JP2014122252A - Manufacturing method and manufacturing apparatus of aqueous resin particulate-mixed liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To disperse aggregates of resin particulates within individual resin particulates.SOLUTION: The provided method for manufacturing an aqueous resin particulate-mixed liquid includes: a low-pressure agitation step A of agitating a primary aqueous liquid mixture L1 provided as a crudely dispersed aqueous liquid mixture in which many individual resin particulates 61 and aggregates 63 generated, as masses, due to aggregations of multiple individual resin particulates 61 are mixed and dispersed in a pressure state lower than atmospheric pressure where the liquid mixture L1 remains even after evaporation; a high velocity impression step B of impressing, onto a secondary aqueous liquid mixture L2 obtained from the primary aqueous liquid mixture L1 as a result of the low-pressure agitation, a velocity greater than the kinetic velocity of the primary aqueous liquid mixture L1 accompanying the agitation; a collision treatment step C of inducing, at a high speed, mutual collisions of the secondary aqueous liquid mixture L2 on which the high velocity is being impressed; and a storing step D of storing a tertiary aqueous liquid mixture L3 obtained from the secondary aqueous liquid mixture L2 as a result of the collision treatment.

Description

  The present invention relates to a method and an apparatus for producing an aqueous resin fine particle mixture.

  In general, aqueous emulsions (polymer emulsions) used for binder resins such as paints, inks, and adhesives are known (see, for example, Patent Document 1 below). This type of aqueous emulsion can be obtained, for example, by a method in which a monomer, a polymerization initiator, a surfactant (emulsifier), etc. are added in water to carry out emulsion polymerization. Resin particles (polymer particles) of various sizes exist over a wide range of diameter (diameter) of 0.1 to several tens of μm.

JP-A-5-194911

  As described above, the resin particles exist over a wide range because a plurality of resin fine particles (primary particles) having a particle size of about several tens of nm to 0.1 μm (100 nm) are aggregated to form an aggregate (secondary). This is because particles are easily generated. An aqueous emulsion with a large amount of agglomerates is significantly inferior in terms of rust prevention (weather resistance), coating film hardness, odor, etc., compared with those containing a large amount of resin fine particles alone. Development of a manufacturing method and a manufacturing apparatus of an aqueous resin fine particle mixed solution capable of achieving separation and nano-ization is desired.

  The present invention has been made to solve the above-mentioned problems, and an object thereof is to provide a method and an apparatus for producing an aqueous resin fine particle mixture capable of satisfactorily dispersing agglomerates of resin fine particles in individual resin fine particles. There is to do.

Means for Solving the Problems and Effects of the Invention

In order to solve the above problems, a method for producing an aqueous resin fine particle mixture according to the present invention includes:
A primary aqueous mixed liquid which is an aqueous coarse dispersion mixed liquid in which a large number of individual resin fine particles and a plurality of individual resin fine particles are aggregated to form agglomerates is mixed and dispersed. A low-pressure stirring step for maintaining the state and stirring under a pressure lower than atmospheric pressure;
A high speed imparting step of imparting to the secondary aqueous mixture obtained from the primary aqueous mixture by the low pressure stirring a speed greater than the motion speed of the primary aqueous mixture accompanying the stirring;
A collision treatment step of causing the secondary aqueous liquid mixture imparted with the high speed to collide with an object at a high speed;
An accommodating step for accommodating a tertiary aqueous mixture obtained from the secondary aqueous mixture by the collision treatment step;
It is characterized by including.
The “aqueous coarse dispersion mixture” and “primary aqueous mixture” are not limited to those having a low viscosity, but also include those having a considerably high viscosity, for example, a yogurt-like fluid.

  In this case, the collision treatment step can be performed by, for example, pressurizing and ejecting the secondary aqueous mixed liquid and causing the ejected liquid to collide with the object. Further, in the collision treatment step, for example, the secondary aqueous mixed liquid is pressurized and jetted so as to face each other, and the secondary aqueous mixed liquids can collide with each other at high speed as objects of collision with each other. .

And in order to implement the above-mentioned manufacturing method, the manufacturing apparatus of the aqueous resin fine particle mixed liquid according to the present invention includes:
A decompression container containing a primary aqueous mixed liquid which is an aqueous coarse dispersion mixed liquid in which a large number of agglomerates in which a plurality of individual resin fine particles and a plurality of individual resin fine particles are aggregated are mixed and dispersed;
A pressure reducing device for reducing the pressure from the atmospheric pressure to a lower pressure state, maintaining the state in which the primary aqueous mixture remains even after evaporation in the reduced pressure vessel;
A stirrer that stirs the primary aqueous mixture under reduced pressure produced by the decompressor;
An injection collision device that is guided from a decompression vessel and pressurizes the secondary aqueous mixed liquid obtained by stirring to a high pressure higher than atmospheric pressure to inject it and collide with an object;
A storage container for storing a tertiary aqueous mixture obtained by the jetting / collision;
It is characterized by including.

  In this case, for example, the jetting collision device causes the guiding passage for guiding the secondary aqueous mixed liquid from the decompression vessel, the cylinder for pressurizing the guided secondary aqueous mixed liquid, and the pressurized secondary aqueous mixed liquid to collide with each other. The cylinder includes a collision part, and the cylinder includes a piston or a plunger that pressurizes the secondary aqueous mixed liquid, and an injection port that injects the pressurized secondary aqueous mixed liquid. It can be set as the structure which a liquid mixture collides with a collision part. The jetting collision device includes, for example, a guide passage that guides the secondary aqueous mixed liquid from the decompression vessel and a cylinder that pressurizes the guided secondary aqueous mixed liquid. The cylinder branches the secondary aqueous mixed liquid. A piston or plunger for pressurization and a mutual injection port for injecting the pressurized secondary aqueous mixed solution to each other, and the secondary aqueous mixed solution injected from the mutual injection ports collide with each other at high speed It can also be configured. At this time, it is preferable that the injection ports are arranged so as to face each other and the secondary aqueous mixed liquids jetted to face each other from the mutual injection ports collide with each other at high speed.

  In the method for producing the aqueous resin fine particle mixture of the present invention, in the low pressure stirring step, the primary aqueous mixture is stirred under a pressure lower than the atmospheric pressure so that the liquid mixture remains even after evaporation. Under low pressure conditions, the cohesive force acting between the resin fine particles becomes weak. For this reason, water permeates between the resin fine particles, and the aggregate itself swells (expands), and the surface of each resin fine particle constituting the aggregate is covered with the surfactant. At this time, in addition to the air (oxygen) dissolved in the primary aqueous mixture, surplus additives such as surfactants and impurities are removed as gas from the primary aqueous mixture. The agglomerates can be made smaller by agitating the primary aqueous mixed solution in this low pressure state.

