JP3291594B2 - Composite polyurea elastomer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is useful for papermaking, steel, rolls for office machines, casters or general molded products, which dislike heat generated by friction and accompanying internal heat storage. And a composite polyurea elastomer having a low coefficient of friction.

[0002]

2. Description of the Related Art The inventors of the present invention have disclosed Japanese Patent Laid-Open Publication No.
No. 417 proposes a composite polyurea elastomer made of carbon fiber, and Japanese Patent Application Laid-Open No. 5-125139 proposes a composite polyurea elastomer made of metal powder and granular carbon. However, the coefficient of friction is still high for application to the object of the present invention, and when applied to applications where heat generation due to friction and associated internal heat storage are disliked, a problem may occur.

[0003]

DISCLOSURE OF THE INVENTION The present invention has high hardness and strength, has heat resistance, can be used for a long time when used for industrial parts such as rolls and casters, and has a reduced coefficient of friction. An object of the present invention is to provide a composite polyurea elastomer which also has a performance of reducing heat generation due to heat and internal heat storage associated therewith.

[0004]

Means for Solving the Problems The present inventors have maintained excellent physical properties and thermal properties, and furthermore, have a low friction coefficient,
As a result of intensive studies to produce a composite polyurea elastomer having the performance of low heat generation due to friction and low internal heat storage, surprisingly, nylon 6 granular filler is represented by the following general formula (Formula 2). After mixing and dispersing in an amine component composed of an amine compound and an aromatic diamine, and reacting with a polyisocyanate, a composite polyurea elastomer having high hardness, excellent heat resistance, and a reduced friction coefficient is obtained. The present invention was completed based on this finding.

That is, the present invention provides a compound represented by the general formula

[0006]

Embedded image (In the formula, R represents a polyalkylene polyether or a polyalkylene polyester having an average molecular weight of 200 or more, which may contain an unsaturated bond in the polyalkylene, and n represents 2 or 3.)

[0007] The present invention provides a composite polyurea elastomer characterized in that nylon 6 granular filler is mixed with an amine component comprising an amine compound represented by the following formula and an aromatic diamine to react with a polyisocyanate component. .

The composite polyurea elastomer of the present invention is easily prepared by mixing an amine component comprising an amine compound represented by the general formula (Formula 2) and an aromatic diamine with a nylon 6 particulate filler and reacting with a polyisocyanate. It has a high coefficient of friction and a low coefficient of friction, while maintaining excellent physical properties and thermal properties such as high hardness, high elasticity, high compressive strength, and a small change in elastic modulus with temperature. It also has the performance of low heat storage. Therefore, the composite polyurea elastomer of the present invention requires papermaking, dyeing, or steel rolls, plastics, plywood, office machine rollers, casters, etc., which require a low coefficient of friction to dislike heat generation due to friction and accompanying internal heat storage. It is suitable for applications such as industrial parts and resins for simple molds.

The composite polyurea elastomer of the present invention can be produced, for example, by the following method.

That is, first, a predetermined amount of an aromatic diamine is mixed with an amine compound represented by the general formula (Formula 2), heated and completely dissolved to obtain an amine component. Thereafter, a predetermined amount of nylon 6 granular filler is mixed with the amine component,
Disperse evenly. This mixture is sufficiently defoamed under reduced pressure of 10 to 20 mmHg, and cooled to room temperature.

Next, a predetermined polyisocyanate is added to the obtained mixed solution, and the mixture is sufficiently mixed and then defoamed. The resulting mixture is poured into a mold previously heated to 80 to 120 ° C., and several minutes at that temperature. Reaction and curing. Thereafter, the molded product is released from the mold, and after-cured in an oven set at 100 to 180 ° C. Furthermore, by aging at room temperature for about one week, the desired high hardness, high elasticity, high compressive strength,
A composite polyurea elastomer having high heat resistance and a reduced coefficient of friction can be obtained.

The amine component used in the production of the composite polyurea elastomer of the present invention comprises an amine compound represented by the general formula (Formula 2) and an aromatic diamine.

