JP3325367B2 - Room temperature curing type polyurethane elastomer composition - Google Patents
Room temperature curing type polyurethane elastomer compositionInfo
- Publication number
- JP3325367B2 JP3325367B2 JP27406193A JP27406193A JP3325367B2 JP 3325367 B2 JP3325367 B2 JP 3325367B2 JP 27406193 A JP27406193 A JP 27406193A JP 27406193 A JP27406193 A JP 27406193A JP 3325367 B2 JP3325367 B2 JP 3325367B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- polyurethane elastomer
- elastomer composition
- viscosity
- group
- 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.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、無発泡の常温硬化型ポ
リウレタンエラストマー組成物に関し、詳しくは塗膜防
水材、床材、陸上競技場やテニスコート等の弾性舗装
材、注型材料、シーリング材、型枠材、下塗り材等に適
した初期硬化性が大きく、タック（ベタツキ）が少く、
作業性が良く、機械的強度が大きいエラストマーを与え
る常温硬化型ポリウレタンエラストマー組成物に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-foamed room temperature-curable polyurethane elastomer composition, and more particularly to a waterproof coating material, a floor material, an elastic pavement material such as an athletic field and a tennis court, a casting material, and a sealing material. Initial curing property suitable for materials, formwork materials, undercoating materials, etc., low tack (stickiness),
The present invention relates to a cold-setting polyurethane elastomer composition which provides an elastomer having good workability and high mechanical strength.
【０００２】[0002]
【従来の技術】ポリウレタンは機械的強度が卓越してい
る上に、耐久性、耐摩耗性、耐候性、高弾性、接着性に
富んでいること等の特徴から、ますますその需要が増大
している。常温硬化型ポリウレタンエラストマーは、一
般にトリレンジイソシアネート（以下ＴＤＩと略称す
る。）と２官能及び／又は３官能のポリエーテルポリオ
ール（以下ＰＰＧと略称する。）との反応によって得ら
れる分子末端にイソシアナト基を有するウレタンプレポ
リマーを主剤とし、他方活性水素化合物からなる硬化剤
（必要に応じて充填剤、触媒、可塑剤、顔料、耐候安定
剤、消泡剤、溶剤等を配合する。）を施工時に混合して
使用するいわゆる２液タイプのポリウレタンエラストマ
ーが主流をしめている。硬化剤中の活性水素化合物とし
ては、ポリアミンとして３，３’−ジクロル−４．４’
−ジアミノジフェニルメタン（以下、ＭＯＣＡと略称す
る。）及び／又は鉱酸の存在下でアニリンと２−クロロ
アニリンとをホルムアルデヒドと縮合させることにより
得られる芳香族ポリアミン（以下、ＣＡ−８００と略称
する。）、並びにポリオールとしてポリエーテルポリオ
ール、多価アルコール等が使用される。また、ポリアミ
ンは常温で固体であるため、一般的にはポリオールに溶
解させて使用する方法がとられている。2. Description of the Related Art Polyurethane has a remarkable mechanical strength and is increasingly demanded due to its characteristics such as durability, abrasion resistance, weather resistance, high elasticity and adhesiveness. ing. The room temperature-curable polyurethane elastomer is generally an isocyanate group at the molecular terminal obtained by the reaction of tolylene diisocyanate (hereinafter abbreviated as TDI) with a bifunctional and / or trifunctional polyether polyol (hereinafter abbreviated as PPG). And a curing agent composed of an active hydrogen compound (comprising a filler, a catalyst, a plasticizer, a pigment, a weather stabilizer, an antifoaming agent, a solvent, etc., if necessary) at the time of construction. The so-called two-pack type polyurethane elastomer used by mixing is the mainstream. As the active hydrogen compound in the curing agent, 3,3′-dichloro-4.4 ′ as a polyamine is used.
-Aromatic polyamine (hereinafter abbreviated as CA-800) obtained by condensing aniline and 2-chloroaniline with formaldehyde in the presence of diaminodiphenylmethane (hereinafter abbreviated as MOCA) and / or mineral acid. ) And polyols such as polyether polyols and polyhydric alcohols. In addition, since polyamines are solid at room temperature, a method is generally used in which they are dissolved in a polyol.
【０００３】塗膜防水材、舗装材等の用途には硬化物は
柔軟で伸びのある性能が要求されることから、通常芳香
族ポリアミンとポリエーテルポリオールが併用される。
イソシアナト基を有するウレタンプレポリマーと活性水
素化合物、特にポリエーテルポリオールとの反応におけ
るウレタン化促進触媒としては一般に有機鉛化合物が使
用され、この有機鉛化合物の添加量により、施工条件
（季節別）に合うように、硬化時間が調整される。[0003] Since the cured product is required to have a flexible and stretchable performance for uses such as a waterproof coating material and a pavement material, an aromatic polyamine and a polyether polyol are usually used in combination.
An organic lead compound is generally used as a urethane-promoting catalyst in the reaction of a urethane prepolymer having an isocyanate group with an active hydrogen compound, particularly a polyether polyol. The curing time is adjusted to suit.
【０００４】[0004]
【発明が解決しようとする課題】ところで、常温硬化型
２液タイプのウレタンエラストマーを例えば防水材、床
材、舗装材等に施工する場合、通常設計による仕上げ膜
厚が決定すると、１回塗布による仕上げは行わず、数回
に分けて塗り重ねて仕上げる方法がとられている。それ
は１回塗布方法で仕上げると、下地（コンクリート、モ
ルタル、アスファルトコンクリート等）の不陸（凹凸）
等により均一な厚み管理ができず、また、膜厚が厚い場
合は、撹拌混合時に巻き込んだ泡が抜けきれず表面に気
泡やピンホールが発生するためである。When a cold-curable two-pack type urethane elastomer is applied to, for example, a waterproof material, a floor material, a pavement material, and the like, when a finished film thickness is determined by a normal design, a single application is performed. The finishing is not performed, but a method is adopted in which the paint is applied over several times and finished. When it is finished with a single application method, the unevenness of the base (concrete, mortar, asphalt concrete, etc.)
For example, when the film thickness is too large, bubbles trapped during stirring and mixing cannot be completely removed, and bubbles and pinholes are generated on the surface.
【０００５】主剤ウレタンプレポリマーと硬化剤とを混
合して現場で施工する場合、ウレタンの初期硬化性（１
８〜２０時間後）が悪いと、ゴム弾性が発現せず更にタ
ックが大きいため翌日には人が乗って塗り重ねができ
ず、工程日数が長くなり、納期の遵守や経済性等の点で
不利になる欠点を有しており、翌日に人が乗れて塗り重
ねができるような初期硬化性の大きい材料の開発が望ま
れていた。[0005] When a urethane prepolymer and a curing agent are mixed and applied on site, the initial curing property of urethane (1)
(After 8 to 20 hours), the rubber elasticity does not appear and the tack is large, so that the next day, people can not ride and re-coat, the number of process days becomes longer, and the delivery date and the economics There is a disadvantage that it is disadvantageous, and it has been desired to develop a material having a high initial curing property so that a person can ride on the next day and recoat.
【０００６】一方、常温硬化型２液タイプのウレタンエ
ラストマーを用いて、例えば防水材、床材、舗装材等を
施工する場合、現場で主剤及び硬化剤の２成分を混合し
常温下で反応させることにより、ゴム弾性のある塗膜が
形成される。この２成分を混合した時の粘度は作業性の
点からなるべく低い方が好ましい。混合物を所定の膜厚
に塗布する時に混合時の粘度が高いとレベリング性が悪
くなり、また膜の表面仕上がり状態としては、コテむら
が生じ易くなり平滑面が得られにくくなる。更に作業者
としては、コテ叉はレーキ等で塗布するが粘度が高いと
腰に負担がかかり作業効率が落ちてしまう。On the other hand, when a waterproofing material, a flooring material, a pavement material and the like are constructed by using a room temperature-curable two-pack type urethane elastomer, two components of a main agent and a curing agent are mixed on site and reacted at room temperature. As a result, a coating film having rubber elasticity is formed. The viscosity when these two components are mixed is preferably as low as possible from the viewpoint of workability. When the mixture is applied to a predetermined film thickness, if the viscosity at the time of mixing is high, the leveling property is deteriorated, and as a surface finish state of the film, unevenness of the iron is liable to occur, and it is difficult to obtain a smooth surface. Further, as a worker, the application is performed with a trowel or a rake, but if the viscosity is high, a burden is placed on the lower back and the working efficiency is reduced.
