JP3199133B2 - Method for producing polyurethane-urea non-aqueous dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyurethane urea non-aqueous dispersion useful as a paint, a coating vehicle and an adhesive.

[0002]

2. Description of the Related Art Processes for producing non-aqueous polyurethane-urea dispersions of the main polymer having a particle size of less than 10 μm are known (US Pat. No. 4,783,502;
European Patent Publication No. 318939).

There is also known a method for producing a polyurethane-urea non-aqueous dispersion in which particles having a main polymer particle diameter of more than 10 μm are dispersed for obtaining a polyurethane-urea powder. Specifically, a urethane prepolymer having isocyanate groups at both ends is reacted with an organic diamine component as a chain extender in an inert non-aqueous dispersion medium such as an aliphatic hydrocarbon under strong stirring. (See, for example, US Pat. No. 3,872,049,
No. 3,917,741 and No. 3,933,759).

In the above-mentioned production method, in the case of a raw material which is insoluble in a non-aqueous dispersion medium at room temperature even if it is insoluble in a non-aqueous dispersion medium, the raw material is heated to a temperature lower than the boiling point of the non-aqueous dispersion medium in order to maintain a dispersed state and promote the reaction smoothly. Melting or dissolving in a non-aqueous dispersion medium in an organic solvent that is insoluble in the solvent, and then mixing the prepolymer and the organic diamine is used. Collision reactions take place exclusively.

In these methods, since the reaction rate between an isocyanate group and an amino group is very high, an urethane prepolymer having isocyanate groups at both ends and an organic diamine component are once mixed uniformly, and then inert inert water It is considered that this method is unavoidable because the reaction is difficult when dispersed in a medium due to an increase in viscosity due to the dispersion.

[0006]

However, when the collision reaction between a urethane prepolymer droplet having isocyanate groups at both ends and an organic diamine component droplet is microscopically observed, the shapes of both component droplets are never uniform. is not. For example,
When both component droplets of different sizes collide and react,
Also NCO / NH ₂ equivalent ratio of the whole of the two components is constant, the necessarily polyurethane urea in the droplets to produce colliding NCO / NH ₂ equivalent ratio of the entire all NCO /
It is believed that the majority of polyurethane urea will not be the same as the NH ₂ equivalent ratio, but rather will have a different NCO / NH ₂ equivalent ratio, taking into account multiple collisions. This means that the molecular weight of each of the polyurethane urea particles finally formed is all different, and if all the product particles are melted together after separation, the NCO as a whole in a homogeneous solution reaction / NH ₂
It is a natural result that the difference in melt viscosity (due to the difference in molecular weight distribution) from polyurethane / urea obtained while maintaining the NCO / NH ₂ equivalent ratio almost the same as the equivalent ratio is a natural result.

[0007] This is the same as in the case of the polyurethane-urea non-aqueous dispersion, except that the produced particle diameter is smaller, and the melt viscosity of the polymer film obtained by removing the dispersion medium from the final dispersion. It is fully expected that the difference in melt viscosity between polyurethane and urea obtained by maintaining the same NCO / NH ₂ equivalent ratio as the overall NCO / NH ₂ equivalent ratio in a homogeneous solution reaction is large. That is, in the conventional method for producing a polyurethane / urea powder, only a polymer having an extremely wide molecular weight distribution can be obtained, and it is difficult to control the molecular weight. In addition, the reproducibility of the reaction itself is very poor. It seems that similar behavior is observed in the polyurethane-urea non-aqueous dispersion obtained in (1).

An object of the present invention is to provide a method for producing a polyurethane / urea non-aqueous dispersion having a very narrow molecular weight distribution and easy molecular weight control.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to efficiently obtain a non-aqueous polyurethane / urea dispersion having a controlled molecular weight, and have reached the present invention.

