JPH0834829A - Production of cold-setting coating film waterproofing agent - Google Patents
Production of cold-setting coating film waterproofing agentInfo
- Publication number
- JPH0834829A JPH0834829A JP6192321A JP19232194A JPH0834829A JP H0834829 A JPH0834829 A JP H0834829A JP 6192321 A JP6192321 A JP 6192321A JP 19232194 A JP19232194 A JP 19232194A JP H0834829 A JPH0834829 A JP H0834829A
- Authority
- JP
- Japan
- Prior art keywords
- curing agent
- coating film
- polyol
- agent
- room temperature
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、常温硬化性ポリウレタ
ン塗膜防水材、塗り床材などの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a room temperature curable polyurethane coating film waterproof material, a coated floor material and the like.
【０００２】[0002]
【従来の技術】ポリウレタン塗膜防水材、塗り床材は現
在ビルディングの屋上、ベランダ、廊下などの防水、ス
ポーツ施設の弾性舗装などの用途に大量に使用されてい
る。この方法は、ポリプロピレンエーテルポリオールな
どのポリオールとトリレンジイソシアネート（ＴＤＩ）
などの芳香族ジイソシアネートとの反応により製造され
るイソシアネート末端プレポリマーを主剤とし、ポリオ
ールおよび４，４’−メチレン−ビス（２−クロロアニ
リン）（ＭＯＣＡ）をイソシアネート反応成分（硬化
剤）とする２液型の手作業現場混合塗布方式による常温
硬化性ポリウレタンウレア防水材、塗り床材が主流を占
めている。2. Description of the Related Art Polyurethane-coated waterproof materials and floor covering materials are currently used in large quantities for waterproofing rooftops, balconies, and corridors of buildings, and elastic paving in sports facilities. This method uses polyols such as polypropylene ether polyols and tolylene diisocyanate (TDI).
An isocyanate-terminated prepolymer produced by a reaction with an aromatic diisocyanate as a main component, and a polyol and 4,4′-methylene-bis (2-chloroaniline) (MOCA) as an isocyanate reaction component (curing agent) 2 Room temperature curable polyurethane urea waterproof materials and floor coating materials, which are liquid-type hand-operated mixed coating methods, are the mainstream.
【０００３】[0003]
【発明が解決しようとする課題】この従来方法において
硬化剤中のイソイアネート反応成分の主成分として使用
するＭＯＣＡは、常温では固体で結晶性が高く、可塑剤
等の溶媒に対する溶解安定性が悪く取り扱い難いもので
あるにもかかわらず、イソシアネートとの反応が比較的
ゆるやかで、防水材として必要とされる可使時間（主剤
と硬化剤とを混合した後、これを支障なく塗布できる限
度の時間、通常混合後粘度が１０万センチポイズに達す
るまでの時間）を確保し易く、更に硬化塗膜がウレタン
塗膜防水材のＪＩＳ規格（ＪＩＳＡー６０２１）に規定
された各種物性を保持できるのでこの種の分野で使用可
能な殆ど唯一の芳香族ポリアミン架橋剤となっている。
ＭＯＣＡは硬化剤中で通常比較的溶解性のよいポリアル
キレンエーテルポリオールに溶解した形で使用されてい
るが、主剤のプレポリマーとの反応性がＭＯＣＡとポリ
オールとでは異なるのでこれらの反応を常温で円滑に進
行させ完結させるために有機金属鉛などの触媒の添加が
必須となっている。このように硬化剤の組成を組み立て
ても、冬場（低温時）にはみかけ上硬化が進行するが塗
膜表面にいつまでもタックが残りトップコートなどの次
工程に移れない場合がある。この不具合を避けるために
触媒の添加量を多くすると硬化塗膜の耐熱性が劣化す
る。夏場（高温時）には可使時間と硬化性のバランスが
とりにくく、高温多湿の条件下では湿分の影響のために
発泡する場合が多く表面の仕上りが悪くフクレの原因と
もなる。MOCA used as the main component of the isocyanate reaction component in the curing agent in this conventional method is solid at room temperature and has high crystallinity, and its solubility in a solvent such as a plasticizer is poor and it is difficult to handle. Despite being difficult, the reaction with isocyanate is relatively slow, and the pot life required as a waterproofing material (the maximum time that can be applied without trouble after mixing the main agent and the curing agent, Usually, it is easy to secure the time until the viscosity reaches 100,000 centipoise after mixing, and the cured coating film can retain various physical properties specified in JIS standard (JISA-6021) of urethane coating film waterproof material. It is almost the only aromatic polyamine crosslinker available in the field.
MOCA is usually used in the form of being dissolved in a polyalkylene ether polyol, which has a relatively high solubility in a curing agent. However, since the reactivity with the prepolymer, which is the main ingredient, differs between MOCA and the polyol, these reactions are performed at room temperature. The addition of a catalyst such as organometallic lead is indispensable for the smooth progress and completion. Even if the composition of the curing agent is assembled in this way, the curing apparently proceeds in the winter (at low temperature), but tack may remain on the surface of the coating film forever and it may not be possible to move to the next step such as top coating. If the amount of catalyst added is increased to avoid this problem, the heat resistance of the cured coating film deteriorates. In the summer (when the temperature is high), it is difficult to balance the pot life and the curability, and under the conditions of high temperature and high humidity, foaming often occurs due to the effect of moisture, resulting in poor surface finish and blister.
【０００４】一方、高反応性のジエチルトルエンジアミ
ン（ＤＥＴＤＡ）を芳香族ポリアミン架橋剤の主成分と
して含有する硬化剤と、４、４’ージフェニルメタンジ
イソシアネート系のイソシアネート成分を含有する主剤
とからなる高反応性２液型ウレタン材料を、高圧衝突混
合機により瞬時に混合して型内に吐出し、型内で２液を
硬化反応させて成型するいわゆるＲＩＭ成型が自動車部
品等の製造に採用されている。また最近ではこの高反応
性２液型ウレタン材料をスプレ−で塗工し、瞬間的に硬
化反応させてポリウレタン塗膜防水材を製造する方法も
普及してきている。かような高反応性の２液型ウレタン
材料は、２液混合からゲル化まで１０秒前後と超速硬化
性のものである。この方法では、スプレー塗工時にミス
トが飛散し、塗工面のレベリング性がなく、さらには手
塗り塗工に望ましい可使時間が得られないという欠点が
ある。このように従来技術には改善を要する種々な困難
があり、防水材塗工当日中に次工程であるトップコート
塗布が可能になるように数時間で硬化し、工期の短縮、
合理化ができ、しかも年間を通して安定な施工ができる
ような処方が望まれていた。On the other hand, a hardener containing highly reactive diethyltoluenediamine (DETDA) as a main component of an aromatic polyamine cross-linking agent and a main agent containing a 4,4'-diphenylmethane diisocyanate isocyanate component. The so-called RIM molding, in which a reactive two-component urethane material is instantaneously mixed by a high-pressure collision mixer and discharged into the mold, and the two liquids are cured and reacted in the mold, is used for manufacturing automobile parts and the like. There is. In addition, recently, a method of producing a polyurethane coating waterproof material by applying the highly reactive two-component type urethane material by spraying and instantaneously curing reaction has become popular. Such a highly reactive two-pack type urethane material is a super fast curable material in about 10 seconds from mixing of two packs to gelation. This method has the drawbacks that mist scatters during spray coating, there is no leveling on the coated surface, and the pot life that is desirable for manual coating cannot be obtained. As described above, the conventional technique has various difficulties that need improvement, and curing is performed in a few hours so that the next step, topcoat application, can be performed on the same day as the waterproof material coating, which shortens the construction period.
A prescription that can be rationalized and that enables stable construction throughout the year has been desired.
【０００５】[0005]
【課題を解決するための手段】本発明者らは種々検討の
結果、芳香族ポリアミン架橋剤として高反応性のＤＥＴ
ＤＡと従来技術のＭＯＣＡとを所定の割合で混合した硬
化剤を使用し、従来から用いられていたＴＤＩプレポリ
マーを主成分とする主剤と施工現場で混合、塗工するこ
とによって低温においても短時間のうちにタックがと
れ、高温においても発泡せず、仕上がり性の良好な、防
水材として好適な物性を有する硬化塗膜が得られること
を見いだした。すなわち本発明は、 １．トリレンジイソシアネート（以下ＴＤＩ）とポリオ
ールとの反応によって得られるイソシアネート末端プレ
ポリマーを主成分とする主剤と、芳香族ポリアミンを主
成分とする硬化剤とからなる２液型常温硬化性塗膜防水
材の製造方法において、 硬化剤の主成分である芳香族
ポリアミンとして、ジエチルトルエンジアミン（以下Ｄ
ＥＴＤＡ）と４，４’−メチレン−ビス（２−クロロア
ニリン）（以下ＭＯＣＡ）の混合物を使用し、該芳香族
ポリアミンの３０〜９０モル％がＤＥＴＤＡであり、１
０〜７０モル％がＭＯＣＡであり、主剤と硬化剤とを施
工現場で主剤のイソシアネート基と硬化剤の芳香族ポリ
アミンのアミノ基との当量比が０．８〜２．０となるよ
うに混合し、塗工し硬化せしめることを特徴とする常温
硬化性塗膜防水材の製造方法。As a result of various investigations, the present inventors have found that DET having high reactivity as an aromatic polyamine cross-linking agent.
