JPH01292068A - Continuous production of emulsion type aqueous coating compound - Google Patents

Abstract

PURPOSE:To continuously obtain the title coating compound free from pollution, by processing a carboxyl group-containing acrylic resin component and a resin component of an epoxy resin (curing agent) in an aqueous solution of amine through a W/O type emulsion into an O/W type emulsion. CONSTITUTION:(A) (i) A solution of a carboxyl group-containing acrylic resin component and/or a resin component of an epoxy resin (curing agent) in an organic solvent together with (ii) an aqueous solution of ammonia or an amine is fed to a first-stage in-line mixer. The solutions are blended in the mixer under pressure to form a W/O type emulsion. The W/O type emulsion together with water is sent to a second-stage in-line mixer, blended in the mixer and subjected to phase conversion to give an O/W type emulsion. Then the formed O/W type emulsion is quantitatively taken out to continuously give the aimed coating compound.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for continuously producing an emulsified water-based paint, and more particularly, it relates to a method for continuously producing an emulsified water-based paint, and more particularly, it relates to a carboxyl group-containing acrylic resin component, an epoxy resin component, and a method for producing an emulsified water-based paint. The present invention relates to a method for continuously producing an emulsified water-based paint containing a curing agent resin component.

(Prior Art) When spraying paint, solvent evaporates into the working environment, causing air pollution and environmental hygiene problems. In order to overcome these drawbacks, water-based paints, ie water-based dispersion paints, have already been developed.

The first type of water-based paint is one in which paint resin is atomized by some means and dispersed in water using a surfactant or a water-soluble or hydrophilic resin as a dispersant (for example, 44-18076), and the second type modifies a coating resin having a functional group such as an epoxy resin by reacting it with a resin having a carboxyl group such as an acrylic resin. It is self-emulsified in an aqueous medium by neutralizing it with ammonia or amines (for example, Japanese Patent Publication No. 59-37
026 Publication).

However, in the former type of water-based paint, the dispersed particle size of the paint resin component tends to be generally coarse or uneven, and the water-based paint has poor dispersion stability, and the performance of the resulting paint film is also similar to that of solvent-based paints. It is inferior to other paints.

Furthermore, even if the latter type of paint is superior to the former type of paint in terms of dispersibility, etc., it is severely limited by the paint resin composition.For example, in the case of epoxy resin paints, the resin curing agent Because it is difficult to increase the content sufficiently, the coating film cannot be cured sufficiently, and therefore the hardness, density, barrier properties against corrosive components, etc. of the coating film are improved to a satisfactory level. The problem arises that it cannot be done.

The present inventors first prepared an organic solvent solution containing a carboxyl group-containing acrylic resin component, an epoxy resin component, and a curing agent resin component for epoxy resin, mixed ammonia or amine and water into the solution, and added water to the acrylic resin. We proposed converting the carboxyl groups in the resin into ammonium salts or amine salts and self-emulsifying the resin content in the solution into an O/W emulsion (patent pending).

(Problems to be Solved by the Invention) However, in the method of the above-mentioned prior art, since the resin solution has a considerably high viscosity, a large amount of organic solvent must be used, and as a result, a large amount of organic solvent must be used during phase inversion. Also, a large amount of water must be mixed, and the resulting aqueous emulsion generally has a low solids concentration, which means that a large amount of liquid must be handled and the equipment becomes large:
There are still disadvantages such as the necessity to remove relatively large amounts of solvent and water from the resulting emulsion by evaporation.

Therefore, an object of the present invention is to eliminate the above-mentioned drawbacks of the prior art and to continuously produce an emulsion-type paint from a carboxyl group-containing acrylic resin component, an epoxy resin component, and its curing agent resin component using a relatively compact device. The purpose is to provide a method for manufacturing.

Another object of the present invention is to provide a method for producing an aqueous emulsion paint with high solid content and small particle size with high efficiency, using relatively small amounts of solvent and water.

(Means for Solving the Problems) According to the present invention, in the form of an organic solvent solution containing a carboxyl group-containing acrylic resin component, an epoxy resin component, and a curing agent resin component for epoxy resin alone or in combination, ammonia or amine W1 is supplied to the first stage in-line mixer together with the aqueous solution of W1 and mixed under pressure in the mixer.
0 type emulsion is formed, this W10 type emulsion is supplied together with water to the second stage in-line mixer, mixed in the mixer to invert the phase to an O/W type emulsion, and the produced O/W type emulsion is quantitatively determined. Provided is a method for continuously producing an emulsified water-based paint, which is characterized in that it can be drawn out in a continuous manner.

