JPH0790041A - Polyurea resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a specific modified polyamine, excellent in the flowability of its reaction mixture in a mold and in the initial rigidity and initial toughness of molded products just after molded, and useful for reaction injection moldings, etc. CONSTITUTION:This composition comprises (A) a polyoxyalkylenepolyamine, (B) an aromatic polyamine and/or xylendiamine, (C) the reactional product of polyglycidylether with an aromatic primary polyamine, and (D) a polyisocyanate compound, where at least one of the components A and B is a modified polyamine in which at least a part of the primary amino groups has been converted into a secondary amino group by the Michael addition reaction of the primary amino group with an unsaturated component of the formula: CH2=C(R)-Y (R is H, methyl; Y is an electron-attracting group).

Description

Detailed Description of the Invention

[0001] FIELD The present invention is reaction injection molding (hereinafter RIM referred.) Relates to a polyurea resin composition for use in such.

Prior art and problems The RIM method for molding urethane bumpers for automobiles and the like at the same time as reacting a resin raw material in a mold is noted, and US Pat. Nos. 4,254,069 and 3,838,076. ,
Those techniques are disclosed in Nos. 4,246,363 and 4,269,945.

In the technique for obtaining a polyurethane molded article by reacting a polyoxyalkylene polyol and a polyisocyanate in a mold, polyurethane is relatively poor in heat resistance, there are restrictions on coating, and the production cost is high. Therefore, polyurea having good heat resistance has been attracting attention thereafter, and for example, JP-A-58-188643 discloses an average molecular weight of 1500.
A technique for obtaining a polyurea molded product excellent in mechanical strength, heat resistance, and other physical properties, which is obtained by reacting the above amine-terminated polyoxyalkylene polyamine, amine-terminated chain extender, polyisocyanate, and in a closed mold It is disclosed.

However, since polyoxyalkylene polyamine has higher reactivity with isocyanate than polyoxyalkylene polyol, a dedicated molding machine is required to obtain a good molded product.

One method for reducing the reactivity of amines with isocyanates is to convert the terminal amino groups of polyoxyalkylene polyamines from aliphatic to aromatic. For example, in JP-A-3-273016, by using an aromatic polyamine compound and an aromatic polyoxyalkylene polyamine synthesized by reacting a polyepoxy compound and a polyoxyalkylene diepoxy compound with an aromatic primary diamine, , RIM moldings having excellent physical properties such as heat resistance and impact resistance as well as increased flowability of the reaction mixture into the mold. However, in this method, the flowability of the reaction mixture is still insufficient, the initial toughness immediately after molding is low, and there is a problem in workability such as the molding remaining in the groove portion of the mold.

Another method for reducing the reactivity between amines and isocyanates is to use a polyoxyalkylene polyamine or a chain extender having a secondary amino group at the end which is less reactive than the primary amino group due to steric hindrance. , For example, in Japanese Patent Application Laid-Open Nos. 1-311116 and 2-41310. The decrease in the reactivity of the amine and the isocyanate by the secondary amination was effective for improving the flowability of the reaction mixture in the mold. However, the initial rigidity immediately after molding is low, and problems such as deformation of the molded product at the time of demolding remain.

The object of the present invention is to provide a polyurea resin composition for RIM or the like which is excellent in the flowability of the polyurea reaction mixture in the mold and the initial rigidity and initial toughness immediately after the molding of the molded product. Is an issue.

[0008] To resolve the above problems, the present invention is (a) a polyoxyalkylene polyamine, (b) an aromatic polyamine and /
Alternatively, in a polyurea resin composition containing xylylenediamine, at least one of the polyamine components (a) and (b) has a primary amino group and a formula CH ₂ ═C (R) —Y.
(In the formula, R means hydrogen or a methyl group, and Y means an electron-withdrawing group.) A polyamine in which at least a part of primary amino groups has been secondary-ized by a Michael addition reaction with an unsaturated compound A modified polyamine comprising, wherein the composition further provides a polyurea resin composition comprising (c) a reaction product of a polyglycidyl ether and an aromatic primary polyamine, and (d) a polyisocyanate compound. .

Preferred Embodiment Polyoxyalkylene Polyamine Component In the present invention, a primary polyoxyalkylene polyamine and / or a primary polyoxyalkylene polyamine is converted to CH.
₂ = C (R) -Y (wherein R represents hydrogen or a methyl group, and Y represents an electron-withdrawing functional group) is subjected to a Michael addition reaction with a compound represented by the formula 2 to partially or partially amino group A polyoxyalkylene polyamine modified to have a primary amino group is used.

