JPH03160016A - Production of rapidly cured polyurethane/polyurea elastomer by spraying - Google Patents

Abstract

PURPOSE:To produce a rapidly cured polyurethane/polyurea elastomer by spraying, by spray-molding a base containing an organic polyisocyanate and a curing agent in which all of the terminals of the components are amino groups with a collision mixing-type high-pressure spray gun. CONSTITUTION:A base (A) containing an organic polyisocyanate (e.g. a partial prepolymer prepared by reacting an organic polyisocyanate compound with a polyol having a mol. wt. of 38-2000 per hydroxyl group in an equivalent ratio (NCO/OH) >=3 and a curing agent (B) : a composition comprising a polyoxyalkylenediamine (1) of the formula (wherein R<1> and R<6>, which may be the same or different, are each H, a 1-12C aliphatic, alicyclic or aromatic hydrocarbon group; R<2>, R<3>, R<4> and R<5>, which may be the same or different, are each H, a 1-10C aliphatic, alicyclic or aromatic hydrocarbon group, R<2>+R<3>+ R<4>+R<5>=0-10C, n=1-100, and x and y are each 1-20), an aromatic amine crosslinking agent (2) and an organic acid curing catalyst (3) are spray-molded with a two-liquid collision mixing-type spray gun to form a rapidly cured polyurethane/polyurea elastomer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing polyurethane/polyurea elastomer, and more particularly to a method for producing a quick-curing type polyurethane/polyurea elastomer by spraying using an impingement mixing type high-pressure spraying device. ．． [Prior art] To produce urethane elastomer by spraying,
Organic polyisocyanate is used as the main ingredient, and a combination of a high molecular weight polyol as a curing agent and a low molecular weight polyol or polyamine as a chain extender is used. For example, as the organic polyisocyanate used as the main ingredient, Ii! In the case of spray foaming of quality urethane foam, crude MDI is used as is. Furthermore, a common method is to add a solvent to the base resin and curing agent to dilute it. For example, JP-A-49-17430 describes an example using a solvent, which is used for coating a relatively thin film. On the other hand, it is possible to select a material with a slightly higher viscosity as the raw material used, but in this case, it is necessary to slow down the curing speed and use a static ξ mixer type as a mixer. JP-A-55-1878 describes an example in which a solvent is partially used. Other methods include, for example, Japanese Patent Application Laid-open No. 5
No. 3-24396 describes a method in which an amino group is reacted with a carbonyl compound to form a ketoimine in order to delay the reactivity of agon with an isocyanate group. On the other hand, as a precept method, these are mixed just before the precept.
It is sprayed with a liquid type spray machine or sprayed with a two-liquid type spray machine. [Problems to be Solved by the Invention] However, these conventionally known methods have the following various problems and are not practically satisfactory. 1) Foaming phenomenon. Conventional technology uses high molecular weight polyols or low molecular weight glycols, etc. In the case of spraying, fine particles are atomized into the air, so they react with moisture present in the atmosphere, causing foaming phenomena and physical properties. A decline occurs. 2) Jelly formation phenomenon that occurs at the beginning of the reaction. As a hardening agent,
For example, when using a high molecular weight polyol and an amine-based crosslinking agent, the reaction rates between the two are significantly different, so even if a curing catalyst is used, there is still a considerable difference between the crosslinking agent and the isocyanate-terminated base agent. The reaction occurs preferentially, only gelation progresses, chain elongation does not progress, and the system becomes cheese-like (so-called jelly). Additionally, if an impact force is applied during this process, the crank may engage. 3) Curing is slow and the development of physical properties is slow, so it is difficult to cure vertical surfaces and
