JPS63183969A - Production of emulsion type water based paint - Google Patents

Abstract

PURPOSE:To obtain the titled paint containing resin component dispersed in the form of fine and uniform particles, suitable for the coating of a can for canned food and producible with decreased amount of water, by melting and kneading a paint resin and an acrylic resin and emulsifying the mixture using a phase-conversion emulsification method. CONSTITUTION:The objective paint can be obtained by kneading (A) a composi tion containing (i) a resin for paint, (ii) 3-30wt.% (based on the component i) acrylic resin having an acid value of 35-350 and optionally (iii) an organic solvent and mixing and kneading the component A with (B) ammonia or an amine and (C) water, thereby converting the carboxyl group in the components (ii) to ammonium salt or amine salt and, at the same time, self-emulsifying the resin component to an O/W-type emulsion. The melt viscosity of the molten mixture of the components (i) and (ii) is 100-30,000cps and the temperature is preferably 20-120 deg.C. The component (iii) is preferably toluene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing an emulsion-type water-based paint, and more specifically, the present invention relates to a method for producing an emulsified water-based paint, and more specifically, it utilizes the surface active action of an acrylic resin blended into a melted paint resin. , relates to a method for producing a water-based paint by a phase change emulsification method.

(Prior art) Conventionally, in the production of canned goods, this was used to prevent metal from leaching into the contents and to prevent metal corrosion.

Various paints are used to paint metal materials and can openings. Not only drawn and ironed cans made of unpainted metal materials, but also drawn cans made of painted metal materials and three-piece cans, it is necessary to apply a corrective coating or top coat to correct scratches on the paint film that occurs during the can manufacturing process. To form this, various paints are spray-painted on the can body and can lid and then baked.

In terms of adhesion to metal substrates, corrosion resistance, flavor characteristics, and film processability, paints made of a combination of epoxy resin and hardener resin and vinyl paints are excellent.

These paints exhibit good performance when applied in the form of an organic solvent solution, but during spray painting, the bath agent 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, 44-1
Publication No. 8076). The second type is modified by reacting a paint resin with a functional group such as an epoxy resin with a resin having a carboxyl group such as an acrylic resin, and neutralizes this modified resin with ammonia or amines. By doing so, it is self-emulsified in an aqueous medium (for example, JP-A-59-213718).

(Problems to be Solved by the Invention) 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. However, the performance of the resulting coating film is also inferior to that of solvent-based 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.

Therefore, an object of the present invention is to provide a new method for producing a water-based paint in which the above-mentioned problems of conventional water-based paints are solved.

Another object of the present invention is that it can be applied to paint materials of any composition, and that it can be applied to water-based paints using the phase change emulsification method by utilizing the surfactant effect of the acrylic resin blended into the melt of the paint resin. The purpose is to provide a method for manufacturing.

Another object of the present invention is to provide a method for producing a water-based paint in which the resin content is fine and controlled to have a uniform dispersed particle size, and which has excellent dispersion stability.

(Means for Solving the Problems) According to the present invention, a paint resin, an acrylic resin whose acid value is in the range of 35 to 350, or Furthermore, a composition containing an organic component is melted, and ammonia or amine and water are mixed and kneaded into this melt to convert the carboxyl group in the acrylic resin into an ammonium salt or an amine salt, and to convert the resin component. Provided is a method for producing an emulsified water-based paint, which is characterized by self-emulsifying into a φ-type emulsion.

(Function) In the present invention, a composition in which a coating resin and a carboxyl group-containing acrylic resin are intimately mixed with each other at a molecular level is first formed. For this purpose, a molten mixture containing a coating resin and a carboxyl group-containing acrylic resin is prepared. At this time, the acid value of the acrylic resin used is 3
5 to 350, especially 70 to 330, and this acrylic resin should be in the range of 3 to 30 i1 per paint resin.
It is important to use i1%, especially in amounts of 5 to 25% by weight.

