JPS584743B2 - paint composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to coating compositions.

More specifically, the present invention relates to a coating composition containing a flaky pigment and capable of producing an iridescent or pearlescent coating film.

In recent years, paint compositions have become pollution-free and resource-saving, and the form of paints is also changing from conventional organic solvent-diluted paints to water-diluted paints, powder paints, or solvent-free paints. .

However, each of these new types of paints has its own distinct characteristics as well as various drawbacks.

For example, conventional paint equipment for solution-type paints cannot be used for powder coatings, water-dilutable paints that use water-soluble resins are difficult to coat in thick films at once, and water-dispersible resins The disadvantage of such paints is that the film performance is not sufficiently high due to the influence of the dispersant.

Furthermore, slurry paints have been developed as having characteristics similar to those of the water-dilutable paints and powder paints.

This slurry-like material mainly uses water as a medium and has a
It is a paint in which particulate resin of about 0 μm is dispersed at a solid content concentration of 10 to 70% by weight.

The manufacturing method involves using the resin as a water-soluble solvent such as alcohols such as methanol and ethanol, ketones such as acetone and diacetone alcohol, and esters such as ethyl lactate and ethylene glycol monomethyl ether acetate.
Alternatively, a method in which particles are dissolved in ether such as ethylene glycol monoethyl ether to form a solution, and then the solution is added to water that is being stirred at high speed to precipitate particles in the water (Japanese Patent Publication No. 48-52,851) ), as well as methods in which a solid resin is pulverized by a general pulverization method and then dispersed in water are known.

The paint created in this way can be applied at a sufficiently high solid concentration of about 40 to 60% by weight, and the coating method can be applied using conventional equipment for applying solution paints. Moreover, the volatile component of the paint is only water, which is a dispersion medium, and this water also contains no soluble components, so it saves resources and does not become a source of pollution. to combine.

For these reasons, the demand for this type of paint is expected to increase significantly in the future.

However, even with this slurry paint, fundamental problems remain unsolved.

One of the problems is that it is not possible to obtain coatings with iridescent color or pearlescent luster using flaky pigments.

This means that when conventional powder paints or slurry paints, which are made into particles after kneading flaky pigments in a color vehicle, are applied to the object to be coated, the flaky pigments remain as they were applied. This is due to the fact that there are far fewer flaky pigments aligned parallel to the surface of the coating than in coatings obtained by applying general solution-based paints.

In other words, when slurry paint particles are applied, the flaky pigments contained in the particles are oriented in their own directions and are not parallel to the coating surface, and when the particles are melted by heating to form a film, the resin This is because the flaky pigments are not sufficiently aligned parallel to the coating surface due to the lack of flow.

Therefore, even if the same amount of flaky pigment as in general solution-type paints was mixed into the resin, the pearlescent luster was low and the result was only a blackish appearance.

The present inventors have found that the above problem can be solved by a coating composition comprising a mixture of an aqueous medium, resin particles, and flaky pigment, and have previously filed an application for the same in Japanese Patent Application No. 119149/1982.

The composition according to the above invention is applied onto an object to be coated, and then, when water evaporates, the flaky pigment becomes aligned almost parallel to the surface of the resin particles.

Generally, when resin particles melt and flow due to heating, there is almost no movement in the center of the particle, and the flow distance on the particle surface is the largest.

Therefore, when the resin particles are melted by heating, the pigment particles are located at a position where the flow distance is the greatest, and by heating and melting, the pigment particles flow together with the resin and are carried parallel to the object to be coated.

Therefore, when formed into a coating film, a coating film having an iridescent color or pearlescent luster similar to that of a coating film coated with a solution-based paint can be obtained.

The present invention aims to further improve the iris color or pearlescent luster of the above-mentioned composition, to improve the storage stability of the flaky pigment by preventing precipitation and aggregation during storage, and to improve the storage stability of the flaky pigment. The purpose is to use hydrophobic additives such as spirit and stearic acid as they are without washing them.

That is, the present invention includes (a) 90 to 30 parts by weight of an aqueous medium;
10 to 70 parts by weight of resin particles with a softening temperature of 5 to 120 C and an average particle size of 0.5 to 80 μ; (c) 0 to the resin particles;
．． 05 to 30% by weight of a flaky pigment, and (d) a coating composition comprising 30% by weight or less of a water-dilutable resin based on the resin particles, and (a) 90 to 30 parts by weight of an aqueous medium. 10 to 70 parts by weight of resin particles with a softening temperature of 5 to 120°C and an average particle diameter of 0.5 to 80 μm; (c) 0.0 parts by weight based on the resin particles;
05 to 30% by weight of a mixture of (a) flaky pigment and (b) flaky aluminum pigment (however, the proportion of the flaky aluminum pigment to the flaky pigment is 5% to 100% by weight) (d) 30% by weight based on the resin particles
The present invention relates to a coating composition comprising the following water-dilutable resin.

Since the coating composition of the present invention contains a specific amount of water-dilutable resin, the flaky pigment is dispersed and stabilized, and the storage stability is improved.
Moreover, the coating film formed from this has a high iridescent color or pearlescent luster.

This is because the water-dilutable resin improves the slippage between the pigment particles, which makes it easier for the pigment particles to run parallel to the object being coated during coating film formation, and the water-dilutable resin improves the surface smoothness of the coating film. This is thought to be for further improvement.

The water-dilutable resin used in the present invention is a resin or water-soluble thickener resin usually used in water-soluble paints or emulsion paints, and includes acrylic resins, alkyd resins, polyester resins, and butadiene resins having an acid value of 20 to 350. system copolymer resin, ionic water-soluble resin such as phthalic acid resin, acrylic emulsion resin, polyvinyl acetate emulsion resin, vinyl acetate-acrylic copolymer emulsion resin, epoxy emulsion resin, polyester emulsion resin, polybutadiene emulsion resin, styrene-butadiene Emulsion resins such as copolymer emulsion resins and polyvinyl butyral emulsion resins, hydroxyalkyl celluloses such as hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxymethyl cellulose, methyl cellulose, polyethylene oxide, polyvinyl alcohol, water-soluble aminoplast resins, water-soluble phenol resins, etc. nonionic water-soluble resins.

