JPH06206934A - Production of aqueous dipersion of fluoroacrylic resin - Google Patents

Abstract

PURPOSE:To readily obtain an aqueous fluoroacrylic resin dispersion having fine particle diameter and uniform particle diameter distribution and excellent in stability under condition of an amount of emulsifying agent reduced compared with conventional method by emulsifying a previously emulsified mixed liquid using a specific emulsifying device. CONSTITUTION:A previously emulsified mixed liquid consisting of water and a fluoroalkyl (meth)acrylate monomer is introduced into a flow path in a chamber of an emulsifying device under pressure and the mixed liquid is allowed to collide with a flat part in the flow path or with each other under high pressure to emulsify the mixed liquid. Then, the resultant monomer emulsion is polymerized to provide the objective dispersion. Concretely, e.g. a previously emulsified mixed liquid fed to a suppressing part 1 in a chamber under pressure is introduced into a disk 3 and directly allowed to collide with the flat part 5 of a disk 4 and collided liquid is allowed to flow to a connecting groove 6 of the disk 3 on the side contacting with the disk 4 while accelerating the liquid and these liquid are allowed to collide with each other in the center of the disk 3 to disperse emulsify the mixed liquid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aqueous fluoroacrylic resin dispersion. More specifically, the present invention relates to a method for producing a fluoroacrylic resin aqueous dispersion, which comprises using a special emulsifying device in an emulsifying and dispersing step of the fluoroacrylic resin aqueous dispersion.

[0002]

2. Description of the Related Art The following is known as a method for producing an aqueous fluoroacrylic resin dispersion.

That is, (1) an emulsifier aqueous solution is added to an organic solvent solution or organic solvent dispersion of a fluoroalkyl (meth) acrylate monomer to obtain an aqueous emulsion dispersion of the monomer, to which a radical polymerization initiator is added and heated. , A method of polymerizing to obtain a fluoroacrylic resin aqueous dispersion, (2) an aqueous emulsified dispersion of an fluoroelastomer resin organic solvent solution or organic solvent dispersion obtained in advance by an emulsifier aqueous solution There are ways to get

In the method for obtaining an aqueous dispersion with the emulsifiers (1) and (2), the fluoroalkyl (meth) acrylate monomer itself or the fluoroacrylic resin previously obtained by any method is hydrophobic. In order to obtain a stable aqueous dispersion, a homomixer, a homogenizer, an ultrasonic emulsifier, etc. are usually used, but there is a drawback that a large amount of emulsifier must be used to reduce the particle size. It was

Therefore, since the fluoroalkyl resin aqueous dispersion thus obtained contains a large amount of an emulsifier, its water repellency, oil repellency or antifouling property is deteriorated, and further the adhesiveness to a substrate, There was a problem that it was inferior in terms of durability, water resistance, washing resistance and the like.

Various methods for reducing the content of these emulsifiers have been investigated in order to eliminate these drawbacks. However, when the content of the emulsifier is reduced, the emulsion dispersion stability is insufficient and fine dispersion becomes difficult. , Various dispersers with stronger shear have been investigated. For example, the method of dispersing by using a homomixer has a problem that a perfect dispersion cannot be obtained because of insufficient shearing force, and separation occurs during storage.

Further, in place of the homomixer, various dispersers such as a homogenizer, a line mill and a colloid mill having a shearing force have been studied. However, these are also limited in rotation speed and slit spacing, and it has been difficult to form fine particles until sufficient stability is achieved.

On the other hand, as an apparatus for emulsifying and dispersing by high pressure, there is a colloid mill manufactured by Manton Gorin Co., Ltd., which has the most effect of atomizing and dispersing among the examined emulsifiers.
Since the structure allows high-pressure predispersion liquid to pass between the slits pressed by the strong spring force, the pressure applied from a safety standpoint is limited, and the amount of premix liquid to be injected is also limited. Since it is injected while pulsating, there is a big problem that the slit spacing changes and the particle diameter of the obtained aqueous dispersion fluctuates. For this reason, repeated emulsification is required for applications requiring long-term stability, and actual production is extremely difficult even if possible on a test scale.

[0009]

The present invention is to provide a method for producing an aqueous fluoroacrylic resin dispersion which is stable with a smaller amount of emulsifier, has a fine particle size, and has a uniform particle system distribution.