(Function) In the present invention, an organic solvent containing a carboxyl group-containing acrylic resin component, an epoxy resin component, and a curing agent resin component for epoxy resin alone or in combination (hereinafter sometimes simply referred to as a resin solution) is used. Supply the solution together with an aqueous solution of ammonia or amine to the first stage in-line mixer and mix under pressure to once form a W10 type (wood-in-oil) emulsion; The remarkable feature is that the mixture is supplied to an in-line mixer and mixed to form an O/W type (oil-in-water) emulsion; and that the O/W type emulsion produced by the phase inversion is quantitatively drawn out.

When producing an O/W type aqueous dispersion from a resin solution by a phase inversion method, mixing and stirring must be carried out while gradually adding ammonia water or amine water, and this addition and mixing must be carried out for an extremely long time. This poses an obstacle to continuous manufacturing methods. In the present invention, prior to phase inversion, a resin solution and an aqueous solution of ammonia or amine are mixed to form a W10 emulsion in which water is dispersed in a fine particle size in the resin solution; This is based on the knowledge that when an emulsion and water are mixed to form an O/W emulsion, the time required for addition and mixing is significantly shortened, and as a result, continuous production becomes possible.

In the production of an emulsion from a resin solution, the acrylic resin exists in a compatible or blended state with other paint resins, but the carboxyl groups in the acrylic resin component are neutralized with added ammonia or amine, and the salt This is done by directing the shape to the interface with water. In the present invention, all ammonia or amine necessary for this neutralization is added in the first W10 emulsion generation step. As a result, W
The phase inversion from 2O type to O/W type is performed by a simpler mechanism.

According to the present invention, an in-line mixer is used to closely mix the resin solution and ammonia water or amine water and the W10 emulsion and water, and to increase the residence time of the treated material in the device. . Furthermore, since the resin solution and the ammonia water or amine water are mixed under extremely high viscosity conditions, the mixing is carried out under pressure to prevent cavitation. In this way, according to the method of the present invention, an extremely uniform and fine W10 type emulsion can be formed, and by forming a uniform and fine W10 type emulsion, a uniform and fine 0/2 emulsion can be formed.
It becomes possible to invert the phase to a W-type emulsion.

(Preferred Embodiment of the Invention) In FIG. 1, which schematically shows the arrangement of an apparatus used in the continuous production method of the present invention, this apparatus consists of a first treatment tank 1 and a second treatment tank 2. The first process 4i1 is for forming a W10 type emulsion and is equipped with an in-line mixer 3 inside.

The second treatment tank 2 is for forming an O/W type emulsion, and is also equipped with an in-line mixer 4 inside.

The first treatment 4iIt includes a resin solution supply line 5, an ammonia water or amine water supply line 6, and an in-tank pressure line 7.
is attached. The first processing tank 1 and the second processing tank 2 communicate with each other via a communication pipe 8. The second treatment tank 2 further includes:
A water supply line 9 and a product withdrawal line 10 are provided, and a metering discharge valve 11 is provided in the product withdrawal line IO.

The resin solution is supplied through the supply line 5, and ammonia water or amine water is supplied through the supply line 6 to the first treatment tank 1, and nitrogen, air, water vapor, etc. are supplied to the first treatment tank 1 from the pressure line 7. Pressurized fluid is supplied to increase the pressure to a predetermined pressure. The in-line mixer 3 is driven to mix both under pressure to produce a W10 emulsion 12. The formed W10 emulsion 12 is sent to the second treatment tank 2 through the communication pipe 8. Water is supplied to the second treatment tank 2 via the water supply line 9, and the W10 type emulsion and water are mixed with the inline mixer 4, and the 0/W type emulsion 1 is mixed.
3 is generated by phase inversion. The generated O/W type emulsion 13 is transferred to the extraction line lO and the quantitative discharge valve 1.
1, the product is quantitatively taken out of the device as a product. In this method, the first treatment tank 1 is pressurized, and the first treatment tank 1 and the second treatment tank 2 are connected via the communication pipe 8, so that the second treatment tank 2 is discharged. O/
An amount of W10 type emulsion commensurate with the W type emulsion will be sent from the first treatment tank 1 to the second treatment tank 2, and the two-stage treatment will be carried out smoothly and continuously.

1. The coating solution used in the present invention contains three components: an acrylic resin component, an epoxy resin component, and a curing agent resin component for epoxy resin. In this case, the carboxyl group-containing acrylic resin component and the epoxy resin component may be contained in the solution in the form of a copolymer, or the carboxyl group-containing acrylic resin component and the epoxy resin component may be contained in the solution in the form of a blend. It may be contained inside.

The acid value of the acrylic resin used is 35 to 3501, especially 70.
and 3 to 30% by weight, especially 5 to 25% by weight of this acrylic resin based on the resin for the coating.
It is generally preferred to use an amount of .

