JPH0616758A - Production of non-aqueous dispersion of polyurethane-urea - Google Patents

Abstract

PURPOSE:To obtain a non-aqueous dispersion of polyurethane.urea having narrow molecular weight distribution and useful for paint, etc., without using a dispersion stabilizer by polymerizing a monomer using a mercapto-containing polyol as an initiator and reacting the polymer with a polyisocyanate and a polyamine in a non-aqueous dispersion medium. CONSTITUTION:(A) A compound having 4-20C alkyl group and containing polymerizable unsaturated bond is polymerized in the presence of (B) a polyol consisting of a mercaptan compound having two hydroxyl groups as an initiator to obtain a polyol. A polyol component containing 1-50wt.% of the above polyol (based on the total polyol) is made to react with a polyisocyanate in a reactor 1, the obtained urethane prepolymer having NCO groups on both terminals is mixed with a polyamine supplied from a polyamine dissolution tank 2 using a motionless pipe mixer 5, a non-aqueous inert dispersion medium is supplied from a tank 3 to the mixture to effect the reaction of the mixture in the medium and finally the reaction product is passed through a pipe-line homogenizer 7 and transferred to a finishing tank 8 to obtain the non-aqueous dispersion of polyurethane-urea.

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 Conventionally, as a technique for producing a non-aqueous dispersion of a polyurethane / urea resin, one using a dispersion stabilizer in a non-aqueous dispersion medium is known.

As a necessary condition for the dispersion stabilizer, the constituent components are (1) solvated in a non-aqueous inert medium, but essentially non-solvated with the soft segment of the polyurethane-urea resin. The component and (2) the component that is non-solvent in the non-aqueous inert medium but is compatible with the soft segment of the polyurethane-urea resin are in proper balance. Examples thereof include (meth) acrylic acid long chain alkyl ester / (meth) acrylic acid methyl ester, (meth) acrylic acid dimethylaminoethyl ester or (meth) acrylic acid glycidyl copolymer or block polymer; poly (meta). ) Graft polymers of methyl (meth) acrylate or glycidyl (meth) acrylate onto acrylic acid long chain alkyl ester; N
-Vinylpyrrolidone / C4 to C20 α-olefin copolymers; polyoxyalkylene polydimethylsiloxane graft or block copolymers; polylactone /
(Meth) acrylic acid long-chain alkyl ester / block or graft copolymer with vinyl monomer; long-chain alkyl isocyanate / hydroxyalkyl (meth) acrylic acid ester urethane polymer or its monomer and (meth) There are copolymers of an acrylic acid derivative and a partial reaction product of two functional group-containing polymer compounds.

This dispersion stabilizer affects the droplet diameter of the polyurethane / urea resin raw material or urethane prepolymer to be dispersed alone or a solution thereof, and the amount of the dispersion stabilizer finally determines the size of the dispersed polymer. Change. The amount is usually about 0.1 to 20 for polyurethane / urea resin.
Weight percent is used.

On the other hand, conventionally, the main polymer particle size is 10
A method for producing a polyurethane-urea non-aqueous dispersion which is difficult to separate particles because it is smaller than μm and can be processed as it is is already known (US Pat. No. 47).
83502, EP 318939). The main polymer particle diameter for obtaining polyurethane / urea powder is 10
A method for producing a polyurethane-urea non-aqueous dispersion in which particles larger than μm are dispersed is also known (for example, US Pat. Nos. 3,872,049, 3,917,741, and 39,337).
59). Both of these production methods generally use N 2 at both ends in an inert non-aqueous dispersion medium such as an aliphatic hydrocarbon.
A method in which a urethane prepolymer having a CO group and an organic diamine component as a chain extender are allowed to react in a droplet state under strong agitation to cause a reaction is exclusively used. Since the reaction rate between the NCO group and the amino group is very fast, the urethane prepolymer having both NCO groups at both ends is once uniformly mixed with the organic diamine component and then dispersed in an inert non-aqueous medium. However, since a rapid reaction occurs and the reaction is difficult due to the increase in viscosity caused by it, it seems that this method is unavoidably taken.

[0006]

However, as long as the dispersion stabilizer is used, when the final polymer-non-aqueous dispersion has a fine dispersion particle size and is post-processed in the form of the non-aqueous dispersion, the de-dispersion is performed. Since the dispersion stabilizer dissolved in the dispersion medium remains in the processed product as it is when the medium is processed, the physical properties of the processed product (particularly, solvent resistance) are adversely affected. Also, when the final polymer-non-aqueous dispersion can be separated from the polymer particles by centrifugal filtration or the like and is further processed in the form of polymer particles,
In order to eliminate adverse effects on the physical properties of processed products, a step of washing the dispersion stabilizer adhering to the polymer particles is necessary, and a washing solvent is essential.

That is, as long as the amount of the dispersion stabilizer does not impair the stability during the production of the polymer non-aqueous dispersion, the smaller the amount, the less the adverse effect on the physical properties of the processed product can be reduced.
It is preferable because the washing process can be simplified.

