JP2966864B2 - Production method of fast-curing polyurethane / polyurea elastomer by spraying - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for producing a polyurethane-polyurea elastomer, and more particularly to a method for producing a quick-curing type polyurea-polyurethane elastomer by spraying using an impingement-mixing type high-pressure spraying apparatus. .

[Conventional technology]

In order to produce a urethane elastomer by spraying, an organic polyisocyanate is used as a main component, and a high molecular weight polyol is added as a curing agent and a low molecular weight polyol or polyamine is added as a chain extender.

For example, as an organic polyisocyanate used as a main ingredient, in the case of spraying and foaming a rigid urethane foam, crude MDI is used as it is. Further, a method of adding a solvent to the main agent and the curing agent and diluting it is common.

For example, JP-A-49-17430 describes an example using a solvent, and is used for coating a relatively thin film.

On the other hand, a slightly higher-viscosity material can be selected as the raw material to be used, but in this case, it is necessary to slow down the curing speed and use a static mixer type mixer.
JP-A-55-1878 describes an example in which a solvent is partially used.

As another method, for example, JP-A-53-24396
Discloses a method of reacting an amino group with a carbonyl compound to give a ketoimine in order to delay the reactivity of an amine with an isocyanate group.

On the other hand, as a molding method, these are mixed immediately before molding and sprayed by a one-component type spray machine or spray molded by a two-component type spray machine.

[Problems to be solved by the invention]

However, these known methods have various problems and have not been practically satisfactory.

The present inventors have improved the prior art and the following points, and have finally reached the present invention.

1) Improvement of Mechanical Strength of Cured Product In the conventional system, there was a drawback that a highly reactive crosslinking agent reacted before a high molecular weight polyol, so that the molecular weight was not so high and the mechanical strength was low.

2) Prevention of foaming In the case of spray molding, since the material becomes fine particles and is atomized in the air, moisture existing in the atmosphere is adsorbed on the fine particle surfaces, and a foaming phenomenon occurs.

3) Prevention of jellying phenomenon occurring at the early stage of reaction When two liquids are subjected to collision mixing, a highly reactive free isocyanate and a crosslinking agent react first.

In this reaction, gelation occurs, but the chain elongation reaction is delayed, and a state in which the system becomes a cheese-like “jellying phenomenon” occurs.

It is known that "cracks" occur when an impact or the like is applied to a charcoal in which this jellification phenomenon has occurred, which is a major problem in molding.

4) By improving the reaction speed of the system and increasing the curing speed, it is possible to perform the work on a standing surface and an inclined surface.

5) A system that reduces the viscosity of the system, enables spraying without adding a solvent, and enables thick film forming and continuous forming.

[Means for solving the problem]

The present inventors have set the terminal of the high-molecular-weight polyol among the curing agents that react with the main agent as an amino group so that the reaction rate ratio with the cross-linking agent can be made closer, and the catalyst to be used can be a conventional catalyst. By using an "organic acid" in addition to the "organic metal catalyst", the conventional problems described above have been solved.

That is, by increasing the reaction rate of the whole system, the molecular weight was increased, and the mechanical strength was improved.

As a result, the ratio of the reaction rate with water is increased, and the foaming phenomenon can be prevented. Also, as the reaction speed of each component becomes closer,
The reaction proceeds uniformly, and no "jellying phenomenon" occurs.

Furthermore, by using an aromatic amine cross-linking agent and a low molecular weight glycol as a cross-linking agent and using an organic acid in combination as a curing catalyst, the degree of aggregation of the "urea group" generated by the reaction between the isocyanate and the amine is controlled, and the mechanical strength is improved. It has the effect of improving.

As a result, it has been found that a urethane elastomer which is quick-curing and has high physical properties can be obtained, and has reached the present invention.

 That is, the present invention is as follows.

