JP3474000B2 - Method for producing urethane elastomer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a urethane elastomer, and more particularly to a method for producing a urethane elastomer by casting or spray molding using a collision mixing type mixing device.

[0002]

2. Description of the Related Art Kneading method, casting method, spray method, RIM method (Reacio
n injection molding).

In the casting method, toluene diisocyanate (hereinafter TDI) and polyol are preliminarily NCO / OH = 2/1.
(Equivalent ratio) Prepolymer obtained by reacting before and after, 3,
3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter MOCA) is used. When molding, 80 ~
The prepolymer heated to 120 ° C. and the MOCA previously melted at 120 ° C. were mixed and cured at 100 ° C. for 24 hours to generate not only urethane / urea bonds but also reaction between excess isocyanato groups and urea bonds. This is a method for obtaining a tough elastomer having a biuret bond.
The urethane elastomer obtained by the casting method has excellent mechanical properties as described above, but since the active hydrogen-containing compound used for curing is MOCA simple substance, it is a polymer for the purpose of adjusting reactivity and imparting various functionalities. Design freedom is limited.

As an example for optimizing the molding temperature and the curing conditions of the casting method, Japanese Patent Laid-Open No. 4-43864 and Journal are available.
l of ELASTOMERS AND PLASTICS (Vol.19, P6-21, Jan.198
7) and Journal of Plymer Science: Part A: Polymer Che
In mistory, Vol.28,3701-3724 (1990), 3,5-dimethylthio- was used as an active hydrogen-containing compound instead of MOCA.
2,4-toluenediamine and 3,5-dimethylthio-
Mixture of 2,6-toluenediamine (Ethacure
# 300; hereinafter E300) alone or 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,
A mixture of 6-toluenediamine (hereinafter DETDA) is shown. In each of the examples, there is no change in the method similar to the conventional casting method using MOCA, and although the molding temperature and the curing temperature are room temperature, the post-curing at high temperature is required.

In the RIM method, the isocyanato group content (hereinafter referred to as NCO%) is set high, and the reactivity is enhanced by combining the prepolymer and the polyol alone or with DETDA.
This is a method of producing a urethane elastomer after injection into a closed mold (mold), followed by gelling time of several seconds and demolding time of about 1 minute. In the RIM method, the molding temperature is 60 ° C,
It is possible to mold at a lower temperature than the casting method,
In the RIM method, which is characterized by a short molding cycle, the curing speed is too fast, so not only large-scale molding equipment is required, but it can also be adhered to an unspecified base material other than a dedicated closed mold (mold), Therefore, it is impossible to mold a building or civil engineering material that requires an arbitrary film thickness.

As an example of using E300 in the RIM method,
Plastics Engineering (Nov. 41-44, 1987) discloses a polyurea RIM using a long-chain active hydrogen-containing compound and a polyether amine having an amino group at the end.
In order to use E300 in the RIM method, a combination with a highly reactive polyether amine is indispensable in order to supplement the low reactivity of E300. In the above example, the conventional RI
It only provides reactivity comparable to the M method.

On the other hand, the spray method is generally a method of molding a urethane elastomer using a low-viscosity material. As a method of adding a solvent to the material, a solvent-diluted product of a prepolymer by the reaction of TDI and polyether and 4,4 A spray molding method using a solvent-diluted product of'-diaminodiphenylmethane (hereinafter referred to as MDA) is shown in the data of DuPont, USA. In this method, the range of use is limited due to environmental problems at the time of molding, physical properties, necessity of post-curing, shrinkage due to solvent volatilization after molding, and the like. An example of a combination of DETDA and polyether is shown in JP-A-61-247721 as a rapid curing type spray method which does not use a solvent. In the above example, since the reaction speed is extremely fast, a high-pressure two-liquid type spray device equipped with a collision mixing type spray gun is indispensable for molding, and the degree of freedom of molding is low.
In addition, the surface of the molded product is poor in smoothness because it cures immediately after spraying. Furthermore, due to the reaction heat and film thickness unevenness associated with thick film molding,
There are problems such as shrinkage and distortion of the molded product.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems in the prior art and to provide a method for producing a urethane elastomer having good workability and mechanical properties of a cured product. More specifically, in the temperature range from room temperature (25 ° C) to medium temperature (50 ° C), all steps from handling to complete curing are possible, and the control range of workability including reactivity and curability in this temperature range. By expanding
It is an object of the present invention to provide a method for producing a urethane elastomer in which the rubber elasticity is rapidly expressed and the cured product has good mechanical properties even though the gelling time can be set long.

More specifically, spraying or casting into fine recesses, which has been difficult to form in the past, securing a post-processing time, insufficient penetration into a substrate such as cloth, and smooth surface property It is to provide a technique for controlling the reaction rate according to the purpose by solving problems such as difficulty in obtaining.

[0010]

[Means for Solving the Problems] The problems were solved by the following methods. That is, the organic isocyanate and the active hydrogen-containing compound are mixed with the isocyanate group (N
CO group) and the active hydrogen (H) in the active hydrogen-containing compound is N
CO / H = isocyanato group-terminated prepolymer (solution A) obtained by reacting in the range of 4/1 to 30/1 molar ratio, 3,5-
Dimethylthio-2,4-toluenediamine and 3,5-
A urethane elastomer is prepared by casting or spray molding using a resin (liquid B) formed by mixing an aromatic diamine consisting of a mixture of dimethylthio-2,6-toluenediamine, a polyol and / or a polyether amine and a curing catalyst. In the production method, the amino group (NH ₂ ) of the aromatic diamine and the active hydrogen (H) of the polyol and / or the polyether amine in the liquid B are NH ₂ / H = 9/1 to 2
The urethane elastomer is produced by adjusting the ratio to / 8 molar ratio.

Various organic isocyanates can be used for producing the liquid A. As an example of a typical organic isocyanate, in the aromatic type, 2,4-tolylene diisocyanate alone or a mixture with 2,6-tolylene diisocyanate (TDI) or 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) is used. -PH) alone or in a mixture with 2,4'-diphenylmethane diisocyanate (hereinafter o-MDI), polymethylene polyphenyl polyisocyanate (hereinafter MDI-Cr), MDI-
Examples include liquid diphenylmethane diisocyanate (hereinafter referred to as MDI-LK) obtained by carbodiimide-modifying a part of PH alone or a mixture of o-MDI. Hexamethylene diisocyanate (H
DI), isophorone diisocyanate (IPDI), hydrogenated MDI-PH (H ₁₂ MDI), trimethylxylene diisocyanate (TMXDI) and / or hydrogenated products thereof.
Examples thereof include xylene diisocyanate (XDI) and / or hydrogenated products thereof (H ₆ XDI), trimethylhexamethylene diisocyanate (TMHDI), cyclohexylene diisocyanate (CHDI), norbornane diisocyanate (NBDI) and the like.

These organic isocyanates may be used alone or as a mixture, or may be used as isocyanurate-modified, carbodiimide-modified, biuret-modified or allophanate-modified ones or a mixture thereof. Among these organic isocyanates, aromatic ones are preferably used in consideration of reactivity and mechanical properties of the cured product, and MDI-PH alone or a mixture with MDI-PH, MDI-Cr, MDI. -PH alone or o-MD
Part of the mixture of I was carbodiimide modified MDI-L
Particularly preferred is one or a mixture of two or more selected from K. When the elongation and mechanical properties are prioritized, it is preferable to increase the content of MDI-PH and / or o-MDI having 2 functional groups, and to use MDI-Cr having a high functional group in the case of a high hardness system.