[0010]

Means for Solving the Problems The inventors of the present invention have made intensive studies by focusing on the above-mentioned problems, and as a result, have found that the problems can be solved by using a specific emulsifying apparatus, and It came to completion.

That is, in the present invention, the pre-emulsified liquid mixture is introduced into the channel in the chamber under pressure, and the liquid mixture is caused to collide with the flat portion in the channel under high pressure, or in the channel under high pressure. A method for producing a fluoroacrylic resin aqueous dispersion, which comprises emulsifying a pre-emulsified mixed liquid of water and a fluoroalkyl (meth) acrylate monomer or a fluoroacrylic resin with an apparatus for emulsifying the mixture by colliding them. It is provided.

Specifically, the pre-emulsified mixed liquid is introduced into the channel in the chamber under pressure, and the mixed liquid is made to collide with the flat surface portion in the channel under high pressure, or in the channel under high pressure. A fluoroacrylic resin characterized by emulsifying a pre-emulsified liquid mixture of water and a fluoroalkyl (meth) acrylate monomer with an apparatus for emulsifying the liquid mixture by colliding with each other and polymerizing the obtained monomer emulsion. A method for producing an aqueous dispersion, and a pre-emulsified mixed solution is introduced into a channel in a chamber under pressure, and the mixed solution is allowed to collide with a flat portion in the channel under high pressure, or in the channel under high pressure. It is intended to provide a method for producing a fluoroacrylic resin aqueous dispersion, which comprises emulsifying a pre-emulsified mixed solution of water and a fluoroacrylic resin with an apparatus for emulsifying by causing the mixed liquids to collide with each other.

Hereinafter, a fluoroalkyl (meth) acrylate monomer is abbreviated as a fluoroacrylic monomer.

Next, the apparatus used in the present invention will be specifically described. The chamber of the device according to the invention consists of restraining parts 1, 2 and discs 3, 4 which withstand ultra-high pressure in FIG. Each of the disks 3 and 4 is provided with two through holes and an extremely narrowed groove that connects the two holes. The groove preferably has a diameter of 50 to 1,000 μm. The disc 3 and the disc 4 are positioned inward so that the connecting grooves of the two discs come into contact with each other because the fluid passes from the disc 3 to the disc 4, and the discs are located at 90 degrees so that the grooves are cruciform. Are combined in.

The disk must be able to withstand the impingement of liquid under high pressure. Therefore, examples of the material of the disk include ceramics such as metal oxides, borides, carbides, nitrides, mixtures thereof, and inorganic sintered bodies such as sintered diamond, which can withstand ultrahigh pressure.

Next, the present invention will be specifically described with reference to the drawings. First, a pre-mixed liquid of fluoroacryl monomer or fluoroacryl resin and water is added in an amount of 5 to 30 kg / cm ^2.
Under pressure to the restraining portion 1 in the chamber. The mixed solution that has entered the restraining portion 1 is divided into two channels,
Is introduced into the disk 4 and collides with the flat surface portion 5 of the disk 4 as it is.

The colliding liquid is accelerated in the connecting groove 6 of the disc 3 on the side in contact with the disc 4 and flows toward the center,
The liquids collide with each other at the center of the disk 3. Ultrafine particle emulsification is caused by collision with this flat surface and collision of liquids. Next, the liquid flows from the center portion to the outside of the connecting member 7 of the disks 4 formed in 90 degrees phase, and can be taken out through two holes in the disk 4.

As the mixed solution passes through the flow path and the groove in the chamber, the mixed solution is pressurized and accelerated. In this case, the pressure is preferably adjusted so as to be 50 to 10,000 Kg / cm ^{2 in} terms of good dispersion, less wear of the base material and long-term use.

Depending on the composition of the fluoroacryl monomer or the fluoroacryl resin, the stability of the aqueous dispersion may not be improved so much due to secondary aggregation, so a pressure of 70 to 3,000 Kg / cm ² is more preferable.

The structure of the apparatus of the present invention is not limited to that shown in FIGS. 1 and 2, and the mixed solution can be made to collide with a predetermined plane portion in the channel of the chamber under high pressure, or under high pressure. Basically, any structure may be used as long as the mixed liquids can collide with each other.

For example, a structure having flat portions A and B as shown in FIG. 3 may be used, or as shown in FIG. 4, after the collision at the center of the connecting structure of the disc 1 ', the hole of the disc 2'is formed. A structure that can be taken out via 7 may be used.