(A) As a main agent, an organic polyisocyanate compound and / or an organic polyisocyanate compound and a polyol having a molecular weight of 38 to 2,000 per OH group are used in an equivalent ratio (NCO /
(A) containing a partial prepolymer reacted with 3 or more OH), and (B) as a curing agent, (1) polyoxyalkylenediamine represented by the following general formula (I) R ¹ NHCR ² R ³ CR ⁴ R ^5- (OCR ² R ³ CR ⁴ R ⁵ ) x _-1 -O- (CH ₂ CH ₂ CH ₂ CH ₂ O) n- (CR ⁴ R ⁵ CR ² R ³ O) y _-1 -CR ⁴ R ⁵ CR ² R ³ NHR ⁶ (I) (wherein R ¹ and R ⁶ may be the same or different, or H or C ₁ -C
Represents ₁₂ aliphatic, alicyclic, aromatic aliphatic hydrocarbon groups,
R ² , R ³ , R ⁴ , and R ⁵ may be the same or different, or H or C ₁ to
A C ₁₀ aliphatic, cycloaliphatic or aromatic hydrocarbon group, wherein R ²
+ R ³ + R ⁴ + R ⁵ = C _{0 to} C ₁₀ , n = 1 to 100, x, y,
Represents an integer of 1 to 20. ) A polyoxyalkylenediamine represented by the formula:

(2) Aromatic amine crosslinking agent (3) Low molecular weight glycol having a molecular weight of 60 to 250 (4) Organometallic catalyst (5) Agent B containing organic acid The present invention relates to a method for producing a quick-curing polyurethane / polyurea elastomer by spraying, characterized by being spray-molded.

The polyoxyalkylenediamine represented by the above general formula (I) used in the present invention can be produced by the method of Japanese Patent Application No. 1-69249.

That is, the following general formula ^{(II), H- (OCR 2} R 3 CR 4 R 5) x-O- (CH 2 CH 2 CH 2 CH 2 O) n (CR 4 R 5 CR 2 R 3 O) y- H ......
(II) (wherein, R ² , R ³ , R ⁴ , R ⁵ , n, x, and y have the same meanings as those described in the above formula (I)), and ammonia, It is obtained by reacting an active hydrogen-containing nitrogen compound selected from the group consisting of primary amines and secondary amines in the presence of a hydrogenation-dehydrogenation catalyst.

The polyoxyalkylene diol represented by the general formula (II) used above can be used, for example, by adding C ₂ to polytetramethylene ether glycol using an alkali metal hydroxide as a catalyst.
It can be obtained by known methods for the addition reaction of the epoxy compound -C _12.

As the epoxy compound C ₂ -C ₁₂ used at this time, ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, 1,2-epoxy hexane, 1,2-epoxy Octane, 1,2-epoxydecane, 1,2-epoxidedodecane, cyclopentene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide and the like can be exemplified.

Examples of the primary amine compound used above include methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, t-butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine,
Decylamine, β-aminopropyl methyl ether, β
-Aminopropylethyl ether, aniline, o-toluidine, m-toluidine, p-toluidine, benzylamine, naphthylamine, cyclopentylamine, cyclohexylamine and the like are exemplified.

In addition, as the secondary amine compound used above, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine,
Dihexylamine, methylethylamine, methylpropylamine, methylisopropylamine, ethylpropylamine, ethylisopropylamine, N-methyldodecylamine, N-methylaniline, N-ethylaniline,
Diphenylamine and the like.

The amount of the active hydrogen-containing nitrogen compound used above is determined depending on the application, but is usually 0.2 to 1 with respect to the hydroxyl group.
00 equivalents, preferably 0.5 to 50 equivalents, are used. Also,
The active hydrogen-containing nitrogen compound is used alone or in combination depending on the use.

As the hydrogenation-dehydrogenation catalyst used above, a conventionally known catalyst can be used.For example, nickel, cobalt or the like, a supported catalyst in which a carrier such as cesium, alumina is supported, a nickel-based or cobalt-based catalyst is used. Raney-type catalysts, copper-chromium-based catalysts, copper-zinc-based catalysts and the like are typical examples. Among them, a supported catalyst is one of particularly suitable catalysts.

