JP3178543B2 - Method for producing aqueous polyurethane resin dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aqueous polyurethane resin dispersion. More specifically, the present invention relates to a method for producing an aqueous polyurethane resin dispersion, which comprises using a special emulsifier in the step of emulsifying and dispersing an aqueous polyurethane resin dispersion.

[0002]

2. Description of the Related Art The following processes are known as processes for producing aqueous polyurethane resin dispersions.

That is, (1) an aqueous emulsifier solution is added to an organic solvent solution or an organic solvent dispersion of a terminal isocyanate group-containing urethane prepolymer to obtain an aqueous emulsion dispersion of a terminal isocyanate group-containing urethane prepolymer. A method of reacting at least two amine compounds, (2) adding water to an organic solvent solution or an organic solvent dispersion of a terminal isocyanate group-containing urethane prepolymer having a hydrophilic group, and adding an aqueous solution of the terminal isocyanate group-containing urethane prepolymer. (3) a method of obtaining an emulsified dispersion and reacting it with an amine compound having at least two active hydrogen atoms, (3) a method of emulsifying an organic solvent solution or an organic solvent dispersion of a high-molecular-weight polyurethane resin by adding an emulsifier aqueous solution, (4) Organic solution of high molecular weight polyurethane resin having hydrophilic group A solution or an organic solvent dispersion is a method of emulsifying by adding water.

In the method for obtaining an aqueous dispersion using the emulsifiers of the above (1) and (3), a urethane prepolymer or polyurethane resin having a terminal isocyanate group is hydrophobic. Uses homomixers, homogenizers, ultrasonic emulsifiers, etc., but has the disadvantage that a large amount of emulsifier must be used to reduce the particle size.

In the above methods (2) and (4), in which the urethane prepolymer or polyurethane resin having a terminal isocyanate group having a hydrophilic group is used, the urethane prepolymer or the polyurethane resin itself is hydrophilic. Although a stable and small particle diameter can be obtained as compared with the methods (1) and (3), the hydrophilic group must have a certain degree of hydrophilicity in order to obtain a stable aqueous dispersion without generation of aggregates during emulsification and dispersion. It is necessary to contain a large amount.

Accordingly, the aqueous polyurethane dispersion thus obtained contains a large amount of an emulsifier or a large number of hydrophilic groups, so that it has poor adhesion to a substrate, transparency of a film, and water resistance. There was a problem of inferiority.

In order to eliminate these disadvantages, various methods for reducing the content of these emulsifiers or hydrophilic groups have been studied. However, if the content of emulsifiers or hydrophilic groups is reduced, very high emulsification or dispersion will occur. Because of the viscosity and the difficulty of dispersion, various dispersers having stronger shearing force have been studied. For example, the method of dispersing using a homomixer has a problem that the shearing force is insufficient, a complete dispersion cannot be obtained, and separation occurs during storage.

Further, instead of the homomixer, various dispersers such as a homogenizer having a shearing force, a line mill, and a colloid mill have been studied. However, these also have limitations on the rotation speed and the slit interval, and it is difficult to form fine particles until they have sufficient stability.

On the other hand, as a device for emulsifying and dispersing under high pressure, there is a colloid mill manufactured by Menton Gorlin Co., Ltd. Among the emulsifiers studied, it has the most effective effect of dispersing fine particles.
Since the high pressure pre-dispersion liquid is passed between the slits pressed by the force of the strong spring, the pressure applied is limited in terms of safety, and the amount of pre-mixed liquid injected Is injected while pulsating, so that there is a great problem that the slit interval changes and the particle size of the obtained aqueous dispersion fluctuates. For this reason, applications requiring long-term stability require repeated treatment, and even if possible on a test scale, actual production is extremely difficult.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing an aqueous polyurethane resin dispersion which is stable even with a smaller amount of emulsifier or a smaller hydrophilic group content and has a uniform particle size distribution. .

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies while aiming at the above-mentioned problems, and have found that it is possible to solve the problem by using a specific emulsifying device. It was completed.

That is, according to the present invention, a pre-emulsified mixed solution is introduced into a channel in a chamber under pressure, and the mixed solution is caused to collide with a flat portion in the channel under high pressure, or Provided is a method for producing an aqueous polyurethane resin dispersion, which comprises emulsifying a pre-emulsified mixed solution of an organic solvent solution of water and a hydrophilic group-containing high molecular weight polyurethane resin with an apparatus for emulsifying the mixture by colliding the mixture with each other. Is what you do.

