JPH1160678A - Production of polyurethane/polyurea elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a coating elastomer which does not suffer from foaming even when applied thick, is capable of being overcoated and is excellent in strengths, etc., by specifying the hydroxyl value and total unsaturation value in coating an object with a component containing an organic polyisocyanate, a polyol having a specified amount of primary OH groups and a component containing a specified chain extender and a catalyst and curing the wet film. SOLUTION: In mixing a component containing an organic polyisocyanate or a prepolymer, derived by reacting a part of the NCO group with a polyol, with a polyol having at least two OH groups and a primary OH content of 50 wt.% or above, a chain extender being a solventless component containing a specified active aromatic polyamine except toluenediamine and an least one organometallic catalyst containing Sn, Pb or Bi in a specified mixing ratio under specified pressure, and coating an article with the mixture and curing the wet film, the hydroxyl value (OHV) of the polyol used is 50-60 mgKOH/g, and the total unsaturation value USV (meq/g) satisfies the relationship: USV <=1.2/OHV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyurethane polyurea elastomer, and more particularly to a method for producing a polyurethane polyurea elastomer using a high pressure spraying apparatus.

[0002]

2. Description of the Related Art In order to produce a polyurethane / polyurea elastomer, an organic polyisocyanate high molecular weight polyol and a low molecular weight polyamine as a chain extender are generally used as essential components. As a technique for coating an object with a polyurethane / polyurea / elastomer, a prepolymer having an isocyanate group at a terminal obtained by reacting an organic polyisocyanate and a polyol is diluted with a solvent, and a highly active aromatic amine such as diphenylmethanediamine is diluted with a solvent. ^2. Description of the Related Art A method of spray coating using a usual two-pack spraying apparatus (pressure: about 70 kg / cm ² ) together with a curing agent dissolved in a solvent is used. In addition, 3
After dissolving a low-active aromatic amine having an electron-withdrawing group in an aromatic nucleus such as 3′-dichloro-4,4′-diaminodiphenylmethane (MOCA) in a solvent or the like, and mixing with a prepolymer diluted with a solvent, A method of spray-coating using a high-pressure one-component spraying device during a pot life is also performed.

In this method, since a large amount of solvent needs to be volatilized from the coating obtained by coating, a large amount of air bubbles are generated from the coating when sprayed once thickly. There is a method in which a solvent having a high boiling point is used to prevent the generation of bubbles, and the solvent is left in the coating (Japanese Patent Publication No. 55-19930). However, in this method, the solvent is lost due to migration, evaporation, and outflow into rainwater during use for a long time, so that the coating is deteriorated, and cracks and shrinkage are caused.

There is also a method of producing a coating by reacting a partial prepolymer of liquid diphenylmethane diisocyanate modified with carbodiimide with a mixture of a high molecular weight polyol and a low molecular weight polyol. In this method, the low-molecular-weight polyol easily absorbs moisture, is likely to foam due to a competitive reaction between hydroxyl groups and moisture, generates pinholes, craters, etc. on the surface of the coating, reduces the specific gravity of the coating, and decreases the strength. Would.

[0005] Accordingly, there is a strong demand for a coating which can be applied repeatedly without causing foaming by being applied thickly. Polyurethane / polyurea / elastomer is used in a wide range of applications, such as lining and protective coatings for steel structures, waterproof protective coatings for concrete, and protective coatings for heat insulating materials. There is a demand for higher performance. By the way, the polyoxyalkylene polyol used for the polyurethane polyurea elastomer,
In a general production method, an alkali metal hydroxide is used as a catalyst.

Generally, in the presence of the above-mentioned catalyst, when a commonly used initiator and propylene oxide, which is most widely used as an alkylene oxide compound, are used, K
It is known that with an OH catalyst, a monol having an unsaturated group at one terminal of a molecule is by-produced as the molecular weight of the polyoxyalkylene polyol increases. Since the monol has a low molecular weight as compared with the polyoxyalkylene polyol produced by the main reaction, the molecular weight distribution of the polyoxyalkylene polyol is greatly widened and the average number of functional groups is reduced. Therefore, when a polyoxyalkylene polyol having a high monol content is used, it causes a decrease in various physical properties such as an increase in hysteresis, a decrease in hardness, a decrease in elongation, and a decrease in cure.

Conventional polyoxyalkylene polyols used in polyurethane / polyurea elastomers include general polyoxyalkylene polyols catalyzed by alkali metal hydroxides, particularly those having a hydroxyl value of 60.
When the following polyoxyalkylene polyol is used, the unsaturated monol contained as a by-product causes a decrease in general physical properties such as tensile strength, tear strength and elongation of polyurethane / polyurea / elastomer.

[0008]

SUMMARY OF THE INVENTION As described above, an object of the present invention is to provide a coating material which does not cause foaming even when the stock solution is thickly applied by spray coating or the like and which can be repeatedly coated, and a method for producing the same. Another object of the present invention is to provide a polyurethane-polyurea elastomer having excellent physical properties such as tensile strength, tear strength and elongation, and a method for producing the same. Is provided.