Using a curing agent in which DA and MOCA of the prior art are mixed in a predetermined ratio, and mixing and coating with a main component, which has been used conventionally, mainly composed of TDI prepolymer, at the construction site, it is possible to shorten even at low temperature. It has been found that a cured coating film can be obtained in a short time, does not foam even at a high temperature, has a good finish and has physical properties suitable as a waterproof material. That is, the present invention is: Two-component type room temperature-curable waterproof film comprising a base compound containing an isocyanate-terminated prepolymer as a main component obtained by a reaction of tolylene diisocyanate (TDI) and a polyol, and a curing agent containing an aromatic polyamine as a main component In the production method of, the toluene polyamine (hereinafter referred to as D
ETDA) and 4,4′-methylene-bis (2-chloroaniline) (hereinafter MOCA) are used, wherein 30 to 90 mol% of the aromatic polyamine is DETDA, and 1
MOCA is 0 to 70 mol%, and the main agent and the curing agent are mixed at the construction site so that the equivalent ratio of the isocyanate group of the main agent and the amino group of the aromatic polyamine of the curing agent is 0.8 to 2.0. Then, a method for producing a room temperature curable waterproof film, which comprises coating and curing.
【０００６】２．ポリオールが分子量４００〜８０００
のポリプロピレンエーテルポリオールまたはポリエチレ
ンープロピレンエーテルポリオールである１記載の常温
硬化性塗膜防水材の製造方法。 ３．ＴＤＩが２，４−異性体含有率が８０重量％以上の
ＴＤＩである１記載の常温硬化性塗膜防水材の製造方
法。 ４．ＴＤＩが２，４−異性体含有率が８５重量％以上の
ＴＤＩである３記載の常温硬化性塗膜防水材の製造方
法。 ５．イソシアネ−ト末端プレポリマーのＮＣＯ含有率が
１．５〜８重量％である１記載の常温硬化性塗膜防水材
の製造方法。 ６．硬化剤中の芳香族ポリアミンの６０〜９０モル％が
ＤＥＴＤＡであり、１０〜４０モル％が４，４’−メチ
レン−ビス（２−クロロアニリン）である１記載の常温
硬化性塗膜防水材の製造方法。2. Polyol molecular weight 400-8000
2. The method for producing a room temperature-curable waterproof coating film according to 1, which is polypropylene ether polyol or polyethylene propylene ether polyol. 3. 2. The method for producing a room temperature curable waterproof film as described in 1, wherein the TDI is TDI having a 2,4-isomer content of 80% by weight or more. 4. 4. The method for producing a room temperature curable waterproof film as described in 3, wherein the TDI is TDI having a 2,4-isomer content of 85% by weight or more. 5. 2. The method for producing a room temperature curable waterproof film as described in 1, wherein the isocyanate-terminated prepolymer has an NCO content of 1.5 to 8% by weight. 6. 60 to 90 mol% of the aromatic polyamine in the curing agent is DETDA and 10 to 40 mol% is 4,4'-methylene-bis (2-chloroaniline). Manufacturing method.
【０００７】本発明の方法において主剤の主成分として
使用されるイソシアネート末端プレポリマーは、ＴＤＩ
とポリオールとの反応によって製造する。この場合得ら
れたプレポリマー中に遊離の状態で残存するＴＤＩの量
をできるだけ少なくするために仕込ＴＤＩとポリオール
とは、ＮＣＯ／ＯＨの当量比で２．１を超えないように
仕込で反応させることが望ましい。本願に係るプレポリ
マーを製造する際に用いるＴＤＩとしては、市販の２，
４ー異性体含有率が６５〜１００重量％のものが使用で
きるが、２，４ー異性体含有率の低いＴＤＩを使用した
プレポリマーは可使時間を短くする傾向があるため所望
の可使時間を得るためには２，４ー異性体含有率８０重
量％以上のＴＤＩを使用するのが好ましく、８５重量％
以上のものが最適である。本発明で得られる防水材は従
来のＭＯＣＡーポリオール使用系のものよりも速硬化性
となり、補修用あるいは小面積施工用としても適したも
のとなるため、可使時間は施工温度下で１５分以上を保
持できることが望ましい。イソシアネート末端プレポリ
マーの原料であるポリオールは、通常のウレタンプレポ
リマー用に使用されるポリエーテルポリオール、ポリエ
ステエルポリオール、ポリカプロラクトンポリオールな
どはいづれも使用できるが、本発明の塗膜防水材用途に
は常温液状で低粘度である分子量４００〜８０００のポ
リアルキレンエーテルポリオールが好ましく、最も好ま
しいポリオールは、ポリプロピレンエーテルポリオール
またはポリエチレンープロピレンエーテルポリオール、
またはこれらの混合物である。イソシアネート末端プレ
ポリマーのイソシアネート含有率は１．５〜８重量％の
範囲であることが好ましい。８重量％を超えると得られ
る塗膜は硬くなりすぎ伸びがでにくくなり、１．５重量
％未満では塗膜の機械的強度が弱くなり本発明用途に必
要とされる物性が保持できなくなる。The isocyanate-terminated prepolymer used as the main component of the base compound in the method of the present invention is TDI.
It is produced by the reaction of a polyol with a polyol. In this case, in order to reduce the amount of TDI remaining in a free state in the obtained prepolymer as much as possible, the charged TDI and the polyol are reacted in such a manner that the equivalent ratio of NCO / OH does not exceed 2.1. Is desirable. As the TDI used for producing the prepolymer according to the present application, commercially available 2,
A 4-polymer having a content of 4-isomer of 65 to 100% by weight can be used. However, a prepolymer using TDI having a low content of 2,4-isomer tends to shorten the pot life, so that a desired pot life is obtained. To obtain the time, it is preferable to use TDI having a 2,4-isomer content of 80% by weight or more, and 85% by weight.
The above is the most suitable. The waterproof material obtained by the present invention has a faster curing property than that of the conventional MOCA-polyol-based system, and is suitable for repair or for construction of a small area. Therefore, the pot life is 15 minutes or more under construction temperature. Is desirable. Polyol, which is a raw material for the isocyanate-terminated prepolymer, can be any of polyether polyol, polyester ester polyol, polycaprolactone polyol, etc. which are used for ordinary urethane prepolymers, but for the waterproof film application of the present invention, A polyalkylene ether polyol having a molecular weight of 400 to 8000, which is liquid at room temperature and has a low viscosity, is preferable, and a most preferable polyol is polypropylene ether polyol or polyethylene-propylene ether polyol,
Or a mixture of these. The isocyanate content of the isocyanate-terminated prepolymer is preferably in the range of 1.5 to 8% by weight. If it exceeds 8% by weight, the obtained coating film becomes too hard and is difficult to stretch, and if it is less than 1.5% by weight, the mechanical strength of the coating film becomes weak and the physical properties required for the use of the present invention cannot be maintained.
【０００８】本発明の方法において硬化剤の必須成分と
して使用するＤＥＴＤＡは３，５−ジエチルトルエン−
２，４および２，６−ジアミンの混合物で、常温液状で
あり、たとえばエタキュア１００（エチルコーポレーシ
ョン社製）などが市販されている。DETDA used as an essential component of the curing agent in the method of the present invention is 3,5-diethyltoluene-
It is a mixture of 2,4 and 2,6-diamine and is liquid at room temperature. For example, Etacure 100 (manufactured by Ethyl Corporation) is commercially available.
【０００９】ＤＥＴＤＡと共に混合して使用する４，
４’−メチレン−ビス（２−クロロアニリン）は、２ー
クロルアニリンとホルマリンの縮合物で、一般にＭＯＣ
Ａと略称されるものである。２ークロロアニリンの他に
若干のアニリンで変性したいわゆる変性ＭＯＣＡも使用
することができる。Used in combination with DETDA 4,
4'-methylene-bis (2-chloroaniline) is a condensate of 2-chloroaniline and formalin, and is generally MOC.
It is abbreviated as A. Besides 2-chloroaniline, so-called modified MOCA modified with some aniline can also be used.