  Next, in the high-speed application step, a speed greater than the motion speed of the primary aqueous mixture accompanying stirring is applied to the primary aqueous mixture obtained by low-pressure stirring. Thereafter, in the collision treatment step, the secondary aqueous mixed liquid provided with a high speed is caused to collide with the object at a high speed. By carrying out the high-speed application step, it is possible to give energy necessary for dispersion to the agglomerates of resin fine particles whose cohesive force has become weak, and by performing the collision treatment step, the agglomerates can be separated into individual resins. It can be well dispersed in the fine particles.

  Further, in the method for producing the aqueous resin fine particle mixed liquid of the present invention, the primary, secondary and tertiary aqueous mixed liquids are aqueous emulsions containing no emulsifier and containing no emulsifier. The pigment fine particles of the coating material can be planned to be mixed later with the tertiary aqueous mixed liquid that is accommodated through the process, the high-speed application process, the collision treatment process, and the accommodation process. Further, the primary aqueous mixed liquid is, for example, an aqueous emulsion containing no emulsifier, which is an aqueous coating material liquid containing no emulsifier. The secondary aqueous mixed liquid obtained by low-pressure stirring contains pigment fine particles that become paint pigments. A high speed application step and a collision treatment step are performed on the pigment-containing secondary aqueous mixed solution, which includes a pigment mixing step of mixing and further stirring as necessary. In the collision treatment step, It is also possible to cause the pigment fine particles to collide with the object. Alternatively, the primary aqueous mixed liquid is, for example, a mixed liquid immediately before the aqueous paint as an emulsion containing fine pigment particles and an emulsifier which are pigments of the aqueous paint, and the pigment-containing primary aqueous mixed liquid is stirred in the low-pressure stirring step. The pigment-containing secondary aqueous mixture obtained by the above step is subjected to a high-speed application step and a collision treatment step, and in that collision treatment step, the pigment fine particles in the mixture are also caused to collide with the object. The pigment-containing tertiary aqueous mixture can be accommodated as an aqueous paint in the accommodating step.

  That is, in the method for producing the aqueous resin fine particle mixture of the present invention, when (1) a pigment-free aqueous emulsion (aqueous paint base liquid) is used from the starting solution to the final solution, (2) the starting solution is a pigment-free aqueous solution. In the case of an emulsion, when a pigment is mixed after low-pressure stirring, and the emulsion containing the pigment is subjected to a high speed imparting treatment and a collision treatment, and the final liquid becomes an aqueous paint containing the pigment, (3) the emulsion containing the pigment as the starting liquid It is possible to adopt a manufacturing pattern in which the pigment is contained up to the end and the final liquid is an aqueous paint.

  According to the production pattern of (1) above, it is possible to obtain an aqueous coating material liquid in which individual resin fine particles are dispersed. According to the production pattern of (2) or (3), it is possible to obtain an aqueous coating material in which not only the individual resin fine particles but also the pigment fine particles are miniaturized.

  According to the apparatus for producing an aqueous resin fine particle mixed liquid of the present invention, for example, it is superior in safety compared with an apparatus that disperses agglomerates of resin fine particles by realizing an ultra-high pressure state using carbon dioxide, for example. The apparatus can be reduced in size and cost.

BRIEF DESCRIPTION OF THE DRAWINGS Schematic of the manufacturing apparatus of the aqueous resin fine particle liquid mixture which concerns on Example 1 of this invention. The principal part sectional drawing which cut | disconnected the vacuum tank shown in FIG. 1 in the center plane different from FIG. The enlarged view of the injection collision apparatus shown in FIG. Explanatory drawing which shows an example of the chemical structure of resin fine particles. Explanatory drawing which shows typically the resin fine particle shown in FIG. Explanatory drawing which shows typically the aggregate which the resin fine particle shown in FIG. 4 aggregated. Explanatory drawing which shows the manufacturing method of the aqueous resin fine particle liquid mixture which concerns on Example 1 of this invention. (A) is explanatory drawing which shows the aggregate of the resin fine particle in a primary aqueous liquid mixture. (B) is explanatory drawing which shows the swelling state of the aggregate in a secondary aqueous liquid mixture. (C) is explanatory drawing which shows the condition where the aggregate in the tertiary aqueous liquid mixture is disperse | distributed. Saturated vapor pressure table with temperature and pressure as parameters. Explanatory drawing which shows the change condition of the primary aqueous liquid mixture under a low-pressure state. Explanatory drawing which shows the state of FIG.8 (b) concretely. Explanatory drawing which shows an example of the characteristic of the vacuum pump shown in FIG. The graph which shows the measurement result of the particle diameter distribution of a primary aqueous liquid mixture. Explanatory drawing which shows the measurement result of the particle diameter distribution of a tertiary aqueous liquid mixture. Explanatory drawing which shows the measurement result of the particle diameter distribution of the tertiary aqueous liquid mixture after having passed for a long time from the state shown in FIG. Explanatory drawing which shows the progress of rust when a salt spray test is conducted. (A) is explanatory drawing which shows the test result when the pencil hardness test of a dry film is done. (B) is explanatory drawing which shows the external appearance state of a dry film. (A) Explanatory drawing which shows the state which apply | coated the coating material surface of the aqueous coating material liquid in which many agglomerates of resin fine particles exist. (B) is explanatory drawing which shows the state which apply | coated the coating material surface with the aqueous | water-based coating raw material liquid which resin fine particle disperses | distributes separately. Explanatory drawing which shows the manufacturing method of the aqueous resin fine particle liquid mixture which concerns on Example 2 of this invention. Explanatory drawing which shows the manufacturing method of the aqueous resin fine particle liquid mixture which concerns on Example 3 of this invention. Explanatory drawing which shows the manufacturing method of the aqueous resin fine particle liquid mixture which concerns on the modification of this invention. Schematic which shows the modification of an injection collision apparatus. Schematic which shows the modification of an injection collision apparatus. Schematic which shows the modification of an injection collision apparatus. Schematic which shows the modification of an injection collision apparatus. FIG. 3 is a schematic view of a charging device that can be added to the manufacturing apparatus of the present invention. 1 is a schematic view of a charging device that can be added to the manufacturing apparatus of the present invention. The schematic of the stirring apparatus which can be added to the manufacturing apparatus of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 illustrates a production apparatus 1 (hereinafter simply referred to as production apparatus 1) of an aqueous resin fine particle mixed solution according to the present invention. The production apparatus 1 performs the low-pressure stirring process, the high-speed application process, the collision treatment process, and the containing process so that the proportion of the aqueous resin fine particle mixed liquid (the ratio of the individual resin fine particles (polymer fine particles) in the liquid is individually Aqueous emulsion larger than the proportion of the aggregates in which the resin fine particles are aggregated to form aggregates), the decompression device 10 and the stirring device 20 for performing the low-pressure stirring step, the high-speed applying step, And a jetting collision device 30 for performing a collision processing step.