That is, the present invention provides: 1) a urethane prepolymer having isocyanate groups at both ends and an organic diamine are instantaneously mixed, and then this mixture is added to a non-aqueous inert solvent insoluble in the mixture; Step of instantaneously dispersing 2) 1)
A step of further dispersing the dispersion produced in the above in a dispersion device,
3) A method for producing a polyurethane-urea non-aqueous dispersion, comprising a step of reacting the dispersion produced in 2) in a finishing tank. Further, the instantaneous mixing of the urethane prepolymer and the organic diamine and the instantaneous dispersion of the mixture in a non-aqueous inert solvent are performed by two or more motionless pipe mixers connected in series. A method for producing a polyurethane / urea powder, characterized by containing a functional amine.

The urethane prepolymer having isocyanate groups at both ends used in the present invention may be a high molecular weight polyol (molecular weight: about 400 to about 6000) alone or a low molecular weight polyol (molecular weight: less than 400). The mixture is obtained by reacting an organic diisocyanate having an NCO equivalent greater than that of the OH component.

The polyol compound preferably has two OH groups, but a limited amount of a compound having a high functionality can also be used. In this case, however, care must often be taken to include some of the monofunctional reactants so that the urethane prepolymer produced retains its thermoplasticity.

Examples of high molecular weight polyols include hydroxy-terminated polyesters, polycarbonates, polyester carbonates, polyethers, polyether carbonates.
And polyester amide. Polyester, polycarbonate and polyether are preferred.

[0014] Suitable polyester polyols contain the reaction product of a dihydric alcohol and a dibasic carboxylic acid. Instead of the free dicarboxylic acids, the corresponding anhydrides or diesters of lower alcohols or mixtures thereof can also be used for the preparation of the polyesters.

The dibasic carboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and can be unsaturated or substituted, for example, by halogen atoms. Examples of these carboxylic acids include, but are not limited to, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimetic acid, phthalic anhydride, tetrahydrophthalic anhydride, anhydride Hexahydrophthalic acid, tetrahydroisophthalic anhydride, hexahydroisophthalic anhydride, endmethylene tetrahydrophthalic anhydride, glutaric anhydride,
Contains maleic anhydride, maleic acid, fumaric acid, dimer fatty acids such as oleic acid, dimethyl terephthalate and mixed terephthalates.

Suitable divalent alcohols include, but are not limited to, ethylene glycol, 1,3- and 1,2.
-Propylene glycol, 1,4- and 1,3- and 2,3-butylene glycol, 1,6-hexane glycol, 1,8-octanediol, neopentyl glycol, cyclohexanediol Methanol, 1,4-bis-
(Hydroxymethyl) -cyclohexane, 2-methyl-
1,3-propanediol, 2,2,4-trimethyl-
1,3-pentaneddiol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol And the like.

[0017] These polyester polyols can also have a portion of the carboxy terminal groups. For example, ε-
Lactones such as caprolactone, or polyesters of hydroxycarboxylic acids such as ε-hydroxycaproic acid can also be used.

Further, the polycarbonate having a hydroxy group is, for example, 1,3-propanediol, 1,4-propanediol.
Diols such as butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol and / or polytetramethylene glycol and phosgene, diallyl carbonate (for example, Diphenyl carbonate) or cyclic carbonate
And products obtained from the reaction with propylene carbonate (for example, propylene carbonate).

Suitable polyether polyols include:
The reaction product of a starting compound having a reactive hydrogen atom with an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, or a mixture of these alkylene oxides is exemplified.