【００１０】ＤＥＴＤＡを硬化剤中の芳香族ポリアミン
の９０モル％以上使用すると主剤のイソシアネート成分
との反応が速いため高温（夏場）には所望の可使時間が
とりにくくなる。ＭＯＣＡを芳香族ポリアミンの７０モ
ル％以上使用すると主剤との反応性が遅くなり、低温時
の硬化性が悪くなるので、本発明の目的の速硬化を達成
することができなくなる。従って本発明では、硬化剤中
のＤＥＴＤＡとＭＯＣＡとは上述の範囲で組み合わせて
使用される。このことにより低温時（冬場）はもちろん
高温時（夏場）においても可使時間と硬化性のバランス
が良好な、すなわち年間を通して安定な施工の可能な処
方を組み立てることができる。速硬化で防水材、塗り床
材用途に好適な機械的物性を有する硬化塗膜とするため
最も好ましいＤＥＴＤＡのの使用量は硬化剤中の芳香族
ポリアミンの６０〜９０モル％である。When DETDA is used in an amount of 90 mol% or more of the aromatic polyamine in the curing agent, the reaction with the isocyanate component of the main component is fast, and it becomes difficult to obtain the desired pot life at high temperatures (in summer). When MOCA is used in an amount of 70 mol% or more of the aromatic polyamine, the reactivity with the main agent becomes slow and the curability at low temperature deteriorates, so that the rapid curing as the object of the present invention cannot be achieved. Therefore, in the present invention, DETDA and MOCA in the curing agent are used in combination within the above range. This makes it possible to assemble a formulation that has a good balance between pot life and curability not only at low temperatures (winter) but also at high temperatures (summer), that is, stable construction throughout the year. The most preferable amount of DETDA used is 60 to 90 mol% of the aromatic polyamine in the curing agent in order to obtain a cured coating film having a mechanical property suitable for use as a waterproofing material and floor coating material in a quick curing manner.
【００１１】硬化剤中にＤＥＴＤＡを使用することによ
り、ＭＯＣＡのみを使用する場合よりも硬化剤中あるい
は施工環境からもたらされる湿分による悪影響が小さく
なるから、発泡によるフクレあるいは仕上がり性の悪さ
などの従来技術のかかえていた困難が防止できる。しか
も本発明の方法による硬化塗膜は従来技術によるよりも
塗膜表面にベタつきが残りにくく、短時間のうちにタッ
クのとれた良好な仕上がりとなる。By using DETDA in the curing agent, the adverse effect of moisture from the curing agent or the construction environment is less than that in the case of using only MOCA, so that blistering due to foaming or poor finishability is caused. It is possible to prevent the difficulties associated with the conventional technology. Moreover, the cured coating film produced by the method of the present invention is less likely to be sticky on the surface of the coating film as compared with the prior art, and has a good tacky finish in a short time.
【００１２】本発明の方法において硬化剤中にＤＥＴＤ
Ａとともに混合して使用されるＭＯＣＡは、常温におい
て固体のものが主体であるから、従来技術と同様にあら
かじめ可塑剤またはポリアルキレンエーテルポリオール
に溶解して使用するのが好ましい。可塑剤はＭＯＣＡの
溶解用として用いる他に硬化剤中に主剤との反応の希釈
剤として使用することもできる。可塑剤としては、フタ
ル酸ジオクチル（ＤＯＰ），アジピン酸ジオクチル（Ｄ
ＯＡ），リン酸トリクレジル（ＴＣＰ），塩素化パラフ
ィンなどの通常の可塑剤が使用できる。可塑剤の使用量
は主剤のプレポリマー１００部に対し１３０部以下の量
が好ましい。１３０部を越えると硬化塗膜表面から可塑
剤がブリードしたり塗膜の機械的強度が弱くなって不適
である。In the method of the present invention, DETD in the curing agent
Since the MOCA used as a mixture with A is mainly solid at room temperature, it is preferably dissolved in a plasticizer or polyalkylene ether polyol in advance as in the prior art. The plasticizer can be used not only for dissolving the MOCA but also as a diluent for the reaction with the main agent in the curing agent. As a plasticizer, dioctyl phthalate (DOP), dioctyl adipate (D
Ordinary plasticizers such as OA), tricresyl phosphate (TCP), and chlorinated paraffin can be used. The amount of the plasticizer used is preferably 130 parts or less with respect to 100 parts of the main polymer prepolymer. If it exceeds 130 parts, the plasticizer bleeds from the surface of the cured coating film and the mechanical strength of the coating film becomes weak, which is not suitable.
【００１３】本発明の方法では、硬化剤中にＤＥＴＤＡ
というかなり高活性な芳香族アミンを必須成分として使
用するので、この使用量により反応速度（可使時間と硬
化性）を調整することができる。従って、有機金属鉛な
どのような触媒の添加は必須ではないが場合により鉛オ
クトエート（鉛含有量２０重量％）などのような触媒を
硬化剤中に２重量％以下の量で添加することができる。
この程度の使用量であれば塗膜の耐熱性は劣化すること
がない。In the method of the present invention, DETDA is added to the curing agent.
Since a fairly highly active aromatic amine is used as an essential component, the reaction rate (pot life and curability) can be adjusted by the amount used. Therefore, it is not essential to add a catalyst such as organometallic lead, but in some cases, a catalyst such as lead octoate (lead content 20% by weight) may be added to the curing agent in an amount of 2% by weight or less. it can.
With this amount of use, the heat resistance of the coating film does not deteriorate.
【００１４】従来技術で硬化剤中にＭＯＣＡの溶解用兼
イソシアネート反応成分として使用されていたポリオー
ルは本発明では不可欠成分ではないが、ポリオールはＤ
ＥＴＤＡよりもイソシアネートとの反応性がかなり低
く、可塑剤と同様の効果をもたらすため場合によりこれ
をＭＯＣＡの溶解用として用いる他に可塑剤的に硬化剤
中に配合することができる。可塑剤的に使用することが
できるポリオールとしては、ポリエーテルポリオール、
ポリエステルポリオール、ポリカプロラクトンポリオー
ルなどがあげられるが、常温液状で、低粘度である分子
量４００〜８０００のポリプロピレンエーテルポリオー
ルまたはポリエチレンープロピレンエーテルポリオール
が好ましく、プレポリマーの使用量１００部に対して３
５部以下の量で使用するのが好ましい。これ以上の量で
配合すると硬化塗膜表面にポリオールがブリードし易く
なり、かつ塗膜の機械的強度が低くなる。The polyol used in the prior art for dissolving MOCA in the curing agent and as an isocyanate reaction component is not an essential component in the present invention, but the polyol is D
Since it has much lower reactivity with isocyanates than ETDA and provides the same effect as a plasticizer, it can optionally be used as a plasticizer in addition to being used for the dissolution of MOCA. As the polyol that can be used as a plasticizer, polyether polyol,
Examples thereof include polyester polyols and polycaprolactone polyols. Preferred are polypropylene ether polyols or polyethylene-propylene ether polyols having a molecular weight of 400 to 8000, which are liquid at room temperature and have a low viscosity, and 3 per 100 parts of the prepolymer used.
It is preferably used in an amount of 5 parts or less. If it is blended in an amount more than this, the polyol tends to bleed on the surface of the cured coating film, and the mechanical strength of the coating film becomes low.
【００１５】本発明の硬化剤には場合により炭酸カルシ
ウム、タルク、カオリン、ゼオライト、硅ソウ土などの
無機充填剤、酸化クロム、酸化チタン、ベンガラ、カー
ボンブラック、酸化鉄などの顔料、またはヒンダードア
ミン系、ヒンダードフェノール系、ベンゾチアゾール系
などの安定剤を添加することができる。The curing agent of the present invention may optionally include inorganic fillers such as calcium carbonate, talc, kaolin, zeolite, and silica, pigments such as chromium oxide, titanium oxide, red iron oxide, carbon black and iron oxide, or hindered amine-based agents. Stabilizers such as hindered phenols and benzothiazoles can be added.
【００１６】本発明を実施するには、ＴＤＩとポリオー
ルとの反応によって得られるイソシアネート末端プレポ
リマーを主成分とする主剤と、ＤＥＴＤＡおよびＭＯＣ
Ａを所定の割合で配合した硬化剤（場合により可塑剤、
ポリオール、充填剤、触媒などを含む）とを施工現場に
おいて主剤のイソシアネート基と硬化剤の芳香族ポリア
ミンのアミノ基との当量比が０．８〜２．０となるよう
に混合して被塗物上に塗工し、硬化せしめるのである。
主剤のイソシアネート基と硬化剤中のアミノ基との当量
比が０．８未満では、未反応のアミンが塗膜表面にブリ
ードしてきて変色の原因となり、２．０を越えると硬化
性が遅くなりすぎ塗膜の機械的強度も低下するので、い
ずれも本発明の目的を達成することができない。To carry out the present invention, a base compound based on an isocyanate-terminated prepolymer obtained by the reaction of TDI with a polyol and DETDA and MOC are used.
