接着
時のタイルとの密着性はもとより、耐温水性、耐熱性、
アルカリ水中浸漬強度の向上が認められず、３．０重量
％を超えるとアミノ系シランカップリング剤のアミノ基
とＮＣＯの反応に基づく増粘及び経済性から問題とな
る。The blending amount of these amino-based and glycidyl-based silane coupling agents is such that the NCO-containing prepolymer 10
It is preferable to use the same amount in the range of 0.05 to 3.0% by weight with respect to 0 parts by weight. More preferably, it is in the range of 0.5 to 1.0% by weight. When it is less than 0.05% by weight, not only the adhesion to the tile at low temperature adhesion but also the hot water resistance and heat resistance,
No improvement in the immersion strength in alkaline water was observed, and if it exceeds 3.0% by weight, there is a problem from the viewpoint of thickening and economical efficiency due to the reaction between the amino group of the amino silane coupling agent and NCO.
【００１８】具体的なアミノ系及びグリシジル系シラン
カップリング剤の使用方法は、先ず、ＮＣＯ含有プレポ
リマーと充填剤を撹拌混合し、アミノ系シランカップリ
ング剤を配合し、約４０℃の温度条件で１５〜３０分間
撹拌混合させＮＣＯ含有プレポリマーとアミノ系シラン
カップリング剤を反応させる。次いで揺変剤、可塑剤、
硬化促進剤を仕込んだ後とグリシジル系シランカップリ
ング剤を仕込むと良い。The specific method for using the amino-based and glycidyl-based silane coupling agents is as follows. First, the NCO-containing prepolymer and the filler are mixed with stirring, the amino-based silane coupling agent is blended, and the temperature condition of about 40 ° C. The mixture is stirred and mixed for 15 to 30 minutes to react the NCO-containing prepolymer with the amino-based silane coupling agent. Then thixotropic agent, plasticizer,
It is advisable to charge the glycidyl silane coupling agent after charging the curing accelerator.
【００１９】以上の構成から成る本発明のタイル用一液
型ウレタン系接着剤は、モルタル、石綿スレート（フレ
キブシルボード）、窯業系サイディング材、ケイカル
板、合板等の下地材と磁器質、陶器質、石器質等のタイ
ルを張り合わせるのに使用され、その他合板同士、ハー
ドボード等の木質板と木材及びプラスチック、金属板と
タイル等の接着剤としても使用できる。従来の二液型エ
ポキシ系接着剤のごとく混合不良や皮膚かぶれ等の問題
がなく、貯蔵安定性を始めとし、低温湿潤下地面への塗
布性に優れ、低温時にタイルを張り合わせても充分な接
着力立ち上がりを示し、耐温水性、アルカリ水中浸漬強
度、耐熱性等ＪＩＳ Ａー５５４８規格に充分適合し得
る極めて有用なタイル用接着剤である。The one-component urethane adhesive for tiles of the present invention having the above-mentioned constitution is a mortar, an asbestos slate (flexible sill board), a ceramic siding material, a calcareous board, a base material such as plywood, and a porcelain, It is used to bond tiles of pottery, stone, etc., and can also be used as an adhesive for plywood, wood board such as hard board and wood, plastic, metal board and tile. It does not have problems such as poor mixing and skin irritation unlike conventional two-component epoxy adhesives, and has excellent storage stability and applicability to low temperature wet base surfaces, and sufficient adhesion even when tiles are stuck at low temperatures. It is an extremely useful adhesive for tiles that exhibits a strength rise and is sufficiently compatible with JIS A-5548 standards such as hot water resistance, immersion strength in alkaline water, and heat resistance.
【００２０】[0020]
【実施例】以下に実施例及び比較例を挙げて本発明を更
に詳しく説明するが、本発明はこれに限定されるもので
はない。また、特に限定のない限り部は重量部を意味す
る。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, unless otherwise specified, parts mean parts by weight.
【００２１】実施例１〜５及び比較例１〜５ プラネタリーミキサーに表１及び表２に掲載している所
定量のポリオキシプロピレンジオール又はポリオキシプ
ロピレントリオール及びこれらの混合物に、４，４’−
ジフェニルメタンジイソシアネートを加え８５℃にて２
時間反応せしめ、４０℃以下冷却しＮＣＯ基含有ウレタ
ンプレポリマーを得る。Examples 1-5 and Comparative Examples 1-5 In a planetary mixer, 4,4 'was added to a predetermined amount of polyoxypropylene diol or polyoxypropylene triol listed in Tables 1 and 2 and mixtures thereof. −
Add diphenylmethane diisocyanate to 2 at 85 ℃
After reacting for a period of time and cooling to 40 ° C. or lower, an NCO group-containing urethane prepolymer is obtained.