E300 is used as an essential component for the aromatic diamine in the liquid B. E300 has a mild speed with an isocyanato group, so it is possible to secure pot life (workable time) even when used alone,
Since it is difficult to balance and control gelation time, rubber elasticity development, and mechanical properties by itself, a part of E300 may be replaced with DETDA. The amount of DETDA used is 50 mol% or less of all the amino groups in the wholly aromatic diamine in the liquid B. When it exceeds 50 mol%, the reaction rate becomes DETD.
It must be avoided because it is pulled by A and becomes extremely fast. Further, the polyether and / or the polyether amine constituting the liquid B is 10 to 80 of the total active hydrogen equivalent in the liquid B.
Mixing in mol% makes it possible to produce a urethane elastomer having a well-balanced gelling time, development of rubber elasticity, and mechanical properties, and easy control of reactivity.

For the production of solutions A and B of the present invention, an active hydrogen-containing compound having a hydroxyl value (or amine value when the terminal is an amino group) of 120 or less is used. Typical active hydrogen-containing compounds include water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, polyhydric alcohols such as pentaerythritol, ethylenediamine, triethylamine, diethylenetriamine, triethanolamine and the like amine initiator ethylene oxide. , A polyether polyol (PPG) obtained by addition polymerization of one or more alkylene oxides such as propylene oxide and butylene oxide, and a polytetramethylene ether glycol (PPG) obtained by addition polymerization of tetrahydrofuran alone or together with alkylene oxide ( PT
MEG), polyester polyol by dehydration condensation of carboxylic acid and low-molecular glycol, polycaprolactone polyol obtained by polymerizing caprolactone, castor oil, polycarbonate polyol and the like.

Among others, mechanical properties can be remarkably improved by using PTMEG. Polymer polyols obtained by graft-polymerizing ethylenically unsaturated compounds such as acrylonitrile, styrene, and methyl methacrylate to these known polyols, 1,2- or 1,4-added polybutadiene polyols, and hydrogenated products thereof can also be used. . It is also possible to use a polyether amine having an amino group as the terminal hydroxyl group (OH group) of the above polyether polyol. The preferred hydroxyl value (the amine value when the terminal is an amino group) of these active hydrogen-containing compounds is in the range of 18 to 120.

On the other hand, the low molecular weight polyol used as a cross-linking agent excluding E300 is preferably one having a hydroxyl value of 400 or less in which the molecular weight per hydroxyl group is reduced. As typical examples, ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (P
G), dipropylene glycol (DPG), tripropylene glycol (TPG), tetrapropylene glycol, glycerin, trimethylolpropane, pentaerythritol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol Etc. The low molecular weight polyols are used alone or as a mixture of two or more kinds, and the amount of the low molecular weight polyols and the total cross-linking agent containing E300 is 9 times the equivalent amount of the entire liquid B.
It is preferably 0% or less.

The molar ratio (NCO / H
The ratio is an important item and is a numerical value showing the number of NCO groups per one active hydrogen group (hydroxyl group and amino group). Theoretically, in the case of an organic isocyanate having 2 functional groups, such as TDI, MDI-PH, etc., when the molar ratio is 2, the entire amount becomes a prepolymer in a state where an isocyanate group is added to all terminals of the active hydrogen-containing compound. . When the molar ratio is less than 2, a sandwich structure is usually adopted, and since there is no free organic isocyanate, the so-called "partial prepolymer" is not commonly known. Therefore, when the molar ratio exceeds 2, free organic isocyanate is present and a partial prepolymer in which the prepolymer and the free organic isocyanate are mixed is formed. When the type of isocyanate is such that MDI-LK or MDI-Cr has a functional group number of more than 2, the partial prepolymer cannot be produced unless the molar ratio is equal to or higher than the functional group number of the isocyanate. Since these organic isocyanates usually have 3 or less functional groups, a molar ratio of 4 or more is required to produce a partial prepolymer. Further, since the viscosity of the liquid A tends to increase when the molar ratio is low, it is necessary to set it higher in order to reduce the viscosity. Therefore, the molar ratio at the time of producing the prepolymer (Liquid A) used in the present invention is preferably 4 to 30, and more preferably 6 to 20. On the other hand, when the molar ratio exceeds 30, the viscosity as a prepolymer (Liquid A) decreases, but the amount of free organic isocyanate increases and it becomes difficult for the chain extension reaction to proceed, so that the rubber elasticity expression and mechanical properties are reduced. It tends to be low, and it is not preferable to increase it more than necessary.

The NCO% of the liquid A is the kind and molar ratio (NCO /
HCO), but the NCO% of the prepolymer (liquid A) obtained when the molar ratio is in the range of 4 to 30.
Is about 2 to 30. In order to satisfy the preferable NCO% of the liquid A of the present invention of about 8 to 22%,
The hydroxyl value (the amine value when the terminal is an amino group) of the active hydrogen-containing compound used for producing the liquid is in the range of 18 to 120, and particularly preferably 18 to 60. The viscosities of the liquids A and B used in the present invention at 25 ° C. are both 2,000.
By setting it to 0 centipoise or less, preferably 1,000 centipoise or less, it is possible to obtain a material most suitable for not only casting but also spray molding.

As the curing catalyst, known urethane catalysts can be used, and among them, the use of an organometallic catalyst is preferable because it can reduce the foaming phenomenon caused by water. Representative examples are lead octylate, dibutyltin dilaurate, bismuth trineodecanoate, bismuth octylate, iron octylate and the like. When the inorganic filler is added, the curing rate of the resin decreases, so it is necessary to increase the addition amount, but it is usually about 0.1 to 5% in the liquid B.

Additives that can be used in the present invention include known plasticizers, flame retardants, stabilizers, compatibilizers, fillers, colorants, etc.
It can be added if necessary. As the plasticizer, for example, a phthalate ester such as dioctyl phthalate (DOP), an adipate ester such as dioctyl adipate (DOA), a sebacate such as dioctyl sebacate (DOS), and a flame retardant such as phosphorus or halogen. The system and the antimony system can be used alone and as a mixture. For example, tricresyl phosphate (TCP), chlorinated paraffin, tris-β-chloropropyl phosphate (TCPP),
Tris-chloroethyl phosphate (CLP), triphenyl phosphate (TPP), tetrabromobisphenol A (TBA), dibromoneopentyl glycol (DBNPG), tribromoneopentyl alcohol (TBNPA), antimony triacid, etc. 5 to 5
About 50% is preferable.

As the stabilizer, a heat resistance stabilizer, an ultraviolet absorber and a weather resistance stabilizer are used alone or in combination. For example, Irganox # 1010 and 1076 (Ciba Geigy), Yoshinox BHT, BB and GSY-93.
0 (Yoshitomi Pharmaceutical Co., Ltd.) and other position-defective phenolic resins, benzotriazoles such as TINUVIN P, 327 and 328 (Ciba Geigy), Tomisorp 800 (Yoshitomi Pharmaceutical Co., Ltd.)
Benzophenones such as Sanol LS-770, 74
It is a position-hindered amine such as 4, 765, etc.
It is about 05 to 3%.