A curing agent containing A in a predetermined ratio (in some cases, a plasticizer,
(Including a polyol, a filler, a catalyst, etc.) is mixed at the construction site so that the equivalent ratio of the isocyanate group of the main agent and the amino group of the aromatic polyamine of the curing agent is 0.8 to 2.0, and coating is performed. It is applied on the object and cured.
If the equivalent ratio of the isocyanate group of the main agent to the amino group of the curing agent is less than 0.8, unreacted amine will bleed to the surface of the coating film and cause discoloration. If it exceeds 2.0, the curability will be slow. Since the mechanical strength of the rinsing coating film is also reduced, neither of the objects of the present invention can be achieved.
【００１７】本発明の方法により、年間を通して安定し
た常温施工ができ、短時間のうちにベタつきのない仕上
り性の良好な、耐熱性に優れた塗膜防水材、塗り床材な
どの用途に好適な硬化塗膜が得られる。本発明の方法は
手作業による混合、塗工に主として用いられるが、可使
時間およびレベリング可能時間が長くとれるため、スタ
チックミキサー、あるいは、ダイナミックミキサー等の
自動混合装置を使用した機械施工にも使用することがで
きる。According to the method of the present invention, stable room temperature construction can be carried out throughout the year, and it is suitable for applications such as waterproof coatings and floor coatings having excellent heat resistance and good finish without stickiness in a short time. A cured coating film is obtained. Although the method of the present invention is mainly used for manual mixing and coating, it can be used for machine construction using an automatic mixing device such as a static mixer or a dynamic mixer because the pot life and leveling possible time are long. Can be used.
【００１８】[0018]
【実施例】以下に実施例および比較例を挙げて、本発明
を具体的に説明する。実施例において使用される各記号
はそれぞれ下記の意味を有する。表中の”←”は左欄の
数値と同じ値であることを示す。 ［主剤］ Ｄ−２０００：ポリプロピレンエーテルジオール 分子
量 ２０００（武田薬品工業社製 商品名：アクトコー
ルＰ−２０２０） Ｄ−３０００：ポリプロピレンエーテルジオール 分子
量 ３０００（武田薬品工業社製 商品名：アクトコー
ルＰ−２３） Ｄ−４００：ポリプロピレンエーテルジオール 分子量
４００（武田薬品工業社製 商品名：アクトコールＰ
−４００） Ｔ−３０００：ポリプロピレンエーテルトリオール 分
子量 ３０００（武田薬品工業社製 商品名：アクトコ
ールＰ−３０３０） Ｔ−５０００：ポリプロピレンエーテルトリオール 分
子量 ５０００（武田薬品工業社製 商品名：アクトコ
ール ３５−３４）EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. The symbols used in the examples have the following meanings. "←" in the table indicates that the value is the same as the value in the left column. [Main Agent] D-2000: Polypropylene ether diol Molecular weight 2000 (Takeda Pharmaceutical Co., Ltd. trade name: Actcor P-2020) D-3000: Polypropylene ether diol Molecular weight 3000 (Takeda Pharmaceutical Co., Ltd. trade name: Actcor P-23 ) D-400: Polypropylene ether diol Molecular weight 400 (Takeda Pharmaceutical Co., Ltd. trade name: ACTCOL P
-400) T-3000: Polypropylene ether triol molecular weight 3000 (Takeda Yakuhin Co., Ltd. trade name: Actcor P-3030) T-5000: Polypropylene ether triol molecular weight 5000 (Takeda Yakuhin Co. Ltd. trade name: Actcor 35-34) )
【００１９】［硬化剤］ ＤＥＴＤＡ：ジエチルトルエンジアミン（エタキュア１
００、エチルコーポレーション社製） ＭＯＣＡ：４，４´−メチレン−ビス（２−クロロアニ
リン）（イハラケミカル社製） ＤＯＰ：フタル酸ジオクチル（可塑剤、大八化学工業所
製） ポリオール：ポリプロピレンエーテルジオール Ｄ−２
０００ 炭酸カルシウム：無機充填材（丸尾カルシウム社製） 鉛オクトエート：触媒、鉛含有率２０重量％、（日本化
学産業社製） ＮＣＯ／ＮＨ2当量比：プレポリマー（主剤）のＮＣＯ
基と硬化剤の芳香族ポリアミン架橋剤のアミノ基との当
量比（但し比較例８のみＮＣＯ基／（ＮＨ2＋ＯＨ）基
の当量比）[Curing agent] DETDA: Diethyltoluenediamine (Etacure 1
00, manufactured by Ethyl Corporation) MOCA: 4,4′-methylene-bis (2-chloroaniline) (manufactured by Ihara Chemical Co., Ltd.) DOP: Dioctyl phthalate (plasticizer, manufactured by Daihachi Chemical Industry Co., Ltd.) Polyol: polypropylene ether diol D-2
000 Calcium carbonate: Inorganic filler (manufactured by Maruo Calcium Co.) Lead octoate: Catalyst, lead content 20% by weight, (manufactured by Nippon Kagaku Sangyo Co., Ltd.) NCO / NH 2 equivalent ratio: NCO of prepolymer (main agent)
Group and the equivalent ratio of the curing agent to the amino group of the aromatic polyamine crosslinking agent (however, in Comparative Example 8 only, the equivalent ratio of NCO groups / (NH 2 + OH) groups)
【００２０】［可使時間と硬化性］ 可使時間：主剤と硬化剤とを混合した後、支障なく塗工
できる限度の時間（分）（混合後の粘度が１０万センチ
ポイズに達するまでの時間） タックフリータイム：塗膜表面にベトつきがなくなるま
での時間（時間）（塗工後塗膜上に人が乗れるようにな
るまでの時間）[Working time and curability] Working time: the maximum time (minutes) after which the main agent and the curing agent are mixed and which can be applied without any trouble (time until the viscosity after mixing reaches 100,000 centipoise) ) Tack free time: Time (hours) until stickiness disappears on the surface of the coating (time until a person can ride on the coating after coating)
【００２１】［硬化塗膜の物性］ 基礎物性：塗工後塗膜を２０℃、７日硬化させた後ＪＩ
ＳＡ−６０２１に準じて行う塗膜物性試験結果（ＪＩＳ
規格では破断伸びは４５０％以上、引張強度は２５ｋｇ
ｆ／ｃｍ2以上） 耐熱性：２０℃、７日間硬化後、８０℃のオーブンで７
日間加熱した後の塗膜物性試験結果 引張強度保持率：耐熱性試験後の引張強度と基礎物性の
それとの強度比（百分率）（ＪＩＳ規格では８０以上１
５０以下）[Physical properties of cured coating] Basic physical properties: After coating, after curing the coating at 20 ° C. for 7 days, JI
Results of coating film physical property test according to SA-6021 (JIS
According to the standard, breaking elongation is 450% or more, tensile strength is 25 kg
f / cm 2 or more) Heat resistance: 7 hours in an oven at 80 ° C after curing at 20 ° C for 7 days
Result of coating film physical property test after heating for days Tensile strength retention ratio: Strength ratio (percentage) between tensile strength after heat resistance test and that of basic physical property (JIS standard 80 or more 1
50 or less)
【００２２】主剤（イソシアネート末端プレポリマー）
の調製 ２リットルのガラスコルベンに表１，表２，表３の配合
表に従ってそれぞれ２，４−異性体対２，６−異性体含
有率（重量比）が６５対３５、８０対２０、８５／１５
または１００対０のＴＤＩを仕込み、窒素気流下にＤ−
２０００、Ｄ−３０００、Ｄ−４００、Ｔ−３０００ま
たはＴ−５０００のポリプロピレンエーテルポリオール
をそれぞれの仕込ＮＣＯ基対ＯＨ基の当量比に従って徐
々に加え、８０〜１０５℃で４〜８時間加熱攪拌し反応
を完結させ、イソシアネート末端プレポリマー（主剤）
を調製した。Main agent (isocyanate-terminated prepolymer)
Preparation of 2 liters of glass Kolben having a content ratio (weight ratio) of 2,4-isomer to 2,6-isomer of 65:35, 80: 20,85 according to the formulations of Table 1, Table 2 and Table 3, respectively. / 15
Alternatively, charge 100 to 0 TDI, and under a nitrogen stream, D-
2000, D-3000, D-400, T-3000 or T-5000 polypropylene ether polyol was gradually added according to the equivalent ratio of the charged NCO group to the OH group, and heated and stirred at 80 to 105 ° C for 4 to 8 hours. Isocyanate-terminated prepolymer (main agent) to complete the reaction
Was prepared.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【表３】 [Table 3]
【００２６】硬化剤の調製 ２リツトルの円筒型開放容器に表１，表２，表３の配合
表に従ってＤＥＴＤＡ、あらかじめＤＯＰに溶解したＭ
ＯＣＡの溶液（比較例３および８ではＭＯＣＡはポリオ
ールとＤＯＰに溶解した）,場合によりポリオール、炭
酸カルシウム、場合により鉛オクトエートを仕込み、室
温でディゾルバーを用いて１５分間攪拌しそれぞれの硬
化剤を調製した。Preparation of Curing Agent In a 2-liter cylindrical open container, DETDA was prepared according to the recipes of Table 1, Table 2 and Table 3, and M was dissolved in DOP beforehand.