Construction on sloped surfaces is impossible. With conventional methods, the curing speed was slow, sagging occurred, and the thickness of each application was limited to 51 liters or less. 4) Thick film molding is not possible because it is a solvent type. [Means for Solving the Problems] The present inventors changed the conventional method by changing the terminals of each component of the curing agent that reacts with the base resin to amino groups to bring the reactivity closer to incyanate. I was able to solve the problem. In other words, since all the terminal reactive groups are amino groups, it is possible to increase the difference in reaction rate with moisture in the air, making it possible to prevent foaming, and because the reaction proceeds uniformly, no diery formation occurs. first time! It is possible to obtain an elastomer that exhibits good tlI physical properties and has a high sheet specific gravity. At this time, by using an organic acid as a curing catalyst instead of the conventionally used amine catalyst or organometallic catalyst, we can improve the reactivity of incyanate and amine and create a reaction rate difference with water. By doing so, we were able to obtain an elastomer that cured quickly and had high physical properties, and finally achieved the present invention. That is, the present invention is as follows. (A) As a main ingredient, an organic polyisocyanate compound and/or the organic polyisocyanate compound and a molecular weight per OH group (3) a polyol as a curing catalyst are reacted at an equivalent ratio (NGO/011) of 3 or more. Part A containing a partial brevolimer, (n) as a curing agent, (+) boroxyachilenediamine R'NHCR"R'CR'R'(OCR"R3CR
'R')x-+O-(CIIzCHzCH*CHz
O)n-(CR'R'CR"R'0)y-+-CR
'R'CR''R'NHR' ・・・・・・・・・
... (1) (In the formula, Rl and R" represent an aliphatic, alicyclic, aromatic aliphatic hydrocarbon group of H or C, ~Cl1, which may be the same or different, R2, R3, R4, RS is an aliphatic, alicyclic, or aromatic hydrocarbon group of H or C, ~C1, which may be the same or different, and R''+Il''+R'+
R'=C*~C+o, n - an integer of 1-100, χ,
y represents an integer from 1 to 20. ) polyoxyalkylene diamine. (2) Aromatic amine crosslinking agent (3) Agent B containing an organic acid as a curing catalyst is sprayed onto the target object using a two-component high-pressure airless spray machine to form a quick curing method. Concerning the manufacturing method of polyurethane/polyurea elastomer. The boroxyalkylene diamine represented by the general formula (0) used in the present invention can be produced by the method of Japanese Patent Application No. 1-69249. Namely, the following general formula (n), H - (OCR"R"CR'R')x-0-(C
HzCHzCH1CH10)n(CR'R'CR"R'
O)y-H... (II) (In the formula, Rl%R1, R3, R4, R5, R&, n%x,y
has the same meaning as shown in the previous formula (1). ) and an active hydrogen-containing nitrogen compound selected from the group consisting of ammonia, primary amines, and secondary amines in the presence of a hydrogenation-dehydrogenation catalyst. can get. The polyoxyalkylene diol represented by the general formula (n) used above can be prepared, for example, by converting polytetramethylene ether glycol into 03
~C. It can be obtained by a known method of addition reaction of epoxy compounds. In addition, as the C3 to C+t epoxy compound used at this time, ethylene oxide, propylene oxide, 1.42
-butylene oxide, 2.3-butylene oxide, isobutylene oxide, 1.2-epoxyhexane, 1.2
- Eboxyoctane, l. 2-Epoxydecane, 1.2
Examples include -epoxide dodecane, cyclopentene oxide, cyclohexene oxide, styrene oxide, and α-methylstyrene oxide. The primary amine compounds used above include methylamine, ethylamine, probylamine, isopropylamine, butylamine, isobutylamine, SeG-butylamine, t-butylamine, amylamine, hexylamine, hebutylamine, octylamine, nonylamine,
Decylamine, β-aminobuvir methyl ether, β
Examples include -acnopropylethyl ether, aniline, 0-toluidine, m-toluidine, p-toluidine, penzylamine, naphthylamine, cyclopentylamine, cyclohexylamine, and the like. In addition, the secondary amine compounds used above include dimethylamine, diethylamine, dibropyluamine, diisopropylamine,
dibutylamine, diamylamine, dihexylamine,
Examples include methylethylamine, methylpropylamine, methylisobrobylamine, ethylbropylamine, ethylisopropylamine, N-methyldodecylamine, N-methylaniline, N-ethylaniline, dibenzylaniline, diphenylamine, etc. ．． The amount of the active hydrogen-containing nitrogen compound used above is determined depending on the application, but is usually 0.2 to 100 equivalents, preferably 0.5 to 50 equivalents, based on the hydroxyl group. In addition, active hydrogen-containing nitrogen compounds may be used alone or in combination depending on the purpose. As the hydrogenation-dehydrogenation catalyst used above, conventionally known catalysts can be used, such as supported catalysts in which nickel, cobalt, etc. are supported on a carrier such as diatomaceous earth or alumina, and nickel- and cobalt-based catalysts. Raney type catalyst, copper
Representative examples include chromium-based catalysts and copper-zinc-based catalysts.