That is, when the acid value of the acrylic resin is lower than the above range, in the neutralization step and the subsequent phase conversion emulsification step, which will be described later,
0/W (oil in water) with fine and uniform particle size for paint resin component
It becomes difficult to emulsify the dispersed particles, and the emulsion stabilizer of the dispersed particles also tends to decrease. Additionally, if the acid value of the acrylic resin is higher than the above range, the acrylic resin tends to separate from the paint resin in a later process and flow into the water phase, resulting in a fine and uniform particle size. It becomes difficult to emulsify the liquid, and the stability of the dispersion liquid also deteriorates.Furthermore, the formed coating film tends to be sensitive to humidity. According to the present invention, by selecting the acid value of the acrylic resin within the above range, it is possible to emulsify the coating resin component to a uniform and fine particle size and improve the dispersion stability of the emulsified resin. The resulting coating film can be made to have excellent moisture resistance, water resistance, etc.

In addition, if the amount of acrylic resin blended is less than the above range, sufficient carboxylate groups may be added to the interface between the water phase and the oil phase (resin phase) in the neutralization step and the subsequent phase conversion step. As a result, it becomes difficult to emulsify the coating resin component into uniform and fine particle sizes, and the dispersion stability of the aqueous dispersion also deteriorates. On the other hand, increasing the blending amount of acrylic resin beyond the above range will have an effect on the physical properties of the paint film due to the mixing of a large amount of acrylic resin into the paint resin, so the blending amount should be within the above range. It is better to

In the present invention, any acrylic resin may be used as the acrylic resin as long as the acid value is within the above range. This acrylic resin is made of an ethylenically unsaturated carboxylic acid or its anhydride that provides a carboxyl group with the above-mentioned acid value in the resin, an acrylic ester or a methacrylic ester, and optionally another ethylene-based carboxylic acid that can be copolymerized with these. Consists of a copolymer with unsaturated monomers. Examples of ethylenically unsaturated carboxylic acids or their anhydrides include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid,
These include itaconic acid, citraconic acid, maleic anhydride, itaconic anhydride, and the like.

Examples of esters of acrylic acid and methacrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylate. ) n-amyl acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, and the like. However, the above (meth)acrylic acid refers to acrylic acid or methacrylic acid.

Other comonomers copolymerized with these monomers include styrene, vinyltoluene, acrylonitrile, methacrylonitrile, and the like.

The acrylic resin used should have a molecular weight sufficient to form a film, generally between 10,000 and 200,000.
000, particularly within the range of 20,000 to 150,000. Examples of suitable combinations of acrylic copolymers include (1) methyl methacrylate/2-ethylhexyl acrylate/acrylic acid;
These include styrene/methyl methacrylate/ethyl acrylate/methacrylic acid, (3) styrene/ethyl acrylate/methacrylic acid, and (4) methyl methacrylate/ethyl acrylate/acrylic acid.

These acrylic resins can be easily obtained by polymerizing these monomers in an organic solvent in the presence of azobisisobutyronitriles or peroxides.

As the epoxy resin, a bisphenol type epoxy resin obtained by polycondensation of bisphenols such as bisphenol A and shrimp helohydrin is suitable, and its epoxy equivalent is generally 400 to 20,000, particularly 1.0
00 to 5,000, and the number average molecular weight is 1
,000 to 20,000. Especially 2.000 to 13,
Preferably, it is in the range of 000.

Examples of resin curing agents that are reactive with epoxy resins include resins that have functional groups that are reactive with hydroxyl groups and oxirane rings of epoxy resins, such as hydroxyl groups, amino groups, and carboxyl groups; for example, resol type and/or or novolak-type phenol formaldehyde resin, urea-
One or a combination of two or more of formaldehyde resins, melamine/formalde resins, alkyd resins, polyester resins, acrylic resins, polyurethane resins, xylene resins, epoxy ester resins, butyral resins, etc. are used. Among these, methylol group-containing thermosetting resins, particularly resol type phenolic resins, are preferred.

In the present invention, even when the composition ratio of the epoxy resin and the curing agent resin is within an arbitrary range, the coating resin can be emulsified and dispersed into fine dispersed particle sizes. The ratio of epoxy resin to curing agent resin is generally in the range of 95:5 to 40:60 by weight, especially 90:10 to 50:50.

In the coating solution used in the present invention, each resin component may exist as a simple mixture, or as a precondensate or copolymer. For example, the epoxy resin component and the acrylic resin component may be a blend or may exist in the form of a copolymer; in this latter case, the copolymer may contain free carboxyl groups. It is. In both the former and the latter case, the acid number per total resin should generally be in the range from 2 to 30, in particular from 5 to 20. Suitable examples of epoxy-acrylic copolymers include:
It is described in Japanese Patent Publication No. 59-37026.