  The decompression device 10 includes a vacuum tank 11 (decompression vessel) containing a primary aqueous mixture L1, that is, an aqueous coarse dispersion mixture in which a large number of individual resin fine particles and agglomerates are mixed and dispersed. A vacuum pump 12 that maintains the state in which the primary aqueous mixed liquid L1 remains even after evaporation and reduces the pressure to a lower pressure than atmospheric pressure is provided.

  For example, the vacuum tank 11 has a total capacity of about 327 l (liter) (φ700 mm × 900 mm), and at least a liquid contact portion is formed of a stainless material (SUS304). On the outer peripheral surface of the side wall of the vacuum tank 11, four leg portions 11 a with wheels are provided so as to be movable. In the upper part of the vacuum tank 11, a vacuum port 11b connected to the vacuum pump 12 via the air pipe T1 is provided, and an injection port (feeding port) for injecting the primary aqueous mixture L1 into the vacuum tank 11 is provided. ) 11c (see FIG. 2).

  The bottom of the vacuum tank 11 is provided with a discharge port 11e for discharging the secondary aqueous mixed liquid L2 obtained by low-pressure stirring to the outside of the vacuum tank 11 in accordance with the opening operation of the manual valve 11d. Moreover, the temperature control part 11f with which the pipe was integrated is attached to the outer peripheral surface of the side wall of the vacuum tank 11, the vacuum tank 11 is warmed by flowing warm water through a pipe, and the vacuum tank 11 is cooled by flowing cold water. It is possible.

The vacuum pump 12 is set to a specification that requires an operation time of 10 to 15 seconds, for example, until the exhaust speed is 1 to 2 m ³ / min, that is, the pressure in the vacuum tank 11 is reduced from atmospheric pressure to a pressure of about 20 Torr. (See the characteristic diagram (solid line) in FIG. 12). The pumping speed is increased by combining the auxiliary pump (roughing pump) and the mechanical booster, and operating the mechanical booster in the high vacuum side pressure range (about 20 Torr) where the pumping speed of the auxiliary pump that exhausts the vacuum tank 11 drops. It is also possible to use a type designed to improve the above (see the characteristic diagram (broken line) in FIG. 12).

  The stirring device 20 includes an inner stirring blade 21 that stirs the primary aqueous mixed liquid L1 on the center side in the vacuum tank 11 under a reduced pressure generated by the vacuum pump 12, and an outer stirring blade that stirs on the side wall side in the vacuum tank 11. 22. The inner stirring blade 21 is set to have a blade diameter of, for example, about φ200 to φ300 mm, and is integrally attached to the tip portion and the intermediate portion of the high-speed drive shaft 23. The high-speed drive shaft 23 is connected to a drive motor 24 (for example, an inverter motor) via a transmission mechanism using, for example, a transmission belt, and the primary aqueous mixed liquid L1 is within a range of, for example, 0 to 2000 rpm (0 to 60 Hz). It is designed to be driven to rotate at a rotation speed suitable for the viscosity.

  The outer agitating blade 22 is set to have a blade diameter of about φ600 to φ700 mm, for example, and is integrally attached to the tip of the low-speed drive shaft 25. The low-speed drive shaft 25 is connected to a drive motor 26 (for example, a motor with a speed reducer) via a transmission mechanism using a chain, for example, and is driven to rotate at a predetermined rotation speed within a range of rotation speeds of 20 to 50 rpm, for example. It has come to be. The low-speed drive shaft 25 is a hollow shaft, and is disposed in a state where the high-speed drive shaft 23 passes therethrough.

  When the inner stirring blade 21 rotates at a high speed, the primary aqueous mixture L1 is pushed away not only in the circumferential direction in the vacuum tank 11 but also in the radial direction. For this reason, when the primary aqueous mixed liquid L1 is stirred only by the inner stirring blade 21, the primary aqueous mixed liquid L1 near the side wall of the vacuum tank 11 stagnates, and the entire primary aqueous mixed liquid L1 is uniformly stirred. It may not be possible. In the first embodiment, the outer stirring blade 22 is formed in a shape in which the primary aqueous mixed liquid L1 is scraped inward, and the primary aqueous mixed liquid L1 is changed by changing the rotational speeds of both the stirring blades 21 and 22. It is comprised so that the whole can be stirred uniformly.

  The jetting collision device 30 is incorporated in the manufacturing apparatus 1 using a commercially available wet atomization device, and is a branched liquid pipe that guides the secondary aqueous mixed liquid L2 obtained from the primary aqueous mixed liquid L1 by low-pressure stirring. T2 (guide passage), a pair of cylinders 31 and 31 that pressurize the secondary aqueous mixture L2 that has been guided, and the cylinders 31 and 31 are connected to each cylinder 31 via a communication passage 33. The housing part 32 is provided. Each cylinder 31 is provided with a port 31b to which each end of the branch liquid pipe T2 is connected, and a pressurizing chamber 31a in which a piston (or plunger) 34 is movably provided. A collision chamber 32 a is formed in the housing portion 32.

  The communication passage portions 33 and 33 are arranged to face each other, and the pressure in the corresponding pressurizing chamber 31a is predetermined in each communication passage portion 33 (set pressure of 100 to 250 MPa). An on-off valve 35 (opening / closing means) is provided which is opened when That is, the injection collision device 30 causes the secondary aqueous mixed liquid L2 obtained from the primary aqueous mixed liquid L1 by low pressure stirring to 100 to 100 by pressing the piston 34 in each cylinder 31 in the closed state of the on-off valve 35. The pressure is set within a pressure range of 250 MPa.