On the other hand, a polyurethane / urea non-aqueous dispersion was obtained.
Urethane prepolymer liquid having NCO groups at both ends for
Microscopic observation of collision reaction between droplet and organic diamine component droplet
By observation, the shapes of both component droplets are never uniform. An example
For example, when both component droplets of different sizes collide and react
Includes NCO / NH as a whole of both components₂The equivalent ratio is one
Polyurethane / urea that is always produced by collision
NCO / NH in the droplet ₂The equivalent ratio is NC as a whole
O / NH₂It will not be the same as the equivalence ratio, but rather
NCO / NH different from the whole considering the collision₂Equivalent
Most polyurethane / ureas with a certain ratio are produced
Considered to be minutes. This will eventually generate
The molecular weights of polyurethane and urea particles are all different.
Means that all the produced particles are removed from the dispersion medium or filtered.
When melted together after the separation, the whole solution is a uniform solution reaction.
NCO / NH as₂NCO / N almost equal to the equivalence ratio
H₂With polyurethane / urea obtained by maintaining the equivalence ratio
Large difference in melt viscosity (due to difference in molecular weight distribution)
This is a natural result. That is, conventional polyurethane / urea
In the method for producing an aqueous dispersion, a polymer having an extremely wide molecular weight distribution is used.
The reaction itself
The reproducibility of was also extremely poor.

The present invention provides a method for producing a polyurethane-urea non-aqueous dispersion which has an extremely narrow molecular weight distribution, is easy to control the molecular weight, and does not use a dispersion stabilizer in the dispersion medium.

[0010]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.

That is, the present invention is a method for producing a polyurethane / urea non-aqueous dispersion by reacting polyol, polyisocyanate and polyamine in a non-aqueous dispersion medium. Using a polyol containing a polyol (C) obtained by polymerizing a compound (B) having a C4 to C20 alkyl group-containing polymerizable unsaturated bond using the mercaptan compound (A) as an initiator Polyurethane characterized by
It is a method for producing a urea non-aqueous dispersion.

The present invention further includes 1) a urethane prepolymer having isocyanate groups at both ends, which is obtained by reacting a polyol containing a polyol (C) with a polyisocyanate, and, if necessary, a polyamine. Using an organic solvent that is insoluble in the dispersion medium, two or more models connected in series are used.
First, a dispersionless mixer is used to instantaneously mix the mixture, and the mixture is instantaneously dispersed in a non-aqueous inert solvent insoluble in the mixture. The step of further dispersing so as to obtain the particle size of 3), the step of completing the reaction of the dispersion produced in 2) in a finishing tank equipped with a stirrer, and removing the organic solvent as necessary. Polyurethane / urea non-water characterized in that the organic diamine component used therein contains a monofunctional amine, and when the organic solvent is used, it azeotropically distills with a non-aqueous inert solvent or has a boiling point difference of at least 20 ° C. It is a manufacturing method of a dispersion.

As the urethane prepolymer having isocyanate groups at both ends used in the present invention, a polymer polyol (molecular weight of about 400 to about 6000) containing a polyol (C) alone or a low molecular weight thereof. It is obtained by reacting a mixture of polyols (molecular weight less than 400) with an organic diisocyanate having an NCO equivalent higher than that of the OH component.

As the OH component-containing compound, two OH
It is preferred to have groups, but it is also possible to use compounds with a limited amount of high functionality. However, in this case, it is often necessary to include a portion of the monofunctional reactant to ensure that the urethane prepolymer produced retains its thermoplasticity.

Examples of polymeric polyols include hydroxy terminated polyesters, polycarbonates, polyester carbonates, polyethers, polyether carbonates.
Polyester, polyester amide, etc., but polyester, polycarbonate and polyether are preferred.

Suitable polyester polyols contain the reaction product of a dihydric alcohol and a dibasic carboxylic acid. Instead of free dicarboxylic acids, the corresponding anhydrides or diesters of lower alcohols or mixtures thereof can also be used for the production of polyesters. The carboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and can be unsaturated or substituted, for example with 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, trimethic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahexahydrate. Hydrophthalic acid, tetrahydroisophthalic anhydride, hexahydroisophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, maleic acid, fumaric acid, dimer
It contains 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, cyclohexane dimethanol, 1,4-bis- (hydroxymethyl) -cyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethyl- 1,3-pentanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, dibutylene glycol, polyethylene glycol
And polypropylene glycol, polytetramethylene glycol and the like. These polyesters can also have some of the carboxy end groups. For example, ε-
Lactones such as caprolactone or hydroxycarboxylic acid polyesters such as e-hydroxycaproic acid can also be used. Further, the polycarbonate having a hydroxy group is, for example, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol.
And diol such as polypropylene, polypropylene glycol and / or polytetramethylene glycol and phosgene, diallyl carbonate (eg diphenyl carbonate) or cyclic carbonate (eg propylene carbonate). -Bonet)
It contains the product obtained from the reaction with.

Suitable polyether polyols are the reaction of starting compounds having reactive hydrogen atoms with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin or mixtures of these alkylene oxides. By a known method.