【０００７】一般的な防水材、舗装材等の主剤粘度は
５，０００〜１１，０００ｃｐｓ／２０℃、硬化剤粘度
は１０，０００〜５０，０００ｃｐｓ／２０℃に設計さ
れており、硬化剤の粘度は主剤の粘度に比べてはるかに
高くなっている。この粘度差は、硬化剤としては反応成
分のポリアミン／ポリオール等の液状アミン、触媒、可
塑剤等の液状分の他に充填剤、顔料、安定剤等の粉体を
配合しているからである。一般的には可塑剤は粘度調整
剤として使用される。また必要に応じて溶剤等も添加さ
れる。硬化剤中に可塑剤、溶剤等を添加すれば、粘度低
下には非常に効果があるが添加量には限度がある。例え
ば可塑剤（ＤＯＰ：フタル酸ジオクチル、ＤＯＡ：アジ
ピン酸ジオクチル）を多量に添加すると、硬化させたシ
ートの耐熱試験（８０℃×７日）ではシート表面にブリ
ードを起こす欠点があり、また、溶剤（トルエン、キシ
レン等）を多量添加すると硬化したシートが収縮を起こ
す欠点がある。従って、可塑剤、溶剤等は無添加または
少量にして硬化剤の粘度を下げる方法が望まれていた。The viscosity of the main agent of a general waterproofing material, pavement material and the like is designed to be 5,000 to 11,000 cps / 20 ° C., and the viscosity of the curing agent is designed to be 10,000 to 50,000 cps / 20 ° C. The viscosity is much higher than the viscosity of the base. This difference in viscosity is due to the fact that as a curing agent, powders of fillers, pigments, stabilizers and the like are blended in addition to liquid components such as liquid amines such as polyamine / polyol as reaction components, liquid components such as catalysts and plasticizers. . Generally, plasticizers are used as viscosity modifiers. Further, a solvent or the like is added as needed. If a plasticizer, a solvent, or the like is added to the curing agent, the viscosity can be greatly reduced, but the amount added is limited. For example, when a large amount of a plasticizer (DOP: dioctyl phthalate, DOA: dioctyl adipate) is added in a large amount, the cured sheet has a drawback of causing bleeding on the sheet surface in a heat resistance test (80 ° C. × 7 days). When a large amount of (toluene, xylene, etc.) is added, there is a disadvantage that the cured sheet shrinks. Therefore, there has been a demand for a method of lowering the viscosity of a curing agent by adding no or small amounts of a plasticizer, a solvent, and the like.
【０００８】[0008]
【課題を解決するための手段】本発明者らは上記の観点
から、初期硬化性が大きく、タックが少く、従って作業
性に優れる高強度の常温硬化型ポリウレタンエラストマ
ー組成物について鋭意検討した結果、主剤ウレタンプレ
ポリマー中又は硬化剤中に、特に、低粘化のためには硬
化剤中に、芳香族カルボン酸及び／又は該芳香族カルボ
ン酸の酸無水物の少くとも１種を配合することにより、
所期の目的が達成できることを見出し、本発明を完成す
るに至った。From the above viewpoints, the present inventors have conducted intensive studies on a high-strength room-temperature-curable polyurethane elastomer composition having a large initial curing property, a small tack, and excellent workability. Incorporation of at least one aromatic carboxylic acid and / or an acid anhydride of the aromatic carboxylic acid in the base urethane prepolymer or the curing agent, particularly in the curing agent for reducing the viscosity. By
The inventor has found that the intended purpose can be achieved, and has completed the present invention.
【０００９】即ち、本発明は次の通りである。 （１）末端にイソシアナト基を有するウレタンプレポリ
マーを主成分とする主剤、及び（２）ＭＯＣＡ及び／又
はＣＡ−８００並びにポリエーテルポリオールを主成分
とする硬化剤、から成るポリウレタンエラストマー組成
物において、該ウレタンエラストマー組成物に対して
０．００５〜５重量％の式１（化２）That is, the present invention is as follows. In a polyurethane elastomer composition comprising (1) a main agent mainly composed of a urethane prepolymer having an isocyanate group at a terminal, and (2) a curing agent mainly composed of MOCA and / or CA-800 and polyether polyol, 0.005 to 5% by weight of the urethane elastomer composition of the formula 1
【化２】 （式中、Ｒは水酸基、ニトロ基、ブロム基、クロル基、
スルホン基又は炭素数１〜２０のアルキル基、ｎは１〜
３の整数を表わすが、ｎが２又は３のとき、Ｒは同じで
あっても異なっていてもよい。ｍは１〜４の整数を表わ
す。）で表わされる芳香族カルボン酸及び該芳香族カル
ボン酸の無水物から選ばれた少くとも１種を、主剤中又
は硬化剤中に、特に、低粘化のためには硬化剤中に、含
有せしめてなることを特徴とする常温硬化型ポリウレタ
ンエラストマー組成物。式１（化２）で表わされる芳香
族カルボン酸が、特にｏ−トルイル酸、ｏ−クロル安息
香酸、又はｏ−ニトロ安息香酸である常温硬化型ポリウ
レタンエラストマー組成物。 Embedded image (Wherein R is a hydroxyl group, a nitro group, a bromo group, a chloro group,
A sulfone group or an alkyl group having 1 to 20 carbon atoms, n is 1 to
Represents an integer of 3, when n is 2 or 3, R is the same and
May be different. m represents an integer of 1 to 4
You. At least one selected from the aromatic carboxylic acids represented by the formula (1 ) and anhydrides of the aromatic carboxylic acids in the base material or the curing agent, particularly in the curing agent for reducing the viscosity. A room-temperature-curable polyurethane elastomer composition, characterized in that it is made at least in the form of: Aroma represented by the formula (1)
Aromatic carboxylic acids, especially o-toluic acid, o-chlorobenzoate
Room temperature-curable polyurethane which is a carboxylic acid or an o-nitrobenzoic acid
A urethane elastomer composition.
【００１０】本発明で使用される末端にイソシアナト基
を有するウレタンプレポリマー用の原料有機ポリイソシ
アネートとしては２，４−トリレンジイソシアネート、
２，６−トリレンジイソシアネート及びその混合物（以
下、ＴＤＩと略称する。）、特に２，４−異性体／２，
６−異性体が重量比８０／２０のもの（以下、ＴＤＩ−
８０と略称する。）及び６５／３５のもの（以下、ＴＤ
Ｉ−６５と略称する。）が好ましい。ポリオールとして
は、各種ポリエーテルポリオール、ポリエステルポリオ
ール、ポリブタジエンポリオール、ひまし油、ポリテト
ラメチレンエーテルグリコールが使用できるが、水、プ
ロピレングリコールなどにプロピレンオキサイド又はプ
ロピレンオキサイド及びエチレンオキサイドを付加した
ポリオキシアルキレングリコール、グリセリン、トリメ
チロールプロパンなどにプロピレンオキサイド又プロピ
レンオキサイド及びエチレンオキサイドを付加したポリ
オキシアルキレントリオールが特に好ましい。このほ
か、低分子のグリコールが使用できる。低分子グリコー
ルとしては、エチレングリコール、ジエチレングリコー
ル、プロピレングリコール、ジプロピレングリコール、
トリプロピレングリコール、１，３−ブチレングリコー
ル、２，３−ブチレングリコールが使用できる。これら
ポリオールは単独又は２種以上混合して使用されるがポ
リオールの平均分子量は７５〜１００００が好ましい。
ウレタンプレポリマーは有機ポリイソシアネートとポリ
オールとを常法に従って、窒素気流中８０〜１００℃で
数時間加熱する方法により製造することができる。The starting organic polyisocyanate for the urethane prepolymer having a terminal isocyanate group used in the present invention includes 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate and a mixture thereof (hereinafter abbreviated as TDI), particularly 2,4-isomer / 2,2
6-isomer having a weight ratio of 80/20 (hereinafter referred to as TDI-
Abbreviated as 80. ) And 65/35 (hereinafter TD)
Abbreviated as I-65. Is preferred. As the polyol, various polyether polyols, polyester polyols, polybutadiene polyols, castor oil, polytetramethylene ether glycol can be used, but polyoxyalkylene glycol obtained by adding propylene oxide or propylene oxide and ethylene oxide to water, propylene glycol, etc., glycerin And polyoxyalkylene triol obtained by adding propylene oxide or propylene oxide and ethylene oxide to trimethylolpropane or the like. In addition, low molecular glycols can be used. As the low molecular weight glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol can be used. These polyols may be used alone or as a mixture of two or more. The average molecular weight of the polyol is preferably from 75 to 10,000.