When using polyacrylic acid resin, hydroxyalkyl cellulose, methyl cellulose, polyethylene oxide, polyvinyl alcohol, etc. having an acid value of 150 or more among the water-dilutable resins, it is preferable to add 6% by weight or less to the resin particles.

The water-dilutable resin is 0.5 to 30% by weight based on the resin particles.
Added.

If the amount added is less than 0.5%, the storage stability of the paint and the iris color or pearlescent luster of the paint film will decrease;
If the amount is larger, the disadvantages of water-dilutable paints mentioned above will become noticeable, and either case is not preferable.

It is generally preferable that the amount of these water-dilutable resins added be approximately the same as the amount of flaky pigment added.

The softening temperature of the resin particles used in the present invention is in the range of 5 to 120°C.

However, when resin particles having a softening temperature lower than 5° C. are tried to be homogenized again by stirring the precipitated particles in an aqueous medium at room temperature, it is not possible to sufficiently return them to individual particles due to their stickiness.

Further, a resin having a softening temperature of 120° C. or higher has the disadvantage that it cannot be sufficiently flowed at the baking temperature of a slurry paint.

The preferred softening temperature is 40C to 80C.

Specific examples of resins constituting the resin particles include water-insoluble acrylic resins, epoxy resins, polyester resins,
Alkyd resin, amine-modified resin, phenolic resin, urea resin, polyether resin, isocyanate block,
Examples include cellulose resin, melamine resin, vinyl chloride resin, vinyl acetate resin, and olefin resin.

Further, the resin particles used have an average particle diameter of 0.5 to 80 μm.

In the above, when the average particle size is smaller than 0.5μ, the viscosity becomes extremely low when the solid content concentration of a normal slurry paint is, for example, 40 to 60% by weight, and the thickness of a normal coating film is, for example, 20 to 80μ. When applied, phenomena such as sagging occur in the coating film, resulting in coating defects.

In addition, if the particle size exceeds 80μ, when the paint is applied to a normal coating thickness, the resin will flow during heating and it will be difficult to form a uniform coating, and the flaky pigment will not be sufficient to cover the base. There must be sufficient surface area to incorporate the particles into the resin.

The particle size that gives the most favorable results in the above is 1 to 3.
It is 0μ.

Further, the amount of resin particles in the aqueous medium is required to be 10% by weight or more in order to obtain a practical film thickness.

Furthermore, the content must be 10% by weight or less in order to agitate the paint, make it uniform, and maintain a suitable viscosity for coating, which is usually 30 to 6%.
0% by weight is optimal.

The resin particles may typically contain organic or inorganic coloring or extender pigments used in paints.

The resin composition composed of a combination of a water-dilutable resin and the above-mentioned resin particles used in the present invention may be either thermoplastic or thermosetting.

When both the water-dilutable resin and the resin particles are thermoplastic, and the resin composition does not contain at least two functional groups that react with each other, the resin composition is naturally thermoplastic.

In addition, when the resin composition contains at least two types of functional groups that react with each other, for example, phenol tree - epoxy resin, epoxy resin - melamine resin, acrylic resin - isocyanate block, acrylic resin - melamine resin. , combinations of polyester resin-melamine resin, polyester resin-isocyate block, alkyd resin-amino resin, alkyd resin-phenol resin, epoxy resin-amine modified resin, or combinations of epoxy resin, acrylic resin, and curing agent, etc. When it contains, the resin composition becomes thermosetting.

When the resin composition contains at least two types of functional groups that react with each other, the curing reaction by heating occurs between one or more types of resin particles, between water-dilutable resins, between resin particles and water-dilutable resins, Alternatively, any combination of all of these may be used.

Furthermore, resin particles having no functional group capable of curing reaction or a water-dilutable resin may be added.

The mutual composition ratio of the resins involved in heat curing may be appropriately adjusted and blended.

For example, when using a thermosetting resin composition as a water-dilutable resin, an acrylic resin or alkyd resin with an acid value of 30 to 80 and a water-soluble aminoplast resin are combined, and 100 parts by weight of at least one of the acrylic resin and alkyd resin is used. It is preferable to mix about 10 to 70 parts by weight of water-soluble aminoplast resin.

In this case, the resin particles may be either thermoplastic or thermosetting.

In addition, in the case of a thermosetting resin composition consisting of a water-dilutable resin and resin particles that can react with each other, a water-soluble aminoplast resin is used as the water-dilutable resin, and the resin particles have a hydroxyl value of 0.0.
5-100, acid value 5-30, number average molecular weight 3000-3
About 5000 acrylic resin is used, and the aminoplast resin is added to the resin particles in an amount of 0.5 to 100% by weight, especially 1
A composition containing ~30% by weight is preferred.

In this case, the resin particles preferably contain at least 30% by weight of acrylic resin.

On the other hand, when the resin particles are thermosetting, at least two types of resins or a resin and a curing agent that can react with each other may coexist in a single particle.

Alternatively, these particles may be formed into separate particles and used as a mixture.

In this case, the water-dilutable resin may be either thermoplastic or thermosetting.