In the present invention, the polyol (C) component is, for example,

[0020]

[Chemical 1] The structural formula of is shown. Of OH and SH, R _a and R _c are linear or branched divalent alkyl residues having 1 to 10 carbon atoms,
R _b is a linear or branched monovalent alkyl residue having 1 to 10 carbon atoms, R ₁ and R ₂ are H or a linear or branched alkyl group having 1 to 10 carbon atoms, and the same or different. May be.
R ₃ is H or CH ₃ , R is a linear or branched alkyl group having 4 to 20 carbon atoms, X is a linear or branched alkyl group having 4 to 20 carbon atoms, COOR ′ (R ′ Is an arbitrary group which does not contain an active group which reacts with a linear or branched alkyl group having 1 to 20 carbon atoms or an isocyanate group), or an arbitrary group which does not contain an active group which reacts with an isocyanate group, m and n are not 0 at the same time and are 0 or an integer of 1 or more, and the repeating unit of the monoolefin is random,
It may be alternating or block.

Polyol (C) represented by the above structural formula
Is a mercaptan compound containing two OH groups having a structure such as (HO) ₂ ZSH (Z is the same as in the above structural formula) and a compound having a polymerizable unsaturated bond containing an alkyl group having 4 to 20 carbon atoms. It is obtained by reacting alone or with another compound having a polymerizable unsaturated bond at a temperature of 30 to 250 ° C. in the absence of a solvent or in the presence of a radical generating catalyst in an organic solvent.

The molecular weight is usually 1,000 to 100,0.
The one of the 00th position is used, and particularly 2,000 to 50,000.
0 is preferred. Examples of the mercaptan compound used in the present invention include 3-mercapto-1,2-propanediol and 2-mercapto-1,2-propanedio-.
2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanedio-
2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-
1,3-propanediol and the like can be mentioned.

Examples of the compound having a polymerizable unsaturated bond containing an alkyl group having 4 to 20 carbon atoms include butyl (meth) acrylate, amyl (meth) acrylate,
Octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butyl (methyl) crotonate, amyl (methyl) crotonate, octyl (methyl) crotonate, lauryl (methyl) crotonate, ( Methyl) acid alkyl esters such as stearyl crotonate, 1-butene, 1-hexene, 1-octene, 1
1-olefins such as decene, 1-undecene, 1-hexadecene, 1-octadecene, 1-eicosene, and 3-
Monoolefins such as octene, 4-decene, 5-hexadecene, 7-octadecene, and 10-eicosene can be mentioned.

Examples of other compounds having a polymerizable unsaturated bond include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, methyl (methyl) crotonate, and (methyl) croton. Ethyl acid,
Propyl (methyl) crotonate, ethylene, propylene, 2-butene, acrylonitrile, methacrylonitrile, dimethylaminoethyl (meth) acrylate, vinyl chloride, vinyl bromide, vinyl fluoride, (chloro) ethyl vinyl ether, styrene, Examples thereof include vinyl acetate, vinyl propionate, vinyl stearate, and other monovinyl compounds containing no active hydrogen that react with an isocyanate group.

The amount of the polyol (C) used is not particularly limited, but if it is too small, the self-dispersibility of the polyurethane-urea resin or the urethane prepolymer alone or their solutions in an inert organic medium becomes insufficient. On the other hand, if the amount is too large, the self-dispersibility is improved, but the raw material cost and the polymer are reduced.
It may adversely affect the physical properties. Therefore, normally 1 to 50%, preferably 5 to 30% of the total polyol component is used.

Examples of low molecular weight polyols include the divalent alcohols used to make the polyester polyols described above. The polyisocyanate is a diisocyanate represented by the formula: R (NCO) ₂ (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
G)), bis- (4-isocyanatocyclohexyl) methane (= hydrogenated MDI), 2- and 4-isocyanatocyclohexyl-2′-isocyanatocyclohexylmethane,
1,3- and 1,4-bis- (isocyanatomethyl)-
Cyclohexane, bis- (4-isocyanato-3-methylcyclohexyl) methane, 1,3- and 1,4-tetramethylxylidene diisocyanate, 2,4- and / or
Or 2,6-diisocyanatotoluene, 2,2'-,
2,4'- and / or 4,4'-diisocyanatodiphenylmethane, 1,5-naphthalene diisocyanate,
Examples thereof include p- and m-phenylene diisocyanate, dimeryl diisocyanate, xylylene diisocyanate and diphenyl-4,4'-diisocyanate.

The conditions for producing the urethane prepolymer are not particularly limited, but are usually 0 ° C. to 120 ° C., preferably 40 ° C. to 100 ° C. in the absence of a solvent or in the presence of an organic solvent insoluble in the non-aqueous dispersion solvent. It is obtained by stirring and mixing without a catalyst or using a known urethanization catalyst. Also, NCO
The / OH equivalent ratio is usually 1.01 to 3.0, preferably 1.05 to 2.0.

On the other hand, the polyamine used in the present invention is not limited, but for example, diaminoethane,
1,2- or 1,3-diaminopropane, 1,2- 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, 1,3
-Diaminopropane and the like, but hydrazine, amino acid hydrazide, hydrazide of semi-carbazide carboxylic 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 together in order to facilitate the control of the molecular weight of the finally obtained polyurethane / urea. Although the amount used will naturally vary depending on the target molecular weight, it is usually used in an amount of about 0.1 to 20 equivalent%, preferably 1 to 10 equivalent% based on the NCO equivalent in the urethane prepolymer.

