JPH07109326A - Quick-curing elastomer - Google Patents

Abstract

PURPOSE:To obtain a quick-curing elastomer consisting of an organic polyisocyanate compound and a specific curing agent, excellent in electric characteristics, water resistance, flame retardance and mechanical strength and useful for electrically insulating coating agents, etc. CONSTITUTION:This quick-curing type elastomer consists of (A) an organic polyisocyanate compound such as 1,4-phenylenediisocyanate, (B) a curing agent composed of (i) one or more kinds of polyols selected from a castor oil-based polyol, a polyolefin polyol and a compound of formula I {X is (OR)pO-ph-Z-ph-O (RO)q [R is 2-4C alkylene; ph is phenylene; Z is CH2, SO2, O, etc.; (p) and (q) are 1-10]; Y is 1-4C alkylene; (m) is 1-80}, (ii) two or more kinds of low molecular weight polyols selected from an amino alcohol or a compound having <=500 molecular weight and obtained by adding a 2-4C alkylene oxide to the amino alcohol, a 2-10C polyol or an organic amine compound and (iii) a catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a fast-curing elastomer.

[0002]

2. Description of the Related Art Fast-curing type elastomers are used for automobile parts such as bumpers, electric parts such as belts and rolls, and building parts such as flooring and waterproofing materials because of their good productivity. ing. As its conventional technology,
A method in which a urethane prepolymer composed of polyether triol having a molecular weight of 3000 and diphenylmethane diisocyanate is used as an agent A, and a polyether triol having a molecular weight of 3000, diethylene glycol and a potassium salt trimerization catalyst as an agent of B are used as a sprayable quick-curing elastomer. 60-179415); a urethane prepolymer composed of polyoxypropylene diol having a molecular weight of 2000 and diphenlmethane diisocyanate as agent A, and polyoxyalkylenediamine, aromatic amine crosslinking agent, low-molecular glycol and catalyst as agent B. Method for producing rapid-curing polyurea-polyurethane elastomer by spraying (JP-A-3-162411); polyphenylmethane polyisocyanate as agent A, castor oil and amine compound as alkylene oxide How to obtain a coating composition polyoxyalkylene polyol and smoothness aid such as zeolite added with the id as B agent (JP 60-32857
No. publication) is known.

[0003]

However, the above-mentioned and the above have a problem that the electrical properties such as electric insulation, dielectric constant and dielectric loss tangent, water resistance and flame retardancy are poor. In addition, since the coating composition is a coating composition, the cured product is brittle and has a low mechanical strength such as impact strength, and a slow curing speed.

[0004]

The present inventors have found that electrical properties such as electric insulation, dielectric constant, and dielectric loss tangent, water resistance, flame retardancy, mechanical strength, flexibility, heat resistance, corrosion resistance, and heat insulation. The present invention has been achieved as a result of extensive studies aimed at obtaining a non-foaming and foaming fast-curing elastomer having good properties, dew condensation prevention and workability. That is, the present invention relates to a two-liquid fast-curing urethane elastomer comprising a main agent and a curing agent, the main agent being an organic polyisocyanate compound (A). Curing agent; polyol (B-1): castor oil-based polyol, polyolefin polyol and the following general formula (1)
One or more polyols selected from the compounds represented by: Low molecular weight polyol (B-2): amino alcohol or amino alcohol, C2-10 polyol, organic amine compound with C2-4 alcohol.
Two or more low molecular weight polyols selected from compounds having a molecular weight of 500 or less to which xylene oxide is added and compounds represented by the following general formula (2). A fast-curing elastomer comprising a catalyst (B-3). Formula _{H (X-Y-) m X} -H (1) H (OR) p O-Ph-Z-Ph-O (RO) q H (2) [ wherein, X is the formula - (OR) _p O-Ph-Z-Ph-
O (RO) _q- , Y is an alkylene group having 1 to 4 carbon atoms, R is an alkylene group having 2 to 4 carbon atoms, and Ph is a phenylene group (substituted by a halogen or an alkyl group having 1 to 18 carbon atoms). , Z is —CH ₂ —, —SO ₂ —, —O.
- or _{-C (CH 3) 2 -,} m is an integer of 1 to 80, p and q each represents an integer of 1 to 10. ]

Examples of the organic polyisocyanate compound (A) constituting the main agent of the present invention include aliphatic polyisocyanate (a), alicyclic polyisocyanate (b),
Examples thereof include araliphatic polyisocyanate (c), aromatic polyisocyanate (d) and modified products (e) of these polyisocyanates.