Next, the device used in the present invention will be specifically described. The chamber of the device according to the invention consists of the restraining parts 1, 2 in FIG. 1 and the discs 3, 4 which withstand very high pressures. Each of the disks 3 and 4 is formed with two through holes and extremely narrow grooves connecting the two holes. The diameter of this groove is preferably 50 to 1,000 μ. The disc 3 and the disc 4 are inwardly positioned so that the connecting grooves of the two discs are in contact with each other and a 90-degree position such that the grooves are cross-shaped so that the fluid passes from the disc 3 to the disc 4. Are combined.

The disk must be able to withstand liquid impingement under high pressure. For this reason, the material of the disk is a material that can withstand ultra-high pressure, such as a ceramic such as a metal oxide, a boride, a carbide, and a nitride, a mixture thereof, and an inorganic sintered body such as a sintered diamond.

Next, the present invention will be specifically described with reference to the drawings. First, a premixed solution of water and an organic solvent solution of a hydrophilic group-containing high molecular weight polyurethane resin is prepared in an amount of 5 to 30 kg / c.
It is supplied to the holding part 1 in the chamber under a pressure of m ² .
The mixed liquid that has entered the suppressing portion 1 is divided into two channels, introduced into the disk 3, and collides with the flat portion 5 of the disk 4 as it is. The liquid that has collided with the disk 3
Are accelerated through the connecting groove 6 and flow toward the center, and the liquids collide with each other at the center of the disk 3. Ultrafine particles are emulsified by collision with this plane and collision between liquids. Next, the liquid is 90
It flows outward from the center through the connecting groove 7 of the disk 4 formed in a phase-shifted manner, and can be taken out through two holes in the disk 4.

When the mixed solution passes through the channels and grooves in the chamber, the mixed solution is accelerated under pressure. In this case, the pressure is preferably adjusted to be 50 to 10,000 kg / cm ² . If it is less than 50 kg / cm ² , the dispersion will be weak, and if it is more than 10,000 kg / cm ² , the base material will be so worn that it cannot withstand long-term use. Depending on the composition of the polyurethane resin, the stability of the aqueous dispersion may not be sufficiently improved due to secondary aggregation, and therefore, a pressure of 70 to 3000 kg / cm ² is particularly preferable.

The structure of the apparatus of the present invention is not limited to those shown in FIGS. 1 and 2, and the structure is such that the mixed liquid can be made to collide with a predetermined flat portion in the flow path of the champer under high pressure, or under high pressure. Basically, any structure may be used as long as the mixed liquid can collide with each other. For example, a structure having flat portions A and B as shown in FIG. 3 may be used. Alternatively, as shown in FIG. It may be of a structure that can be taken out.

Specific examples of the new emulsifying device used in the present invention include a microfluidizer manufactured by Microfluidics Co., USA and a nanomizer manufactured by Cosmo Keiso Co., Ltd. of Japan.

The method for producing the aqueous polyurethane resin dispersion of the present invention itself may be any of the conventionally well-known methods, for example, the following method.

That is, a polyurethane resin having a hydrophilic atomic group or an atomic group that can be made hydrophilic by neutralization (A-1)
When an organic solvent solution or an organic solvent dispersion liquid is used in which the polyurethane resin has a hydrophilic atomic group, a method of obtaining an aqueous dispersion by mixing with water, or the polyurethane resin can be made hydrophilic by neutralization. When using those having atomic groups, mix with the aqueous solution containing the whole or a part of the neutralizing agent and add the remaining neutralizing agent as necessary, or first mix with water and then neutralize To obtain an aqueous dispersion by adding an emulsifier in advance to an organic solvent solution or an organic solvent dispersion of a polyurethane resin (A-2) having no hydrophilic atomic group or an atomic group that can become hydrophilic by neutralization. A method of obtaining an aqueous dispersion by mixing water afterwards or directly mixing an aqueous emulsifier solution, a urethane ram having a hydrophilic atom group or an atom group that can be made hydrophilic by neutralization, and also having an isocyanate group at a terminal When the urethane prepolymer has a hydrophilic atomic group in the polymer (B-1), the urethane prepolymer is mixed with water and dispersed in water, or the urethane prepolymer having an atomic group that can become hydrophilic by neutralization is used. If so, mix with the aqueous solution containing the whole or a part of the neutralizing agent and add the remaining neutralizing agent as necessary, or add the whole or a part of the neutralizing agent in the prepolymer beforehand. A method of mixing water and dispersing in water, and then reacting with diamine and / or diimine and, if necessary, remaining neutralizing agent,
When the urethane prepolymer (B-1) has a hydrophilic atomic group or an atomic group that can be made hydrophilic by neutralization and also has an isocyanate group at a terminal, the urethane prepolymer has a hydrophilic atomic group and a diamine. And / or a method in which an aqueous dispersion is obtained by mixing with an aqueous solution containing diimine, or in the case where a urethane prepolymer having an atomic group capable of becoming hydrophilic by neutralization is used, the diamine and / or diimine and the whole or a part thereof A method of obtaining an aqueous dispersion by mixing with an aqueous solution containing a neutralizing agent and adding the remaining neutralizing agent as necessary, having no hydrophilic atomic group or an atomic group that can be made hydrophilic by neutralization, and An emulsifier is added in advance to the urethane prepolymer (B-2) having an isocyanate group at the end, and then water is mixed, or directly mixed with an emulsifier aqueous solution to emulsify, The method is reacted with amine and / or diimine or in each method described above, and a method of containing an atomic group which can be a hydrophilic with a hydrophilic atomic groups or neutralized, and a method to use a method of using an emulsifier.

