JPS63105018A - Normal temperature-curable polyurethane-polyurea elastomer - Google Patents

Abstract

PURPOSE:To obtain the titled elastomer of enhanced levellability and workability in the coating operations, suitable as an undercoating material for film waterproofing materials, by reaction between urethane prepolymer, active hydrogen compound, etc., in the presence of a specific aromatic amine-based chain extender and reinforcing filler. CONSTITUTION:The objective elastomer can be obtained by reaction between urethane prepolymer, active hydrogen compound (pref. polyoxyalkylene diol) and other aids (e.g., plasticizer, colorant) in the presence of an aromatic amine- based chain extender and reinforcing filler (pref. carbon black). Said chain extender can be prepared by mixing aniline and 2-chloroaniline in a molar ratio 0.1-0.35:1 followed by condensation between 1.65-1.85mol of the mixture and 1mol of formaldehyde in the presence of a mineral acid (e.g., hydrochloric acid).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a two-component polyurethane polyurea elastomer. Polyurethane and
Regarding polyurea elastomers.

(Prior art) Generally, aromatic amines used in polyurethane, polyurea, and elastomers are 3,3°-dichloro-4,4
°-Diaminodiphenylmethane (MOCA) is used, but aromatic amines prepared by condensing aniline and 2-chloroaniline with formaldehyde are also used, as shown in Japanese Patent Publication Nos. 49-35077 and 54-6257, etc. .

(Problems to be solved by the invention) MOCA is used as a chain extender in waterproof coating materials, elastic paving materials, flooring materials, etc., and a large amount of carbon or white carbon is used as an inorganic filler with reinforcing properties. It is often used, and in that case, the initial viscosity when mixed with the prepolymer (liquid A) tends to increase. As a result, workability and smoothness of the coating film are lost due to poor liquid flow during coating.

Also, in winter, the temperature of the stock solution decreases, which increases the viscosity.Usually, a solvent is added to ensure workability, but in systems containing large amounts of carbon, etc., thixotropy occurs and the smoothness of the coating film is lost. In order to further improve the liquid flowability, the amount of liquid components (plasticizer, solvent) is increased, but this method causes serious problems such as bleeding or shrinkage to the surface. It becomes.

(Means for Solving the Problems) The present inventors previously obtained an aromatic amine constituting polyurethane, polyurea, and elastomer by condensing aniline and 2-chloroaniline with formaldehyde in the presence of a mineral acid. The molar ratio of aniline to chloraniline is (0,1 to 0°35): 1, and the molar ratio of total amine to formaldehyde is (1,65 to 1.8
5): We found that using aromatic amine 1 as a crosslinking agent is effective in preventing interlayer blistering during overcoating and the sherry phenomenon during curing, and filed a patent application. (Patent Application No. 6O-100629) As a result of further research on this aromatic amine, it was discovered that when used in combination with a reinforcing optical fiber material, the above-mentioned problems that occur when using MOCA can be solved, and the present invention has been made. reached.

That is, the present invention provides a urethane prepolymer, an active hydrogen compound,
and other auxiliary agents, aniline and 2-
An aromatic compound obtained by mixing chloroaniline in a (0.1 to 0.35):1 molar ratio and condensing 1.65 to 1.85 mol of the mixture to 1 mol of formaldehyde in the presence of a mineral acid. It is a room temperature curable polyurethane polyurea elastomer containing an amine chain extender and a reinforcing filler as essential components.

By using the aromatic amine chain extender according to the present invention, 1) the initial mixing viscosity of the stock solution is significantly lowered, and the liquid flow is improved, resulting in a smooth coating surface; 2) Even when the temperature of the stock solution drops during winter construction and it is necessary to add a solvent, thixotropy is reduced and leveling properties are improved.

Although it is possible to apply a moisture base to the base as long as the amount is normally 8% or less, the chain extender of the present invention has less influence from moisture, so
Construction is possible even with a moisture content of 0% or more.

Furthermore, when the chain extender of the present invention is used, the initial physical properties of the applied polyurethane/polyurea elastomer are improved.

In the present invention, when the molar ratio of aniline to 2-chloroaniline is less than o, t:i, the effects of 1) and 2) above are greatly reduced, approaching those obtained when MOCA is used alone.

On the other hand, the molar ratio of aniline to 2-chloroaniline is 0.
If the ratio exceeds 35:1, the reaction with the urethane prepolymer will be too rapid and sufficient pot life will not be obtained for coating work.

Also, the molar ratio of total amine to formaldehyde is
If it is less than 1.65:1, the number of functional groups in the generated amine will be too high, resulting in a decrease in elongation, tear strength, etc. of the resulting polyurethane, polyurea, and elastomer. 1
．． If the thickness exceeds 85:1, the effect of 2 above will be reduced, which is not preferable.