Examples of the amine compound represented by the general formula (Formula 2) which constitutes the amine component of the composite polyurea elastomer of the present invention include, for example, polyethylene ether glycol bis (4-aminobenzoate), Methylene ether glycol bis (4-aminobenzoate), polypropylene ether glycol bis (4
-Aminobenzoate), poly (oxyethylene-oxypropylene) glycol bis (4-aminobenzoate), polyoxybutylene glycol bis (4-aminobenzoate), polypropylene ether glycerol tris (4-aminobenzoate) and the like. .

These amine compounds can be used alone or in combination of two or more.

In these amine compounds, the average molecular weight of the central polyalkylene polyether or polyalkylene polyester [partial structure represented by R in the general formula (Chemical Formula 2)] always falls within the range of 200 or more. .

The aromatic diamine constituting the amine component used in the production of the composite polyurea elastomer of the present invention may have any substituent such as a halogen atom, an alkyl group, a trifluoromethyl group or an alkoxycarbonyl group on the aromatic ring. May be introduced, and when a plurality of substituents are introduced, the introduced substituents may be the same or different.

Such an aromatic diamine has a general formula

[0018]

Embedded image (Wherein X and Y each independently represent a halogen atom, an optionally branched alkyl group, a trifluoromethyl group, an alkoxycarbonyl group, or a hydrogen atom, and n ′ and m each independently represent an integer of 1 to 4. And when n ′ and / or m is 2 or more, X and Y may be independently the same or different.)

A diaminodiphenylmethane aromatic diamine represented by the following formula, specifically, 4,4'-methylenebisaniline, 4,4'-methylenebis (2-chloroaniline), 4,4'-methylenebis (2, 3-dichloroaniline) (TCDAM), 4,4'-methylenebis (2,
5-dichloroaniline), 4,4'-methylenebis (2
-Methylaniline), 4,4'-methylenebis (2-ethylaniline), 4,4'-methylenebis (2-isopropylaniline), 4,4'-methylenebis (2,6-
Dimethylaniline), 4,4'-methylenebis (2,6
-Diethylaniline), 4,4'-methylenebis (2-
Ethyl-6-methylaniline), 4,4′-methylenebis (2-chloro-6-methylaniline), 4,4′-methylenebis (2-chloro-6-ethylaniline),
Diaminodiphenylmethanes such as 4'-methylenebis (3-chloro-2,6-diethylaniline), 4,4'-methylenebis (2-trifluoromethylaniline), and 4,4'-methylenebis (2-methoxycarbonylaniline) Aromatic diamine of the general formula

[0020]

Embedded imageIn the formula, A represents a group [—CO—O— (CH_Two)_i-O-CO
-] Or a group [-CO- (OCH_TwoCH_Two)_i-O-CO
−] (However, i represents an integer of 1 to 4. )
And X, Y, n 'and m have the same meaning as described above, and n' and
And / or when m is 2 or more, X and Y are each independent
May be the same or different. ｝

Or the general formula

[0022]

Embedded image (In the formula, R ′ represents a lower alkyl group which may be branched, n ″ represents an integer of 1 to 3, and X has the same meaning as described above.)

An aminobenzoic acid ester-based aromatic diamine represented by the following formula, specifically, 1,3-propanediol bis (4-aminobenzoate), 1,4-butanediol (4-aminobenzoate), diethylene glycol ( Aminobenzoic ester-based aromatics such as 4-aminobenzoate), triethylene glycol (4-aminobenzoate), isopropyl 4-chloro-3,5-diaminobenzoate, and isobutyl 4-chloro-3,5-diaminobenzoate Diamines can be mentioned.