Among these, supported catalysts are one of the most suitable catalysts. In the above, the catalyst is usually 0.1 to 20 wt%, preferably 0.1 to 20 wt%, preferably 0.1 to 20 wt%, based on the polyoxyalkylene diol.
3-10 wt% is used, most preferably 0.5-5 wt%. The above reaction conditions generally include a reaction temperature of 150 to 280
°C, preferably 180~250''C, reaction pressure 20~
150kg/cdG, preferably 30-100kg/
c4G, reaction time 1-20 hours, preferably 5-10
Do it in time. Hydrogen may coexist in the reaction system,
You don't have to do it. The lower the reaction temperature, the lower the reaction rate, and if it is too high, the polyoxyalkylene diol will decompose, which is not preferable. After the reaction is completed, the desired product, a polyoxyalkylene diamine having an ξ group at the molecular end, can be obtained by appropriately combining methods such as recovery of unreacted active hydrogen-containing nitrogen compounds by evaporation, catalyst filtration, water washing, and drying. can be obtained. The organic polyisocyanate used in the present invention is, for example, 2
．． 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), diphenylmethane-4,4°-diisocyanate (MDI), xylylene diisocyanate (XDI), dicyclohexylmethane-4,4°- Diisocyanate (hydrogenated MD
I), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (MDI), hydrogenated xylylene diisocyanate (HXDI), crude TDI,
Polymethyleneborifhenyl polyisocyanate (crude M
DI), and these isocyanates! Isocyanurated modified products of 1f, carbodiyl ξ-doped modified products, Bieulet modified products, etc. are suitable. Among these organic polyisocyanates, MDI, crude M
DI and its variants are particularly preferred. The organic polyisocyanate of the present invention can be directly reacted with a polyoxyalkylene diamine and a crosslinking agent, or a part of the isocyanate groups can be reacted with a polyol in a nitrogen stream.
Partial prebolimers obtained by heating at 70-80°C for several hours can be used. Examples of polyols that can be used in the production of the above-mentioned partial polymers include water, polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, trimethylolpropane, and pentaerythritol, or ethylene oxide. , polyether polyol (PPG) obtained by addition polymerization of one or more alkylene oxides such as brobylene oxide and butylene oxide.
; Polytetramethylene ether glycol (PTMEG) obtained by addition polymerization of tetrahydrofuran alone or together with ethylene oxide, castor oil, polycarbonate polyol, etc. are suitable. In addition to the above, polyester polyols obtained by reacting polycarboxylic acids with low-molecular-weight polyols and polyester polyols obtained by polymerizing cabrolactone can also be used. Furthermore, polymer polyols obtained by graft polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, methyl methacrylate, etc. to the above-mentioned known polyether polyols or polyester polyols, and 1.2- or 1.4-polybutadiene polyols. All or hydrogenated products of these can also be used. The above-mentioned polyols may be used alone or in a mixture of two or more, and the polyol or a mixture thereof preferably has a molecular weight per OH group of 38 to 2,000.

Examples of active aromatic polyamines used as chain extenders in this invention include 4,4-diamino diphenyl, 4,
Mixture of 4°-diamino diphenyl ether, 2,3-diaminotoluene and 3,4-diaminotoluene, 2
．． 4- and z. 6-diaphragm toluene (80:20
(!!!)], 2, 4-1 and/or 4,
4°-dia≧nodiphenylmethane, 1,3-and 1.