The mineral acids used in the present invention include, for example, hydrochloric acid and sulfuric acid.

Examples of organic polyisocyanates for producing urethane prepolymers include 2.4-) lylene diisocyanate, 2.6
- ) lylene diisocyanate and mixtures thereof (TDI
), especially the 2.4-isomer and 2.6-isomer at 80:
A mixture of 20 and 65:35 (by weight) is preferred. As the polyol, various polyether polyols (PP(1,), polyester polyols, polyether polyols, castor oil, polytetramethylene ether glycol can be used, but water, Particularly preferred are polyoxyalkylene glycols obtained by adding propylene oxide or propylene oxide and ethylene oxide to propylene glycol, and polyoxyalkylene triols obtained by adding propylene oxide or propylene oxide and ethylene oxide to glycerin, trimethylolpropane, and the like.

In addition, low molecular weight glycols can be used. As the low molecular weight glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, and 2,3-butylene glycol can be used.

These polyols may be used alone or in a mixture of two or more, but the average molecular weight of the polyol is 60-s, ooo
is preferred.

Urethane prepolymers are produced by heating organic polyisocyanates and polyols at 80 to 100°C for several hours in a nitrogen stream.

As the active hydrogen compound used in the present invention, in addition to the aromatic amine described above, various polyols having a molecular weight of 400 to 8,000 are used. (and) polyoxyalkylene diols and polyoxyalkylene triols are preferred.

The reinforcing filler used in the present invention can improve the physical properties of polyurethane, polyurea, and elastomer by adding it, and carbon black, ultrafine silica, and the like are suitable for the present invention. The amount used is preferably 2 to 25% by weight based on the total amount of raw materials used. These reinforcing fillers can be used alone or in combination, and can also be used in combination with other general fillers. can. Preferred examples of other general fillers include calcium carbonate, cruzi, clay, zeolite, and titanium dioxide.

In the present invention, organic metal catalysts are used, and among them, organic lead catalysts are particularly preferred.

Examples of the organic lead catalyst used in the present invention include lead 2-ethylhexoate, lead octoate (lead octylate), and lead naphthinate. The amount used is preferably 0.1 to 5% by weight based on the total amount of raw materials used.

Other auxiliary agents used in the present invention include plasticizers, colorants, weathering stabilizers, antifoaming agents, and solvents as required. As a plasticizer, for example, dioctyl phthalate (D
OP), dibutyl phthalate (DBP), dioctyl heptadipate (DoA), tricresyl phosphate (TCP), chlorinated paraffin, etc.

Colorants include inorganic pigments such as chromium oxide and red iron, and organic pigments such as phthalocyanine pigments and azo pigments.

As a weathering stabilizer, the trade name is Tsucrak l300, N5.
-6 (manufactured by Ohmukai Shinko Kagaku), trade name Irganox 10
10 and 1076 (Ciba Geigy Co., Ltd., Yoshinox BHT, BB and GSY-930 (manufactured by Yoshitomi Pharmaceutical)
Positionally hindered phenols such as Tinuvin P, 327
and benzotriazoles such as 328 (manufactured by Ciba Geigy); benzophenones such as Tomisorp 800 (manufactured by Yoshitomi Pharmaceutical); and positionally hindered amines such as Sanol LS-770 and 744 and Tinuvin 144.

Examples of antifoaming agents include dimethylsiloxane-based agents and polyacrylate-based agents such as Disparon 710 and 720.

Solvents include aromatic hydrocarbons such as toluene and xylene,
Examples include aliphatic hydrocarbons such as Isopar H and M, esters such as ethyl acetate, and ketones such as methyl ethyl ketone.

Application methods of the polyurethane/polyurea elastomer of the present invention include ordinary working methods such as coating waterproofing materials, elastic paving materials, flooring materials, etc.

At this time, the equivalent ratio of NCO groups to active hydrogen in the prepolymer is 0.9 to 1.4, particularly preferably 1.05 to 1.1.
The blending amount of each component is determined so that the amount becomes 0.

(Function) When the pot life is kept the same, the aromatic amine chain extender of the present invention has a significantly lower initial mixing viscosity than MOCA. Furthermore, even if a large amount of solvent is added during winter construction, thixotropic properties are less likely to occur, and the influence of substrate moisture is reduced.

(Example) The present invention will be specifically described below with reference to production examples and examples.

In the present invention, parts represent parts by weight.

Production Example 1 Production of urethane prepolymer.

600 parts of a polyoxypropylene triol with a molecular weight of 6000 obtained by addition polymerization of propylene oxide using glycerin as an initiator, and a molecule obtained by addition polymerization of propylene oxide using propylene glycol as an initiator [2000 parts]
560 parts of polyoxypropylene diol, 2.4-T
Mixture 15 of DI and 2.6-TDI in a 65:35 weight ratio
9.5 parts were mixed and reacted in a nitrogen stream at 80°C for 22 hours, then at 100°C for 1.2 hours.