Specific examples of the new emulsifying apparatus used in the present invention include Microfluidizer manufactured by Microfluidics Co., Ltd. in the United States and Nanomizer manufactured by Cosmo Instrumentation Co., Ltd. in Japan.

As the method for producing the fluoroacrylic resin aqueous dispersion itself of the present invention, any method well known in the art may be used, and examples thereof include the following methods.

That is, (1) an aqueous emulsifier aqueous solution is added to an organic solvent solution or organic solvent dispersion of a fluoroacrylic monomer to obtain an aqueous emulsion dispersion of a fluoroacrylic monomer, and a radical polymerization initiator is added to this to heat and polymerize the resulting fluoropolymer. There are a method of obtaining an acrylic resin aqueous dispersion, a method of (2) adding an emulsifier aqueous solution to an organic solvent solution of a fluoroacrylic resin or an organic solvent dispersion, and emulsifying to obtain an aqueous emulsion dispersion.

In the production method of the present invention, it is an essential condition to use the emulsifying device in the step of dispersing in water in each of the above methods.

In any case of the present invention, when the fluoroacryl monomer (A) or the fluoroacryl resin (B) is dispersed in water by the above apparatus, the fluoroacryl monomer (A) or the fluoroacryl resin (B) is previously prepared. ) And an emulsifier or an aqueous solution containing an emulsifier must be premixed.

Examples of such a premixing method include:
The above emulsifier or an aqueous solution containing the emulsifier is added to an organic solvent solution of the fluoroacrylic monomer (A) or the fluoroacrylic resin (B), or the fluoroalkyl monomer (A) or the fluoroacrylic resin ( A batch method in which the organic solvent solution of B) is charged and mixed may be used, or these may be continuously mixed.

As a mixer for that purpose, various kinds of mixers can be used. For example, static mixers, line mills, rotor-stator mixers, Harel homogenizers, and others, “Chemical Engineering Handbook, No. 779-7”.
82 page (1989) ”, a high-speed rotating pipe-in mixer, a pressure nozzle type emulsifying machine, an ultrasonic emulsifying machine and the like.

The fluoroacrylic monomer (A) and the fluoroacrylic resin (B) according to the present invention can be produced by a conventionally known method or can be easily obtained.
For example, the fluoroacryl monomer compound and the fluoroacryl resin-containing compound can be easily obtained from Dainippon Ink and Chemicals, Inc.

Such a fluoroacrylic monomer (A)
Examples thereof include (meth) acrylic acid S-based monomers, and the following are used, but the present invention is not limited thereto.

[0031]

Embedded image A-1: C ₄ F ₉ SO ₂ NHCH ₂ CH ₂ OCOCH = CH ₂ A-2: C ₄ F ₉ SO ₂ NHCH ₂ CH ₂ OCOC (CH ₃ )
_{= CH 2 A-3: C} 6 F 13 SO 2 N (CH 3) CH 2 CH 2 OCOC
_{H = CH 2 A-4:} C 6 F 13 SO 2 N (CH 3) CH 2 CH 2 OCOC
_{(CH 3) = CH 2 A} -5: C 6 F 13 CH 2 CH 2 OCOCH = CH 2 A-6: C 6 F 13 CH 2 CH 2 OCOC (CH 3) = CH 2 A-7: C 8 F ₁₇ SO ₂ N (CH ₃ ) CH ₂ CH ₂ OCOC
_{H = CH 2 A-8:} C 8 F 17 SO 2 N (CH 3) CH 2 CH 2 OCOC
_{(CH 3) = CH 2 A} -9: C 8 F 17 CH 2 CH 2 OCOCH = CH 2 A-10: C 8 F 17 CH 2 CH 2 OCOC (CH 3) = CH
_{2 A-11: C 10 F} 21 CH 2 CH 2 OCOCH = CH 2 A-12: C 10 F 21 CH 2 CH 2 OCOC (CH 3) = C
H ₂

Various methods have been proposed for producing a fluoroacrylic resin aqueous dispersion. For example, Japanese Patent Publication Sho 37-10
As described in Japanese Patent Application No. 090, as a fluorinated alkyl group-containing compound, C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) CH ₂ C is used.
There is a method of synthesizing an aqueous dispersion using H ₂ OCOC (CH ₃ ) ═CH ₂ and using a cosolvent.