Specific examples of the aliphatic polyisocyanate (a) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Examples thereof include lysine diisocyanate and 1,3,6-hexamethylene triisocyanate.

Specific examples of the alicyclic polyisocyanate (b) include isophorone diisocyanate (IPDI),
Dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), 1,4-cyclohexane diisocyanate, methylcyclohexane-2,4-diisocyanate (hydrogenated TDI), 1,4-bis (2-isocyanatoethyl) cyclohexane, etc. Can be mentioned.

Specific examples of the araliphatic polyisocyanate (c) include p-xylene diisocyanate, α,
Examples include α, α ′, α′-tetramethylxylene diisocyanate.

Specific examples of the aromatic polyisocyanate (d) include 1,4-phenylene diisocyanate, 2,
4- and / or 2,6-toluene diisocyanate (TDI), diphenylmethane-2,4'- and / or 4,4'-diisocyanate (MDI), naphthalene-1,5-diisocyanate, 3,3'-dimethyldiphenylmethane -4,4'-diisocyanate, o-tolidine diisocyanate, crude TDI, polyphenylmethane polyisocyanate (crude MDI) and the like can be mentioned.

As the modified product (e) of polyisocyanate, carbodiimide group, uretidione group, uretoimine group, urea group, buret group, isocyanurate group, urethane group, etc. are introduced by using the above (a) to (d). And modified products thereof. As a specific example of the (e),
For example, an active hydrogen-containing compound (D) such as castor oil, a castor oil derivative, an olefin polyol, a compound represented by the general formula (1) or (2), and the above (a) to (d).
Urethane prepolymer having an isocyanate group at the end derived from the polyisocyanate of 5 to 40% by weight (for example, castor oil and 4,
A urethane prepolymer having an isocyanate group content of 20% by weight derived from 4'-diphenylmethane diisocyanate; an isocyanate group content of 22% by weight derived from isophorone diisocyanate and a polyol having a molecular weight of 600 in which propylene oxide is added to bisphenol-A. Urethane prepolymer of bisphenol-
Urethane having an isocyanate group content of 25% by weight derived from a polyol having a molecular weight of 600 to which propylene oxide is added to A and a polyol having a molecular weight of 1200 jumped with bromochloromethane, 4,4′-diphenylmethane diisocyanate and carbodiimide-modified diphenylmethane diisocyanate. Prepolymer) and carbodiimide-modified diphenylmethane diisocyanate. Organic polyisocyanate compound (A)
A mixture of two or more kinds may also be used.
Preferred among (a) to (e) are (b),
(C), (d) and (e), and particularly preferred are (d) and (e).

Among the polyols (B-1) constituting the curing agent in the present invention, castor oil-based polyols include, for example, castor oil, castor oil derivatives [castor oil fatty acid and polyhydric alcohol or polyoxyalkylene polyol. Polyester polyols (castor oil fatty acid mono- or diglyceride, castor oil fatty acid mono- or diester with trimethylolpropane, castor oil fatty acid mono- or diester with polyoxypropylene glycol); castor oil Alkylene oxide (having 2 to 4 carbon atoms) added thereto; a hydroxyl group-terminated prepolymer derived from castor oil and diphenylmethane diisocyanate, etc.], castor oil-based polymer polyols, and mixtures of two or more thereof.