If the acid value of the acrylic resin is lower than the above range, the paint resin is dispersed in a ΦW (oil-in-water) type with fine and uniform particle size in the neutralization process and phase conversion emulsification process described later. It is difficult to emulsify the particles, and the emulsion stability 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 transfer to the aqueous phase, resulting in a fine and uniform particle size. It becomes difficult to emulsify and the stability of the dispersion liquid decreases,
A further disadvantage is that the coating film formed 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 paint resin component to a uniform and fine particle size and improve the dispersion stability of the emulsified resin. Moreover, the formed coating film can have excellent moisture resistance, water resistance, etc.

In addition, if the blending amount of the paint resin component of the acrylic resin is less than the above range, sufficient carboxylic acid may be added to the interface between the water phase and the oil phase (resin phase) in the neutralization step and phase conversion step. It is not possible to form salt groups, and it becomes difficult to emulsify the coating resin component into uniform and fine particle sizes, resulting in a decrease in the dispersion stability of the aqueous dispersion. On the other hand, increasing the blending amount of acrylic resin beyond the above range may affect the physical properties of the paint film due to the mixing of a large amount of acrylic resin into the paint resin. should be within the above range.

According to the present invention, the melt containing the coating resin and the acrylic resin is an oil-in-water type emulsion, that is, a φ type emulsion.

In the dispersed resin particles of this φ-type emulsion, the coating resin and the acrylic resin are in a blended or compatible state, but the ammonium salt or amine salt group of calgenic acid formed in the acrylic resin is It is thought that the particles are present on the surface of the dispersed resin particles, that is, on the interface with water.

Formation of such an emulsion involves adding ammonia or amine and water to a melt containing a coating resin and an acrylic resin, mixing the mixture, and converting the carboxyl group in the acrylic resin into an ammonium salt or an amine salt. It is formed by a phase conversion method in which the resin content in the melt is self-emulsified into a ΦW-type emulsion. In this case, it is of course possible to supply ammonia or amine to the system separately from water, but it is generally preferable to supply ammonia or amine to the system together with water in the form of an aqueous solution.

When ammonia water or amine water is added to a melt of paint resin or acrylic resin while mixing continues, the resin melt will have a continuous phase and a dispersed aqueous phase at the initial stage of addition or at the beginning of mixing. However, as the amount of water added increases and the crosstalk continues, the resin melt undergoes a phase transformation into a Koga-type emulsion in which the dispersed particle phase and water become the continuous phase.

This phase transformation is surprisingly as low as 10
It was found that addition of water as small as % by weight caused this phenomenon. The reason why the phase inversion to an O/W type emulsion occurs with the addition of a small amount of water is because a molten mixture of coating resin and acrylic resin is used, and ammonia water or amine water is mixed in the bath melt kneading. This was made possible for the first time by the method of the present invention, and is a novel feature completely unrecognized by conventional methods.

By adding ammonia water or amine water to the resin melt, groups of ammonium salt or amine salt of carboxylic acid of the acrylic resin are generated at the contact interface of the melt with the aqueous phase. However, under molten cross-contact conditions, the surface tension of water is significantly lowered, the water is stretched into a thin layer by the shear force during cross-contact, and the resin melt is mixed with the above-mentioned ammonium salt or amine salt. This is thought to be due to the fact that the group becomes fine particles due to its surface tension with the group on the interface side.

Paint Resin - If the melting point or softening point of the acrylic resin melt is low or the melt viscosity is high, the melting point or softening point of the resin may be lowered and the melt viscosity may be lowered. An organic solvent can be added during melting. However, since the solvent used in this case is used for the above purpose, it is sufficient to use a smaller amount than in the case of a normal solution, and the phase inversion to an aqueous dispersion also uses a resin solution as a raw material. It should be understood that the phase inversion itself occurs with the addition of a smaller amount of water than would otherwise be the case. As described above, according to the present invention, a self-emulsifying water-based paint in which the particle size of the dispersed resin is fine and uniform and has excellent dispersion stability can be obtained by the phase conversion emulsification method of the melt. Of course, the addition of ammonia water or amine water may be terminated at the stage where phase inversion occurs, or further ammonia water or amine water may be added to homogenize the entire system and dilute it to a predetermined degree. Of course you can go.

