JPH03195738A - Production of aqueous synthetic resin dispersion - Google Patents

Abstract

PURPOSE:To obtain the subject stabilized aqueous dispersion useful as auxiliaries, etc., for the textile industry at a low cost by mixing a solution of a water- dispersible synthetic resin in an organic solvent, etc., with water in a specific mixer, dispersing the resultant mixture in water, etc., and then distilling and removing the organic solvent in the aforementioned solution. CONSTITUTION:For example, if a solution of a hydrophilic group-containing isocyanate-terminated prepolymer in an organic solvent, etc., are preferably used as a solution or dispersion of a water-dispersible synthetic resin in an organic solvent, the above-mentioned solution is continuously mixed with a mixture obtained by adding a diamine or diimine to water at (0:1)-(1:1) ratio based on the isocyanate and further a base or acid other than the diamine, etc., as a neutralizing agent thereto in a tubular mixer (tubular mixer) in which plural mixing elements without any mobile part are fixed to the interior thereof to dissolve and disperse the aforementioned solution, etc., in water. The organic solvent is then removed by a stirred film type thin film evaporator to afford the objective aqueous dispersion with 15-60wt.% solid content.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to a method for producing a synthetic resin aqueous dispersion.

<Prior art> A general method for producing an aqueous polyurethane dispersion is to partially copolymerize a compound containing a hydrophilic functional group during a urethanization reaction in the presence of an organic solvent. A method is known in which an organic solvent solution or an organic solvent dispersion of an isocyanate-terminated prepolymer is dispersed in water and chain-extended with an amine. These reaction methods are batch methods, in which an organic solvent solution or organic solvent dispersion of a hydrophilic group-containing isocyanate-terminated urethane prepolymer is usually obtained in a first container, and then the solution or dispersion is obtained in the same or a second container. It is common to extend the chain using an amine while dispersing the dispersion in water.

However, when this reaction is carried out in a batch manner, there are the following problems.

(1) In the large reaction vessels required for commercial production, a stirrer capable of generating high energy and strong shearing force is used to disperse the organic solvent solution or organic solvent dispersion of the hydrophilic group-containing isocyanate-terminated prepolymer in water. I need.

(2) When scaling up from a laboratory scale to a commercial scale, the stirring conditions or stirring efficiency may differ, and water or amine may be mixed into the prepolymer organic solvent solution or organic solvent dispersion, or vice versa. Because the rate and time at which a solvent solution or organic solvent dispersion is added to an aqueous amine solution cannot be precisely controlled, it is difficult to maintain the same physical properties as products obtained on a laboratory scale, such as particle size and molecular weight. It is.

(3) When dispersing an organic solvent solution or organic solvent dispersion of an isocyanate-terminated prepolymer containing a hydrophilic group in water and carrying out a chain extension reaction with an amine, not only the reaction between the isocyanate group and the amine but also the side reaction with water occur. As the reaction progresses, it is extremely difficult to control the reaction, and physical properties tend to fluctuate between lofts in commercial production.

Therefore, as a method for producing an aqueous polyurethane polyurea dispersion using a low shear mixer instead of the high shear mixer described above, there is a method described in US Pat. No. 4,742,095.

<Problem to be solved by the invention> However, the method described in U.S. Pat. Since rotational operation is required, there is a drawback that polyurethane polyurea particles dispersed in water tend to aggregate, and energy is also required to operate the stirrer.

Means for Solving the Problems From this point of view, the present inventors have conducted extensive research on a method for continuously and economically producing a stable polyurethane polyurea aqueous dispersion that overcomes the above drawbacks, and have found that When a so-called static tubular mixer is used to mix water with an organic solvent solution or dispersion of a synthetic resin that can be dispersed in water, The present invention was achieved by discovering that even if the solvent is removed from the liquid, it is difficult to aggregate.

That is, the present invention mixes an organic solvent solution or an organic solvent dispersion of a synthetic resin that can be dispersed in water with water in a tubular mixer in which a plurality of mixing elements with no moving parts are fixed. and a method for producing an aqueous synthetic resin dispersion, which comprises dissolving or dispersing an organic solvent solution or dispersion of the synthetic resin in water, and then removing the organic solvent in the solution or dispersion by distillation. This is what we provide.

Hereinafter, a tubular mixer according to the present invention having a plurality of mixing elements fixed inside without any movable parts will be simply referred to as a "tubular mixer".

The water-dispersible synthetic resin according to the present invention is not particularly limited, and may be either a so-called dead polymer that does not have a functional group that reacts with water or a polymer that has a functional group that reacts with water. Examples of such water-dispersible synthetic resins include water-dispersible polyolefins, polyesters, polyethers, polythioethers, polysulfones, polycarbonates, polyureas, polyurethanes,
Polyurethane polyurea, polyurea, polyamide, phenolic resin, urea resin, melamine resin, guanamine resin,
Examples include epoxy resin, acrylic resin, fluororesin, and silicone resin.

The organic solvent solution or organic solvent dispersion of a synthetic resin that can be dispersed in water in the present invention refers to an organic solvent solution or an organic solvent dispersion of a synthetic resin as exemplified above, and these solutions or dispersions are usually It can be easily obtained by reacting raw materials for each synthetic resin with at least a hydrophilic functional group or a compound having a functional group capable of becoming hydrophilic in an organic solvent. There are no restrictions.

Examples of compounds having hydrophilic functional groups include groups consisting of repeating units of ethylene oxide, groups consisting of repeating units of ethylene oxide and other repeating units of alkylene oxide, groups consisting of salts of sulfonic acids, and salts of carboxylic acids. Examples of functional groups that can be hydrophilic include carboxylic acid groups, sulfonic acid groups, and tertiary amine salt groups.
Examples include compounds having a grade amino group. Specific compounds will be described later.