Organic solvents for resin solutions include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as ethanol, propatool, and butanol; and ethyl cellosolve. , cellosolve solvents such as butyl cellosolve; and ester solvents such as ethyl acetate and butyl acetate.6 The resin concentration in the raw material solution is generally 5 to 80%.
It is preferably in the range of 20 to 70% by weight. This raw material solution contains a known paint compounding agent,
For example, plasticizers, lubricants, pigments, fillers, stabilizers, etc. may be added as desired.

Ammonia water or amine water is used to neutralize the resin solution in the first step. Examples of amines used for neutralization include alkyl amines such as trimethylamine, triethylamine, and n-butylamine, and alcohol amines such as 2-dimethylaminoethanol, jetanolamine, triethanolamine, aminomethylpropanol, and dimethylaminomethylpropanol. etc. are used. Also, ethylenediamine,
Polyvalent amines such as diethylenetriamine can also be used. Furthermore, amines and heterocyclic amines having branched alkyl groups are also preferably used. Examples of amines having a branched alkyl group include isopropylamine, 5ec-butylamine, t
3 carbon atoms such as ert-butylamine, isoamylamine, etc.
Branched alkylamines having from 3 to 6 carbon atoms, especially from 3 to 4 carbon atoms, are used. As the heterocyclic amine, saturated heterocyclic amines containing one nitrogen atom such as pyrrolidine, veridine, and morpholine are used. Ammonia and amines are at least 0.0% relative to the carboxyl group of the acrylic resin.
It is preferable to use an amount of 3 chemical equivalents, particularly 0.7 to 1.3 chemical equivalents.

When mixing the resin solution (A) and ammonia water or amine water (B), the weight ratio of both liquids is A:B=10:10 to 1.
It is preferable to supply the liquid to the first treatment at a ratio of 0:1, particularly 10:9 to 10:4.

In other words, if the amount of ammonia water or amine water is larger than the above range, the phase of the O/W emulsion that is produced will change to an O/W emulsion without stably producing a W10 emulsion. If the particle size of the dispersed phase tends to become coarse and the amount of liquid is less than the above range, a relatively large amount of water may be added when inverting the resulting W10 emulsion to an O/W emulsion. The phase inversion becomes unstable and the particle size of the dispersed phase tends to become irregular.

As mentioned above, it is important to perform the mixing in the first stage in-line mixer under pressure.
．． 5 to 7 g/cm" (gauge).

The temperature during mixing is generally 10 to 90°C, especially 1
It is preferably within the range of 5 to 70°C. It should be understood that since the mixing in the first stage involves a neutralization reaction and involves vigorous stirring, the temperature may rise to 100° C. or higher due to heat generation. Of course, if a high temperature is desired, it can be heated externally, and if a rise in temperature is not desirable, it can be externally cooled.

The degree of mixing by the first-stage inline mixer is expressed in the formula, where vI is the amount of supply to the inline mixer (J!/5
in), and ■2 represents the discharge rate (j!/n+in) measured using water from the agitator in the in-line mixer. It is better to do it as you see fit. If this value is smaller than the above range, it may not be possible to form a uniform and fine W10 type emulsion, whereas if the value is larger than the above range, the production rate of water-based paint may be reduced. They tend to be smaller and less industrial.

Second Step In the second step of the present invention, the W10 type emulsion produced in the first step is supplied together with water to the second stage in-line mixer and phase inverted to a 0/W type emulsion.

Used in this second step. The amount of water is W from the first step.
Although it depends on the amount of water in the type 10 emulsion, the amount is such that phase inversion to an O/W type emulsion is sufficiently carried out, and generally, 30% of water per type W10 emulsion is used.
The amount is from 100 parts by weight, especially from 35 to 80 parts by weight.

This phase inversion step is easier to perform than the W10 emulsion generation step in the first step, and there are no particular restrictions such as temperature and time. Since the mold emulsion is in communication with the mold emulsion, it is carried out under approximately the same temperature and pressure conditions.

The generated O/W type emulsion is quantitatively drawn out to the outside through a quantitative discharge valve. This quantitative emission is
Of course, it may be carried out continuously at a constant flow rate, or may be carried out intermittently at regular intervals.

Due to post-treatment phase inversion, the aqueous dispersion contains both water and organic solvent. By subjecting this aqueous fraction to azeotropic vacuum distillation, the organic solvent can be removed azeotropically with water, and the aqueous dispersion can be concentrated. It should be understood that azeotropic distillation of an organic solvent can also be carried out while supplementing water from the outside.

The concentration of paint resin solids in the final water-based paint is preferably in the range of 10 to 70% by weight, particularly 20 to 60% by weight, and the content of organic solvent in the water-based paint is preferably 15 to 70% by weight.
It is desirable that the amount is not more than 5% by weight, especially not more than 5% by weight.

Furthermore, for the purpose of improving the dispersion stability of the resin component in the paint, it is permissible to add a small amount of a surfactant or a polymer dispersant to the system at any stage.