In the method described in the above publication, acetone is used as a co-solvent to assist the water dispersibility of the fluoroacryl monomer (A), and the mixture is emulsified and dispersed by an emulsifier, followed by emulsion polymerization to obtain an acetone-containing aqueous dispersion (emulsion). Liquid).

The fluoroacrylic resin can be produced in the absence of a solvent, but an organic solvent can be used for the purpose of controlling the reaction of the reaction system or reducing the viscosity. The organic solvent is not particularly limited, for example, toluene,
Aromatic hydrocarbons such as xylene; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; acetic acid esters such as ethyl acetate and butyl acetate; amides such as dimethylformamide and N-methylpyrrolidone.

The amount of such an organic solvent affects the content in the finally obtained fluoroacrylic resin aqueous dispersion, and it is preferable to keep the amount used to the minimum necessary in view of the flash point, working environment, performance and the like.

Fluoroacrylic resin (B) to be emulsified
May be a fluoroacrylic monomer homopolymer, but is often used as a copolymer in combination with a fluorine-free copolymerizable monomer (C).

Of course, the fluoroacryl monomer to be emulsified may be the fluoroacryl monomer alone, but it is often used in combination with the fluorine-free copolymerizable monomer (C).

As the copolymerizable monomer (C), for example, the following ones are used.

[0039]

Embedded image C-1: CH ₃ OCOC (CH ₃ ) ═CH ₂ C-2: C ₄ H ₉ OCOCH═CH ₂ C-3: C ₆ H ₁₃ OCOC (CH ₃ ) ═CH ₂ C-4: _{C 8 H 17 OCOCH = CH 2} C-5: C 12 H 25 OCOC (CH 3) = CH 2 C-6: C 18 H 37 OCOCH = CH 2 C-7: CH 2 = CHCOOH C-8: CH 2 _{= C (CH 3) COOH C} -9: CH 2 = CHCOOCH 2 CH 2 OH C-10: CH 2 = C (CH 3) COOCH 2 CH 2 OH C-11: CH 2 = C (CH 3) COOCH 2 CH (O
_{H) CH 2 Cl C-12} : CH 2 = CHCONHCH 2 OH C-13: CH 2 = CHCOO (CH 2 CH 2 O) n H C-14: CH 2 = C (CH 3) COO (CH 2 CH ( C
_{H 3) O) n H C} -15: CH 2 = C (CH 3) COO (CH 2 CH 2 O)
_l [CH ₂ CH (CH ₃₎ O] _{m (CH 2 CH 2 O)} n H C-16: CH 2 = CHCl C-17: CH 2 = CH-CH = CH 2 C-18: CH 2 = C _{(Cl) -CH = CH 2 C} -19: CH 2 = C (Cl) 2 C-20: CH 2 = CF 2 C-21: CH 2 = CHOCOCH 3 C-22: CH 2 = CHOCH 3

The composition and the monomer of the fluoroacrylic resin to be emulsified and dispersed may have any composition, but when the composition to be emulsified and dispersed is the fluoroacrylic resin, it is usually mixed with the fluoroacrylic monomer (A). A polymer obtained by combining these copolymerizable monomers (C) in various proportions and polymerizing, and when the one to be emulsified is a monomer, the fluoroacrylic monomer (A) and these copolymerizable monomers (C) are combined. It is a monomer mixture combined in various proportions.

The monomer composition (copolymerization ratio) of the fluoroacrylic resin (B) and the monomer mixture is usually 10 to 100 parts by weight of the copolymerizable monomer (C) per 100 parts by weight of the fluoroacrylic monomer (A). Is.

Specific examples of the fluoroacrylic resin (B) include the following.

B-1: A-8 / C-6 = 80/20 B-2: A-9 / C-4 = 90/10 B-3: A-8 / C-2 / C-4 / C -12 = 85/5
/ 5/5 B-4: A-9 / C-1 / C-11 / C-12 = 85 /
5/5/5 B-5: A-5 / A-12 / C-1 / C-9 / C-18
= 45/45/3/5/2

In the method of the present invention, known and commonly used emulsifiers can be used. Examples thereof include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether,
Nonionic emulsifiers such as polyoxyethylene styrenated phenyl ether and polyoxyethylene sorbitol tetraoleate; fatty acid salts such as sodium oleate, alkyl sulfate salts, alkylbenzene sulfonates, alkylsulfosuccinates, naphthalene sulfonates, poly Examples thereof include anionic emulsifiers such as oxyethylene alkyl sulfate, sodium alkane sulfonate, and sodium alkyldiphenyl ether sulfonate; cationic emulsifiers such as amine salt; and fluoroalkyl group-containing fluorosurfactants.