  As shown in FIG. 3, when each on-off valve 35 is opened, an injection passage 33a (injection port) for injecting the secondary aqueous mixed liquid L2 pressurized in the pressurizing chamber 31a to face each other is formed. It is like that. Since both pistons 34 and 34 are set so as to be pressed in synchronization with each other, the secondary aqueous mixed liquid L2 injected oppositely from the mutual injection passage 33a is accelerated when passing through the injection passage 33a. , They collide at high speed in the collision chamber 32a. The tertiary aqueous mixed liquid L3 obtained from the secondary aqueous mixed liquid L2 by such injection / collision is stored in the storage container 40 through the discharged liquid pipe T3 (discharged liquid passage) connected to the port 32b ( (See FIG. 1).

  The vacuum pump 12 of the decompression device 10 described above, the drive motors 24 and 26 of the stirring device 20, the piston 34 in each cylinder 31 of the injection collision device 30, and the like are determined in advance by operations from the control panel 100 (control means). Act to carry out the process.

  Next, the primary aqueous mixed liquid L1 used in Example 1 will be described. The primary aqueous mixed liquid L1 is an aqueous emulsion containing no emulsifier and is an aqueous emulsion containing no pigment. In Example 1, a commercially available acrylic emulsion (for example, Nippon NS Product number “AD157”) is used. As schematically shown in FIG. 4, this acrylic emulsion uses an acrylate ester or the like as a monomer (hydrophobic monomer) that is a polymer compound, and a persulfate that is soluble in water as a polymerization initiator ( Ammonium persulfate) is used, and an anionic sodium alkylsulfonate is used as a surfactant (emulsifier), and these are added in water and polymerized. The surfactant is not limited to an anionic type, and can be appropriately changed to a cationic type or a nonionic type. Further, the primary aqueous mixed liquid L1 is not limited to one using acrylic as a monomer, and can be appropriately changed to one using, for example, vinyl acetate, vinyl chloride, or synthetic rubber. Moreover, not only emulsion polymerization but what was polymerized by well-known polymerization methods, such as suspension polymerization and seed polymerization, can be used suitably.

  In such a primary aqueous mixed liquid L1, as schematically shown in FIG. 5, the surface of each fine resin particle 61 (primary particle) having a particle diameter of less than 0.1 μm is a surfactant 62 (emulsifier). As schematically shown in FIG. 6, the surface of each of the aggregates 63 (secondary particles) in which the resin fine particles 61 aggregate and have a particle diameter of 1 μm or more, as shown in FIG. A large number of particles covered with 62 are mixed and dispersed.

  The aggregate 63 obtained by agglomerating the resin fine particles 61 is subjected to the above-described low-pressure agitation process by the decompression device 10 and the agitation device 20, and the high-speed application step and the collision treatment step by the jetting collision device 30. 61 can be dispersed. Hereafter, each process implemented with the manufacturing apparatus 1 is demonstrated concretely with reference to FIG. In addition, in the explanatory view showing the manufacturing apparatus 1 after FIG. 7, the components of the manufacturing apparatus 1 shown in FIG. 1 are omitted as appropriate.

  First, the primary aqueous mixed liquid L1 is prepared and poured into the vacuum tank 11 as shown in FIGS. 7 (a) and 7 (b). At this stage, as shown in FIG. 8A, a large number of aggregates 63 in which the resin fine particles 61 are aggregated exist in the liquid.

  Next, in the low pressure stirring step A, first, the inside of the vacuum tank 11 is evacuated by the vacuum pump 12 (see FIG. 12), and the pressure is lower than the atmospheric pressure so that the primary aqueous mixture L1 remains even after evaporation. Depressurize until. Specifically, as shown in the saturated vapor pressure table of FIG. 9, the pressure in the vacuum tank 11 is set to 6 to 18 Torr (torr) corresponding to the case where the temperature in the vacuum tank 11 is 4 to 20 ° C. Set to the range.

  At this time, in the vacuum tank 11, as shown in FIGS. 10 (a) and 10 (b), the liquid level S once rises as the pressure decreases, and the air (oxygen) dissolved in the primary aqueous mixture L 1. ) Expands to form bubbles and is removed from the primary aqueous mixture L1 (vacuum degassing / vacuum defoaming). In this state, if the vacuum tank 11 is still evacuated, the liquid level S descends toward the initial position as shown in FIG. Thereafter, the primary aqueous mixture L1 starts to boil rapidly. In the first embodiment, for example, the operator checks the position of the liquid level S using the scale provided in the vacuum tank 11 as a guide, and the scale becomes invisible due to the rise of the liquid level S. Is started again, that is, immediately before the primary aqueous mixture L1 starts boiling, or immediately after the primary aqueous mixture L1 starts boiling, the drive of the vacuum pump 12 is stopped. I have to.

  Under the low pressure state as described above, the cohesive force acting between the resin fine particles 61 is weaker than under atmospheric pressure. For this reason, as shown in FIG. 8B, the water 64 enters between the resin fine particles 61, and the aggregate 63 itself swells (expands). At this time, for example, as schematically shown in FIG. 11, the surface of the individual resin fine particles 61 constituting the aggregate 63 is covered with the surfactant 62 and dissolved in the primary aqueous mixed liquid L1. In addition to air, excess additives such as surfactants and impurities are converted into gas and removed from the primary aqueous mixture L1.

  Then, under this low pressure state, the primary aqueous mixed liquid L1 is stirred by rotation of the inner stirring blade 21 and the outer stirring blade 22 around the central axis by the drive motors 24 and 26, as shown in FIG. 8B. In addition, some of the aggregates 63 may be separated so as to be aggregates smaller than the original size, while others may be separated so as to be a single resin fine particle 61 (primary dispersion (separation) of the aggregates 63). ).

  7 (a) and 7 (b), the secondary aqueous mixed liquid L2 obtained from the primary aqueous mixed liquid L1 by low pressure stirring is transferred into the pressurizing chamber 31a of each cylinder 31 through the branch liquid pipe T2. To do.

  In the high speed application process B, first, the secondary aqueous mixed liquid L2 in each pressurizing chamber 31a is pressurized by the pressing operation of each piston 34. Specifically, the secondary aqueous mixed liquid L2 is pressurized within a pressure range of 100 to 250 MPa (megapascal). When each pressurizing chamber 31a reaches the set pressure, the opening / closing valve 35 is opened, and the secondary aqueous mixed liquid L2 flowing through the injection passage 33a is given a speed higher than the motion speed of the primary aqueous mixed liquid L1 accompanying the low pressure stirring. Become so.