Further, 4,4'-diaminodiphenylether, 4,4'-diamino-3,3'-dichlorodiphenylether, 4,4'-diaminodiphenylsulfone, 4,4'-diamino-3,3'-dichloro Contains oxygen or sulfur atoms such as diphenylsulfone, bis (4-aminophenoxyphenyl) sulfone, 1,2-bis (2-aminophenylthio) ethane, bis [2- (2-aminophenylthio) ethyl] terephthalate Aromatic diamines, 2,4-toluenediamine, 2,6-
Toluenediamine, 3,5-diethyl-2,4-toluenediamine, 3,5-diethyl-2,6-toluenediamine, 3,5-dimethylthio-2,4-toluenediamine, 3,5-dimethylthio-2, Toluene diamine-based aromatic diamine such as 6-toluenediamine, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4
-Amino-3-methylphenyl) propane, 2,2-bis (4-amino-3-ethylphenyl) propane, 2,
2-bis (4-amino-3-isopropylphenyl) propane, 2,2-bis (4-amino-3,5-dimethylphenyl) propane, 2,2-bis (4-amino-3,
5-diethylphenyl) propane, 2,2-bis (4-
Amino-3,5-diisopropylphenyl) propane,
Diaminodiphenylpropane-based aromatic diamines such as 2,2-bis (4-amino-3-ethyl-5-methylphenyl) propane, 3,3′-diaminobenzophenone,
Aromatic diamines such as m- or p-xylylenediamine are also mentioned as specific examples of the aromatic diamine constituting the amine component used in the production of the composite polyurea elastomer of the present invention.

These aromatic diamines can be used alone or in admixture of two or more, and the use of diaminodiphenylmethane-based or aminobenzoate-based aromatic diamines is preferred.

The amine component of the composite polyurea elastomer of the present invention comprises an amine compound represented by the general formula (Chemical Formula 2) and an aromatic diamine, and the ratio of the two depends on desired physical properties, workability and the like. The proportion of the aromatic diamine in the amine component is 5 to 70% by weight, preferably 10 to 60%.
% By weight.

5% by weight of an aromatic diamine in the amine component
If it is less than 70%, the physical properties of the obtained composite polyurea elastomer are insufficient, and if it exceeds 70% by weight, a mixed solution (amine component) of the amine compound represented by the general formula (Formula 2) and the aromatic diamine becomes liquid. It becomes difficult to maintain, and even if the liquid is maintained, the viscosity becomes high, and handling and molding work become difficult. At the time of molding, polyurea crystals precipitate during the molding, and a uniform resin may not be obtained.

The nylon 6 granular filler used in the production of the composite polyurea elastomer of the present invention has an average particle size of 5 to 50 μm and any shape such as spherical or amorphous can be used as long as it is substantially granular. Can be used.

In the production of the composite polyurea elastomer of the present invention, the mixing ratio of the amine component and the nylon 6 particulate filler varies depending on the particle size of the amine component and the nylon 6 particulate filler. Six granular fillers may be in the range of 100: 1 to 100: 100.

If the proportion of the nylon 6 particulate filler in the mixture of the amine component and the nylon 6 particulate filler exceeds 50% by volume, the viscosity of the amine component increases and handling becomes difficult.

It is preferable that the nylon 6 particulate filler is usually uniformly dispersed in the amine component, but it is also possible to impart a characteristic by intentionally biasing the filler.

As the polyisocyanate component used in the production of the composite polyurea elastomer of the present invention, for example, hexamethylene diisocyanate (HMD)
I), 2,2,4-trimethylhexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, cyclohexane diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), , 6-Tolylene diisocyanate (2,6-TDI), 2,4-
Mixture of TDI and 2,6-TDI, dimer of 2,4-tolylene diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, meta-xylylene diisocyanate (MXDI), tetramethyl xylylene diisocyanate Nart, isophorone diisocyanate, (IPD
I), m-phenylene diisocyanate, 4,4'-biphenyl diisocyanate, diphenyl ether-4,
4'-diisocyanate, 3,3'-ditoluene-4,
4'-diisocyanate (TODI), dianisidine diisocyanate (DADI), 4,4'-diphenylmethane diisocyanate (MDI), liquid MDI (4
4′-diphenylmethane diisocyanate partially carbodiimide-modified and liquefied), hydrogenated MDI,
3'-dimethyl-4,4'-diphenylmethane diisocyanate, 1,5-naphthalenediisocyanate (ND
I), triphenylmethane triisocyanate (TT
Any polyisocyanate commonly used in the production of polyurethane elastomers, such as I), can be used.

These polyisocyanates may be used alone or in combination of two or more.

In the production of the composite polyurea elastomer of the present invention, the mixing ratio of the amine component [comprising the amine compound represented by the general formula (Formula 2) and the aromatic diamine] and the isocyanate component is as follows: the molar ratio of the group (-NCO) and amino group (-NH _2), i.e. -NCO /
The value of -NH ₂ is usually 0.9 to 1.5, preferably 1.
It may be 0 to 1.3.