A wetting / dispersing agent can be added if necessary, but the addition is effective because the addition of the wetting / dispersing agent tends to improve the mixing property of the A / B solution and increase the mechanical strength. . The type of compatibilizer may be either anion or cation type, but electrically neutral type shows good results. Either A / B solution may be added, but considering the storage stability of the material, It is preferable to add it. As the electrically neutral type, anti-tera U (long-chain polyaminoamide and a salt of a polar acid ester) manufactured by Big Chemie, W002 (ionizing neutral long-chain type polyaminoamide and polymeric acid) manufactured by Yusho Co., Ltd. Ester salt), Floren G-8
20 (Kyoeisha fats and oils), Disparlon # 1830 (Kusumoto Kasei), etc., and the amount used is about 0.2 to 5% in the resin.

Further, in the case of producing a non-foamed cured product, it is effective to add an antifoaming agent. As the defoaming agent, both silicon-based and non-silicon-based defoaming agents can be used. For the silicon-based one, L-45 (Nippon Unicar Co., Ltd.) or the like, and for the non-silicon-based one, Floren AC-1190 (Kyoeisha Oil & Fat), etc. It is about 10 to 500 ppm in the liquid.

As the filler, an inorganic filler can be added to improve hardness, mechanical strength, acid resistance / alkali resistance and the like. Known materials can be used as the inorganic filler, for example, ground calcium carbonate, talc, kaolin clay, fine powder of mica, colloidal silica and acicular crystals of calcium silicate. The amount used is 5 to 70 because the viscosity of the system increases as the amount used increases.
%, Preferably 10 to 50%. In the case of the casting method, it is possible to use a high-viscosity material with a high content of inorganic filler, but in the case of spray molding, due to the wear of the molding machine, the inorganic filler is mixed with a relatively soft filler and fine particles are selected. At the same time, it is necessary to reduce the compounding amount.

As the colorant, it is possible to use an inorganic type or an organic type such as carbon black, red iron oxide, chromium oxide and titanium oxide. At the time of use, it is preferable to use a toner dispersed in a plasticizer or a polyol in terms of workability and dispersibility. As a molding method, a casting method of injecting a resin into a metal mold or a resin bag and a spray method of atomizing a material in the air can be performed.

The molding machine used in the present invention is not particularly limited, but a machine generally used for molding urethane can be used. For example,
Low-pressure gear pump called low-pressure casting machine + dynamic mixer (mixing and stirring by rotating rotor) machine, axial piston pump developed for RIM +
These are a collision mixing head machine and a spray molding machine. The spraying machine body can be used for both low and high pressure machines such as gear pumps, radial pumps and plunger type homps. Examples of the two-component high-pressure spray machine include THD-2K manufactured by Toray Engineering Co., which uses a high-pressure gear pump as a pump, and NR-23 manufactured by Toho Machine Industry Co., which uses an axial piston pump.
For example, H-2000 type manufactured by US Gasmer Co. using a 0 type high pressure polyurethane molding machine and a plunger pump.

As the spray gun used for mixing the two liquids, there can be used a dynamic mixer for agitating and mixing by rotating a rotor, a static in-pipe mixing (static mixer) type and a collision mixing type spray gun. When the reaction time is set to be short or when it is difficult to collect the washing solvent, it is preferable to use the collision mixing type. Examples of the collision mixing type spray gun include a mechanical cleaning system (GX-7; manufactured by Gasmer Co., USA) by putting in and out a rod, and a cleaning method by air (Probler gun; manufactured by Grasscraft Co., USA).

[0028]

EXAMPLES Examples and comparative examples of the present invention will be described below.
The numbers in the examples (including tables) represent g or parts by weight, unless otherwise specified.

(Description of raw materials used) MDI-PH: 4,4'-diphenylmethane diisocyanate (manufactured by Mitsui Toatsu Chemicals, Inc .; NCO% = 33.6) MDI-LK: carbodiimide modified liquid MDI (Mitsui Toatsu Chemicals) MDI-Cr: Polymeric MDI (Mitsui Toatsu Chemical Co., Ltd .; NCO% = 31) TDI-80: Tolylene diisocyanate (2,4-)
/ 2,6-ratio = 80/20; manufactured by Mitsui Toatsu Chemicals, Inc .; NCO
% = 48.2) ・ IPDI: isophorone diisocyanate (Daicel
Manufactured by Huls; NCO% = 37.6)

Diol-12000: Bifunctional polypropylene glycol (PPG) [hydroxyl value = 9.3] Triol-7000EO: Trifunctional EO cap polyene glycol [hydroxyl value = 22] = Propylene oxide is added and polymerized to a constant value. After the chain extension to the molecular weight of, PPG was added with ethylene oxide to increase the ratio of the primary OH at the terminal = -Diol-3000EO: Bifunctional terminal EO-capped polypropylene glycol [hydroxyl value = 37.4] -Diol-3000: Bifunctional polypropylene glycol [hydroxyl value = 37.4] Diol-2000: Bifunctional polypropylene glycol [hydroxyl value = 56.1]

MN-1500: trifunctional polypropylene glycol [hydroxyl value = 113] Diol-1000: bifunctional polypropylene glycol [hydroxyl value = 112] Diol-400: bifunctional polypropylene glycol [hydroxyl value = 280] PTMEG -1000: Polytetramethylene glycol (manufactured by DuPont; Terratan 1000E) [hydroxyl value =
112] -R-15HT: polybutadiene containing terminal OH group (manufactured by Idemitsu Petrochemical Co., Ltd.) [hydroxyl value = 105]

PTMEG-650: Bifunctional polytetramethylene ether glycol (DuPont; Terratan 650) [hydroxyl value = 173] JD-2000: Bifunctional polyetheramine (Texaco Chemical; Jeffamine 2000) [ Hydroxyl value = 55]: Note (value converted to hydroxyl value (OHv) with the terminal amino group as one active hydrogen. All amino groups are converted below) LAV: Dehydrated castor oil (manufactured by Ito Oil Co., Ltd.) [hydroxyl value =
160] -Diol-2000EO: bifunctional terminal EO cap polypropylene glycol [hydroxyl value = 56.1] -EA-2000: polyester polyol synthesized from ethylene glycol and adipic acid [hydroxyl value = 54] -MN-1500: trifunctional Polypropylene glycol [hydroxyl value = 113] 1,4-BD: 1,4-butylene glycol [hydroxyl value = 1247] TPG: tripropylene glycol [hydroxyl value = 58]
4] -E300: 80:20 mixture of 3,5-dimethylthio-2,4-toluenediamine and 3,5-dimethylthio-2,6-toluenediamine (manufactured by Ethyl Corporation) [hydroxyl value = 523] -DETDA: 80:20 mixture of 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2,6-toluenediamine (manufactured by Ethyl Corporation)
[Hydroxyl value = 630]

G-40: Needle-like crystals of calcium silicate (NYCO MINERALS, Inc .; Wollastonite G-40) -Whiteon SSB [red]: Fine powder of heavy calcium carbonate (calcium shiraishi) -Irganox # 1010: Antioxidant; tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-
4'-hydroxyphenyl) propionate] methane (manufactured by Ciba Geigy) -Tinuvin # 327: UV absorber; 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl)-
5-Chlorobenzotriazole (Ciba Geigy) -Floren AC-1190: Non-silicon antifoaming agent (Kyoeisha Yushi) -Coscat # 83: Bismuth trineodecanoate (B
i = 16.6%) (manufactured by Kosan Chemical Co., Ltd.) P-25: 25% solution of lead octylate (manufactured by Harima Kasei Co., Ltd.)