【００２２】別途プラネタリーミキサーに表１及び表２
に示した割合のＮＣＯ含有プレポリマーと充填剤を仕込
み、窒素シール下で４０℃に保温し１５分間撹拌混合す
る。次いでアミノ系シランカップリング剤を仕込み、同
温度条件で３０分間撹拌混合しＮＣＯ含有プレポリマー
とアミノ系シランカップリング剤を反応させる。引き続
き揺変剤を仕込み３０分、粘度調整用の可塑剤を仕込み
３０分間撹拌混合後、所定の粘度範囲であることを確認
し、硬化促進剤、グリシジル系シランカップリング剤の
順で仕込み１５分混合後、７００ｍｍＨｇ以上で真空脱
泡を行ない本発明のタイル用一液ウレタン系接着剤を調
整した。本接着剤の粘度は３５０〜４００ポイズ（ＥＨ
型粘度計Ｎｏ３コーン１０ｒｐｍ／２５℃）、揺変性
（１ｒｐｍ／１０ｒｐｍ粘度比）５〜１０であった。A separate planetary mixer is provided in Tables 1 and 2.
The NCO-containing prepolymer and the filler in the proportions shown in 1 are charged, and the mixture is kept at 40 ° C. under a nitrogen blanket and stirred and mixed for 15 minutes. Next, an amino-based silane coupling agent is charged, and the mixture is stirred and mixed under the same temperature condition for 30 minutes to react the NCO-containing prepolymer with the amino-based silane coupling agent. Then, a thixotropic agent was charged for 30 minutes, a viscosity-adjusting plasticizer was charged for 30 minutes, and the mixture was stirred and mixed. After confirming that the viscosity was within a predetermined range, a curing accelerator and a glycidyl silane coupling agent were charged in this order for 15 minutes. After mixing, vacuum degassing was performed at 700 mmHg or more to prepare the one-pack urethane adhesive for tiles of the present invention. The viscosity of this adhesive is 350-400 poise (EH
Type viscometer No. 3 cone 10 rpm / 25 ° C.), and thixotropic (1 rpm / 10 rpm viscosity ratio) were 5 to 10.
【００２３】実施例及び比較例にて製造した本発明のタ
イル用接着剤をＪＩＳ Ａ−５５４８に規定された下記
試験に供し、その評価結果を表１及び表２に示した。 １） 接着強さ（ＪＩＳ Ａ−５５４８に準じた評価） ＪＩＳ Ａ−５５４８の接着強さ測定方法に準じ、１週
間水中浸漬した高含水率モルタルに、ＪＩＳ Ｇ−３１
０１に規定された標準くし目ごてを用いて塗布し、各条
件で２０分間の待ち時間をとり、４×４ｃｍに切断した
磁器質タイル（（株）ＩＮＡＸ製、商品名セラロング）
を張り合わせ、各試験方法に則り、インテスコ引張試験
機（３ｍｍ／ｍｉｎ）にて接着強さを測定し、ｋｇ／ｃ
ｍ2 で表示すると共に、破壊状態を下記のごとく表示し
た。 Ａ −接着剤の凝集破壊（モルタル及びタイルとの密着
性良好） Ｇ −モルタル下地材の破壊（ 同上 ） ＡＢ−接着剤とタイルの界面剥離（タイルとの密着性に
欠ける） ＧＡ−モルタル板と接着剤の界面剥離（モルタルとの密
着性に欠け好ましくない）The tile adhesives of the present invention produced in Examples and Comparative Examples were subjected to the following tests specified in JIS A-5548, and the evaluation results are shown in Tables 1 and 2. 1) Adhesive strength (evaluation according to JIS A-5548) According to the adhesive strength measuring method of JIS A-5548, JIS G-31 was used for a high water content mortar immersed in water for 1 week.
Porcelain tiles (made by INAX Co., Ltd., trade name CERALONG) that were applied using a standard comb iron specified in 01, waited for 20 minutes under each condition, and cut into 4 x 4 cm.
