JPS61247721A - Production of polyurethane polyurea elastomer - Google Patents

Abstract

PURPOSE:To obtain the titled elastomer which is useful for, e.g., a lining for an iron structure and can give a film of a desired thickness within a short time, by applying a specified partial prepolymer and a liquid mixture of a polyol, an active aromatic polyamine, etc., to an object by a high-pressure two-feed spray gun and curing the applied film. CONSTITUTION:A mixture (A) of an organic polyisocyanate or its partial prepolymer obtained by reacting part of its NCO groups with a polyol of a MW of 40-8,000 (a) and, optionally, a plasticizer (b) and a mixture (B) of a polyol (c) having at least two OH groups, MW of 1,000-8,000, such as a polyether polyol in an amount providing 0.90-1.30 equivalent of active hydrogens, per equivalent of NCO groups of component a, 30-160wt%, based on component c, active aromatic polyamine (d) containing no electron- withdrawing group in the aromatic nucleus, as a chain extender and 0.001-5wt%, based on the total, organometallic catalyst (e) (e.g., lead naphthenate), etc., are sprayed at a predetermined ratio between the feed rates by means of a high-pressure two-feed spray gun, and the applied film is cured.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing polyurethane-polyurea elastomer, particularly a method for producing polyurethane-polyurea elastomer using a high-pressure spraying device (Prior art) Polyurethane - To produce polyurea elastomer TG, organic polyisocyanates, high-volume polyols, and low-molecular-weight polyamines as chain extenders are generally used as essential components. The technique for coating objects with polyurethane, polyurea, and entomers involves diluting a prepolymer with isocyanate groups at the ends obtained by completely reacting organic polyisocyanate and polyol with a solvent, and applying highly active aromatic amines such as diphenylmethanediamine. For normal two-component spraying, use a machine with a curing agent dissolved in a solvent (
Pressure spraying (70 kf/cm2) is carried out by painting. In addition, 3,31-dichloro-4,41-diaminodiphenylmethane (MOC
Using a low-activity aromatic amine having an electron-withdrawing group in the aromatic nucleus such as A) dissolved in a solvent, etc., it is mixed with a prepolymer diluted with a solvent, and then sprayed with high pressure liquid type within the pot life. There is also a method of spray painting using equipment.

(Problems to be Solved by the Invention) In this method, it is necessary to volatilize a large amount of solvent from the coating, so if the solvent is sprayed thickly at once, a large amount of bubbles will be generated from the coating.

In order to prevent the generation of bubbles, there is a method of using a high boiling point solvent and leaving the solvent in the coating (Japanese Patent Publication No. 55-19
930). However, with this method, during long-term use, the solvent is lost due to migration, evaporation, runoff into rainwater, etc., and the coating deteriorates, causing cracks, shrinkage, etc.

There is also a method of producing a coating by reacting, for example, a carbodiimide-modified liquid diphenylmethane diisocyanate or a partial prepolymer of diphenylmethane diisocyanate with a mixture of high and low molecular weight polyols. In this method, the low molecular weight polyol easily absorbs moisture, and the competitive reaction between hydroxyl groups and water causes foaming, which produces pinholes, craters, etc. on the coating surface, and the specific gravity of the coating decreases, resulting in a decrease in strength. Resulting in.

(Means for Solving the Problems) The present inventors have conducted various studies on a method for manufacturing a coating that does not cause foaming even when coated thickly and can be coated over and over again, and as a result, the present invention has been arrived at. .

That is, the present invention is as follows.

(1) a, a partial prepolymer obtained by reacting an organic polyisocyanate or a part of an isocyanate group with a polyol having a molecular weight of 60 to s, ooo, b, a molecular weight of 1,000 to s containing at least two hydroxyl groups, oo
When reacting the polyol o, the active aromatic polyamine whose aromatic nucleus does not contain an electron-withdrawing group as a C2 chain extender, and the organometallic catalyst d, a mixture of liquid a and liquids b, c, and d.
Polyurethane, polyurea, and
Method of manufacturing elastomers.