In the above, the catalyst is usually 0.1 to 20% by weight, preferably 0.3 to 10% by weight based on the polyoxyalkylene diol.
%, Most preferably 0.5 to 5% by weight.

The above reaction conditions are generally used at a reaction temperature of 150 to 280.
° C, preferably 180 to 250 ° C, reaction pressure 20 to 150 kg / cm ² G,
The reaction is preferably performed at 30 to 100 kg / cm ² G for a reaction time of 1 to 20 hours, preferably 5 to 10 hours.

Hydrogen may or may not be present in the reaction system. The lower the reaction temperature, the lower the reaction rate. If the reaction temperature is too high, the polyoxyalkylene diol is undesirably decomposed.

After completion of the reaction, the desired polyoxyalkylenediamine having an amino group at the molecular terminal is obtained by appropriately combining methods such as recovery by evaporation of the unreacted active hydrogen-containing nitrogen compound, filtration of the catalyst, washing with water, and drying. be able to.

Organic polyisocyanate used in the present invention, for example,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), xylylene diisocyanate (XDI), dicyclohexylmethane-4,4 '
-Diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrogenated xylene diisocyanate (HXDI),
Crude TDI, polymethylene polyphenyl polyisocyanate (crude MDI), and modified isocyanurates, carbodiimides, and burettes of these isocyanates are used.

Among these organic polyisocyanates, MDI, crude MDI
And its modified products are particularly preferred.

The organic polyisocyanate of the present invention can be reacted with polyoxyalkylene diamine and a cross-linking agent as it is, or can be obtained by heating a part of the isocyanate group with a polyol and a nitrogen stream at 70 to 80 ° C. for several hours. Can be used.

Examples of the polyol that can be used for producing the partial prepolymer include, for example, water, ethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerin, trimethylolpropane,
Polyhydric alcohols such as pentaenthritol alone or
Polyether polyols obtained by addition polymerization of one or more alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide (PP
G); polytetramethylene ether / glycol (PTMEG) obtained by addition polymerization of tetrahydrofuran alone or together with ethylene oxide; castor oil, polycarbonate polyol and the like are suitable.

In addition to the above, a polyester polyol obtained by reacting a polycarboxylic acid with a low molecular polyol and a polyester polyol obtained by polymerizing caprolactone can be used.

Further, acrylonitrile, styrene,
Polymer polyol obtained by graft polymerization of an ethylenically unsaturated compound such as methyl methacrylate and 1,2-
Alternatively, 1,4-polybutadiene polyol or a hydrogenated product thereof can also be used.

The above-mentioned polyols are used alone or as a mixture of two or more kinds. The polyol or a mixture thereof preferably has a molecular weight of 38 to 2,000 per OH group.

As the aromatic polyamine of the chain extender used in the present invention, for example, a mixture of 4,4'-diaminodiphenyl, 4,4'-diaminodiphenylether, 2,3-diaminotoluene and 3,4-diaminotoluene , 2,4- and 2,6-
Diaminotoluene (including a mixture of 80:20 (weight)),
2,4- and / or 4,4'-diamino-diphenylmethane,
1,3- and 1,4-phenylenediamine, naphthylene-1,5
Liquid polymer of polyphenyl-polymethylenepolyamine of the type obtained by diamine, aniline-formaldehyde condensation, 1,3-dimethyl-2,4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1 , 3-Diethyl-2,5-diaminobenzene, 1,4-diisopropyl-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'-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, 3,3 ', 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; 3,3 ', 5,5'-tetraethyl-4, 4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl ether; 2-in the presence of 3,3'-dichloro-4,4'-diaminodiphenylmethane and mineral acid Polyamine mixture obtained by condensing chloroaniline and aniline with formaldehyde; tert-butyltoluenediamine; 1,3,5-triisopropyl-2,4-diaminobenzene; 4,4'-bis (sec-butylamino) diphenylmeta 1,4- (sec-butylamino) benzene and the like.