Starting compounds having a reactive hydrogen atom include water, bisphenol A and polyester polyols.
The divalent alcohols described above for the production of alcohols.
The organic diisocyanate has the formula: R (NCO)
₂ is a diisocyanate represented by the formula (wherein R is any divalent organic group). Examples thereof include, but are not limited to, tetramethylene diisocyanate, 1,6-
Hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,3- and 1,4-
Diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (=
Isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (= hydrogenated MDI), 2- and 4-isocyanatocyclohexyl-2'-isocyanatocyclohexylmethane, 1,3- and 1,4 -Screw-
(Isocyanatomethyl) -cyclohexane, bis- (4
-Isocyanato-3-methylcyclohexyl) methane,
1,3- and 1,4-tetramethylxylidene diisocyanate, 2,4- and / or 2,6-diisocyanatotoluene, 2,2'-, 2,4'- and / or 4,
4'-diisocyanatodiphenylmethane, 1,5-naphthalene diisocyanate, p- and m-phenylene diisocyanate, dimeryl diisocyanate, xylylene diisocyanate, diphenyl-4, 4'-diisocyanate and the like.

The production conditions of the urethane prepolymer are not particularly limited, but are usually 0 to 120 ° C., preferably 40 to 100 ° C., without a solvent or in the presence of a suitable organic solvent, without a catalyst or It is obtained by stirring and mixing using a known urethanation catalyst. The NCO / OH equivalent ratio is
Usually, 1.01 to 3.0, preferably 1.05 to 2.0 is used.

On the other hand, the organic diamine used in the present invention is not particularly limited. For example, diaminoethane, 1,2- or 1,3-diaminopropane, 1,2-diamine
Or 1,3- or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N'-bis- (2-aminoethyl) piperazine, 1-amino-3- Aminomethyl-3,5,5-trimethyl-cyclohexane (= isophoronediamine), bis- (4-aminocyclohexyl) methane, bis- (4
-Amino-3-butylcyclohexyl) methane, 1,2
-, 1,3- and 1,4-diaminocyclohexane,
There are 1,3-diaminopropane and the like, but hydrazine, amino acid hydrazide, hydrazide of semi-carbazidecarboxylic acid, bis (hydrazide), bis (semicarbazide) and the like can also be used.

Further, in the present invention, it is preferable to use a monofunctional amine in combination in order to easily control the molecular weight of the finally obtained polyurethane / urea. Monofunctional amines include, but are not limited to, diisopropylamine, di-n-butylamine, di-sec-butylamine, di-2-ethylhexylamine, di-n-octylamine, N-methyl-hexylamine, and the like. Piperidine, piperidine derivatives such as piperidine, pipecoline isomers (2-, 3- or 4-), and lupetidine isomers (2,4-, 2,6- or 3,5-); dibenzylamine;
Aromatic amines such as N-methylbenzylamine, phenylcyclohexylamine and 4-benzylpiperidine;
And pyrrolidine. However, usually, those having extremely high volatility or strong odor at the reaction temperature should be avoided.

The amount used naturally varies depending on the target molecular weight, but usually, the amount of N in the urethane prepolymer is
About 0.1 to 20 equivalent%, preferably 1 equivalent to CO equivalent
% To 10 equivalent% are used.

Next, as to whether or not an organic solvent is used in the production of the urethane prepolymer, as a rule, when the prepolymer and the organic diamine are mixed instantaneously, they are completely mixed with the organic diamine component or its solution. The determination is made based on whether a liquid having the obtained viscosity can be obtained, whether compatibility with the organic diamine component is sufficient, or whether the compound is insoluble in a non-aqueous inert solvent. For example, when the prepolymer is in a solid state at the time of the above-mentioned instantaneous mixing, even if the prepolymer is in a liquid state, it has a high viscosity, so that the feed pump of the motionless pipe mixer is overloaded or an organic diamine component. Alternatively, when it is difficult to completely mix the solution with the solution, when the compatibility with the organic diamine component is poor, or when the solution is soluble in a non-aqueous inert solvent, an organic solvent should be used.

On the other hand, when the organic diamine component is solid under the conditions used in the motionless pipe mixer, it is used in a feed pump of the motionless pipe mixer because it has a high viscosity even in a liquid state. An organic solvent is used when overload is applied or when it is difficult to completely mix the urethane prepolymer alone or its solution, when the compatibility with the urethane prepolymer is poor, or when the urethane prepolymer is soluble in a non-aqueous inert solvent. Should.