These emulsifiers may be used alone or in combination. The amount used is not particularly limited, but it is preferable to use the minimum amount possible. When the emulsifier is used alone, it is preferably contained in an amount of at least 1 part by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the finally obtained fluoroacrylic resin solid content.

The thus-obtained fluoroacrylic resin aqueous dispersion may be used as it is, but it is also possible to distill away the organic solvent as necessary to use it as a fluoroacrylic resin aqueous dispersion.

In the production method of the present invention, if necessary, in addition to water, other aqueous dispersions or aqueous dispersions such as vinyl acetate-based, ethylene vinyl acetate-based, acrylic-based, acrylic styrene-based emulsions are used. Styrene / butadiene based, acrylonitrile / butadiene based, acrylic / butadiene based latex; polyethylene / polyolefin based ionomers; various aqueous dispersions of polyurethane, polyester, polyamide, epoxy resins, etc. May be.

The fluoroacrylic resin aqueous dispersion thus obtained is usually an aqueous dispersion having a solid content of about 15 to 60% by weight, preferably 20 to 40% by weight. At this time, even if it is unavoidable that an organic solvent having a boiling point of 100 ° C. or higher must be used for the production of the fluoroacrylic resin aqueous dispersion,
The amount of such organic solvent used should be limited to 20% based on the total weight of the aqueous dispersion.

The fluoroacrylic resin water dispersion obtained by the method of the present invention includes various plastics such as fiber, leather, paper, wood, vinyl chloride, nylon, polyester, polyurethane, metal such as aluminum, copper and iron, glass, It is used to impart water repellency, oil repellency, and stain resistance to ceramics and the like.

[0050]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples without departing from the technical idea of the present invention. Hereinafter, "parts" and "%" are "parts by weight" and "% by weight", respectively, unless otherwise specified.

Production Example 1 100 parts of a monomer mixture of A-8 / C-6 = 80/20 (weight ratio) was added to a 4-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube. , 150 parts of methyl isobutyl ketone (hereinafter referred to as MIBK), sufficiently replaced with nitrogen and stirred and mixed, and then 1 part of octyl mercaptan and 0.5 part of azobisisobutyronitrile (hereinafter referred to as AIBN). And heat to 80 ° C.
Polymerize at this temperature for 10 hours to prepare fluoroacrylic resin M
An IBK solution (B-1) was obtained.

Production Example 2 A-9 / C-1 / C-11 / C-12 = 85/5 / in a 4-necked flask equipped with a thermometer, a stirrer and a reflux condenser.
100 parts of a mixture of 5/5 was added, 50 parts of acetone was added, and an emulsifier mixture consisting of 3 parts of polyoxyethylene nonylphenyl ether having an ethylene oxide addition mole number of 5 and 1 part of dodecyl-trimethylammonium chloride was added, and 300 parts of water was added. Add and stir and mix to prepare the crude preliminary emulsion (B
-4) was obtained. However, this was inferior in stability, and when stirring was stopped, agglomeration and coalescence started quickly.

Example 1 To 250 parts of the solution (B-1) obtained in Preparation Example 1 was added an emulsifier mixture consisting of 3 parts of polyoxyethylene nonylphenyl ether having 10 moles of ethylene oxide added and 1 part of hexadecyl-trimethylammonium chloride. After adding 250 parts of ion-exchanged water containing the mixture and stirring, 8 kg of the mixed solution was added to a microfluidizer (manufactured by Microfluidic Co., Ltd.) of an apparatus according to the present invention having a chamber connected with disks having an inner diameter of 100 μm. / Cm ²
Introduced with a pressurized compressor at a flow rate of 200 m /
Second, it was treated once at a pressure of 1500 Kg / cm ² and dispersed in water. As a result, a fluoroacrylic resin aqueous dispersion having a nonvolatile content of 20% was obtained.

The average particle size of the obtained aqueous dispersion is 0.2 μm.
storage stability after storage for 3 months at room temperature,
There was no separation or precipitation.

Comparative Example 1 The mixed solution of Example 1 was used as a Manton-Gorlin colloid mill TY.
PE-15M (manton golin company) 350 kg /
It was dispersed in water by passing it 3 times with a pressure of cm ² ,
Insufficient dispersion resulted in sedimentation in the storage stability test.