A solution of OCA (MOCA was dissolved in polyol and DOP in Comparative Examples 3 and 8), optionally polyol, calcium carbonate, and optionally lead octoate were charged, and each curing agent was prepared by stirring at room temperature for 15 minutes using a dissolver. did.
【００２７】実施例１ ２リットルのガラスコルベンに２，４−異性体／２，６
−異性体重量比が６５／３５のＴＤＩを１４８．２ｇ仕
込み、６８１．４ｇのＤ−２０００と１７０．４ｇのＴ
−３０００（Ｄ−２０００／Ｔ−３０００＝８０／２０
重量比）を徐々に加え、窒素気流下に８０℃に加熱し攪
拌しながら９０〜１００℃に昇温しこの温度で５時間保
ち反応を完結させ、ＮＣＯ含有率３．５重量％のプレポ
リマー１０００ｇを調製した。これとは別に、２リット
ルの円筒型開放容器に４９ｇのＤＥＴＤＡ、あらかじめ
４３２ｇのＤＯＰに１９ｇのＭＯＣＡを溶解した溶液
（硬化剤中の芳香族ポリアミン中にＤＥＴＤＡが８０モ
ル％およびＭＯＣＡが２０モル％含有）および炭酸カル
シウム５００ｇを仕込み、室温でディゾルバーにて１５
分間攪拌し１０００ｇの硬化剤を調製した。上記で調整
した主剤と硬化剤とを３分し、１０℃（冬場を想定）、
２０℃および３５℃（夏場を想定）の雰囲気に２時間以
上静置した後、それぞれの雰囲気で主剤と硬化剤を重量
比１／１（主剤のＮＣＯ基／硬化剤のＮＨ2 基当量比＝
１．２）の割合に混合し、可使時間をチェックしながら
プライマー処理したスレート板にコテまたはヘラを用い
て厚さ１．５〜２ｍｍになるように塗布した。２０℃で
混合したものの１部をガラス板上に厚さ１．５〜２ｍｍ
になるように流延し、このまま２０℃で硬化させ塗膜物
性（基礎物性および耐熱性）測定用の試験片とした。 Example 1 2,4-isomer / 2,6 in 2 liters of glass Kolben
Charged 148.2 g of TDI with an isomer weight ratio of 65/35, 681.4 g of D-2000 and 170.4 g of TDI.
-3000 (D-2000 / T-3000 = 80/20
(Weight ratio) is gradually added, the temperature is raised to 90 to 100 ° C. with stirring under heating in a nitrogen stream at 80 ° C., the temperature is maintained for 5 hours to complete the reaction, and the prepolymer having an NCO content of 3.5% by weight is added. 1000 g was prepared. Separately, 49 g of DETDA was dissolved in a 2-liter cylindrical open container, and 19 g of MOCA was dissolved in 432 g of DOP in advance (80 mol% of DETDA and 20 mol% of MOCA in the aromatic polyamine in the curing agent). (Containing) and 500 g of calcium carbonate are charged, and a dissolver is used for 15 at room temperature.
After stirring for 1 minute, 1000 g of a curing agent was prepared. 3 minutes of the main agent and curing agent adjusted above, 10 ℃ (assuming winter),
After standing in an atmosphere of 20 ° C and 35 ° C (assuming summer) for 2 hours or more, the weight ratio of the main agent to the curing agent is 1/1 in each atmosphere (NCO group of the main agent / NH 2 group equivalent ratio of the curing agent =
The mixture was mixed in the ratio of 1.2) and, while checking the pot life, it was applied to a slate plate treated with a primer with a trowel or a spatula so as to have a thickness of 1.5 to 2 mm. Part of the mixture at 20 ° C on a glass plate with a thickness of 1.5-2 mm
Then, it was cast at the temperature of 20 ° C. and cured at 20 ° C. to obtain a test piece for measuring coating film physical properties (basic physical properties and heat resistance).
【００２８】[0028]
【表４】 [Table 4]
【００２９】その結果表４のように１０℃、２０℃およ
び３５℃の可使時間はそれぞれ４２分、２５分および１
５分であり高温時（夏場）においても所望の可使時間が
保持でき、タックフリータイムはそれぞれ５時間、２．
５時間および１．５時間と低温においても硬化性が良好
であり、発泡もなく良好な仕上り性を示した。２０℃、
７日後の塗膜の基礎物性および耐熱性は表の通りであり
塗膜防水材のＪＩＳ規格を充分に満足する性能を示し
た。As a result, as shown in Table 4, the pot life at 10 ° C., 20 ° C. and 35 ° C. was 42 minutes, 25 minutes and 1 respectively.
5 minutes, the desired pot life can be maintained even at high temperatures (summer), and the tack free time is 5 hours and 2.
The curability was good even at low temperatures of 5 hours and 1.5 hours, and there was no foaming and good finish was exhibited. 20 ℃,
The basic physical properties and heat resistance of the coating film after 7 days are as shown in the table, and the performance of the coating film waterproof material sufficiently satisfies the JIS standard.
【００３０】実施例２〜５ 実施例２〜４は、主剤の原料ＴＤＩとして２，４−異性
体／２，６−異性体の重量比が８０／２０、８５／１５
または１００／０のものを用いて調製したプレポリマー
を使用し、主剤と硬化剤の重量比１／１（主剤のＮＣＯ
基／硬化剤のＮＨ2 基の当量比＝１．２）の割合に混合
し実施例２および３は２０℃で、実施例４は１０℃およ
び３５℃のテストも実施した 結果は表４の通りであ
る。すなわち２，４−異性体含有率の多いものほど可使
時間が長くなり所望の可使時間を保持し易くなるが、硬
化性はやや遅くなる傾向を示す。しかしながら実施例４
にみられるように、硬化が遅いものであっても低温（１
０℃）においてさえ８時間でタックフリーとなり速硬化
性であり（比較例８の従来法ではこれが３０〜４０時
間）、また高温（３５℃）においても３０分の可使時間
が保持でき、発泡もなく仕上り性良好な塗膜となった。
これらの硬化塗膜はいづれも防水材として好適な物性を
示した。すなわち年間を通して支障なく施工が可能であ
ることが示された。 実施例５は実施例４の組成で硬化
剤に触媒を小量添加した例であるが、実施例４より速硬
化性となり、この程度の触媒の添加量であれば所望の可
使時間を保持しながら耐熱性が劣化しないことを示して
いる。 Examples 2-5 In Examples 2-4, the weight ratio of 2,4-isomer / 2,6-isomer was 80/20, 85/15 as the raw material TDI of the main agent.
Alternatively, a prepolymer prepared using 100/0 is used, and the weight ratio of the main agent to the curing agent is 1/1 (NCO of the main agent).
The test was carried out at 20 ° C. in Examples 2 and 3 and in Example 4 at 10 ° C. and 35 ° C. by mixing at a ratio of (group / equivalent ratio of NH 2 group of curing agent) = 1.2). On the street. That is, the higher the 2,4-isomer content, the longer the pot life and the easier it is to maintain the desired pot life, but the curability tends to be slightly slower. However, Example 4
As can be seen from Fig. 1, even if the curing is slow,
It becomes tack-free in 8 hours even at 0 ° C. and is rapidly curable (30 to 40 hours in the conventional method of Comparative Example 8), and can retain a pot life of 30 minutes even at a high temperature (35 ° C.) and foam. It was a coating film with good finish.
Each of these cured coating films showed suitable physical properties as a waterproof material. In other words, it was shown that construction can be done without any problem throughout the year. Example 5 is an example in which a small amount of the catalyst was added to the curing agent with the composition of Example 4, but the curing rate was faster than that of Example 4, and the desired pot life was maintained at this level of the amount of catalyst added. However, it shows that the heat resistance does not deteriorate.