In the present invention, as the acrylic resin, any acrylic resin can be used as long as the acid value is within the above-mentioned range. This acrylic resin can be copolymerized with ethylenically unsaturated carboxylic acid or its anhydride, acrylic ester or methacrylic ester, and optionally with these, to give a carboxyl group with the above-mentioned acid value to the resin. It consists of a copolymer with other ethylenically unsaturated monomers.

As ethylenically unsaturated cargonic acid or its anhydride,
Acrylic acid, methacrylic acid, crotonic acid, maleic acid,
These include fumaric acid, 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, ffn-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, h-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, especially in the range of 20,000 to 150,000.

Examples of suitable combinations of acrylic copolymers include (1) methyl methacrylate/2-ethylhexyl acrylate/acrylic acid, (2) styrene/methyl methacrylate/ethyl acrylate/methacrylic acid, and (3) styrene/acrylic. (4) ethyl methacrylate/methacrylic acid, (4) ethyl methacrylate/acrylic acid, and the like.

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

On the other hand, the coating resin may be any thermosetting resin or thermoplastic resin, for example, at least one thermosetting resin that satisfies the condition of being meltable.

Phenol-formaldehyde resin, furan-formaldehyde resin, xylene-formaldehyde resin, ketone-formaldehyde resin, urea formaldehyde resin, melamine-formaldehyde resin, alkyd resin, unsaturated polyester resin, epoxy resin, bismaleimide resin, triallyl cyanurate resin, Thermosetting acrylic resin, silicone resin, oil-based resin, vinyl chloride-vinyl acetate copolymer, partially saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-maleic acid copolymer, vinyl chloride-maleic acid-acetic acid Vinyl co-merged, acrylic polymer,
Saturated polyester resin, etc.

These resin coatings may be used alone or in combination of two or more.

Examples of paint resins suitable for can manufacturing paints include:
Examples include combinations of epoxy resins and curing agent resins for the epoxy resins. As the epoxy resin, bisphenol type I resin obtained by polycondensation of bisphenols such as bisphenol A and epihalohydrin is suitable, and the epoxy resin generally has a molecular weight of 400 to 20,
000°, particularly preferably in the range of 1,000 to s, ooo. 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 one or more of Novolac's phenol formaldehyde resin, urea formaldehyde resin, melamine formaldehyde resin, alkyd resin, 4-lyester resin, acrylic resin, polyurethane resin, xylene resin, epoxy ester resin, butyral resin, etc. combinations are used. Among these, methylol group-containing thermosetting resins, particularly resol type phenolic resins, are preferred.

A remarkable feature of the present invention is that the coating resin can be emulsified and dispersed into fine dispersed particle sizes even when the composition ratio of the epoxy resin and the curing agent resin is within an arbitrary range. The ratio of epoxy resin to curing agent resin is 95:5 to 40:
It is common to have a heavy lid ratio of 60, especially a heavy basin ratio of 90:10 to 50:50.

According to the present invention, the resin component of the paint, which is generally called a solvent-based vinyl paint or an organosol-based vinyl paint, can also be made into an emulsion-type water-based paint.

The former solvent-based vinyl paint is generally a solvent-soluble vinyl chloride copolymer containing carboxyl or hydroxyl groups (4).
and a thermosetting resin (B) are used.