Hereinafter, a compound having a hydrophilic functional group and a compound having a functional group capable of becoming hydrophilic will be collectively referred to simply as a "compound having a hydrophilic functional group."

The organic solvent solution or organic solvent dispersion of a synthetic resin that can be dispersed in water is preferably an organic solvent solution or an organic solvent dispersion of a synthetic resin that has a functional group that can react with an active hydrogen atom. Particularly preferred are solutions or dispersions of isocyanate-terminated prepolymers in organic solvents.

That is, by dispersing in water an organic solvent solution or organic solvent dispersion of the water-dispersible isocyanate-terminated prepolymer and simultaneously performing a chain extension reaction.
A high molecular weight polyurethane polyurea aqueous dispersion is obtained,
This is because if the organic solvent is removed, an aqueous polyurethane polyurea dispersion containing almost no organic solvent can be obtained. Of course, in order to disperse polyurethane polyurea only in water, it is necessary that the polyurethane polyurea finally obtained has sufficient hydrophilicity to be able to be dispersed only in water.
This will be discussed later.

Hereinafter, an isocyanate-terminated prepolymer having a hydrophilic functional group or a functional group that can become hydrophilic in an amount sufficient to allow the final polyurethane polyurea to be dispersed only in water is simply referred to as "hydrophilic group-containing isocyanate-terminated prepolymer". "prepolymer".

The hydrophilic group-containing isocyanate-terminated prepolymer used in the present invention is, for example, a compound having a hydrophilic functional group (
A) is essential, a conventionally known diisocyanate compound (B) and, if necessary, a diol other than the component (A) (
C).

Examples of the compound (A) having a hydrophilic functional group include at least one active hydrogen atom in the molecule,
and a group consisting of a repeating unit of ethylene oxide, a group consisting of a repeating unit of ethylene oxide and another repeating unit of alkylene oxide, a group such as a carboxylic acid salt, a sulfonic acid salt, a tertiary amine salt, a carboxylic acid group,
Examples include compounds containing at least one functional group selected from the group consisting of a sulfonic acid group and a tertiary amino group.

Examples of the compound (A) containing such a hydrophilic functional group include 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, l,3- Sulfonic acid-containing compounds such as phenylenediamine-4,6-disulfonic acid and 2,4-diaminotoluene-5-sulfonic acid, derivatives thereof, or polyester polyols obtained by copolymerizing these; 2,2-dimethylolpropion acids, carboxylic acid-containing compounds such as 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, 3,4-diaminobenzoic acid, and derivatives thereof, or their derivatives. Polyester polyol obtained by copolymerization; polyoxyethylene glycol or polyoxyethylene-polyoxypropylene copolymer glycol containing at least a repeating unit of ethylene oxide and one or more active hydrogen atoms;
Compounds containing nonionic groups such as polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol, or their monoalkyl ethers, or polyester polyether polyols obtained by copolymerizing these These can be used alone or in combination.

Polyoxyethylene glycol, polyoxyethylene-
The polyoxyalkylene copolymer glycol or its monoalkyl ether preferably has ethylene oxide repeating units in an amount of at least 30% by weight of its molecular weight, and has a molecular weight of 300 to 10,000.

The most preferable hydrophilic group-containing compound (A) is a carboxyl group-containing compound, a derivative thereof, or a polyester polyol obtained by copolymerizing these.

Examples of the diisocyanate compound (B) that can be used in the present invention include 2.4-) lylene diisocyanate, 2.6-) lylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. , 2.4'-diphenylmethane diisocyanate, 2
．． 2'-diphenylmethane diisocyanate, 3,3
'-Dimethyl-4,4'-biphenylene diisocyanate, 3.3'-dimethoxy-4,4'-biphenylene diisocyanate, 3.3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1.5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-
Hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1
．． 4-cyclohexylylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4.
4'-dicyclohexylmethane diisocyanate, 3.
Examples include 3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.

Examples of diols (C) other than component (A) include ethylene glycol, propylene glycol, 1.3-propanediol, 3-butanediol, 1.4-butanediol, 1.5-bentanediol, 3-butanediol, Methyl-
1,5-bentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1°4-cyclohexane In addition to relatively low molecular weight diols such as diol, 1,4-cyclohexane dimetatool, bisphenol A1 hydrogenated bisphenol A, and hydroquinone, these diols are combined with succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. , maleic anhydride, fumaric acid, ■, 3-cyclopenkune dicarboxylic acid, l, 4-cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid,
2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane=p,p'-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid Ring-opening polymerization reaction of cyclic ester compounds such as polyester diol and ε-caprolactone obtained by dehydration condensation reaction with acid components such as p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these hydroxycarboxylic acids. propylene oxide, butylene oxide, styrene oxide, Polyether diol, poly (tetramethylene carbonate) diol, poly (hexamethylene carbonate) obtained by addition polymerization of one or more types of heptamines such as epichlorohydrin, tetrahydrofuran, and cyclohexylene by a conventional method.
Examples include compounds obtained by reacting the above-mentioned relatively low-molecular-weight diols such as diols with diphenyl carbonate, phosgene, chloroformic acid ester, and the like.

Other natural diols, including dihydroxy compounds containing urethane or urea groups, as well as castor oil, carbohydrates, and optionally modified ones, can also be used.