【００３１】実施例６〜７ 主剤のプレポリマーは実施例４と同一のものを使用し、
硬化剤の芳香族ポリアミン架橋剤中のＤＥＴＤＡとＭＯ
ＣＡの使用割合を実施例１〜５の場合と異り実施例６お
よび７ではＤＥＴＤＡ／ＭＯＣＡ＝６５／３５または４
０／６０モル％として実施例４と同様にテストした。
結果は表４からわかるように実施例４に比較してＭＯＣ
Ａの使用割合が増加する（実施例６および７）に従って
可使時間が長くなり、それに伴って硬化性が遅くなりか
つ塗膜がやや軟く強度が低下する傾向を示すが実施例７
のように２０℃におけるタックフリータイムが１２時間
とやや遅くなってもなお比較例８の従来法に比べて速硬
化性であり、硬化塗膜の物性も防水材として好適な性能
を保持することが示された。 Examples 6 to 7 The same prepolymer as the main component was used as in Example 4,
DETDA and MO in Aromatic Polyamine Crosslinking Agent for Curing Agent
The use ratio of CA is different from those in Examples 1 to 5, and in Examples 6 and 7, DETDA / MOCA = 65/35 or 4
The same test as in Example 4 was carried out with 0/60 mol%.
As can be seen from Table 4, the results are compared with those of Example 4 by using MOC.
As the use ratio of A increases (Examples 6 and 7), the pot life increases, the curability slows accordingly, and the coating film tends to be slightly soft and the strength tends to decrease.
Even if the tack free time at 20 ° C. is slightly delayed as 12 hours, it is still quick-curing as compared with the conventional method of Comparative Example 8, and the physical properties of the cured coating film should also maintain suitable performance as a waterproof material. It has been shown.
【００３２】実施例８ 主剤のプレポリマーとして実施例４〜７と同一のものを
使用し、硬化剤中のＤＥＴＤＡとＭＯＣＡの混合割合が
８０／２０モル比のものを使用し、これにポリオールＤ
−２０００を可塑剤的に配合した場合の例である。結果
は表４のように可使時間と硬化性は所望の範囲内であ
り、硬化塗膜も防水材として好適な物性をもつことを示
し、硬化剤中にポリオールを可塑剤的にこの程度配合し
ても本発明の目的を保持できることが示された。 Example 8 The same prepolymer as the main component used in Examples 4 to 7 was used, and the curing agent used had a mixing ratio of DETDA and MOCA of 80/20 in molar ratio.
This is an example in which -2000 is blended as a plasticizer. The results show that, as shown in Table 4, the pot life and the curability are within the desired ranges, and the cured coating film also has physical properties suitable as a waterproof material. However, it was shown that the object of the present invention can be retained.
【００３３】実施例９ 主剤のプレポリマーのＮＣＯ含有率が２．４重量％と実
施例１〜８（ＮＣＯ含有率３．５重量％）より小さいも
のを使用し、硬化剤中のＤＥＴＤＡとＭＯＣＡの混合割
合が８０／２０モル比と実施例１〜４と同じ比率のもの
を使用した場合の例である。結果は、表５のように可使
時間が６０分（２０℃）および３５分（３５℃）、タツ
クフリータイムが７時間（２０℃）、３〜４時間（３５
℃）と実施例４に比較して硬化性はやや遅くなるがいず
れも所望の範囲内にあり速硬化性である。硬化塗膜は軟
らかくなるが、防水材としては好適な物性であることが
示された。 Example 9 Using a prepolymer of the main agent having a NCO content of 2.4% by weight, which is smaller than those of Examples 1 to 8 (NCO content of 3.5% by weight), DETDA and MOCA in the curing agent were used. In this example, the mixing ratio is 80/20 and the same ratio as in Examples 1 to 4 is used. As shown in Table 5, the pot life was 60 minutes (20 ° C) and 35 minutes (35 ° C), and the tack free time was 7 hours (20 ° C) and 3 to 4 hours (35 ° C).
C.) and the curability is slightly slower than in Example 4, but both are within the desired range and fast curability. Although the cured coating film became soft, it was shown to have suitable physical properties as a waterproof material.
【００３４】[0034]
【表５】 [Table 5]
【００３５】実施例１０ 主剤のプレポリマーのＮＣＯ含有率が７重量％と実施例
１〜８（ＮＣＯ含有率３．５重量％）よりも大きいもの
を使用し、硬化剤中のＤＥＴＤＡとＭＯＣＡの混合割合
が実施例６と同様に６５／３５モル比のものを使用した
場合の例である。 結果は表５のように可使時間が４５
分（１０℃）、２８分（２０℃）または１５分（３５
℃）と実施例４または６と比較して短くなるがいづれも
所望の範囲内であり、それに伴ってタックフリータイム
は速くなり実施例４または６よりはさらに速硬化性とな
り、硬化塗膜は防水材として好適な物性であることが示
された Example 10 The main polymer prepolymer having an NCO content of 7% by weight, which is higher than those of Examples 1 to 8 (NCO content 3.5% by weight), was used, and DETDA and MOCA in the curing agent were used. This is an example of the case where the mixing ratio is 65/35 as in Example 6 and used. As shown in Table 5, the pot life is 45
Minutes (10 ° C), 28 minutes (20 ° C) or 15 minutes (35
C.) and Example 4 or 6 are shorter, but each is within a desired range, and accordingly, tack free time becomes faster and becomes faster curing than Example 4 or 6, and the cured coating film becomes It was shown that it has suitable physical properties as a waterproof material.
【００３６】実施例１１および１２ 主剤としてＮＣＯ含有率３．５重量％と実施例４〜８と
同一のものを使用し、硬化剤中の芳香族ポリアミン架橋
剤の使用量を増減し、主剤のＮＣＯ基／硬化剤のＮＨ2
基の当量比を０．９または１．７と実施例６（ＮＣＯ／
ＮＨ2＝１．２）に比較して増減させた。硬化剤中のＤ
ＥＴＤＡとＭＯＣＡの混合割合は６５／３５モル比と実
施例６と同じ混合比で実施した。結果は表５からわかる
ようにＮＣＯ基／ＮＨ2基当量比が０．９（ 実施例１
１）と実施例６より小さくすると可使時間は３５分と短
くなり、一方タックフリータイムは３時間と硬化性は速
くなる。ＮＣＯ基／ＮＨ2 基の当量比が１．７（実施例
１２）と大きくすると可使時間は６５分と長くなり、一
方タックフリータイムは８時間とやや硬化性は遅くなる
がいづれも所望の可使時間と硬化性の範囲内にある。塗
膜物性はいづれも防水材のＪＩＳ規格に合格する良好な
性能を示した Examples 11 and 12 Using the same NCO content of 3.5% by weight as that of Examples 4 to 8 as the main agent, the amount of the aromatic polyamine cross-linking agent in the curing agent was increased or decreased, NCO group / hardener NH 2
The equivalent ratio of the groups was set to 0.9 or 1.7 and Example 6 (NCO /
The amount was increased / decreased in comparison with NH 2 = 1.2). D in the curing agent
The mixing ratio of ETDA and MOCA was 65/35 and the same mixing ratio as in Example 6. As can be seen from Table 5, the result shows that the NCO group / NH 2 group equivalent ratio is 0.9 (Example 1
When it is smaller than 1) and Example 6, the pot life is shortened to 35 minutes, while the tack free time is 3 hours and the curability is fast. When the equivalent ratio of NCO group / NH 2 group was increased to 1.7 (Example 12), the pot life was extended to 65 minutes, while the tack free time was 8 hours, and the curability was slightly delayed, but any desired value was obtained. It is within the range of pot life and curability. The physical properties of the coating film all showed good performance that passed the JIS standard for waterproof materials.
【００３７】比較例１ 主剤のプレポリマーの原料ＴＤＩとして２，４−異性体
／２，６−異性体の重量比が８０／２０のもの（実施例
２と同じ）を使用し、硬化剤中のＤＥＴＤＡとＭＯＣＡ
のモル比が２５／７５と実施例の諸例（実施例２、４、
６および７）と比較してＤＥＴＤＡの使用割合を少く
し、ＭＯＣＡの使用割合を多くした場合をテストし結果
を表６に示した。 Comparative Example 1 As the raw material TDI of the main polymer prepolymer, a TDI having a 2,4-isomer / 2,6-isomer weight ratio of 80/20 (same as in Example 2) was used. DETDA and MOCA
The molar ratio of is 25/75 and various examples (Examples 2, 4,
6 and 7), the use ratio of DETDA was decreased and the use ratio of MOCA was increased, and the results are shown in Table 6.