The liquid A was prepared by the following method. (A-1) MDI-PH (236g) to MDI-LK
After adding (236 g), Diol-3000EO (5
28 g) was added and reacted under a nitrogen stream at 80 ° C. for 3 hours while stirring to cause NCO% = 13.2, viscosity (cps / 25 ° C.)
= 1,000 and a specific gravity (23/23 ° C) = 1.12 was obtained. At this time, the molar ratio (NCO / OH
The ratio) is 10. This liquid A has a low viscosity and is a material suitable for spraying.

(A-2) After adding MDI-LK (253 g) to MDI-PH (379 g), Diol-30
00 (276 g) and Diol-1000 (92 g) were added, and the mixture was reacted under a nitrogen stream at 80 ° C. for 3 hours with stirring to cause NC.
O% = 18.4, viscosity (cps / 25 ° C.) = 1,20
A partial prepolymer having 0 and a specific gravity (23/23 ° C.) = 1.15 was obtained. At this time, the molar ratio (NCO / OH ratio) is 13.

(A-3) Diol-3000 (686 g) was added to MDI-PH (314 g) under a nitrogen stream of 80.
The mixture was reacted with stirring at ℃ for 3 hours, NCO% = 8.4, viscosity (cps / 25 ℃) = 6,500, specific gravity (23/23
C.) = 1.09 was obtained. At this time, the molar ratio (NCO / OH ratio) is 5.5.

(A-4) Triol-7000EO (485 g) was added to MDI-Cr (515 g), and the mixture was reacted under a nitrogen stream at 80 ° C. for 4 hours with stirring to give NCO% = 1.
A partial prepolymer having a viscosity of 5.1, a viscosity (cps / 25 ° C.) = 1,600 and a specific gravity (23/23 ° C.) = 1.14 was obtained. The molar ratio (NCO / OH ratio) at this time is 20.

(A-5) Diol-1500 (657 g) was added to TDI-80 (343 g) under a nitrogen stream.
NCO% = 12.7 while reacting at 0 ° C. for 3 hours with stirring,
Viscosity (cps / 25 ° C) = 5,500, specific gravity (23/2
A partial prepolymer of 3 ° C.) = 1.07 was obtained. At this time, the molar ratio (NCO / OH ratio) is 4.5.

(A-6) IPDI (533 g) with Tr
iol-7000EO (467 g) was added and under a nitrogen stream 1
The reaction was carried out while stirring at 00 ° C. for 8 hours, and NCO% = 19.
1, viscosity (cps / 25 ° C) = 500, specific gravity (23/2
A partial prepolymer of 3 ° C.) = 1.12 was obtained. At this time, the molar ratio (NCO / OH ratio) is 26.

(A-7) After adding MDI-LK (286 g) to MDI-PH (286 g), Diol-12
000 (428 g) was added and reacted under a nitrogen stream at 90 ° C. for 3 hours while stirring, and NCO% = 17.5, viscosity (cps
/ 25 ° C.) = 2,600, specific gravity (23/23 ° C.) = 1.
11 partial prepolymers were obtained. The molar ratio at this time (NC
The O / OH ratio) is 60.

(A-8) Diol-400 (434 g) was mixed with TDI-80 (566 g), and the mixture was mixed under a nitrogen stream at 80.
When the reaction was carried out while stirring at ℃ for 3 hours, the overall viscosity rapidly increased and gelled. The calculated NCO% is 18.1,
The molar ratio (NCO / OH ratio) is 3.0, and the molar ratio is 4
It is considered that gelation occurred because the molecular weight of PPG used was low.

(A-9) After adding MDI-LK (226 g) to MDI-PH (451 g), PTMEG-1
000 (323 g) was added and reacted under a nitrogen stream at 80 ° C. for 3 hours while stirring to cause NCO% = 18.8, viscosity (cps
/ 25 ° C) = 1,400, specific gravity (23/23 ° C) = 1.
10 partial prepolymers were obtained. The molar ratio at this time (NC
The O / OH ratio) is 8.

(A-10) MDI-PH (421 g)
After adding MDI-LK (211g) to R-15HT
(368 g) was added and reacted under a nitrogen stream at 80 ° C. for 3 hours while stirring to cause NCO% = 17.1, viscosity (cps / 25
C.) = 8,200, specific gravity (23 / 23.degree. C.) = 1.12 was obtained. At this time, the molar ratio (NCO / O
H ratio) is 7. The raw materials used and the synthesis results are shown in Table 1.

[0044]

[Table 1]

The solution B was prepared by the following method. (B-1) PTMEG-1000 (822 g) as a polyol and aromatic diamine E300 (162 g) were charged as a polyol in a mixer (dissolver manufactured by Inoue Seisakusho) and heated to 80 ° C., and then Irganox # 1010 as a stabilizer. (2
g) and Tinuvin # 327 (3 g), Floren AC-1190 (1 g) as an antifoaming agent, and Cosca as a catalyst.
Add t # 83 (10 g) at 80 ° C. for 1 hour under nitrogen stream,
Mixing was performed under the condition of 800 rpm for 1 minute. Then 3 mixers
The pressure was reduced to 0 mmHg, and defoaming was performed for 30 minutes while stirring at 200 rpm for 1 minute. At this time, the equivalent of the wholly aromatic diamine was 81%, the viscosity was 900 cps / 25 ° C., and the specific gravity was 1.0.

(B-2) Diol-1000 (164 g) and MN were used as polyols using the same mixer as B-1.
-1500 (164g), E30 as aromatic diamine
0 (307 g) was charged, the temperature was raised to 80 ° C, and the mixture was stirred for 30 minutes.
After mixing, walalstonite G as an inorganic filler
-40 (350 g) was added and the mixture was heated at 80 ° C. for 3 hours under a nitrogen stream.
Mixing was performed under the condition of 1,000 revolutions per minute. Next, Irganox # 1010 (2 g) and Tinuvin # 327 (2 g) as stabilizers, and Floren AC-11 as an antifoaming agent.
90 (1 g) and P-25 (10 g) as a catalyst were added and mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 1,000 revolutions per minute. Next, reduce the pressure of the mixer to 30 mmHg, and
The mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the equivalent of the wholly aromatic diamine was 83%, the viscosity was 20,000 cps / 25 ° C., and the specific gravity was 1.3.

(B-3) Diol-2000EO (650 g) as a polyol using the same mixer as B-1
And E300 (235 g) as an aromatic diamine and DE
TDA (100 g) was charged. At this time, the DETDA molar ratio is 34%. Subsequently, the mixture was mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 800 revolutions per minute. Next, P-25 (15 g) was added as a catalyst, and the mixture was mixed at 80 ° C. under a nitrogen stream for 3
The mixture was mixed for 0 minutes and 1 minute under the condition of 800 revolutions. Next, the pressure of the mixer was reduced to 30 mmHg, and the mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the total aromatic diamine equivalent was 84% and the viscosity was 600 cps / 25.
C., specific gravity was 1.0.