Examples of high-pressure two-component spray equipment used in the present invention include:
Glasscuts7to's rim (RIM) series, MODE
LT-3, MODEL-1 manufactured by Gasmer, etc. are preferred. These high-pressure two-component spray devices are 60 to 150 kf/
Because it is sprayed onto the construction surface with a discharge pressure of 1 cm, the raw solution mixture becomes fine particles and a smooth construction surface can be obtained.
The polyurethane stock solution used in the present invention is extremely reactive and loses fluidity within 1 to 10 seconds after mixing the stock solution.

The organic polyisocyanate used in the present invention is, for example, 2.
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof (TDI), diphenylmethane-4,4'-diisocyanate (MDI), xylylene diinocyanate (XDI)'.

Dicyclohexylmeth 7-4-4'-diisocyanate (hydrogenated MDI), inphorone diisocyanate (IP
DI), hexamethylene diisocyanate (HDI),
Hydrogenated xylylene diisocyanate (HXDI), crude TDI, polymethylene poly7enylbolyisocyanate (crude MDI), and incyanurate-modified products, carbodiimide-modified products, biuret-modified products of these isocyanates, etc. be.

Among these organic polyisocyanates, MDI.

Crude MDI and its modified products are particularly preferred.

The polyol used in the present invention includes water, polyhydric alcohol such as ethylene glycol, glopylene glycol, glycerin, trimethylolpropane, and pentaerythritol, and one or more alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Polyether polyol (PPG) obtained by addition polymerization
): polytetramethylene ether glycol (PTMEG) obtained by addition polymerization of tetrahydrofuran alone or together with ethylene oxide: polytetramethylene-ethylene ether glycol; castor oil, polycarbonate polyol, etc.

In addition to the above, polyester polyols obtained by reacting polycarboxylic acids with low molecular weight polyols and polyester polyols obtained by polymerizing caprolactone can also be used.Furthermore, acrylonitrile, styrene, Polymer polyol obtained by graft polymerization of ethylenically unsaturated compounds such as methyl methacrylate and 1
- 2- or 1,4-polybutadiene polyols or hydrogenated products thereof can also be used.

Polyols can be used alone or in combination of two or more types, but
The molecular weight of the polyol or its mixture is i, ooo~s
, o o o are preferred.

In order to increase the reactivity, it is desirable that the hydroxyl groups of the polyol contain 50 or more primary hydroxyl groups by weight. Therefore, it is preferable that the polyether polyol obtained by addition polymerizing propylene oxide or butylene oxide to a polyhydric alcohol is terminally capped with ethylene oxide.

It is desirable that the low molecular weight polyol used for producing the bulk polyester polyol has a primary hydroxyl group at the end.

The organic polyisocyanate of the present invention can be reacted with its it polyol and a chain extender, or alternatively some of the isocyanate groups can be reacted with a polyol in a nitrogen stream from 70 to 8
It is also possible to use partial prepolymers obtained by heating at 0° C. for several hours.

As polyols that can be used to produce the partial prepolymer, in addition to the polyols described above, the following low molecular weight polyols can be used. Low molecular weight polyols include propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and mixtures thereof; diethylene glycol% 1,3-
7-ethylene glycol, 2,3-butylene glycol: In addition, water, polyhydric alcohols such as ethylene glycol, fluoropylene gellicol, glycerin, trimethylolpropane, and pentaerythritol, and alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Examples include polyether polyols with a molecular weight of less than 1,000 obtained by addition polymerization of one or more types, and polytetramethylene ether glycols with a molecular weight of 1.0 (0).