4-phenylene diamine, naphthylene-1,5-diamine, liquid polymer of polyphenylene-polymethylene polyamine of the type obtained by aniline-formaldehyde condensation, 1,3-dimethyl-2,4-diatonobenzene, 1 .3-diethyl-2,4-diaminobenzene, 1.
3-dimethyl-2.5-diaminobenzene, 1,4-diisopropyl-2.5-diaminobenzene, 2,4-diatonomesitylene, 1,3.5-4 riethyl-2.4-
Diaξnobenzene, 1,3.5-triethyl-2.6-
Diaminobenzene, 1,3,5-triisopropyl-2
4-diaminobenzene, 1-methyl-3.5-diethyl-2.4-diaminobenzene, 1-methyl-3.5-diethyl-2.6-diaξnobenzene (and mixtures of the latter 2 diamines in different proportions) , and the like; 2.3-dimethyl-1,4diaξnonaphthalene, 2.
6-dimethyl-1,5-diaminonaphthalene, 2,6-
Diisoprobyl-1,5-dia [nonaphthalene, 2.6
Dibutyl-1,5-diaξnonaphthalene and the like; 3.3°,5,5°-tetraisobenzidine and the like;3,3',5.
5'-tetramethyl-4,4゜diaminodiphenylmethane, 3.3'',5.5'-tetraethyl-4,4'-
Diaminodiphenylmethane, 3.3''.5.5゜-tetraisopropyl-4,4゜-diaminodiphenylmethane, 3.3',5.5''-tetraptyl-4.4゛-diaminodiphenylmethane, 3.5 -diethyl-3゜methyl 2゜ 4-diaminodiphenylmethane, 3,5-diisopropyl-3゜ monomethyl-2゜. 3.3'
3,3'
Dichloro4.4-Polyamine mixture of 2-chloroaniline and aniline condensed with formaldehyde in the presence of diaminodiphenylmethane and mineral acids; terL-butyltoluenediamine; 1,3.5-triisobrobyl-2,4-diamino Benzene; 4,4'-bis(sec
-butylamino)diphenylmethane; l, 4 -
(sec-butylamino)benzene and the like. These aromatic polyacrylates can be used alone or in combination, and the usage ratio is 3 to 100 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of polyoxyalkylene diamine. Offfi section is appropriate.

The amount of polyisocyanate or partial prepolymer, polyol, and crosslinking agent to be used is determined by the equivalence ratio (NCO/H'') of NCOI in the organic polyisocyanate or partial prepolymer to active hydrogen (H) in the polyol and crosslinking agent. The organic acid of the curing catalyst is a compound having at least one acidic group such as a COOH group, a 302H group, or a phenolic OH group.In particular, fatty acids, Oxycarboxylic acid, aliphatic dicarboxylic acid,
Aromatic carboxylic acids, sulfonic acids, nonylphenols, etc. are preferred. The amount used is 0.001 to 5% of the total amount of raw materials used.
Weight % is preferred. In the present invention, auxiliary agents such as plasticizers, flame retardants, antifoaming agents, colorants, stabilizers, and fillers may be used as necessary. As a plasticizer, for example, dioctyl phthalate (DOP
), dibutyl phthalate (DBP), dioctyl adipate (DOA), fig}licresil (TCP), chlorinated paraffin, etc. The flame retardant is, for example, Tris(
β-chloropropyl) phosphate, (phyllol P
Phosphate esters such as CF (manufactured by Akzo Japan Co., Ltd.), tris-dichloroethyl phosphate (CRP: made by Daihachi Chemical Co., Ltd.), tris-chloroethyl phosphate (CLP: made by Daihachi Chemical Co., Ltd.), dibrome These include bromine compounds such as neopentylene glycol and tribrome neopentyl alcohol. As the coloring agent, a mixture of an organic or inorganic pigment with the above-mentioned plasticizer (toner) and a dye are used. As a stabilizer, for example, Irganox 110 (trade name)
Positionally hindered phenols such as 10 and 11076 (manufactured by Ciba Geigy), Yoshinox BHT, BB, and GSY-930 (manufactured by Yoshino Pharmaceutical); Tinuvin P, 32
Penzotriazoles such as 7, 32B (manufactured by Ciba Geigy); Penzophenones such as Tomisorp 800 (manufactured by Yoshino Pharmaceuticals); Positional obstruction type agars such as Sanol LS-77 0 and 744, Tinuvin 144 (manufactured by Ciba Geigy) You can use various types. Fillers include carbon black, calcium carbonate,
These include silica, talc, kaolin, zeolite, diatomaceous earth, perlite, permuelite, and titanium dioxide. As antifoaming agents, silicone-based ones commonly used in polyurekne, polyacrylic acid ester-based ones, etc. can be used. The two-component high-pressure spray machine used in the present invention is, for example, a model H-2000 model manufactured by Gasmer Co., Ltd.