Monofunctional amines include, but are not limited to, diisopropylamine, di-n-butylamine, diamine.
-Dialkylamines such as sec-butylamine, di-2-ethylhexylamine, di-n-octylamine, N-methyl-hexylamine, etc .; piperidine, pipecoline isomers (2-, 3- or 4-), lupetidine isomers (2,4-, 2,6- or 3,5-) and other piperidine derivatives; dibenzylamine, N-methylbenzylamine,
Aromatic ring-containing amines such as phenyl / cyclohexylamine and 4-benzylpiperidine; and pyrrolidine. However, ones that are extremely volatile or have a strong odor at the reaction temperature should usually be avoided.

Next, as to whether or not an organic solvent is used in the production of the urethane prepolymer, the prepolymer can be thoroughly mixed with the organic diamine component or the solution thereof under the conditions of using the motionless pipe mixer. It is determined by whether it can be made into a liquid with a viscosity, whether it has sufficient compatibility with the organic diamine component, or whether it is insoluble in a non-aqueous inert solvent. For example, if the prepolymer is a solid under the conditions of use of the motionless pipe mixer, even if it is in a liquid state, the viscosity of the prepolymer is high, so that the feed pump of the motionless pipe mixer is overloaded. Alternatively, an organic solvent should be used when it is difficult to completely mix it with the organic diamine component or its solution, when it is poorly compatible with the polyamine component, or when it is soluble in a non-aqueous inert solvent.

On the other hand, the organic solvent is used instead of the polyamine component alone because when the polyamine component is solid under the conditions of the motionless pipe mixer, it is highly viscous even if it is liquid. -Sionless pipe mixer-
In the case where the feed pump is overloaded, it is difficult to completely mix it with the urethane prepolymer alone or its solution, the compatibility with the urethane prepolymer is poor, or it is soluble in a non-aqueous inert solvent. Conceivable. But,
If organic solvents are used, they should all be removed eventually, so the amount used should be minimized.

The organic solvent for the urethane prepolymer and the organic solvent for the polyamine component may be the same or different, but essentially contain no active hydrogen capable of reacting with the NCO group and dissolve the prepolymer or polyamine component. If it does, there is no particular limitation as long as it is incompatible with the non-aqueous inert solvent. In some cases, an alcohol solvent can be used only as the organic solvent for the polyamine component. Further, it is particularly preferable that the organic solvent is azeotropic with the non-aqueous inert solvent or has a boiling point difference of at least 20 ° C. or more in order to remove the organic solvent.

The non-aqueous inert solvent is usually an aliphatic saturated hydrocarbon solvent, for example, linear or / and isomers of pentane, hexane, cyclohexane, heptane, octane, nonane, decane and the like, or a mixture thereof. Are preferably used, but examples of the organic solvent insoluble in them include highly polar nitrile solvents (acetonitrile, propionitrile, etc.), amide solvents (dimethylformamide, diethylformamide, dimethylacetamide, etc.), sulfoxides. A system solvent (dimethyl sulfoxide, diethyl sulfoxide, etc.), an N-alkylpyrrolidone system solvent (N-methylpyrrolidone, N-ethylpyrrolidone, etc.) alone or a mixture of two or more thereof is 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, but in consideration of the removal of the heat of reaction and the kettle 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.

A mixture of the urethane prepolymer / organic diamine component obtained by using the polyol containing the polyol (C) of the present invention or the polyurethane formed therefrom.
When a urea polymer alone or an organic solution thereof is dispersed in a non-aqueous inert solvent, the self-dispersibility is imparted by the introduction of the polyol (C). Even if the dispersion stabilizer of (1) is not used or if it is used, a smaller amount than the conventional amount is sufficient. That is, the amount of the dispersion stabilizer used is 0 to 10% by weight, preferably 0 to the prepolymer / organic diamine component mixture as the polyurethane-urea polymer or its precursor.
-5 wt% is normally used.

As the dispersion stabilizer, a mixture of a urethane prepolymer / organic diamine component or a polyurethane / urea polymer formed therefrom, which is soluble in a non-aqueous inert solvent, is used.
There is no particular limitation as long as it is used alone or as long as it can stably disperse those organic solutions, but a polymer type as described in the section of the prior art is usually used.

Next, the instantaneous mixing device in the present invention is not particularly limited, but a motionless pipe mixer is used.
Is preferred. It is preferable to use two or more mixers connected in series, and the mixing time is determined by the pipe mixer internal volume and the constant feed pump discharge rate.
In the present invention, in order to uniformly disperse the urethane prepolymer component and the diamine component while the reaction between the NCO group and the NH ₂ group in the prepolymer hardly progresses, the urethane prepolymer component and the diamine component are dispersed in the non-aqueous inert solvent. The respective mixing time should be within 1 second, preferably within 0.5 seconds.