The water-based paint according to the present invention has a viscosity suitable for coating and can be used for coating various metal materials, can bodies, pipes, and other members. This water-based paint is not only used for regular spray painting and electrostatic painting, but also for roller application,
Brush application, doctor coater, air knife coater,
It can be used for coating work with various coaters such as reverse coaters.

(Effects of the Invention) According to the present invention, a step of mixing a paint solution containing a carboxyl group-containing acrylic resin component and ammonia water or amine water with an in-line mixer to form a W10 emulsion; By combining the process of mixing with water using an in-line mixer and inverting the phase to an O/W type emulsion, even from a resin solution with extremely high viscosity, a water-based emulsion type paint with fine particle size and homogeneity can be continuously produced. It became possible to manufacture Therefore, according to the present invention, it has become possible to produce an aqueous emulsion type paint with a high solid content concentration with high efficiency using relatively small amounts of solvent and water.

(Example) In the examples, unless otherwise specified, parts are expressed as parts by weight.

In addition, unless otherwise specified, evaluations of paints or coated plates were performed in the following manner throughout each of the Examples and Comparative Examples.

(1) Stability of paint over time 100a+g of emulsified water-based paint to be tested with a content of 100m
Place the container in a wide-mouthed glass bottle, seal it tightly, and store it in a constant temperature bath at 50°C for one month, then open it and investigate the presence or absence of a skin on the liquid surface, the viscosity of the emulsified water-based paint, and the average number of resin particles. Particle size was investigated and compared with before storage.

(2) Paintability The emulsified water-based paint to be tested was coated on an electrolytic chromic acid treated steel sheet (hereinafter referred to as TFS) using a roll coater.
It was cured by baking at 0°C for 10 minutes. Coating film thickness is approximately 5μ
It was set as m. The unevenness of the painted surface of this painted board was evaluated by visual judgment.

(3) Adhesion and retort whitening The above-mentioned coated plates were cut into 5 mm width pieces and adhered using a nylon adhesive by pressing for 2 minutes in a hot press heated to 200°C. The peel strength was measured using T-Beer, and the initial peel strength immediately after adhesion and the peel strength over time after being immersed in hot water at 90°C for one week were determined. Further, a part of this coated board was subjected to retort treatment at 125° C. for 30 minutes, and the presence or absence of whitening of the coating film due to the retort treatment was investigated.

(4) Actual can evaluation For some emulsion-type water-based paints, the test water-based paint was applied to one side of TFS using a roll coater, baked and dried at 210°C for 10 minutes, and then the other side was painted in the same manner.・Prepared a double-sided painted board by baking.

The thickness of each coating film was approximately 4 μm. Using this painted board and nylon adhesive, we glued 202 diamonds to the can body (both ends were necked in to become 200 diamonds).
After making the can, the canopy was double-sealed, the contents were filled, the bottom lid was double-sealed, and the can was filled. This canned product was retort sterilized at 120° C. for 90 minutes, cooled and air-dried, and then stored in a warehouse.

After six months of storage, the cans were opened and inspected for abnormalities such as whitening of the paint film and internal corrosion. In addition, some of the painted plates were molded into blanks and used for evaluation.

Further, the discharge amount of the agitator in the in-line mixer was measured in the following manner. The first stage treatment tank 1 is fixed alone, the resin solution supply line 5 is closed, and the ammonia water or amine water supply line 6 is fixed in the water tank, and the communication pipe 8 is left open. In this state, when the treatment tank 1 is primed with water and the in-line mixer is driven, the agitator pumps up the water in the water tank and discharges the pumped water from the communication pipe 8. After the operation reached steady state, water discharged through the communication pipe 8 during a certain period of time was sampled and its volume was measured to determine the discharge amount under the relevant operating conditions of the agitator.

Example 1 Number average molecular weight 3,750, epoxy equivalent approximately 3,00
Prepare a solution in which 800 parts of 0 bisphenol A type epoxy resin is dissolved in 800 parts of a mixed solvent of butyl acetate and n-butanol (butyl acetate/n-butanol = 6/4),
200 parts of a resol-type phenol resin (bisphenol A/para-cresol = 80/20, number average molecular weight 650) derived from bisphenol A, vala-cresol, and formaldehyde using an ammonia catalyst are mixed with xylene, methyl isobutyl ketone, and cyclohexanone. A solution dissolved in 400 parts of a solvent (xylene/methyl isobutyl ketone/cyclohexanone = 1/1/1) was prepared and mixed with the epoxy resin solution.