-V type, GlassCraft model T-3H type, Binks model G, etc. are preferred. These two-component high pressure spray machines are rated at 50kg/c++
Two temperature-controlled liquids can be quantitatively delivered at a pressure of "more than, preferably about 100 kg/c+*" or more. 2
The spray gun that mixes and atomizes liquid is GX manufactured by Gasma.
Preferred are the -7 gun, the AR-A gun, the Glasscraft Bloppler gun, and the Binks Model 43P gun. The spray gun is mainly of the collision rinsing type, but a static mixer can also be used to form a spray gun. Moreover, since no solvent is used in the present invention, 1
It is possible to achieve a fairly thick coating with one spray, and it is also possible to build up continuous layers. The polyurethane stock solution used in the present invention has very high reactivity and loses fluidity within 1 to 60 seconds after mixing the stock solution. The present invention is a "solvent-free" system that does not use solvents, and improvements have been made to the adjustment of raw materials and machine settings to enable spraying.However, the following problems can also be solved. was completed. 1) Preventing foaming: When sprayed in a high temperature and humid atmosphere, there is little decrease in density and almost no change in mechanical strength. 2) Preventing jelly formation: The hardening state of the sheet was checked immediately after forming, but none of the sheets of the present invention became cheese-like, and it is presumed that there is a rubbery element and polymerization is proceeding smoothly. ．． 3) Fast curing: development of physical properties to 30
The hardness and mechanical strength were measured at 3"J, 1 hour, 4 hours, and 24 hours, and the development of hardness and mechanical strength was good, and when used as a flooring material, it was found that sufficient strength for walking was developed within 30 minutes. (Example) In order to explain the present invention more specifically, Examples and Comparative Examples will be given below, but the present invention is not limited to these Examples. The polyisocyanate of ゛C was prepared by the following method. Reference Example 1 Pure MDI (manufactured by Mitsui Toatsu Chemical Co., Ltd.; MDI-P}!) and carbodiimide modified liquid MDI (manufactured by Mitsui Toatsu Chemical Co., Ltd.) M
DI-LK, NCO-28.5% by weight) at a weight ratio of 7
1.000 g of PPG-Dio mixed with
I-1500 (Mitsui Toatsu Chemical Co., Ltd. 01 {Value -75)
After adding 750 g of DOP (dioctyl phthalate) as a thinner and reacting for 3 hours at 80°C under a nitrogen stream, NGO-14% by weight and viscosity (eps/2) were added.