In the production of the composite polyurea elastomer of the present invention, a catalyst can be used if necessary.

Here, the catalyst is preferably one that dissolves in a mixed solution (amine component) of the amine compound represented by the general formula (Formula 2) and the aromatic diamine.

Examples of such a catalyst include, for example, triethylenediamine, triethylamine, tripropylamine, tributylamine, hexamethylenetetramine, N-alkylmorpholine, N-pentamethyldiethylenetriamine, N-hexamethyltriethylenetetramine, N, N-diethylaniline, N, N-dimethylbenzylamine, N, N-dimethyllaurylamine,
N, N-dimethylpiperidine, N, N-dimethylpiperazine, N, N, N ′, N′-tetramethyleneethyldiamine, N, N, N ′, N′-tetramethylpropyldiamine, N, N, N ′ , N'-tetramethyl-1,3-butanediamine, N, N, N ', N'-tetramethylhexamethylenediamine, N, N, N', N ', N "-pentamethyldiethylenetriamine, tris (dimethyl Aminomethyl) phenol, N, N ', N "-tris (dialkylaminoalkyl) hexahydro-s-triazine, 1,8-diazabicyclo [5.4.0] undeca-
Tertiary amines such as 7-ene and 1,8-diazabicyclo [5.4.0] undecene-methylammonium methosulfate; aziridinyl compounds;

In addition to these catalysts, organometallic catalysts can be used for the same purpose.

Specific examples of such organometallic catalysts include, for example, tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate, dibutyltin dichloride. Organotin compounds such as 2-ethylhexoate, stannas octoate, zinc acetylacetone, aluminum acetylacetone, metal salts acetylacetone such as cobalt acetylacetone, zinc naphthenate, lead naphthenate, lead caprylate, Metal salts of naphthenic acid such as cobalt naphthenate, organic mercury compounds such as phenylmercury acetate, phenylmercury oleate, phenylmercury octoate, phenylmercury naphthoate, lead octoate, lead naphthalate Or a basic metal salt of an organic borate ester and an organic boron compound, an alkali metal salt of a carboxylic acid having 2 to 12 carbon atoms (for example, potassium acetate, potassium propionate, potassium 2-ethylhexane, benzoic acid) Sodium, etc.), carbon number 1
Basic substances such as alkali metal salts of three or more carboxylic acids (eg, sodium oleate, potassium linoleate, etc.), alkali metal salts of weak acids other than carboxylic acids such as sodium phenolate, sodium methoxide, benzyltrimethylammonium hydroxy , A strongly basic substance such as an alkali metal hydroxide, a chelate compound represented by a chelate compound of salicylaldehyde and potassium or a cocatalyst (for example, phenols, epoxide compounds,
Alkyl carbonates and the like).

These catalysts may be used alone or as a mixture of two or more.

When the catalyst is used, it is used in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the mixed solution of the amine compound represented by the general formula (Formula 2) and the aromatic diamine. It is 0.05 to 3 parts by weight.

Further, in the production of the composite polyurea elastomer of the present invention, an antioxidant, an ultraviolet absorber, a coloring inhibitor, a hydrolysis inhibitor, a deodorant, a flame retardant, which are usually used for polyurethane elastomers and the like, Coloring agents, extenders, and the like can be appropriately added according to the use of the obtained composite polyurea elastomer.

The amine compound represented by the general formula (Chemical Formula 2) used in the composite polyurea elastomer of the present invention can be prepared by, for example, a method described in JP-B-60-32641 and JP-A-56-135514. Can be synthesized by

That is, the general formula

[0045]

Embedded image (In the formula, R and n represent the same meaning as described above.)

And n-equivalent o- and m-polyol compounds represented by the formula
Alternatively, the nitro compound obtained by reacting p-nitrobenzoyl chloride with p-nitrobenzoyl chloride in the presence of a dehydrochlorinating agent is reduced by an ordinary method, or the polyol compound represented by the above general formula (Chemical Formula 6) and n equivalents are used. And isatoic anhydride.