As the hydrophilic group-containing isocyanate-terminated prepolymer according to the present invention, any prepolymer produced by a conventionally known method can be used, but for example, the diisocyanate compound (B), a compound having a hydrophilic functional group, etc. (A)
, Diol (C) other than component (A) is mixed with an equivalent ratio of isocyanate groups to active hydrogen groups of 1.1:1 to 3:1, preferably 1.2:1 to 2:1, and 120°C1
Preferably, those reacted at 30 to 100°C are mentioned.

When producing a hydrophilic group-containing isocyanate-terminated prepolymer by using only a compound having only one active hydrogen atom as component (A) and reacting it with components (B) and (C), For example, it goes without saying that it is preferable to use a higher proportion of component (B) than before, or to appropriately use a compound having three or more active hydrogen or isocyanate groups as described below.

Of course, when producing the isocyanate-terminated prepolymer loaded with a hydrophilic group, the reaction may be carried out using a tubular mixer.

These reactions can be carried out without a solvent, but an organic solvent can also be used for the purpose of controlling the reaction system or reducing the viscosity. Examples of such organic solvents include aromatic hydrocarbons such as toluene and xylene; acetone;
Ketones such as methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetate esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile;
Amides such as dimethylformamide and N-methylpyrrolidone are mentioned. Particularly preferred organic solvents in the present invention include solvents that have a boiling point of 100°C or lower, are inert to isocyanate groups, and are hydrophilic, such as acetone,
Examples include methyl ethyl ketone.

The content of hydrophilic functional groups or functional groups capable of becoming hydrophilic in the hydrophilic group-containing isocyanate-terminated prepolymer according to the present invention is, for example, hydrophilic groups such as carboxylic acid groups, sulfonic acid groups, and tertiary amine groups. In the case of functional groups capable of becoming hydrophilic, such as carboxylic acid groups, sulfonic acid groups, and tertiary amine bases, the amount is at least 0.01 equivalent or more, preferably 0.01 equivalent or more, per 100 parts by weight of the final polyurethane polyurea solid content. An amount equivalent to 0.01 to 0.2 equivalent is required,
In the case of a group consisting of an alkylene oxide repeating unit that essentially contains a repeating unit of ethylene oxide, which is a hydrophilic functional group, for example, the weight of the repeating unit of ethylene oxide is 100% by weight of the final polyurethane polyurea solid content. An amount corresponding to at least 3% by weight or more, preferably 5 to 30% by weight per part is required.

In the method of the present invention, the viscosity of the prepolymer is not particularly limited, but is usually 10 to 2,000 cps, preferably 20 to 1,000 cps. If the viscosity is within the above range, not only will the pressure loss in the piping be reduced, but the difference in viscosity between the water and the water to be mixed can be reduced, so the mixing effect of the tubular mixer will be sufficient, and a stable aqueous dispersion will be obtained. It is economical because the amount of organic solvent used for dilution can be reduced.

In the present invention, an organic solvent solution or an organic solvent dispersion of a water-dispersible synthetic resin as described above and water are mixed in a tubular mixer in which a plurality of mixing elements having no moving parts are fixed. be done.

When an organic solvent solution or organic solvent dispersion of a synthetic resin is dispersed in water using a tubular mixer, the average particle size of the dispersed or dissolved synthetic resin can be made smaller compared to conventional methods.
Moreover, the particle size distribution can be significantly narrowed.

The tubular mixer used in the present invention is, for example, a Ross-E-Niss-Ge mixer (manufactured by Achener Minshu Land Knetmaschinen Fabric) R
oss-ISG m1xer (Aachener Mi
schund Knet machinen Fbri
K, Aachen)], Pulsating Mixing Reactor (Primacnik, Frankfurt/
Made by Mine) [Pulsating mixing re
actor (Prematechnik, Fr.
ankfurt/Main)], Peanis M Mixer (Betschild, Frankfurt/Main) (
PSM m1xer (Petzholdt, Fra
nkfurt/Main) ), Kenics mixer (Ott Partlibs Gesellschaft, Leon Birk) (Kenics m1xer (Ott
Vertriebsgesselschaft, L
Erestat mixer (YXZET, made by Affalterpusche) (Erestat m1xer (YXZET,
Affalterbsh), N-shaped pipe mixer (Plan & Love, manufactured by Nordelstad) (N-shaped pipe m1xer)
(Bran & Lubbe, Nordersted
t)), Sulzermixer (made by Sulzer, Winterzur) (Sulzermixer (Su
Winterthur) and the like.

Among these, the Kenisix-type tubular mixer has no blind spots in the mixer, the structure of the mixing element is simple, and it is difficult for leather etc. to adhere (and even if it does, it is easy to maintain to remove it). (Kenics m1xer)
is particularly preferred.

The Kenix-type tubular mixer has a mixing element in the tube, for example, a rectangular plate twisted at 180 degrees. In order to efficiently mix water and obtain a stable aqueous dispersion with a homogeneous particle size distribution, the number of mixing elements must be at least 12 to 60, preferably 15 to 50. be. When the number of mixing elements is within the above range, a sufficient mixing effect can be obtained and the particle size distribution will be homogeneous, resulting in significantly improved stability.Moreover, the pressure loss in the tubular mixer will be small, so that the organic The capacity (horsepower) of the pump for transporting the solvent solution or organic solvent dispersion and water can be within the normal range, or it is preferable because the equipment cost can be reduced because reinforcement of the joint part of the piping is unnecessary. .

Further, each mixing element of the tubular mixer used in the present invention must be fixed within the tube during normal mixing, but it may be of a type that allows the mixing element to be removed other than during mixing, for example, during maintenance.

The latter is more advantageous when considering the maintainability of the tubular mixer.