These aromatic polyamines can be used alone or as a mixture, and the use ratio is 3 to 100 parts by weight, preferably 100 parts by weight of polyoxyalkylenediamine, preferably
10 to 70 parts by weight are suitable.

The low molecular weight glycol used in the present invention has a molecular weight of 60.
~ 250 are preferable, and for example, ethylene glycol, diethylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-butanediol and the like are suitable.

These low molecular weight glycols can be used as a mixture with the aromatic amine as the crosslinking agent.

In this case, the compounding ratio is suitably about 0.2 to 0.8 in terms of the equivalent ratio of NH ₂ / OH.

The amount of the polyisocyanate or the partial prepolymer and the polyol and the crosslinking agent is used in an equivalent ratio (NCO / H) between the NCO group in the organic polyisocyanate or the partial prepolymer and the active hydrogen (H) in the polyol and the crosslinking agent. The range is 0.9 to 1.30.

The organometallic catalyst of the curing catalyst used in the present invention is generally used for curing the urethane reaction, for example,
Fatty salts of tin, lead, bismuth, zinc, etc. (eg dibutyltin dilaurate, lead octylate, bismuth octoate)
The use of lead and bismuth is preferred from the viewpoint of preventing foaming.

The amount used is suitably from 0.01 to 5% by weight based on the total amount of the raw materials used.

The organic acid of the curing catalyst is COOH group, SO ₃ H group, phenolic
A compound having at least one acidic group such as an OH group.

Particularly, fatty acids, oxycarboxylic acids, aliphatic dicarboxylic acids, aromatic carboxylic acids, sulfonic acids, nonylphenols and the like are preferred.

The amount used is suitably from 0.01 to 5% by weight based on the total amount of the raw materials used.

Other auxiliaries that can be used as needed in the present invention include plasticizers, flame retardants, defoamers, coloring agents, stabilizers, and fillers.

As the plasticizer, for example, dioctyl phthalate (DO
P), dibutyl phthalate (DBP), dioctyl adipate (DOA), tricresyl phosphate (TCP), chlorinated paraffin, and the like.

Examples of the flame retardant include tris- (β-chloropropyl) phosphate, (Pyrrol PCF: manufactured by Akzo Japan), tris-dichloropropyl phosphate (CRP: manufactured by Daihachi Chemical Co., Ltd.), and tris-chloroethyl phosphate (CL
P: manufactured by Daihachi Chemical Co., Ltd.), and bromo compounds such as dibromoneopentyl glycol and tribromoneopentyl alcohol.

As the coloring agent, an organic or inorganic pigment kneaded with the above plasticizer (toner) and a dye are used.

As the stabilizer, for example, trade name Irganox # 10
10 # 1076 (made by Ciba Geigy), Yoshinox BHT, B
B and phenols such as GSY-930 (manufactured by Yoshino Pharmaceutical); benzotriazoles such as Tinuvin P, 327, 328 (manufactured by Ciba Geigy); benzophenones such as Tomisorp 800 (manufactured by Yoshino Pharmaceutical): SANOL LS-770
And 744 and Tinuvin 144 (manufactured by Ciba Geigy), and position-hindered amines can be used.

Examples of the filler include carbon black, calcium carbonate, silica, talc, kaolin, zeolite, diatomaceous earth, perlite, permucurite, and titanium dioxide.

As the defoaming agent, silicone-based and polyacrylate-based agents commonly used for polyurethane can be used.

The two-liquid high-pressure spray machine used in the present invention includes:
For example, the main body is Gasmer's model H-2000, H-2000.
V-type, Glasscraft Model T-3H, Binks Model G and the like are preferred.

These two-liquid high-pressure spray machines can quantitatively send two liquids whose temperature has been adjusted at a pressure of about 100 kg / cm ² or more.