This solvent-soluble vinyl chloride copolymer (4) contains 5 to 500 mmol/10 carmexyl groups and/or hydroxyl groups.
0p resin, particularly preferably 10 to 300 mmol/10
It is preferable to contain the resin at a concentration of 0 g resin, and suitable examples thereof include:
Vinyl chloride-vinyl acetate copolymer partially saponified product, vinyl chloride-vinegar modified vinyl-acrylic acid copolymer, vinyl chloride-
Partially saponified/partially butyralized vinyl acetate copolymer,
Vinyl chloride-vinyl acetate-methacrylic acid copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinyl chloride-vinyl acetate-hydroxyethyl acrylate copolymer, vinyl chloride-vinyl acetate-hydroxyethyl methacrylate copolymer, Partially saponified vinyl chloride-vinyl acetate-acrylic acid copolymer and the like. Thermosetting resin (B
) are exemplified as epoxy resins and curing agent resins for epoxy resins. Vinyl chloride copolymer (4) and thermosetting resin (B) are 99:1 to 50
:50 weight ratio, especially 95:5 to 60:40 weight ratio.

The organosol type paint is obtained by dispersing vinyl chloride resin particles (C) in an organic solvent solution of the components (4) and (B). The vinyl chloride resin particles (C) used are:
Vinyl chloride alone or vinyl chloride and other vinyl monomers,
For example, it is produced by emulsion or suspension polymerization in combination with small amounts of comonomers such as butadiene, styrene, vinyl acetate, etc., and its particle size generally ranges from 0.01 to 1.
0 microns, especially in the range from 0.02 to 5 microns. In this type of paint, the resin solid fraction A is between 5 and 5.
B is preferably present in an amount of 1 to 20% by weight and C in an amount of 5 to 50% by weight.

In the present invention, a melt containing a coating resin, an acrylic resin, and needles is prepared. The melt viscosity of this melt is generally in the range of KIO to ioo, ooo centipoise, particularly 100 to 30,000 centipoise, and if the viscosity is higher than the above range, dense and uniform crosstalk between the two will occur. It can be difficult. Also, the temperature of the melt is 10
A temperature range of 150°C to 150°C, especially 20°C to 120°C is appropriate; temperatures higher than the above range are not preferred because partial molecularization and early glumaturization of paint resin components tend to occur. . An organic solvent can be used for the purpose of lowering the crosstalk temperature and melt viscosity. In this case, the organic solvent includes aromatic hydrocarbon solvents such as toluene and xylene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. One or more of the following can be used: ketone solvents; alcohol solvents such as ethanol, clopanol, and phthanol; cellosolve solvents such as ethyl cellosolve and butyl cellonorp; and ester solvents such as ethyl acetate and butyl acetate.

It is appropriate that the amount of the organic solvent used is 303 ifit% or less (resin fraction), particularly 15 weight percent or less. Of course, one or both of the resin components may be supplied to the kneading process in the form of an organic solvent ha.

Melt-kneading can be carried out using a Niegu mixer, a Pampari mixer, or a single-screw or twin-screw extrusion kneading device. When cross-mixing, the melt may be blended with known coating compounding agents, such as plasticizers, lubricants, pigments, fillers, stabilizers, etc., as desired. trimethylamine, triethylamine,
Alkylamines such as butylamine, 2-dimethylaminoethanol, jetanolamine, triethanolamine, aminomethylprononol, dimethylaminomethyldialolamines, alcoholamines, morpholine, and the like are used. Polyvalent amines such as ethylenediamine and diethylenetriamine can also be used.

Ammonia and amines have a chemical equivalent of at least 0.3, especially 0.7, relative to the carboxyl group of the acrylic resin.
It is preferable to use it in an amount of 1.3 to 1.3 chemical equivalents.

The amount of water used for phase conversion varies depending on the type of resin and the concentration of the raw material solution, but it is generally 0.5 to 2.0 times the weight of the raw resin melt, especially 0.7 to 1.5 times the weight of the raw resin melt. It is recommended to use twice the weight of water.

Addition of ammonia water or amine water is carried out in the above-mentioned melt mixing device. Of course, the melt mixing after adding water can also be carried out in a separate device from the one used for kneading the resins.

When an organic solvent is used in combination, the aqueous dispersion produced by phase transformation contains a partner of water and the organic solvent. By subjecting this aqueous dispersion 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 between 10 and 70 mft. It is desirable that the content of the organic solvent in the water-based paint is in the range of 20 to 60% 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.