A modified polyisocyanate (A-1) having a temperature of -500 and a specific gravity of -1.15 was obtained. Reference Example 2 1,000 g of a mixture of pure MDI/liquid MDI-8/2 (weight ratio) was interring-polymerized with tetrahydrofuran. -114)
After adding 530g and reacting for 3 hours at 80°C under a nitrogen stream, NC〇1〇8% by weight, viscosity (CPS/25°C) -
800, modified polyisocyanate with a specific gravity of -1.18 (
A-2) was obtained. Reference Example 3 1.000 g of liquid MDI (mentioned above) and 239 g of liquid flame retardant (Phylor PCF manufactured by Akzo Japan) were stirred for 1 hour under a nitrogen stream to give an NC○-23% by weight and a viscosity (c
A polyisocyanate (A-3) having a specific gravity of -1.20 and a specific gravity of -1.20 was obtained. Reference example 4 Crude MDI (MDI-CR manufactured by Mitsui Toatsu Chemical Co., Ltd.; NC
825.4 g of O-31% by weight) and 115.9 g of chlorinated paraffin (salt paraffin #40 manufactured by Ajinomoto Co., Ltd.) were stirred for 1 hour under a nitrogen stream to obtain NGO-20% by weight and viscosity (cps/
25°C) -400 and a specific gravity of -1.22 (A-4) was obtained. Reference Example 5 Xylylene diisocyanate (MXDIi manufactured by Takeda Pharmaceutical Company) 1,000. , PPD-Diol-100
0 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added, and after reacting for 3 hours at 80"C under a nitrogen stream, the temperature was further raised to 100°C and the reaction was continued for another 3 hours. As a result, NGO-20% by weight, Toluene was added to 667 g of f: Kai polyisocyanate (A-2). 333g was added to reduce the viscosity.NCO%-
12% by weight, viscosity (cps/25°C) -70, ratio f [
-1.08 Polyisocyanate (Comparative Example-2) preparation results are shown in Table 1l. Table 1 Results of preparation of polyisocyanate Box 1 Reference example 7 of 200 ml of high-pressure autoclave, 4 g of nickel diatomaceous earth catalyst (nickel content -50%) and polytetra obtained by ring-opening polymerization of tetrahydrofuran. Polyoxyalkylene diol (hydroxyl value -112m gκOH/g) obtained by addition polymerizing propylene oxide to methylene ether glycol (average molecular weight -650)
, average molecular weight -1,000; hereinafter abbreviated as polyol P) and 47.2 g of isobrobylamine were charged in this order, and nitrogen substitution was performed 5 times (10 kg/sQ.cs+G
), hydrogen was added to an initial pressure of 50 kg/gq. c+w
Prepared with G. The temperature was raised to 220°C while stirring, and the reaction was carried out for 8 hours. At this time, the pressure was 75kg/sq.
It was cmG. After the reaction was completed, the catalyst was filtered off and dried under reduced pressure to produce a novel polyoxyanolekylene diane (B-1) containing an amino group at the end of the molecule. of the obtained polyoxyalkylene diamine! The absorption of AminoGo was confirmed by the R spectrum (3330 cm-1, 3
400cm-1). The nitrogen content by elemental analysis is 2.
It was 4%. In addition, when the amine value was measured by the azomethine method and the acetylated perchloric acid method, the total amine value was −9.
4.3mgKOH/g, primary amine value 40.4mg
XOH/g, secondary amine value 53.6tagKOH/g
, tertiary amine value 0. At 3tsgKQH/g, the conversion rate of hydroxyl group was 94.0%, and the selectivity of primary amine and secondary amine were 42.8% and 56.8%, respectively. Reference Example 8 In B-1, the reaction was carried out under the same conditions as in Example 1, except that diisobropylaramine was used instead of isobrobylamine (B-2). Reference Example 9 In B-1, diisopropyramine was added so that the equivalent ratio of diol P/isopropylamine/diisopropylamine ξ was 1/2/8, and the reaction temperature was changed to 200°C. The reaction was carried out under the same conditions as in Example 1.
However, the amount of diol P charged was SOg (B-3)
．． Reference Example 9 In B-3, instead of diol P, polyoxyalkylene glycol (hydroxyl value 47) obtained by addition polymerizing propylene oxide to polytetramethylene ether glycol (average molecular weight 2000) obtained by ring-opening polymerization of tetrahydrofuran was used. .8mgκOH/g,
It is abbreviated as diol Q with an average molecular weight of 312,350 i.
) was used, but the reaction was carried out under the same conditions as B-3. Table 2 shows the combined results of polyalkylene diamine (B-4).
It is shown in 51: U4 Friendship Examples 1 to 5, Comparative Examples 1 to 2 Examples 1, 2, 4, 5 and Comparative Example 1 are a certain type of machine, H-2 manufactured by Gasmer 0 0 0 As a spray gun for the high-pressure spray machine, use Glass Craft's bobbler gun (mixing chamber: Round N).
o. 1) was used. Example-3 and Comparative Example-1 are manufactured by Glass Craft Co., Ltd. MIN! -2 was used as a spray gun using a Binks 43P collision mixing type with a static mixer installed with 4 elements.