In the production method of the present invention, it is an essential condition that the emulsifying apparatus is used in the step of dispersing in water in each of the above methods. In any of the methods (1) to (4) of the present invention, when the polyurethane resin (A) or the urethane prepolymer (B) is dispersed in water by the above-mentioned apparatus, the polyurethane resin (A) or the urethane prepolymer (B) is previously prepared. And a neutralizing agent, an emulsifier, or an aqueous solution containing these, must be premixed.

As a method of such pre-mixing, for example,
The neutralizing agent, the emulsifier, or the aqueous solution containing them is charged into the polyurethane resin (A) or the urethane prepolymer (B), or the polyurethane resin (A) or the urethane prepolymer ( A batch-type method of adding and mixing B) may be used,
Alternatively, these may be continuously mixed. Various mixers can be used as the mixer for that purpose. For example, a static mixer, a line mill, a rotor-stater type mixer, a harel homogenizer, and others are described in “Chemical Engineering Handbook, pp. 779-782 (1989)”. The high-speed rotating pipe-in mixer, the pressurized nozzle emulsifier, the ultrasonic emulsifier and the like described above can be used.

The polyurethane resin (A) used in the present invention comprises a polyurethane resin (A-1) having a hydrophilic atomic group or an atomic group which can be made hydrophilic by neutralization and a hydrophilic atomic group or a hydrophilic resin by neutralization. There is a polyurethane resin (A-2) having no atomic group that can be used.

The urethane prepolymer having a terminal isocyanate group (B) used in the present invention has a hydrophilic atom group or an atom group which can be made hydrophilic by neutralization, and also has a terminal isocyanate group. There is a urethane prepolymer (B-2) which does not have a polymer (B-1) and a hydrophilic atom group or an atom group which can be made hydrophilic by neutralization and has an isocyanate group at a terminal.

The polyurethane resin (A) and the urethane prepolymer containing terminal isocyanate groups (B) are
For example, a conventionally known polyisocyanate compound, a hydrophilic atomic group or an active hydrogen-containing compound that does not have an atomic group that can be made hydrophilic by neutralization but can react with an isocyanate group, and, if necessary, a hydrophilic atomic group Alternatively, it is produced from an active hydrogen-containing compound having an atomic group which can be made hydrophilic by neutralization and capable of reacting with an isocyanate group.

The polyurethane resin (A) and the urethane prepolymer containing terminal isocyanate groups (B) according to the present invention
Is manufactured by a conventionally known method. For example, the polyisocyanate compound and an active hydrogen-containing compound (including an active hydrogen-containing compound containing a hydrophilic atomic group or an atomic group that can be made hydrophilic by neutralization, if used)
In the case of the polyurethane resin (A), the equivalent ratio of the isocyanate group to the active hydrogen group is 0.8: 1 to 1.
In a ratio of 2: 1, preferably 0.9: 1 to 1.1: 1, and in the case of the urethane prepolymer containing terminal isocyanate groups (B), 1.1: 1 to 3: 1, preferably 1.
At a ratio of 2: 1 to 2: 1, 20 to 120 ° C, preferably 3
React at 0-100 ° C.

These reactions can be carried out in the absence of a solvent, but an organic solvent can also be used for the purpose of controlling the reaction of the reaction system or reducing the viscosity. Such organic solvents are not particularly limited, but include, for example, aromatic hydrocarbons such as toluene and xylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; acetates such as ethyl acetate and butyl acetate; dimethylformamide; Amides such as methylpyrrolidone are exemplified. When such an organic solvent is removed by distillation from the finally obtained polyurethane resin aqueous dispersion, it is preferable to use a solvent having a relatively low boiling point which is easily removed by distillation. Even when it is necessary to use an organic solvent having a boiling point of 100 ° C. or higher, it is preferable to keep the amount of use to a minimum.