The urethane prepolymer can be produced by heating an organic polyisocyanate and a polyol in a nitrogen stream at 80 to 100 ° C. for several hours according to a conventional method.
【００１１】本発明に用いられる硬化剤は、架橋剤とし
てＭＯＣＡ及び／又はＣＡ−８００並びに、ポリエーテ
ルポリオールを主成分とし、他に触媒として有機鉛化合
物及び必要により充填剤、可塑剤、顔料、耐候安定剤、
消泡剤、溶剤等を含有してなる。架橋剤としては、ＭＯ
ＣＡ及び／又はＣＡ−８００を分子量４００〜８，００
０の各種ポリエーテルポリオールで溶解した液状アミン
が用いられる。ポリエーテルポリオールとしては、特に
ポリオキシアルキレンジオール、ポリオキシアルキレン
トリオールが好ましい。また、芳香族アミンをポリエー
テルポリオール及び／又は可塑剤で液状化した市販品、
例えばＭＣ−５０６（三井東圧化学社製ＭＯＣＡ ２４
重量％、ＣＡ−８００ ２４重量％、ポリエーテルポリ
オール５２重量％からなる液状アミン）も使用できる。The curing agent used in the present invention contains MOCA and / or CA-800 as a cross-linking agent as a main component and polyether polyol as a main component. In addition, as a catalyst, an organic lead compound and, if necessary, a filler, a plasticizer, a pigment, Weathering stabilizer,
It contains an antifoaming agent, a solvent and the like. As a crosslinking agent, MO
CA and / or CA-800 having a molecular weight of 400 to 8,000
A liquid amine dissolved in various polyether polyols of No. 0 is used. As the polyether polyol, polyoxyalkylene diol and polyoxyalkylene triol are particularly preferable. In addition, a commercially available product obtained by liquefying an aromatic amine with a polyether polyol and / or a plasticizer,
For example, MC-506 (MOCA 24 manufactured by Mitsui Toatsu Chemicals, Inc.)
% Of liquid amine consisting of 24% by weight of CA-800 and 52% by weight of polyether polyol).
【００１２】触媒としては、公知のウレタン化触媒が用
いられるが、特に有機金属化合物が適当で、中でも有機
鉛化合物、例えば鉛オクトエート、鉛ナフテネート等の
ような有機酸の鉛塩が好適に用いられる。その使用量は
硬化剤の総量に対し０．１〜５重量％が好ましい。As the catalyst, known urethanization catalysts are used. In particular, organic metal compounds are suitable, and among them, organic lead compounds, for example, lead salts of organic acids such as lead octoate and lead naphthenate are preferably used. . The amount used is preferably 0.1 to 5% by weight based on the total amount of the curing agent.
【００１３】充填材は、例えば炭酸カルシウム、タル
ク、クレー、カーボンブラック、無水ケイ酸（ホワイト
カーボン）、ゼオライト、二酸化チタン等が好ましい。
これらの充填材は単独又は混合して使用することができ
る。その使用量は硬化剤の総量に対し２〜２５重量％が
好ましい。The filler is preferably, for example, calcium carbonate, talc, clay, carbon black, silicic anhydride (white carbon), zeolite, titanium dioxide or the like.
These fillers can be used alone or in combination. The amount used is preferably from 2 to 25% by weight based on the total amount of the curing agent.
【００１４】本発明に用いる他の助剤としてはすべての
公知の可塑剤、顔料、耐候安定剤、消泡剤又は必要に応
じて溶剤等を用いることができる。可塑剤としては、例
えば、フタル酸ジオクチル（ＤＯＰ）、フタル酸ジブチ
ル（ＤＢＰ）、アジピン酸ジオクチル（ＤＯＡ）、リン
酸トリクレジル（ＴＣＰ）、塩素化パラフィン、Ｕ−レ
ックス（脂環族重合体変性天然樹脂エステル、東京樹脂
工業社製）等がある。As other auxiliaries used in the present invention, all known plasticizers, pigments, weather stabilizers, defoamers or, if necessary, solvents can be used. Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate (DOA), tricresyl phosphate (TCP), chlorinated paraffin, U-rex (naturally modified alicyclic polymer) Resin ester, manufactured by Tokyo Resin Industries).
【００１５】顔料の例としては酸化クロム、ベンガラ等
の無機顔料、フタロシアニン顔料、アゾ顔料等の有機顔
料が挙げられる。耐候安定剤の例としては、商品名ノク
ラック３００及びノクラックＮＳ−６（大内新興化学社
製）商品名イルガノックス１０１０及び１０７６（チバ
ガイギー社製）、ヨシノックスＢＨＴ、ＢＢ及びＧＳＹ
−９３０（吉富製薬社製）などの位置障害型フェノール
類、チヌビンＰ、３２７及び３２８（チバガイギー社
製）等のベンゾトリアゾール類、トミソーブ８００（吉
富製薬社製）などのベンゾフェノン類、サノールＬＳ−
７７０及び７４４（三共社製）、チヌビン１４４（チバ
ガイギー社製）などの位置障害型アミン類等がある。消
泡剤の例としては、ジメチルシロキサン系、ディスパロ
ン７１０及び７２０（楠本化成社製）などのポリアクリ
レート系のものが挙げられる。溶剤の例としては、トル
エン、キシレン等の芳香族炭化水素、ヘキサン、シクロ
ヘキサン、商品名アイソパーＨ、Ｍ（エクソン社製）等
の脂肪族炭化水素、酢酸エチル等のエステル類、メチル
エチルケトン等のケトン類等が挙げられる。Examples of the pigment include inorganic pigments such as chromium oxide and red iron oxide, and organic pigments such as phthalocyanine pigment and azo pigment. Examples of the weather stabilizer include Nocrack 300 and Nocrack NS-6 (manufactured by Ouchi Shinko Chemical Co., Ltd.) Irganox 1010 and 1076 (manufactured by Ciba Geigy), Yoshinox BHT, BB and GSY
-930 (manufactured by Yoshitomi Pharmaceutical), benzotriazoles such as Tinuvin P, 327 and 328 (manufactured by Ciba Geigy), benzophenones such as Tomisorb 800 (manufactured by Yoshitomi Pharmaceutical), and Sanol LS-
Positionally hindered amines such as 770 and 744 (manufactured by Sankyo) and Tinuvin 144 (manufactured by Ciba-Geigy). Examples of the defoaming agent include dimethylsiloxane-based and polyacrylate-based ones such as Disparon 710 and 720 (manufactured by Kusumoto Chemicals). Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, hexane, cyclohexane, aliphatic hydrocarbons such as Isopar H and M (manufactured by Exxon), esters such as ethyl acetate, and ketones such as methyl ethyl ketone. And the like.
【００１６】本発明で使用される式１で表わされる芳香
族カルボン酸及び該芳香族カルボン酸の無水物として
は、例えば安息香酸、フタル酸、無水フタル酸、トルイ
ル酸、クロル安息香酸、ニトロ安息香酸、ブロム安息香
酸、フェニル酢酸、トリメリット酸、無水トリメリット
酸、ピロメリット酸、無水ピロメリット酸等がある。式
１においてベンゼン核に結合するアルキル基としては、
炭素数２〜９のアルキル基がより好ましい。芳香族カル
ボン酸及び該芳香族カルボン酸の無水物は、主剤及び硬
化剤のいずれに添加してもよいが、硬化剤の低粘化の要
請からは、硬化剤中に予め添加するのが、より好まし
い。芳香族カルボン酸及び該芳香族カルボン酸の無水物
の含有量としては、主剤及び硬化剤の合計重量に対し
０．００５〜５重量％が好ましく、より好ましくは０．
０５〜２．０重量％である。The aromatic carboxylic acid represented by the formula 1 and the anhydride of the aromatic carboxylic acid used in the present invention include, for example, benzoic acid, phthalic acid, phthalic anhydride, toluic acid, chlorobenzoic acid, nitrobenzoic acid. Acids, bromobenzoic acid, phenylacetic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride and the like. In the formula 1, as the alkyl group bonded to the benzene nucleus,
Alkyl groups having 2 to 9 carbon atoms are more preferred. The aromatic carboxylic acid and the anhydride of the aromatic carboxylic acid may be added to any of the main agent and the curing agent. More preferred. The content of the aromatic carboxylic acid and the anhydride of the aromatic carboxylic acid is preferably 0.005 to 5% by weight, more preferably 0.1 to 5% by weight, based on the total weight of the main agent and the curing agent.