An average molecular weight of 200 to 10,000,
Aliphatic primary polyoxyalkylene polyamines preferably in the range of 400 to 8,000 may be used.

The polyoxyalkylene polyamine having an aliphatic primary amino group at the molecular end used in the present invention is a polyoxyalkylene polyol having at least two or more hydroxyl groups per molecule, which has a primary alcoholic hydroxyl group. It is produced by converting to an amino group (or aminoalkyl group). For this, (1) a method in which ammonia is allowed to act on the polyoxyalkylene polyol in the presence of a metal catalyst using nickel, ruthenium, copper or the like to directly primary-aminate the alcoholic hydroxyl group (eg, JP-A-61) -204225, JP-A-6-6
(1-278528, JP-A-2-38425, JP-A-2-127425, etc.) (2) Acrylonitrile is added to the terminal hydroxyl group of the polyoxyalkylene polyol, and then the cyano group is reduced to convert it to a primary amino group. Method (US Pat. No. 3,491,61)
No. 38) is included.

Here, the polyoxyalkylene polyol which is a raw material of the primary polyoxyalkylene polyamine is obtained by subjecting an alkylene oxide to ring-opening polymerization in the presence of a basic catalyst such as an alkali metal hydroxide based on an appropriate starting material. Obtained by Starting materials include ethylene glycol, diethylene glycol, triethylene glycol and other polyethylene glycols, propylene glycol, dipropylene glycol, tripropylene glycol, other polypropylene glycols, glycerin,
Diglycerin, pentaerythritol, sorbitol,
Examples include sucrose, other polyhydric alcohols, bisphenol A, bisphenol S, bisphenol F, resole, other polyhydric phenols, diethanolamine, triethanolamine, and other amines. Also,
The alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran alone,
Alternatively, they may be used in any combination.

A variety of such terminal aliphatic primary polyoxyalkylene polyamines are commercially available. For example, as the terminal aliphatic primary polyoxyalkylene polyamine, Jeffamine D-2000 (manufactured by Texaco Chemical, amine equivalent is about 1000). ), As a terminal aliphatic primary polyoxyalkylene triamine, Texlim TR-505
0 (same as above, amine equivalent 1900), Jeffermin T-
403 (same as above, amine equivalent 160) and the like, all of which are conveniently used in the present invention.

[0014]Aromatic polyamine In the present invention, aromatic primary polyamine and / or aromatic
CH primary polyamine ₂= C (R) -Y (where R is
Hydrogen or methyl group, Y means electron-withdrawing functional group
By the Michael addition reaction with the compound represented by
Or a fragrance obtained by modifying some amino groups into secondary amino groups
Group polyamines are used.

Examples of the aromatic primary polyamine used in the present invention include 2,3-diaminotoluene and 3,4.
-Diaminotoluene, 2,4-diaminotoluene, 2,
6-diaminotoluene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, (both also referred to as diethyltoluenediamine or DETDA Be done),
1,3,5-triethyl-2,6-diaminobenzene,
4,4'-diaminodiphenylmethane, 3,5,3'-
5'-Tetraethyl-4,4'-diaminodiphenylmethane, polymeric methylenedianiline, 3,5-dimethylthio-3,5-toluenediamine and the like are included. Particularly preferred aromatic primary polyamine compounds are 2,3-diaminotoluene, 3,4-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, 1-methyl-3,5-diethyl-2, 4-diaminobenzene, 1
-Methyl-3,5-diethyl-2,6-diaminobenzene, 4,4'-diaminodiphenylmethane, or a mixture of these compounds.

Various aromatic primary polyamines are commercially available, for example, 1-methyl-3,5-diethyl-2,
Ethacure-100 (manufactured by Asano Chemicals Co., Ltd.) as a mixture of 4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-diaminotoluene and 3,4-diaminotoluene OTD (Mitsui Toatsu Chemicals, Inc.) as a mixture, MT as a mixture of 2,4-diaminotoluene and 2,6-diaminotoluene
D (manufactured by Mitsui Toatsu Chemical Co., Ltd.) and MDA-220 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) as 4,4′-diaminodiphenylmethane.