A particularly preferred curing reaction system is ([) hydroxyl value 20 to 120, number average molecular weight 3000 to
35,000 acrylic resin and blocked isocyanate resin in a weight ratio of 100/5 to 100, particularly preferably 100
/10 to 50, in particular, the isocyanate equivalent of the blocked isocyanate resin is 100 to 200.
Composition (1i) in which the mixing ratio with the acrylic resin is 0.4 to 1.2 in terms of functional group ratio of isocyanato groups/hydroxyl groups.
An acrylic copolymer containing 0.5 to 30% by weight of a glycidyl group-containing α,β monoethylenic monomer segment in the molecule, and at least one of a dibasic acid, a polybasic acid, and an acid anhydride. The ratio is 10073 to 30, particularly preferably 100/5 to
Composition consisting of a ratio of 20 (111) 0.5 to 30% by weight of blocked isocyanate group-containing α,β-ethylenic monomer segments in the molecule
A composition in which the acrylic copolymer and the polyhydric alcoholic hydroxyl group-containing compound are in a weight ratio of 100/5 to 100, in particular, the isocyanate equivalent of the blocked isocyanate group-containing copolymer is 100 to 2000, The mixing ratio with the polyhydric alcoholic hydroxyl group-containing compound is isocyanato group/
Composition 11v) having a functional group ratio of hydroxyl groups of 0.4 to 1.2) Epoxy equivalent: 400 to 5,000, softening temperature: 4
0 to 120°C epoxy resin and at least one of amines, polybasic acids, aminoplast resins, imidazoles, acid anhydrides, blocked isocyanates, triazoles, and dicyandiamine in a weight ratio of 100 /0.5~3
Composition consisting of a ratio of 0 (■) hydroxyl value 30-100, softening temperature 20-120°C
A composition comprising a polyester resin and at least one of an acid anhydride and a block isocyanate in a weight ratio of 100/5 to 80, particularly a resin in which the block isocyanate has an isocyanate equivalent of 100 to 2000, and the polyester Composition (vi) Acrylic having a hydroxyl value of 0.05 to 100, an acid value of 5 to 301, and a number average molecular weight of 3,000 to 35,000. resins, aminoplast resins, particularly preferably methylolated products of urea, penzoguanamine, or melamine, methyl etherified products or butyl etherified products of the methylolated products,
and a mixture with one or more of these condensates, and the weight ratio of the acrylic resin and aminoplast resin is 10.
0/10 to 100, particularly preferably 90/10 to 50/
Examples include compositions having a ratio of 50%.

The flake-like pigment used in the present invention is a flake-like pigment in which microcrystals are arranged in a certain direction and imparts sufficient iridescent color or pearlescent luster to the coating film.

For this purpose, it is generally preferable that the major diameter of the particles be 200 μm or less, and most of the particles be 50 μm or less.

Specifically, foil flakes of titanium dioxide, zirconium dioxide,
Examples include lead carbonate, tungstate, bismuth salt, mica, and fish scale.

Examples of flaky pigments available on the market include "Aflair Pearl", "Aflair Gold", "Satin Aflair" (product of I DuPont, USA), "Marlin-A-Pearl" (product of Marl Corporation, USA), and ulriod.
in Ti100J[lriodinTil00FJ[
1riodin color B Ti 100jrl
riodincoior GTi100J[lriod
in color KTi 100J[lriodin
color Y Ti IOOJ[1riodin
color DY Ti IOOJ (German E.M.
erck product) [ACGJ[ACLJrAcsJrAcEJrAcHB
J[AcHGJIACHLJ[AcHPJrDcGjr
DcEJrDcHBJrDcHLJrDCHPJrRC
GJrRCLJrRcsJrRcFjrRcEJrRc
HBJrRcHGJrRcHLJIRCHPjIVCG
JrVcs-100JrVcs-200JrVcEJr
VcHBJrVcHGJrVcHLJrVcHPJrX
cs-IOOJIHCG-150JrHcs-150J
rHcE-150JrSCS-250JISCE-25
0JrscHBJrscHGJrscHLJrSCHP
JrDZE-100JIDZE-241JrDZE-2
87JrWZEJrDBs-200JrXBs-200
JrDBs-200JrWBsj (Nihon Koken Kogyo ■
products), etc.

The flaky pigment needs to be added in an amount of 0.05% by weight or more based on the amount of resin in order to impart iridescent color or pearlescent luster to the coating film.

On the other hand, if the amount of the flaky pigment is too large, the adhesion of the coating film to the object to be coated and the flowability of the coating film will deteriorate, so the amount should be limited to a maximum of 30% by weight.

In addition, a flaky aluminum pigment can be added together with these flaky pigments in order to give the iris-colored or pearl-like coating film scattered high-luminance areas or to improve the brightness of the entire coating film.

The amount of flaky aluminum pigment added is 5% by weight based on the flaky pigment.
The amount added within this range is from 100% by weight to less than 100% by weight, and good results are obtained.

The amount of the flaky pigment or a mixture of it and the flaky aluminum pigment added is 0.1 to 20% by weight based on the resin particles when forming an iridescent or pearl-like coating with a one-coat finish to improve the appearance and appearance of the coating. Good performance.

In addition, when a colorless or colored clear paint is applied on top of the paint of the present invention to form a rainbow-colored or pearl-like coating film by 2 coats, 1 bake, or 2 coats, 2 bakes, the above-mentioned flaky pigment is used as the paint composition. Alternatively, adding a mixture of this and a flaky aluminum pigment in an amount of 5 to 30% by weight based on the resin particles provides better results in terms of brightness, appearance, and cost savings of the coating film.

The scale-like aluminum pigment has a flat shape with a ratio of the short axis to the long axis of the particles of 1:10 or more, and the long axis is 100 μ or less, and the majority of the particles are 30 μ or less, according to Japanese Industrial Standard JISK5910. Those corresponding to the specified type 1 (fine particles) are preferable.

Specific examples of scaly aluminum pigments include commercially available rStapa 15 HKJ and rstapa 10H.
KJrstapa Cristal SupcrJ, [
stapaCrystalJ, [Stapa Mobi
l R707J, rstapas Mobil R60
7J, rStapa 15HKn. l. J, IStap
al OHKn. l. J (German ECKART-W)
ERKE product name) [Fine Leafing SAP1
20J (product name manufactured by Showa Denko ■) and the like.