  In the collision processing step C, the secondary aqueous mixed liquids L2 are caused to collide with each other at high speed in the collision chamber 32a (acceleration is drastically reduced). By performing the high speed imparting step B and the collision treatment step C, as shown in FIG. 8C, the aggregate 63 of the resin fine particles 61 whose cohesive force is weakened by swelling obtains energy necessary for dispersion. Then, it is dispersed in the individual resin fine particles 61 (secondary dispersion (separation) of the aggregate 63).

  Returning to FIGS. 7A and 7B, in the storage process D, the tertiary aqueous mixed liquid L3 obtained from the secondary aqueous mixed liquid L2 in the collision processing process C passes through the discharge liquid pipe T3 in the storage container 40. Is housed in. An aqueous coating material is completed by mixing pigment fine particles of the coating material with the tertiary aqueous mixed liquid L3.

  FIG. 13 shows the measurement results of the particle size distribution (frequency / cumulative rate) of the primary aqueous mixed liquid L1 (hereinafter also referred to as nano-sized or normal), and FIG. 14 shows the tertiary aqueous mixed liquid. The measurement result of the particle diameter distribution (frequency / cumulative rate) of L3 (hereinafter also referred to as nano-ized) is shown. In this case, the pressure at which the on-off valve 35 was opened in the high speed application step B of FIG. 7 was set to about 245 MPa. A laser diffraction / scattering particle size distribution measuring device (MT3300 type, manufactured by Nikkiso Co., Ltd.) was used as a measuring device.

  From FIG. 13 and FIG. 14, by carrying out each process using the manufacturing apparatus 1, an aqueous emulsion in which individual resin fine particles 61 and small aggregates whose particle diameter does not reach 1 μm are mixed and dispersed is obtained. I understand that.

  FIG. 15 shows the measurement results of the particle size distribution (frequency / cumulative rate) of the tertiary aqueous mixture L3 after a long period (about 1 year) has passed since the nanonization. From FIG. 15, in the case where each process is performed using the manufacturing apparatus 1, the resin fine particles 61 reaggregate after a long period of time, but even in that case, the particle diameter does not exceed 1 μm. It can be seen that it is difficult to form a large agglomerate having a particle diameter exceeding 1 μm.

  A salt spray test was performed using a test sample obtained by applying the nano-sampled and non-nano-coated ones to the iron plate surface on which the grooves were formed. In this salt spray test, each test sample is allowed to stand in a predetermined constant temperature bath (the temperature in the bath is set to 35 ° C.) for a predetermined time (30 hours and 150 hours) with a concentration of 5 % Of salt water was continuously sprayed, and the progress of rust in each test sample was observed when the thermostat was returned to room temperature and dried for 20 days.

  FIG. 16 shows the test result of the salt spray test. 16A to 16D show the spraying time (test time) of 30 hours, and FIGS. 16E to 16H show the spraying time (test time) of 150 hours. 16 (b), (d), (f), and (h) are after nano-nization, and FIGS. 16 (a), (c), (e), and (g) are before nano-nano. is there. Furthermore, each test sample in FIGS. 16C, 16D, 16G, and 16H was subjected to a baking treatment for stabilizing the coating film at 150 ° C. for 30 minutes before spraying with salt water. Therefore, from the whole of FIG. 16, the test conditions are the same for the combinations of (a) and (b), (c) and (d), (e) and (f), and (g) and (h). ing.

  From FIG. 16, when the same test conditions are compared, the progress of rust is clearly slower after the nano-ization than that before the nano-ization. It is also suppressed well. That is, it was confirmed that the material after nano-ization is extremely excellent in rust prevention compared to the material before nano-ization.

  Moreover, the thing after nano-ized and the thing before nano-ized were each dried on the glass plate, and the pencil hardness (scratch hardness) of the dry film (coating film) was measured. Specifically, a test sample that was allowed to stand for 7 days in an atmosphere of 23 ° C. and 65% RH (relative humidity) and a sample for 3 hours in an atmosphere of 60 ° C. Test samples with dry conditions were prepared. FIG. 17A shows the measurement result. In any of the test samples, it was confirmed that the pencil hardness was increased in the nano-sampled sample compared to that before the nano-ized sample.

  Furthermore, the nano-ized one and the one before nano-ized were each dried on a glass plate at room temperature, and the appearance of the dried film (coating film) was observed. FIG. 17B shows the observation result. The thing before nano-ization is a yuzu skin-like, and the thing after nano-ization was smooth. In this case, it was confirmed that the thing after nano-ization has almost no odor compared with the thing before nano-ization.

  The results shown in FIG. 16 and FIG. 17 were obtained because, for example, as shown schematically in FIG. 18, many aggregates 63 exist in the liquid before the nano-ization, While the lump 63 is in contact with the coating material surface (FIG. 18 (a)), in the nano-sized one, the resin fine particles 61 are present in the liquid, and the resin fine particles 61 are in contact with the coating material surface. This is because the adhesive force with the coating material surface becomes stronger after the nano-ization than in the case before the nano-ization (FIG. 18B). That is, by nano-ization, a tough coating film is formed which is difficult to peel off from the coating material surface.

  In addition, in the case before the nano-ization, when the resin fine particles 61 at the upper part (coating surface side) of the agglomerate 63 starts to deteriorate due to, for example, ultraviolet rays, the deterioration progresses to the lower part (coating material surface side) of the agglomerate 63. It is easy and the deterioration progresses quickly over the entire coating film, whereas in the case of the nano-coated one, even when the resin fine particles 61 located on the coating surface side deteriorate, the resin fine particles 61 located on the coating material surface side are moved to. Degradation is difficult to proceed (because they are independent of each other), and degradation over the entire coating film is suppressed. Moreover, it becomes odorless by removing impurities, such as an excessive additive, from a liquid mixture by nano-ization.

  In the first embodiment, the manufacturing apparatus 1 is used to perform the low pressure stirring process A, the high speed applying process B, the collision processing process C, and the containing process D. In addition to these processes, for example, FIG. As shown in (a) and 19 (b), the pigment mixing step A ′ may be performed. Since the manufacturing apparatus 1 used in the second embodiment has the same configuration as that of the first embodiment, a detailed description of the manufacturing apparatus 1 and a low-pressure stirring process A, a high-speed applying process B, a collision processing process C, and accommodation are performed. Detailed description of the process D will be omitted.