The size of the tubular mixer is determined depending on the target processing amount of the aqueous synthetic resin dispersion, but the flow rate of the mixed fluid in the tubular mixer is at least 20 to 400 cm/sec, preferably 30 to 300 cm/sec. /second.

When the flow rate is within the above range, the mixing effect within the tubular mixer is sufficient and the particle size distribution of the synthetic resin becomes homogeneous, so that the stability of the aqueous dispersion finally obtained is significantly improved.

Moreover, the processing capacity (flow rate, pressure resistance) of the pump that transfers an organic solvent solution or organic solvent dispersion of a synthetic resin that can be dispersed in water and a large amount of water can be used within the normal range, and the pipe joint It is very economical as there is no need to reinforce the parts.

Examples of the pump used for continuously transporting the organic solvent solution or organic solvent dispersion of the water-dispersible synthetic resin and water according to the present invention include a piston pump, a plunger pump, a Nuyafram pump, and a gear pump. , a screw pump, a thin-wound pump, a mixed-flow pump, an axial-flow pump, etc., but a non-pulsation type pump is particularly preferable for mixing using the tubular mixer according to the present invention. This is because if there is pulsation, it is difficult to continuously control the mixing ratio of the organic solvent solution or organic solvent dispersion/water to a constant level, and the quality and physical properties of the final synthetic resin aqueous dispersion are kept constant. This is because it is difficult to maintain.

The temperature of the organic solvent solution or organic solvent dispersion of the synthetic resin used in the method of the present invention is not particularly limited, but is 5 to 80°C.
C1 is preferably 20 to 60°C.

The temperature of the water used in the method of the present invention is not particularly limited, but is 0 to 50°C, preferably 5 to 40°C.

Needless to say, it is preferable that the temperature of the organic solvent solution or organic solvent dispersion of the synthetic resin and the temperature of the water be approximately the same.

When the liquid temperature and water temperature are within the above temperature range, it is economical because the utility cost for cooling is low, and in particular, the reaction between the hydrophilic group-containing isocyanate-terminated prepolymer and the diamine or diimine described below is selective. This is preferable because there is little concern that the particle size will become coarse due to the progress of the process.

In the present invention, when a hydrophilic group-containing isocyanate-terminated prepolymer is used as an organic solvent solution or organic solvent dispersion of a synthetic resin that can be dispersed in water, it is preferable to use a diamine or a diimine in combination with the water described above. .

By using this combination, dispersion of an organic solvent solution or dispersion of the prepolymer in water and a chain extension reaction between the prepolymer and the diamine or diimine can be performed simultaneously, and a high molecular weight polyurethane polyurea can be easily obtained. Therefore, it is very preferable.

Examples of the diamine or diimine used in the present invention include ethylene diamine, 1,2-propanediamine, 1
．． 6-hexamethylene diamine, piperazine, 2,5-
Dimethylpiperazine, isophoronediamine, 4.4'-
Examples include diamines or diimines such as dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and hydrazine.

The diamine or diimine used in the present invention is usually used dissolved in water as a dispersion medium necessary to obtain a polyurethane polyurea aqueous dispersion, and the amount used is determined in the isocyanate-terminated prepolymer containing a hydrophilic group. O:1 to 1:1, preferably 0 in equivalent ratio to isocyanate groups
．． It is necessary that the amount used be 6:1 to 0.98:1. The amount of water to be used is the minimum amount required to form an o/w water dispersion after mixing and reacting the organic solvent solution or organic solvent dispersion of the prepolymer with water containing diamine or diimine. 100 to 1% based on the final polyurethane polyurea solid content weight.
, 000% by weight is preferred. Of course, the tubular mixer may also be used when preparing water containing diamine or diimine.

When the hydrophilic group-containing isocyanate-terminated prepolymer is an isocyanate-terminated prepolymer that has a functional group that can become hydrophilic, it can be used as a neutralizing agent necessary to convert the functional group that can be hydrophilic into a functional group that has hydrophilic property. A base other than a diamine or diimine, or an acid is added to the above water in an equivalent ratio of O,S:X to 1.5:1, preferably 1:1 to 1.3:1 to a functional group that can become hydrophilic. It is preferable to contain it. Of course, the above-mentioned tubular mixer may be used when preparing water containing a base other than diamine or diimine, or an acid. When using a base, it can be added in advance to the isocyanate-terminated prepolymer containing a hydrophilic group, but in that case, the base is also a strong catalyst for the urethanization reaction, so side reactions are likely to occur, and the prepolymer is likely to be colored. Therefore, it is preferable to mix the base into the prepolymer solution or dispersion as water containing the base.

Examples of the base include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic tertiary amines such as trimethylamine and triethylamine. Among them, organic tertiary amines having a relatively low boiling point are preferred.

Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and sulfonic acid, and organic acids such as formic acid, acetic acid, and propionic acid. Among them, organic acids with a relatively low boiling point are preferred.

In the present invention, an organic solvent solution or organic solvent dispersion of a hydrophilic group-containing isocyanate-terminated prepolymer, a diamine or diimine, and, if necessary, a base other than the diamine or diimine, or water containing an acid, as described above. By adjusting the flow rate and continuously feeding into the tubular mixer using the pump, dispersion in water and chain extension reaction by amine proceed almost simultaneously to obtain a polyurethane polyurea aqueous dispersion. I can do it.

Of course, the three components of an organic solvent solution or organic solvent dispersion of an isocyanate-terminated prepolymer containing a hydrophilic group, water containing a diamine or a base other than a diimine, or an acid, and water containing a diamine or diimine are placed in a tubular reactor. An aqueous polyurethane polyurea dispersion can also be obtained by continuously supplying the polyurethane polyurea.