Further, the polymerizing (ureaizing) reaction temperature is
It is usually carried out at a temperature of 80 ° C. or lower, preferably 0 to 70 ° C. From the moment of instantaneous mixing to the completion of the polymerizing reaction, as a general rule, the temperature is controlled so as to fall within these temperature ranges.

The motionless pipe mixer is not limited, and examples of commercially available products thereof include Static Mixer (Noritake Co.) and T.M. K. ROSS LPD
There are mixers (special machine engineering), through-the-mixers (Sumitomo Machinery), and the like. However, in both cases, it is necessary to install appropriate pipes and quantitative feed pumps so that the non-aqueous inert solvent can be supplied immediately after the uniform mixing by the first pipe mixer and immediately before the preliminary dispersion at the time of connection arrangement. . Furthermore, if appropriate, a device equipped with a suitable heating or heat removal jacket or the like is used.

On the other hand, the dispersion device is a device used to disperse a continuous liquid flow by a strong mechanical force. K. Line homogenizer such as homomixer (special machine engineering), Mantongo
The colloid mill such as a phosphorus colloid mill (Mantong Gorin Co.), a high pressure collision disperser such as a microfluidizer (Microfluidizer Co.), a nanomizer (Cosmo Instrumentation Co.), etc. are available and not particularly limited. It is necessary to have a variable adjustment mechanism that can obtain a desired dispersed droplet diameter when the flow rate is changed.

Further, the finishing tank is not limited, but one having a stirring device is preferable. For example, a reaction kettle equipped with a high-performance stirrer such as a homogenizer or a high-speed disperser such as a disperser in combination with a stirrer having excellent dispersion performance, a high-speed specification ring-corn stirrer, or the like is used for temperature control by a heating or cooling jacket. Since it can be easily carried out, it is usually used. Further, under reaction conditions in which the polymerization (ureaization) reaction rate is very high, the reaction vessel equipped with an ordinary ring cone stirrer can also be applied.

In place of this finishing tank, a method of further connecting a motionless pipe mixer to complete the polymerization reaction may be applied, but the reaction rate is high, so that it is in the middle of passage through the pipe. Therefore, the dispersion effect may decrease due to the increase in the viscosity of the reaction liquid droplets, and it is necessary to have a delicate dispersion performance and arrangement of the mixer 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 reaction is completed, if necessary,
For example in a reaction vessel equipped with a heating jacket and a condenser,
It is common to carry out fractional removal under atmospheric pressure or reduced pressure with stirring. At this time, if the organic solvent is azeotropically distilled with a non-aqueous inert solvent, distillation is particularly easy, which is very preferable.

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 droplets of the prepolymer and the polyamine component and the non-aqueous inert solvent, and the dispersion apparatus Depending on the 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 an average particle diameter of about 10 μm.

Further, the molecular weight distribution of the produced polymer is almost the same as that obtained by the solution reaction, and both the urethane prepolymer droplets and the polyamine which have been conventionally applied to obtain the polyurethane / urea powder are not mixed. Reaction in the case of being insoluble in an aqueous inert solvent, collision reaction between a prepolymer droplet in which the prepolymer is soluble and an organic solvent is applied and polyamine droplets, and prepolymer applicable in the case where the polyamine is soluble in an inert solvent -A narrower molecular weight 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 colorant, an antiaging agent, a foaming agent, an antifoaming agent, a filler, and an anti-calcining agent may be added, if necessary. Polyacrylic acid resin, vinyl chloride resin, vinyl acetate resin, ethylene / vinyl acetate copolymer resin, etc. may be added. The additive may be added before, during, or after the production of the polyurethane-urea non-aqueous dispersion.

[0048]

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

Example 1 (1) Production of urethane prepolymer 3-methylpentanediol adipate having a molecular weight of 1000
Of 400 parts and a macromonomer having an average molecular weight of 10,000 (in the presence of thioglycerin, methyl methacrylate and lauryl methacrylate were copolymerized at a ratio of 5/5 (weight ratio) to one end diol group. Was added to a reaction flask, the temperature was raised to 60 ° C. with stirring, and 164 parts of isophorone diisocyanate was added. Next, 300 ppm of dibutyltin dilaurate (relative to the total amount charged) was added and the temperature was raised to 70 ° C. by utilizing heat generation. Then 3 more
Hold at 70 ℃ for NCO terminal urethane prepolymer
Got (Apparent NCO% = 4.2) (2) Preparation of Organic Diamine Solution 62.1 parts of 4,4′-diaminodicyclohexylmethane, 5.9 parts of di-n-butylamine, and 1.5 parts of ethanol were further added. An organic diamine solution was prepared by dissolving it in 46.3 parts of acetonitrile.

(3) Mixing, Dispersing and Finishing Steps of Prepolymer and Organic Diamine Components The prepolymer obtained in (1) above is kept at 40 ° C., while the organic diamine solution obtained in (2) is kept at room temperature. It was kept below (about 20 ° C).
Moreover, each flow rate is (1) / (2) = 5.734 /
The flow rate of each fixed amount supply pump was set so that it would be 1.00 (wt ratio) and the residence time of the first one of the seriesless pipeless mixers was 0.2 seconds.