05 to 2.0% by weight.
【００１７】本発明による常温硬化型ポリウレタンエラ
ストマー組成物の施工方法としては、塗膜防水材、弾性
舗装材、床材、下塗り材等の通常の施工方法によること
ができる。この際プレポリマー中のＮＣＯ基と活性水素
との当量が０．９〜１．４、特に好ましくは１．０５〜
１．１０となるように各成分の配合量を決定する。The cold-setting polyurethane elastomer composition according to the present invention can be applied by a usual application method such as a coating film waterproofing material, an elastic pavement material, a flooring material and a primer material. At this time, the equivalent of the NCO group and active hydrogen in the prepolymer is 0.9 to 1.4, particularly preferably 1.05 to 1.5.
The amount of each component is determined so as to be 1.10.
【００１８】本発明においてタックの測定は次のように
行った。離型剤を塗布したガラス板上に枠を置き、その
中に主剤と硬化剤との混合液を流し込み、常温で硬化さ
せて得たシートをタック測定試料とし、混合液を流し込
みから１８時間後（前日の夕方施工し翌日の朝方より塗
り重ねを行なう想定）に上面を測定する。上面につまみ
を付けたポリプロピレン製円版（表面積６．２ｃｍ2)の
下面を溶剤で洗浄し、試料シートの上に置く。この上に
１００ｇのおもりを１５秒間乗せた後除去する。つまみ
にばね秤をかけ、秤を垂直に引き上げた際に生ずる最大
荷重を翌日のタックとする。In the present invention, the tack was measured as follows. Place a frame on a glass plate coated with a release agent, pour a mixture of the main agent and the curing agent into it, set the sheet obtained by curing at room temperature as a tack measurement sample, and 18 hours after pouring the mixture Measure the upper surface (assuming construction is performed in the evening of the previous day and repainting is performed in the morning of the next day). The lower surface of a polypropylene circular plate (surface area: 6.2 cm 2 ) having a knob on the upper surface is washed with a solvent and placed on a sample sheet. A 100 g weight is placed on this for 15 seconds and then removed. A spring scale is applied to the knob, and the maximum load generated when the scale is pulled up vertically is defined as the tack of the next day.
【００１９】[0019]
【実施例】以下に実施例により本発明を具体的に説明す
る。例中の部は重量部を表わす。まず、主剤として用い
るウレタンプレポリマーの製造を行った。 ウレタンプレポリマー（Ａ）の製造 平均分子量５０００のポリオキシプロピレントリオール
４００部、平均分子量２０００のポリオキシプロピレン
ジオール４３０部、ＴＤＩ−６５ １２３部、減粘剤５
０部を混合し、窒素気流中８０℃で２時間、ついで１０
０℃で２時間反応させた。ＮＣＯ基含有量２．９重量
％、粘度 ６０００ｃｐｓ／２５℃のウレタンプレポリ
マー（Ａ）を得た。このウレタンプレポリマー（Ａ）を
実施例１５〜１７及び比較例３〜４に、また、ウレタン
プレポリマー（Ａ）に所定量の芳香族カルボン酸又はそ
の無水物を添加したものを実施例１〜１１及び比較例１
に供した。 ウレタンプレポリマー（Ｂ）の製造 平均分子量４０００のポリオキシプロピレントリオール
２７２部、平均分子量２０００のポリオキシプロピレン
ジオール４２６部、平均分子量３０００のポリオキシプ
ロピレンジオール１２４部、ＴＤＩ−６５ １２７部、
減粘剤５０部を混合し、窒素気流中８０℃で２時間、次
いで１００℃で２時間反応させた。ＮＣＯ基含有量２．
８重量％、粘度７０００ｃｐｓ／２５℃のウレタンプレ
ポリマー（Ｂ）を得た。このウレタンプレポリマー
（Ｂ）に所定量のｏ−トルイル酸を添加したものを実施
例１２〜１４及び比較例２に供した。 ウレタンプレポリマー（Ｃ）の製造 平均分子量３０００のポリオキシプロピレントリオール
２４３部、平均分子量２０００のポリオキシプロピレン
ジオール４７５部、平均分子量１０００のポリオキシプ
ロピレンジオール５６部、ＴＤＩ−８０ １７３部、耐
熱安定剤ノクセラーＴＥＴ（大内新興化学社製）３部、
減粘剤ＤＯＡ５０部を混合し、窒素気流中８０℃で３時
間反応させた。ＮＣＯ基含有量４．７重量％、粘度 ３
６００ｃｐｓ／２５℃のウレタンプレポリマー（Ｃ）を
得た。このウレタンプレポリマー（Ｃ）を実施例１８及
び比較例５に供した。The present invention will be specifically described below with reference to examples. Parts in the examples represent parts by weight. First, a urethane prepolymer used as a main ingredient was produced. Production of urethane prepolymer (A) 400 parts of polyoxypropylene triol having an average molecular weight of 5,000, 430 parts of polyoxypropylene diol having an average molecular weight of 2,000, 123 parts of TDI-65, and a viscosity reducing agent 5
0 parts in a nitrogen stream at 80 ° C. for 2 hours, then 10
The reaction was performed at 0 ° C. for 2 hours. A urethane prepolymer (A) having an NCO group content of 2.9% by weight and a viscosity of 6000 cps / 25 ° C. was obtained. The urethane prepolymer (A) was used in Examples 15 to 17 and Comparative Examples 3 to 4, and the urethane prepolymer (A) was prepared by adding a predetermined amount of an aromatic carboxylic acid or an anhydride thereof to Examples 1 to 7. 11 and Comparative Example 1
Was served. Production of urethane prepolymer (B) 272 parts of polyoxypropylene triol having an average molecular weight of 4000, 426 parts of polyoxypropylene diol having an average molecular weight of 2,000, 124 parts of polyoxypropylene diol having an average molecular weight of 3000, 127 parts of TDI-65,
50 parts of a viscosity reducing agent were mixed and reacted at 80 ° C. for 2 hours and then at 100 ° C. for 2 hours in a nitrogen stream. 1. NCO group content
A urethane prepolymer (B) having 8% by weight and a viscosity of 7000 cps / 25 ° C. was obtained. Those obtained by adding a predetermined amount of o-toluic acid to this urethane prepolymer (B) were used in Examples 12 to 14 and Comparative Example 2. Production of urethane prepolymer (C) 243 parts of polyoxypropylene triol having an average molecular weight of 3,000, 475 parts of polyoxypropylene diol having an average molecular weight of 2,000, 56 parts of polyoxypropylene diol having an average molecular weight of 1,000, 173 parts of TDI-80, and a heat stabilizer Noxeller TET (Ouchi Shinko Chemical Co., Ltd.) 3 copies,
50 parts of DOA was mixed and reacted at 80 ° C. for 3 hours in a nitrogen stream. NCO group content 4.7% by weight, viscosity 3
A urethane prepolymer (C) at 600 cps / 25 ° C. was obtained. This urethane prepolymer (C) was used in Example 18 and Comparative Example 5.
【００２０】実施例１ ＭＯＣＡ７．５部、平均分子量３０００のポリオキシプ
ロピレンジオール２０部、平均分子量５０００のポリオ
キシプロピレントリオール２０部、ＤＯＰ ５部、耐候
安定剤イルガノックス１０１０（チバガイギー社製）
１．０部を均一に溶解したのち、ミニコＰ−２５（活材
ケミカル社製、オクチル酸鉛触媒、ｐｂ含量２５重量
％）２．０部、炭酸カルシウム３９．５部、顔料ベンガ
ラ５．０部を加え、均一に混練して、弾性舗装材用の硬
化剤（Ａ）を得た。この硬化剤（Ａ）と主剤ウレタンプ
レポリマー（Ａ）にｏ−トルイル酸を０．１５％添加し
たものとを重量比１／１の割合でスパチユラを用いて均
一に混合した後、内容１００ｍｌのポリエチレン製カツ
プに移し、２０℃の室内に放置し初期混合粘度及びポッ
トライフを測定した。回転粘度計Ｂ−８Ｍ型を使用しロ
ーターＮｏ４、回転数６ｒｐｍの条件により粘度を測定
し、原液を混合し５分経過後の粘度を初期混合粘度とし
た。また粘度が１０万ｃｐｓに達するまでに要した時間
をポットライフとした。次にこの原液混合物を離型剤を
塗布したガラス板上に金ゴテを用いて厚さ２mmに塗布
し、２３℃恒温、恒湿室に放置した。１８時間放置した
後測定した物性を初期物性とし、７日放置した後測定し
た物性を常態物性とした。測定方法はＪＩＳ Ｋ−６３
０１に準拠した。Example 1 7.5 parts of MOCA, 20 parts of polyoxypropylene diol having an average molecular weight of 3000, 20 parts of polyoxypropylene triol having an average molecular weight of 5,000, 5 parts of DOP, Irganox 1010 (Ciba-Geigy Co., Ltd.)