Comparative Example 2 The mixture of Example 1 obtained by doubling the amount of emulsifier used.
Manton Gorin Colloid Mill TYPE-15M
(Menton Gorin Co., Ltd.) 350 kg / cm ²Pressure of
Was passed three times to disperse in water. Average particle system 0.
4 μm, a small amount of
Separation and sedimentation were observed.

Comparative Example 3 The mixture of Example 1 was agitated for 15 minutes at 10,000 rpm in a TK-Automixer (manufactured by Tokushu Kika Co., Ltd.), but the dispersion was insufficient and sedimentation occurred in the storage stability test. Things were occurring.

Example 2 Production Example 2 immediately after the preparation and the start of aggregation / coalescence
While stirring 350 g of the crude pre-emulsion (B-4), a pressure of 8 Kg / cm ² was applied to an emulsifying machine Microfluidizer (manufactured by Microfluidic) having a chamber in which disks having holes having an inner diameter of 100 μm were connected. Introduced with a compressed compressor, flow rate 200m / sec, 1500Kg
Dispersion was performed in water at a pressure of / cm ² .

The pre-emulsified liquid thus obtained was returned to the four-necked flask of Production Example 2 and, after purging with nitrogen, 0.5 part of benzoyl peroxide was added with stirring, and the mixture was heated to 80 ° C.
Polymerization was carried out for 10 hours. The average particle size of the fluoroacrylic resin aqueous dispersion after the polymerization was 0.22 μm. The obtained resin aqueous dispersion was desolvated under reduced pressure to remove acetone, and a fluoroalkyl resin aqueous dispersion having a nonvolatile content of 30% was obtained. The average particle size of the final aqueous dispersion after solvent removal was 0.23 μm, which was extremely fine, and the storage stability after standing for 3 months at room temperature was good, and no separation or sedimentation occurred.

COMPARATIVE EXAMPLE 4 Manton-goulin colloid mill TY was mixed with the mixed solution of Example 2.
PE-15M (manton golin company) 350 kg /
It was dispersed in water by passing it 3 times with a pressure of cm ² ,
Insufficient dispersion resulted in settling separation in the storage stability test and subsequent emulsion polymerization could not be carried out.

Comparative Example 5 The mixture of Example 3 obtained by doubling the amount of emulsifier used.
Manton Gorin Colloid Mill TYPE-15M
(Menton Gorin Co., Ltd.) 350 kg / cm ²Pressure of
Was passed three times to disperse in water. Average particle system 0.
A 5 μm monomer dispersion was obtained. This B-4 monomer
-Return the emulsion to the 4-neck flask of Production Example 2 and replace with nitrogen.
After stirring, 0.5 part of benzoyl peroxide was added.
In addition, polymerization was performed at 80 ° C. for 10 hours. After completion of polymerization
The average particle size of the fluoroacrylic resin aqueous dispersion is 0.6μ.
It was m. Desolvation of the obtained resin aqueous dispersion under reduced pressure
Acetone is removed to remove fluoroalkyl with a nonvolatile content of 30%.
An aqueous resin dispersion was obtained. Final aqueous dispersion after solvent removal
The average particle size of the body is 0.8 μm, and after standing for 3 months at room temperature
Sediment was observed in the dispersion liquid.

Comparative Example 6 The mixture of Example 2 was stirred in a TK-Automixer (made by Tokushu Kika Co., Ltd.) at 10,000 rpm for 15 minutes, but the dispersion was insufficient and sedimentation occurred in the storage stability test. A lot of things were generated. It was not possible to carry out the subsequent emulsion polymerization as in Comparative Example 4.

Application Example 1 compares the water- and oil-repellent performance of the fluoroalkyl resin aqueous dispersion obtained in the present invention with respect to the fiber of a conventional high emulsifier concentration product used in an emulsifier.

Application Example 1 (Water Repellent Treatment of Nylon Taffeta and Polyester Taffeta) Each base cloth was subjected to a water and oil repellent treatment under the following conditions.
The results are shown in Table-1.