【００３８】[0038]
【表６】 [Table 6]
【００３９】結果は表６のように可使時間は８５分と長
くなる一方タックフリータイムは２４時間と遅くなり施
工当日にトップコート塗布などの次工程に移れない程度
にまで硬化性は遅くなる。さらに硬化塗膜は機械的強度
が弱く、耐熱性にも劣り、総じて防水材のＪＩＳ規格を
満足しないものとなることが示された。すなわち実施例
１から７の結果を勘案すると、本発明の目的を達成する
ためには硬化剤中の芳香族ポリアミン架橋剤であるＤＥ
ＴＤＡとＭＯＣＡの使用混合割合には限界的な所定の範
囲が存在し、比較例１はその限界外であることを示して
いる。As shown in Table 6, the pot life was as long as 85 minutes, while the tack free time was as late as 24 hours and the curability was so slow that it could not be transferred to the next step such as top coat application on the day of construction. . Further, it was shown that the cured coating film had weak mechanical strength and poor heat resistance, and generally did not satisfy the JIS standard for waterproof materials. That is, considering the results of Examples 1 to 7, in order to achieve the object of the present invention, DE which is an aromatic polyamine crosslinking agent in the curing agent is used.
The mixing ratio of TDA and MOCA used has a certain limit, and Comparative Example 1 shows that it is out of the limit.
【００４０】比較例２および３ 主剤として実施例４〜８、１０、１１および１２と同じ
プレポリマーを使用し、比較例２は硬化剤中の可塑剤量
が多い場合、比較例３は硬化剤中に可塑剤的に使用する
ポリオールの配合量が多い場合をそれぞれテストした。
いづれも硬化剤中のＤＥＴＤＡとＭＯＣＡの混合割合と
して８０／２０モル比のものを使用した。比較例２は可
塑剤量が多いので主剤と硬化剤との重量混合比を１／
２．５とし、比較例２、３は両方とも主剤のＮＣＯ基／
硬化剤のＮＨ2 基の当量比が１．２となるように調整し
た。結果は表６のように比較例２では可塑剤が、比較例
３では未反応ポリオールが硬化塗膜表面にブリードして
しまい、いづれも本発明の目的とする防水材とすること
ができないことが示された。 Comparative Examples 2 and 3 The same prepolymer as in Examples 4 to 8, 10, 11 and 12 was used as the main component, Comparative Example 2 contained a large amount of plasticizer in the curing agent, and Comparative Example 3 contained a curing agent. Each case was tested in which a large amount of polyol used as a plasticizer was used.
In each case, the mixing ratio of DETDA and MOCA in the curing agent was 80/20. Since Comparative Example 2 has a large amount of plasticizer, the weight mixing ratio of the main agent and the curing agent is 1 /.
2.5 and Comparative Examples 2 and 3 are both NCO groups of the main agent /
The equivalent ratio of NH 2 groups in the curing agent was adjusted to 1.2. As shown in Table 6, as shown in Table 6, the plasticizer in Comparative Example 2 and the unreacted polyol in Comparative Example 3 bleed to the surface of the cured coating film, and thus neither of them can be used as the waterproof material intended by the present invention. Was shown.
【００４１】比較例４および５ 比較例４および５は、主材のＮＣＯ基／硬化剤中のＮＨ
2基の当量 比が小さい場合と大きい場合の例である。結
果は表６に示すようにＮＣＯ基／ＮＨ2 基の当量比を
０．７（比較例４）と小さくすると塗膜表面に未反応ア
ミンがブリードして変色が大となり、当量比を２．４
（比較例５）と大きくすると可使時間が８０分と長くな
り硬化性が遅くなる上、塗膜が発泡してしまい、いづれ
も本発明の目的の防水材を得ることができなくなる。す
なわち実施例４〜７、１１および１２の結果を勘案する
と、本発明の目的を達成するためには、主剤のＮＣＯ基
／硬化剤のＮＨ2 基の当量比は限界的な所定の範囲が存
在することを示している。 Comparative Examples 4 and 5 In Comparative Examples 4 and 5, the NCO group of the main material / NH in the curing agent was used.
This is an example when the equivalence ratio of the two units is small and when it is large. As shown in Table 6, when the equivalent ratio of NCO group / NH 2 group is reduced to 0.7 (Comparative Example 4), unreacted amine bleeds on the surface of the coating film to cause large discoloration, and the equivalent ratio is 2. Four
When the ratio is increased to (Comparative Example 5), the pot life is extended to 80 minutes, the curability is slowed, and the coating film is foamed, so that the waterproof material for the purpose of the present invention cannot be obtained in any case. That is, considering the results of Examples 4 to 7, 11 and 12, in order to achieve the object of the present invention, the equivalent ratio of the NCO group of the main agent / the NH 2 group of the curing agent has a critical predetermined range. It shows that you do.
【００４２】比較例６および７ 比較例６および７は主剤のＮＣＯ含有率が実施例より低
い場合と高い場合であり、硬化剤中の芳香族ポリアミン
架橋剤であるＤＥＴＤＡとＭＯＣＡの混合割合を８０／
２０モル比と一定にしてその使用量を増減し、主剤のＮ
ＣＯ基／硬化剤のＮＨ2 の当量比がいづれも１．２とな
るように調整して実施した。結果は表６からわかるよう
に主剤のＮＣＯ含有率が１．２重量％（比較例６）まで
低くなると、可使時間は７５分と充分長くなるがタック
フリータイムが２０時間と実施例４および９に比較して
遅くなる上、硬化塗膜は機械的強度が弱く、耐熱性も劣
るものとなる。主剤のＮＣＯ含有率が９重量％（比較例
７）と高くなると、タックフリータイムは１時間と速硬
化性ではあるが可使時間は７分と短く手塗り塗工が困難
となり、硬化塗膜も堅く脆くなり弾性に欠け防水材とし
ては不向きな性能となることが示された。 Comparative Examples 6 and 7 In Comparative Examples 6 and 7, the NCO content of the main agent was lower and higher than that of the examples, and the mixing ratio of aromatic polyamine cross-linking agents DETDA and MOCA in the curing agent was 80. /
The amount of N used as the main agent was adjusted by increasing or decreasing the amount used while maintaining a constant 20 molar ratio.
The adjustment was performed so that the equivalent ratio of CO group / NH 2 of the curing agent was 1.2 in each case. As can be seen from Table 6, when the NCO content of the main agent was reduced to 1.2% by weight (Comparative Example 6), the pot life was 75 minutes, which was sufficiently long, but the tack free time was 20 hours. In addition to being slower than No. 9, the cured coating film has weak mechanical strength and poor heat resistance. When the NCO content of the main agent was as high as 9% by weight (Comparative Example 7), the tack-free time was 1 hour, which was fast-curing, but the pot life was short at 7 minutes, making hand-coating difficult. It was shown to be hard and brittle, lacking elasticity and not suitable as a waterproof material.
【００４３】比較例８ 比較例８は従来技術のＭＯＣＡ−ポリオール併用硬化剤
を使用した例である。主剤の原料ＴＤＩとして２，４−
異性体／２，６−異性体の重量比が８０／２０のものを
使用し、ＭＯＣＡ−ポリオール併用系の硬化剤と触媒を
使用した。結果は表６からわかるように可使時間は充分
長いが、タックフリータイムは２０℃でも２０時間と遅
く、１０℃の低温においては３０〜４０時間となり、施
工翌日になっても次工程（トップコート塗布など）に移
れない場合がある程に硬化が遅いことを示した。 Comparative Example 8 Comparative Example 8 is an example using a conventional MOCA-polyol combination curing agent. 2,4-as the raw material TDI of the main agent
An isomer / 2,6-isomer weight ratio of 80/20 was used, and a curing agent and a catalyst of the MOCA-polyol combination system were used. As can be seen from Table 6, the pot life is sufficiently long, but the tack free time is as slow as 20 hours even at 20 ° C, which is 30 to 40 hours at a low temperature of 10 ° C. It was shown that the curing was slow enough so that it could not be transferred to coating.