Xylylenediamine In the present invention, xylylenediamine and / or CH ₂ =
C (R) -Y (wherein R represents hydrogen or a methyl group, Y
Represents an electron-withdrawing functional group), and a modified xylylenediamine obtained by modifying all or part of amino groups into secondary amino groups by a Michael addition reaction is used.

The xylylenediamine used in the present invention has 1,2-, 1,3-, and 1,4-positional isomers. These regioisomers and mixtures thereof are referred to as xylylenediamine.

The xylylenediamine can be obtained by hydrogenating the corresponding dinitrile using a nickel- or cobalt-based catalyst. Such xylylenediamine is commercially available, for example, Shoamine X (manufactured by Showa Denko KK).

Michael Addition Reaction In the present invention, at least one of the component (a) primary polyoxyalkylene polyamine and the component (b) aromatic primary polyamine and / or xylylenediamine is at least partially converted by the Michael addition reaction. It must be a modified polyamine including a polyamine in which the primary amino group is secondaryized. Used for the CH ₂ = C (R) -
Y (provided that R is hydrogen or a methyl group, Y is an electron-withdrawing functional group such as an ester residue, a ketone residue, a cyano group, an unsubstituted or substituted amide group, a sulfone residue, or a sulfonic acid ester residue. As an unsaturated compound represented by, for example, acrylic acid esters (methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate). , T-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, etc.), acrylamide, substituted acrylamide (N, N) -Dimethyl acrylamide, stearyl acrylamide, etc. , Acrylonitrile, methacrylic acid esters (methyl methacrylate, ethyl methacrylate,
N-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, hydroxyethyl methacrylate, methacryl Acid 2
-Hydroxypropyl, 4-hydroxybutyl methacrylate, etc.), methacrylamide, substituted methacrylamide (N, N-dimethylmethacrylamide, stearylmethacrylamide, etc.), methacrylonitrile, methyl vinyl ketone, ethyl vinyl ketone, methyl vinyl sulfone, Examples include ethyl vinyl sulfone, methyl vinyl sulfonate, and ethyl vinyl sulfonate. Any of these are conveniently used in the present invention.

Polyoxyalkylene polyamine and formula CH
In Michael addition reaction of ₂ = C (R) -Y, unsaturated compounds wherein R is hydrogen atom when using the _{(CH 2 = CH-Y)} , an electron donating group other than hydrogen as substituents and /
Alternatively, the reaction is preferably performed in the coexistence of an aromatic compound having at least one electron withdrawing group.

Examples of the aromatic compound having at least one electron-donating group and / or electron-withdrawing group other than hydrogen in the aromatic ring include hydrocarbon-substituted aromatic compounds (toluene, xylene, ethylbenzene, t-butylbenzene, Diphenylmethane, etc.), amino group-substituted aromatic compound (aniline, N, N-dimethylaniline, diaminotoluene, xylidine, diaminodiphenylmethane, aminonaphthalene, etc.), hydroxyl group-substituted aromatic compound (phenol, cresol, naphthol, hydroquinone, etc.), halogen Substituted aromatic compounds (fluorobenzene,
Chlorobenzene, bromobenzene, iodobenzene, fluoronaphthalene, chloronaphthalene, bromonaphthalene, iodonaphthalene, etc.), nitro-substituted compounds (nitrobenzene, nitrotoluene, dinitronaphthalene, etc.), cyano group-substituted aromatic compounds (benzonitrile, naphthonitrile, etc.), Examples thereof include aromatic compounds substituted with a ketone group (acetophenone, propionphenone, etc.), quinones (benzoquinone, naphthoquinone), and compounds obtained by combining a plurality of these substituents. Among these compounds, one kind or a mixture of two or more kinds is used as needed, and an action of increasing the Michael addition reaction rate was found.

A low molecular weight compound having at least one electron-donating group and / or electron-withdrawing group other than hydrogen on the aromatic ring is preferably used in the case of modifying an aliphatic primary polyoxyalkylene polyamine. It was confirmed that the Michael addition reaction rate was improved by adding even a small amount. Usually, 100 equivalent% or less based on the amino group is used.

The Michael addition reaction used in the present invention is
It is promoted by using a catalyst commonly used in the esterification reaction as a catalyst for the reaction. When such an catalyst is used, when an unsaturated compound in which R is a methyl group in the formula CH ₂ ═C (R) —Y is used or when the primary polyamine is aromatic, a high conversion rate is obtained. Practically needed to get.