The spray gun that mixes and atomizes the two liquids is Gasmer's
The use of GX-7 guns, AR-A guns, Glasscraft prober guns and Binks model 43P guns is preferred.

The spray gun mainly uses a collision mixing type, but it is also possible to spray-mold using a static mixer as an auxiliary.

Examples of the static mixer include products sold by Toray Engineering and Nippon Gray.

Moreover, in the present invention, since no solvent is used,
With a single spraying, it is possible to apply a considerably thick coating or to continuously laminate.

The undiluted polyurethane solution used in the present invention has a very high reactivity, and loses fluidity in 1 to 60 seconds after mixing the undiluted solution.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Preparation of Organic Polyisocyanate The preparation of the polyisocyanate was performed by the following method.

Reference Example 1 729 g of pure MDI (manufactured by Mitsui Toatsu Chemical; MDI-PH) and carbodiimide modified liquid MDI (MDI-LK manufactured by Mitsui Toatsu Chemical; NC0 = 2)
(8.5% by weight) and 312 g of PPG-Diol-2000 (OH number = 56, manufactured by Mitsui Toatsu Chemicals) are added in an amount of 1000 g. After reacting at 80 ° C. for 3 hours in a nitrogen stream, DOP (dioctyl phthalate) is reduced in viscosity. 510g as an additive, NCO = 11.3% by weight, viscosity (cps / 25 ° C)
= 850, specific gravity = 1.14 modified polyisocyanate (A-
1) was obtained.

Reference Example 2 1,000 g mixed with pure MDI / liquid MDI = 8/2 (weight ratio)
Is a ring-opening polymer of tetrahydrofuran with a molecular weight of 1,000.
530 g of TMEG (Terratan-1000E; manufactured by DuPont, OH value = 114)
In addition, after reacting at 80 ° C for 3 hours under a nitrogen stream, NCO = 18
A modified polyisocyanate (A-2) having a weight% of viscosity (cps / 25 ° C.) = 800 and specific gravity = 1.18 was obtained.

Reference Example 3 Crude MDI (MDI-CR manufactured by Mitsui Toatsu Chemicals; NC0 = 31% by weight)
825.4 g, 59.2 g of tripropylene glycol and 115.9 g of paraffin chloride (Ajinomoto's salt para # 40) were stirred for 1 hour under a nitrogen stream, and NCO = 23% by weight, viscosity (cps / 25 ° C.) = 400,
A polyisocyanate (A-3) having a specific gravity of 1.22 was obtained.

Reference Example 4 PPD-Diol-1000 (manufactured by Mitsui Toatsu Chemicals) 855 in 1,000 g of xylylene diisocyanate (MXDI; manufactured by Takeda Pharmaceutical)
g was added, and the mixture was reacted at 80 ° C. for 3 hours under a nitrogen stream, and then further raised to 100 ° C. and further reacted for 3 hours.

As a result, NCO = 20% by weight, viscosity (cps / 25 ° C) = 1,000,
A modified polyisocyanate (A-4) having a specific gravity of 1.21 was obtained.

Reference Example 5 A mixture of pure MDI (manufactured by Mitsui Toatsu Chemicals; MDI-PH) and liquid MDI at a weight ratio of 7/3, 1,000 g, and PPG-Diol-1500
After adding 750 g (OH number = 75, manufactured by Mitsui Toatsu Chemicals Co., Ltd.) and reacting at 80 ° C. for 3 hours under a nitrogen stream, 200 g of DOP (dioctyl phthalate) as a thickener was added, NCO = 14% by weight, and viscosity ( (cps / 25 ° C.) = 500, and a modified polyisocyanate (A-5) having a specific gravity of 1.15 was obtained.

Comparative Reference Example Toluene was added to 667 g of the modified polyisocyanate (A-2).
Use 333g with reduced viscosity. Table 1 shows the adjustment results of polyisocyanates (Comparative Example-2) having NC 0% = 12% by weight, viscosity (cps / 25 ° C) = 70, and specific gravity = 1.08.