After uniformly dissolving 1.0 part, 2.0 parts of Minico P-25 (manufactured by Active Materials Chemical Co., Ltd., lead octylate catalyst, pb content: 25% by weight), 39.5 parts of calcium carbonate, and 5.0 pigment bengara 5.0 parts Was added and kneaded uniformly to obtain a curing agent (A) for an elastic pavement material. The curing agent (A) and the base urethane prepolymer (A) obtained by adding 0.15% of o-toluic acid were uniformly mixed at a ratio of 1/1 by weight using a spatula, and the content was 100 ml. It was transferred to a polyethylene cup and left in a room at 20 ° C. to measure the initial mixing viscosity and the pot life. Using a rotational viscometer B-8M, the viscosity was measured under the conditions of rotor No. 4 and the number of rotations of 6 rpm, and the stock solution was mixed, and the viscosity after 5 minutes had passed was defined as the initial mixed viscosity. The time required for the viscosity to reach 100,000 cps was defined as the pot life. Next, this undiluted solution mixture was applied to a glass plate coated with a release agent to a thickness of 2 mm using a gold iron, and left in a constant temperature and humidity room at 23 ° C. Physical properties measured after standing for 18 hours were defined as initial physical properties, and physical properties measured after standing for 7 days were defined as normal physical properties. The measuring method is JIS K-63
01.
【００２１】実施例２ 実施例１においてｏ−トルイル酸の添加量を０．５０％
に増し、他は同様に行った。Example 2 The amount of o-toluic acid added in Example 1 was 0.50%
Others performed similarly.
【００２２】実施例３ 実施例１のｏ−トルイル酸の代わりにｍ−トルイル酸を
０．２０％添加し、他は同様に行った。Example 3 The procedure of Example 1 was repeated except that 0.20% of m-toluic acid was added instead of o-toluic acid.
【００２３】実施例４〜７、９〜１０ 実施例３のｍ−トルイル酸の代わりにｐ−トルイル酸、
安息香酸、無水安息香酸、ｏ−ニトロ安息香酸、テレフ
タル酸又はトリメリット酸をそれぞれ使用し、同様に行
った。Examples 4 to 7, 9 to 10 In place of m-toluic acid of Example 3, p-toluic acid was used.
The same procedure was performed using benzoic acid, benzoic anhydride, o-nitrobenzoic acid, terephthalic acid or trimellitic acid.
【００２４】実施例１１ ＭＯＣＡ７．５部、平均分子量３０００のポリオキシプ
ロピレンジオール２０部、平均分子量５０００のポリオ
キシプロピレントリオール ２０部、ＤＯＰ５部、耐候
安定剤としてイルガノックス１０１０（チバガイギー社
製）１．０部を均一に溶解したのち、ミニコＰ−２５
（活材ケミカル社製オクチル酸鉛触媒、Ｐｂ含量２５重
量％）２．０部、ｏ−トルイル酸０．１５部、炭酸カル
シウム３９．５部、顔料（ベンガラ）５．０部を加え、
ディゾルバーで均一に混練して、弾性舗装材用の硬化剤
（Ｂ）を得た。この硬化剤（Ｂ）と主剤ウレタンプレポ
リマー（Ａ）（一般式１の酸類を添加しないもの）とを
重量比１／１の割合でスパチユラを用いて均一に混合し
た後、内容１００ｍｌのポリエチレン製カツプに移し、
２０℃の室内に放置し初期混合粘度及びポットライフを
測定した。回転粘度計Ｂ−８Ｍ型を使用しローターＮｏ
４、回転数６ｒｐｍの条件により粘度を測定し、原液を
混合し５分経過後の粘度を初期混合粘度とした。また粘
度が１０万ｃｐｓに達するまでに要した時間をポットラ
イフとした。次にこの原液混合物を離型剤を塗布したガ
ラス板上に金ゴテを用いて厚さ２mmに塗布し、２３℃恒
温、恒湿室に放置した。１８時間放置した後測定した物
性を初期物性とし、７日放置した後測定した物性を常態
物性とした。測定方法はＪＩＳ Ｋ−６３０１に準拠し
た。Example 11 7.5 parts of MOCA, 20 parts of polyoxypropylene diol having an average molecular weight of 3000, 20 parts of polyoxypropylene triol having an average molecular weight of 5,000, 5 parts of DOP, and Irganox 1010 (manufactured by Ciba Geigy) as a weathering stabilizer. After dissolving 0 parts uniformly, Minico P-25
(Lead octylate catalyst manufactured by Active Materials Chemical Co., Pb content: 25% by weight) 2.0 parts, o-toluic acid 0.15 parts, calcium carbonate 39.5 parts, and pigment (Vengara) 5.0 parts were added.
The mixture was uniformly kneaded with a dissolver to obtain a curing agent (B) for an elastic pavement material. The curing agent (B) and the base urethane prepolymer (A) (without the addition of the acids of the general formula 1) are uniformly mixed with a spatula at a weight ratio of 1/1, and then the content is 100 ml made of polyethylene. Transfer to a cup,
The mixture was left in a room at 20 ° C., and the initial mixing viscosity and the pot life were measured. Rotor viscometer B-8M type and rotor No.
4. The viscosity was measured under the conditions of a rotation speed of 6 rpm, the stock solution was mixed, and the viscosity after 5 minutes had passed was defined as the initial mixed viscosity. The time required for the viscosity to reach 100,000 cps was defined as the pot life. Next, this undiluted solution mixture was applied to a glass plate coated with a release agent to a thickness of 2 mm using a gold iron, and left in a constant temperature and humidity room at 23 ° C. Physical properties measured after standing for 18 hours were defined as initial physical properties, and physical properties measured after standing for 7 days were defined as normal physical properties. The measuring method was based on JIS K-6301.
【００２５】比較例１ 実施例１においてｏ−トルイル酸の添加を省略し、他は
同様に行った。Comparative Example 1 The procedure of Example 1 was repeated except that the addition of o-toluic acid was omitted.
【００２６】以上の結果をまとめて表１に示す。The above results are summarized in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】実施例１２ ＭＣ−５０６ ９．４部、ＰＰＧ・ＥＰ−２４０（三井
東圧化学社製）４７．３部、Ｕ−レックス１７０（東京
樹脂工業社製）３６部、カーボンブラック４０部、炭酸
カルシウム５５．４０部、触媒オクチル酸鉛（Ｐｂ含有
量２５％）０．８５部、ノクラック３００ １．０部、
キシレン１０部、消泡剤シリコンオイル（動粘度１００
０センチストークス）０．０５部を加え、ディゾルバー
で均一に混練して、塗膜防水材用の硬化剤（Ｃ）を得
た。この硬化剤（Ｃ）と主剤ウレタンプレポリマー
（Ｂ）にｏ−トルイル酸を０．５０％添加したものとを
重量比１／２の割合でスパチユラを用いて均一に混合し
た後、内容１００ｍｌのポリエチレン製カツプに移し、
２０℃の室内に放置し初期混合粘度及びポットライフを
測定した。回転粘度計Ｂ−８Ｍ型を使用しローターＮｏ
４、回転数６ｒｐｍの条件により粘度を測定し、原液を
混合し５分経過後の粘度を初期混合粘度とした。また粘
度が１０万ｃｐｓに達するまでに要した時間をポットラ
イフとした。次にこの原液混合物を離型剤を塗布したガ
ラス板上に金コテを用いて厚さ２mmに塗布し、２３℃恒
温、恒湿室に放置した。１８時間放置した後測定した物
性を初期物性とし、７日放置した後測定した物性を常態
物性とした。測定方法はＪＩＳ Ａ−６０２１に準拠し
た。Example 12 9.4 parts of MC-506, 47.3 parts of PPG / EP-240 (manufactured by Mitsui Toatsu Chemicals), 36 parts of U-Rex 170 (manufactured by Tokyo Resin Industries), 40 parts of carbon black 55.40 parts of calcium carbonate, 0.85 part of lead catalyst octylate (Pb content 25%), 1.0 part of Nocrack 300,
Xylene 10 parts, antifoam silicone oil (kinematic viscosity 100
(0 centistokes) and uniformly kneaded with a dissolver to obtain a curing agent (C) for a coating film waterproofing material. This curing agent (C) and a mixture obtained by adding 0.50% of o-toluic acid to the base urethane prepolymer (B) were uniformly mixed at a weight ratio of 1/2 using a spatula, and then 100 ml of the content was added. Transfer to a polyethylene cup,
The mixture was left in a room at 20 ° C., and the initial mixing viscosity and the pot life were measured. Rotor viscometer B-8M type and rotor No.