As the esterification catalyst, a homogeneous system,
Any of heterogeneous systems can be used, for example, inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, etc.), organic acids (formic acid,
Acetic acid, propionic acid, dichloroacetic acid, trichloroacetic acid,
Trifluoroacetic acid, benzoic acid, paratoluene sulfonic acid, etc.), organotin compounds (dibutyltin oxide, dibutyltin dilaurate, etc.) and organoaluminum compounds (trialkoxy compounds, chelate compounds, acylate compounds, etc., such as aluminum isopropylate,
Mono sec-butoxy aluminum diisopropylate, aluminum ethylate, aluminum ethylacetoacetate diisopropylate, amylnium tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum bisethylacetoacetate monoacetylacetonate, etc.) Organic titanium compounds (tetraalkoxy compounds, acylate compounds, chelate compounds, etc., such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrakis-
2-Ethylhexoxytitanium, tetrastearoxytitanium, di-iso-propoxy-bis (acetonato) titanium, isopropoxy (2-ethylhexanediolato) titanium, di-n-butoxy-bis (triethanolanamito) titanium , Hydroxy-bis (lactato) titanium, etc.), unitary inorganic oxides (Al ₂ O
₃ , SiO ₂ , Nb ₂ O _5, etc.), composite inorganic oxides (SiO ₂ —Al ₂ O ₃ , SiO ₂ —P ₂ O ₅ , SiO _{2
2 -TiO 2, Al 2 O 3} -TiO 2, and various zeolites), clay minerals (acid clay, montmorillonite, etc. kaolinite), inorganic sulfides (such as zinc sulfide), metal sulfates acid (nickel sulfate, copper sulfate, etc. ), Inorganic chlorides (aluminum chloride, copper chloride, etc.) and ion exchange resins. These are also conveniently used in the present invention.

The primary polyoxyalkylene polyamine and / or the aromatic primary polyamine and / or xylin diamine may be used after mixing individually after the Michael addition reaction, but may be mixed in the state of primary amine. At the same time, the Michael addition reaction may be carried out. 1 in each case
The primary amine and the unsaturated compound are a primary amine group and a carbon-
The equivalent ratio of carbon unsaturated bond is 1 / 0.01 to 1/100,
The reaction is preferably carried out at a ratio of 1 / 0.1 to 1/10. The homogeneous esterification catalyst is usually used in an amount of 5 equivalent% or less with respect to the primary amino group. Therefore, the resulting modified polyamine is allowed to remain unreacted primary polyamine and unsaturated compound. Although a specific post-treatment is not required after the completion of the reaction, a suitable polymerization initiator may be added after the completion of the reaction to polymerize the residual unsaturated compound, if necessary. When a homogeneous catalyst is used, the catalyst may be left or a treatment for removing the catalyst may be performed.

Although the reaction conditions depend on the kind and amount of the catalyst, they are generally carried out at a reaction temperature in the range of room temperature to 150 ° C, preferably in the range of 80 to 120 ° C.

Polyglycidyl ether and aromatic primary poly
Reaction Product with Amine The component (c) of the present invention is a polyglycidyl ether (hereinafter referred to as “polyether polyepoxy compound”) obtained by reacting a polyhydroxy compound such as polyphenol, polyoxyalkylene polyol, or diglycerin with epiclohydrin. .) And an aromatic primary polyamine that can be used as the above-mentioned component (b). The average molecular weight of the polyether polyepoxy compound is preferably smaller than the average molecular weight of the largest average molecular weight component in the component (a), generally 200 to 1
It is preferably 10,000. The polyglycidyl ether preferably has an average molecular weight of 270 to 800.

Various kinds of such polyether polyepoxy compounds are commercially available, for example, Denacol EX-2000 (epoxy equivalent = 1100, manufactured by Nagase Chemical Industry Co., Ltd.), Denacol EX-931 (epoxy equivalent = 528). , Nagase Kasei Co., Ltd.), Denacol EX-421 (epoxy equivalent = 155, Nagase Kasei Co., Ltd.), Epolite 400P (epoxy equivalent = 32)
0-360, Kyoeisha Yushi Kagaku Kogyo Co., Ltd., SR-T
PG (epoxy equivalent = 200, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.)
Etc., all of which are conveniently used in the present invention.