When producing an aqueous polyurethane polyurea dispersion using the method for producing an aqueous dispersion of the present invention, in addition to the various reaction raw materials described above, sucrose, anicotose sugar, triglyceride, and Mellitic acid, hemimellitic acid, phosphoric acid, diethylenetriamine, triethylenetetramine, triisopropazuramine, pyrogallol, dihydroxybenzoic acid, hydroxyfucuric acid, 1,2,3-propane trithiol, pentaerythritol, glycerin, trimethylol ethane , trimethylolpropane, sorbitol, etc., as well as compounds other than those used in the production of the hydrophilic group-containing isocyanate-terminated prepolymer containing a hydroxyl-, carboxyl-, amino-1 or mercapto-group at the terminal, such as polyester polyol. , polyhydroxy compounds such as polyacetal polyols, polyether polyols, polythioether polyols, polyamide polyols and polyesteramide polyols, hexamethylene diisocyanate 3I,
Trimethylolpropane-tolylene diisocyanate adducts, tolylene diisocyanate 21, or blocked polyisocyanates obtained by partially reacting these with phenol, tertiary butanol, phthalimide, or caprolactam, and the like can also be used.

This polyurethane polyurea aqueous dispersion is preferably transferred to, for example, the next solvent removal step before the chain extension reaction with the diamine or diimine is completed, or after the chain extension reaction is completed. When the reaction is completed, it is transferred to a tank or reaction vessel and aged with stirring or standing still.

The polyurethane polyurea aqueous dispersion thus obtained may be used as is, but the organic solvent is usually removed and the dispersion is used as an aqueous dispersion.

When performing this organic solvent removal, various types of distillation/evaporators can be used as appropriate, and conventional batch vacuum distillation can also be used. It is preferable because it does not change and the particle size distribution can be narrowed, and among these, a stirring demolding thin film evaporator is particularly preferable.

The average resin particle size of the aqueous dispersion obtained using a conventional electric stirring blade equipped reaction vessel other than a tubular mixer is larger than that obtained using a tubular mixer. It has also been found that distilling off the organic solvent using a thin film evaporator results in an even larger average resin particle size.

In the present invention, a thin film evaporator refers to an evaporator that spreads a liquid on a heated surface to form a thin film, and evaporates the liquid from above the film.

The continuous thin film evaporator that can be used in the present invention is, for example, an agitation-molding thin film evaporator of the type described in "Chemical Equipment Handbook, pages 404 to 407"; for example, Sebucon manufactured by Hitachi, Ltd. Evaporator, horizontal control device or vertical control device, WF of Shinko Faudler Co., Ltd.
Among them, a vertical evaporator with a rotating shaft installed in a vertical direction may be used without a liquid pool. More preferably, in order to suppress the occurrence of skin formation due to the scattering of the aqueous dispersion onto the rotary blades in the evaporator and the mixing of dirt into the desolvated aqueous dispersion, it is preferable to spray water for washing. Preferably, the opening or nozzle is installed on the rotating shaft and/or the inner bottom of the evaporator. This makes it possible to stabilize the evaporation operating conditions and reduce the number of maintenance operations, and also prevents scaling or skinning when removing organic solvents from soft polyurethane polyurea aqueous dispersions that tend to form films. (Stable evaporation is possible.)

Evaporation generally occurs at jacket temperatures of approximately 20-100°C.
Preferably the temperature is 30-90°C and the degree of vacuum is about 5-300°C.
The reaction is carried out under conditions of mmHg, preferably 10 to 200 mmHg. For example, when an aqueous polyurethane polyurea dispersion is used, most of the organic solvent contained therein is removed.

When removing the organic solvent in an aqueous polyurethane polyurea dispersion, the distillate obtained from the thin film evaporator contains, in addition to the organic solvent and some water, a functional group that can make the hydrophilic groups in the prepolymer hydrophilic. In the case of a hydrophilic functional group, it contains a neutralizing agent (a base if the functional group that can become hydrophilic is an acid group, and an acid if it is a tertiary amino group), and is usually crushed with a decanter or the like. The solvent phase and aqueous phase are separated and treated separately. The organic solution phase is separately subjected to simple distillation or rectification and is recovered and used as a reaction solvent or diluent for the prepolymer. In addition to water, the aqueous phase contains a small amount of organic solvent and a neutralizing agent if the hydrophilic group of the prepolymer is a functional group that can become hydrophilic, and is recovered as part of the water containing diamine or diimine. Can be reused. Recovering and reusing the aqueous phase in distillate not only reduces the cost of processing distillate;
Since the same organic solvent as the prepolymer solution is added to the water containing diamine or diimine, the affinity between the prepolymer and water is improved compared to water using only water as a solvent, making it easier to disperse in water. It has the advantage of being easy.

The aqueous phase (organic solvent/water or organic solvent/neutralizing agent/water lower layer component) mainly composed of water distilled off in the above distillation process is used to prepare water containing diamine or diimine. It is possible to use it in place of some parts.

Conventionally, this lower layer component has been treated with viscous sludge or incinerated to prevent pollution, which requires a large amount of expense, but according to the present invention, the physical properties of the resulting polyurethane polyurea aqueous dispersion are impaired. It is very economical because it can be collected and reused without any waste. In this recovery and reuse, the amount of water in the aqueous phase is adjusted to a predetermined amount depending on the composition of the lower layer component, that is, the content of water in the aqueous phase. At this time, by fixing the distillation conditions of the thin film evaporator used in the present invention, a lower layer component of constant quality can be obtained, and therefore adjustment for recovery and reuse is easy.