  In the pigment mixing step A ′, after the secondary aqueous mixed liquid L2 is obtained by the low pressure stirring step A, the pigment fine particles P1 serving as the paint pigment are wetted while the secondary aqueous mixed liquid L2 is held in the vacuum tank 11. It mixes with an agent and a dispersing agent, and stirs with the stirring apparatus 20 as needed. Then, the high-speed application step B and the collision treatment step C are performed on the pigment-containing secondary aqueous mixed liquid L2 ′ obtained in the pigment mixing step A ′. In the collision treatment step C, the mixture liquid L2 ′ The agglomerates 63 of the resin fine particles 61 collide with each other, and pigment particles (a mixture of agglomerates in which a plurality of individual pigment fine particles P1 and a plurality of individual pigment fine particles P1 agglomerate to form agglomerates) are also present. Collide with each other.

  In addition to the individual resin fine particles 61 being obtained by the collision treatment step C, the finely divided pigment fine particles P1 are obtained. Therefore, the pigment-containing tertiary aqueous mixture obtained from the pigment-containing secondary aqueous mixture L2 ′. In L3 ′ (water-based paint as the final liquid), the surface of the finely divided pigment fine particles P1 is covered with the individual resin fine particles 61, and is the same as the tertiary aqueous mixed liquid L3 obtained in Example 1 above. Based on this reason, the water-based paint as the final liquid exhibits excellent effects in terms of rust prevention and the like.

  In Example 2 described above, the pigment fine particles P1 are mixed with the secondary aqueous mixed liquid L2 obtained in the low-pressure stirring step A. Instead, for example, as shown in FIG. In the stage before carrying out A, a pigment-containing primary aqueous mixed liquid L1 ′, that is, a mixed liquid immediately before an aqueous paint as an emulsion containing resin particles, emulsifier 62, water 64 and pigment fine particles P1 may be prepared. Good.

  In Example 3, since the low-pressure stirring step A is performed on the pigment-containing primary aqueous mixture L1 ′, the pigment-containing secondary aqueous mixture L2 ′ obtained by the low-pressure stirring as a whole has impurities such as oxygen. As well as the aggregate 63 of the resin fine particles 61, the aggregate of the pigment fine particles P <b> 1 also exhibits a particle mode in which the cohesive force is weakened due to swelling.

  Thus, the high-speed application step B and the collision treatment step C are performed on the pigment-containing secondary aqueous mixed liquid L2 ′. In the collision treatment step C, the aggregate 63 of the resin fine particles 61 in the mixed liquid L2 ′ is obtained. While colliding each other, pigment particles are also collided with each other, and the pigment-containing tertiary aqueous mixed liquid L3 ′ obtained by the collision treatment is accommodated as an aqueous paint in the accommodating step D.

  Thus, as in Example 2, in the pigment-containing tertiary aqueous mixture L3 ′ obtained from the pigment-containing secondary aqueous mixture L2 ′ by the collision treatment step C, the surfaces of the finely divided pigment fine particles P1 are individually Therefore, the water-based paint as the final liquid exhibits an excellent effect in terms of rust prevention and the like.

(Modification)
Instead of the second and third embodiments, for example, as shown in FIG. 21, a plurality of the manufacturing apparatuses 1 used in the first embodiment are used, and the tertiary aqueous mixture L3 is accommodated in the same manner as in the first embodiment. On the other hand (steps A to D), a low-pressure stirring step is performed on the primary pigment liquid L4 in which a large number of aggregates formed by agglomerating a plurality of individual pigment fine particles P1 and individual pigment fine particles P1 are mixed and dispersed. A is performed, and the high-speed application step B and the collision treatment step C are performed on the secondary pigment liquid L5 obtained by the low-pressure stirring. In the collision treatment step C, the pigment particles in the secondary pigment liquid L5 Each other is caused to collide with each other, and the tertiary pigment liquid L6 obtained by the collision treatment is accommodated (steps A to D). In the mixing step E, the tertiary aqueous mixed liquid L3 and the tertiary pigment liquid L6 are mixed (stirred if necessary), and in the containing step F, the aqueous paint L7 obtained by mixing is accommodated.

  According to this modification, for example, when a different color pigment is to be used, the inside of the vacuum tank 11 for the pigment liquid may be washed. Compared with cleaning the inside of the vacuum tank 11, it is not necessary to remove oil stains, so that the cleaning work becomes easier.

  In the manufacturing apparatus 1 used in the first to third embodiments, the communication passage portions 33 of the injection collision device 30 are arranged to face each other, and the injection passage 33a when the on-off valve 35 is opened is relatively However, instead of this, for example, as shown in FIG. 22, the mutual communication passage portion 33 of the injection collision apparatus 130 is 90 degrees or more and 180 degrees in the collision chamber 32a of the housing portion 32. It is good also as a structure arrange | positioned so that it may have the axis lines O1 and O2 of the positional relationship which cross | intersect at angle (theta) of less than degree. Since the other configuration is the same as that of the first embodiment, members having the same function are denoted by the same reference numerals and description thereof is omitted.

  In the manufacturing apparatus 1 used in the first to third embodiments, the injection collision device 30 is disposed between the pair of cylinders 31 and 31 and both the cylinders 31 and 31, and the communication passage portion 33 is provided in each cylinder 31. However, instead of this, for example, as shown in FIG. 23, the injection collision device 230 is connected to the cylinder 31 and the cylinder 31 via the communication path portion 33. The housing portion 32 may be provided. In this case, the collision chamber 32a in the housing portion 32 has a collision energy received from a ceramic member 36 (secondary aqueous mixed liquid L2, pigment-containing secondary aqueous mixed liquid L2 ′ or secondary pigment liquid L5) as an object of collision. The impact portion formed in a spherical shape having a predetermined radius of curvature is fixedly disposed. In addition, since the other structure is the same as the said Example 1, the same code | symbol is attached | subjected to the member which performs the same function, and description is abbreviate | omitted.

  Even when this jetting collision device 230 is used, in the high speed application step B, the secondary aqueous mixed liquid L2 or the like guided into the pressurizing chamber 31a by the pressing operation of the piston 34 is a predetermined pressure (100 to 250 Mpa). ) Until pressure is reached. When the pressurizing chamber 31a reaches the set pressure, the open / close valve 35 is opened, and the secondary aqueous mixed liquid L2 and the like flowing through the injection passage 33a is given a speed larger than the motion speed of the primary aqueous mixed liquid L1 and the like accompanying the low pressure stirring. Is done. In the collision treatment step C, the secondary aqueous mixed liquid L2 and the like collide with the ceramic member 36 at high speed in the collision chamber 32a.