Further, it can be obtained by a transesterification reaction of a polyol compound represented by the general formula (Formula 6) with n equivalents of an alkyl ester of o-, m- or p-aminobenzoic acid. Aminobenzoic acid and an aliphatic alcohol can be used in place of the benzoic acid alkyl ester.

In the amine compound represented by the above general formula (Chemical Formula 2) thus produced, an unreacted hydroxyl group may remain as a terminal group at the time of its production in some cases, but the amount of the hydroxyl group is small. If so, it can be used as it is.

The polyol compound represented by the general formula (Formula 6) includes, for example, polyethylene adipate, polybutylene adipate, and polypropylene obtained by condensing aliphatic glycol with dicarboxylic acid to extend the chain length. Aliphatic polyester glycols such as adipate, ethylene oxide, propylene oxide, such as tetrahydrofuran, obtained by ring-opening polymerization of polyalkylene oxide or polyalkylene intramolecular ether,
Polyalkylene ether glycols such as polypropylene ether glycol and tetramethylene ether glycol, polyester glycols obtained by ring-opening polymerization of ε-caprolactone and polybutadiene having a hydroxyl group at the terminal group, and copolymers of two or more alkylene oxides And long-chain diols such as copolymers of two or more glycols and dicarboxylic acids and mixtures of aromatic glycols, glycerin, polyols such as trimethylolpropane, and aliphatic glycols and dicarboxylic acids. Or a polyether polyol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran, or the like using a polyol such as glycerin or trimethylol as an initiator. , It may be mentioned polyalkylene ether ester polyols obtainable by ring-opening polymerization of ε- caprolactone and tetrahydrofuran.

In the present invention, the polyols used in the prepolymer method in the production of the existing polyurethane urea elastomer can also be used.

[0051]

Industrial Applicability The present invention can be easily obtained by mixing an amine component comprising an amine compound represented by the general formula (Chemical Formula 2) and an aromatic diamine with a nylon 6 particulate filler and reacting with a polyisocyanate component. High hardness,
While maintaining excellent physical properties and thermal characteristics such as high elasticity, high compressive strength, and little change in elastic modulus with temperature, it also has excellent performance such as lower friction coefficient, lower heat generation and associated internal heat storage. A composite polyurea elastomer is provided.

Since the composite polyurea elastomer of the present invention has the above-mentioned excellent performance, it does not like the heat generated by friction and the internal heat storage associated therewith, and can be used for papermaking, dyeing, or steel rolls, plastics, plywood, and office machines. It is suitable for applications requiring a low coefficient of friction, such as industrial parts such as rollers and casters, or resins for simple molds.

[0053]

The present invention will be described below in detail with reference to examples.

(Production Example) First, the production of the amine compound represented by the general formula (Formula 2) will be described below.

(Production Example 1) Polytetramethylene ether glycol 9 having an average molecular weight of 970 was placed in a 5 l four-necked flask equipped with a thermometer, a cooler, a dropping funnel and a stirrer.
70 g (1.0 mol), 242.5 g of triethylamine
(2.4 mol) and 1 l of toluene. on the other hand,
390 g (2.1 mol) of p-nitrobenzoyl chloride
Was dissolved in 1 l of toluene to prepare a dropping solution. The above reaction solution was heated to 40 to 50 ° C. with stirring, and the above-prepared dropping solution was dropped in one hour. After completion of the dropwise addition, the reaction solution was heated and heated, and an aging reaction was performed under reflux for 1.5 hours. After cooling, the reaction solution was filtered to remove the precipitated triethylamine hydrochloride. The filtrate was washed with a 5% aqueous potassium carbonate solution and water, and concentrated under reduced pressure to obtain a yellow transparent viscous liquid dinitro intermediate. The yield was 1217.5 g, and the yield was 96.0%.