And the adhesive strength is measured with an Intesco tensile tester (3 mm / min) according to each test method, and kg / c
In addition to displaying in m 2 , the state of destruction was displayed as follows. A-Cohesive failure of adhesive (good adhesion to mortar and tile) G-Destruction of mortar base material (same as above) AB-Peeling interface between adhesive and tile (lacking adhesion to tile) GA-Mortar board Interfacial peeling of adhesive (lack of adhesion to mortar and not desirable)
【００２４】標準強度：ＪＩＳ Ａ−５５４８の６５％
ＲＨにて１週間養生後測定。 温水：ＪＩＳ Ａ−５５４８の接着強さ測定方法に準
じ、タイル張り合わせ後５℃１週間養生後、５０℃温水
浸漬２４時間浸漬後測定した。 アルカリ水中：ＪＩＳ Ａ−５５４８の接着強さ測定方
法に準じ、２０℃６５％ＲＨにて１週間養生後、水酸化
カルシウム飽和水溶液浸漬４８時間後測定した。 低温硬化性（ＪＩＳ Ａ−５５４８規格の６７２時間を
下記に短縮）：タイル張り合わせ後、５℃９０％ＲＨ以
上の湿潤状態にて４８時間養生後測定した。 熱劣化：ＪＩＳ Ａ−５５４８の６５％ＲＨにて１週間
養生品を、６０±２℃乾燥機に６７２時間放置後測定し
た。Standard strength: 65% of JIS A-5548
Measured at RH for 1 week. Hot water: In accordance with the adhesive strength measuring method of JIS A-5548, after tile bonding, curing was performed at 5 ° C for 1 week, then immersed in warm water at 50 ° C for 24 hours, and measured. Alkaline water: According to the adhesive strength measuring method of JIS A-5548, it was cured at 20 ° C. and 65% RH for 1 week and then immersed in a saturated aqueous solution of calcium hydroxide for 48 hours, and then measured. Low temperature curability (672 hours of JIS A-5548 standard is shortened to the following): After tile bonding, it was measured after curing for 48 hours in a wet state at 5 ° C. and 90% RH or higher. Heat deterioration: Measured at 65% RH of JIS A-5548 for 1 week after allowing the cured product to stand in a dryer at 60 ± 2 ° C. for 672 hours.
【００２５】２）貯蔵安定性 ５０℃恒温室に２週間放置後の初期粘度に対する粘度上
昇率で下記のごとく表示した。 ○−粘度の上昇変化率０〜２０％ △− 〃 ２１〜４０％ ×− 〃 ４１％以上 ３）タイルのずれ抵抗性 ＪＩＳ Ａ−５５４８のずれ抵抗性試験方法に準じ、２
０℃６５％ＲＨにて、各接着剤をスレート板にＪＩＳ
Ｇ−３１０１に規定された標準くし目ごてを用いて塗布
し、１００ｍｍ角のタイルを張り合わせ質量５ｋｇのお
もりを載せた後、直ちにに試験体を垂直に立てずれ長さ
を測定した。 ４）可使時間 ＪＩＳ Ａ−５５４８の接着強さ測定方法に準じ、１週
間水中浸漬した高含水率モルタルに、ＪＩＳ Ｇ−３１
０１に規定された標準くし目ごてを用いて塗布し、２０
℃６５％ＲＨにての標準接着強さを満足する（６ｋｇ／
ｃｍ2 ）最長の時間で表示した。 例：２０分表示は塗布後２０分以上経過させタイルを張
り合わせた場合、ＪＩＳＡ−５５４８規格値を満足しな
いことを示し、最低３０分以上の可使時間が要求され
る。2) Storage stability The viscosity increase rate relative to the initial viscosity after standing in a thermostatic chamber at 50 ° C. for 2 weeks is shown as follows. ○ -Rise change rate of viscosity 0 to 20% △ -〃 21-40% × -〃 41% or more 3) Tile shift resistance According to the JIS A-5548 shift resistance test method, 2
Each adhesive is applied to the slate plate according to JIS at 0 ° C and 65% RH.
The test piece was applied using a standard comb iron specified in G-3101, 100 mm square tiles were stuck together, a weight of 5 kg was placed thereon, and immediately the vertical deviation of the test body was immediately measured. 4) Pot life In accordance with the adhesive strength measuring method of JIS A-5548, JIS G-31 was applied to a high water content mortar immersed in water for 1 week.
Apply using a standard comb iron specified in 01
Satisfies the standard adhesive strength at ℃ 65% RH (6kg /
cm 2 ) Displayed at the longest time. Example: A 20-minute display indicates that when tiles are pasted together for 20 minutes or more after application, they do not satisfy the JIS A-5548 standard value, and a pot life of at least 30 minutes is required.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【発明の効果】表１及び表２から明らかなごとく、本発
明のタイル用一液型ウレタン系接着剤は、従来の二液型
エポキシ系接着剤に見られた、二液混合の繁雑さと計量
ミスによる硬化不良トラブル、ポットライフ、低温硬化
性、可撓性を始め、アミン系硬化剤による臭気及び皮膚
障害等の問題が解消され、合わせて従来の一液ウレタン
系接着剤で問題となっていた貯蔵安定性、エポキシ樹脂
配合の変性シリコーン系接着剤の価格問題も著しく改善
されたものであり、ＪＩＳ Ａ−５５４８に定めるタイ
ル用接着剤のタイプＩグレード、即ち低温湿潤下地面へ
の塗布性と、タイルとの密着性に優れ、標準強度、温水
強度、アルカリ水中強度等の接着物性は元より、タイル
のずれ抵抗性も具備していることからタイル用接着剤と
して有効でありその実用価値が高い。As is clear from Tables 1 and 2, the one-pack type urethane adhesive for tiles of the present invention has a complicatedness and metering of two-pack mixing, which is seen in the conventional two-pack type epoxy adhesive. Problems such as curing failure due to mistakes, pot life, low temperature curability, flexibility, and odors and skin disorders due to amine curing agents have been resolved, and it has become a problem with conventional one-component urethane adhesives. The storage stability and the price problem of the modified silicone adhesive containing the epoxy resin have also been remarkably improved, and the tile adhesive type I grade defined in JIS A-5548, that is, the coating property on a low temperature wet substrate surface. It is effective as a tile adhesive because it has excellent adhesiveness to tiles and has adhesive strength such as standard strength, hot water strength and alkaline water strength, and also has resistance to tile shift. High practical value.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 永田 桂 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 (72)発明者 末若 耕介 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Katsura Nagata 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Kosuke Suekaka 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Inside Chemical Co., Ltd.