In the present invention, in order to disperse the flake-like material in a paint, it is preferable to first mix and disperse these pigments in a water-dilutable resin and then mix them with resin particles or an aqueous dispersion thereof.

Specifically, when the water-dilutable resin used is a resin that becomes water-soluble as a salt with a basic compound, such as a polycarboxylic acid resin, a flaky pigment and a water-soluble solvent solution of the resin are added. If necessary, by adding and mixing a flaky aluminum pigment, a hydrophobic resin is adsorbed to the pigment surface and dispersed in the resin solution, and then the resin is made water-soluble as a salt of a basic compound to achieve stable pigment dispersion. A liquid can be formed.

On the other hand, when the water-dilutable resin is a nonionic water-soluble resin such as a polyether resin or a water-soluble melamine resin, the pigment is mixed and dispersed in an aqueous solution of these resins, or more preferably, the pigment is mixed and dispersed at the interface. A stable pigment dispersion can be formed by mixing and dispersing the pigment in an activator aqueous solution, lowering the viscosity with a water-soluble solvent if necessary, and then adding and mixing it to a resin aqueous solution.

Further, when the water-dilutable resin is an emulsion resin, by adding and mixing the pigment into the emulsion, the dispersion can be easily stabilized by the surfactant contained in the emulsion.

The coating composition of the present invention is prepared in a conventional manner using known mixing means.

That is, in the coating composition of the present invention, an iridescent or pearlescent coating composition is obtained by mixing resin particles or an aqueous dispersion thereof with the above-mentioned uniform pigment dispersion.

When the pigment dispersion and the resin particle dispersion are mixed in the above, the dispersion of the pigment and the resin particles is stabilized by making the pH of the two substantially the same.

In addition, the present invention enables the flaky pigment to be prepared by first dispersing the flaky pigment in an aqueous solution or aqueous dispersion of a water-dilutable resin, and then mixing it with resin particles or an aqueous dispersion of resin particles. It can be stably dispersed in water without washing.

That is, since the aqueous solution or aqueous dispersion of the water-dilutable resin contains a large amount of water-soluble solvent or surfactant, the hydrophobic additives in the flaky pigment such as mineral spirit and stearic acid are dissolved or emulsified. It is believed that a stable pigment dispersion is formed by being absorbed by the water-dilutable resin, and by adsorbing the resin, surfactant, etc. on the surface of the pigment particles.

The present invention will be explained in more detail with reference to Examples below. In the examples, "part" or "%" means "part by weight" or 1% by weight.
” indicates.

Example 1 110 parts of a 60% acetone solution of acrylic resin with a softening temperature of 45°C, a molecular weight of 17,000, and a hydroxyl value of 60, a softening temperature of 6
8°C, 50 parts of a 60% acetone solution of blocked isocyanate resin with an inocyanate equivalent of 770, 0.5 parts of an organic tin compound (dissociation reaction catalyst), 0.5 parts of a surface conditioner, 8 parts of cyanine blue at the lid, and carbon. After uniformly mixing and dispersing 0.3 parts of black, the mixture was sprayed into 5,000 parts of water under vigorous stirring to emulsify the resin solution and extract the solvent into the water to form resin particles.

After the resin particles were filtered, they were washed with an equal weight of water and filtered to obtain a water-containing resin particle cake with a solid content of 60%.

0.2 parts of nonionic surfactant per 100 parts of this water-containing cake
1 part, 0.5 part of polycarboxylate thickener, and 20 parts of water were mixed uniformly and then finely pulverized in a Pall mill to give 70 parts of resin particles.
A slurry-like paint having a particle size of 5 to 30 μm was obtained.

On the other hand, 15 parts of methacrylic acid was added to an aqueous solution consisting of 65 parts of water, 2 parts of anionic surfactant, and 3 parts of nonionic surfactant.
and 15 parts of butyl methacrylate were dropwise polymerized according to a conventional method to obtain an acid value of about 330 and a glass transition temperature of about 80°C.
The emulsion was made of an acrylic resin having a number average molecular weight of about 60,000, had a solid content of 30%, and had a pH of 3.6.

Foil flake pigment (product name: 1riodin Ti IOOs,
E. Merck (Doi 7)) 26 parts, nonionic surfactant 5 parts, isopropyl alcohol 20 parts, and water 4 parts.
9 parts of the mixture was added to loO parts of the above emulsion to uniformly mix and disperse the flaky pigment, and further 10 parts of dimethylethanolamine was added to stabilize the dispersion of the emulsion and pigment.

Add 4 parts of this pigment dispersion liquid to 100 parts of the slurry uniform paint, stir and mix uniformly to create a paint with a weight ratio of resin particles/flake pigment/water dilutable resin of 100/1.01/1.15. A composition was obtained.

This paint was spray-painted onto a polished mild steel plate and baked and dried at 150° C. for 30 minutes. The resulting coating film had high iris gloss.

Further, although the coating composition was kept in a closed container and allowed to stand at room temperature for one week, no precipitation or aggregation of the flaky pigment was observed.

Example 2 Epoxy resin having an epoxy equivalent of 450 to 525 and a softening temperature of 64 to 76°C, 83 parts (trade name: Kou Peacoat 1001, Shell Chemical Co., Ltd.), 6 parts of dicyandiamine, 0.5 part of a silicone surface conditioner, titanium white A mixture consisting of 10 parts and 0.5 parts of phthalocyanine blue was melt-kneaded, mechanically crushed and sieved to obtain resin particles of 200 mesh or less.

A homogeneous mixture of 50 parts of this resin powder, 0.5 parts of water-soluble thickening stabilizer, 0.2 parts of nonionic surfactant, and 50 parts of water was pulverized in a Pall mill, and 85% of the resin particles had a particle size of 10.
A slurry paint of ~30μ was prepared.