As the castor oil-based polymer polyol, among the castor oil and the castor oil derivative [I] exemplified above, for example, the ethylenically unsaturated monomer [II] described in JP-A-4-292683 is disclosed. Polymer polyols obtained by polymerizing The content of the ethylenically unsaturated monomer [II] constituting the polymer polyol is usually 1 to
90% by weight, preferably 5 to 80% by weight. As a method for producing a polymer polyol, for example, a method of polymerizing an ethylenically unsaturated monomer [II] in [I] in the presence of a polymerization initiator (US Pat. No. 3,383,351, Japanese Patent Publication No. 39-39). 24737, Japanese Patent Publication No. 47-47999.
Japanese Patent Laid-Open No. 50-15894 and the like).

Among the polyols (B-1), examples of the olefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol and polyisoprene polyol.

Among the polyols (B-1), examples of the compound represented by the general formula (1) include bisphenol A, bisphenol S, bisphenol F and alkylene oxide having 2 to 4 carbon atoms (ethylene oxide,
Examples thereof include propylene oxide, butylene oxide, and a combination of these), and a polyol derived from a compound to which an alkylene halide (bromochloromethane, dibromoethane, etc.) is added (blocking or random addition may be used in combination). Specific examples include those in which propylene oxide 3 mol adduct of bisphenol A and bromochloromethane jumped to an average molecular weight of 1200, and those of bisphenol A ethylene oxide 2 mol adduct and bromochloromethane jumped to an average molecular weight of 800. And so on. The active hydrogen equivalent of the compound represented by the general formula (1) is usually 274 to 10,000.
It is 0, preferably 274 to 5,000. These (B
The polyols exemplified as -1) have a low water absorption rate of the obtained elastomer, so that water resistance, electrical characteristics, corrosion resistance,
Dew condensation prevention properties, water-resistant adhesion properties, etc. are good and preferred.

As the low molecular weight polyol (B-2) constituting the curing agent of the present invention, (a) amino alcohol (triethanolamine, methyldiethanolamine, etc.); (b) polyol having 2 to 10 carbon atoms {for example, Aliphatic dihydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, etc.), low molecular weight diols having a cyclic group [1, 4-bis (hydroxymethyl) cyclohexane, m- and p-xylylene glycol, 1,4-bis (2-hydroxyethoxy) benzene, etc.] and trihydric alcohols (glycerin, trimethylolpropane, hexanetriol, etc.) are mentioned. Be used; (c) Organic amine A compound having a molecular weight of 500 or less obtained by adding an alkylene oxide having 2 to 4 carbon atoms to a compound (for example, an alkylenediamine having 2 to 6 carbon atoms (such as ethylenediamine, tetramethylenediamine, hexamethylenediamine) as an organic amine compound); polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, methylaminopropylamine, methyliminobispropylamine, etc.]; fat Cyclic or heterocyclic polyamines (C4-15) [N-aminoethylpiperazine, 1,3-
Diaminocyclohexane, isophoronediamine, hydrogenated methylenedianiline, etc.]; Aliphatic polyamines having an aromatic ring (C8 to C15) [xylenediamine, tetrachloro-p-xylenediamine, etc.]; Aromatic polyamines (C6 To 20) [phenylenediamine, toluenediamine, methylenedianiline, diaminodiphenylsulfone, benzidine, thiodianiline, methylenebis (o-chloroaniline), m-aminobenzylamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane. Etc.]; amino alcohols (triethanolamine, methyldiethanolamine, etc.); monoamines (butylamine, octylamine, etc.) with 2 carbon atoms
~ 4 alkylene oxides (ethylene oxide, propylene oxide, butylene oxide and combinations thereof) added (blocked or random addition when combined)}; (d) represented by the above general formula (2). Compound [for example, bisphenol A, bisphenol S, bisphenol F was added with an alkylene oxide having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, butylene oxide and a combination thereof) (in the case of combination, block addition or random addition may be performed)) Thing].

Specific examples of the compound (d) represented by the general formula (2) include a propylene oxide 6 mol adduct of bisphenol A and an ethylene oxide 2 mol adduct of bisphenol A. The active hydrogen equivalent of (d) is usually 134 to 700. Active hydrogen equivalent is 7
If it exceeds 00, the concentration of the alkylene oxide chain in the molecule is excessively increased and the electrical properties such as electric insulation and dielectric constant are deteriorated, which is not preferable.