Claims (2)
合物を反応させて得られる活性イソシアネート基含有ウ
レタンプレポリマーに、含水率０．１重量％未満の充填
剤及び揺変剤、可塑剤、硬化促進剤、並びにアミノ系及
びグリシジル系シランカップリング剤を配合して成るこ
とを特徴とするタイル用一液型ウレタン系接着剤。1. An active isocyanate group-containing urethane prepolymer obtained by reacting a polyol with an excess of a polyisocyanate compound, a filler having a water content of less than 0.1% by weight, a thixotropic agent, a plasticizer, a curing accelerator, A one-pack type urethane adhesive for tiles, characterized in that it is mixed with an amino-based and glycidyl-based silane coupling agent.
リマー１００重量部に対して、アミノ系及びグリシジル
系シランカップリング剤を各々０．０５〜３．０重量部
配合して成ることを特徴とする請求項１記載のタイル用
一液型ウレタン系接着剤。2. An amino-based and glycidyl-based silane coupling agent is blended in an amount of 0.05 to 3.0 parts by weight with respect to 100 parts by weight of an active isocyanate group-containing urethane prepolymer. The one-pack urethane adhesive for tiles according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2176695A JPH08218053A (en) | 1995-02-09 | 1995-02-09 | One-pack urethane-based adhesive for tile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2176695A JPH08218053A (en) | 1995-02-09 | 1995-02-09 | One-pack urethane-based adhesive for tile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08218053A true JPH08218053A (en) | 1996-08-27 |
Family
ID=12064202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2176695A Pending JPH08218053A (en) | 1995-02-09 | 1995-02-09 | One-pack urethane-based adhesive for tile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08218053A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6366338B1 (en) | 1997-12-22 | 2002-04-02 | Citizen Watch Co. Ltd. | Line-scanning optical printer |
| JP2005075877A (en) * | 2003-08-29 | 2005-03-24 | Nippon Nsc Ltd | Moisture-curable hot-melt adhesive composition |
| JP2006045287A (en) * | 2004-08-02 | 2006-02-16 | Inax Corp | Elastic adhesive and tiling wall |
| KR100626501B1 (en) * | 2000-07-19 | 2006-09-20 | 에스케이케미칼주식회사 | Thermoplastic polyurethane and preparation thereof, and polyurethane adhesives |
| CN100349902C (en) * | 2003-12-22 | 2007-11-21 | 张家港市国泰华荣化工新材料有限公司 | Process for preparing silicane containing isocyanate group |
| JP2022516133A (en) * | 2019-01-04 | 2022-02-24 | ダウ グローバル テクノロジーズ エルエルシー | Moisture curable adhesive composition |
-
1995
- 1995-02-09 JP JP2176695A patent/JPH08218053A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6366338B1 (en) | 1997-12-22 | 2002-04-02 | Citizen Watch Co. Ltd. | Line-scanning optical printer |
| KR100626501B1 (en) * | 2000-07-19 | 2006-09-20 | 에스케이케미칼주식회사 | Thermoplastic polyurethane and preparation thereof, and polyurethane adhesives |
| JP2005075877A (en) * | 2003-08-29 | 2005-03-24 | Nippon Nsc Ltd | Moisture-curable hot-melt adhesive composition |
| CN100349902C (en) * | 2003-12-22 | 2007-11-21 | 张家港市国泰华荣化工新材料有限公司 | Process for preparing silicane containing isocyanate group |
| JP2006045287A (en) * | 2004-08-02 | 2006-02-16 | Inax Corp | Elastic adhesive and tiling wall |
| JP2022516133A (en) * | 2019-01-04 | 2022-02-24 | ダウ グローバル テクノロジーズ エルエルシー | Moisture curable adhesive composition |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Effective date: 20040302 Free format text: JAPANESE INTERMEDIATE CODE: A02 |