(B-4) MN-1500 (301 g) as a polyol and E300 (453 g) as an aromatic diamine and DETDA (30) using the same mixer as B-1.
g) was charged. At this time, the DETDA molar ratio is 7%. Subsequently, the temperature was raised to 80 ° C. and the mixture was stirred and mixed for 30 minutes, and then whiten SSB [red] (20
0 g), and at 80 ° C for 1 hour under a nitrogen stream, 1 per minute
Mixing was performed under the condition of 000 rotations. Next, Irganox # 1010 (2 g) and Tinuvin # 327 as stabilizers.
(3 g), Floren AC-1190 (1 as an antifoaming agent
g), P-25 (10 g) as a catalyst was added, and the mixture was mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 1,000 revolutions per minute. Next, the mixer was evacuated to 30 mmHg and 2 minutes per minute.
The mixture was defoamed for 30 minutes while stirring under the condition of 00 rotation. At this time, the total aromatic diamine equivalent was 88% and the viscosity was 12.0.
It was 00 cps / 25 ° C. and the specific gravity was 1.2.

(B-5) Diol-2000EO (756 g) as a polyol using the same mixer as B-1
Then, E300 (234 g) as an aromatic diamine was charged and mixed under a nitrogen stream at 80 ° C. for 1 hour and 1 minute under the condition of 800 rotations. Next, P-25 (10 g) as a catalyst
Was added and mixed under a nitrogen stream at 80 ° C. for 30 minutes under the condition of 800 revolutions per minute. Next, the pressure of the mixer was reduced to 30 mmHg, and the mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. The equivalent weight of wholly aromatic diamine at this time is 74%
The viscosity was 550 cps / 25 ° C., and the specific gravity was 1.0.

(B-6) JD-2000 (648 g) as a polyether amine and 1,4-BD (29 g) as a low molecular weight polyol crosslinking agent using the same mixer as B-1.
And E300 (257g) and DE as aromatic diamine
Charge TDA (50 g). At this time, the DETDA molar ratio is 37%. Then, the mixture was mixed under a nitrogen stream at 80 ° C. for 30 minutes under the condition of 800 rpm for 1 minute. Next, Irganox # 1010 (2 g) and Tinuvin # 327 (3 g) as stabilizers, and Floren AC-1 as an antifoaming agent.
190 (1 g) and P-25 (10 g) as a catalyst were added and mixed under a nitrogen stream at 80 ° C. for 30 minutes under the condition of 800 revolutions per minute. Next, reduce the pressure of the mixer to 30 mmHg,
The mixture was defoamed for 30 minutes while stirring at 200 rpm for 1 minute. At this time, the equivalent of the wholly aromatic diamine was 70%, the viscosity was 700 cps / 25 ° C., and the specific gravity was 1.0.

(B-7) Using the same mixer as in B-1, Diol-1000 (165 g) as a polyol and MN
-1500 (165g), E30 as aromatic diamine
0 (305 g) was charged, the temperature was raised to 80 ° C, and the mixture was stirred for 30 minutes.
After mixing, as an inorganic filler, wollastonite G-
40 (350 g) was added, and under nitrogen flow at 80 ° C for 3 hours, 1
Mixing was performed under the condition of 1000 revolutions per minute. Next, Irganox # 1010 (2 g) and Tinuvin # as stabilizers
327 (2 g), Floren AC-119 as an antifoaming agent
0 (1 g) and P-25 (10 g) as a catalyst were added and mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 1,000 revolutions per minute. Next, the pressure of the mixer was reduced to 30 mmHg, and the mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the equivalent weight of the wholly aromatic diamine was 81%, the viscosity was 31,000 cps / 25 ° C., and the specific gravity was 1.3.

(B-8) R-15HT (604 g) and LAV (1) were used as polyols using the same mixer as B-1.
00g) was charged with aromatic diamine E300 (281g) and heated to 80 ° C, and then Irganox # 1010 (1.5g) and Tinuvin # 327 (2.5g) as stabilizers.
g), Floren AC-1190 (1 as an antifoaming agent
g), Coscat # 83 (10 g) as a catalyst was added, and the mixture was mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 800 revolutions per minute. Next, reduce the pressure of the mixer to 30 mmHg, and
The mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the equivalent weight of the wholly aromatic diamine was 63%, the viscosity was 9,800 cps / 25 ° C., and the specific gravity was 1.0.

(B-9) Using the same mixer as in B-1, Diol-1000 (179 g) as a polyol and MN
-1500 (179g), DET as aromatic diamine
After charging DA (277 g), heating to 80 ° C., stirring and mixing for 30 minutes, wollastonite G as an inorganic filler
-40 (350 g) was added, and the mixture was mixed under a nitrogen stream at 80 ° C. for 3 hours under the condition of 1,000 revolutions per minute. Next, Irganox # 1010 (2 g) and Tinuvin # 327 (2 g) as stabilizers, and Floren AC- as a defoaming agent.
1190 (1 g) and P-25 (10 g) as a catalyst were added, and the mixture was mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 1,000 revolutions per minute. Next, the pressure of the mixer was reduced to 30 mmHg, and the mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the equivalent of the wholly aromatic diamine was 81%, the viscosity was 21,000 cps / 25 ° C., and the specific gravity was 1.3.

(B-10) PTMEG-1000 (331 g) and PTMEG-650 (400 g) as polyols and E300 (254 g) as aromatic diamine were charged using the same mixer as B-1 and as a stabilizer. Irganox # 1010 (1.5 g) and Tinuvin # 327
(2.5 g), Floren AC-1190 as an antifoaming agent
(1 g) and Coscat # 83 (10 g) as a catalyst were added, and the mixture was mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 800 revolutions per minute. Next, the pressure of the mixer was reduced to 30 mmHg, and the mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the equivalent weight of the wholly aromatic diamine was 56%, the viscosity was 750 cps / 25 ° C., and the specific gravity was 1.0.

(B-11) Diol-1000 (256 g) and M were used as polyols using the same mixer as in B-1.
N-1500 (256g), 1,4-BD (112g)
Was added, the temperature was raised to 80 ° C., the mixture was stirred and mixed for 30 minutes, and then Whiten SSB [red] (350 g) as an inorganic filler.
Is added at 80 ° C. for 1 hour under nitrogen stream, and 1000 per minute.
Mixed under the conditions of rotation. Next, Irganox # 1010 (2 g) and Tinuvin # 327 (3 as stabilizers
g), Floren AC-1190 (1 as an antifoaming agent
g) and P-25 (20 g) as a catalyst were added, and the mixture was mixed under a nitrogen stream at 80 ° C. for 1 hour under the condition of 1,000 revolutions per minute. Next, the mixer was evacuated to 30 mmHg and 2 minutes per minute.
The mixture was defoamed for 30 minutes while stirring under the condition of 00 rotation. The viscosity of this product is 1 because aromatic diamine is not added.
The specific gravity was 7,000 cps / 25 ° C.