【００４４】[0044]
【発明の効果】以上の説明からわかるように本発明によ
れば、ＴＤＩとポリオールとの反応によって得られるイ
ソシアネート末端プレポリマーを主成分とする主剤と、
ＤＥＴＤＡとＭＯＣＡとの所定混合割合の芳香族ポリア
ミンを硬化剤とし、主剤のイソシアネート基と硬化剤中
のアミノ基との当量比が所定範囲内となるように施工現
場で混合し、手塗り塗工して硬化させることによって、
年間を通して安定した常温施工ができ、短時間のうちに
発泡せず、表面タックを残さず、仕上り性よくかつ耐熱
性にすぐれたポリウレタン硬化塗膜を得ることができ
る。したがって本発明の方法は、常温施工の塗膜防水材
や塗り床材などに効果的に適用できるものである。As can be seen from the above description, according to the present invention, a main component containing an isocyanate-terminated prepolymer as a main component, which is obtained by the reaction of TDI and a polyol,
Aromatic polyamine in a predetermined mixing ratio of DETDA and MOCA is used as a curing agent, and is mixed at the construction site so that the equivalent ratio of the isocyanate group of the main agent and the amino group in the curing agent is within a predetermined range, and hand-coating And cure
It is possible to carry out stable room-temperature application throughout the year, do not foam in a short time, leave no surface tack, and obtain a polyurethane cured coating film with excellent finish and heat resistance. Therefore, the method of the present invention can be effectively applied to waterproof membranes, floor coverings, etc. that are applied at room temperature.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｄ 175/08 ＰＨＶ Ｃ０９Ｋ 3/18 １０１ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C09D 175/08 PHV C09K 3/18 101
Claims (6)
との反応によって得られるイソシアネート末端プレポリ
マーを主成分とする主剤と、芳香族ポリアミンを主成分
とする硬化剤とからなる２液型常温硬化性塗膜防水材の
製造方法において、 硬化剤の主成分である芳香族ポリ
アミンとして、ジエチルトルエンジアミンと４，４’−
メチレン−ビス（２−クロロアニリン）の混合物を使用
し、該芳香族ポリアミンの３０〜９０モル％がジエチル
トルエンジアミンであり、１０〜７０モル％が４，４’
−メチレン−ビス（２−クロロアニリン）であり、 主剤と硬化剤とを施工現場で主剤のイソシアネート基と
硬化剤の芳香族ポリアミンのアミノ基との当量比が０．
８〜２．０となるように混合し、塗工し硬化せしめるこ
とを特徴とする常温硬化性塗膜防水材の製造方法。1. A two-part type room temperature curable waterproof coating film comprising a base material containing an isocyanate-terminated prepolymer as a main component obtained by a reaction of tolylene diisocyanate and a polyol, and a curing agent containing an aromatic polyamine as a main component. In the method for producing a material, diethyltoluenediamine and 4,4'- are used as the aromatic polyamine which is the main component of the curing agent.
A mixture of methylene-bis (2-chloroaniline) was used, 30-90 mol% of the aromatic polyamine was diethyltoluenediamine and 10-70 mol% of 4,4 '.
-Methylene-bis (2-chloroaniline), the equivalent ratio of the isocyanate group of the main agent to the amino group of the aromatic polyamine of the curing agent is 0.
A method for producing a room-temperature-curable waterproof film, comprising mixing, coating and curing so as to be 8 to 2.0.
ポリプロピレンエーテルポリオールまたはポリエチレン
ープロピレンエーテルポリオールである特許請求の範囲
第１項記載の常温硬化性塗膜防水材の製造方法。2. The method for producing a room temperature curable waterproof film according to claim 1, wherein the polyol is polypropylene ether polyol having a molecular weight of 400 to 8000 or polyethylene-propylene ether polyol.
性体含有率が８０重量％以上のトリレンジイソシアネ−
トである特許請求の範囲第１項記載の常温硬化性塗膜防
水材の製造方法。3. Tolylene diisocyanate having a 2,4-isomer content of tolylene diisocyanate of 80% by weight or more.
The method for producing a room temperature-curable waterproof coating film according to claim 1, which is
性体含有率が８５重量％以上のトリレンジイソシアネ−
トである特許請求の範囲第３項記載の常温硬化性塗膜防
水材の製造方法。4. Tolylene diisocyanate having a 2,4-isomer content of tolylene diisocyanate of 85% by weight or more.
The method for producing a room temperature curable coating film waterproof material according to claim 3, wherein
Ｏ含有率が１．５〜８重量％である特許請求の範囲第１
項記載の常温硬化性塗膜防水材の製造方法。5. NC of isocyanate terminated prepolymer
Claim 1 in which the O content is 1.5 to 8% by weight.
Item 7. A method for producing a room temperature-curable coating film waterproof material according to item.
０モル％がジエチルトルエンジアミンであり、１０〜４
０モル％が４，４’−メチレン−ビス（２−クロロアニ
リン）である特許請求の範囲第１項記載の常温硬化性塗
膜防水材の製造方法。6. The aromatic polyamine in the curing agent, 60 to 9
0 mol% is diethyltoluenediamine, 10-4
The method for producing a room temperature curable waterproof film according to claim 1, wherein 0 mol% is 4,4'-methylene-bis (2-chloroaniline).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19232194A JP3445371B2 (en) | 1994-07-25 | 1994-07-25 | Method for producing cold-setting waterproof coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19232194A JP3445371B2 (en) | 1994-07-25 | 1994-07-25 | Method for producing cold-setting waterproof coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0834829A true JPH0834829A (en) | 1996-02-06 |
| JP3445371B2 JP3445371B2 (en) | 2003-09-08 |
Family
ID=16289343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19232194A Expired - Fee Related JP3445371B2 (en) | 1994-07-25 | 1994-07-25 | Method for producing cold-setting waterproof coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3445371B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09278858A (en) * | 1996-04-17 | 1997-10-28 | Hodogaya Chem Co Ltd | Production of cold-setting waterproofing agent for coating film |
| JPH1017819A (en) * | 1996-06-28 | 1998-01-20 | Hodogaya Chem Co Ltd | Production of polyurethane coating film material |
| JP2000044871A (en) * | 1998-07-28 | 2000-02-15 | Hodogaya Chem Co Ltd | Composition for polyurethane urea non-slip material and its coating method |
| JP2001288357A (en) * | 2000-04-03 | 2001-10-16 | Dyflex Corp | Urethane resin composition, coating, sealing material and method for producing cured product |
| JP2007246691A (en) * | 2006-03-16 | 2007-09-27 | Yokohama Rubber Co Ltd:The | Two-part type ordinary temperature-curable urethane coating film water-resistant material composition |
| KR100817817B1 (en) * | 2007-08-24 | 2008-03-31 | 강남화성 (주) | Polyurethane composition for elastomer having high durability and high strength, and method of manufacturing polyurethane supporting member for civil engineering and construction |
| JP2009091414A (en) * | 2007-10-05 | 2009-04-30 | Aica Kogyo Co Ltd | Urea resin composition |
| JP2009235214A (en) * | 2008-03-27 | 2009-10-15 | Aica Kogyo Co Ltd | Urea urethane resin composition |
| JP2010095996A (en) * | 2009-11-16 | 2010-04-30 | Hodogaya Chem Co Ltd | Composition for polyurethane urea nonslip material |
| JP2014031503A (en) * | 2012-07-13 | 2014-02-20 | I C K Kk | Two-part type urethane waterproof material composition |
| JP2015151492A (en) * | 2014-02-17 | 2015-08-24 | アイシーケイ株式会社 | Two component environment-friendly urethane waterproof material composition |
| JP2018171675A (en) * | 2017-03-31 | 2018-11-08 | 富士紡ホールディングス株式会社 | Polishing pad |
-
1994
- 1994-07-25 JP JP19232194A patent/JP3445371B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09278858A (en) * | 1996-04-17 | 1997-10-28 | Hodogaya Chem Co Ltd | Production of cold-setting waterproofing agent for coating film |
| JPH1017819A (en) * | 1996-06-28 | 1998-01-20 | Hodogaya Chem Co Ltd | Production of polyurethane coating film material |
| JP2000044871A (en) * | 1998-07-28 | 2000-02-15 | Hodogaya Chem Co Ltd | Composition for polyurethane urea non-slip material and its coating method |
| JP2001288357A (en) * | 2000-04-03 | 2001-10-16 | Dyflex Corp | Urethane resin composition, coating, sealing material and method for producing cured product |
| JP2007246691A (en) * | 2006-03-16 | 2007-09-27 | Yokohama Rubber Co Ltd:The | Two-part type ordinary temperature-curable urethane coating film water-resistant material composition |
| KR100817817B1 (en) * | 2007-08-24 | 2008-03-31 | 강남화성 (주) | Polyurethane composition for elastomer having high durability and high strength, and method of manufacturing polyurethane supporting member for civil engineering and construction |
| JP2009091414A (en) * | 2007-10-05 | 2009-04-30 | Aica Kogyo Co Ltd | Urea resin composition |
| JP2009235214A (en) * | 2008-03-27 | 2009-10-15 | Aica Kogyo Co Ltd | Urea urethane resin composition |
| JP2010095996A (en) * | 2009-11-16 | 2010-04-30 | Hodogaya Chem Co Ltd | Composition for polyurethane urea nonslip material |
| JP2014031503A (en) * | 2012-07-13 | 2014-02-20 | I C K Kk | Two-part type urethane waterproof material composition |
| JP2015151492A (en) * | 2014-02-17 | 2015-08-24 | アイシーケイ株式会社 | Two component environment-friendly urethane waterproof material composition |
| JP2018171675A (en) * | 2017-03-31 | 2018-11-08 | 富士紡ホールディングス株式会社 | Polishing pad |
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|---|---|
| JP3445371B2 (en) | 2003-09-08 |
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