The hydrophilic group or the group that can be made hydrophilic by neutralization in the polyurethane resin (A-1) and the urethane prepolymer (B-1) according to the present invention include, for example, a carboxyl group and a sulfone group. Examples include an acid group, a sulfonate group, a tertiary amino group, a quaternary amino group, and a repeating unit of ethylene oxide. The compound has a hydrophilic atomic group or an atomic group that can be made hydrophilic by neutralization, and reacts with an isocyanate group. It can be obtained by copolymerizing at least one or more active hydrogen-containing compounds that can be used during production of the polyurethane resin (A-1) or urethane prepolymer (B-1).

The polyurethane resin (A) used in the present invention
-1) or the urethane prepolymer (B-1), the content of the hydrophilic group bonded to the molecule or the group capable of becoming hydrophilic by neutralization is determined by the hydrophilic group or neutralization. If the atomic group that can become hydrophilic is an anionic group such as a carboxyl group, a sulfonic acid group, or a sulfonate group, or a cationic group such as a tertiary amino group or a quaternary amino group, At least 0.005 equivalent or more, preferably 0.01 to 0.2 per 100 parts by weight of the obtained polyurethane resin solids.
In the case of a nonionic atomic group, it must be contained in an amount of at least 2 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the finally obtained polyurethane resin solids.

Examples of the polyisocyanate compound which can be used in producing the polyurethane resin (A) or urethane prepolymer (B) used in the present invention include 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. Isocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
2,4′-diphenylmethane diisocyanate, 2,
2'-diphenylmethane diisocyanate, 3,3'-
Dimethyl-4,4'-biphenylenediisocyanate,
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,
4-cyclohexylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,
4'-dicyclohexylmethane diisocyanate, 3,
3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate and the like.

In the production of the polyurethane resin (A) or urethane prepolymer (B) used in the present invention, it does not have a hydrophilic atom group or an atom group which can be made hydrophilic by neutralization, but can react with an isocyanate group. The active hydrogen-containing compound has an average molecular weight of 300 to 1 for convenience.
It is classified into a high molecular weight compound having a molecular weight of preferably 5,000 to 5,000, and a low molecular weight compound having a molecular weight of 300 or less.

Examples of the high molecular weight compound include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols,
Polyacrylate polyol, polyesteramide polyol, polythioether polyol and the like can be mentioned.

As the polyester polyol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, glycol components such as hydroquinone and their alkylene oxide adducts, and succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid Acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4
-Naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and the dicarboxylic acids An anhydride or an ester-forming derivative; a polyester obtained by a dehydration condensation reaction from an acid component such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and an ester-forming derivative of these hydroxycarboxylic acids. Other examples include polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymerized polyesters thereof.

As the polyether, ethylene glycol, diethylene glycol, triethylene glycol,
Propylene glycol, trimethylene glycol, 1,
3-butanediol, 1,4-butanediol, 1,6
-Hexanediol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose, aconit sugar, trimellitic acid, hemi-mellitic acid, phosphoric acid, ethylenediamine, diethylenetriamine, triisopropanolamine, pyrogallol, dihydroxybenzoic acid, Ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, using one or more compounds having at least two active hydrogen atoms such as hydroxyphthalic acid and 1,2,3-propanetrithiol as initiators One obtained by subjecting one or more monomers such as tetrahydrofuran and cyclohexylene to addition polymerization by a conventional method is exemplified.

As the polycarbonate polyol,
1,4-butanediol, 1,6-hexanediol,
Compounds obtained by reacting a glycol such as diethylene glycol with diphenyl carbonate or phosgene are exemplified.

The low molecular weight compounds include those having a molecular weight of 30
A compound containing at least two or more active hydrogens in a molecule of 0 or less, for example, a glycol component used as a raw material of a polyester polyol; glycerin, trimethylolethane, trimethylolpropane, sorbitol,
Polyhydroxy compounds such as pentaerythritol; ethylenediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine;
3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, 1,2
Amine compounds such as propanediamine, hydrazine, diethylenetriamine and triethylenetetramine;