  Therefore, by performing the high-speed imparting step B and the collision treatment step C using the jetting collision device 230, the agglomerates 63 of the resin fine particles 61 are favorably formed into the individual resin fine particles 61 as in the first embodiment. The pigment fine particles P1 can be finely dispersed.

  Further, instead of the jetting collision devices 30, 130, and 230 in the first embodiment, for example, as shown in FIG. 24, the suction pump 13 is used, and the suction to the secondary aqueous mixed liquid L <b> 2 or the like is obtained. A concave shape having a predetermined radius of curvature is applied to disperse the collision energy received from the ceramic member 37 (secondary aqueous mixed liquid L2 or the like) as an object of collision by giving a large speed and ejecting from the discharge port of the suction pump 13 It is also possible to cause a collision at a high speed.

  Further, for example, as shown in FIG. 25, the vacuum pump 12 is driven in the reverse direction to pressurize the inside of the vacuum tank 11 to give a large speed to the secondary aqueous liquid mixture L2 and the like, and eject it from the nozzle of the ejection device 133. Thus, the ceramic member 37 as a collision target may be caused to collide at high speed.

  Furthermore, as shown in FIG. 26, for example, as a mode of exposing a part of the drainage pipe T3, a charging device 50 may be provided corresponding to the exposed portion. The charging device 50 charges the tertiary aqueous mixed liquid L3 and the like after the collision treatment step C positively or negatively by, for example, corona discharge, and outputs a ground electrode 51 and a positive or negative high voltage. The high voltage generating unit 52 having 52a and the controller 53 for controlling the output voltage of the discharge electrode 52a are configured. The tertiary aqueous mixed liquid L3 and the like charged by the charging device 50 are stored in the storage container 40 through the lower part of the discharge liquid pipe T3.

  Using the charging device 50, for example, when the dissociated surfactant is a cationic compound (cationic), the tertiary aqueous mixture L3 or the like is charged positively, and the anionic compound (anionic) is used. In some cases, by performing a charging step of negatively charging the tertiary aqueous mixed liquid L3 and the like, the repulsion of the resin fine particles 61 is effectively suppressed by the electric repulsive force acting between the resin fine particles 61. Can do. As a result, the dispersed state of the resin fine particles 61 can be satisfactorily maintained over a long period.

  In place of the charging device 50 shown in FIG. 26, for example, a charging device 150 as shown in FIG. 27 may be used. The charging device 150 includes a base 151 on which the storage container 40 is placed, and the base 151 has electrodes and coils that can apply an electric field to the tertiary aqueous mixed liquid L3 and the like in the storage container 40. And the like, and the electric field generator 152 controls the electric field. Such a charging device 150 can also charge the tertiary aqueous mixed liquid L3 or the like positively or negatively.

  Further, in addition to the stirring device 20 used in Example 1 and the like, for example, as shown in FIG. 28, the bottom of the vacuum tank 11 is vibrated by an ultrasonic generator 122 (ultrasonic transmission circuit, ultrasonic generation means). The ultrasonic vibrator 121 is attached, and the kinetic energy by the stirring blades 21 and 22 and the acoustic energy by the ultrasonic vibrator 121 are used to give a stirring effect to the primary aqueous mixture L1 and the like in the vacuum tank 11 It may be.

  Moreover, the manufacturing apparatus 1 described above can be constructed as a control system in which each process is automatically performed by using various sensors such as a pressure sensor and a temperature sensor.

1 Production equipment (Production equipment for aqueous resin fine particle mixture)
10 Pressure reducing device 11 Vacuum tank (pressure reducing container)
12 Vacuum pump 20 Agitator 21 Inner agitating blade 22 Outer agitating blade 30, 130, 230 Injection collision device 31 Cylinder 31a Pressurization chamber 32 Housing portion 32a Collision chamber 33 Communication passage portion 33a Injection passage (injection port)
34 Piston 35 On-off valve 36, 37 Ceramic member (object, collision part)
40 container 61 resin fine particle 62 emulsifier 63 agglomerate 64 water T2 branch liquid pipe (guide passage)
T3 Drainage pipe (drainage passage)
100 Control Panel L1 Primary Aqueous Mixture L2 Secondary Aqueous Mixture L3 Tertiary Aqueous Mixture P1 Pigment Fine Particle L1 ′ Pigment Containing Primary Aqueous Mixture L2 ′ Pigment Containing Secondary Aqueous Mixture L3 ′ Pigment Containing Tertiary Aqueous Mixing liquid

In order to solve the above problems, a method for producing an aqueous resin fine particle mixture according to the present invention includes:
A primary aqueous mixed liquid which is an aqueous coarse dispersion mixed liquid in which a large number of individual resin fine particles and a plurality of individual resin fine particles are aggregated to form agglomerates is mixed and dispersed. Maintaining the state, a low pressure stirring step of stirring under a low pressure state of 6 to 18 Torr ;
A high- speed application step in which the secondary aqueous mixture obtained from the primary aqueous mixture is pressurized to a high pressure of 100 to 250 Mpa by the low-pressure stirring to give a speed greater than the motion speed of the primary aqueous mixture accompanying the stirring. When,
A collision treatment step of injecting the secondary aqueous mixed liquid provided with the high speed so as to face each other and causing the secondary aqueous mixed liquid to collide with each other at high speed ;
An accommodating step for accommodating a tertiary aqueous mixture obtained from the secondary aqueous mixture by the collision treatment step;
It is characterized by including.
The “aqueous coarse dispersion mixture” and “primary aqueous mixture” are not limited to those having a low viscosity, but also include those having a considerably high viscosity, for example, a yogurt-like fluid.

And in order to implement the above-mentioned manufacturing method, the manufacturing apparatus of the aqueous resin fine particle mixed liquid according to the present invention includes:
A decompression container containing a primary aqueous mixed liquid which is an aqueous coarse dispersion mixed liquid in which a large number of agglomerates in which a plurality of individual resin fine particles and a plurality of individual resin fine particles are aggregated are mixed and dispersed;
A pressure reducing device for reducing the pressure from the atmospheric pressure to a lower pressure state, maintaining the state in which the primary aqueous mixture remains even after evaporation in the reduced pressure vessel;
A stirrer that stirs the primary aqueous mixture under a reduced pressure of 6 to 18 Torr generated in the decompressor;
An injection collision device that is guided from a decompression vessel and pressurizes the secondary aqueous mixed liquid obtained by stirring to a high pressure of 100 to 250 Mpa higher than atmospheric pressure to inject it into an object;
A storage container for storing a tertiary aqueous mixture obtained by the jetting / collision ,
The jetting collision device includes a guide passage that branches and guides the secondary aqueous mixed liquid from the decompression vessel, and a cylinder that pressurizes the guided secondary aqueous mixed liquid,
The cylinder includes a piston or plunger that individually pressurizes the branched secondary aqueous mixture and a mutual injection port that injects the pressurized secondary aqueous mixture to each other;
The secondary aqueous mixed liquids ejected from the mutual ejection ports collide at high speed with each other as an object of collision .