NCO group content: 25% by weight, viscosity: 7000cps/
A prepolymer at 25°C was obtained.

Next, the raw materials used in the reaction with this prepolymer in the examples are as follows.

- Koko Amin U Masa AB BiC...Aniline,
Polyamine amine chain extender obtained by reacting 2-chloroaniline and formaldehyde with the following mole numbers, respectively.
ABC Aniline (mol) 0.1? 0.23
0.302-Chloraniline (mol”) 1.68
1.57 1.40 Formaldehyde (mol) 1.
0 1.0 1.0EP-240...Molecular 1t60 obtained by adding glycerin as an initiator, adding propylene oxide, and then capping with ethylene oxide.
00 polyoxyalkylene triol.

EP-330: Polyoxyalkylene triol with a molecular weight of 3700 obtained by addition polymerizing propylene oxide using glycerin as an initiator and then capping with ethylene oxide.

Example 1 15 parts of aromatic amine chain lengthening agent AO, triol EP-24
030 parts, Triol EP-33020 parts, carbon black 50 parts, particulate calcium carbonate 53.38 parts, catalyst lead octylate (lead content t25χ) 1.1 parts, plasticizer DOP 30 parts, xylene 10 parts, antifoaming agent Silicone oil (viscosity 1000 centistokes > O, OS part,
A curing agent was prepared by uniformly kneading 13,000.5 parts of the stabilizer Tsukrac using a disilver.

After uniformly mixing this curing agent with the same amount of prepolymer using a spatula, it was transferred to a polyethylene cup with a content of Lot + 1, and was left in a room at 20°C to measure the initial mixing viscosity and pot life. The viscosity was measured using a viscometer model B-8M under the conditions of rotor No. 4 and rotation speed 6 rpa, and the viscosity after 5 minutes of mixing the stock solution was taken as the initial mixed viscosity. Further, the pot life was defined as the time until the viscosity reached 100,000 cps.

Next, this stock solution mixture was coated onto the coated glass plate to a thickness of 2III l using a metal spatula and left in a room at 23°C. The physical properties measured after being left for 18 hours are the initial physical properties,
The physical properties after being left for 7 days were taken as the normal physical properties, and the measurement method was J.
Compliant with IS K-6301.

Next, to check the influence of the substrate moisture, we used a Kerato moisture meter HL-5.
The moisture content of concrete pavement slabs was measured using Model 00. The raw solution mixture was applied to this pavement board and left in an atmosphere of 30°C and 68% humidity, and the normal state of blistering was observed according to the following criteria.

0------------ No blisters △------------ Small blisters X --------1 Medium blisters X X----1 Large blisters Next, check the leveling property. 30 x 30C1+ to measure
Paste a 511II thick adhesive spacer around the slate board. The stock solution mixture as it is and 10% of this
After adding and mixing the amount of toluene, it was placed on a slate board to a thickness of 2
It was applied to 11m. The coated surface was rubbed using a sawtooth with a height of 8m+w and a 45@ angle to create a score.

This was left at 20°C, and after curing, it was visually inspected to see if there were any remaining crevices.

X ----------Stripes clearly remaining 0---------
- Example 2 The results obtained from the above tests are shown in Table 1. 5.0 parts of the aromatic amine extender B, 53.33 parts of particulate calcium carbonate, and the catalyst lead octylate The process was carried out in the same manner as in Example 1, except that 1.3 parts of .

The results were as shown in Table 1.

Example 3 The same procedure as in Example 1 was carried out except that 5.0 parts of aromatic amine chain extender C, 53.08 parts of finely divided calcium carbonate, and 1.5 parts of lead octylate catalyst were used.

The results were as shown in Table 1.

Comparative Example 1 0.5 part of MOCA instead of aromatic amine chain extender,
The same process as in Example 1 was carried out except that 53.45 parts of particulate calcium carbonate and 1.0 part of catalyst lead octylate were used.

The results were as shown in Table 1.

(Effects) As is clear from Table 1, by carrying out the present invention, the workability of room-temperature curing polyurethane, polyurea, and elastomer is improved, the initial physical properties after construction are improved, and they are less susceptible to the influence of substrate moisture. Improves leveling properties during application.

Table 1 Sansho Taku Pressed Character Erasing Public Corporation

Claims (1)

[Claims] When reacting the urethane prepolymer, active hydrogen compound, and other auxiliary agents, aniline and 2-chloroaniline are mixed at a ratio of (0.1 to 0.35):1 mole, and 1 mole of formaldehyde is added in the presence of mineral acid. to 1.6
A cold-curable polyurethane/polyurea elastomer containing as essential components an aromatic amine chain extender obtained by condensation of 5 to 1.85 moles and a reinforcing filler.