Xylol dispersion containing 40% flaky pearl pigment (
30 parts of HCGI50 (trade name, Nihon Koken Kogyo) were mixed and dispersed in 20 parts of an emulsion with a solid content of 50% and a viscosity of 3500 CPS (trade name Yodozol 32A108, Kanebuchi Boseki Sardine), and then water-soluble aminoplast resin (trade name A pigment dispersion liquid was obtained by mixing 6 parts of SUMITEX M-40W (Sumitomo Chemical Co., Ltd.).

200 parts of the above slurry paint was added to 56 parts of this pigment dispersion to obtain a pale blue slurry paint with pearlescent luster.

The resin particles/flake pigment/water dilutable resin in this paint is 1
It was 00/12.1/14.9.

This paint was spray-painted on a polished mild steel plate and then baked and dried at 180° C. for 20 minutes. The resulting paint film had a good pearlescent luster.

Further, when the storage stability test of the paint was carried out in the same manner as in Example 1, no precipitation or aggregation of the flaky pigment was observed.

Example 3 50 parts of clear powder coating made of thermoplastic polyester resin with a softening temperature of about 90C (trade name: VPET≠1360, Dainippon Paint Co., Ltd.), 50 parts of water, and a surfactant (trade name: Eirosol OT, American Paint Co., Ltd.). Cyanamid Company)
0.3 part was added and mixed and pulverized using a Pall mill to obtain a slurry-like paint in which 80% of the resin particles had a particle size of 20 to 50 μm.

On the other hand, in a nitrogen stream, epoxy resin (trade name Epicote≠8
28, Shell Chemical 40 parts of sardine) and 100 parts of linseed oil fatty acid were heated and stirred at 230C for 3 hours to create an epoxy resin ester with an acid value of 10, and 20 parts of maleic anhydride was added to 100 parts of linseed oil fatty acid.
The mixture was heated and stirred at 80° C. for 4 hours to obtain a maleated epoxy resin having an acid value of 140.

100 parts of isopropyl alcohol was added to this to dissolve the resin.

Add 10 parts of this resin liquid to gold-colored pearly mica (trade name: MP).
-23, Rona Pearl Company, U.S.A.) and mixed, 1.5 parts of diethanolamine and 4 parts of water were added to make a uniform pigment dispersion, and this was mixed with 200 parts of the above slurry paint to form resin particles. A paint having a weight ratio of /pearl mica/water-dilutable resin of 100/10/6 was obtained.

Spray paint this paint on the polished mild steel plate surface and apply it at 150C for 20 minutes.
The coating film formed by heating for 1 minute had a good golden pearlescent luster.

Furthermore, when the paint was tested in the same manner as in Example 1, it was found to have excellent storage stability.

Comparative Example 1 26 parts of flaky pigment of Example 1, 5 parts of nonionic surfactant
20 parts of isopropyl alcohol, and 49 parts of water were gradually added and mixed to 200 parts of the slurry paint prepared in Example 1 to obtain an iris-colored paint composition. Agglomerated particles of about 0.5 mm were formed in some parts of the pigment, making stable pigment dispersion impossible.

Spray paint this paint on a polished mild steel plate while stirring.15
The coating film obtained by baking and drying at 0°C for 30 minutes was visually judged to be somewhat inferior in smoothness and lacking in iris gloss compared to the coating film prepared in Example 1.

Furthermore, when this paint was stored under the same conditions as in Example 1, flaky pigments aggregated and precipitated, and even when stirred with a rotary blade stirrer,
Agglomerates of flaky pigment of approximately 0 μm (determined by a grind gauge, the same applies hereinafter) remained and could not be completely redispersed.

Comparative Example 2 40 parts of the xylene dispersion of the flaky pearl pigment used in Example 2 was mixed with 5 parts of a nonionic surfactant, 20 parts of isobrobyl alcohol, and 35 parts of water to obtain a uniform pigment dispersion.

29 parts of this pigment dispersion was gradually added to 78 parts of the slurry paint prepared in Example 2 while stirring, but after a few minutes only the pearl pigments agglomerated, making it impossible to obtain a uniform paint composition. .

Comparative Example 3 5 parts of golden colored pearly mica (MP-23) and 8 parts of water were added to 100 parts of the slurry paint prepared in Example 3, and the mixture was uniformly stirred and mixed to obtain a paint composition.

This paint was spray-painted on a polished mild steel plate and baked and dried at 150°C for 20 minutes. Visual evaluation of the paint film showed that it had almost the same level of smoothness as the paint film of Example 3, but had some golden pearlescent luster. It was inferior.

The above slurry paint was applied onto this paint film and baked and dried at 150° C. for 20 minutes to form a single clear layer.The paint film exhibited a golden pearlescent luster comparable to that of Example 3.

When this paint was stored under the same conditions as in Example 1, pigment precipitation occurred and aggregates of about 100 microns remained even after stirring.

Example 4 The same acrylic resin acetone solution as Example 1 (resin content 60
%), 50 parts of a blocked isocyanate resin acetone solution (resin 60%), and 0.5 part of an organic tin compound were mixed with 0.5 part of a surface conditioner and uniformly dissolved.

This was sprayed into 5,000 parts of water in the same manner as in Example 1 to form resin particles, and then washed and filtered to obtain a water-containing resin particle cake with a solid content of 60%.

0.2 parts of nonionic surfactant per 100 parts of this water-containing cake
0.5 parts of a polycarboxylate thickener and 20 parts of water were mixed uniformly and then finely ground in a ball mill to give 85 parts of resin particles.
A slurry-like paint having a particle diameter of 1 to 30 μm was obtained.

On the other hand, 3.6 parts of diethanolamine and 47.4 parts of water were added to 14 parts of the golden colored pearly mica used in Example 3 and 24 parts of the isopropyl alcohol solution of the maleated epoxy resin, and the pigment dispersion was uniformly mixed and dispersed. Obtained.