[0009]

Means for Solving the Problems The present inventors have set forth the above-mentioned object, namely, a coating which is thick and does not cause foaming, can be applied repeatedly, and has excellent physical properties. As a result of intensive studies on a method of manufacturing a product, the present invention has been achieved. That is, the present invention provides the following (1) to
(6) is provided. (1) a a partial prepolymer obtained by reacting a part of an organic polyisocyanate or an isocyanate group with a polyol; b containing at least two hydroxyl groups, wherein at least 50% by weight of the hydroxyl groups is a primary hydroxyl group; C, an active aromatic polyamine which does not contain an electron-withdrawing group in the aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to the amino group, excluding toluenediamine as a chain extender; To 100 parts by weight of the polyol shown in
When reacting a tin-based and / or lead-based and / or bismuth-based organometallic catalyst in an amount of 0.001 to 5% by weight based on the total amount of the raw materials used, a component A containing a
A solvent-free type B component containing b, c and d
Equivalent ratio of the NCO group of the component to the active hydrogen group of the B component (NCO
/ H) is 0.9-1.30 and the pressure is 60-150 kg
A method for producing a polyurethane-polyurea elastomer obtained by impinging and mixing under a condition of f / cm ² by a high-pressure two-component spraying device, applying the mixture to an object, and curing the mixture. And / or the polyol used in b has a hydroxyl value OHV (mg KOH / g) of 5 to 60 and a total unsaturation USV (meq / g) of the following formula (1)

[0010]

Embedded image A process for producing a polyurethane / polyurea elastomer, wherein the polyol satisfies USV ≦ 1.2 / OHV (1). (2) a partial prepolymer obtained by reacting a part of an organic polyisocyanate or an isocyanate group with a polyol; b containing at least two hydroxyl groups, and 50% by weight or more of the hydroxyl groups is a primary hydroxyl group. C, an active aromatic polyamine which does not contain an electron-withdrawing group in the aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to the amino group, excluding toluenediamine as a chain extender; To 100 parts by weight of the polyol shown in
When reacting a tin-based and / or lead-based and / or bismuth-based organometallic catalyst in an amount of 0.001 to 5% by weight based on the total amount of the raw materials used, a component A containing a
A solvent-free type B component containing b, c and d
Equivalent ratio of the NCO group of the component to the active hydrogen group of the B component (NCO
/ H) is 0.9-1.30 and the pressure is 60-150 kg
A method for producing a polyurethane-polyurea elastomer obtained by impinging and mixing under a condition of f / cm ² by a high-pressure two-component spraying device, applying the mixture to an object, and curing the mixture. And / or the polyol used in b is a compound represented by the following general formula (2) [formula 8] or the general formula (3)
[Formula 9]

[0011]

Embedded image

[0012]

Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. A process for producing a polyurethane-polyurea elastomer, which is a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by the formula (1). (3) a partial prepolymer obtained by reacting a part of an organic polyisocyanate or an isocyanate group with a polyol; and b containing at least two hydroxyl groups, wherein 50% by weight or more of the hydroxyl groups is a primary hydroxyl group. C, an active aromatic polyamine which does not contain an electron-withdrawing group in the aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to the amino group, excluding toluenediamine as a chain extender; To 100 parts by weight of the polyol shown in
When reacting a tin-based and / or lead-based and / or bismuth-based organometallic catalyst in an amount of 0.001 to 5% by weight based on the total amount of the raw materials used, a component A containing a
A solvent-free type B component containing b, c and d
Equivalent ratio of the NCO group of the component to the active hydrogen group of the B component (NCO
/ H) is 0.9-1.30 and the pressure is 60-150 kg
A method for producing a polyurethane-polyurea elastomer obtained by impinging and mixing under a condition of f / cm ² by a high-pressure two-component spraying device, applying the mixture to an object, and curing the mixture. And / or the polyol used in b is the following general formula (2) [formula 10] or the general formula (3)
[Formula 11]

[0013]

Embedded image

[0014]

Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. A) a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by the formula (1), wherein the polyol has a hydroxyl value OHV (mgKOH / g) of 5 to 60:
And the total degree of unsaturation USV (meq / g) is represented by the following formula (1):

[0015]

Embedded image A process for producing a polyurethane-polyurea elastomer, wherein the polyol satisfies USV ≦ 1.2 / OHV (1). (4) The polyurethane / polyurea according to any one of (1) to (3), wherein the organic polyisocyanate is diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI) or a modified product thereof. -Elastomer manufacturing method. (5) The polyurethane / polyurea / dye according to (4), wherein the modified product is a carbodiimide-modified product.
Elastomer manufacturing method. (6) An active aromatic polyamine which does not contain an electron-withdrawing group in an aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to an amino group, except for toluenediamine,
1,3-dimethyl-2,4-diaminobenzene, 1,3
-Diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-
2,5-diaminobenzene, 1,4-diisopropyl-
2,5-diaminobenzene, 1,4-dibutyl-2,5
-Diaminobenzene, 2,4-diaminomethylene, 1,
3,5-triethyl-2,4-diaminobenzene, 1,
3,5-triethyl-2,6-diaminobenzene, 1,
Compounds of 3,5-triisopropyl-2,6-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene The method for producing a polyurethane / polyurea elastomer according to any one of (1) to (5), wherein the method is one or a mixture of two or more kinds selected from the group consisting of:

In the present invention, the polyol used especially for the polyurethane / polyurea elastomer has a hydroxyl value OHV (mgKOH / g) of 5 to 60 and a total unsaturation USV (meq / g) of the following formula (1). ) [Formula 1
3]

[0017]

By using a polyol that satisfies USV ≦ 1.2 / OHV (1), the content of unsaturated monool in the polyol as a raw material thereof is reduced, whereby the above-mentioned polyurethane. It has been found that various physical properties of the polyurea elastomer can be improved.