Preparation of polyalkylenediamine Reference Example 6 In a 200 ml high-pressure autoclave, 4 g of nickel diatomaceous earth catalyst (nickel content = 50%), polytetramethylene ether glycol (average molecular weight = 650) obtained by ring-opening polymerization of tetrahydrofuran, and propylene oxide 80 g of polyoxyalkylene diol (hydroxyl value = 112 mg KOH / g, average molecular weight = 1,000; hereinafter abbreviated as polyol P) obtained by addition polymerization of isopropylamine 4
7.2 g was charged in this order, and nitrogen replacement was performed 5 times (10 kg / sq.cm
G) After performing, hydrogen was charged at an initial pressure of 50 kg / sq.cmG. The temperature was raised to 220 ° C. with stirring, and the reaction was carried out for 8 hours. At this time, the pressure was 75 kg / sq.cmG.

After completion of the reaction, a novel polyoxyalkylenediamine containing an amino group at the molecular terminal was purified by filtering off the catalyst and drying under reduced pressure.

Of the resulting polyoxyalkylenediamine (B-1)
The absorption of the amino group was confirmed by IR spectrum (3330
cm-1, 3400 cm-1).

The nitrogen content by elemental analysis was 2.4%. When the amine value was measured by the azomethine method and the acetylated perchloric acid method, the total amine value was 94.3 mgKOH / g, the primary amine value was 40.4 mgKOH / g, the secondary amine value was 53.6 mgKOH / g, and the tertiary amine value. At 0.3 mg KOH / g, the conversion of the hydroxyl group was 94.0%, the selectivity of the primary amine and the selectivity of the secondary amine were 42.8% and 5%, respectively.
It was 6.8%.

Reference Example 7 Reference Example 6 was the same as Reference Example 6 (B-1) except that diisopropylamine was used instead of isopropylamine.
The reaction was carried out under the same conditions as described above to synthesize polyoxyalkylenediamine (B-2).

Reference Example 8 In Reference Example 6 (B-1), diisopropylamine was added so that the equivalent ratio of diol P / isopropylamine / diisopropylamine became 1/2/8, and the reaction temperature was set to 20.
The reaction was carried out under the same conditions as in Reference Example 6 except that the reaction time was changed to 0 ° C. and the reaction time was changed to 10 hours, to synthesize polyoxyalkylenediamine (B-3). However, the charged amount of diol P is
50 g.

Reference Example 9 In Reference Example 8 (B-3), instead of diol P, polytetramethylene ether glycol (average molecular weight: 200) obtained by ring-opening polymerization of tetrahydrofuran was used.
0) to a polyoxyalkylene glycol obtained by addition polymerization of propylene oxide (having a hydroxyl value of 47.8 mgKOH /
g, average molecular weight 2350; hereinafter abbreviated as diol Q. The reaction was carried out under the same conditions as in B-3 except that the above was used to synthesize polyoxyalkylenediamine (B-4).

 Table 2 shows the synthesis results of the polyalkylene diamine.

Spray molding method Examples 1-4, Comparative examples 1-2 Examples-1, 3, 4 and Comparative example-1 are glass craft as a spraying machine as a spray gun in a H-2000 high pressure spraying machine manufactured by Gasmer. The company's prober gun (mixing chamber: round No. 1) was used.

In Example-2 and Comparative Example-2, as a molding machine, MINI-2 manufactured by Glass Craft Co., Ltd. was used.
Used to put elements.

 See the attached table for spray setting conditions.

The atmosphere of the spray was experimented by creating a closed room with a vinyl sheet and blowing hot air and steam into the inside to create high temperature and high humidity conditions.

Example 1 is suitable as a waterproof material for a fast-curing roof.

[Effects of the Invention] The present invention is a `` solvent-free type '' system that does not use a solvent, and has been improved in the adjustment of raw materials and the setting of the machine so that spray molding is possible. I was able to solve it.