A base paint was prepared by uniformly mixing 100 parts of this pigment dispersion and 100 parts of the slurry paint.

This base paint has a weight ratio of resin particles/pearl mica/water dilutable resin of 100/28.2/29.7.

This base paint was spray-coated to a thickness of 30μ on a polished mild steel plate, set, and after the coated layer was dry to the touch, the slurry-like paint was spray-painted to a thickness of 25μ, and then baked and dried at 150°C for 30 minutes. The resulting coating film had good golden pearlescent luster.

Further, when the base paint was kept in a closed container and the storage stability test of the paint was conducted in the same manner as in Example 1, no precipitation or aggregation of the pigment was observed.

Example 5 56 parts of a 60% acetone solution of an acrylic resin with a softening temperature of 41°C, a molecular weight of 15,000, a hydroxyl value of 40, and an acid value of 18, 24 parts of a 60% acetone solution of melamine resin (trade name RESIMENRF-3403 Monsanto 1), cellulose acetate 5 parts of a 20% acetone solution of butyrate (trade name: EAB-551-02 Eastman Kodakku), 8 parts of a 20% acetone solution of dimethyl phthalate (plasticizer, trade name: D.M.P. Shinnihon Rika Sarin) 0.5 part of a silicone surface conditioner, 0.5 part of carbon black, and 6 parts of phthalocyanine green were added to the mixture and mixed uniformly to disperse the pigment to obtain a solution paint.

This solution paint was sprayed into water in the same manner as in Example 1 to form resin particles in the water, and then the resin particles were washed with water and centrifugally filtered to obtain a cake of water-containing resin particles with a solid content of 65%.

To 100 parts of this cake of water-containing resin particles, 0.2 parts of nonionic surfactant, O. Add 4 parts and 35 parts of water, mix uniformly, and then pulverize in a ball mill until 75% of the resin particles have a particle size of 4 to 30μ.
A slurry paint having a range of

On the other hand, a flaky pigment (product name: 1riodin Color)
GTilOO, E. Merck) and 10 parts of a water-dispersible scaly aluminum pigment (trade name: Water Dispersible Standard Non-Leafing 1500MA Toyo Aluminum - solid content 70%) were mixed with a water-soluble alkyd resin (trade name: Watersol S-123 Nippon Reich). Hold - solid content 50%) 484 parts, water-soluble melamine resin (
The mixture was uniformly dispersed in a mixed resin solution of 12 parts (trade name: WATERSOL S-695 Nippon Reichhold (solid content: 66%)) and 9 parts of water to obtain a pigment dispersion.

Add 25 parts of this pigment dispersion to 136 parts of the slurry paint and mix by stirring uniformly so that the weight ratio of resin particles/total of aluminum pigment and flaky pigment/water dilutable resin is 100/10.
A coating composition of 8/12.3 was obtained.

This paint was sprayed onto a polished mild steel plate and baked and dried at 160° C. for 30 minutes. The resulting paint film had good iris brightness.

Further, although the coating composition was kept in a closed container and allowed to stand at room temperature for one week, no precipitation or aggregation of the flaky pigment or aluminum pigment was observed.

Comparative Example 4 136 parts of the slurry paint of Example 5, 5 parts of the flaky pigment (the above-mentioned 1riodin Color G.Ti100), and the water-dispersible flaky aluminum pigment (the above-mentioned Water Dispersible Standard Non-Leafing 1500MA)
) 2.5 parts and stir and mix uniformly to obtain a weight ratio of resin particles/total of aluminum pigment and flaky pigment/water dilutable resin of 10.
A coating composition of 0/10.38/0 was obtained.

This paint was spray-painted onto a polished mild steel plate and baked and dried at 160° C. for 30 minutes. The resulting paint film had a gloss value of 53 (60 degree specular reflection value) and an appearance similar to that of a matte paint film.

When this paint was stored under the same conditions as in Example 1, pigment precipitation occurred and pigment aggregates of about 90 μm remained even after stirring.

Example 6 50 parts of methyl methacrylate, 19.7 parts of hydroxypropyl methacrylate, 28.3 parts of 2-ethylhexyl methacrylate, and 2 parts of acrylic acid were solution polymerized in 67 parts of acetone by a conventional method to obtain a hydroxyl group with a softening temperature of 50°C. Value 76
．． 5. An acrylic resin solution with an acid value of 15, a molecular weight of 17,000, and a nonvolatile content of 60% was obtained.

80 parts of this acrylic resin solution and 0.0 parts of a fluorine-based surface conditioner.
5 parts, and 15 parts of a 20% acetone solution of a plasticizer (the above D.M.P.) were added, and further a red pigment (trade name Paliogen Red GG, Badische Anilin-&Soda-
Fabrik A. G, West Germany) were mixed and dispersed to obtain a red solution paint.

This red solution paint was sprayed into water in the same manner as in Example 1 to form resin particles, which were washed with water and centrifuged to form solids with a solid content of 6.
A cake containing 0% resin particles was obtained.

100 parts of this resin particle water-containing cake, 0.6 parts of a polymeric nonionic surfactant, and a thickener (trade name: Bengel Kamihojun Yoko)
Add 0.4 parts and 19 parts of water, stir and mix uniformly, and pulverize with a vibrating mill until 85% of the resin particles have a particle size of 0.5 to 10.
On the other hand, 9 parts of a flaky pearl pigment (product name MP-10, Rona Co., Ltd., USA) and aluminum flakes (product name Ruby Series As≠20 Nile Green, Fukuda Metal Foil Powder Industry Co., Ltd.) were prepared. ) was mixed and dispersed in a resin solution of 10 parts of water-soluble aminoplast resin (trade name Sumitex Resin M-3 Sumitomo Chemical - solid content 80%) and 10 parts of water, and then added to 120 parts of the slurry paint and mixed uniformly. The weight ratio of resin particles/total of flaky pearl pigment and aluminum flakes/water-dilutable resin is 100/16.67.
A coating composition of /13.33 was obtained.