Examples of the active hydrogen-containing compound having a hydrophilic atomic group or an atomic group that can be made hydrophilic by neutralization and reacting with an isocyanate group include, for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, and sulfobenzoic acid. ,
Sulfonic acid-containing compounds such as sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 2,4-diaminotoluene-5-sulfonic acid and derivatives thereof, or Polyester polyol obtained by copolymerization; 2,2-
Carboxylic acid-containing compounds such as dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2,6-dioxybenzoic acid, and 3,4-diaminobenzoic acid, and derivatives thereof Or a polyester polyol obtained by copolymerizing them;
3 such as methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, oleyldiethanolamine, N, N-dioxyethylaniline, N, N-dioxyethyltoluidine, alkyldiisopropanolamine, allyldiisopropanolamine, dioxyethylpiperazine, etc.
Tertiary amino group-containing compounds and derivatives thereof or polyester polyols or polyether polyols obtained by copolymerizing them; tertiary amino group-containing compounds and derivatives thereof or polyester polyols or polyethers obtained by copolymerizing them Polyol, methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate,
A reaction product of a quaternizing agent such as benzyl chloride, p-nitrobenzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromohydrin, epichlorohydrin, or bromobutane; a polymer containing at least 30% by weight of ethylene oxide repeating units, Having a molecular weight of 300 to 10,000 containing at least one active hydrogen therein
Nonoxy group-containing compounds such as polyoxyethylene-polyoxyalkylene copolymer or a polyester polyether polyol obtained by copolymerizing these, and
These are used alone or in combination.

As the neutralizing agent that can be used in the production of the aqueous polyurethane resin dispersion of the present invention, a polyurethane resin having an atomic group capable of becoming hydrophilic by neutralization (A-
1) or, particularly, any one capable of neutralizing or ionizing an atomic group capable of becoming hydrophilic of the urethane prepolymer (B-1) having an atomic group capable of becoming hydrophilic by neutralization and having an isocyanate group at a terminal. There are no restrictions,
For example, nonvolatile bases such as sodium hydroxide and potassium hydroxide; tertiary amines such as trimethylamine and triethylamine; volatile bases such as ammonia; inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; formic acid, acetic acid, lactic acid and citric acid And organic acids such as tartaric acid; quaternary such as methyl chloride, methyl bromide, dimethyl sulfate, diethyl sulfate, benzyl chloride, p-nitrobenzyl chloride, benzyl bromide, ethylene chlorohydrin, ethylene bromhydrin, epichlorohydrin, and brombutane Agents.

Examples of the emulsifier that can be used in the method of the present invention 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, alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkane sulfonates, sodium alkyl diphenyl ether sulfonates, etc. Anionic emulsifiers are exemplified.
These emulsifiers may be used in combination with the aforementioned hydrophilic atomic group or an atomic group that can be made hydrophilic by neutralization. The amount of use is not particularly limited, but when the emulsifier is used alone, at least 1 part by weight or more, preferably 2 to 10 parts by weight, per 100 parts by weight of the finally obtained polyurethane resin solids.
It is preferred that the content be contained by weight.

Examples of the amine compound having at least two active hydrogen atoms which can be used in the production of the aqueous polyurethane resin dispersion of the present invention include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, and piperazine. Diamines such as 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, and 1,4-cyclohexanediamine; diethylenetriamine, diethylenetriamine, Polyamines such as propylene triamine and triethylene tetramine; hydrazines; acid hydrazides;
These may be used alone or in combination.

The amount of the amine compound used in the present invention is 0: 1 to 1: 1, preferably 0.6: 1 to 1 in isocyanate group in the urethane prepolymer (B).
It must be 0.98: 1.

In the method of the present invention, the polyurethane resin (A) or the urethane prepolymer (B) is dispersed in water using the above-mentioned emulsifying apparatus, and then a neutralizing agent is added.
The emulsifier, diamine and / or diimine or an aqueous solution containing these may be mixed. As a method of such mixing, as in the case of the above-mentioned pre-mixing, mixing may be performed by either a batch method or a continuous method. Is also good.

The aqueous polyurethane resin dispersion thus obtained may be used as it is, but the organic solvent may be removed by distillation if necessary, and used as an aqueous polyurethane resin dispersion.

Various distillation apparatuses can be used to remove the organic solvent by distillation. However, a distillation apparatus that does not release the organic solvent from the distillation efficiency or the removed organic solvent to the atmosphere is preferable, and a thin film evaporator is particularly preferable.

As a particularly preferred continuous type thin film evaporator used in the present invention, for example, “Chemical Equipment Handbook, No. 4
04-407 (1989) ", for example, a Cebcon evaporator, a horizontal control device or a vertical control device, manufactured by Hitachi, Ltd.
Shinko Faudler Co., Ltd.'s WFE thin film distillation apparatus may be mentioned. Among them, a vertical apparatus having a rotating shaft installed in a vertical direction may not have a liquid pool.