Further, when the polyol is a polyol containing a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound, the unsaturated monool of the polyoxyalkylene polyol in the raw material may be used. It has been found that since the content can be reduced, various physical properties of the polyurethane / polyurea / elastomer listed above can be improved.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The high-pressure two-component spraying device used in the present invention includes:
For example, Rim (RIM) series of Glasscraft
MODEL T-3, MODEL-〓 manufactured by Gasmer, and the like are preferable. These high-pressure two-component spraying devices are 60 to 15
The spray solution is sprayed at a discharge pressure of 0 kg / cm2, so that the undiluted liquid mixture becomes fine particles and a smooth construction surface can be obtained.
In addition, even a single spraying enables considerable thick coating.

The polyurethane stock solution used in the present invention has a very high reactivity, and loses fluidity within 1 to 10 seconds after mixing the stock solution. Examples of the organic polyisocyanate used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and a mixture thereof (TDI), diphenylmethane-4,4′-diisocyanate (MDI), xylene diisocyanate ( X
DI), dicyclohexylmethane-4,4 ′ diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (H
DI), hydrogenated xylene diisocyanate (HXD
I), crude TDI, polymethylene polyphenyl polyisocyanate (crude MDI), and modified isocyanurates, carbodiimides, and burets of these isocyanates. Among these organic polyisocyanates, MDI, crude MDI and modified products thereof are particularly preferred.

The polyol used in the present invention includes polyhydric alcohols such as water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, and ethylene oxide, propylene oxide,
Polyether polyol (PPG) obtained by addition polymerization of one or more alkylene oxides such as butylene oxide; polytetramethylene ether glycol (PTMEG) obtained by addition polymerization of tetrahydrofuran alone or with ethylene oxide; Examples include methylene ethylene ether glycol, castor oil, and polycarbonate polyol.

In addition to the above, polyester polyols obtained by reacting a polycarboxylic acid with a low molecular weight polyol and polyester polyols obtained by polymerizing caprolactone can also be used. Further, a polymer polyol and 1,2- or 1,4-polybutadiene polyol obtained by graft-polymerizing an ethylenically unsaturated compound such as acrylonitrile, styrene, and methyl methacrylate onto the above-mentioned known polyether polyol or polyester polyol, Can also be used.

The polyol may be used alone or as a mixture of two or more kinds. The polyol in the present invention has a hydroxyl value O
HV (mgKOH / g) is 5 to 60, and total unsaturation USV (meq / g) is represented by the following formula (1)

[0024]

Embedded image The polyol satisfies USV ≦ 1.2 / OHV (1) or a general formula (1):
Further, it is preferable that the polyoxyalkylene polyol is a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of the phosphazenium compound represented by the general formula (2), or a polyoxyalkylene polyol having both of them.

Here, the total degree of unsaturation (C = C) in the polyoxyalkylene polyol refers to an unsaturated group at a molecular terminal generated mainly by a side reaction of propylene oxide when a polyoxyalkylene polyol is synthesized. It is an index of the amount of monools. Since the monol has a low molecular weight as compared with the polyoxyalkylene polyol produced by the main reaction, the molecular weight distribution of the polyoxyalkylene polyol is significantly widened and the average number of functional groups is reduced. Therefore, when a polyoxyalkylene polyol having a high monol content is used, various physical properties such as an increase in hysteresis, a decrease in hardness and a decrease in elongation are caused. Therefore, monool (C = C)
Is preferably completely absent, if possible, but should be as small as possible.

The above polyoxyalkylene polyol is, for example, a metal cyanide complex such as Zn ₃ [Co (CN) ₆ ] ₂ described in JP-B-44-551, and JP-A-7-278289. The compound is obtained by adding an alkylene oxide to an active hydrogen compound using a cesium hydroxide or a phosphazenium compound as described in (1) as a catalyst. In particular, when a phosphazenium compound is used as a catalyst, metal components that adversely affect the properties and the like of the polyurethane elastomer do not remain in the generated polyoxyalkylene polyol,
More preferred. It is not preferable to use a commonly used catalyst such as KOH because the total unsaturation is increased.

Here, the polyoxyalkylene polyol obtained by using the phosphazenium compound used as a catalyst in the present invention refers to a phosphazenium compound represented by the general formula (2) or (3):
It is a polyol produced by polymerizing an alkylene oxide compound.

In the present invention, the phosphazenium compound is represented by the following general formula (2) [formula 15] or the general formula (3)
It is a salt of a phosphazenium cation having the structure represented by the following formula and an anion of an active hydrogen compound, wherein the phosphazenium cation has an ultimate structural formula whose charge is localized on a central phosphorus atom. As a representative, countless other extreme structural formulas are drawn, and the charges are actually nonpolarized as a whole.

[0029]

Embedded image

[0030]

Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. )

A, b and c in the phosphazenium compound represented by the general formula (2) are each a positive integer of 0 or 3 or less, preferably 0 or 2 or less. More preferably, regardless of the order of a, b and c, (2, 1, 1), (1, 1, 1), (0, 1, 1)
Or a number in the combination of (0, 0, 1). D in the phosphazenium compound represented by the general formula (3),
e, f and g are each a positive integer of 0 or 3 or less, and preferably a positive integer of 0 or 2 or less. More preferably, regardless of the order of d, e, f and g,
(2, 1, 1, 1), (1, 1, 1, 1), (0, 1,
1, 1), (0, 0, 1, 1) or (0, 0, 0, 1)
Is the number in the combination. More preferably,
(1,1,1,1), (0,1,1,1), (0,0,
1, 1) or (0, 0, 0, 1).