A preferable blending weight ratio of the curing agent is 1 to 70 parts by weight of the low molecular weight polyol (B-2) based on 100 parts by weight of the polyol (B-1). (B-
If 2) is less than 1 part by weight, the mechanical strength of the elastomer will be insufficient, and if it exceeds 70 parts by weight, the flexibility will decrease. By blending (a) and / or (b) as an essential component, the sea-island structure of the hard segment and the soft segment becomes clear, and it becomes a high-strength elastomer excellent in mechanical strength, flexibility, heat resistance, etc. .

As the catalyst (B-3), dibutyltin dilaurate, alkyl titanate, organosilicon titanate, stannas octoate, lead octylate, zinc octylate, bismuth octylate, bismuth neodecanoate, dibutyltin. Metal-based catalysts such as diorsophenylphenoxite, reaction products of tin oxide and ester compounds (dioctyl phthalate, etc.); monoamines [triethylamine, etc.], diamines [N, N, N ′, N′-tetramethylethylenediamine, etc. ], Triamines [N,
N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and the like], cyclic amines [triethylenediamine and the like], and other amine-based catalysts. You may use these catalysts in combination of 2 or more types. The type and blending amount of the catalyst can be selected according to the purpose, and the blending amount is usually 0.1 to 100 parts by weight of the fast-curing elastomer.
It is 10 parts by weight, preferably 0.1 to 3 parts by weight. In particular, when the amount of the metal catalyst exceeds 10 parts by weight, the heat resistance becomes poor, which is not preferable.

In the present invention, a flame retardant (C) can be used for the purpose of improving the flame retardancy of the elastomer.
Examples of the (C) include metal hydroxides (aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide, etc.), metal carbonates (magnesium carbonate, calcium carbonate, nickel carbonate,
Strontium carbonate, barium carbonate, etc.), halogen-containing phosphate ester flame retardants [trischloroethyl phosphate, trisdichloropropyl phosphate, trischloropropyl phosphate, tris (tribromophenyl) phosphate, trisdibromopropyl phosphate, tris (Dibromophenylphenyl) phosphate, tris (tribromoneopentyl) phosphate, etc.], active hydrogen-containing flame retardant [di (isopropyl) N, N-bis (2-hydroxyethyl) aminomethylphosphate, brominated bisphenol A] Alkylene oxide adduct, etc.], brominated bisphenol A, urea, urea derivative (reaction product of urea and formalin, etc.), thiourea, melamine, melamine derivative (reaction product of melamine and formalin Etc.), antimony trioxide, antimony pentoxide, zinc oxide, and the like Jinkuboreto. You may use these in combination of 2 or more types.

The flame retardancy is judged by JIS-K7201 and classified by oxygen index. Flame retardancy expressed by oxygen index is
Generally, an oxygen index of 21% or more is indicated, and an oxygen index of 25 to 35% is normally used, and a high flame retardant grade is 27 to 35%.
% Things are required. The type and amount of flame retardant is
It can be selected according to the purpose, and the compounding amount is usually 1 to 100 parts by weight with respect to 100 parts by weight of the fast-curing elastomer.

If desired, the fast-curing elastomer of the present invention may contain known additives such as a filler, a plasticizer, an antiaging agent and a solvent. As the filler, talc,
Mica, carbon black, titanium oxide, fine powder silica,
Examples include straight asphalt and cutback asphalt. Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, dioctyl sebacate, chlorinated paraffin, petroleum resin and the like. As the antiaging agent, hindered amine-based [4-benzoyloxy-2,2,6,6-tetramethylpiperidine (“Sanol LS-744” manufactured by Sankyo) and the like], hindered phenol-based [octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate (“IRGANOX 1076” manufactured by Ciba-Geigy, Japan, etc.), benzophenone-based (2-hydroxy-4-methoxybenzophenone, etc.), benzotriazole-based [2- (5-methyl-2-hydroxyphenyl) benzotriazole, etc.] Can be mentioned. As the solvent, toluene, xylene, cyclohexane, heptane, ethyl acetate, butyl acetate, methyl ethyl ketone,
Examples include methyl isobutyl ketone and dichloromethane.