(B-12) PTMEG-1000 (862 g) as a polyol and 1,30-BD (30 g) as a polyol and E30 as an aromatic diamine using the same mixer as B-1.
0 (87 g), Irganox # 1010 (2 g) and Tinuvin # 327 (3 g) as stabilizers,
Floren AC-1190 (1 g) as a defoaming agent and P-25 (15 g) as a catalyst were added, and the mixture was stirred at 80 ° C. under a nitrogen stream for 1 hour.
The mixing was performed under the condition of 800 rpm for 1 hour. Next, the pressure of the mixer was reduced to 30 mmHg, and the mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the equivalent of the wholly aromatic diamine is 25% and the viscosity is 850 cps / 25.
C., specific gravity was 1.0.

(B-13) Diol-2000EO (757 g) as a polyol using the same mixer as B-1
EPG as TPG (60g) and aromatic diamine
After charging (167 g), Irganox # 1010 (2 g) and Tinuvin # 327 (3 g) as stabilizers,
Floren AC-1190 (1 g) as a defoaming agent and P-25 (10 g) as a catalyst were added, and the mixture was stirred at 80 ° C. under a nitrogen stream for 1 hour.
The mixing was performed under the condition of 800 rpm for 1 hour. Next, the pressure of the mixer was reduced to 30 mmHg, and the mixture was degassed for 30 minutes while stirring under the condition of 200 revolutions per minute. At this time, the total aromatic diamine equivalent was 53% and the viscosity was 550 cps / 25.
C., specific gravity was 1.0.

(B-14) Using the same mixer as in B-1, EA-2000 (562 g) as a polyol was charged with E300 (422 g) as an aromatic diamine, and Irganox # 1010 (2 g as a stabilizer). ) And Tinuvin # 327 (3 g), Floren AC- as an antifoaming agent
1190 (1 g) and P-25 (10 g) as a catalyst were added and mixed under a nitrogen stream at 80 ° C. for 1 hour and 1 minute under the condition of 800 revolutions. Next, reduce the pressure of the mixer to 30 mmHg,
The mixture was defoamed for 30 minutes while stirring at 200 rpm for 1 minute. At this time, the equivalent of the wholly aromatic diamine was 88%, the viscosity was 15,000 cps / 25 ° C., and the specific gravity was 1.0. Table 2 shows the raw materials used and the adjustment results.

[0059]

[Table 2] Tables 3 and 4 collectively show Examples and Comparative Examples.

[0060]

[Table 3]

[0061]

[Table 4]

Example-1 As liquid A, liquid A-1 and liquid B-1 were used in a volume ratio of A / B.
= 1/1 was used. NCO Inde at this time
x (ratio of NCO groups in solution A to active hydrogen groups in solution B: N
The CO / H ratio) is 1.1. As the molding method, spray molding was carried out by attaching a collision-mixing type spray gun GX-7 to an H-2000 type manufactured by US Gasmer Co. as a two-liquid type spray machine. The molding conditions are as follows: both A / B liquid temperature is 65 ° C., liquid pressure is 100 Kg / cm ² , discharge rate is 5 Kg / min, and room temperature (RT:
It was blow-molded at a temperature of 25 ° C. onto a polypropylene plate to a thickness of 2 mm. As workability, the gelling time at room temperature is 120
Second, the rubber elasticity was developed for 10 minutes, and the physical properties were good despite the long gelation time. Then, after curing in an oven (40 ° C. × 1 hour), as a result of a physical property test according to JIS K-6301, specific gravity (0.93) hardness (80
A), tensile strength (150kgf / cm ² ), elongation (400
%), Tear strength (65kgf / cm), Taber wear (80mg)
/ H-22 wear wheel, 1 kg load, 1000 rpm). Since this product has 120 seconds to gel after spraying, it is a liquid flow, so it is suitable for molding intricately shaped molds, open mold molding of small products, and coating of thin products. Since the time until expression was short, it had a short-term demolding property.

Example-2 As liquid A, liquid A-2 and liquid B-2 were used in a volume ratio of A / B.
= 1/1 was used. NCO Inde at this time
x is 1.1. The molding method was as a two-liquid casting machine, in which a liquid was fed by a gear pump and mixing was performed by a 20-stage static mixer, and the mixture was discharged from the tip of a pipe to mold a 20 mm thick block and a 3 mm thick sheet. Molding condition is A
/ B both liquid temperature 25 ℃, liquid pressure 20Kg / cm ² , discharge rate 5Kg
/ min. As workability, the gelling time at room temperature (25 ° C) is 40 seconds and the expression of rubber elasticity is 3 minutes, which tends to become faster as the temperature of the entire system rises. The expression of rubber elasticity was good. Then, it was cured at room temperature, but practical strength (50% or more of final physical properties) was developed in 2 hours. JIS K-6
As a result of the physical property test based on 301, specific gravity (1.15),
The hardness (65D), the tensile strength (200 kgf / cm ² ), the elongation (150%) and the tear strength (90 kgf / cm). Since the block body can be easily molded despite its high hardness, it can be used as a filling material by injecting into a gap or as a substitute for wood.

Example 3 As liquid A, liquid A-3 was used as liquid B, and liquid B-3 was used in a volume ratio of A / B.
= 1 / 0.5 was used. NCO In at this time
Dex is 1.1. As a molding method, a mixing head of dynamic mixing type was attached to NR-210 manufactured by Toho Machine Industry Co., Ltd. as a two-component casting machine to mold a block and a sheet having a thickness of 10 mm. Molding condition is that both A / B liquid temperature is 4
The mold was cast at 0 ° C., the liquid pressure was 10 kg / cm ² , and the discharge rate was 6 kg / min. The gelling time is 40 seconds and the rubber elasticity is as fast as 2 minutes.
Considering that it takes about 1 hour to remove the mold at 00 ° C, the work can be performed at a low temperature in a short time. Then, it was cured at 40 ° C. for 2 hours, and after 1 week, as a result of a physical property test based on JIS K-6301, specific gravity (1.05) hardness (70 A),
The tensile strength (90 kgf / cm ² ), the elongation (550%) and the tear strength (45 kgf / cm) were obtained. This one is generally
Despite the low hardness product with slow reactivity, there is also the combined effect of DETDA, and it exhibits moderate reactivity and rubber elasticity expression (demolding is possible in a short time). As a result, it was suitable for molding of intricately shaped molds, open molding of small products, and coating of thin products.

Example-4 As liquid A, liquid A-4 was used as liquid B, and liquid B-4 was used as A / B in volume ratio.
= 1 / 0.6 was used. NCO In at this time
Dex is 1.1. The molding method is PSM-70 manufactured by Isotherm and SP-300 as a two-component spray machine.
A mold impingement mixing type spray gun was attached and molded. This machine converts the stroke of the plunger
It is possible to change the ratio of / B liquid. Molding conditions were that both A / B liquid temperature was 65 ° C., liquid pressure was 100 Kg / cm ² , discharge rate was 3 Kg / min, and a 2 mm thick block and a 20 mm thick block were produced on a polypropylene plate. .
As workability, the gelling time at room temperature is 60 seconds, the rubber elasticity is 3 minutes, and the gelling time is long. Room temperature is sufficient as the curing condition, and heating is not particularly required. After aging at room temperature for 7 days, as a result of physical property test according to JIS K-6301, specific gravity (1.1), hardness (75D), tensile strength (240 kgf / cm ² ), elongation (140%), tearing The strength was 98 kgf / cm. This is a formulation that can be sprayed with high hardness, and a film with high rigidity can be easily produced, and was effective as a backup material.