Next, the second motionless pipe mixer is connected to the first pipe mixer and the n-octane solvent line through a three-way cock, and n-octane / (prepolymer) is used. + Solid content in the organic diamine mixture) = 1/1 (wt ratio) and the flow rate of the constant supply pump of the n-octane tank was set so that the residence time in the second pipe mixer was 0.5 seconds. . Note that n-
No dispersion stabilizer was added to octane.

Further, a pipeline homogenizer is connected to the outlet of the second pipe mixer, and a target is set for the flow rate of the preliminary dispersion liquid from the second pipe mixer under the predetermined turbine rotation speed. The intervals of the internal passage slits were adjusted so that the polymer particle diameter was 1. The outlet is connected to a finishing tank with a jacket, which has a special stirring blade excellent in dispersion ability and a high-speed ring-cone stirring machine.

After the above set was completed, mixing, dispersing and finishing operations were carried out as follows. (I) The constant supply pumps for the prepolymer and the organic diamine solution were each started, and 0.2 seconds later, the constant supply pump for the n-octane solvent was started. (II) Further, 0.5 seconds after that, the pipeline homogenizer was started, and the high speed ring cone agitator in the finishing tank in which jacket heating was previously set to 50 ° C. was started. (III) After that, the steady operation was continued until the raw material prepolymer and the organic diamine solution were used up, and the temperature in the finishing tank was kept at 50 ° C. for 1 hour after the consumption of the raw material. (4) Desolvation from generated polymer The finishing bath temperature was raised to 70 ° C, and acetonitrile was distilled off under reduced pressure to obtain a final polymer-nonaqueous dispersion. The particle diameter of the produced polymer was 0.2 to 3 μm, and the melting point of the film-forming polymer was 143 to 155 ° C. The molecular weight distribution was Mw (weight average molecular weight) / Mn (number average molecular weight) = 4.4. Incidentally, the polymer obtained by the solution polymerization method using the same raw material and composition ratio has Mw / Mn =
It was 4.3 and had a polymer-molecular weight distribution almost the same.

Example 2 In Example 1, the molecular weight was 1000.
800 g of polycaprolactone diol having a molecular weight of 2000 was used instead of 3-methylpentanediol adipate.
Parts, the same macromonomer 200 parts, and acetonitrile 388 parts were used together to obtain an NCO-terminated urethane prepolymer solution in the same manner as in Example 1. (Apparent NCO% = 1.8) Next, using the same organic diamine solution as in Example 1, the prepolymer solution flow rate / organic diamine solution flow rate = 13.4.
Polymerization was completed in the finishing tank under the same setting conditions as in Example 1 except that the ratio was 0 / 1.00 (wt ratio).
Thereafter, the same procedure as in Example 1 was carried out to obtain a final polymer-nonaqueous dispersion. The particle size of the produced polymer is 0.2 to 3.5.
μm, and the melting point was 147 to 160 ° C.
The molecular weight distribution was Mw / Mn = 4.7.
The polymers obtained by the solution polymerization method using the same raw materials and composition ratios had Mw / Mn = 4.5, and had almost the same polymer molecular weight distribution.

[Example 3] In Example 1, antalone V-216 (copolymer of N-vinylpyrrolidone / hexadecene-1 in n-octane, manufactured by GAF) was previously prepared.
Polymer particles obtained in exactly the same manner as in Example 1 except that was dissolved at a concentration of 3 wt% were 0.1 to 2 μm. The polymer melting point and the molecular weight distribution were the same as in Example 1.

[Examples 4 to 8] In the same reaction method as in Example 1, urethane prepolymers shown in Table 1, Table 2 and Table 3 were used.
Polyurethane / urea non-aqueous dispersion was prepared using the organic diamine component. Their particle size, melting point and molecular weight distribution were as shown in Table 4.

[0057]

[Table 1] In the table, the polyol (C) was radically polymerized in the presence of thioglycerin using azobisisobutyronitrile as an initiator.

LMA; lauryl methacrylate AN;
Acrylonitrile HD-1; Hexadecene-1 ATMA; Stearyl Methacrylate MMA; Methyl Methacrylate

[0059]

[Table 2] In the table, acetonitrile was used as the solvent.

IPDI; isophorone diisocyanate H12MDI; 4,4'-dicyclohexylmethane diisocyanate

[0061]

[Table 3] In the table, acetonitrile was used as the solvent.

IPDA; isophoronediamine DBA;
Di-n-butylamine ETOH; Ethanol H12MDA; 4,4'-Dicyclohexylmethanediamine

[0063]

[Table 4] [Embodiment 9] A final polymer was prepared in the same manner as in Embodiment 1 except that the interval between the internal passage slits of the pipeline homogenizer at the outlet of the second motionless pipe mixer was set wider. A non-aqueous dispersion was obtained. Then, after that, the produced polymer is centrifuged by a conventional method,
It was dried under reduced pressure at 40 ° C. without particular washing. The particle size of the produced polymer was 30 to 300 μm, and the melting point and the molecular weight distribution of the polymer were those obtained in Example 1.
Was similar to.