Next, iron powder 61 was placed in a 10 l four-necked flask equipped with a thermometer, a cooler, a dropping funnel and a stirrer.
4 g (11.0 mol), 30 g of acetic acid as a catalyst and 2.5 l and 1 l of toluene and water as solvents were charged. On the other hand, the entire amount of the dinitro intermediate obtained in the above reaction was dissolved in 1 l of toluene to prepare a dropping solution. The reaction solution was heated in an oil bath, and the resulting solution was added dropwise over 1.5 hours under reflux with stirring. After completion of the dropwise addition, the mixture was aged at the same temperature for 5 hours to complete the reaction. Next, sodium bicarbonate was added to the obtained reaction mixture to neutralize acetic acid, and then filtered while hot to remove iron sludge, and water was separated by liquid separation. The filtrate is washed with water and concentrated under reduced pressure to obtain the desired polytetramethylene ether glycol bis (4-aminobenzoate)
I got

The target product was a light yellow-brown transparent viscous liquid, the yield was 1078.7 g, and the yield was 93.0%.

The amine value of the amine compound represented by the general formula (Chemical Formula 2) thus obtained is 89.0 KOH mg.
/ g, and the hydroxyl value was 2.3 KOHmg / g.

The amine value was determined by the method of JIS K 7237 except that the solution of the sample was changed to acetic acid.
The hydroxyl value was measured according to the method of JIS K0070.

(Production Example 2) Polytetramethylene ether glycol 1 having an average molecular weight of 970 was placed in a 1 l four-necked flask equipped with a thermometer, a water separator equipped with a condenser and a stirrer.
94 g (0.2 mol), ethyl p-aminobenzoate 6
5.9 g (0.4 mol), tetrabutyl titanate 0.
018 g were charged. The reaction solution was heated to 200 ° C. while stirring under a nitrogen stream to distill out ethyl alcohol.
Distilled ethyl alcohol was 82% of the theoretical amount.
After raising the temperature to 215 ° C and aging for 2 hours, unreacted ethyl p-aminobenzoate was distilled off under reduced pressure to obtain the desired polytetramethylene ether glycol bis (4
-Aminobenzoate).

The target substance was a brown viscous liquid, and the yield was 224.
7 g, yield was 93.0%.

The amine value measured in the same manner as in Production Example 1 was 81.4 KOH mg / g, and the hydroxyl value was 14.5 KOH.
OH mg / g.

Example 1 100 parts by weight of the polytetramethylene ether glycol bis (4-aminobenzoate) obtained in Production Example 1 was added to 4,4'-methylenebis (2-
Chloroaniline), and then, to this amine component, nylon 6 granular filler [Nippon Rilsan Co., Ltd.]
And an average particle size of 20 μm] were mixed and defoamed in a heated state. At room temperature, 73 parts by weight of liquid MDI was mixed and defoamed, poured into a mold preheated to 100 ° C., cured for 20 minutes, and demolded. Next, after further curing in a forced air oven, the mixture was aged at room temperature for 1 week to obtain a composite polyurea elastomer.

The physical properties and compounding of the composite polyurea elastomer thus obtained are shown in Table 1 below.

The physical properties were determined according to JIS K 6301, JI
SK6902, ASTM D257 and ASTM
It was measured according to the method of D 1894.

The compressive strain of the obtained composite polyurea elastomer was expressed as a percentage of the amount of strain under a load of 500 kg / cm ² with respect to the original thickness.

[0067]

[Table 1]

Example 2 Polytetramethylene ether glycol bis (4-aminobenzoate) obtained in Production Example 2 was replaced with 100 parts by weight of polytetramethylene ether glycol bis (4-aminobenzoate) obtained in Production Example 1. ) A composite polyurea elastomer was obtained in the same manner as in Example 1 except that 100 parts by weight was used.

The physical properties and composition of the obtained composite polyurea elastomer are shown in Table 1.

Comparative Example 1 A polyurea elastomer was obtained in the same manner as in Example 1 except that no nylon 6 granular filler (manufactured by Nippon Rilsan Co., Ltd., average particle size: 20 μm) was added.

Table 1 shows the physical properties and the composition of the obtained composite polyurea elastomer.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C08L 75 / 02,77 / 02

Claims (1)

(57) [Claims] 1. A compound of the general formula (Wherein, R is n-valent, represents a polyalkylene polyether or a polyalkylene polyester having an average molecular weight of 200 or more and may contain an unsaturated bond in the polyalkylene, and n represents 2 or 3). A composite polyurea elastomer, comprising mixing an amine component comprising an amine compound and an aromatic diamine with nylon 6 particulate filler and reacting with a polyisocyanate component.