The active aromatic polyamine that does not contain an electron-withdrawing group in its aromatic nucleus and is used as a chain extender in the present invention is, for example, 4.4'-
Diamino Diphenyl % 4e4'-Diamino diphenyl ether sz, mixture of 3-diaminotoluene and 3,4-diaminotoluene 2.4-△ and 2,6-diaminotoluene (containing a mixture of 80:20 (by weight)) , 2,4- and/or ° are obtained by 4,4'-diamino-diphenylmethane, 1,3- and 1,4-7 di-2-diamine, naphthylene-1,5-cyamine, aniline-formaldehyde condensation. Liquid polymers of polyphenyl-polymethylene polyamines of type 1
．． 3-dimethyl-2,4-diaminobenzene, 1.3-
Diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2
, 5-diaminobenzene, 1,4-diisopropyl-2
, 5-diaminobenzene, 1,4-diptyl-2,5-
Diaminobenzene, 2.4-diaminomesitylene, 1.
3゜5-17ethyl-2,4-diaminobenzene,
1゜3.5-)diethyl-2,6-diamitbenzene,
1.3.5-triinopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-
Diaminobenzene (and mixtures of the latter 2 diamines in different proportions) and the like: 2,3-
Dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-cyptyl-1,5-diaminonaphthalene, and the like ; 3°3', 5.5'-tetramethyl-benzidine, 3.3', 5°5'-tetraisopropyl-benzidine, and the like: 3.3', 5.
Ditetramethyl-4゜4'-diaminodiphenylmethane, 3.3', 5. Detetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5.5'-tetraisoprobyl-4,4'-diaminodiphenylmethane, 3.3', 5.5'-tetrabutyl-4 , 4'-diaminodiphenylmethane, 3.5-diethyl-3'-methyl-2', 4-diaminodi7-enylmethane, 3.5-
Diisopropyl-3'-methyl-2', 4-diaminodiphenylmethane, 3.3'-diethyl-2,2'-diamino-diphenylmethane, 3°3'-diethyl-4,4
'-Diamino diphenylmethane and similar: 3.3', 5.5'-tetraethyl-4,4'
-diaminodiphenyl ether11. ,3゜3', 5
．． 5'-tetraisopropyl-4,4'-diaminodiphenyl ether and the like. These aromatic polyamines may be used alone or in a mixture of two or more, and the appropriate amount to be used is 30 to 160 parts per 100 parts by weight of the polyol (in the present invention, parts represent parts by weight). be.

The amounts of the organic polyisocyanate or partial prepolymer, polyol, and chain extender to be used are such that the equivalent ratio of the NCO groups in the organic polyisocyanate or partial prepolymer to the active hydrogen in the polyol and chain extender is 0. 90-1
．． Make it 30.

Examples of the organometallic catalyst used in the present invention include tin acetate,
These include tin octoate, tin 2-ethylhexoate, tin laurate, tin maleate, diptyltin diacetate, diptyltin dilaurate, dioctyltin dilaurate, lead octoate, lead 2-ethylhexoate, lead tin 7thenate, and the like.

These organometallic compounds may be used alone or in combination. The amount used is preferably 0.001 to 5% by weight based on the total amount of raw materials used.Other auxiliary agents that can be used in the present invention include plasticizers, flame retardants, fillers,
Stabilizers, colorants, etc.

As a plasticizer, for example, dioctyl phthalate (DOP
), dibutyl phthalate (DBP), dioctyl adipate (DOA), tricresyl phosphate (TCP), chlorinated paraffin, etc.

Flame retardants include, for example, tris-(β-chloropropyl phosphate (manufactured by Phyrol PCF1st7A Japan Co., Ltd.), tris-dichloropropyl phosphate (CRP), tris-chloroethyl phosphate (CRP, manufactured by Daihachi University Chemical Co., Ltd.),
These include phosphoric acid esters such as LP (manufactured by Otona Kagaku Co., Ltd.), and nobrome compounds such as dibrome neopentyl glycol and tribrome neopentyl alcohol.