(Effects of the Invention) According to the present invention, by melting and kneading a paint resin and an acrylic resin and applying a phase conversion emulsification method thereto, it is possible to create a resin of any desired composition with a small amount of water. could be made into an emulsified water-based paint. In this water-based paint, the resin component was dispersed with a fine and uniform particle size, and the dispersion stability was also good.

In the examples, unless otherwise specified, parts are indicated in double digits.

Example 1 20 parts of ethyl acrylate, 20 parts of methyl methacrylate
parts, 40 parts of methacrylic acid, 20 parts of methylene t@rt
- preparing a mixture of 1 part of butyl hydroperoxide;
Stirrer, thermometer, addition funnel.

50 parts of ethyl cellosolve and 25 parts of the above mixture were charged into a flask equipped with a reflux condenser and an inert gas inlet, and the temperature was raised to 90°C while stirring under a nitrogen stream, and then the temperature was raised to 90°C. The remaining amount of the above monomer mixture was added dropwise over 3 hours to copolymerize, and then t
After adding 0.1 part of ert-butylhydro-oxide and continuing stirring for 3 hours, 50 parts of ethyl cellosolve was added and cooled to complete one reaction. The weight average molecular weight of the obtained acrylic resin (acrylic resin 1) is approximately 12
The acid value was 124, and the solid content of the resin solution was 50. This acrylic resin solution was gradually poured into 500 parts of deionized water while being vigorously stirred to precipitate solid content, and the obtained solid acrylic resin was further vacuum-dried.

On the other hand, the number average molecular weight is about 3,750. Nixie equivalent: approx. 3
,000 bisphenol Afi epoxy resin (epoxy resin 1), 80 parts by weight of bisphenol A, para-cresol, and resol type phenol resin derived from formaldehyde using an ammonia catalyst (phenol resin 1: bisphenol A/para-cresol = 8072
Amine water was prepared by dissolving 10 parts of dimethylaminoethanol in 150 parts of deionized water, 12 parts by weight of hexyl cellosolve, and 150 parts of deionized water.

The total amount of the above epoxy resin and phenol resin and 10% of the above solid acrylic resin were put into a kneader maintained at 80°C.
of hexyl cellosolve was added and mixed to form a uniform, concentrated solution.
The above amine water kept at ℃ was gradually added dropwise. As the amine water was added, the system became white and creamy, and as the amine water was added, the viscosity of the system decreased rapidly. When the amine/water was continued to be added dropwise, a stable o/w type emulsion was formed after the entire amount had been added. This emulsion (emulsion type water-based paint 1) had resin particles with an average particle size of 0.60 μm and contained 4.3 liters of organic solvent per paint.

This emulsified water-based paint (100ffi) was placed in a glass wide-mouth bottle with a lid of 100d, sealed tightly, and stored in a constant temperature bath at 50°C for one month. When the seal was opened and examined, no skin spots had formed on the liquid surface. There wasn't. Also.

Both the viscosity of the emulsified water-based paint and the average particle size of the resin particles did not change compared to before storage.

This emulsified water-based paint was applied to an electrolytic chromic acid treated steel sheet (hereinafter referred to as TFS) using a reverse roll coater and baked at 210° C. for 10 minutes to harden it.

This coated plate was bonded using a nylon adhesive by pressing it for 2 minutes with a hot press heated to 200°C. When the peel strength was measured using T-Beer, the initial peel strength immediately after adhesion was approximately 7 kg/5 m width, and the peel strength over time after being immersed in 90°C hot water for one week was 4.5)Cf15 m width or more. held the value of. Also,
When this adhesive test piece was subjected to retort treatment at 125°C for 30 minutes and evaluated, no whitening of the coating film was observed, and the score was 4.5.
It maintained an adhesive strength of 115 mm or more.