The component (c) used in the present invention comprises a polyether polyepoxy compound and an aromatic primary polyamine in an amount of 1 mol or more of aromatic 1 per 1 equivalent of epoxy group.
It is obtained by reacting with a compounding agent containing a graded polyamine. In the present invention, the polyether polyepoxy compound and the aromatic 1
A graded polyamine may be reacted. Therefore, it is allowed that unreacted aromatic primary polyamine remains in the reaction product.

An aliphatic 2 obtained by a Michael addition reaction of a primary polyoxyalkylene polyamine, an aromatic primary polyamine and / or xylylenediamine with an unsaturated compound of CH ₂ ═C (R) -Y In the primary polyamine or the aromatic secondary polyamine or a mixture thereof, the aromatic primary polyamine and the polyether polyepoxy compound may be reacted with 1 mol of the aromatic primary polyamine per equivalent of the epoxy group. The addition reaction between the secondary polyamine obtained by the above Michael addition reaction and the polyether epoxy compound is extremely low, and in the above system, the reaction between the polyether epoxy compound and the aromatic primary polyamine proceeds preferentially. The above polyether polyepoxy compound causes an addition reaction with a secondary polyamine obtained by a Michael addition reaction having a low reactivity. Therefore, in addition to the product obtained from the addition reaction of the aromatic primary polyamine and the polyether epoxy compound, the addition reaction product leaving a trace of the addition reaction of the secondary polyamine and the polyether epoxy compound obtained by the Michael addition reaction, Mixing of unreacted aromatic primary polyamine is also allowed.

The reaction is generally carried out without a catalyst and at a reaction temperature in the range of room temperature to 150 ° C., preferably 70
It is carried out at a reaction temperature in the range of 120 ° C.

The wide variety of polyisocyanates as polyisocyanate compound used in the polyisocyanate compound of the present invention is used. Typical aromatic polyisocyanates include, for example, carbodiimide-modified liquid diphenylmethane diisocyanate or a partial prepolymer of diphenylmethane diisocyanal, 2,4-tolylene diisocyanate, diphenylmethane-4,4′-. Examples thereof include diisocyanate, xylylene diisocyanate, crude tolylene diisocyanate, polymethylene polyphenyl isocyanate and their carbodiimidated modified products, buret modified modified products, prepolymerized modified products and the like. A particularly preferred aromatic polyisocyanate is pure diphenylmethane-4,4'-.
It is diisocyanate (hereinafter abbreviated as MDI), a prepolymer thereof, or a modified product.

These types of materials can be used to make suitable RIM moldings. Pure MD
Liquid products based on MDI, which are often used because I is a solid and therefore inconvenient to use, are also included in the MDI or diphenylmethane-4,4'-diisocyanate used in the present invention. U.S. Pat. No. 3,394,164 discloses examples of liquid MDI modifications. More generally uretonimine modified MDI
Is also included in the above definition. Commercial products of this type include Millionate MTL and Millionate MTL-C (both manufactured by Nippon Polyurethane Industry Co., Ltd.).

Examples of the aliphatic and alicyclic polyisocyanates used in the present invention include dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and hydrogen. And xylylene diisocyanate and their isocyanurate-modified products, carbodiimide-modified products, prepolymer-modified products and the like. Particularly preferable aliphatic or alicyclic polyisocyanate is hexamethylene diisocyanate (hereinafter abbreviated as HMDI) or a prepolymer thereof, or a modified product. Coronate HX, Coronate H are commercially available products of this type.
K (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Sumijour N3200 (manufactured by Sumitomo Bayer Urethane Co., Ltd.) and the like.

Polyurea Resin Composition The object of the present invention is for reaction injection molding to obtain a polyurea reaction injection molded article having favorable moldability (particularly liquid flowability) and having excellent rigidity and toughness immediately after molding. It is to provide a resin composition. In order to conveniently achieve such an object, the average amino group equivalent of the mixture containing (a), (b) and (c) and the average isocyanate equivalent of the polyisocyanate component mainly composed of (d) are The equivalence ratio is 1 / 0.7 to 1 / 1.5, preferably 1 / 0.95
~ 1 / 1.25, more preferably 1 / 1.01 ~ 1 /
It is 1.10. Further, the content of the secondary polyamine contained in the component (a) is 5.0% or more based on the total amount of the resin, and the content of the component (c) is 2 to 40%, preferably 5 to 20% of the total amount of the resin. It is preferably within the range.