4. The viscosity was measured under the conditions of a rotation speed of 6 rpm, the stock solution was mixed, and the viscosity after 5 minutes had passed was defined as the initial mixed viscosity. The time required for the viscosity to reach 100,000 cps was defined as the pot life. Next, the undiluted solution mixture was applied to a glass plate coated with a release agent to a thickness of 2 mm using a metal iron and left in a constant temperature and humidity room at 23 ° C. Physical properties measured after standing for 18 hours were defined as initial physical properties, and physical properties measured after standing for 7 days were defined as normal physical properties. The measuring method conformed to JIS A-6021.
【００２９】実施例１３ ＭＣ−５０６ ９．４部、ＰＰＧ・ＥＰ−２４０（三井
東圧化学社製）４７．３部、Ｕ−レックス１７０ ３６
部、カーボンブラック４０部、炭酸カルシウム５５．５
５部、触媒オクチル酸鉛（Ｐｂ含有量２５％）０．８５
部、ｏ−トルイル酸０．３５部、ノクラック３００
１．０部、キシレン１０部、消泡剤シリコンオイル（動
粘度１０００センチストークス）０．０５部を加え、デ
ィゾルバーで均一に混練して、塗膜防水材用の硬化剤
（Ｄ）を得た。この硬化剤（Ｄ）と主剤ウレタンプレポ
リマー（Ｂ）にｏ−トルイル酸を０．１５％添加したも
のとを重量比１／２の割合でスパチユラを用いて均一に
混合した後、内容１００ｍｌのポリエチレン製カツプに
移し、２０℃の室内に放置し初期混合粘度及びポットラ
イフを測定した。回転粘度計Ｂ−８Ｍ型を使用しロータ
ーＮｏ４、回転数６ｒｐｍの条件により粘度を測定し、
原液を混合し５分経過後の粘度を初期混合粘度とした。
また粘度が１０万ｃｐｓに達するまでに要した時間をポ
ットライフとした。次にこの原液混合物を離型剤を塗布
したガラス板上に金ゴテを用いて厚さ２mmに塗布し、２
３℃恒温、恒湿室に放置した。１８時間放置した後測定
した物性を初期物性とし、７日放置した後測定した物性
を常態物性とした。測定方法はＪＩＳ Ａ−６０２１に
準拠した。Example 13 9.4 parts of MC-506, 47.3 parts of PPG-EP-240 (manufactured by Mitsui Toatsu Chemicals), U-Rex 170 36
Part, 40 parts of carbon black, 55.5 calcium carbonate
5 parts, catalytic lead octylate (Pb content 25%) 0.85
Part, o-toluic acid 0.35 part, Nocrack 300
1.0 part, 10 parts of xylene, and 0.05 parts of a defoamer silicone oil (kinematic viscosity: 1000 centistokes) were added and uniformly kneaded with a dissolver to obtain a curing agent (D) for a coating film waterproofing material. . This curing agent (D) and a mixture obtained by adding 0.15% of o-toluic acid to the base urethane prepolymer (B) were uniformly mixed at a weight ratio of 1/2 using a spatula, and then 100 ml of the content was added. It was transferred to a polyethylene cup and left in a room at 20 ° C. to measure the initial mixing viscosity and the pot life. Using a rotational viscometer B-8M type, the viscosity was measured under the conditions of rotor No. 4 and rotation speed of 6 rpm,
The stock solution was mixed, and the viscosity after 5 minutes was defined as the initial mixed viscosity.
The time required for the viscosity to reach 100,000 cps was defined as the pot life. Next, this undiluted solution mixture was applied on a glass plate coated with a release agent to a thickness of 2 mm using a gold iron,
It was left in a constant temperature and humidity room at 3 ° C. Physical properties measured after standing for 18 hours were defined as initial physical properties, and physical properties measured after standing for 7 days were defined as normal physical properties. The measuring method was based on JIS A-6021.
【００３０】実施例１４ ＭＣ−５０６ ９．４部、ＰＰＧ・ＥＰ−２４０（三井
東圧化学社製）４７．３部、Ｕ−レックス１７０ ３６
部、カーボンブラック４０部、炭酸カルシウム５５．５
５部、触媒オクチル酸鉛（Ｐｂ含有量２５％）０．８５
部、ｏ−トルイル酸０．５０部、ノクラック３００（大
内新興化学社製）１．０部、キシレン１０部、消泡剤シ
リコンオイル（粘度１０００センチストークス）０．０
５部を加え、ディゾルバーで均一に混練して、塗膜防水
材用の硬化剤（Ｅ）を得た。この硬化剤（Ｅ）と主剤ウ
レタンプレポリマー（Ｂ）（一般式の酸類を添加しない
もの）とを重量比１／２の割合でスパチユラを用いて均
一に混合した後、内容１００ｍｌのポリエチレン製カツ
プに移し、２０℃の室内に放置し初期混合粘度及びポッ
トライフを測定した。回転粘度計Ｂ−８Ｍ型を使用しロ
ーターＮｏ４、回転数６ｒｐｍの条件により粘度を測定
し、原液を混合し５分経過後の粘度を初期混合粘度とし
た。また粘度が１０万ｃｐｓに達するまでに要した時間
をポットライフとした。次にこの原液混合物を離型剤を
塗布したガラス板上に金コテを用いて厚さ２mmに塗布
し、２３℃恒温、恒湿室に放置した。１８時間放置した
後測定した物性を初期物性とし、７日放置した後測定し
た物性を常態物性とした。Example 14 9.4 parts of MC-506, 47.3 parts of PPG / EP-240 (manufactured by Mitsui Toatsu Chemicals), U-Rex 170 36
Part, 40 parts of carbon black, 55.5 calcium carbonate
5 parts, catalytic lead octylate (Pb content 25%) 0.85
Parts, 0.50 part of o-toluic acid, 1.0 part of Nocrack 300 (manufactured by Ouchi Shinko Chemical Co., Ltd.), 10 parts of xylene, 0.0 of defoamer silicone oil (viscosity of 1,000 centistokes) 0.0
5 parts were added and uniformly kneaded with a dissolver to obtain a curing agent (E) for a coating film waterproofing material. The curing agent (E) and the base urethane prepolymer (B) (to which no acid of the general formula is added) are uniformly mixed at a weight ratio of 1/2 using a spatula, and then a 100 ml polyethylene cap is added. And left in a room at 20 ° C. to measure the initial mixing viscosity and the pot life. Using a rotational viscometer B-8M, the viscosity was measured under the conditions of rotor No. 4 and the number of rotations of 6 rpm, and the stock solution was mixed, and the viscosity after 5 minutes had passed was defined as the initial mixed viscosity. The time required for the viscosity to reach 100,000 cps was defined as the pot life. Next, the undiluted solution mixture was applied to a glass plate coated with a release agent to a thickness of 2 mm using a metal iron and left in a constant temperature and humidity room at 23 ° C. Physical properties measured after standing for 18 hours were defined as initial physical properties, and physical properties measured after standing for 7 days were defined as normal physical properties.
【００３１】比較例２ 実施例１２においてｏ−トルイル酸の添加を省略し、他
は同様に行った。Comparative Example 2 The procedure of Example 12 was repeated except that the addition of o-toluic acid was omitted.
【００３２】以上の結果をまとめて表２に示す。The above results are summarized in Table 2.
【００３３】[0033]
【表２】 [Table 2]
【００３４】以上の表１〜２の実施例及び比較例の対照
から、ポットライフを同一にした場合に、本発明の芳香
族カルボン酸及び該芳香族カルボン酸の無水物から選ば
れた化合物を含有せしめたものは、そうでないものに比
べて初期硬化性が大きく、タックが少く、混合後の粘度
が低いため作業性が良好で、高強度のポリウレタンエラ
ストマーが得られることがわかる。From the above Examples and Comparative Examples in Tables 1 and 2, the compounds selected from the aromatic carboxylic acids and anhydrides of the aromatic carboxylic acids of the present invention were obtained when the pot lives were the same. It can be seen that the polyurethane elastomer having high initial curing property, low tackiness and low viscosity after mixing has good workability and high strength compared to the one containing no polyurethane elastomer.