On the other hand, 200 parts of ethyl acrylate, 200 parts of methyl methacrylate, 400 parts of methacrylic fi, 2
00 parts of ethyl cellosolve and 10 parts of tert-butyl hydroperoxide were prepared, and in a flask equipped with a stirrer, a thermometer, a dropping funnel, a reflux condenser, and an inert gas inlet, 500 parts of ethyl cellosolve and 250 parts of the above mixture were added. Preparation,
After raising the temperature to 90°C with stirring under a nitrogen stream, the remaining amount of the 1,000 ml mixture was added dropwise to the flask maintained at the same temperature over 3 hours to cause copolymerization, and further, t
After adding 1 part of ert-butyl hydroperoxide and continuing stirring at the same temperature for 3 hours, ethyl cellosolve 500
of the mixture was added and cooled to complete the reaction. The weight average molecular weight of the obtained acrylic resin was approximately 120,000, the acid value was 124,
The solids content of the resin solution was 50%.

Next, 20 parts of the above acrylic resin solution was added to 160 parts of the above mixed solution of epoxy resin and phenol resin and stirred to uniformly mix to obtain an organic solvent solution of paint resin. On the other hand, amine water was prepared by dissolving 4 parts of dimethylaminoethanol as a neutralizing agent in 90 parts of deionized water. Furthermore, deionized water to be supplied to the second stage treatment tank was prepared.

The discharge rate measured using water from the agitator in the first stage inline mixer was set to 25 f/win, and the organic solvent solution of paint resin was pumped at 1 Bji7 min using a metering pump.
and amine water were supplied to the first stage treatment tank at a ratio of 0.95p/1IIin, and the stirrer was driven. 4
! The pressurized line inside I was sealed off. Also, the discharge amount of the agitator in the second stage processing tank is 201! /Win and add 1.4'J of deionized water into this! The stirrer was driven while supplying the mixture at /win. Furthermore, adjust the metering discharge valve to reduce the discharge amount from the second stage treatment tank to approximately 4-2 g/win.
And so. As a result, the internal pressure of the treatment tank was approximately 1.2 on the gauge.
Kg/ca+". At this time, the stirring efficiency of the first-stage in-line mixer was about 9.1, and the stirring efficiency of the second-stage in-line mixer was about 4.8.

The discharged material for 30 seconds at the beginning of the operation was discarded, and the subsequent discharged material was collected. This discharged material was a stable OZW type emulsion, and the average particle size of the dispersed phase was 0.65 μm. 420 parts of this OZW type emulsion was concentrated and solvent removed using a rotary evaporator, and 120 parts of water and 95 parts of organic solvent were recovered to obtain an emulsified water-based paint (paint 1) with a solid content of 40.2%.

Furthermore, the order of the 10 types of amines shown in Table 1 as neutralizing agents,
Ten types of emulsion-type water-based paints (Paints 2 to 11) were prepared according to the manufacturing method of Paint 1, except that they were used respectively. The average particle size of the resin particles of the obtained emulsified water-based paint is also listed in Table 1.

When we investigated the stability over time of these emulsion-type water-based paints (paints 1 to 11), we found that none of the emulsion-type water-based paints had a skin on the liquid surface. Both the average particle diameter of the resin particles did not change compared to before storage. The coating properties when applied with a roll coater are good with any emulsion type water-based paint.
The unevenness of the painted surface was of a level that did not pose a practical problem. Furthermore,
The adhesion and retort whitening were evaluated, and the actual cans filled with consommé soup were evaluated, and the results are also listed in Table 1.

Example 2 An organic solvent solution of the coating resin used in Example 1, amine water, and deionized water were prepared. Seven types of emulsified water-based paints (paints 12 to 18) were prepared according to Example 1, except that these were supplied to the first and second stage treatment tanks at the quantitative ratios shown in Table 2. . The stirring efficiency in the first stage in-line mixer and the internal pressure of the processing tank at this time are shown in Table 2 along with the average particle size of the dispersed phase in the obtained O/W type emulsion.
Also listed.

These O/W type emulsions were concentrated and solvent removed using a rotary evaporator to obtain an emulsion type water-based paint with a solid content of about 40%. The stability over time of these emulsified water-based paints and the coating properties when applied with a roll coater were evaluated, and the results are also listed in Table 2.

Example 3 An organic solvent solution of the coating resin used in Example 1, amine water, and deionized water were prepared. The procedure of Example 1 was followed except that these were supplied to the first-stage and second-stage processing tanks, respectively, and the rotational speed of the first-stage agitator was adjusted to adjust the discharge amount of the agitator in the in-line mixer. Six types of emulsified water-based paints (paints 19 to 24) were produced. The stirring efficiency in the first-stage inline mixer, the internal pressure of the processing tank, and the liquid temperature in the processing tank at this time are listed in Table 3 along with the average particle size of the dispersed phase in the obtained O/W emulsion. did.

These O/W type emulsions were concentrated and solvent removed using a rotary evaporator to obtain an emulsion type water-based paint with a solid content of about 40%. The stability over time of these emulsified water-based paints and the paintability when applied with a roll coater were evaluated, and the results are also listed in Table 3.