The distillation is generally carried out at an apparatus jacket temperature of about 20 to 100 ° C., preferably 30 to 90 ° C., and a degree of vacuum of about 5 to 300 mmHg, preferably 10 to 200 mmHg.
g, whereby most of the organic solvent contained in the aqueous polyurethane resin dispersion is removed.

Further, in the production method of the present invention,
If necessary, in addition to water, other aqueous dispersions and aqueous dispersions, for example, emulsions of vinyl acetate, ethylene vinyl acetate, acrylic, acrylic styrene, etc .; styrene / butadiene, acrylonitrile / butadiene, acrylic Latexes such as butadiene; ionomers such as polyethylene and polyolefin; various aqueous dispersions such as polyurethane, polyester, polyamide and epoxy resins;
An aqueous dispersion may be used in combination.

The aqueous dispersion of a polyurethane resin obtained by removing the organic solvent is a substantially solvent-free aqueous dispersion having a solid content of about 15 to 60%, preferably 20 to 50%. However, even when the organic solvent having a boiling point of 100 ° C. or more must be used for the production of the aqueous polyurethane resin dispersion, 20% by weight of the total weight of the aqueous dispersion is required.
By that time the use of such organic solvents should be stopped.

The aqueous polyurethane resin dispersion obtained by the method of the present invention can be used in combination with other aqueous dispersions, for example, emulsions of vinyl acetate, ethylene vinyl acetate, acrylic, acrylic styrene, etc .; styrene / butadiene, acrylonitrile / Butadiene-based, acrylic-butadiene-based latex, etc .; polyethylene-based, polyolefin-based ionomer, etc .; polyurethane, polyester, polyamide, and epoxy-based water dispersions can be blended and used at an arbitrary ratio. Further, fillers such as carbon black, clay, talc, and aluminum hydroxide; additives such as silica sol, alumina sol, plasticizer, and pigment; film-forming assistants such as alkylene glycol derivatives; epoxy resins, melamine resins, isocyanate compounds, and aziridines Compounds, cross-linking agents such as polycarbodiimide compounds, etc .;

The aqueous polyurethane dispersion obtained by the method of the present invention includes various plastics such as polyvinyl chloride, nylon, polyester, and polyurethane, textile products, synthetic leather products, metals such as aluminum, copper, and iron, paper, wood, and the like. Excellent adhesion to glass, etc., for example, as a base resin for fibers, impregnating agents or coating agents for synthetic leather products, adhesives for various substrates, coating agents, aqueous paints, aqueous inks, or sizing agents for organic and inorganic fibers Can be used widely.

[0051]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.

Production Example 1 First, 660 parts of 1,4-butanediol / adipic acid polyester (OH value: 102) was added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser.
After dehydration at 0 to 130 ° C., the mixture was cooled to 50 ° C., 19.2 parts of neopentyl glycol and 582 parts of methyl ethyl ketone were added, and the mixture was sufficiently stirred and mixed. After that, 174 parts of Coronate T-80 (2. ,
4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 8/2 mixture), heated to 80 ° C., and reacted at this temperature for 2 hours to obtain a prepolymer solution having a terminal isocyanate group. . After completion of the reaction, the mixture was cooled to 40 ° C., and 20.8 parts of dimethylolpropionic acid was added.
The reaction is continued and cooled at 70 ° C. until the NCO% reaches 0.01% or less. Then, 10% aqueous ammonia 26.4
The mixture was stirred well, and a viscous resin solution A having a nonvolatile content of 59% was obtained.

Production Example 2 First, 731.2 parts of 1,4-butanediol / adipic acid polyester (OH value: 56) was added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. Lower one
After dehydration at 20 to 130 ° C., the mixture was cooled to 50 ° C., and 33.2 parts of 1,4-butanediol and 795 parts of methyl ethyl ketone were added.
A portion of 4,4'-dicyclohexylmethane diisocyanate was added, the mixture was heated to 80 ° C, and reacted at this temperature for 2 hours to obtain a prepolymer solution having a terminal isocyanate group. After completion of the reaction, the reaction mixture is cooled to 40 ° C, 35.5 parts of dimethylolpropionic acid is added, and the reaction is continued at 70 ° C until the NCO% reaches 2.1%, followed by cooling. A viscous resin solution B having a nonvolatile content of 60% was obtained.