Example-5 As liquid A, liquid A-5 was used as liquid B, and liquid B-5 was used as A / B in volume ratio.
= 1/1 was used. NCO Inde at this time
x is 1.1. The molding method used was the same machine as in Example-3. Molding conditions were such that both the A / B liquid temperature was 40 ° C., the liquid pressure was 10 kg / cm ² , and the discharge rate was 5 kg / min. As workability, gelation time at room temperature is 240 seconds, and rubber elasticity is 15
Post cure in minutes was 40 ° C. for 1 hour. As a result of physical property test,
Specific gravity (1.05), hardness (50A), tensile strength (80kg
f / cm ² ), elongation (640%), tear strength (35 kgf / cm)
Met. As a low hardness casting material, this material had good results in terms of physical property development and mechanical properties.

Example 6 As liquid A, liquid A-6 was used as liquid B, and liquid B-6 was used as A / B.
= 1/1 was used. NCO Inde at this time
x is 1.2. As the molding method, the same machine as in Example-1 was used, and molding was performed under the same conditions. As workability, the gelation time at 50 ° C. was 300 seconds and the rubber elasticity was developed for 20 minutes. As a curing condition, after curing at 50 ° C. for 1 hour, aging at room temperature for 1 week and performing a physical property test, the specific gravity (0.9
8), hardness (85 A), tensile strength (110 kgf / cm ² ),
The elongation was 500% and the tear strength was 43 kgf / cm.
This is a non-yellowing type material and is suitable for mold molding and coating of thin products with intricate shapes such as automobile parts, usually using a slow-reactive aliphatic or alicyclic isocyanate. Therefore, even though the gelation time was short, the system had a liquid release time and a short demolding property despite the system having a long demolding time.

Example 7 As liquid A, liquid A-9 was used, and liquid B-10 was used as liquid A / A.
Used at a ratio of B = 1/1. NCO Ind at this time
ex is 1.15. The molding method was the same as in Example 1 with the machine and molding conditions. 2 on polypropylene board
When sprayed to a thickness of mm, the gelling time at room temperature is 50
Second, the development of rubber elasticity is 3 minutes, and the development of rubber elasticity is rapid despite the long gelation time. Practical strength was developed at 40 ° C x 1 hour after molding, and as a result of a physical property test after curing and curing at room temperature for 1 week, specific gravity (0.92) hardness (50D), tensile strength (2
30kgf / cm ^2), elongation (360%), tear strength (75kg
f / cm). Despite its high hardness, this product has a short mold release property by securing a liquid flow time and developing rubber elasticity. Therefore, it was suitable as a molding material for industrial parts with high hardness and for relatively complicated shape timekeeping.

Example-8 As liquid A, liquid A-10 was used as liquid B, and liquid B-8 was used as A / A in volume ratio.
Used at a ratio of B = 1/1. NCO Ind at this time
ex is 1.1. The molding method was performed using the same machine and molding conditions as in Example-3. 2 on polypropylene board
Gelation time at room temperature is 90 when sprayed to a thickness of mm
Second, the development of rubber elasticity is 4 minutes, and the chain elongation is extremely fast despite the long gelation time. Curing is sufficient at room temperature and practical physical properties are developed after 1 hour. As a result of a physical property test after 1 week, specific gravity (0.90) hardness (43D), tensile strength (1
20 kgf / cm ^2), elongation (270%), tear strength (50 kg
f / cm). This system uses a material that has a high reactivity with isocyanates such as polybutadiene-based polyols and castor oil as the polyol to be used, but it is a combination system with a reaction-delayed aromatic diamine, so it will react appropriately. It has properties and physical properties. This material was useful as a material that was constantly immersed in water and used because the material used was hydrophobic.

Example 9 As liquid A, liquid A-1 was used as liquid B, and liquid B-12 was used as A /.
Used at a ratio of B = 1/1. NCO Ind at this time
ex is 1.1. The molding method was performed using the same machine and molding conditions as in Example-1. When spray-molded inside a 10 mm thick mold, the gelling time at 40 ° C was 1
The development of rubber elasticity was 80 seconds and 12 minutes. Then 4
When cured at 0 ° C for 1 hour, physical properties are developed up to practical strength, and the physical property test after curing at room temperature for 1 week shows specific gravity (0.94) hardness (50A) and tensile strength (76kgf / cm).
² ), elongation (700%) and tear strength (37 kgf / cm). This product had gelation and demolding property in a short time despite the spray material having a low hardness.

Example 10 As liquid A, liquid A-5 was used as liquid B, and liquid B-13 was used as A / A.
Used at a ratio of B = 1/1. NCO Ind at this time
ex is 1.1. The molding method was performed using the same machine and method as in Example 3. When spray molding was performed inside a 10 mm thick mold, the gelling time at 40 ° C. was 160 seconds,
The development of rubber elasticity was 11 minutes. Then 1 at 40 ℃
When cured for a period of time, physical properties are developed to a level of practical strength, and as a result of a physical property test after curing at room temperature for 1 week, specific gravity (0.9
5), hardness (60 A), tensile strength (86 kgf / cm ² ), elongation (630%) and tear strength (40 kgf / cm).
This product had gelation and demolding property in a short time despite the spray material having a low hardness.

Example 11 As liquid A, liquid A-9 was used as liquid B, and liquid B-14 was used as A / A in volume ratio.
Used at a ratio of B = 1/1. NCO Ind at this time
ex is 1.1. The molding method was performed using the same machine and conditions as in Example 3. Molded on polypropylene board 2
It was sprayed to a thickness of mm. As for workability, the gelling time at room temperature is 120 seconds, and the rubber elasticity is manifested for 5 minutes, which is fast in spite of the long gelling time. After that, when it is cured at 50 ° C for 1 hour, practical strength is developed. As a result of physical property test after curing at room temperature for 1 week, specific gravity (1.02), hardness (60D), tensile strength (260kg)
f / cm ² ), elongation (380%), tear strength (90 kgf / cm)
Met. This system is capable of working / molding at low temperature despite the use of ester-based polyol, and exhibited physical properties by curing at low temperature for a short time.

Comparative Example-1 (Comparison with Example-2) As liquid A, liquid A-7 is used as liquid B, and liquid B-7 is A / B in volume ratio.
= 1 / 0.93 was used. NCO I at this time
The index is 1.1. The molar ratio (NH ₂ / OH) was the same as that of the liquid B (B-2) used in Example-2. The molding method, the machine used, and the molding conditions were the same as in Example-2. As workability, gelation time at room temperature (25 ° C) is 1
The rubber elasticity is expressed for 200 seconds and 120 minutes, and the reaction between the isocyanate monomer and the aromatic diamine proceeds to some extent and aggregation occurs, but the chain extension reaction does not proceed, and the rubber state cannot be obtained easily. After that, it was cured at room temperature, but it took 24 hours to develop practical strength (50% or more of final physical properties). As a result of the physical property test after curing for one week at room temperature,
Specific gravity (1.15), hardness (55D), tensile strength (50kg
f / cm ² ), elongation (50%), tear strength (35 kgf / cm) and hardness due to aggregation are high, but mechanical strength is not expressed. It is presumed that this is due to the large amount of free MDI monomer because the molar ratio (NCO / OH) of liquid A is high.