Example 4 160 parts of the epoxy resin solution prepared in Example 1 and 40 parts of the acrylic resin solution were mixed, 5 parts of morpholine was added, and the mixture was stirred at 120°C for 90 minutes under reflux to mix the epoxy resin and acrylic resin. The resins were reacted to form a copolymer. Per 200 parts of this copolymer solution in an organic solvent, 60 parts of the solution of the resol type phenol resin used in Example 1 was added and stirred to obtain an organic solvent solution of a coating resin. −
Meanwhile, amine water and deionized water were prepared according to Example 1.

Using these, O/W according to the method shown in Example 1
A mold emulsion was prepared and further concentrated and solvent removed to obtain an emulsion type water-based paint (Paint 25). The average particle size of the dispersed phase of this emulsified water-based paint was 0.52 μm. When its stability over time was investigated, no skin formed on the liquid surface. Further, both the viscosity and the average particle size of the resin particles did not change compared to before storage. Furthermore, as a result of evaluating the coating properties when applied with a roll coater, the coating properties were good, and the unevenness of the coated surface was of a level that would not cause any practical problems.

Example 5 Example 1 except that the organic solvent solution of the coating resin used in Example 4, amine water, and deionized water were used to adjust the amount of deionized water supplied to the second stage in-line mixer. Six types of O/W type emulsions were prepared according to the method.

Table 4 shows the amount of deionized water supplied to the second stage in-line mixer per 100 parts of W10 emulsion supplied to the second stage in-line mixer. Furthermore, the average particle size of the dispersed phase of the obtained O/W type emulsion is also listed in Table 4.

These O/W type emulsions were concentrated and solvent removed using a rotary evaporator to obtain emulsified water-based paints (Paints 26 to 31) with a solid content of approximately 40%. When we investigated their stability over time, we found that none of the emulsion-type water-based paints developed a skin on the liquid surface. In addition, both the viscosity and the average particle size of resin particles of each of the emulsified water-based paints did not change compared to before storage. Furthermore, as a result of evaluating the coating properties when applied with a roll coater, the coating properties of all emulsified water-based paints were good, and the unevenness of the coated surface was of a level that would not cause any practical problems.

Example 6 The organic solvent solution of the coating resin of Example 1 was heated at 80°C using a rotary evaporator. I41a, solid content 60
%, 70%, and 80% solutions were prepared.

Furthermore, the organic solvent solution of the coating resin of Example 1 was diluted by adding butyl acetate to give a solid content of 10% and 20%.
%, 30% solutions were prepared. These solutions were made into an O/W emulsion according to the method shown in Example 1 using morpholine as a neutralizing agent. At this time, the organic solvent solution of the coating resin was heated or cooled and supplied. In addition, the inside of the treatment tank was pressurized in order to efficiently perform stirring and mixing. Table 5 shows the temperature of the organic solvent solution of coating resin supplied to the in-line mixer and the internal pressure of the treatment tank. Further, these O/W type emulsions were concentrated and solvent removed to obtain emulsion type water-based paints (paints 32 to 37).

Table 5 also shows the results of evaluating the average particle size and stability over time of the resin particles of these emulsified water-based paints.

Example 7 Six types of epoxy resins having the molecular weights and epoxy equivalents shown in Table 6 were prepared and dissolved in the same mixed solvent used in Example 1. Using these epoxy resin solutions, the same phenol resin solution as used in Example 1, and the acrylic resin solution, an organic solvent solution of a coating resin was prepared.

Six types of emulsified water-based paints (paints 38 to 43) were prepared according to the method of Example 1, except that morpholine was used as a neutralizing agent.

When the stability over time of these emulsified water-based paints was investigated, no skin formed on the liquid surface of any of the emulsified water-based paints. In addition, both the viscosity and the average particle size of resin particles of each of the emulsified water-based paints did not change compared to before storage. The coating properties when applied with a roll coater were good for all emulsion type water-based paints, and the unevenness of the coated surface was of a level that would not cause any practical problems. Furthermore, evaluations of adhesion and whitening of the retort, as well as evaluations of actual cans filled with coffee beverages as can bodies, were conducted, and the results are also listed in Table 6.

Example 8 Four types of effect agent resins shown in Table 7 were dissolved in the same manner as in Example 1, and an organic solvent solution of paint resin was prepared using the epoxy resin solution of Example 1 and the acrylic resin. The 4f!
Emulsified water-based paints (paints 44 to 47) were prepared.