The curing reactivity of the resin composition of the present invention is reduced as compared with the conventional composition mainly containing a primary polyoxyalkylene polyamine and an aromatic primary polyamine when mixed and cured with the main agent and the curing agent. A molded product having a fluidity retention time of 1.5 seconds or more when the resin composition is filled in a mold and having excellent initial rigidity and initial toughness immediately after molding is obtained. Therefore, compared with conventional polyurea Therefore, the moldability and workability are significantly improved.

When the resin composition of the present invention is used for reaction injection molding, a suitable surfactant, foaming agent, foam stabilizer, flame retardant, plasticizer, dye, filler, bactericide, if necessary. , A bactericidal agent, various reinforcing agents, an internal release agent, an antioxidant, a weather resistance stabilizer and the like may be appropriately mixed.

As described above, the resin composition of the present invention has sufficient workability as a material for reaction injection molding, moldability, and initial rigidity and initial toughness immediately after molding, and will become larger and more complicated in the future. It is an extremely useful material in the field of reaction injection molding.

Further, the present invention is not only a resin composition for molding in a closed mold but also a solventless / multi-liquid mixed type coating resin composition excellent in curability, drying property and coating workability. Applicable.

[0041] Examples will now be described by way of examples and comparative examples for explaining the present invention more specifically. However, the present invention is not limited to these examples.

(Production Example 1) 480 parts by weight of Jeffamine T-403 (amine equivalent = 160), which is a trifunctional polyoxyalkylene polyamine, 552 parts by weight of 2-ethylhexyl acrylate, and 1.8 parts by weight of acetic acid. A modified polyamine A was obtained by charging a separable flask equipped with a stirrer, a condenser, and a nitrogen introducing tube, and reacting at 80 ° C. for 20 hours while introducing nitrogen and stirring. C. D. The method of Wagner et al. [J. Am. Che
m. Soc. , 69 , 2609 (1947) and 6
9 , 2611 (1947)], the conversion rate from the primary amino group to the secondary amino group was measured. As a result, the conversion rate of the modified polyamine A to the secondary amino group was 95%.

Production Example 2 Showamine X (bifunctional, amine equivalent weight 68, molecular weight 136) and 2-ethylhexyl acrylate were added to a separable flask in an equivalent ratio of 1/1 in the same manner as in Production Example 1, and nitrogen was introduced. Then, the mixture was reacted with stirring at 80 ° C. for 14 hours to obtain a modified polyamine B.
The conversion rate to secondary amino groups was 87%.

Production Example 3 SR-TPG (epoxy equivalent = 2) which is a bifunctional polyether polyepoxy compound
00) 200 parts by weight and MTD which is an aromatic polyamine
(Amine equivalent = 61) 122 parts by weight and etacure 10
534 parts by weight of 0 (amine equivalent = 89) was charged in the same separable flask as in Production Example 1, and the reaction was carried out at 90 ° C. for 5 hours while introducing nitrogen and stirring to obtain a reaction product.

(Production Example 4) 316.8 parts by weight of Denacol EX-931 (epoxy equivalent = 528) which is a bifunctional polyether polyepoxy compound and MDA-220 (amine equivalent = 99) which is an aromatic polyamine. 118.
8 parts by weight and Etacure 100 (amine equivalent = 89)
320.4 parts by weight were placed in a separable flask similar to that used in Production Example 1, and stirred at 100% while introducing nitrogen.
The reaction was performed at 6 ° C for 6 hours to obtain a reaction product.

Production Example 5 Denacol EX-2000, which is a bifunctional aromatic polyether polyepoxy compound
(Epoxy equivalent = 1100) 495 parts by weight, and Etakyur 100 (amine equivalent = 8) which is an aromatic polyamine
9) 320.4 parts by weight was charged into a separable flask similar to that in Production Example 1, and the mixture was stirred and introduced with nitrogen to 1
Reaction was carried out at 40 ° C. for 3 hours to obtain a reaction product.

(Production Example 6) Denacol EX-421 which is a trifunctional aromatic polyether polyepoxy compound
(Epoxy equivalent = 155) 77.5 parts by weight, and Ethacure 100 as aromatic polyamine (amine equivalent = 8
9) 712 parts by weight were placed in a parable flask similar to that used in Production Example 1, and the mixture was stirred and introduced with nitrogen at 110 ° C.
The reaction was carried out for 6 hours to obtain a reaction product.