This paint composition is applied to a substrate that has been undercoated with white paint.
By baking and curing at 50° C. for 30 minutes, a coating film with pearlescent luster due to the pearl pigment and a large sparkle effect due to the aluminum pigment was obtained.

Furthermore, since the acrylic resin particles and the water-soluble aminoplast resin were cured by reaction, the coating film had excellent solvent resistance, water resistance, etc.

Further, this paint was kept in a closed container as in Example 1 and allowed to stand at room temperature for one week, but no precipitation or aggregation of the flaky pearl pigment or aluminum flakes was observed.

Example 7 17.1 parts of glycidyl methacrylate, 8.5 parts of hydroxy methacrylate, 10.4 parts of methyl methacrylate
parts, 45.5 parts of styrene, 7 parts of inbutyl methacrylate
．． 9 parts, 10.6 parts of ethyl methacrylate to 6 parts of acetone
133 parts of an acrylic resin with a glass transition point of 65C solution-polymerized in a conventional manner in 7 parts, 20 parts of sebacic acid, and 0 parts of a surface conditioner.
．． 5 parts of phthalocyanine blue and 0.3 parts of carbon black were uniformly dispersed and sprayed into water in the same manner as in Example 1 to form resin particles, washed with water and centrifuged to obtain a resin with a solid content of 65%. A particle water-containing cake was obtained.

0.5 parts of thickener, 0.2 parts of nonionic surfactant and 23 parts of water were added to 77 parts of this water-containing cake of resin particles, stirred and mixed uniformly, and pulverized in a ball mill so that 90% of the resin particles had a particle size of 1. Slurry paints in the range of ~35μ were prepared.

6.4 parts of an aliphatic hydrocarbon solvent dispersion containing 65% of a flaky aluminum pigment of 325 mesh or less (trade name: Aluminum Paste HighSPAKLE Toyo Aluminum Ichi) and a xylene dispersion containing 40% of a flaky pearl pigment ( Product name HCGI50, Nihon Koken Kogyo Co., Ltd.) 22 parts with solid content of 50%
, mixed and dispersed in 20 parts of an emulsion with a viscosity of 3500 cPs (trade name: Yodozol 32A108, Kagamifuchi Boseki Sardine), and then water-soluble aminoplast resin (trade name: Sumitex M-
40W. 6 parts of Sumitomo Chemical Co., Ltd. and 7.5 parts of water were added and mixed to obtain a pigment dispersion.

Add 200 parts of the above slurry paint to 61.9 parts of this pigment dispersion.
A pale blue slurry paint with high brightness and iridescent color was obtained.

Resin particles in this paint/sum of flaky aluminum pigment and flaky pearl pigment/water dilutable resin is 100/12.1/1
It was 4.9.

This paint was spray-painted on a polished mild steel plate and then baked and dried at 180°C for 20 minutes. The resulting paint film had high brightness and iridescent color.

Further, when the storage stability test of the paint was carried out in the same manner as in Example 1, no precipitation or aggregation of the flaky aluminum pigment or the flaky pigment was observed.

Claims (1)