The fast-curing type elastomer may be produced by a usual method, and the main component is, for example, an organic polyisocyanate compound and castor oil, castor oil derivative, olefin polyol, alkylene oxide adduct of phenols and the like active hydrogen. The containing compound (D) was charged, and the reaction temperature was 5
It is produced by reacting at 0 to 120 ° C., and a hardener is, for example, a castor oil, an amino alcohol, a polyol having 2 to 8 carbon atoms, an organic amine compound to which an alkylene oxide having 2 to 4 carbon atoms is added, and having a molecular weight of 500 or less. The compound and the compound represented by the general formula (2) and, if necessary, the flame retardant or water are kneaded and produced by a planetary mixer or the like, and the obtained main agent and curing agent are mixed to obtain a mixture at room temperature to 100 ° C. When cured it becomes an elastomer.

As a method of applying the fast-curing elastomer of the present invention to various uses, the mixing ratio of the main agent and the curing agent is usually
Collision mixing chamber type two-component high-pressure air equipped with a spray gun for collision mixing inside the gun, with an equivalent ratio of the isocyanate group of the main agent to the active hydrogen of the curing agent being in the range of 1: (0.7 to 1.5) A method of spraying an object with a less spray machine or an air spray machine and curing it at room temperature to 50 ° C to obtain an elastomer; mixing using a reaction injection molding machine and casting into a mold, at room temperature to 50 ° C Examples of the method include a method of curing and curing; a method of mixing using a two-component type casting machine for rapid curing, casting the mixture on a potting object, and curing at room temperature to 50 ° C. Preferred application methods are a collision mixing chamber type two-liquid high-pressure airless spray machine equipped with a spray gun of collision mixing inside the gun or a method of spraying with an air spray machine and a two-liquid casting machine for rapid curing. It is a method of casting by using.

The fast-curing elastomer of the present invention is a member for automobiles which is required to have electrical properties, water resistance, flame retardancy, mechanical strength, flexibility, weather resistance, heat resistance, movement followability, adhesiveness, etc. It is suitable as a member for electric appliances, a member for construction, a paint, a potting agent for electric insulation, a sealant, an adhesive, and the like.

[0025]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following,
Parts are parts by weight,% is% by weight, and ratios are weight ratios. The meanings of the abbreviations in the examples and the evaluation test methods are as follows. (Symbols) CO; molecular weight = 1060, refined castor oil, [Toyokuni Oil Co., Ltd., trade name: ELA-DR] BP-600; molecular weight 600, propylene oxide adduct of bisphenol-A BP-1200; A compound obtained by jumping the average molecular weight to 1200 with propylene oxide 3 mol adduct of bisphenol-A and bromochloromethane 15HT; molecular weight = 1100, polybutadiene polyol, manufactured by Idemitsu Petrochemical Co., Ltd., trade name: Pol
y-Bd R-15HT] BD; 1,4-butanediol TEA: triethanolamine MI; 2,4'-diphenylmethane diisocyanate / 4,4'-diphenylmethane diisocyanate = 50
/ 50, [BSF Japan Co., Ltd., trade name: luplanate MI] MDI; 4,4'-diphenylmethane diisocyanate MTL; carbodiimide-modified diphenylmethane diisocyanate, [Nippon Polyurethane Industry Co., Ltd., trade name:
Millionate MTL] C-MDI; crude diphenylmethane diisocyanate,
[Nippon Polyurethane Industry Co., Ltd., trade name: Millionate MR-100] C-301; aluminum hydroxide, [Sumitomo Chemical Co., Ltd., trade name: C-301] CR-900; flame retardant, Tris ( Tribromoneopentyl) phosphate, [manufactured by Daihachi Chemical Industry Co., Ltd., trade name: CR-900] TCPP; trischloropropyl phosphate DTD; dibutyltin dilaurate