Claims (13)

A primary aqueous mixed liquid which is an aqueous coarse dispersion mixed liquid in which a large number of individual resin fine particles and a plurality of individual resin fine particles are aggregated to form agglomerates is mixed and dispersed. A low-pressure stirring step for maintaining the state and stirring under a pressure lower than atmospheric pressure;
A high speed imparting step of imparting to the secondary aqueous mixed liquid obtained from the primary aqueous mixed liquid by the low pressure stirring a speed larger than the motion speed of the primary aqueous mixed liquid accompanying the stirring;
A collision treatment step of causing the secondary aqueous liquid mixture imparted with the high speed to collide with an object at a high speed;
An accommodating step for accommodating the tertiary aqueous mixture obtained from the secondary aqueous mixture by the collision treatment step;
The manufacturing method of the aqueous resin fine particle liquid mixture characterized by including.   2. The method for producing an aqueous resin fine particle mixture according to claim 1, wherein in the collision treatment step, the secondary aqueous mixed liquid is pressurized and ejected, and the ejected liquid collides with an object.   3. The aqueous solution according to claim 2, wherein the collision treatment step pressurizes and jets the secondary aqueous mixed solution so as to face each other, and causes the secondary aqueous mixed solutions to collide with each other at high speed as objects of collision. A method for producing a resin fine particle mixture.   The primary, secondary, and tertiary aqueous mixed liquid is a water-based emulsion containing no emulsifier and is an aqueous emulsion that does not contain a pigment. The low-pressure stirring process, the high-speed application process, the collision treatment process, and the containment process. The method for producing an aqueous resin fine particle mixture according to any one of claims 1 to 3, wherein the pigment fine particles of the paint are planned to be mixed later with the tertiary aqueous mixed solution accommodated through the step.   The primary aqueous mixed liquid is an aqueous emulsion containing no emulsifier and is an aqueous emulsion not containing a pigment. The secondary aqueous mixed liquid obtained by the low-pressure stirring is mixed with pigment fine particles serving as a paint pigment. In addition, the high-speed application step and the collision treatment step are performed on the pigment-containing secondary aqueous mixed solution, which includes a pigment mixing step of further stirring as necessary. In the collision treatment step, The method for producing an aqueous resin fine particle mixture according to any one of claims 1 to 3, wherein the pigment fine particles are also collided with an object.   The primary aqueous mixed liquid is a mixed liquid immediately before the aqueous paint as an emulsion containing pigment fine particles and an emulsifier which are pigments of the aqueous paint, and the pigment-containing primary aqueous mixed liquid is stirred in the low pressure stirring step, thereby The high-speed imparting step and the collision treatment step are performed on the obtained pigment-containing secondary aqueous mixture, and in the collision treatment step, the pigment fine particles in the mixture are also collided with the object, and thus obtained. The method for producing an aqueous resin fine particle mixture according to any one of claims 1 to 3, wherein the pigment-containing tertiary aqueous mixture is accommodated as an aqueous paint in the accommodation step. A decompression container containing a primary aqueous mixed liquid which is an aqueous coarse dispersion mixed liquid in which a large number of agglomerates in which a plurality of individual resin fine particles and a plurality of individual resin fine particles are aggregated are mixed and dispersed;
A pressure reducing device for reducing the pressure from the atmospheric pressure to a lower pressure state, maintaining the state in which the primary aqueous mixture remains even after evaporation in the reduced pressure vessel;
A stirrer for stirring the primary aqueous mixture under reduced pressure generated in the decompressor;
An injection collision device that is guided from the decompression vessel and pressurizes the secondary aqueous mixed liquid obtained by the stirring to a high pressure higher than atmospheric pressure so as to be collided with an object;
A storage container for storing a tertiary aqueous mixture obtained by the jetting / collision;
An apparatus for producing an aqueous resin fine particle mixed solution, comprising: The jetting collision device includes a guide passage that guides the secondary aqueous mixed liquid from the decompression vessel, a cylinder that pressurizes the induced secondary aqueous mixed liquid, and a collision that collides the pressurized secondary aqueous mixed liquid. Part
The cylinder includes a piston or plunger that pressurizes the secondary aqueous mixture, and an injection port that injects the pressurized secondary aqueous mixture.
The apparatus for producing an aqueous resin fine particle mixture according to claim 7, wherein the secondary aqueous mixture injected from the injection port collides with the collision part. The jetting collision device includes a guide passage that guides the secondary aqueous mixed liquid from the decompression container, and a cylinder that pressurizes the guided secondary aqueous mixed liquid.
The cylinder includes a piston or a plunger that branches and pressurizes the secondary aqueous mixed liquid, and a mutual injection port that injects the pressurized secondary aqueous mixed liquid to each other.
The apparatus for producing an aqueous resin fine particle mixture according to claim 7, wherein the secondary aqueous mixture injected from the mutual injection ports collides with each other at a high speed.   The said injection port is arrange | positioned mutually, and manufacture of the aqueous resin microparticles | fine-particles liquid mixture of Claim 9 with which the said secondary aqueous liquid mixture injected in opposition from the mutual injection port collides at high speed mutually. apparatus.   11. The aqueous resin fine particle mixture according to claim 7, wherein the primary, secondary, and tertiary aqueous mixed liquid is an aqueous emulsion that does not include a pigment, which is a raw material liquid of an aqueous paint including an emulsifier. Liquid production equipment.   The primary aqueous mixed liquid is an aqueous emulsion containing no emulsifier and is an aqueous emulsion containing no pigment. The secondary and tertiary aqueous mixed liquid contains pigment fine particles and an emulsifier that are pigments of the aqueous paint. The apparatus for producing an aqueous resin fine particle mixture according to any one of claims 7 to 10, which is a pigment-containing aqueous emulsion.   The aqueous resin fine particle mixed solution according to any one of claims 7 to 10, wherein the primary, secondary and tertiary aqueous mixed solution is a pigment-containing aqueous emulsion containing pigment fine particles and an emulsifier which are pigments of an aqueous paint. Manufacturing equipment.