R in the phosphazenium compound represented by the general formula (2) or (3) is the same or different and is an aliphatic or aromatic hydrocarbon group having 1 to 10 carbon atoms. Typically, this R is, for example, methyl, ethyl, normal-propyl, isopropyl, allyl, normal-butyl, sec-butyl, tert-butyl,
-Butenyl, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, isopentyl, tert
-Pentyl, 3-methyl-2-butyl, neopentyl,
Normal-hexyl, 4-methyl-2-pentyl, cyclopentyl, cyclohexyl, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-
Aliphatic or aromatic such as hexyl, 1,1-dimethyl-3,3-dimethylbutyl (commonly called tert-octyl), nonyl, decyl, phenyl, 4-toluyl, benzyl, 1-phenylethyl or 2-phenylethyl Selected from the hydrocarbon groups of Of these, methyl, ethyl, normal-propyl, isopropyl, tert-butyl,
tert-pentyl or 1,1-dimethyl-3,3
-An aliphatic hydrocarbon group having 1 to 10 carbon atoms such as dimethylbutyl is preferable, and a methyl group or an ethyl group is more preferable.

When two Rs on the same nitrogen atom in the phosphazenium compound represented by the general formula (2) or (3) are bonded to each other to form a ring structure, The divalent group (RR) is a divalent hydrocarbon group having a main chain having 4 to 6 carbon atoms (the ring is a 5- to 7-membered ring containing a nitrogen atom), for example, tetramethylene , Pentamethylene or hexamethylene, and the main chain thereof is substituted with an alkyl group such as methyl or ethyl. Preferably, it is tetramethylene or pentamethylene. Such a ring structure may be used for all possible nitrogen atoms in the phosphazenium cation, or a part thereof may be used.

In the phosphazenium compound represented by the general formula (2) or (3), x is not uniform depending on the type of the active hydrogen compound, but is usually 1 to 8, preferably 1. The phosphazenium compound represented by the general formula (2) or the general formula (3) is, for example, a salt of the phosphazenium cation and the inorganic anion in the general formula (2) or the general formula (3) and an active hydrogen compound. A method of reacting a salt of an alkali metal or an alkaline earth metal, or reacting a salt of a phosphazenium cation in the general formula (2) or (3) with an anion of another active hydrogen compound and an active hydrogen compound And the like. The phosphazenium compound represented by the general formula (2) is, for example, a phosphazenium compound represented by the following general formula (4)

[0035]

Embedded image (In the formula, a, b and c are each a positive integer of 0 or 3 or less, but not all 0 at the same time. R is the same or different and is a hydrocarbon group having 1 to 10 carbon atoms.) In some cases, two Rs on the same nitrogen atom may be bonded to each other to form a ring structure.) And an active hydrogen compound. In addition, general formula (2) or general formula (3)
Any method may be used as long as the method obtains the phosphazenium compound represented by

The active hydrogen compound in the present invention is a compound having an active hydrogen atom on an oxygen atom, for example, water, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, lauric acid, stearic acid, oleic acid. Acid, phenylacetic acid, dihydrocinnamic acid, cyclohexanecarboxylic acid,
A carboxylic acid having 1 to 20 carbon atoms such as benzoic acid, paramethylbenzoic acid or 2-carboxynaphthalene, for example, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, itaconic acid, butanetetracarboxylic acid 2 to 20 carbon atoms such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid or pyromellitic acid
Polycarboxylic acids having 2 to 6 carboxyl groups, for example, N, N-diethylcarbamic acid,
N-carboxypyrrolidone, N-carboxyaniline,
Carbamic acids such as N, N'-dicarboxy-2,4-toluenediamine; for example, methanol, ethanol, normal-propanol, isopropanol, normal-butyl alcohol, sec-butyl alcohol;
tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, normal-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl alcohol, 1-phenyl Alcohols having 1 to 20 carbon atoms such as ethyl alcohol, triphenylcarbinol or cinnamyl alcohol; for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
C2-C2 such as 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or dipentaerythritol
Polyhydric alcohols having 0 to 2 hydroxyl groups, such as sugars such as glucose, sorbitol, dextrose, fructose or sucrose or derivatives thereof, such as phenol, 2-naphthol, 2,6-dihydroxy Aromatic compounds having 1 to 3 hydroxyl groups having 6 to 20 carbon atoms, such as naphthalene or bisphenol A, such as polyethylene oxide, polypropylene oxide or copolymers thereof, having 2 to 8 terminals. And polyalkylene oxides having 1 to 8 hydroxyl groups at their terminals.

Further, the active hydrogen compound in the present invention is a compound having an active hydrogen atom on a nitrogen atom, for example, methylamine, ethylamine, normal-propylamine, isopropylamine, normal-butylamine, isobutylamine, sec. -Butylamine, t
tert-butylamine, cyclohexylamine, benzylamine, β-phenylethylamine, aniline, o-
Aliphatic or aromatic primary amines having 1 to 20 carbon atoms such as toluidine, m-toluidine or p-toluidine, such as dimethylamine, methylethylamine, diethylamine, di-normal-propylamine,
Aliphatic or aromatic secondary amines having 2 to 20 carbon atoms such as ethyl-normal-butylamine, methyl-sec-butylamine, dipentylamine, dicyclohexylamine, N-methylaniline or diphenylamine, for example, ethylenediamine, di ( 2-aminoethyl) amine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, tri (2-aminoethyl) amine, N, N'-dimethylethylenediamine, N, N'-
2 to 3 carbon atoms having 2 to 20 carbon atoms such as diethylethylenediamine or di (2-methylaminoethyl) amine;
Polyamines having a primary or secondary amino group, such as pyrrolidine, piperidine, morpholine or 1,2,3,4-tetrahydroquinoline.
To 20 saturated cyclic secondary amines having 4 to 20 carbon atoms such as 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole or purine.
Unsaturated cyclic secondary amines such as piperazine, pyrazine, 1,4,7-triazacyclononane and the like. Trivalent amines such as acetamido, propionamido, N-methylpropionamido,
Unsubstituted or N-methyl having 2 to 20 carbon atoms such as N-methylbenzoic acid amide or N-ethylstearic acid amide
Monosubstituted acid amides such as 2-pyrrolidone, ε
And 5- to 7-membered cyclic amides such as caprolactam, for example, imides of dicarboxylic acids having 4 to 10 carbon atoms such as succinimide, maleic imide or phthalimide.