(Evaluation Test Method) 1. Tack-free time (TFT); main component and curing agent adjusted to 25 ° C at a specified mixing ratio are used in a collision mixing chamber type two-liquid high-pressure airless spray machine at a depth of 3 m at 25 ° C.
Spray the m mold and measure the time when tack disappears. Unit = second 2. Water absorption rate; conforms to JIS-K6911. Immersion water temperature =
20 ° C (unit =%) 3. Flame retardance; conforms to JIS-K7201. (Unit =%) 4. Dielectric constant and dielectric loss tangent; conforms to JIS-K6911. Value of 100 KHz. 5. Electrical insulation; conforms to JIS-K6911. (Unit =
Ω · cm) Dry state: Measured after curing for 24 hours at 20 ° C. × 60% RH. Wet state: Measured after immersion in water at 20 ° C. for 24 hours. 6. Mechanical strength; conforms to JIS-K6301. Tensile strength: conforming to JIS-K6301, unit = Kg / c
m ² Tensile elongation rate: in accordance with JIS-K6301, unit =% Brittleness test: 1 with a nipper on a 50 × 70 × 3 mm test piece
Make a cut of 0 mm and measure the crack length at the cut end. [Display] ◎: No crack, X: Crack length 20 mm or more

Production Examples 1 to 4 [Production of Main Agent] A 4-necked Kolben was charged with the organic polyisocyanate compound (A) and the active hydrogen-containing compound (D) shown in Table 1, respectively,
By reacting at 90 ° C. for 5 hours, the main agents <1> to <4> of the present invention were obtained.

[0028]

[Table 1]

Production Examples 5 to 12 [Production of Curing Agent] The components shown in Tables 2 and 3 were charged in a planetary mixer, and the mixture was stirred and mixed at 25 ° C. for 1 hour, and the curing agents [1] to [8] of the present invention were mixed. ]

[0030]

[Table 2]

[0031]

[Table 3]

Example 1 Obtained by spraying a main component and a curing agent in the ratio of parts shown in Table 4 in a collision mixing chamber type two-liquid high-pressure airless spray machine, and by curing the mold at a depth of 3 mm at 25 ° C. for 16 hours. The test results of the dielectric constant, dielectric loss tangent, electric insulation and water absorption coefficient of the test specimens and T measured during spraying
The FT is shown in Table 4. The mechanical strength of the test piece is tensile strength = 3
00 Kg / cm ² , tensile elongation = 75%, brittleness test = ◎
Met.

Examples 2 to 5 A main component and a curing agent having a ratio of parts shown in Table 4 were sprayed on a mold having a depth of 3 mm by a collision mixing chamber type two-liquid high pressure airless spray machine and cured at 25 ° C. for 16 hours. The dielectric constant, dielectric loss tangent, electric insulation and water absorption were tested using the obtained test body, and T measured during spraying
The FT is shown in Table 4.

[0034]

[Table 4]

Examples 6 to 9 A main component and a curing agent having a part ratio shown in Table 5 were sprayed on a mold having a depth of 3 mm by a collision mixing chamber type two-liquid high pressure airless spray machine and cured at 25 ° C. for 16 hours. Table 5 shows the results of tests of flame retardancy, dielectric constant, dielectric loss tangent, electric insulation and water absorption using the obtained test pieces, and TFTs measured during spraying.

[0036]

[Table 5]

Example 10 A main component <1> whose temperature was controlled at 30 ° C. and a curing agent [7] whose temperature was controlled at 50 ° C. were used in a ratio of 1: 2 using a collision mixing chamber type two-liquid high pressure airless spray machine. 3 Kg / m ^{2 was} sprayed on the concrete floor on which the primer was applied. Five minutes after the spraying, a flexible flame-retardant floor could be constructed without exhibiting hardening and foaming such that it could walk on the floor.