Further, according to the thin film evaporator, which is a preferable evaporator that can be used in the present invention, the evaporation conditions can be made constant compared to the conventional batch-based desolvation process, and the heating for evaporation within the device can be made constant. Since the time, that is, the residence time on the heating surface, can be extremely short, there is no effect on the obtained polyurethane polyurea aqueous dispersion, such as hydrolytic deterioration or deterioration of particle size, and it is stable and has good physical properties. It is easy to obtain a polyurethane polyurea aqueous dispersion, and furthermore, even in a soft polyurethane polyurea aqueous dispersion that easily forms a film, it is possible to easily remove the solvent without causing scaling etc., and the removed organic solvent can be easily removed. It is extremely safe as it does not release into the atmosphere.

Thus the solids content is about 15-60% by weight, preferably 20% by weight.
A substantially solvent-free aqueous polyurethane polyurea dispersion of ˜50% by weight is obtained.

In the present invention, the polyurethane polyurea aqueous dispersion or aqueous dispersion obtained as necessary may be mixed with other emulsions, latex aqueous dispersions, or additives such as coating aids, crosslinking agents, fillers, etc. External emulsifiers may be used to improve solution stability. The timing of their addition is not particularly limited, but they can be added at any time, for example, before, during or after the prepolymer reaction, addition to water, or addition after exiting the tubular mixer. Examples of such emulsifiers include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrenated phenyl ether, and polyoxyethylene sorbitol tetraoleate; fatty acid salts such as sodium oleate; Examples thereof include anionic emulsifiers such as alkyl sulfate salts, alkylbenzene sulfonate salts, alkyl sulfosuccinates, naphthalene sulfonate salts, polyoxyethylene alkyl sulfate salts, alkanesulfonate sodium salts, and alkyldiphenyl ether sulfonate sodium salts. It is preferable not to add these emulsifiers, but
When added, the amount added must be suppressed to an extent that does not impair the water resistance of the polyurethane polyurea aqueous dispersion finally obtained, and is 5% by weight or less, preferably 3% by weight based on the solid content of the polyurethane polyurea. It is as follows.

Examples of emulsions, latexes, and aqueous dispersions that can be added to the polyurethane polyurea aqueous dispersion obtained by the method of the present invention include emulsions such as vinegar-based, ethylene-vinyl acetate-based, acrylic-based, and acrylic-styrene-based emulsions; Latexes such as acrylonitrile-butadiene-based, acrylonitrile-butadiene-based, and acrylic-butadiene-based; ionomers such as polyethylene-based and polyolefin-based; water dispersions of polyurethane, polyester, polyamide, and epoxy. Furthermore, fillers include carbon flanks, clay, talc, aluminum hydroxide, silica sol, alumina sol, etc., film-forming aids include alkylene glycol derivatives, and crosslinking agents include epoxy resins, melamine resins, and isocyanate compounds. , aziridine compounds, polycarbodiimide compounds, etc., and they can also be used in combination with plasticizers, pigments, leveling agents, etc.

The polyurethane polyurea aqueous dispersion obtained by the method of the present invention can be applied to various plastics such as vinyl chloride, nylon, polyester, and polyurethane, textile products, synthetic leather products, metals such as aluminum, copper, and iron, paper, wood, and glass. It can be widely used as an impregnating treatment agent or coating agent for fibers and synthetic leather products, an adhesive for various substrates, a coating agent, a water-based paint, a water-based ink, or a hess resin for a sizing agent.

<Examples> The present invention will be further described below with reference to Examples, but the present invention is not limited thereto. Note that parts and percentages hereinafter are based on weight unless otherwise specified.

Fruit 1111 Polyester with a molecular weight of 2.000 (1,6-hexanediol/neopentyl glycol/adipic acid) 3.1
20 parts, 1,4-butanediol 165 parts, dimethylolpropionic acid 215 parts, tolylene diisocyanate)
1,313 parts of methyl ethyl ketone, 2.591 parts of methyl ethyl ketone and anhydrous piperazine 1.
An aqueous solution obtained by uniformly mixing 94 parts of triethylamine, 178 parts of triethylamine, and 8.168 parts of water was pumped from each tank into a Kenix-type tubular mixer (manufactured by Noritake Company) using a non-pulsating plunger pump. , number of mixing elements 24
) for mixing, dispersion, and reaction at the same time. At that time, the temperature of the prepolymer solution was 35°C, and the flow rate was 36 kg/
The aqueous solution of anhydrous piperazine and triethylamine was transferred at a flow rate of 41.5 kg/hour at a temperature of 25°C.

The flow rate in the tubular mixer was 110 cm/sec.

When we sampled a portion of this aqueous dispersion and measured the average particle diameter, it was 0.2 μm, with no particles larger than 1 μm.
The particle size distribution was sharp. The aqueous dispersion thus obtained was then passed through a vertical stirring demolding thin film evaporator (Hitachi, Ltd.).
Co., Ltd.), and the solvent was continuously removed at a reduced pressure of 55 mmHg and a jacket temperature of 60°C. The solid content of the finally obtained aqueous polyurethane polyurea dispersion was 40%, and almost no methyl ethyl ketone remained.

Further, the average particle diameter of the polyurethane polyurea in this aqueous dispersion was 0.2 μm, and there were no particles larger than 1 μm, and the particle size distribution was sharp. This aqueous dispersion had no sediment at all even after being left standing for one month, and had good stability.

The aqueous solution of anhydrous piperazine and triethylamine used in Example 1 was placed in a container of I, ooo Z, and while stirring, the prepolymer solution used in Example I was added all at once at 35°C. The mixture was sufficiently stirred in a reaction vessel equipped with an electric stirring blade to mix, disperse, and react.