However, when an organic solvent is used, the amount of the organic solvent should be minimized since it is eventually removed. The organic solvent of the urethane prepolymer and the organic solvent of the organic diamine may be the same or different, but essentially contains no active hydrogen capable of reacting with an isocyanate group and dissolves the prepolymer or the organic diamine. There is no particular limitation as long as it is incompatible with the non-aqueous inert solvent. In some cases, only as an organic solvent for the organic diamine component, alcohol-
It is also possible to use a toluene-based solvent.

The non-aqueous inert solvent is usually an aliphatic saturated hydrocarbon solvent such as a straight-chain and / or isomer such as pentane, hexane, cyclohexane, heptane, octane, nonane and decane, or a mixture thereof. Are preferably used. Examples of the organic solvent which is insoluble therein include, for example, a highly polar nitrile solvent (acetonitrile, propionitrile, etc.), an amide solvent (dimethylformamide, diethylformamide, dimethylacetamide, etc.), Sulfoxide-based solvents (dimethylsulfoxide, diethylsulfoxide, etc.), N-alkylpyrrolidone-based solvents (N-methylpyrrolidone, N-ethylpyrrolidone, etc.) alone or a mixture of two or more thereof are preferably used. Any solvent may be mixed with the organic solvent as long as it does not affect the solubility of the urethane prepolymer or the organic diamine and does not adversely affect the insolubility with the non-aqueous inert solvent.

The amount of the non-aqueous inert solvent used is not particularly limited. However, in consideration of the reaction heat removal and the yield (productivity) of the produced polymer, the total solid content of the prepolymer and the amine component is Usually, 0.25 to 9 times, preferably 0.4
~ 3 times is used.

Next, as a device for instantly mixing the urethane prepolymer and the organic diamine in the present invention and dispersing the same in a non-aqueous inert solvent, a motionless pipe mixer is used. It is preferable to use more than one in series. The mixing and dispersing time is determined by the internal volume of the pipe mixer and the discharge amount of the metering feed pump. In the present invention, the urethane prepolymer component and the diamine component are uniformly mixed while the reaction between the isocyanate group and the amino group in the prepolymer hardly progresses.
In order to disperse in a non-aqueous inert solvent, each mixing time should be within 1 second, preferably within 0.5 seconds.

The motionless pipe mixer of the present invention is not limited, but examples of commercially available products include a static mixer (manufactured by Noritake Co.) and a T.M. K. ROS
SLPD mixer (manufactured by Tokushu Kika), Sulzer mixer (manufactured by Sumitomo Machinery) and the like. However, at the time of connecting and disposing, first, after uniform mixing in the first pipe mixer, a non-aqueous inert solvent can be supplied immediately before performing preliminary dispersion.
Appropriate piping and metering feed pumps need to be installed. Further, in some cases, a device equipped with a suitable heating or heat removal jacket or the like is used.

The dispersion stabilizer is usually dissolved in the non-aqueous inert solvent. The dispersion stabilizer is not particularly limited as long as it can be dissolved in a non-aqueous inert solvent and can stably disperse a mixture droplet of a urethane prepolymer and an organic diamine component. Is used. Examples thereof include N-vinylpyrrolidone / C4-4
20 α-olefin copolymer, polyoxyalkylene / polydimethylsiloxane graft or block copolymer, polylactone / (meth) acrylic acid long chain alkyl ester / vinyl monomer block or graft copolymer, long chain alkyl isocyanate And / or a copolymer of a urethane polymer of hydroxyalkyl (meth) acrylate or a monomer thereof and a partially reacted product of a (meth) acrylic acid derivative and two functional group-containing polymer compounds.

The amount used is generally about 0.1 to 20% by weight based on the mixture (solid content) of the urethane prepolymer and the organic diamine component. Further, the polymerization (ureaization) reaction temperature is usually 80 ° C. or lower, preferably 0 to 70 ° C., and in principle, these temperature ranges are from the instant mixing to the completion of the polymerization reaction. Temperature is adjusted as follows.