Of these active hydrogen compounds, preferred is water, for example, methanol, ethanol, normal-propanol, isopropanol, normal-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol.
Butyl alcohol, isopentyl alcohol, tert
-Pentyl alcohol, normal-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol,
Alcohols having 1 to 20 carbon atoms such as crotyl alcohol, methyl vinyl carbinol, benzyl alcohol, 1-phenylethyl alcohol, triphenyl carbinol or cinnamyl alcohol; for example, ethylene glycol, propylene glycol, diethylene glycol, Propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol or Polyhydric alcohols having 2 to 8 carbon atoms and having 2 to 8 hydroxyl groups, such as dipentaerythritol, such as glucose, sorbitol, dextrose, fructose or sucrose. Saccharides and derivatives thereof, such as polyethylene oxide, polypropylene oxide and copolymers thereof, having 2 to 8 terminals and having a molecular weight of 100 to 50, having 1 to 8 hydroxyl groups at the terminals. 000 polyalkylene oxides, for example, ethylenediamine, di (2-aminoethyl) amine, hexamethylenediamine, 4,4 ′
-Diaminodiphenylmethane, tri (2-aminoethyl) amine, N, N'-dimethylethylenediamine,
N, N'-diethylethylenediamine or poly (amine) having 2 to 3 carbon atoms and having 2 or 3 primary or secondary amino groups such as di (2-methylaminoethyl) amine, for example, pyrrolidine, piperidine , Morpholine or 1,2,3,4-tetrahydroquinoline or other saturated cyclic secondary amines having 4 to 20 carbon atoms, such as piperazine, pyrazine or 1,4,7-triazacyclononane. Cyclic polyvalent amines containing 4 to 20 2 to 3 secondary amino groups.

Among these active hydrogen compounds, water is more preferable, and for example, methanol, ethanol, normal-propanol, isopropanol, normal-
Butyl alcohol, sec-butyl alcohol, ter
t-butyl alcohol, isopentyl alcohol, te
alcohols having 1 to 10 carbon atoms, such as rt-pentyl alcohol and normal-octyl alcohol;
For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4
-Polyhydric alcohols having 2 to 10 carbon atoms and having 2 to 4 hydroxyl groups, such as butanediol, trimethylolpropane, glycerin or pentaerythritol, such as polyethylene oxide, polypropylene oxide or copolymers thereof; 2 to 6
Polyalkylene oxides having a molecular weight of 100 to 10,000 and having 2 to 6 hydroxyl groups at the terminals, such as N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine or di ( Polyhydric amines having 2 to 3 carbon atoms and having 2 to 3 secondary amino groups such as 2-methylaminoethyl) amine, such as piperazine, pyrazine,
4 to 20 carbon atoms such as 4,7-triazacyclononane
Cyclic polyamines containing two or three secondary amino groups.

Of these active hydrogen compounds, water is more preferable, and examples thereof include water such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, trimethylolpropane, glycerin, and pentaerythritol. Polyhydric alcohols having 2 to 4 hydroxyl groups having 2 to 10 carbon atoms, such as polyethylene oxide, polypropylene oxide or copolymers thereof, having 2 to 6 terminals and having 2 to 6 terminals Having a molecular weight of 100 to 10,000 having one hydroxyl group
00 polyalkylene oxides.

Examples of the alkylene oxide compound in the present invention include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, and methylglycidyl. Epoxy compounds such as ether, allyl glycidyl ether and phenyl glycidyl ether. These may be used in combination of two or more. When used in combination, a method of simultaneously using a plurality of alkylene oxide compounds,
A method of sequentially using the method or a method of repeating the method may be employed.

Of these alkylene oxide compounds, ethylene oxide, propylene oxide, 1,2-
Butylene oxide or styrene oxide is preferred,
Ethylene oxide and propylene oxide are more preferred. Subject to a polymerization reaction of the alkylene oxide compound,
The amount of the phosphazenium compound to be used is not particularly limited, but is usually 1 to 1 mol of the alkylene oxide compound.
× 10 ^{-15 to} 5 × 10 ^-1 mol, preferably 1 × 10 ^-7 to
It is in the range of 1 × 10 ^-2 mol.

The reaction temperature of the polymerization reaction depends on the temperature
Depending on the type and amount of the alkylene oxide compound and other components
Although not uniform, it is usually 150 ° C. or less, preferably
Is in the range of 10 to 130 ° C, more preferably 50 to 120 ° C.
It is an enclosure. The pressure during the reaction depends on the alkylene oxide used.
Type or amount of sid compound or other component or polymerization
Although not uniform depending on the temperature, the pressure during the polymerization reaction is usually
30kg / cm ^Two(Absolute pressure, the same applies hereinafter)
Preferably 0.1 to 15 kg / cm^Two, More preferred
1 to 10 kg / cm^TwoRange.