The average particle size of this aqueous dispersion was 0.4 μm and 1 μm.
27% of the total particles contained particles larger than m, and the particle size distribution was broad. The organic solvent in this aqueous dispersion was then distilled off under reduced pressure in a batchwise manner.

The polyurethane polyurea aqueous dispersion thus obtained had a solid content of 40% and almost no solvent remained. or,
Compared to the manufacturing method of Example 1, the power consumption was higher and the efficiency of recovering the organic solvent was also lower. Furthermore, the average particle diameter of this aqueous dispersion was 0.6 μm, and particles with a diameter of 1 μm or more comprised 45% of the total particles, and the particle size distribution was also broad. This aqueous dispersion had sediments formed after it was allowed to stand for one month.

1,00% as in Comparative Example 1 (Pour the aqueous solution of anhydrous piperazine and triethylamine used in Example 1 into a container R1, and add 35% of the prepolymer solution used in Example 1 to it while stirring). The mixture was added all at once at °C, thoroughly stirred in a reaction pot equipped with an electric stirring blade, and mixed, dispersed, and reacted.

When a part of this polyurethane polyurea aqueous dispersion was collected and the average particle diameter was measured, it was 0.4 μm and 1 μm.
The above particles accounted for 27% of the total particles, and the particle size distribution was also broad.

This aqueous polyurethane polyurea dispersion was subsequently transferred to the same vertical stirred membrane type thin film evaporator as in Example 1, and the solvent was continuously removed under the same conditions.

The polyurethane polyurea aqueous dispersion thus obtained had a solid content of 40% and almost no solvent remained. The average particle diameter of this aqueous dispersion was 0.5 μm, particles with a diameter of 1 μm or more were included in 33% of the total particles, and the particle size distribution was also broad. After this water dispersion was allowed to stand still for a month, sediment still formed.

Disaster 1 Polytetramethylene glycol 2 with 11,000 molecules,
129 parts, polytetramethylene glycol 1 with a molecular weight of 2,000, 593 parts, dimethylolpropionic acid 27
8 parts of 4,4'-dicyclohexylmethane diisocyanate, 1,834 parts of methyl ethyl ketone and 95.1 parts of hydrated hydrazine with a solution of prepolymer in methyl ethyl ketone with an NGO content of 1.7% in the molecule obtained from 3,889 parts of methyl ethyl ketone. parts, triethylamine 209.5 parts, water 10 parts,
The aqueous solution obtained by homogeneously mixing 480 parts was transferred from each tank to a tubular mixer (manufactured by Noritake Co., Ltd., number of elements: 24) using a non-pulsating plunger pump, where it was mixed, dispersed and reacted at the same time. Ta. At this time, the prepolymer solution was transferred at a temperature of 40°C and a flow rate of 60 kg/hour, and the aqueous solution of hydrated hydrazine and triethylamine was transferred at a temperature of 25°C and a flow rate of 66.6 kg/hour. The flow rate inside the vessel was 180 cm/sec. When a portion of this aqueous dispersion was sampled and the average particle size was measured, it was found to be 0.
．． The particle diameter was 1 μm, and there were no particles larger than 1 μm, and the particle size distribution was sharp. The aqueous dispersion thus obtained was then passed through a vertical stirring demolding thin film evaporator (Hitachi, Ltd.).
(manufactured by) and the vacuum level was 55 mmHg and the jacket temperature was 6.
Solvent removal was carried out continuously at 0°C. The solid content of the final polyurethane polyurea aqueous dispersion was 40%,
Almost no methyl ethyl ketone remained. Moreover, the average particle diameter of this aqueous dispersion is 0.1 μm, and 1 μm.
There were no particles larger than m, and the particle size distribution was sharp.

This aqueous dispersion had no sediment at all even after being left standing for one month, and had good stability.

The aqueous solution of hydrazine hydrate and triethylamine used in Example 2 was placed in a 1.000 f container, and the prepolymer solution used in Example 4 was added to it while stirring.
The mixture was added all at once at 0°C, thoroughly stirred in a reaction vessel equipped with an electric stirring blade, and mixed, dispersed, and reacted.

The average particle size of this aqueous dispersion was 0.3 μm and 1 μm.
21% of all particles contained particles larger than m, and the particle size distribution was also broad. Next, the organic solvent in this aqueous dispersion was distilled off under reduced pressure in a batchwise manner.

The polyurethane polyurea aqueous dispersion thus obtained had a solid content of 40% and almost no solvent remained. or,
Compared to the manufacturing method of Example 2, the power consumption was higher and the efficiency of recovering the organic solvent was also lower. Furthermore, the average particle diameter of this aqueous dispersion was 0.5 μm, and particles with a diameter of 1 μm or more were included in 37% of the total particles, and the particle size distribution was also broad. This aqueous dispersion produced sediment after being left standing for one month.

As in Comparative Example 3, the aqueous solution of hydrated hydrazine and triethylamine used in Example 2 was placed in a 1.00042 container, and while stirring, the prepolymer solution used in Example 2 was added at 35°C. The mixture was added all at once and sufficiently stirred in a reaction pot equipped with electric stirring blades to mix, disperse, and react. When a part of this polyurethane polyurea aqueous dispersion was sampled and the average particle size was measured, it was found to be 0.3 μm, and particles of 1 μm or more comprised 21% of the total particles, and the particle size distribution was also broad. This aqueous polyurethane polyurea dispersion was subsequently transferred to the same vertical stirring molded thin film evaporator as in Example 2, and the solvent was continuously removed under the same conditions.