A pipeline homogenizer is used as a homogenizer used for further dispersing the dispersion produced by mixing and dispersing with a motionless pipe mixer. A pipeline homogenizer is a device used to disperse or emulsify a continuous liquid stream with strong mechanical force. This apparatus is not particularly limited, but needs to have a variable adjusting mechanism that can obtain a desired dispersed droplet diameter when the flow rate is changed in order to obtain a target particle diameter. As commercially available products, for example, T.I. K. A line homogenizer such as a homomixer (manufactured by Tokushu Kika), a colloid mill such as a mantongo-phosphorus colloid mill (mantongo-rin), and a microfluidizer.
(Manufactured by Microfluidizer) and Nanomizer (manufactured by Cosmo Keiso).

The finishing tank of the present invention is not limited, but preferably has a stirring device. For example, a reactor equipped with a high-speed disperser such as a homogenizer or a high-speed disperser such as a disperser in combination with a stirring blade having excellent dispersion performance, a high-speed specification ring cone stirrer, or the like, is capable of controlling the temperature by a heating or cooling jacket. Is usually used because it can be easily carried out. Further, under the reaction conditions in which the polymerization (ureaization) reaction rate is very high, a reaction vessel equipped with a usual ring cone stirrer can be applied.

Instead of this finishing tank, a method of completing the polymerization reaction by further connecting a motionless pipe mixer may be applied. However, since the reaction speed is high, the reaction is carried out during passage through the pipe. There is a possibility that the dispersion effect may be reduced due to the increase in the viscosity of the liquid droplets, and it is necessary to have a delicate dispersion performance and arrangement of mixers in consideration of the final polymer particle diameter and the reaction completion time.

As a method for removing the organic solvent from the polymer dispersion after the completion of the reaction, if necessary,
For example, in a reaction vessel equipped with a heating jacket and a condenser,
A method of removing by distillation under normal pressure or reduced pressure while stirring is general. At this time, it is particularly preferred that the organic solvent and the non-aqueous inert solvent are azeotropic or the difference in boiling point between the two is at least 20 ° C., since distillation is particularly easy.

According to the method of the present invention, the amount of the dispersion stabilizer dissolved in the non-aqueous inert solvent, the weight ratio of the mixture droplet of the prepolymer and the organic diamine component to the non-aqueous inert solvent, the dispersion device According to the above operating conditions and other conditions, it is possible to obtain particles in a wide range from fine particles having an average particle diameter of about 0.01 μm to coarse particles having a mean particle diameter of about 10 μm.
The molecular weight distribution of the produced polymer is almost the same as that obtained by the solution reaction, and both the urethane prepolymer droplet and the organic diamine which have been conventionally used for obtaining polyurethane urea powder are non-aqueous non-aqueous. Reaction in the case of insolubility in an active solvent, collision reaction between prepolymer droplets in which the prepolymer is soluble and an organic solvent is applied and organic diamine droplets, and prepolymers applicable in the case where the organic diamine is soluble in an inert solvent A narrower distribution is obtained compared to the molecular weight distribution of the polymer obtained by the droplet interface reaction.

In the method for producing the polyurethane / urea non-aqueous dispersion of the present invention, additives such as a coloring agent, an antioxidant, a foaming agent, an antifoaming agent, a filler and an anti-king agent may be used, if necessary. Or a polyacrylic resin, a vinyl chloride resin, a vinyl acetate resin, an ethylene / vinyl acetate copolymer resin, or the like. The timing of adding these additives may be before, during or after the production of the polyurethane-urea non-aqueous dispersion.

[0040]

Next, embodiments of the present invention will be described with reference to specific examples, but the present invention is not limited to these examples. The parts and percentages in the examples relate to weight unless otherwise specified.