In the present invention, in order to increase the reactivity, the hydroxyl group of the polyol preferably contains at least 50% by weight of a primary hydroxyl group. Therefore, the polyether polyol obtained by addition polymerization of propylene oxide or butylene oxide to a polyhydric alcohol preferably has a terminal capped with ethylene oxide. Further, it is desirable that the terminal of the low molecular weight polyol used for producing the polyester polyol is a primary hydroxyl group.

The organic polyisocyanate of the present invention can be directly reacted with a polyol and a chain extender,
Alternatively, it is also possible to use a partial prepolymer obtained by heating a part of the isocyanate group with a polyol at 70 to 80 ° C. for several hours in a nitrogen stream.

As the polyol which can be used for the production of the partial prepolymer, the following low-molecular-weight polyols can be used in addition to the above-mentioned polyols. Examples of low molecular weight polyols include propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and mixtures thereof, diethylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, water, ethylene glycol, propylene glycol , Glycerin, trimethylolpropane,
Polyether polyols having a molecular weight of less than 1000, polytetramethylene ether glycols having a molecular weight of less than 1000 obtained by addition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to polyhydric alcohols such as pentaerythritol and so on.

The active aromatic polyamine having no electron-withdrawing group in the aromatic nucleus used as a chain extender in the present invention is, for example, 1,3-dimethyl-2,4-diaminobenzene,
1,3-diethyl-2,4-diaminobenzene, 1,3
-Dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-
2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 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-diaminobenzene (and mixtures of the latter two diamines in different proportions) and the like; 2,
3-dimethyl-1,4-diaminonaphthalene, 2,6-
Dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, and the like; 3,3 ′, 5,5 ′ -Tetramethyl-benzene, 3,3 ', 5,5'-tetraisopropyl-benzidine 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 ', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,5-diisopropyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane and the like.

These aromatic polyamines may be used alone or as a mixture of two or more kinds.
3 parts per 00 parts by weight (parts by weight in the present invention).
0 to 160 parts is suitable. The amount of the organic polyisocyanate or partial prepolymer, polyol and chain extender used is such that the equivalent ratio of NCO groups in the organic polyisocyanate or partial prepolymer to active hydrogen in the polyol and chain extender is 0.90 to 1 .30.

The organometallic catalyst used in the present invention includes, for example, tin acetate, tin octate, tin 2-ethylhexoate, tin laurate, tin maleate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, lead acetate, lead acetate Octate, lead 2-ethylhexoate, lead laurate, lead maleate, dibutyl lead diacetate, dibutyl lead dilaurate, dioctyl lead dilaurate, lead naphthenate, bismuth acetate, bismuth octate, bismuth 2-ethylhexoate,
Bismuth laurate, bismuth maleate, dibutyl bismuth diacetate, dibutyl bismuth dilaurate,
Dioctyl bismuth dilaurate, bismuth naphthenate and the like. These organometallic catalysts are used alone or as a mixture. The amount used is preferably 0.001 to 5% by weight based on the total amount of the raw materials used.

Other auxiliaries which can be used in the present invention are plasticizers, flame retardants, fillers, stabilizers, colorants and the like. Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adipate (DOA),
Tricresyl phosphate (TCP), chlorinated paraffin and the like. The flame retardant is, for example, tris-β-chloropropyl phosphate (Phirol PC manufactured by Stoffa Japan)
F), phosphates such as tris-dichloropropyl phosphate (CPR manufactured by Daihachi Chemical Co., Ltd.) and tris-chloroethyl phosphate (CLP manufactured by Daihachi Chemical Co., Ltd.), and bromines such as dibromoneopentylglycol and tribromoneopentylalcohol. And the like.

The filler is, for example, glass fiber, carbon black, calcium carbonate, talc, kaolin, zeolite, diatomaceous earth, perlite, vermiculite, titanium dioxide and the like. Stabilizers are, for example, trade names Irganox 1010 and 1076 (manufactured by Ciba Geigy),
Positionally hindered phenols such as Yoshinox BHT, BB and GSY-930 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.);
Benzotriazoles such as 327 and 328 (manufactured by Ciba-Geigy); benzophenones such as Tomisorp 800 (manufactured by Yoshitomi Pharmaceutical); Sanol LS-770 and 77
4, positionally hindered amines such as Tinuvin 144 (manufactured by Ciba-Geigy).

In practicing the present invention, the organic polyisocyanate or the partial prepolymer is used as it is, or an appropriate amount of a plasticizer is blended to adjust the flow ratio of the components.
As the component A, a polyol, a chain extender, a catalyst, a colorant, and the like are mixed to obtain a component B. Both components A and B are ejected from a high-pressure two-liquid type spraying device at a predetermined flow rate ratio and are sprayed on an object. In that case, when using glass fiber, the glass long fiber is blown with air while being cut into a predetermined length at the position of the head of the gun, and is mixed with both components A and B while flying in the air. The mixture of the A and B components adhered to the object cures in one second to several tens of seconds. This operation is repeated several times as necessary to obtain a coating having a predetermined thickness.

The polyurethane / polyurea according to the present invention
Elastomers are used for lining or protective coatings on pipes, tanks and other steel structures, thick protective coatings such as concrete, waterproof coatings (roof waterproofing, outer wall waterproofing, etc.), rigid polyurethane foam,
It is used for thick protective coating of thermal insulation such as polystyrene foam and board, open floor molding using a seamless flooring and a mold made of metal or resin.