When we investigated the stability over time of these emulsified water-based paints, we found that none of the emulsified water-based paints developed a skin on the liquid surface. In addition, both the viscosity and the average particle size of resin particles of each of the emulsified water-based paints did not change compared to before storage. The coating properties when applied with a roll coater were good for all emulsion type water-based paints, and the unevenness of the coated surface was of a level that would not cause any practical problems. These coated plates were formed into end caps, wrapped tightly around cans filled with coffee beverages, and stored. After 6 months, the condition of the closed surfaces was evaluated and the results are also listed in Table 7.

Example 9 A resin solution containing the epoxy resin and phenol resin of Example 1 in the ratio shown in Table 8 was prepared, and the acrylic resin solution of Example 1 was added thereto to obtain an organic solvent solution of paint resin. The epoxy resin and phenol resin were dissolved in the same manner as in Example 1, and the amount of the acrylic resin solution added was in accordance with Example 1 in terms of resin solid content. Furthermore, six types of emulsion-type water-based paints (paints 48 to 53) were prepared according to the method shown in Example 1, except that morpholine was used as a neutralizing agent.

When the stability over time of these emulsified water-based paints was investigated, no skin formed on the liquid surface of any of the emulsified water-based paints. In addition, both the viscosity and the average particle size of resin particles of each of the emulsified water-based paints did not change compared to before storage. The coating properties when applied with a roll coater were good for all emulsion type water-based paints, and the unevenness of the coated surface was of a level that would not cause any practical problems. Furthermore, the actual cans were evaluated as can bodies by filling them with consommé soup, and the results are also listed in Table 8.

Example 10 Eight types of acrylic resins having acid values as shown in Table 9 were added in the amounts shown in Table 9, but according to Example 1.
Seed emulsion type water-based paints (paints 54 to 61) were prepared. The amount of acrylic resin added is expressed in parts per 100 parts of the total amount of epoxy resin and phenol resin in terms of resin solid content.

The stability of these emulsified water-based paints over time was investigated. In addition, TFS was coated with a roll coater, and an actual can was evaluated as a can body by filling it with consommé soup, and these results are also listed in Table 9.

Example 11 220 parts of a mixed solution of the epoxy resin solution and phenol resin solution of Example 1, 1 of the acrylic resin solution of Example 1,
0 parts and 5 parts of oleic acid were uniformly stirred and mixed to prepare an organic solvent solution of a coating resin. O/
A W-type emulsion was obtained, and further concentrated and solvent removed to obtain an emulsified water-based paint (Paint 62).

This emulsion type water-based paint has resin particles with an average particle size of approximately 0.56.
μm, and did not settle even after being stored at 50° C. for one month, nor did it develop a crust or notice a significant change in viscosity.

Table 4

[Brief explanation of the drawing]

FIG. 1 shows a schematic arrangement of equipment used in the continuous manufacturing method of the present invention. 1... First processing tank, 2... Second processing tank, 3.4...
・Inline mixer, 5...resin solution supply line,
6... Ammonia water or amine water supply line, 7...
・Pressure line, 8...Communication pipe, 9...Water supply line, 10...Drawer line, 11...Quantitative discharge valve, 12...W10 type emulsion, 13...0/W
type emulsion.

Claims (7)

[Claims] (1) A carboxyl group-containing acrylic resin component, an epoxy resin component, and an epoxy resin curing agent resin component are supplied to the first stage in-line mixer in the form of an organic solvent solution containing alone or in combination, together with an aqueous solution of ammonia or amines. , mixed under pressure in the mixer to form a W/O type emulsion, this W/O type emulsion is fed together with water to the second stage in-line mixer, and mixed in the mixer to form an O/W type emulsion. A method for continuously producing an emulsion-type water-based paint, which comprises inverting the phase of an emulsion and quantitatively drawing out the resulting O/W type emulsion. (2) supplying the organic solvent solution (A) and the ammonia or amine aqueous solution (B) at a weight ratio of A:B = 10:10 to 10:1 in the first stage in-line mixer; 2. The method of claim 1, further comprising mixing. (3) The method according to claim 1, wherein the mixing in the first stage in-line mixer is carried out at a temperature of 10 to 90°C and a pressure of 0.2 to 10 kg/cm^2 (gauge). (4) Mixing in the first stage in-line mixer is expressed by the formula K=V
_2/V_1 In the formula, V_1 represents the feed rate (l/min) to the in-line mixer, and V_2 represents the discharge rate (l/min) measured using the water of the agitator in the in-line mixer. The method according to claim 1, wherein the method is carried out so that the stirring efficiency (K) is 5 to 50. (5) The method according to claim 1, wherein the carboxyl group-containing acrylic resin component and the epoxy resin component are contained in the solution in the form of a copolymer. (6) The method according to claim 1, wherein the carboxyl group-containing acrylic resin component and the epoxy resin component are contained in the solution in the form of a blend. (7) The method according to claim 1, wherein water is supplied and mixed at a ratio of 30 to 100 parts by weight per 100 parts by weight of the W/O emulsion in the second stage in-line mixer.