<Example 1> (1) Production of urethane prepolymer 3-methylpentanedioyl adipate having a molecular weight of 1,000
In a reaction flask, 400 parts of isophorone diisocyanate was charged, and the mixture was heated to 60 ° C. with stirring. Next, 300 ppm of dibutyltin dilaurate (to the total amount charged) was added, and the temperature was raised to 70 ° C. using the heat generated. Thereafter, the mixture was kept at 70 ° C. for further 3 hours to obtain an NCO-terminated urethane prepolymer. (NCO% = 4.3) (2) Preparation of organic diamine solution 52.9 parts of 4,4'-diaminodicyclohexylmethane, 5.1 parts of di-n-butylamine, and 1.3 parts of ethanol were further mixed with acetonitrile. The organic diamine solution was prepared by dissolving in 39.5 parts.

(3) Mixing, dispersing and finishing steps of the prepolymer and the organic diamine component The prepolymer obtained in the above (1) is kept at 40 ° C.
On the other hand, the organic diamine solution obtained in (2) is cooled at room temperature (about 2
(0 ° C.). Also, each flow rate is (1) /
(2) = The flow rates of the respective metering supply pumps so that 5.577 / 1.00 (wt ratio) and the residence time of the first unit of the serially connected motionless pipe mixer is 0.2 seconds. It was set.

Next, the second motionless pipe mixer is connected to the first pipe mixer and the n-octane solvent line via a three-way cock, and the n-octane / (prepolymer) is connected. + Solid content in the organic diamine mixture) = 1/1 (wt ratio) and the flow rate of the metering pump of the n-octane tank was set such that the residence time in the second pipe mixer was 0.5 seconds. . In addition, n-
In octane, 10% by weight of Antalon V-
216 (copolymer of N-vinylpyrrolidone / hexadecene-1, manufactured by GAF) is dissolved in advance.

Further, a pipeline homogenizer is connected to the outlet of the second pipe mixer, and the internal flow rate of the pre-dispersed liquid from the second pipe mixer is increased at a predetermined turbine rotation speed. The gap between the passing slits was adjusted to a minimum. The outlet is connected to a jacketed finishing tank having a special stirring blade excellent in dispersing ability and a high-speed ring cone stirrer.

After completing the above set, mixing, dispersion and finishing operations were performed as follows. (I) The quantitative supply pumps for the prepolymer and the organic diamine solution were each started, and 0.2 seconds later, the quantitative supply pumps for the n-octane solvent were started. (II) Further, 0.5 seconds later, the pipeline homogenizer was started, and the high-speed ring cone stirrer in the finishing tank, which was previously set to jacket heating at 50 ° C., was started. (III) Thereafter, the steady operation was continued until the raw material prepolymer and organic diamine solution disappeared, and the temperature in the finishing tank was kept at 50 ° C. for another hour after the raw material was consumed.
(4) Desolvation from Polymer Produced The temperature of the finishing tank was raised to 70 ° C., and acetonitrile was distilled off under reduced pressure to obtain a final polymer dispersion.

The particle size of the resulting polymer was 0.5 to 5 μm, and the melting point of the film polymer was 147 to 157 ° C. The molecular weight distribution is Mw (weight average molecular weight)
/ Mn (number average molecular weight) = 4.5. The polymer obtained by the solution polymerization method using the same raw materials and the same composition ratio was used.
Had Mw / Mn = 4.4 and had almost the same polymer-molecular weight distribution.

<Example 2> In Example 1, the molecular weight was 1,000.
NCO-terminated urethane prepolymer was prepared in the same manner as in Example 1 except that 800 parts of polycaprolactone diol having a molecular weight of 2000 was used in place of 3-methylpentaneditol adipate, and 317 parts of acetonitrile were used in combination. A solution was obtained. (Apparent NCO% = 1.85) Next, using the same organic diamine solution as in Example 1, prepolymer solution flow rate / organic diamine solution flow rate = 12.8.
Polymerization was completed in the finishing tank under the same setting conditions as in Example 1 except that the ratio was 34 / 1.00 (wt ratio).