Example 10 In Example 1, no di-n-butylamine was used at the time of preparing the organic diamine solution,
Instead, the polymer-nonaqueous dispersion finally obtained was prepared in the same manner as in Example 1 except that the amount of ethanol was increased to 3.6 parts and the amount of acetonitrile was increased to 43.8 parts. 0.3-3.0 μm, its melting point is 155
Was ~ 166 ° C. The molecular weight distribution is Mw / Mn
= 6.9, showing a wider distribution than that obtained in Example 1.

Comparative Example 1 In Example 1, (1) in the preparation of the urethane prepolymer, only 500 parts of 3-methylpentanediol adipate was used, no macromonomer was used at all, and isophorone diisocyanate was used. 2 nets
A urethane prepolymer was obtained in the same manner as in Example 1 except that the amount was increased to 00 parts. (Apparent NCO% = 4.8) Further, (2) in the preparation of the organic diamine solution, 75.8 parts of 4,4′-diaminodicyclohexylmethane, 7.2 parts of di-n-butylamine, and further ethanol 1. 8 parts were dissolved in 56.5 parts acetonitrile.

Further, in (3) the mixing, dispersing and finishing steps of the prepolymer and organic diamine components, the respective flow rate ratios are (1) / (2) = 4.954 / 1.00.
When mixing and dispersing operations were performed in the same manner as in Example 1 except that (wt) was used, the particles produced in the finishing tank were non-uniform and some became block-shaped.

Comparative Example 2 In exactly the same manner as in Example 2,
Urethane prepolymer and organic diamine solutions were prepared, respectively. After that, the operation was performed as follows. (1) Using a motionless pipe mixer and a pipeline homogenizer, first, only the urethane prepolymer solution is supplied and n is adjusted so that the prepolymer solid / n-octane = 1/1 (wt ratio). -After premixing with octane, the internal slit spacing of the pipeline homogenizer was adjusted to disperse the droplets so that the droplet diameter was 0.5 to 5 µm, and the mixture was supplied to the finishing tank in which stirring was started as in Example 2. . (2) Next, while continuing to stir the finishing tank, separate the outlet of the pipeline homogenizer from the finishing tank, supply n-octane into the motionless pipe mixer, and pass through the pipeline homogenizer. Then, the inside was thoroughly washed. (3) After connecting the outlet of the pipeline homogenizer to the finishing tank again, this time, using the motionless pipe mixer and the pipeline homogenizer, only the organic diamine solution is supplied and the organic diamine component solid / n
-Octane = 1/1 (wt ratio) After premixing with n-octane, adjust the internal slit spacing of the pipeline homogenizer and disperse so that the droplet diameter becomes 0.5 to 5 µm. It was supplied to the finishing tank while stirring. (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. Thereafter, the same procedure as in Example 2 was carried out to obtain a final polymer-nonaqueous dispersion. The produced polymer has a particle size of 0.8 to 10 μm and a melting point of 137 to 1
It was a wide range of 64 ° C. The molecular weight distribution is Mw /
It was a high value of Mn = 8.9.

Comparative Example 3 A urethane prepolymer was produced in exactly the same manner as in Example 5. 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
After pre-mixing with n-octane so as to obtain (wt ratio), the internal slit spacing of the pipeline homogenizer was adjusted to disperse so that the droplet diameter would be 0.2 to 3 μm, and the same as Example 3. It was supplied to the finishing tank where the stirring was started. (2) Next, while continuing to stir the finishing tank, separate the outlet of the pipeline homogenizer from the finishing tank, supply n-octane into the motionless pipe mixer, and pass the pipeline homogenizer. , The inside was thoroughly washed. (3) After the outlet of the pipeline homogenizer was connected to the finishing tank again, an organic diamine mixture was prepared with the same composition as in Example 5 except that acetonitrile was not used, and the mixture was dissolved in n-octane of the same weight. Then,
It was supplied to a finishing tank under stirring through a shearless pipe mixer and a pipeline homogenizer with a maximum internal slit distance. (4) After maintaining the internal temperature of the finishing tank at 50 ° C. and stirring for 1 hour,
Raise to 70 ° C. Thereafter, the same procedure as in Example 1 was carried out to obtain a final polymer-nonaqueous dispersion. The produced polymer has a particle size of 0.15 to 2.8 μm and a melting point of 132.
It was a wide range of ˜171 ° C. The molecular weight distribution is M
It was a high value of w / Mn = 11.9.

[Comparative Example 4] Comparative Example 4 was the same as Example 1 except that the antalon V-216 used in Example 3 was previously dissolved at a concentration of 10 wt% in n-octane of the non-aqueous dispersion medium. The final polymer-non-aqueous dispersion was obtained in exactly the same manner.

The particle size of the produced polymer was 0.5 to 5 μm, and the melting point of the film-forming polymer was 150 to 160 ° C. The molecular weight distribution was Mw / Mn = 4.5.

[Application Example 1, Comparative Application Example 1] This polymer
When a test piece was cut out from the film (thickness 0.3 mm) and immersed in a toluene solvent at room temperature, the smoothness of the surface was lost after 1 day (Comparative Application Example 1). On the other hand, Example 1
A polymer film was similarly prepared from the polymer-non-aqueous dispersion obtained in 1. and cut out, and the surface smoothness was maintained even after 1 day of immersion in toluene at room temperature (Application Example 1).