Production Example 3 First, 848.2 parts of polytetramethylene glycol (OH value: 56) and 51.8 parts of 1,4-butane were placed in a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser. After the diol and 565.4 parts of toluene are added and thoroughly stirred and mixed, 419.2 parts of isophorone diisocyanate is added, and the reaction is continued and cooled at 80 ° C. until the NCO% reaches 2.6%. A viscous resin solution C having a nonvolatile content of 60% was obtained.

Example 1 After 884 g of ion-exchanged water was added to 1000 g of the above resin solution A and stirred, the mixed solution was mixed with a microfluidic device of the present invention having a chamber connected to a disk having a hole having an inner diameter of 100 μm. introduced in Daiza pressurized compressors (microfluidic Co.) to 8 Kg / cm ^2, a flow rate of 200 meters / Sec, the dispersion in water at a pressure of 500 Kg / cm ² was performed.

The resulting aqueous dispersion was desolvated under reduced pressure to remove methyl ethyl ketone, and a polyurethane resin aqueous dispersion having a nonvolatile content of 45% was obtained. The particle size of the obtained aqueous dispersion was 0.4 μm, the storage stability after standing at room temperature for 3 months was good, and no separation or sediment was generated.

Comparative Example 1 The mixed solution of Example 1 was used in
350 kg / PE-15M (manton golin)
Dispersed in water by passing 5 times at a pressure of cm ² ,
The dispersion was insufficient and the storage stability test showed two layers separated.

Comparative Example 2 The mixture of Example 1 was stirred in a TK-Automixer (manufactured by Tokushu Kika) at 10,000 rpm for 15 minutes, but the dispersion was insufficient and sediment was generated in the storage stability test. Was.

Example 2 Triethylamine was added to 1,000 g of the above resin solution A.
After 5 parts and 900 g of ion-exchanged water were added and stirred, the mixture was added to an emulsifier Microfluidizer (manufactured by Microfluidic) having a chamber connected to a disk having an inner diameter of 100 μm at 8 kg / cm ² . Introduced by pressurized compressor, flow rate 200m / Sec, 50
Dispersion was performed in water at a pressure of 0 Kg / cm ² .

Anhydrous piperazine 2 was added to the obtained aqueous dispersion.
After 206 parts of an aqueous solution containing 0.6 part was charged and subjected to a chain elongation reaction, the solvent was subsequently removed under reduced pressure to remove methyl ethyl ketone, whereby an aqueous polyurethane resin dispersion having a nonvolatile content of 45% was obtained.

The particle size of the obtained aqueous dispersion is 0.35 μm.
After storage at room temperature for three months, the storage stability was good, and no separation or sediment was generated. Comparative Example 3 The mixed solution of Example 2 was applied to a manton gaulin colloid mill TY
350 kg / PE-15M (manton golin)
Dispersed in water by passing 5 times at a pressure of cm ² ,
The dispersion was insufficient and the storage stability test showed two layers separated.

Comparative Example 4 The mixture of Example 2 was stirred in a TK-Automixer (manufactured by Tokushu Kika Co., Ltd.) at 10,000 rpm for 15 minutes, but the dispersion was insufficient and sediment was generated in the storage stability test. Was.

Example 3 To 1000 g of the above resin solution A was added 595 parts of an aqueous solution obtained by dissolving 35.8 parts of polyoxyethylene nonylphenyl ether having 25 moles of ethylene oxide, and the mixture was stirred. 8 kg / cm in an emulsifier Microfluidizer (manufactured by Microfluidic Co., Ltd.) having a chamber connected to a disc having holes
Introduced by ² pressurized compressor, flow rate 200m
/ Sec, dispersed in water at a pressure of 500 kg / cm ² .

Anhydrous piperazine 26 was added to the obtained aqueous dispersion.
Then, 260 parts of an aqueous solution containing 2 parts by weight was added and a chain extension reaction was carried out to obtain an aqueous polyurethane resin dispersion having a nonvolatile content of 41%. The particle size of the obtained aqueous dispersion is 0.7 μm,
The storage stability after standing for months was good, and no separation or sediment was generated.

Comparative Example 5 The mixed solution of Example 3 was mixed with a Menton-Gaulin colloid mill TY
350 kg / PE-15M (manton golin)
Dispersed in water by passing 5 times at a pressure of cm ² ,
Dispersion was insufficient and storage stability test showed that two layers separated and sediment was also generated.

Comparative Example 6 The mixture of Example 3 was stirred in a TK-Automixer (manufactured by Tokushu Kika) at 10,000 rpm for 15 minutes. However, the dispersion was insufficient and a large amount of sediment was found in the storage stability test. Had occurred.