In addition, one side of TFS was coated with a roll coater and 210
After baking and drying at ℃ for 10 minutes, paint and bake the other side in the same way to prepare a double-sided coated board. Using this coated board and nylon adhesive, glue the 202 diamond can body (both ends are After the bottom lid was double-sealed, the canned coffee beverage was filled with coffee beverage and the top lid was double-sealed to produce a canned coffee beverage. The canned coffee beverage was retort sterilized at 125° C. for 30 minutes, cooled and air-dried, and then stored in a warehouse.

When the can was opened and evaluated after 6 months of storage, no abnormalities such as whitening of the paint film or internal corrosion were observed.

Example 2 The same epoxy resin as shown in Example 1, phenol resin, and acrylic resin were prepared, and epoxy resin 8
0 parts and 20 parts of phenol resin, acrylic resin in the amounts shown in Table 1 and 12 parts of hexyl cellosolve were added and mixed in a kneader maintained at 80°C to prepare six types of paints. A concentrated solution of resin was obtained.

Meanwhile, add 20 l of concentrated ammonia water to 150 parts of deionized water.
Prepare aqueous ammonia in which .
A seed emulsion type water-based paint was prepared.

Table 1 shows the obtained emulsions together with the average particle size of the resin particles of the water-based paint. ! Table 1 also shows the evaluation of the performance of the emulsified water-based paint obtained according to the method shown in Example 1.
Also listed.

Example 3 300 parts by weight of a resol type phenol resin (phenol resin 2: number average molecular weight 500) prepared from bisphenol A and formaldehyde using an ammonia catalyst,
300 parts of Epoxy Resin 1 of Example 1 was prepared.

In addition, eight types of acrylic resins having the compositions shown in the second example were produced by a suspension polymerization method. In the table, the monomer composition is shown as a mixing ratio of a mixed monomer of ethyl acrylate/methyl methacrylate/styrene=1/1/2 and methacrylic acid.

Benzoyl peroxide was used as a polymerization initiator, and I-rivinyl alcohol was used as a suspension stabilizer. The acid value and molecular weight of the obtained acrylic resin are shown in Table 2.

50 parts of the above epoxy resin, 50 parts of phenol resin, and 10 parts of acrylic resin were melted and mixed in a Ni-Goo maintained at 95°C. A kept aqueous solution of dimethylaminoethanol was added to the mixture to cause phase transformation to a ≠ type emulsion, and the emulsion was made into a water-based paint.

The average particle diameter of resin particles in the obtained emulsified water-based paint is shown in Table 2.
It is also shown in . However, emulsifying water-based paint 8 could not be emulsified by the method shown in Example 1.

Therefore, the following evaluation of coating film performance was not performed.

Apply ordinary solvent paint to one side of the tin plate and heat it to 180℃.
After baking in a hot air dryer for 10 minutes at 200° C., a water-based emulsion paint was applied to the other side of the tin plate, and the plate was baked at 200° C. for 10 minutes to dry. This painted plate was formed into a 211 diamond can lid so that the surface coated with the emulsified water-based paint was on the inside surface, and double-sealed to one end of the 211 diamond welded can body.
The can was filled with tuna pickled in oil, and the above-mentioned can lid was double-sealed to the other end in a vacuum. This canned tuna pickled in oil was heated to 115℃ for 10
After being heat sterilized for 0 minutes, it was stored at room temperature. After 6 months had passed, the cans were opened and the condition of the inner surface of the can lid and the adhesion of the paint film were investigated. The results are also listed in Table 2.

Example 4 Emulsified water-based paint 16 was produced in the following manner.

1085 parts of epoxy resin of Example 1, 15 parts of urea formaldehyde resin, 1 part of acrylic resin of Example 1
Example 1
According to the method shown in , an aqueous solution of dimethylaminoethanol kept at 95° C. was added to cause phase conversion to a ΦW emulsion, and an emulsified water-based paint was obtained.

The average particle size of the resin particles in the obtained emulsified water-based paint was 0.
It has a diameter of 58 μm and does not settle even after being stored at 50°C for one month.
Moreover, neither skin tension nor significant change in viscosity occurred.