Comparative Example 5 In Comparative Example 4, Antalon V-21 dissolved in n-octane of the non-aqueous dispersion medium was used.
The amount of 6 was halved to 5 wt%, and the second motionless pipe mixer-a pipeline homogenizer at the outlet-
A final polymer-non-aqueous dispersion was obtained in exactly the same manner as in Example 1 except that the interval between the internal passage slits was set wider.

After that, the produced polymer was centrifuged by a conventional method, half was not washed with a solvent and the other half was sufficiently washed with a solvent, and then dried at 40 ° C. under reduced pressure. Generated polymer
Had a particle size of 40 to 350 μm, and its melting point and polymer molecular weight distribution were the same as those of the polymer obtained in Example 1.

[Application Example 2 and Comparative Application Example 2] These two kinds of polymer particles having different washing conditions are respectively heated at 230 ° C.
The sheet was spread evenly in the sheet preheated sheet and held for 2 minutes, and the obtained sheet was observed. The sheet from the unwashed particles was colored a little brown (comparison). Application example 2). Almost no coloration of the sheet from the washed ones was seen.

On the other hand, when the polymer particles obtained in Example 9 were sheeted under the same conditions, almost no coloring was observed (Application Example 2).

[0076]

EFFECT OF THE INVENTION The polyurethane / urea non-aqueous dispersion obtained by the present invention is a conventional non-aqueous inert dispersion medium in which the urethane prepolymer and the organic diamine component are subjected to a collision reaction of the respective droplets and the former case. The molecular weight distribution is narrower and the molecular weight can be easily controlled as compared with the polymer-non-aqueous dispersion obtained by the interfacial reaction between the liquid droplet and the organic diamine component dissolved in the dispersion medium. Further, by containing the specific polyol, it has self-dispersibility in a non-aqueous dispersion medium, and it is possible to use no dispersion stabilizer or reduce the amount from the conventional amount.

From these facts, the polymer obtained in the present invention has a sharp melt viscosity gradient with respect to temperature,
Not only is it particularly useful as a paint, coating vehicle and adhesive due to its excellent melt moldability, but it also shows little deterioration of physical properties due to the residual dispersion stabilizer, and even when a polymer washing step is required during production. It requires less labor and cleaning solvent.

[Brief description of drawings]

1 is a schematic tubing diagram of a mixing, dispersion, finishing tank, desolvation apparatus for the production of polyurethane-urea non-aqueous dispersion used in one embodiment of the method of the present invention.

[Explanation of symbols]

 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

Claims (9)

[Claims] 1. A method for producing a polyurethane-urea non-aqueous dispersion by reacting polyol, polyisocyanate and polyamine in a non-aqueous dispersion medium, which is a mercaptan compound having two hydroxyl groups as a polyol. Using (A) as an initiator, a polyol containing a polyol (C) obtained by polymerizing a compound (B) having a C 4-20 alkyl group-containing polymerizable unsaturated bond is used. A method for producing a polyurethane / urea non-aqueous dispersion, which comprises: 2. The polyol (C) is used in an amount of from 1 to
The method for producing a polyurethane-urea non-aqueous dispersion according to claim 1, wherein 50% by weight is used. 3. A polyol containing a polyol (C).
First, a urethane prepolymer having isocyanate groups at both ends obtained by reacting a polyamine and a polyisocyanate is first mixed with a polyamine, and then this mixed solution is a non-aqueous inert solvent insoluble in the mixed solution. A step of instantaneously dispersing in step 2) a step of further dispersing the dispersion produced in 1) with a dispersing device 3) a step of completing the reaction of the dispersion produced in 2) in a finishing tank. Item 3. A method for producing the polyurethane-urea non-aqueous dispersion according to Item 1 or 2. 4. A motionless pipe mixer for instantaneously mixing a urethane prepolymer and a polyamine and for instantaneously dispersing this mixed solution in a non-aqueous inert solvent. The method for producing the polyurethane-urea non-aqueous dispersion according to item 1. 5. The method for producing a polyurethane / urea non-aqueous dispersion according to claim 4, wherein two or more motionless pipe mixers are connected in series. 6. The method for producing a polyurethane-urea non-aqueous dispersion according to any one of claims 1 to 5, wherein the polyamine contains a monofunctional amine. 7. When instantaneously mixing the urethane prepolymer and the polyamine, an organic solvent insoluble in the urethane prepolymer and the polyamine is used, and the organic solvent is removed from the reaction-completed polymer dispersion. The method for producing the polyurethane-urea non-aqueous dispersion according to claim 3, which is characterized in that. 8. The method for producing a polyurethane-urea non-aqueous dispersion according to claim 3, wherein the finishing tank has a stirrer. 9. When removing an organic solvent from a reaction-completed polymer dispersion, the organic solvent and a non-aqueous inert solvent are azeotropically distilled, or a difference in boiling point between the organic solvent and the non-aqueous inert solvent. Is at least 20 ° C. 8. The method for producing a polyurethane-urea non-aqueous dispersion according to claim 3, wherein the temperature is at least 20 ° C.