Examples of fillers include glass fiber, carbon black, calcium carbonate, talc, kaolin, zeolite, diatomaceous earth, perlite, vermicelli: L-lite, titanium dioxide, and the like.

Examples of stabilizers include trade names Irganox 1010 and 1076 (manufactured by Ciba Geigy), Yoshinox BHT,
% BB and positionally hindered phenols such as GSY-930 (manufactured by Yoshitomi Pharmaceutical Co., Ltd.); Tinuvin p, 327 and 328
Benzotriazoles such as (manufactured by Ciba Geigy) Benzophenones such as Tomisorb 800 (manufactured by Yoshitomi Pharmaceuticals): Sanol LS-770 and 744, Tinuvin 144 (
These are positionally hindered amines such as Ciba Geigy (manufactured by Ciba Geigy).

When carrying out the present invention, the organic polyisocyanate or partial prepolymer is used as it is, or is mixed with an appropriate amount of plasticizer to adjust the flow rate ratio of the components, and is used as component A.
A polyol, a chain extender, a catalyst, a colorant, etc. are mixed to form the B component. Both components A and B are ejected from a high-pressure spray device at a predetermined flow rate ratio and sprayed onto the object. When glass fiber is used, the long glass fiber is cut into a certain length at the head of the gun and blown with air, and mixed with both components A and B while flying through the air. The mixture of components A and B attached to the molded article is cured in 1 second to more than ten seconds. This operation is repeated several times as necessary to obtain a coating of a predetermined thickness.

The polyurethane-polyurea nidistomer according to the present invention can be used as a protective coating for lining pipes, tanks, and other steel structures, thick protective coatings with waterproof performance for concrete, etc. (roof waterproofing materials, exterior wall waterproofing materials, etc.), hard polyurethane coatings, etc. 7 ohm, polystyrene, 7 ohm, used for thick protective coating of insulation materials such as boards, seamless flooring, and open mold molding using molds made of metal or resin.

According to the present invention, the coating can be completed by simply spraying the stock solution using a high-pressure spraying device, and the stock solution hardens within a few seconds after being sprayed, and does not produce bubbles even when thickly coated. Therefore, multiple coats can be applied in a short period of time, and a coating of the required thickness can be completed in a short period of time.

Furthermore, since bubbles are not generated, complex shapes such as uneven patterns on the surface of the object can be accurately reproduced on the surface of the coating with a simple operation.

(Example) Examples of the present invention will be described below.

Preparation of organic polyisocyanate: The polyisocyanate was prepared by the following method.

(A-1) Carbodiimide-modified liquid MDI (MD I-LK manufactured by Mitsui Nisso Urethane Co., Ltd.; NCO = 28.
5% by weight) 1.00Or and 239t of flame retardant (Fyroll PCF manufactured by Stow 7A Japan Co., Ltd.) were stirred for 1 hour under a nitrogen stream to obtain NGO weight% = 23 and viscosity (cps/25).
A polyisocyanate having a temperature of 70° C.) was obtained.

(A-2) Pure MDI (MDI manufactured by Mitsui Nisso Urethane Co., Ltd.)
PH) and liquid MDI (mentioned above) at a weight ratio of 70/30 to make 1,000 fKPPG-Diol-1000.
(Mitsui Nisso Urethane Co., Ltd. OH value = 56) to 750? After addition, DOP (
Dioctyl 7 tallate) 190F added as total diluent,
A modified polyisocyanate having NGO weight %=13.2 and viscosity (cps/25° C.)=Δ600 was obtained.

(A-3) PTMEG with a molecular weight of 2.000 fully ring-opened with tetrahydrofuran and isocyanate 1.0009 mixed at a weight ratio of pure MDI/liquid MDI = 80/20.
(Teratare-2000: manufactured by Dupot Rights, OH value 56) 1,
After adding 245F and carrying out a heating reaction at 80° C. for 3 hours in a nitrogen stream, DOP (mentioned above)-2049 was added to obtain a modified polyisocyanate (A-3). N00wt%-
11.0, viscosity (cps/25℃) 1,000゜(
A-4) After carrying out the reaction in the same manner as (A-3), D
OP (supra) 6915' was added to obtain a modified polyisocyanate (A-4).