1) Prevention of foaming: When spray-molded in a high-temperature, high-humidity atmosphere, the density is small and the functional strength is hardly changed.
(Example-1 and Comparative Example-1) 2) Prevention of gelling: The cured state of the sheet was checked immediately after molding. However, none of the present inventions became cheese-like, and there was a rubber-like element and the polymerization was high. It is presumed that it is proceeding smoothly.

3) Fast-curing property: The properties of physical properties were measured. The properties of hardness and mechanical strength were good, and it was confirmed that when used as a floor material, sufficient walking strength was exhibited in about one hour. Was.

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Claims (8)

(57) [Claims] 1) A agent containing an organic polyisocyanate as a main agent, and 2) a curing agent as a curing agent. (1) Polyoxyalkylenediamine R ¹ NHCR ² R ³ CR ⁴ represented by the following general formula (I): R ^5- (OCR ² R ³ CR ⁴ R ⁵ ) _x-1 -O- (CH ₂ CH ₂ CH ₂ CH ₂ O) _n- (CR ⁴ R ⁵ CR ² R ³ O) _y-1 -CR ⁴ R ⁵ CR ² R ³ NHR ⁶ (I) (wherein R ¹ and R ⁶ may be the same or different, or H or C ₁ -C
_Represents an aliphatic, alicyclic or aromatic hydrocarbon group of 12, R ² ,
R ³ , R ⁴ and R ⁵ may be the same or different, or H or C ₁ -C ₁₀
An aliphatic, alicyclic, or aromatic hydrocarbon group represented by R ² +
R ³ + R ⁴ + R ⁵ = C _{0 to} C ₁₀ , n = 1 to 100, x and y are 1 to 2
Represents an integer of 0. (2) Aromatic amine cross-linking agent (3) Low molecular weight glycol having a molecular weight of 60 to 250 (4) Organometallic catalyst (5) Agent B containing organic acid as two components, Agent A and Agent B, A method for producing a quick-curing polyurethane / polyurea elastomer by spraying, comprising spraying and molding an object using a two-liquid high-pressure airless spray machine. 2. An organic polyisocyanate comprising an organic polyisocyanate compound and / or an organic polyisocyanate compound and a polyol having a molecular weight of 38 to 2,000 per OH group, having an equivalent ratio (NCO / OH) of 3 or more. The method for producing a polyurethane / polyurea elastomer according to claim 1, which is a partial prepolymer reacted in the above. 3. The method according to claim 1, wherein the organic polyisocyanate compound is MDI,
3. The process for producing a polyurethane / polyurea elastomer according to claim 2, which is a mixture of at least one of crude MDI or a modified product thereof, or a partial prepolymer of the organic polyisocyanate. 4. The process for producing a polyurethane / polyurea elastomer according to claim 1, wherein the aromatic amine crosslinking agent is used in an amount of 3 to 100 parts by weight per 100 parts by weight of the polyoxyalkylenediamine. 5. The low molecular weight glycol comprises an amino group (NH2) of an aromatic amine crosslinking agent and a hydroxyl group (OH) of a low molecular weight glycol.
2. The process for producing a polyurethane / polyurea elastomer according to claim 1, wherein the equivalent ratio (NH2 / OH) is 0.2 to 0.8. 6. The process for producing a polyurethane / polyurea elastomer according to claim 1, wherein the organic acid of the curing catalyst is a compound having at least one group exhibiting acidity. 7. The process for producing a polyurethane / polyurea elastomer according to claim 1, wherein the organic acid of the curing catalyst is a fatty acid, oxycarboxylic acid, aliphatic dicarboxylic acid, aromatic carboxylic acid, sulfonic acid, or nonylphenol. 8. The process for producing a polyurethane / polyurea elastomer according to claim 1, wherein the organic acid of the curing catalyst is used in an amount of 0.001 to 5% by weight based on the total amount of raw materials used.