, see the attached table for spray setting conditions. The atmospheric conditions for spraying were tested by creating a sealed chamber with a vinyl sheet and blowing hot air and steam into it to create high temperature and high humidity conditions. The formulation is shown in Table 3, and the test results are shown in Table 4. [Effects of the Invention] The present invention is a "solvent-free" system that does not use solvents, and improvements have been made to the adjustment of raw materials and machine settings so that spraying can be performed.However, there are problems as described below. We were able to solve the problem as follows. 1) Preventing foaming: When sprayed in a high temperature and humid atmosphere, there is little decrease in density and almost no change in mechanical strength. (Example 1.2 and Comparative Example 1)
, 1) 2) Prevention of jelly formation: The hardening state of the sheet was checked immediately after being fashioned, and none of the sheets of the present invention were cheese-like, indicating that there was a rubbery element and polymerization was proceeding smoothly. Presumed. 3) Rapid curing property: The development of physical properties was measured at 30 minutes, 1 hour, 4 hours and 24 hours.
It is clear from Table 4 that the development of hardness and mechanical strength is good, and that when used as a flooring material, sufficient strength for walking is developed within 30 minutes.

Claims (1)

[Claims] 1. 1) A containing an organic polyisocyanate as a main ingredient
and 2) as a curing agent, (1) polyoxyalkylene diamine R^1NHCR^2R^3CR^4R^5-(OCR^) represented by the following general formula (I).
2R^3CR^4R^5) x_-_1-O-(CH_2
CH_2CH_2CH_2O)n-(CR^4R^5C
R^2R^3O)y_-_1-CR^4R^5CR^2
R^3NHR^6・・・・・・・・・・・・(I)(
In the formula, R^1 and R^6 represent H or C_1 to C_1_2 aliphatic, alicyclic, or aromatic hydrocarbon groups, which may be the same or different, and R^2, R^3, R^4, R^5 is an aliphatic, alicyclic, or aromatic hydrocarbon group of H or C_1 to C_1_0, which may be the same or different, and R^2+R^3+R^4+R^5=C_0 to C_1
_0, n=an integer of 1 to 100; x, y represent an integer of 1 to 20; ) (2) Aromatic amine crosslinking agent (3) Agent B containing an organic acid as a curing catalyst is spray-molded onto an object using a two-liquid high-pressure airless spray machine. Method for producing polyurethane/polyurea elastomer. 2. The organic polyisocyanate is made by reacting an organic polyisocyanate compound and/or the organic polyisocyanate compound with a polyol having a molecular weight per OH group of 38 to 2000 at an equivalent ratio (NCO/OH) of 3 or more. The method for producing a polyurethane/polyurea elastomer according to claim 1, wherein the polyurethane/polyurea elastomer is a partially prepolymer. 3. The organic polyisocyanate compound is MDI, crude M
3. The method for producing a polyurethane/polyurea elastomer according to claim 2, which is any one type or a mixture of two or more types of DI or modified products thereof, or a partial prepolymer of the organic polyisocyanate. 4. The method for producing a polyurethane/polyurea elastomer according to claim 1, wherein the aromatic amine crosslinking agent is used in an amount of 3 to 100 parts by weight per 100 parts by weight of polyoxyalkylene diamine. 5. The organic acid of the curing catalyst is a COOH group, SO_3H group,
The method for producing a polyurethane/polyurea elastomer according to claim 1, wherein the compound is a compound having at least one acidic group such as a phenolic OH group. 6. The organic acid of the curing catalyst is fatty acid, oxycarboxylic acid,
Aliphatic dicarboxylic acids, aromatic carboxylic acids, sulfonic acids,
The polyurethane according to claim 1, which is nonylphenol.
Method for producing polyurea elastomer. 7. The organic acid of the curing catalyst is 0.0% based on the total amount of raw materials used.
001 to 5% by weight of the polyurethane according to claim 1.
Method for producing polyurea elastomer.