According to the present invention, the solvent is not required to be dried just by spraying the undiluted solution with the high-pressure two-component spraying device, and is cured in about ten seconds even at room temperature, and the coating is completed without the need for post-curing. Bubbles do not form even when applied thickly. Therefore, recoating is possible in a short time, and even a polyurethane / polyurea elastomer having a thickness of 10 mm can be completed easily in a short time. Further, since no bubbles are generated, a complicated shape such as an uneven pattern on the surface of the target object can be accurately reproduced on the surface of the coating object by a simple operation.

[0055]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Preparation of component A: Preparation of component A was performed by the following method.

(A-1) A pure MDI (Cosmonate PH manufactured by Mitsui Toatsu Chemicals) and a carbodiimide-modified liquid MDI (Cosmonate LK manufactured by Mitsui Toatsu Chemicals) are 70/3 by weight.
Of the polyoxypropylene diol (hydroxyl value 112 mgKOH / g, total unsaturation 0.00)
7meq / g), and after reacting at 80 ° C. for 3 hours under a nitrogen stream, 190 g of DOP (dioctyl phthalate) as a diluent was added, and the A component (A-1) of NCO weight% = 13.2 was added. I got

(A-2) A pure MDI (Cosmonate PH manufactured by Mitsui Toatsu Chemicals) and a carbodiimide-modified liquid MDI (Cosmonate LK manufactured by Mitsui Toatsu Chemicals) are 70/3 by weight.
0 to 1000 g of the polyoxypropylene diol PPG-
Diol-1000 (manufactured by Mitsui Toatsu Chemicals, Inc .; hydroxyl value 11)
2mgKOH / g, total unsaturation 0.017meq / g)
Was added thereto, and the mixture was reacted at 80 ° C. for 3 hours under a nitrogen stream. Then, 1 ml of DOP (dioctyl phthalate) was used as a diluent.
90 g, and the A component (A-
2) was obtained. Preparation of component B: Preparation of component B was performed by the following method.

(B-1) DETDA was added to 727 g of polyoxypropylene polyoxyethylene triol (having a hydroxyl value of 32.9 mgKOH / g and a total degree of unsaturation of 0.010 meq / g) prepared using a phosphazenium compound catalyst.
263 g of (a mixture of 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine) was added, and 1 g of lead naphthenate (pb 24% by weight) was added thereto as a catalyst. (B-1) was obtained.

(B-2) Polyoxypropylene polyoxyethylene triol PPG-EP-330N (manufactured by Mitsui Toatsu Chemicals; hydroxyl value: 32.9 mgKOH / g, total unsaturation: 0) produced using a potassium hydroxide catalyst .07me
To 727 g of q / g), 263 g of DETDA (a mixture of 3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine) was added, and lead naphthenate (pb24 wt. %)
In addition, a B component (B-2) was obtained.

Example 1 The component (A-1) was kept at a temperature of about 50 ° C. as the component A. On the other hand, (B-
1) was kept warm at about 60 ° C.

The two were mixed at a volume ratio of 1/1 and a high pressure 2 shown below.
Spraying was performed using a liquid spraying device. The supply of liquid to the high-pressure two-component spraying device is performed using a supply pump (air-driven 2: 1 type 208-177) manufactured by Graco, with an air pressure of 5 kgf / c.
It was carried out in m ^2.

The high-pressure two-liquid type spraying apparatus uses a RIM series manufactured by Class-Craft Co., Ltd. at a stock solution pressure of about 140 kgf / c at rest.
m ² , stock solution pressure at spraying 105 to 119 kgf / cm ²
Used in. To control the temperature of the stock solution, the heat exchanger of the main body was set to 50 ° C. for the A component and 60 ° C. for the B component, and the current of the hose heater was set to 4 A. Spray gun with flat chamber (N
o. 1) A + tip (043-25) was used. A 1 mm thick polypropylene plate was used as a mold and sprayed 3 to 5 times to obtain a sheet having a thickness of about 2 mm. Spraying atmosphere conditions were 28 ° C. and 75% relative humidity. After the obtained sheet was cured in a constant temperature room at 23 ° C for 7 days, JIS
Physical properties were measured according to K-6301. The results are shown in Table 1.

[Examples 2, 3 and Comparative Example 1] Table 1
The procedure was performed in the same manner as in Example 1 except for the stock solution combinations shown in (1). Table 1 shows the stock solution combinations and physical properties.

[0064]

[Table 1]

[0065]

According to the embodiment, the tack-free time is shorter than that of the comparative example, and there is no after-tack (the tack remains at the portion where the mist is scattered). Also, there is little foaming even at high temperatures (less decrease in density). In terms of physical properties, tensile strength, elongation, and tear strength are extremely excellent.

Therefore, according to the method of the present invention, the solvent is not required to be dried just by spraying the undiluted solution with the high-pressure two-component spraying device, and is cured in ten and several seconds even at room temperature, and the coating can be performed without the need for post-curing. Since it is completed, no bubbles are generated even if it is applied thickly. Therefore, recoating is possible in a short time, and even a polyurethane / polyurea elastomer having a thickness of 10 mm can be completed easily in a short time.