【００３５】実施例１５ ＭＯＣＡ７．５部、平均分子量３０００のポリオキシプ
ロピレンジオール２０部、平均分子量５０００のポリオ
キシプロピレントリオール２０部、耐候安定剤イルガノ
ックス１０１０（チバガイギー社製）１．０部及びｏ−
トルイル酸１．２部を均一に溶解したのち、ミニコＰ−
２５（活材ケミカル社製、オクチル酸鉛触媒、ｐｂ含量
２５重量％）２．０部、炭酸カルシウム４３．３部、顔
料ベンガラ５．０部を加え、均一に混練して、弾性舗装
材用の硬化剤（Ｆ）を得た。硬化剤の粘度は、２０℃の
室内に放置し恒温になったところで回転粘度計Ｂ−８Ｍ
形使用しローターＮｏ４、回転数６ｒｐｍで測定した
（以下の実施例も同様。）。この硬化剤（Ｆ）と主剤ウ
レタンプレポリマー（Ａ）とを重量比１／１の割合で撹
拌機を用いて３分間均一に混合した後、内容１００ｍｌ
のポリエチレン製カップに移し、２０℃の室内に放置し
初期混合粘度及びポットライフを測定した。回転粘度計
Ｂ−８Ｍ形使用しローターＮｏ４、回転数６ｒｐｍの条
件により粘度を測定し、原液を混合し５分経過後の粘度
を初期混合粘度とした。また粘度が１０万ｃｐｓに達す
るまでに要した時間をポットライフとした。次にこの原
液混合物を離型剤を塗布したガラス板上に金コテを用い
て２mmに塗布し、２０℃恒温、恒湿室に放置した。７日
放置した後測定した物性を常態物性とした。測定方法は
ＪＩＳ Ｋ−６３０１に準拠した。Example 15 7.5 parts of MOCA, 20 parts of polyoxypropylene diol having an average molecular weight of 3000, 20 parts of polyoxypropylene triol having an average molecular weight of 5,000, 1.0 part of Irganox 1010 (manufactured by Ciba-Geigy) and o −
After uniformly dissolving 1.2 parts of toluic acid, Minico P-
25 (manufactured by Active Materials Chemical Co., Ltd., lead octylate catalyst, pb content: 25% by weight), 2.0 parts of calcium carbonate, 43.3 parts of calcium carbonate, and 5.0 parts of pigment bengara were added and uniformly kneaded to prepare an elastic pavement material. Of a curing agent (F) was obtained. When the viscosity of the curing agent was allowed to stand at room temperature of 20 ° C. and reached a constant temperature, a rotational viscometer B-8M was used.
The shape was used and measured at rotor No. 4 and rotation speed of 6 rpm (the same applies to the following examples). The curing agent (F) and the base urethane prepolymer (A) were uniformly mixed at a weight ratio of 1/1 using a stirrer for 3 minutes, and then the content was 100 ml.
And left in a room at 20 ° C. to measure the initial mixing viscosity and the pot life. Using a rotational viscometer B-8M, the viscosity was measured under the conditions of rotor No. 4 and the number of rotations of 6 rpm, and the stock solution was mixed, and the viscosity after 5 minutes had passed was defined as the initial mixed viscosity. The time required for the viscosity to reach 100,000 cps was defined as the pot life. Next, the undiluted solution mixture was applied to a glass plate coated with a release agent to a thickness of 2 mm using a metal iron, and allowed to stand in a constant temperature and humidity room at 20 ° C. The physical properties measured after standing for 7 days were defined as normal physical properties. The measuring method was based on JIS K-6301.
【００３６】実施例１６ 実施例１５においてｏ−トルイル酸１．２部の代わりに
ｏ−クロロ安息香酸を１．２部とし、それ以外は同様に
して、弾性舗装材用の硬化剤（Ｇ）を得た。この硬化剤
（Ｇ）と主剤ウレタンプレポリマー（Ａ）とを重量比１
／１の割合で用い、他は実施例１５に準じて行った。Example 16 In Example 15, 1.2 parts of o-chlorobenzoic acid was used in place of 1.2 parts of o-toluic acid, and the other conditions were the same, except that the curing agent (G) for elastic pavement material was used. I got The curing agent (G) and the base urethane prepolymer (A) were added at a weight ratio of 1
/ L, and the others were carried out according to Example 15.
【００３７】実施例１７ ＭＯＣＡ４．９部、平均分子量３０００のポリオキシプ
ロピレンジオール２６部、平均分子量５０００のポリオ
キシプロピレントリオール１３部、ＤＯＰ ３０部、耐
候安定剤ノクラック＃３００（大内新興化学社製）１．
０部及びｏ−トルイル酸０．６５部を均一に溶解したの
ち、ミニコＰ−２５（活材ケミカル社製オクチル酸鉛触
媒、ｐｂ含量２５重量％）２．８部、炭酸カルシウム１
１６．６５部、顔料５．０部を加え、均一に混練して、
床の下塗り材用硬化剤（Ｈ）を得た。この硬化剤（Ｈ）
と主剤ウレタンプレポリマー（Ａ）とを重量比１／２の
割合で用い、他は実施例１５に準じて行った。Example 17 4.9 parts of MOCA, 26 parts of polyoxypropylene diol having an average molecular weight of 3000, 13 parts of polyoxypropylene triol having an average molecular weight of 5,000, 30 parts of DOP, weather cracking stabilizer Nocrack # 300 (manufactured by Ouchi Shinko Chemical Co., Ltd.) ) 1.
After uniformly dissolving 0 parts and 0.65 parts of o-toluic acid, 2.8 parts of Minico P-25 (lead octylate catalyst manufactured by Active Materials Chemical Co., Ltd., pb content: 25% by weight), calcium carbonate 1
Add 16.65 parts and 5.0 parts of pigment, knead uniformly,
A floor undercoat hardener (H) was obtained. This curing agent (H)
And the base urethane prepolymer (A) at a weight ratio of 1/2, and the others were carried out according to Example 15.
【００３８】実施例１８ ＭＯＣＡ７．４部、平均分子量３０００のポリオキシプ
ロピレンジオール２８部、ＤＯＰ １４部、耐候安定剤
イルガノックス１０７６（チバガイギー社製）０．５部
及びｏ−トルイル酸３部を均一に溶解したのち、ミニコ
Ｐ−２５（活材ケミカル社製オクチル酸鉛触媒、ｐｂ含
量２５重量％）４．３５部、炭酸カルシウム３７．４５
部、トナー５．３部、を加え、均一に混練して、速硬化
のカラー防水材用硬化剤（Ｉ）を得た。この硬化剤
（Ｉ）と主剤ウレタンプレポリマー（Ｃ）とを重量比１
／１．３の割合で用い、他は実施例１５に準じて行っ
た。Example 18 7.4 parts of MOCA, 28 parts of polyoxypropylene diol having an average molecular weight of 3,000, 14 parts of DOP, 0.5 parts of Irganox 1076 weathering stabilizer (manufactured by Ciba Geigy) and 3 parts of o-toluic acid were uniformly mixed. 4.35 parts of Minico P-25 (lead octylate catalyst manufactured by Active Materials Chemical Co., Ltd., pb content: 25% by weight), and 37.45 of calcium carbonate
Parts and 5.3 parts of the toner were added and kneaded evenly to obtain a curing agent (I) for a color curing material which was rapidly cured. The curing agent (I) and the base urethane prepolymer (C) were added at a weight ratio of 1
/1.3 was used, and the others were carried out according to Example 15.
【００３９】比較例３ 実施例１５においてｏ−トルイル酸を省略し、ミニコＰ
−２５（活材ケミカル社製、オクチル酸鉛触媒、ｐｂ含
量２５重量％）を増量して３．２部とし、それ以外は同
様にして、弾性舗装材用の硬化剤（Ｊ）を得た。 この
硬化剤（Ｊ）と主剤ウレタンプレポリマー（Ａ）とを重
量比１／１の割合で用い、他は実施例１５に準じて行っ
た。Comparative Example 3 In Example 15, o-toluic acid was omitted, and Minico P
-25 (manufactured by Active Materials Chemical Co., Ltd., lead octylate catalyst, pb content: 25% by weight) was increased to 3.2 parts, and otherwise, a curing agent (J) for an elastic pavement material was obtained. . This curing agent (J) and the base urethane prepolymer (A) were used at a weight ratio of 1/1, and the others were carried out according to Example 15.