Test cloth: Nylon taffeta (190 pieces, 70d) undyed cloth Polyester taffeta (170 pieces, 70d) undyed cloth Processing conditions: Immersion draw 1Dip1Nip Wet Pick-up Nylon taffeta 37% Polyester taffeta 41% Preliminary Drying 100 ℃ × 2 minutes Curing 170 ℃ × 30 seconds

Measurement item: Water repellency (WR) ... JIS L-1092
Spray method (the higher the number, the higher the water repellency) Oil repellency (OR) ... AATCC 118 (The higher the number, the higher oil repellency) Wash resistance (WR, OR after 10 times water wash) ... JIS-0
217/103 method (The higher the value, the better the washing resistance)

[0067]

[Table 1]

Note) Beckamine J-101 (crosslinking agent, melamine resin manufactured by Dainippon Ink and Chemicals, Inc.) Catalyst 376 (catalyst manufactured by Dainippon Ink and Chemicals, Inc.)

Formula 1 and Formula 3, Formula 2 and Formula 4, Formula 3
As can be seen from the comparison between Formulation 6 and Formulation 6, the treated cloth treated with the water and oil repellent prepared using the fluoroacrylic resin aqueous dispersion obtained according to the production method of the present invention has Due to the fact that the amount used is halved and the emulsion particle system is made finer, it is clear that the water and oil repellency effect does not decrease significantly even after washing, and it has a high degree of durability. Is recognized.

[0070]

EFFECTS OF THE INVENTION According to the production method of the present invention, it is difficult to obtain a stable aqueous dispersion with a conventional emulsifying machine. Even at a level where the amount of emulsifier used is smaller than before, the particle size distribution is extremely fine. It is possible to easily produce a fluoroalkyl resin aqueous dispersion that is uniform and has excellent long-term stability or mechanical stability.

Since the fluoroalkyl resin aqueous dispersion obtained in the present invention has an extremely small content of an emulsifier, it is excellent not only in water repellency, oil repellency, antifouling property, etc., but also in transparency after drying. It has the characteristics of excellent smoothness, gloss, water resistance, and mechanical strength, as well as excellent adhesion to various substrates.

The fluoroalkyl resin aqueous dispersion thus obtained can be treated in the same manner as a conventional fluoroalkyl resin aqueous dispersion, and the aqueous dispersion obtained by removing the organic solvent from the aqueous dispersion is treated with an organic solvent. Very little concern about pollution and fire.

[Brief description of drawings]

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

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

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

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

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

[Explanation of symbols]

 1, 2 Suppressing part 3, 3a, 3b, 4, 4a, 4b Disk 5, 6 Flat surface of disk 7 Disk connecting groove 8 Central part of connecting groove 9 Disk connecting groove 10 Disk hole

Claims (7)

[Claims] 1. A pre-emulsified liquid mixture is introduced into a channel in a chamber under pressure, and the liquid mixture is caused to collide with a flat surface portion in the channel under high pressure, or the liquid mixture in the channel under high pressure. A fluoroacrylic resin aqueous dispersion characterized by emulsifying a pre-emulsified mixed liquid of water and a fluoroalkyl (meth) acrylate monomer by an apparatus for emulsifying by colliding with each other and polymerizing the obtained monomer emulsion. Manufacturing method. 2. The method according to claim 1, wherein the fluoroalkyl (meth) acrylate monomer is used as an organic solvent solution containing at least one perfluoroalkyl group-containing (meth) acrylic acid ester monomer. 3. The production method according to claim 1, wherein, based on 100 parts by weight of the fluoroalkyl (meth) acrylate monomer, 10 to 100 parts by weight of another monomer copolymerizable therewith is used in combination. 4. A pre-emulsified mixed solution is introduced under pressure into a channel in a chamber, and the mixed solution is made to collide with a flat surface portion in the channel under high pressure, or the mixed solution in the channel under high pressure. A method for producing an aqueous fluoroacrylic resin dispersion, which comprises emulsifying a pre-emulsified mixed liquid of water and a fluoroacrylic resin with an apparatus for emulsifying by colliding with each other. 5. The method according to claim 4, wherein a solution of an acrylic polymer containing a perfluoroalkyl group in an organic solvent is used as the fluoroacrylic resin, and the water is an aqueous emulsifier solution. 6. The fluoroacrylic resin is a copolymer of 100 parts by weight of a fluoroalkyl (meth) acrylate monomer and 10 to 100 parts by weight of another monomer copolymerizable therewith. Production method. 7. The pressure at the time of collision is 50 to 10,000 kg /
Claim 1, 2, 3, 4, characterized in that cm ^2, and
The production method according to 5 or 6.