Comparative Example-2 (Comparison with Example-2) As liquid A, liquid A-2 is used as liquid B, and liquid B-11 is A / by volume ratio.
Used at a ratio of B = 1/1. NCO Ind at this time
ex is 1.1. The molar ratio (NH ₂ / OH) of the liquid B was OH alone, and no aromatic diamine was used. The molding method, the machine used, and the molding conditions were the same as in Example-2. As workability, the gelling time at room temperature (25 ° C) is 6
The reaction time of the whole system seems to be slow at 00 seconds and the development of rubber elasticity is 60 minutes, and the demolding time becomes long because it is difficult to reach a rubber state. After that, in order to promote curing,
Practical strength was developed by curing for a time. After that, as a result of the physical property test after curing at room temperature for 1 week, specific gravity (0.70), hardness (93A), tensile strength (80kgf / cm
² ), elongation (120%), tear strength (45 kgf / cm), low specific gravity and foaming (reaction with water also occurred), and overall mechanical strength was low. It is presumed that this is because the aromatic diamine is not used in the liquid B, and the urea group generated by the reaction with isocyanate is not included in the polymer constitution.

Comparative Example-3 (corresponding to Example-2) A-2 as liquid A and liquid B-9 as volume A / B
= 1 / 0.92 was used. NCO I at this time
The index is 1.1. The molding method, rubbing and molding conditions were the same as in Example-2. 100 ° C as workability
The gelation time in 2 seconds and the development of rubber elasticity are 0.25 minutes (15 seconds), which is very fast and spray molding is possible.
Since the reaction was quick and the surface became uneven, it was impossible to mold a smooth plate or fine mold. Then, it was cured at room temperature, but practical strength was developed in 0.5 hours. As a result of a physical property test after one week at room temperature, specific gravity (0.95), hardness (70
D), tensile strength (120 kgf / cm ² ), elongation (60%),
It had a tear strength (65 kgf / cm).

Comparative Example-4 (Heat-curing L-100) Hyprene L-100 (manufactured by Mitsui Toatsu Chemicals) used as a casting type elastomer was molded. Liquid A uses PTMEG as a polyol, and isocyanate is TDI with NCO% = 4.2, viscosity (cps / 25 ° C.)
= 22,000. Solution B is a single use of MOCA. Molding can be done by hand stirring. First, weigh 1 liter of solution A into a 2 liter stainless beaker.
After the temperature is raised to 00 ° C., the temperature of the liquid is set to 80 ° C. under vacuum until the bubbles are intermittently generated. Solution B is
Since the melting point is 104 ° C., a required amount (12.5 parts by weight with respect to 100 parts by weight of solution A) is weighed and dissolved in a stainless steel cup at 120 ° C. Stir both to avoid bubbles.
After mixing, pour into a mold heated to 100 ° C. Gelation time is 900 seconds (100 ° C) and demolding time is 45 minutes (10
It was then cured at 0 ° C) for 24 hours at 100 ° C. 1 at room temperature
The physical property test results after a week show specific gravity (1.03) and hardness (9
0A), tensile strength (350kgf / cm ² ), elongation (450
%) And tear strength (89 kgf / cm). Although this system has good mechanical properties, it has a drawback that it requires a high temperature and a long time for working and curing, and its application is limited. Also,
As for the material, since the liquid B is MOCA alone, the formation of the cross-linking point is caused by the reaction of the excess isocyanate and the urea bond (generated by the reaction of the isocyanate and the diamine), so that heating is indispensable.

[0077]

By the method of the present invention, a material system capable of casting and spray molding is used, and at the time of working and curing.
It has made it possible to lower the curing temperature, improve the degree of freedom in polymer design, control the gelation time, early develop rubber elasticity, and secure mechanical properties.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-6-157700 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 18/65-18/66

Claims (8)

(57) [Claims] 1. A single substance of 4,4′-diphenylmethane diisocyanate or a mixture with 2,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, a single substance of 4,4′-diphenylmethane diisocyanate or 2,4′-diphenylmethane diisocyanate. A mixture of 1,4,4'-diphenylmethane diisocyanate and one part or a mixture of two or more kinds selected from liquid diphenylmethane diisocyanate obtained by carbodiimide modification, and organic isocyanate and active hydrogen containing
The compound of the isocyanato group (N
CO group) and the active hydrogen (H) in the active hydrogen-containing compound is N
CO / H = obtained by reacting in the range of 4/1 to 30/1 molar ratio
Isocyanato group-terminated prepolymer (Liquid A), and 3,
5-dimethylthio-2,4-toluenediamine and 3,
Mixture of 5-dimethylthio-2,6-toluenediamine
Aromatic diamine and polyol and / or polyester
-A resin (B liquid) made by mixing a teramine and a curing catalyst
Urethane foam by casting or spray molding.
In the method for producing a stoma, the aromatic dia
Minamino group (NH2) and polyol and / or poly
The active hydrogen (H) of ether amine is NH2 / H = 9/1
A method for producing a urethane elastomer, which comprises adjusting the molar ratio to 2/8. 2. An organic isocyanate and a hydroxyl value of 120 or more.
The active hydrogen-containing compound below is the organic isocyanate
Isocyanato group (NCO group) and active hydrogen-containing compound in
The active hydrogen (H) inside is NCO / H = 4/1 to 30/1
Of the isocyanate-terminated prepoly
Mer (solution A) and 3,5-dimethylthio-2,4-to
Ruenediamine and 3,5-dimethylthio-2,6-to
Aromatic diamine and poly consisting of a mixture of ruenediamine
Mix all and / or polyether amine with curing catalyst
Casting or spraying using resin (solution B)
In the method of manufacturing urethane elastomer by molding
And the amino group (NH2) of the aromatic diamine in solution B
Active hydrogen of lyol and / or polyether amine
Adjust (H) in the range of NH2 / H = 9/1 to 2/8 molar ratio
A method for producing a urethane elastomer, which comprises: 3. A liquid production method of the urethane elastomer of claim 1 wherein the hydroxyl value of the active hydrogen-containing compound is 120 or less used in the preparation of. 4. The viscosity of both liquid A and liquid B at 25 ° C. is 2,000 centipoise or less.
A method for producing the urethane elastomer described above. 5. An equivalent amount of 50% or less of all amino groups in the aromatic diamine used for producing the liquid B is 3,5-diethyl-2,4-toluenediamine and 3,5-diethyl-2. The method for producing a urethane elastomer according to claim 1, wherein the mixture is replaced with a mixture of 6,6-toluenediamine. 6. The cross-linking agent used in the production of the liquid B is a low molecular weight polyol having a hydroxyl value of 400 or more, 3,5-dimethylthio-2,4-toluenediamine and 3,5-dimethylthio-2,6-toluenediamine. 6. The method for producing a urethane elastomer according to claim 1, which comprises an aromatic diamine which is a mixture with and the amount of the crosslinking agent is 90% or less of the total amount of the liquid B. 7. The polyol used in the production of solution B is polytetramethylene ether glycol.
The method for producing a urethane elastomer according to 2, 3, 4, 5 or 6. 8. The method for producing a urethane elastomer according to claim 1, wherein the mixing device used for casting or spray molding is a collision mixing system.