【００４０】比較例４ 実施例１７においてｏ−トルイル酸を省略し、ミニコＰ
−２５（活材ケミカル社製、オクチル酸鉛触媒、ｐｂ含
量２５重量％）を増量して３．４５部とし、それ以外は
同様にして、弾性舗装材用の硬化剤（Ｋ）を得た。 こ
の硬化剤（Ｋ）と主剤ウレタンプレポリマー（Ａ）とを
重量比１／２の割合で用い、他は実施例１６に準じて行
った。Comparative Example 4 In Example 17, o-toluic acid was omitted, and Minico P
-25 (manufactured by Active Materials Chemical Co., Ltd., lead octylate catalyst, pb content: 25% by weight) was increased to 3.45 parts, and otherwise the same procedure was performed to obtain a hardener (K) for an elastic pavement material. . This curing agent (K) and the base urethane prepolymer (A) were used in a weight ratio of 1/2, and the other steps were the same as in Example 16.
【００４１】比較例５ 実施例１８においてｏ−トルイル酸を省略し、ミニコＰ
−２５（活材ケミカル社製、オクチル酸鉛触媒、ｐｂ含
量２５重量％）を増量して７．３５部とし、それ以外は
同様にして、弾性舗装材用の硬化剤（Ｌ）を得た。この
硬化剤（Ｌ）と主剤ウレタンプレポリマー（Ｃ）とを重
量比１／１．３の割合で用い、他は実施例１７に準じて
行った。Comparative Example 5 O-toluic acid was omitted in Example 18, and Minico P
-25 (manufactured by Active Materials Chemical Co., Ltd., lead octylate catalyst, pb content: 25% by weight) was increased to 7.35 parts, and in the same manner as above, a curing agent (L) for an elastic pavement material was obtained. . This curing agent (L) and the base urethane prepolymer (C) were used in a weight ratio of 1 / 1.3, and the other steps were performed in the same manner as in Example 17.
【００４２】以上の結果をまとめて表３に示す。Table 3 summarizes the above results.
【００４３】[0043]
【表３】 [Table 3]
【００４４】以上の表３の実施例及び比較例の対照か
ら、本発明のｏ−トルイル酸叉はｏ−クロロ安息香酸を
含有させた硬化剤は、含有させないものに比べて粘度が
大巾に低下し、更に硬化試験においてはポットライフを
同一にした場合に混合時の粘度が低いため作業性が良好
であり、かつ高強度のポリウレタンエラストマーが得ら
れることがわかる。From the control of the examples and comparative examples shown in Table 3 above, the curing agent containing o-toluic acid or o-chlorobenzoic acid of the present invention has a much larger viscosity than those not containing it. It can be seen that, in the curing test, when the pot life was the same, the viscosity at the time of mixing was low, so that the workability was good and a high-strength polyurethane elastomer was obtained.
【００４５】[0045]
【発明の効果】本発明のポリウレタンエラストマー組成
物を用いることにより、初期硬化性が大きく、タックが
少く、特に硬化剤の粘度を大巾に低下させることができ
るため作業性に優れ、防水材、床材、舗装材等に適した
高強度のポリウレタンエラストマーが得られる。EFFECT OF THE INVENTION By using the polyurethane elastomer composition of the present invention, the initial curing property is large, the tackiness is small, and particularly, the viscosity of the curing agent can be greatly reduced. A high-strength polyurethane elastomer suitable for floor materials, pavement materials and the like can be obtained.
フロントページの続き (56)参考文献 特開 昭59−51943（ＪＰ，Ａ) 特開 昭61−261313（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 18/00 - 18/87 C08K 5/09 C08L 75/00 - 75/12 Continuation of the front page (56) References JP-A-59-51943 (JP, A) JP-A-61-261313 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 18 / 00-18/87 C08K 5/09 C08L 75/00-75/12
Claims (3)
レタンプレポリマーを主成分とする主剤、及び（２）ポ
リアミンとして３，3'−ジクロル−４，４’−ジアミノ
ジフェニルメタン及び／又は鉱酸の存在下でアニリンと
２−クロロアニリンとをホルムアルデヒドと縮合させる
ことにより得られた芳香族ポリアミンを、ポリオールと
して活性水素１個当たりの平均分子量が７５〜１０００
０の２価もしくは３価のポリエーテルポリオールを用
い、両者の当量比がポリアミン／ポリオール＝１０／９
０〜９０／１０であるものを主成分とする硬化剤、から
成るポリウレタンエラストマー組成物において、該ポリ
ウレタンエラストマー組成物に対して０．００５〜５重
量％の式１（化１） 【化１】 （式中、Ｒは水酸基、ニトロ基、ブロム基、クロル基、
スルホン基又は炭素数１〜２０のアルキル基であり、ｎ
は１〜３の整数を表わすが、ｎが２又は３の時Ｒは同じ
であっても異なっていてもよい。ｍは１〜４の整数を表
わす。）で表わされる芳香族カルボン酸及び該芳香族カ
ルボン酸の無水物から選ばれた少くとも１種を含有せし
めて成ることを特徴とする常温硬化型ポリウレタンエラ
ストマー組成物。1. A (1) main agent mainly composed of a urethane prepolymer having an isocyanate group at a terminal, and (2) a 3,3′-dichloro-4,4′-diaminodiphenylmethane and / or a mineral acid as a polyamine. An aromatic polyamine obtained by condensing aniline and 2-chloroaniline with formaldehyde in the presence is converted into a polyol having an average molecular weight per active hydrogen of 75 to 1000.
0 divalent or trivalent polyether polyol, and the equivalent ratio of both is polyamine / polyol = 10/9
In a polyurethane elastomer composition comprising a curing agent whose main component is 0 to 90/10, 0.005 to 5% by weight of the polyurethane elastomer composition of the formula 1 (Wherein R is a hydroxyl group, a nitro group, a bromo group, a chloro group,
A sulfone group or an alkyl group having 1 to 20 carbon atoms, n
Represents an integer of 1 to 3, and when n is 2 or 3, R is the same
Or different. m represents an integer of 1 to 4
I forgot. A cold-setting polyurethane elastomer composition comprising at least one member selected from the group consisting of an aromatic carboxylic acid represented by the formula (1 ) and an anhydride of the aromatic carboxylic acid.
物を、予め（２）の硬化剤中に含有せしめて得られる常
温硬化型ポリウレタンエラストマー組成物。2. The room-temperature-curable polyurethane elastomer composition according to claim 1, wherein the compound of the formula 1 (formula 1) is previously contained in the curing agent (2).
ン酸がｏ−トルイル酸、ｏ−クロル安息香酸、及びｏ−
ニトロ安息香酸である請求項１又は２記載の常温硬化型
ポリウレタンエラストマー組成物。3. The method of claim 1, wherein the aromatic carboxylic acid represented by the formula 1 is o-toluic acid, o-chlorobenzoic acid, and o-toluic acid.
The cold-setting polyurethane elastomer composition according to claim 1 or 2, which is nitrobenzoic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27406193A JP3325367B2 (en) | 1992-11-18 | 1993-11-02 | Room temperature curing type polyurethane elastomer composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30884392 | 1992-11-18 | ||
| JP4-308843 | 1992-11-18 | ||
| JP27406193A JP3325367B2 (en) | 1992-11-18 | 1993-11-02 | Room temperature curing type polyurethane elastomer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06206964A JPH06206964A (en) | 1994-07-26 |
| JP3325367B2 true JP3325367B2 (en) | 2002-09-17 |
Family
ID=26550879
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27406193A Expired - Lifetime JP3325367B2 (en) | 1992-11-18 | 1993-11-02 | Room temperature curing type polyurethane elastomer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3325367B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR970702313A (en) * | 1994-04-08 | 1997-05-13 | 유미꾸라 레이이찌 | Process for Producing Hydroxyl-Terminated Polycarbonate |
| DE19610390C1 (en) * | 1996-03-16 | 1997-11-20 | Kvs Korrosions Und Verschleiss | Method of coating vehicle floor, especially buses, train carriages, aeroplanes floor with elastomer |
| JP2002212541A (en) * | 2001-01-18 | 2002-07-31 | Konishi Co Ltd | Two component system polyurethane sealing material |
| CN101180378B (en) * | 2005-04-28 | 2011-09-21 | 东洋油墨制造株式会社 | Adhesive and packaging laminate using the same |
-
1993
- 1993-11-02 JP JP27406193A patent/JP3325367B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06206964A (en) | 1994-07-26 |
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