NGO weight% = 9.2, viscosity (cps/25°C) 300
゜(A-5) Carbodiimide modified liquid MDII, 0
001 and the plasticizer DOP (mentioned above) 1409 were mixed for 1 hour under a nitrogen gas flow, NGO weight % = 25.0° viscosity (c
ps/25°C) 40 modified polyisocyanate (A-5
) was obtained.

Example 1 As a polyisocyanate, A-2'' was kept at about 50°C. On the other hand, as a resin, EP-33ON (72
DETDA (26.3 parts) was added to DETDA (26.3 parts) and lead naphthenate (PB24% by weight, 0 parts) was added thereto as a catalyst and kept at about 60°C.The volume ratio of both was 1/1.
In step 1, spraying was performed using the following machine. Liquid is sent to the spray machine using Graf's supply pump (air drive 2:
1 tire 208-177) t-air pressure 5 kf/Cm
I went with 2.

The spray machine is a Glass-Craft RIM series with a static pressure of approximately 140 kW/cm2 and a spray speed of 105 kW/cm2.
Used at ~119 kf/cfn2. To adjust the temperature of the liquid, the heat exchanger in the main body was set to 50°C for liquid A and 60°C for liquid B, and the current of the hose heater was 4A. The spray gun is a gropler gun with a flat chamber (1) and 10 tips (0
43-25) was attached and used. The mold has a thickness of 1
Using a polypropylene plate of mm, spraying 3 to 5 times is about 2
A sheet of mm thickness was obtained (spray conditions = 28°C,
After curing the obtained sheet in a constant temperature room at 23° C. for 7 days, the physical properties were measured in accordance with JIS K-6301 and in accordance with Example 1 except for the formulation shown in Clothing 2.

Example 3 A-3t' as isocyanate, PT as resin
MEG-2000 (27, 2 copies), DETDA (21,
DBTDL (0.8 parts) was used as a catalyst and sprayed using the following machine at a volume ratio of A/B=2/1.

When spraying, both A and B liquids were kept at a temperature of about 60°C, and a graph supply pump (air drive 2:1) was used to pump the liquids L7'C at an air pressure of 7 kW/cm2. The spray machine used was Gasmer FF. Hydraulic pressure is approximately 70 kW/cm2 when stationary, and 60 to 70 kf/cm when in operation.
2, and the temperature was set by setting the heat exchanger of the main body to about 60° C. and the current of the heater hose to about 5 A''.

The spray gun used was an AR-A gun equipped with a pattern control disc 3182-201-A, which provides good mixing, instead of a normal D gun. The mold uses a 1mm thick polypropylene plate,
The following treatment was carried out in the same manner as in Example 1.

Table 1 shows the working conditions of Comparative Examples and Examples, including those mentioned above, and Table 2 shows the formulations and physical properties.

(Left below) (Effects of the invention) The tack-free time of the example was shorter than that of the comparative example,
Also, there is no after tack (tack remains in the area where the mist is scattered). There is also less foaming (less density loss) even at high temperatures. In addition, in terms of physical properties, elongation and tear strength are extremely excellent.

Claims (1)

[Claims] (1) a. Partial prepolymer obtained by reacting a part of an organic polyisocyanate or isocyanate group with a polyol having a molecular weight of 60 to 8,000; b. A molecular weight of 1,000 to 8 containing at least two hydroxyl groups; 000 polyol, c, an active aromatic polyamine whose aromatic nucleus does not contain an electron-withdrawing group as a chain extender, and d, an organometallic catalyst.
Polyurethane, polyurea, and
Method of manufacturing elastomers.