Thereafter, a final polymer dispersion was obtained in exactly the same manner as in Example 1. The resulting polymer has a particle size of 0.3-5 μm and a melting point of 151-162.
° C. Its molecular weight distribution is Mw / Mn = 4.7.
Met. The polymer obtained by the solution polymerization method using the same raw materials and the same composition ratio had Mw / Mn = 4.5, and had substantially the same polymer molecular weight distribution.

<Examples 3 to 7> Polyurethane / urea non-aqueous dispersions were produced in the same manner as in Example 1 by using urethane prepolymers and organic diamines as shown in Tables 1 and 2.

[0050]

[Table 1] IPDI; isophorone diisocyanate H12MDI; 4,4'-dicyclohexylmethane diisocyanate IPDA; isophorone diamine

[0051]

[Table 2] * 1: In all examples, 5.1 parts of di-n-butylamine and 1.3 parts of ethanol were added.

H12 MDA: 4,4'-dicyclohexylmethanediamine Polyurethane-urea non-aqueous dispersion has a particle diameter, melting point and molecular weight distribution as shown in Table 3.

[0053]

[Table 3] * 2: Polymer obtained by solution polymerization with the same raw materials and composition ratio. <Example 8> In Example 1, no di-n-butylamine was used at the time of preparing an organic diamine solution, and ethanol was used instead. Of the polymer dispersion obtained in the same manner as in Example 1 except that the amount of acetonitrile was changed to 3.1 parts and the amount of acetonitrile was changed to 37.3 parts. 5 μm, and the melting point is 156-16
6 ° C. The molecular weight distribution is Mw / Mn = 7.
2 and a distribution wider than that obtained in Example 1.

<Comparative Example 1>
A urethane prepolymer and an organic diamine solution were prepared respectively. Thereafter, the operation was performed as follows. (1) Using a motionless pipe mixer and a pipeline homogenizer, first, supply only a urethane prepolymer solution, and n such that prepolymer solid / n-octane = 1/1 (wt ratio). -After premixing with octane, the internal slit interval of the pipeline homogenizer was adjusted to disperse the droplets so that the droplet diameter became 0.5 to 5 µm, and the mixture was supplied to the finishing tank that had been stirred in the same manner as in Example 2. . (2) Next, while continuing to stir the finishing tank, the outlet of the pipeline homogenizer is separated from the finishing tank, and n-octane is supplied into the motionless pipe mixer to pass through the pipeline homogenizer. And the inside was thoroughly washed. (3) After connecting the outlet of the pipeline homogenizer to the finishing tank again, this time, only the organic diamine solution was supplied using the motionless pipe mixer and the pipeline homogenizer. n
-After pre-mixing with n-octane so that octane = 1/1 (wt ratio), the internal slit interval of the pipeline homogenizer was adjusted and dispersed so that the droplet diameter became 0.5 to 5 μm. The mixture was supplied to a finishing tank being stirred. (4) After maintaining the internal temperature of the finishing tank at 50 ° C. and stirring for 1 hour,
The temperature was raised to 70 ° C. After that, a final polymer dispersion was obtained in exactly the same manner as in Example 2.

The particle size of the produced polymer is 0.8 to 10 μm.
And its melting point was as wide as 141-165 ° C. The molecular weight distribution was as high as Mw / Mn = 9.2.