[0067]

According to the production method of the present invention, it has been difficult to obtain a stable aqueous dispersion with a conventional emulsifier, and the content of a hydrophilic atomic group or the amount of an emulsifier used is at a level lower than before. In addition, an aqueous polyurethane resin dispersion which is extremely fine, has a uniform particle size distribution, and is excellent in long-term stability or mechanical stability can be easily produced.

Further, according to the method of the present invention, even under the same composition, the ratio of the premixed liquid, that is, the mixing ratio of the polyurethane resin or urethane prepolymer and water, and the setting conditions of the pressure of the emulsifier can be changed. Thereby, the particle diameter can be easily changed.

Since the aqueous polyurethane resin dispersion obtained in the present invention has a very small content of a hydrophilic atomic group or a very small amount of an emulsifier, the film after drying has high transparency,
Excellent smoothness, gloss, water resistance, and mechanical strength,
It also has the feature of excellent adhesion to various substrates. In a particularly preferred embodiment of the present invention, in a series of continuous treatments from premixing, particularly when the urethane prepolymer (B) of the present invention is used, the urethane prepolymer (B) is dispersed in water or simultaneously with water. Since it reacts with diamine and / or diimine immediately after the reaction, a conventional batch process cannot avoid a side reaction with water and is difficult to produce due to problems such as generation of aggregates or poor emulsification due to the side reaction. It has become possible to stably produce an aqueous polyurethane resin dispersion.

The aqueous polyurethane resin dispersion thus obtained can be handled in the same manner as a conventional aqueous polyurethane dispersion. The aqueous dispersion obtained by removing the organic solvent from the aqueous dispersion is subjected to pollution or fire caused by the organic solvent. Worry is extremely small.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view of a chamber of the present apparatus.

FIG. 2 is a sectional view of a chamber of the apparatus.

FIG. 3 is an assembled perspective view of a disk of a chamber of the apparatus.

FIG. 4 is an assembled perspective view of a disk of a chamber of the apparatus.

FIG. 5 is an assembled perspective view of a disk of a chamber of the apparatus.

[Explanation of symbols]

 1, 2 suppression part 3, 3a, 3b, 4, 4a, 4b disk 5, 6 disk flat part 7 disk connection groove 8 center of connection groove 9 disk connection groove 10 disk hole

Claims (5)

(57) [Claims] 1. A pre-emulsified mixed liquid is introduced into a flow path in a chamber under pressure, and the mixed liquid is caused to collide with a flat portion in the flow path under high pressure, or the mixed liquid is mixed in the flow path under high pressure. A method for producing an aqueous polyurethane resin dispersion, comprising emulsifying a pre-emulsified mixture of water and an organic solvent solution of a high molecular weight polyurethane resin containing a hydrophilic group in an apparatus for emulsifying the polyurethane resin by colliding each other. 2. A pre-emulsified mixed liquid is introduced into a flow path in a chamber under pressure, and the mixed liquid is caused to collide with a flat portion in the flow path under high pressure, or the mixed liquid is mixed in the flow path under high pressure. A device for emulsifying by colliding each other, characterized by emulsifying a pre-emulsified mixture of an emulsifier aqueous solution and an organic solvent solution of a high molecular weight polyurethane resin containing no hydrophilic group,
A method for producing an aqueous polyurethane resin dispersion. 3. A pre-emulsified mixed liquid is introduced into a flow path in a chamber under pressure, and the mixed liquid is caused to collide with a flat portion in the flow path under high pressure, or the mixed liquid is mixed under high pressure in the flow path. A device for emulsifying by colliding with each other, emulsifying a pre-emulsified mixed solution of water and a isocyanate group-terminated urethane prepolymer containing a hydrophilic group, and then reacting with a diamine and / or diimine, A method for producing an aqueous polyurethane resin dispersion. 4. A pre-emulsified mixed liquid is introduced under pressure into a flow path in a chamber, and the mixed liquid is caused to collide with a flat portion in the flow path under high pressure, or the mixed liquid is mixed under high pressure in the flow path. A device for emulsifying by colliding with each other, emulsifies a pre-emulsified mixture of an aqueous emulsifier solution and a isocyanate group-terminated urethane prepolymer containing a hydrophobic group, and then diamine and / or
Alternatively, a method for producing an aqueous polyurethane resin dispersion, characterized by reacting with a diimine. 5. The pressure at the time of collision is 50 to 10,000 kg /
The method for producing an aqueous polyurethane resin dispersion according to any one of claims 1 to 4, wherein the aqueous dispersion is cm ² .