Further, since no bubbles are generated, a complicated shape such as a concavo-convex pattern on the surface of the object can be accurately reproduced on the surface of the coating by a simple operation. Furthermore, the polyurethane-polyurea elastomer obtained by the method of the present invention is excellent in its physical properties, in particular, various physical properties such as tensile strength, tear strength and elongation.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C08G 18/48 C08G 18/48 Z // C08G 65/10 65/10 (72) Inventor Ugi Sanji Takagi Ueharu Kanagawa Prefecture Sakae-ku, Yokohama 1190 Kasama-cho Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Satoshi Yamazaki 2-1-1 Tango-dori, Minami-ku, Nagoya-shi, Aichi Prefecture Mitsui Toatsu Chemical Co., Ltd. 2-1-1 Tango-dori Ward, Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. A partial prepolymer obtained by reacting a part of an organic polyisocyanate or an isocyanate group with a polyol. B At least two hydroxyl groups are contained, and 50% by weight or more of the hydroxyl groups is primary. A polyol which is a hydroxyl group of c, excluding toluenediamine as a chain extender, an active aromatic polyamine which does not contain an electron-withdrawing group in an aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to an amino group. , B, 100 parts by weight of the polyol
When reacting a tin-based and / or lead-based and / or bismuth-based organometallic catalyst in an amount of 0.001 to 5% by weight based on the total amount of the raw materials used, a component A containing a
A solvent-free type B component containing b, c and d
Equivalent ratio of the NCO group of the component to the active hydrogen group of the B component (NCO
/ H) is 0.9-1.30 and the pressure is 60-150 kg
A method for producing a polyurethane-polyurea elastomer obtained by impinging and mixing under a condition of f / cm ² by a high-pressure two-component spraying device, applying the mixture to an object, and curing the mixture. And / or the polyol used in b has a hydroxyl value OHV (mgKOH / g) of 5 to 60 and a total unsaturation USV (meq / g) of the following formula (1). ≦ 1.2 / OHV (1) A process for producing a polyurethane / polyurea elastomer, characterized in that the polyol satisfies (1). 2. A partial prepolymer obtained by reacting a part of an organic polyisocyanate or an isocyanate group with a polyol. B At least two hydroxyl groups are contained, and 50% by weight or more of the hydroxyl groups is primary. A polyol which is a hydroxyl group of c, excluding toluenediamine as a chain extender, an active aromatic polyamine which does not contain an electron-withdrawing group in an aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to an amino group. , B, 100 parts by weight of the polyol
When reacting a tin-based and / or lead-based and / or bismuth-based organometallic catalyst in an amount of 0.001 to 5% by weight based on the total amount of the raw materials used, a component A containing a
A solvent-free type B component containing b, c and d
Equivalent ratio of the NCO group of the component to the active hydrogen group of the B component (NCO
/ H) is 0.9-1.30 and the pressure is 60-150 kg
A method for producing a polyurethane-polyurea elastomer obtained by impinging and mixing under a condition of f / cm ² by a high-pressure two-component spraying device, applying the mixture to an object, and curing the mixture. And / or the polyol used in b is the following general formula (2) [formula 2] or the general formula (3)
[Formula 3] [Formula 2] Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. A process for producing a polyurethane-polyurea elastomer, which is a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by the formula (1). 3. A partial prepolymer obtained by reacting a part of an organic polyisocyanate or an isocyanate group with a polyol. B At least two hydroxyl groups are contained, and 50% by weight or more of the hydroxyl groups is primary. A polyol which is a hydroxyl group of c, excluding toluenediamine as a chain extender, an active aromatic polyamine which does not contain an electron-withdrawing group in an aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to an amino group. , B, 100 parts by weight of the polyol
When reacting a tin-based and / or lead-based and / or bismuth-based organometallic catalyst in an amount of 0.001 to 5% by weight based on the total amount of the raw materials used, a component A containing a
A solvent-free type B component containing b, c and d
Equivalent ratio of the NCO group of the component to the active hydrogen group of the B component (NCO
/ H) is 0.9-1.30 and the pressure is 60-150 kg
A method for producing a polyurethane-polyurea elastomer obtained by impinging and mixing under a condition of f / cm ² by a high-pressure two-component spraying device, applying the mixture to an object, and curing the mixture. And / or the polyol used in b is the following general formula (2) [formula 4] or the general formula (3)
[Formula 5] [Formula 4] Embedded image (However, a, b and c in the general formula (2) or d, e, f and g in the general formula (3) are each 0 or 3
The following positive integers are not all 0 at the same time. R
Is a same or different hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may combine with each other to form a ring structure. x represents the number of phosphazenium cations, and Z ^x- represents the x-valent anion of the active hydrogen compound. A) a polyoxyalkylene polyol produced by polymerizing an alkylene oxide compound in the presence of a phosphazenium compound represented by the formula (1), wherein the polyol has a hydroxyl value OHV (mgKOH / g) of 5 to 60:
And a polyol having a total degree of unsaturation USV (meq / g) satisfying the following formula (1): embedded image USV ≦ 1.2 / OHV (1)・ Polyurea elastomer production method. 4. The polyurethane / polyurea according to claim 1, wherein the organic polyisocyanate is diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI) or a modified product thereof. -Elastomer manufacturing method. 5. The method for producing a polyurethane-polyurea elastomer according to claim 4, wherein the modified product is a carbodiimide-modified product. 6. An active aromatic polyamine which does not contain an electron-withdrawing group in an aromatic nucleus and has an alkyl substituent having 5 or less carbon atoms at a position adjacent to an amino group, except for toluenediamine, is 1,3-dimethyl. -2,4-diaminobenzene,
1,3-diethyl-2,4-diaminobenzene, 1,3
-Dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 1,4-dibutyl-
2,5-diaminobenzene, 2,4-diaminomethylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 1,3,5- Triisopropyl-2,6-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,
6. A mixture of one or more compounds selected from the group consisting of 6-diaminobenzene.
5. The method for producing a polyurethane / polyurea elastomer according to any one of the above items 5.