Comparative Example 2 A urethane prepolymer was produced in exactly the same manner as in Example 3. Next, the operation was performed as follows. (1) Using a motionless pipe mixer and a pipeline homogenizer, only urethane prepolymer is supplied and prepolymer solid / n-octane = 1/1
(Preliminary mixing with n-octane so as to obtain (wt ratio), and then dispersing the droplets so that the droplet diameter becomes 0.2 to 3 μm by adjusting the internal slit interval of the pipeline homogenizer. Was supplied to the finishing tank which had been stirred. (2) Next, while the stirring of the finishing tank is continued, the outlet of the pipeline homogenizer is separated from the finishing tank, and n-octane is supplied into the motionless pipe mixer and passed through the pipeline homogenizer. The inside was thoroughly washed. (3) After connecting the outlet of the pipeline homogenizer to the finishing tank again, an organic diamine mixture was prepared with the same composition as in Example 3 except that acetonitrile was not used, and dissolved in n-octane of the same weight. And it is
The mixture was supplied to a finishing tank under stirring through a pipeless homogenizer having a maximum internal slit interval with a shockless pipe mixer. (4) After maintaining the internal temperature of the finishing tank at 50 ° C. and stirring for 1 hour,
Raise the temperature to 70 ° C. After that, a final polymer dispersion was obtained in exactly the same manner as in Example 2. The particle size of the produced polymer was 0.15 to 2.8 µm, and its melting point was a wide range of 134 to 171 ° C. The molecular weight distribution was as high as Mw / Mn = 12.3.

[0057]

The polyurethane-urea non-aqueous dispersion obtained according to the present invention can be used for a conventional non-aqueous inert dispersion medium in which a collision reaction of each droplet of a urethane prepolymer and an organic diamine component, Compared with the polymer dispersion obtained by the interfacial reaction between the former droplet and the organic diamine component dissolved in the dispersion medium, the molecular weight distribution is narrower and the molecular weight can be easily controlled. From this, the polymer obtained in the present invention has a shear viscosity gradient with respect to temperature.
Paints and cores
It is useful as a vehicle for binding and as an adhesive.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a mixing, dispersing, finishing tank, and desolvating apparatus for producing a polyurethane / urea nonaqueous dispersion used in one embodiment of the method of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 urethane prepolymer reactor 2 organic diamine melting (dissolving) tank 3 non-aqueous inert dispersion medium tank 4 metering supply pump 5, 6 motionless pipe mixer 7 pipeline homogenizer 8 finishing tank 9 storage tank

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08G 18/00-18/87

Claims (8)

(57) [Claims] 1. A method for producing a polyurethane / urea non-aqueous dispersion comprising the following steps 1) to 3). 1) A step of instantaneously mixing a urethane prepolymer having isocyanate groups at both ends and an organic diamine, and then instantaneously dispersing the mixture in a non-aqueous inert solvent insoluble in the mixture 2). Step of further dispersing the dispersion produced in 1) by a dispersing device 3) Step of reacting the dispersion produced in 2) in a finishing tank 2. The polyurethane according to claim 1, wherein the instantaneous mixing of the urethane prepolymer and the organic diamine and the instantaneous dispersion of the mixture in a non-aqueous inert solvent are performed by a motionless pipe mixer. A method for producing a urea non-aqueous dispersion. 3. The method for producing a polyurethane-urea non-aqueous dispersion according to claim 2, wherein two or more motionless pipe mixers are connected in series. 4. The method for producing a non-aqueous polyurethane urea dispersion according to claim 1, wherein the organic diamine contains a monofunctional amine. 5. The polyurethane / urea non-aqueous disperser according to claim 1, wherein an organic solvent insoluble in the urethane prepolymer and the organic diamine is used when the urethane prepolymer and the organic diamine are instantaneously mixed. -John's manufacturing method. 6. The polyurethane / urea non-aqueous dispersion according to claim 1, wherein the finishing tank has a stirring device.
John's manufacturing method. 7. The polyurethane / urea non-aqueous solution according to claim 1, wherein the organic solvent and the non-aqueous inert solvent are azeotropically removed when removing the organic solvent from the reaction-completed polymer dispersion. Dispersion manufacturing method. 8. The method according to claim 1, wherein the difference in boiling point between the organic solvent and the non-aqueous inert solvent is at least 20 ° C. when the organic solvent is removed from the polymer dispersion after the completion of the reaction. A method for producing a polyurethane-urea non-aqueous dispersion of the invention.