The polyurethane polyurea aqueous dispersion thus obtained had a solid content of 40% and almost no solvent remained. The average particle diameter of this aqueous dispersion was 0.4 μm, particles with a diameter of 1 μm or more were included in 26% of the total particles, and the particle size distribution was also broad. After this water dispersion was allowed to stand still for a month, sediment still formed.

1 boat Main The lower layer component of the distillate obtained by distillation using a thin film evaporator instead of 8,168 parts of water in Example 1 (water/methyl ethyl ketone/triethylamine = 75/24.510.5
An aqueous solution of anhydrous piperazine and triethylamine was prepared in the same manner as in Example 1 except that 878 parts (weight ratio) and 7509 parts of water were used, and then mixed in a KEX type tubular mixer in the same manner as in Example 1. Dispersion and reaction were performed. However, the flow rate of the prepolymer was 36 kg/hour, and the flow rate of the aqueous solution of anhydrous piperazine and triethylamine was 42.6 kg/hour. When a portion of this polyurethane polyurea aqueous dispersion was sampled and the average particle diameter was measured, it was found to be 0.2 μm, with a sharp distribution. Thereafter, the solvent was removed using a thin film falling evaporator in the same manner as in Example 1.

The solid content of the finally obtained aqueous polyurethane polyurea dispersion was 40%, and almost no methyl ethyl ketone remained. Furthermore, the lower layer component of the distillate obtained by removing the solvent can be reused, making it very economical. Further, the average particle diameter of this aqueous dispersion was 0.2 μm, and it had a sharp distribution. Even after standing for one month, there was no sediment at all, and it had good stability.

<Effects of the present invention> According to the method of the present invention, compared to conventional batch methods or methods using a shear force mixer in commercial production, there is no need for a powerful stirrer or shear force mixer for dispersion in water. , these operations require no energy at all and are economical, and have excellent scale-up properties.Furthermore, no mechanical shearing force is applied when mixing the synthetic resin organic solvent solution or organic solvent dispersion with water. Therefore, even if almost all of the organic solvent is removed by distillation, there are fewer problems such as aggregation of the resulting aqueous dispersion, and it has superior storage stability and mechanical stability compared to conventional products.
Furthermore, an aqueous polyurethane polyurea dispersion with stable physical properties can be obtained.

Furthermore, when a thin film evaporator is used to remove organic solvents by distillation,
Not only is it possible to remove the solvent without coarsening the fine and stable particles obtained in the tubular mixer and widening the particle size distribution, but it is also possible to significantly improve the efficiency of distillation removal of organic solvents. The release of organic solvent into the outside air is extremely small, making it safe.

Furthermore, the components recovered by distillation can be reused, making it very economical.

The aqueous polyurethane polyurea dispersion obtained by the method of the present invention can be used for many purposes. For example, coating textiles, paper, leather, wood, metals, impregnating fibers and textiles, binders for fur, adhesives, backing agents,
Hydrophobizing agent, elasticity component or crushing prevention component in the construction industry (e.g. additive to evaporated concrete mixtures and asphalt mixtures), vehicles for various paints,
It can be used for external paints, household aerosol paints, etc. Also, coal powder, wood powder, glass fiber,
It can also be used as a binder for asbestos, paper, plastic or rubber scraps, ceramic materials, etc. Furthermore, the polyurethane polyurea liquid obtained by the method of the present invention can be used as a softening agent in the production of elastic films, foils, and yarns, as an auxiliary agent in textile printing and yarn industries, and as an additive for synthetic resin dispersions. It can be used in a wide range of applications, including as a sizing agent and as a leather finishing agent.

Claims (1)

[Claims] 1. An organic solvent solution or organic solvent dispersion of a synthetic resin that can be dispersed in water and water are mixed in a tubular mixer in which a plurality of mixing elements with no moving parts are fixed. A method for producing an aqueous synthetic resin dispersion, which comprises mixing, dissolving or dispersing an organic solvent solution or dispersion of the synthetic resin in water, and then removing the organic solvent in the solution or dispersion by distillation. . 2. The manufacturing method according to claim 1, wherein the organic solvent in the solution or dispersion is removed by distillation using a thin film evaporator. 3. The manufacturing method according to claim 1, wherein the organic solvent in the solution or dispersion is removed by distillation using a stirred membrane type thin film evaporator. 4. The manufacturing method according to claim 1, wherein the water-dispersible synthetic resin is polyurethane or polyurethane polyurea. 5. The manufacturing method according to claim 1, wherein the water-dispersible synthetic resin is an isocyanate-terminated urethane prepolymer containing a hydrophilic group. 6. The production method according to claim 1, wherein the water-dispersible synthetic resin is an isocyanate-terminated urethane prepolymer containing a hydrophilic group, and a diamine or diimine is used in addition to water. 7. The method according to claim 1, wherein the water-dispersible synthetic resin is an isocyanate-terminated urethane prepolymer containing an ionic hydrophilic group, and in addition to water, a diamine or diimine and a neutralizing agent other than the diamine or diimine are used. Production method. 8. A plurality of mixing elements with no moving parts are fixed inside to mix an organic solvent solution or organic solvent dispersion of a carboxyl group-containing isocyanate-terminated urethane prepolymer and an aqueous solution containing a diamine or diimine and other bases. A urea bond forming reaction between the isocyanate group of the urethane prepolymer and the amino group or imino group of the diamine or diimine, and a neutralization reaction between the carboxyl group of the urethane prepolymer and a base. simultaneously, the polyurethane polyurea produced in the reaction is dissolved or dispersed in a mixed medium of an organic solvent and water, and then the organic solvent in the solution or dispersion is distilled off using a stirring model evaporator. A method for producing a polyurethane polyurea aqueous dispersion.