Example 11 A main agent <1> whose temperature was adjusted to 50 ° C. and a curing agent [8] were mixed at a ratio of 1: 1.
Using a collision mixing chamber type two-liquid high-pressure airless sprayer at a ratio of 2, 1 Kg / m ^{2 was} sprayed on the concrete wall on which the primer was applied. Two minutes after spraying, a cured elastomer foamed about 3 times could be formed on the wall, and a cloth was attached to the surface to finish the wall. The wall had a good effect of preventing dew condensation as well as flexibility, heat insulation and flame retardancy.

Example 12 H-type steel frame placed in a building using a collision mixing chamber type two-liquid high-pressure airless sprayer in which a main agent <1> whose temperature was adjusted to 50 ° C. and a curing agent [8] were used in a ratio of 1 :. 1 Kg / m ^{2 was} sprayed on. Two minutes after spraying, a cured elastomer foamed about 3 times could be formed on the H-shaped steel frame. The H-type steel frame had good corrosion resistance and dew condensation resistance.

Example 13 A substrate was potted with a main component (C-MDI) temperature-controlled at 25 ° C. and a curing agent [7] at a ratio of 63: 200 using a two-component casting machine for rapid curing. The curing was completed after 5 minutes, and the productivity was about 10 times higher than that of the conventional potting agent.

Comparative Example 1 Manufacture of main ingredient: "Sannicx FA-703" [polyoxyethylene oxypropylene triol, molecular weight = 50]
00, manufactured by Sanyo Chemical Industry Co., Ltd.] 396 parts and MTL 60
4 parts were charged into a 4-neck Kolben and reacted at 90 ° C. for 5 hours to obtain a main agent having an NCO group content = 16.5%. Manufacturing of curing agent: "Sannick FA-
703 "[polyoxyethylene oxypropylene triol, molecular weight = 5000, manufactured by Sanyo Chemical Industry Co., Ltd.] 80
0 part, BD 200 parts, DTD 0.3 part and triethylenediamine 0.3 part were charged and mixed by stirring at 50 ° C. for 1 hour to obtain a curing agent having active hydrogen equivalent = 203. Using a collision mixing chamber type two-liquid high-pressure airless sprayer at a ratio of 100: 76, the main agent and the curing agent were sprayed on a mold having a thickness of 3 mm and cured at 25 ° C. for 16 hours to obtain a test body. Obtained. Flame retardancy tested on the specimen,
Table 6 shows the results of the dielectric constant, dielectric loss tangent, electric insulation and water absorption.

Comparative Example 2 Manufacture of Main Agent: "Sannicx PP-2000" [polyoxypropylene diol, molecular weight = 2000, manufactured by Sanyo Chemical Industry Co., Ltd.] 397 parts, MDI 277 parts, MTL
126 parts and dioctyl phthalate 200 parts were charged into a 4-neck Kolben and reacted at 90 ° C. for 5 hours to obtain NCO.
A base compound having a group content of 11.3% was obtained. Manufacturing of hardener: "Jeffermin D-
2000 "[polyoxypropylene diamine, molecular weight =
2000, manufactured by Mitsuishi Texaco Chemical Co., Ltd.] 900 parts,
Toluenediamine 70 parts, BD 30 parts, DTD 3
Parts and octylic acid 3 parts were charged and mixed with stirring at 90 ° C. for 1 hour to obtain a curing agent having active hydrogen equivalent = 371. Using a collision mixing chamber type two-liquid high-pressure airless sprayer with a ratio of 100: 100 of these main components and a curing agent, a 3 mm-thick mold was sprayed and cured at 25 ° C. for 16 hours to obtain a test body. Obtained. Table 6 shows the results of the flame retardancy, dielectric constant, dielectric loss tangent, electrical insulating property and water absorption rate tested on the test body.