Example 5 Emulsified water-based paint 17 was produced in the following manner.

Copolymer resin of vinyl chloride, vinyl acetate, and vinyl alcohol (Vinylite made by Union Carbide)
GH, vinyl chloride/ff [vinyl/vinyl alcohol=
91/3/6, polymerization degree of about 500), 10 parts of the acrylic resin 1 of Example 1, and 10 parts of a mixed solvent of butanol and butyl cellosolve (butanol/butyl cellosolve = 1/4) at 95°C. After melting and mixing by putting the mixture into a kneader, a water bath solution of dimethylaminoethanol kept at 95°C was added to form a 0/W emulsion according to the method shown in Example IK. It was made into an emulsion type water-based paint.

The average particle size of the resin particles in the obtained emulsified water-based paint was 0.
77#? Even after storage at 50° C. for one month, no sedimentation occurred, nor did any skin stiffness or significant change in viscosity occur.

Example 6 Emulsified water-based paint 18 was produced in the following manner.

Copolymer resin of vinyl chloride, vinyl acetate, and maleic acid (U
Vinylite VMCH manufactured by Nion Carbids.

Vinyl chloride/vinyl acetate/maleic acid = 86/13/
1. 45 parts of epoxy resin Epiny) 834 (manufactured by Shell Chemical Co., Ltd.) with a degree of polymerization of about 450, 106 parts of the phenolic resin of Example 1, 45 parts of vinyl chloride resin Zeon 121 (manufactured by Nippon Zeon Co., Ltd.), and butyl cellosolve 10
After melting and mixing in a kneader maintained at 60°C, an aqueous solution of methylaminoethanol kept at 60°C was added to form a VW type emulsion according to the method shown in Example 1. The phase was transformed into an emulsified water-based paint.

The average particle size of the resin particles in the obtained emulsified water-based paint is l,
It has a diameter of 40 μm and does not settle even when stored at 50°C for 1 month.
Moreover, neither skin tension nor significant change in viscosity occurred.

Example 7 Emulsified water-based paint 19 was produced in the following manner.

5 parts of acrylic resin 1 of Example 1, 80 parts of epoxy resin 1, 20 parts of phenol #fat 1, 5 parts of oleic acid,
20 parts deionized water and 1 part dimethylamine ethanol
After pre-mixing 0 parts, it was put into a twin-screw kneading/extrusion device maintained at 90°C and kneaded. 1. It was phase-converted to an O/W emulsion, and then 80 parts of deionized water was added in a homomixer. The extrudate was diluted by pouring it into vigorous stirring to obtain an emulsified water-based paint.

The average particle size of the resin particles in the obtained emulsified water-based paint was 0.
It has a diameter of 54 μm and does not settle even after being stored at 50°C for one month.
Moreover, neither skin tension nor significant change in viscosity occurred.

Example 8 Emulsified water-based paints 20 to 24 were produced in the following manner.

The use of the phenol resin of Example 3 (Phenol Resin 2) in the amount ratio shown in Table 3 to the epoxy resin by using the Nyexy resin having the engineering I-xy equivalent as shown in Table 3.
According to the method shown in Example 1 except for using
Five types of emulsified water-based paints were prepared.

The average particle diameter of the resin particles in the obtained emulsified water-based paint is shown in Table 3.
Also listed. All of the emulsified water-based paints did not settle even after being stored at 50° C. for one month, nor did they develop a crust or a significant change in viscosity.

Procedural amendment printing April 13, 1986

Claims (1)

[Claims] (1) A composition containing a coating resin and an acrylic resin containing 3 to 30% by weight of the coating resin and an acid value within the range of 35 to 350, or an organic solvent, and Emulsification characterized by mixing and kneading ammonia or amine and water, converting the carboxyl group in the acrylic resin into ammonium salt or amine salt, and self-emulsifying the resin component into an O/W emulsion. Manufacturing method of mold water-based paint.