(Example 1) Jeffamine D-2000
30 parts by weight, 15 parts by weight of Techslim TR-5050, 21 parts by weight of Etacure-100, 15 parts by weight of modified polyamine A, and 19 parts by weight of the reaction product of Production Example 3, and 80 parts by weight of MDI modified polymer, and The mixture of 15 parts by weight of the HMDI prepolymer was injected into the mold while being collision-mixed, and the following conditions were measured: Mold size: 400 mm in length, 300 mm in width, thickness: 3
mm Raw material temperature 45 ± 2 ° C. Injection pressure 150 ± 20 Kg / cm ² Mold injection rate Approx. 420 ml / sec Reaction injection molding was performed at a mold temperature of 70 ± 2 ° C., and 20 seconds later, the mold was demolded. Then, it was post-cured at 120 ° C. for 30 minutes to obtain a reaction injection molded product. This was evaluated according to the method described below. The results are shown in Table 1.
It was shown to.

(Examples 2, 3, 4 and Comparative Examples 1, 2)
With the formulation shown in Table 1, reaction injection molding was performed under the same conditions as in Example 1, and the obtained molded product was evaluated in the same manner as in Example. The results are shown in Table 1.

[Performance Evaluation Method] 1. Moldability The moldability of the raw material mixture was evaluated. Judgment should be made within 1.5 seconds from the start of filling the raw material into the mold if the fluidity that can be filled into the mold is maintained for 1.5 seconds after starting the filling of the raw material into the mold. If it is lost and filling into the mold is clearly impossible: x. 2. Deformability at the time of demolding When a molded article molded under the above conditions is not plastically deformed at the time of demolding and a molded article faithful to the mold shape is obtained: ○ When demolding the molded article under the above conditions When the permanent plastic transformation occurs and the original shape is not retained: × 3. Strength of thin burr part When the molded product obtained by molding under the above conditions is completely removed from the molded product together with the molded product: ○ When the thin burr part is torn from the molded product and remains in the mold: × 4 ． Stress-Strain Property A sample was cut out from the molded product according to ASTM D638, and the stress-strain property was measured at a pulling rate of 5 mm / min.

[0051]

[Table 1]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Yamamoto 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Koji Izumo 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Mitsuharu Kaneko 3-1, Shinchi, Fuchu-cho, Aki-gun, Hiroshima Mazda Co., Ltd.

Claims (7)

[Claims] 1. A polyurea resin composition containing (a) a polyoxyalkylene polyamine, (b) an aromatic polyamine and / or xylylenediamine, wherein at least one of the polyamine components (a) and (b) is a primary amino. At least a part of a group by a Michael addition reaction with an unsaturated compound of the formula CH ₂ = C (R) -Y (wherein R represents hydrogen or a methyl group, and Y represents an electron-withdrawing group). A modified polyamine containing a polyamine in which a primary amino group is secondary, wherein the composition further comprises (c) a reaction product of a polyglycidyl ether and an aromatic primary polyamine, and (d) a polyisocyanate compound. A polyurea resin composition characterized by the above. 2. The polyurea resin composition according to claim 1, wherein the average molecular weight of the polyglycidyl ether which is one of the reactants of the component (c) is smaller than the average molecular weight of the largest average molecular weight component in the component (a). object. 3. The polyurea resin composition according to claim 1 or 2, wherein the aromatic primary polyamine which is another reactant of the component (c) is toluylenediamine. 4. The components (a) to (d) of the component (c).
The polyurea resin composition according to any one of claims 1 to 3, wherein the ratio of the components to the total weight is 2 to 40%. 5. The polyurea resin composition according to claim 1, wherein the ratio of the modified component (a) or component (b) to the total weight of the components (a) to (d) is 5% or more. object. 6. The electron withdrawing group Y of the unsaturated compound of the formula CH ₂ ═C (R) —Y is an ester residue, a ketone residue, a cyano group, an unsubstituted or substituted acid amide group, a sulfonic acid residue. Or a sulfonic acid ester residue, the polyurea resin composition according to any one of claims 1 to 5. 7. The equivalent ratio of all amino groups in the components (a) to (c) to the isocyanate groups in the component (d) is 1 / 0.7 to 1 / 1.6. The polyurea resin composition according to any one of 1 to 6.