Comparative Example 3 Preparation of curing agent: 728 parts of CO in 4-necked Kolben,
"SANNIX NP-300" [Propylene oxide adduct of ethylenediamine, molecular weight = 300, Sanyo Chemical Industries, Ltd.] 242 parts and "Molecular Sieves 3"
"AB" [manufactured by Union Showa Co., Ltd.]
The mixture was stirred and mixed at 0 ° C. for 1 hour to obtain a curing agent having active hydrogen equivalent = 187. C-MDI and its curing agent at a ratio of 100: 130 using a collision mixing chamber type two-liquid high pressure airless spray machine,
A mold having a thickness of 3 mm was sprayed and cured at 25 ° C. for 16 hours to obtain a test body. Table 6 shows the results of the flame retardancy, dielectric constant, dielectric loss tangent, electrical insulating property and water absorption rate tested on the test body. Mechanical strength is tensile strength = 210 Kg / c
m ² , tensile elongation = 15%, brittleness test = X.

[0044]

[Table 6]

[0045]

The quick-curing elastomer of the present invention has electrical characteristics (electrical insulation, dielectric constant, dielectric loss tangent, etc.), water resistance, flame retardancy, mechanical strength, corrosion resistance, and heat insulation as compared with conventional ones. Excellent in anti-condensation property, weather resistance, heat resistance, movement followability and adhesiveness. From the above effect, the fast-curing elastomer of the present invention is a member for automobiles such as a chipping paint, a member for electric products such as a potting agent for electric insulation, a floor material, a waterproof material, a wall material, a sealant, an anticorrosion coating material, It is useful for construction materials such as dew condensation prevention materials, lining materials such as steel pipes, adhesives, and anticorrosion paints.

Claims (9)

[Claims] 1. A two-component rapid-curing urethane elastomer comprising a main agent and a curing agent, wherein the main agent is an organic polyisocyanate compound (A). Curing agent; polyol (B-1): castor oil-based polyol, polyolefin polyol and the following general formula (1)
One or more polyols selected from the compounds represented by: Low molecular weight polyol (B-2): amino alcohol or amino alcohol, C2-10 polyol, organic amine compound with C2-4 alcohol.
Two or more low molecular weight polyols selected from compounds having a molecular weight of 500 or less to which xylene oxide is added and compounds represented by the following general formula (2). A fast-curing elastomer comprising a catalyst (B-3). Formula _{H (X-Y-) m X} -H (1) H (OR) p O-Ph-Z-Ph-O (RO) q H (2) [ wherein, X is the formula - (OR) _p O-Ph-Z-Ph-
O (RO) _q- , Y is an alkylene group having 1 to 4 carbon atoms, R is an alkylene group having 2 to 4 carbon atoms, and Ph is a phenylene group (substituted by a halogen or an alkyl group having 1 to 18 carbon atoms). , Z is —CH ₂ —, —SO ₂ —, —O—
Or _{-C (CH 3) 2 -,} m is an integer of 1 to 80, p and q each represents an integer of 1 to 10. ] 2. An organic polyisocyanate compound (A)
Is a castor oil-based polyol, a polyolefin polyol, a compound represented by the general formula (1) and a general formula (2).
The fast-curing elastomer according to claim 1, which is a urethane prepolymer derived from at least one polyol selected from the compounds represented by and an aromatic or alicyclic polyisocyanate. 3. The weight ratio of the polyol (B-1) to the low molecular weight polyol (B-2) in the curing agent is 100: (1 to 7).
0) The fast-curing elastomer according to claim 1 or 2. 4. The fast-curing elastomer according to claim 1, wherein the curing agent contains 0.05 to 5% by weight of water, and the fast-curing elastomer is a foamed elastomer. 5. The fast-curing elastomer according to claim 1, wherein the main agent and / or the curing agent contains a flame retardant (C). 6. The fast-curing elastomer according to claim 1, which is used as an electrically insulating coating agent or a potting agent for electrical insulation. 7. The method according to claim 1, which is used as an anticorrosion coating agent.
5) The rapid-curing elastomer according to any one of 5 to 5. 8. The fast-curing elastomer according to claim 1, which is used as a heat insulating material or a coating agent for preventing dew condensation. 9. The fast-curing elastomer according to claim 1, which is used as a floor material or a waterproof material.