[Scope of Claims] 1 (a) 90 to 30 parts by weight of aqueous medium, (portion) Softening temperature of 5 to 120°C, average particle size of 0.5 to 80
10 to 70 parts by weight of μ resin particles, (c) 0.05 to 30% by weight of a flaky pigment based on the resin particles, and (d) water dilutability of 30% by weight or less based on the resin particles. A paint composition consisting of resin. 2 The component (c) has a content of 0.1 to 2 with respect to the resin particles.
The coating composition according to claim 1, which contains 0% by weight of flaky pigment. 3. Component (2) is a mixture of an acrylic resin and/or alkyd resin with an acid value of 30 to 80 and a water-soluble aminoplast resin in a solid content weight ratio of 100/10 to 70. The coating composition according to any one of Item 2. 4. Claims 1 and 2, wherein the component (0) is a mixture of an acrylic resin with a hydroxyl value of 20 to 120 and a number average molecular weight of 3,000 to 35,000 and a blocked isocyanate resin in a weight ratio of 100/5 to 100. or the coating composition according to any one of Item 3. 5 The (mouth) component is an acrylic resin with a hydroxyl value of 0.05 to 100, an acid value of 5 to 30, and a number average molecular weight of 3000 to 35000, and an aminoplast resin in a weight ratio of 100/10.
The coating composition according to any one of claims 1, 2 or 3, which is a mixture of 1 to 100. 6. The above (original) component is an acrylic polymer containing 0.5 to 30% by weight of a glycidyl group-containing α,β monoethylenic monomer segment in the molecule, and a small amount of dibasic acids, polybasic acids, and acid anhydrides. The coating composition according to any one of claims 1, 2, and 3, wherein both are a combination of one type and the blending ratio of both is 100/3 to 30 by weight. 7 The (mouth) component contains a blocked incyanate group α
, β-ethylenic monomer segment in the molecule with 0.5
Claim 1: A combination of an acrylic copolymer containing ~30% by weight and a polyhydric alcoholic hydroxyl group-containing compound, with a weight ratio of 100/5 to 100.
The coating composition according to any one of Items 2 and 3. 8 The component (0) has an epoxy equivalent of 400 to 5000,
Epoxy resin with a softening temperature of 40 to 120°C, amines,
Contains a combination of at least one of polybasic acids, aminoplast resins, imidazoles, acid anhydrides, blocked incyanates, triazoles, and dicyandiamide, with a weight ratio of 100/0.5 to 30. A coating composition according to any one of claims 1, 2, and 3. 9 The (mouth) component is a combination of at least one of a polyester resin with a hydroxyl value of 30 to 100 and a softening temperature of 20 to 120°C, an acid anhydride, and a butane isocyanate, and the blending ratio of both is 100 by weight. The coating composition according to any one of claims 1, 2, or 3, which has a coating composition of /5 to 80. 10 Component (0) has a hydroxyl value of 0.5 to 40 and an acid value of 0
．． 1-10, molecular weight 2000-7000, softening temperature 40
The coating composition according to any one of claims 1, 2, or 3, comprising a thermoplastic polyester resin having a temperature of -120°C. 11 The component (1) contains 30 to 100% by weight of an acrylic resin having a hydroxyl value of 0.05 to 100, an acid value of 5 to 30, and a number average molecular weight of 3,000 to 35,000, and the component (2) is a water-soluble aminoplast resin. and the ratio of the acrylic resin to the water-soluble aminoplast resin is 1 by weight.
00/0.5 to 100/100, the coating composition according to claim 1 or 2. 12 Component (0) contains 0.5 to 30% by weight of a glycidyl group-containing α/β monoethylenic monomer segment in the molecule.
Acrylic copolymer containing 30 to 100% by weight in particles
0.5 to 30% by weight of at least one monomer segment from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic anhydride in the molecule.
resin particles containing 30 to 100% by weight of a carboxyl group-containing acrylic copolymer, and the ratio of the glycidyl group-containing acrylic copolymer to the carboxyl group-containing acrylic copolymer is 99% by weight. /1~1/99
The coating composition according to any one of claims 1, 2, or 3. 13 The isocyanate equivalent of the blocked isocyanate resin is 100 to 2000, and the mixing ratio with the acrylic resin is 0.4 to 1 in the functional group ratio of incyanate groups/hydroxyl groups,
2. The coating composition according to claim 4, which is 14 The aminoplast resin is one or more of a methylolated product of urea, penzoguanamine or melamine, a methyl etherified product or a butyl etherified product of the methylolated product, and a condensate thereof, and the acrylic resin and the aminoplast resin Ratio is 9m/ml by weight
The coating composition according to claim 5, which is 5/5. 15 The isocyanate equivalent of the acrylic copolymer containing 0.5 to 30% by weight of the blocked isocyanato group-containing α,β-ethylenic monomer segment in the molecule is 10
0 to 2000, and the mixing ratio with the polyhydric alcoholic hydroxyl group-containing compound is 0 in terms of functional group number ratio of incyanate group/hydroxyl group.
．． The coating composition according to claim 7, which has a molecular weight of 4 to 1.2. 16 The blocked isocyanate is a resin having an isocyanate equivalent of 100 to 2000, and the mixing ratio with the polyester resin is 0.4 in terms of functional group ratio of incyanate group/hydroxyl group.
1.2. 17 (a) 90 to 30 parts by weight of aqueous medium, (0) Softening temperature of 5 to 120°C, average particle size of 0.5 to 80
10 to 70 parts by weight of μ resin particles; (c) 0.05 to 30 parts by weight of the resin particles;
A mixture of a) a flaky pigment and (b) a flaky aluminum pigment (however, the proportion of the flaky aluminum pigment is 5% by weight or more and less than 100% by weight relative to the flaky pigment)
, and (d) a water-dilutable resin in an amount of 30% by weight or less based on the resin particles. 18. The method according to claim 17, wherein the component (d) is a mixture of an acrylic resin and/or alkyd resin having an acid value of 30 to 80 and a water-soluble aminoplast resin in a solid content weight ratio of 100/10 to 70. Paint composition. 19. Claim 11 or 18, wherein the (oral) component is a mixture of an acrylic resin with a hydroxyl value of 20 to 120 and a number average molecular weight of 3,000 to 35,000 and a blocked isocyanate resin in a weight ratio of 10,075 to 100. The coating composition according to any of paragraphs. 20 The (mouth) component is an acrylic resin with a hydroxyl value of 0.05 to 100, an acid value of 5 to 30, and a number average molecular weight of 3000 to 35000, and an aminoplast resin in a weight ratio of 100/1.
The coating composition according to claim 17 or 18, which is a mixture of 0 to 100. 21 The above (oral) component contains 0.5 to 30% by weight of a glycidyl group-containing α,β monoethylenic monomer segment in the molecule.
Claim 17 or The coating composition according to any one of Item 18. 22 The above (original) component contains a block isocyanate group-containing α,β-ethylenic monomer segment in the molecule with 0.
Claim 11 or 18, which is a combination of an acrylic copolymer containing 5 to 30% by weight and a polyhydric alcoholic hydroxyl group-containing compound, and the blending ratio of both is 10,075 to 100 by weight. A coating composition according to claim 1. 23 The above (mouth) component has an epoxy equivalent of 400 to 5000
Epoxy resin with a softening temperature of 40 to 120°C, amines,
A patent comprising a combination of at least one of polybasic acids, aminoplast resins, imidazoles, acid anhydrides, blocked isocyanates, triazoles, and dicyandiamide, with a weight ratio of 100/0.5 to 30. The coating composition according to claim 17 or 18. 24 Component (0) is a combination of at least one of a polyester resin with a hydroxyl value of 30 to 100 and a softening temperature of 20 to 120°C, an acid anhydride, and a blocked isocyanate, and the blending ratio of both is 100/5 by weight. The coating composition according to claim 17 or 18, which has a molecular weight of 80 to 80. 25 The above (mouth) component has a hydroxyl value of 0.5 to 40 and an acid value of 0
．． 1-10, molecular weight 2000-7000, softening temperature 40
The coating composition according to claim 17 or 18, comprising a thermoplastic polyester resin having a temperature of -120°C. 26 The component (1) contains 30 to 100% by weight of an acrylic resin having a hydroxyl value of 0.05 to 100, an acid value of 5 to 30, and a number average molecular weight of 3,000 to 35,000, and the component (2) is a water-soluble aminoplast resin. and the ratio of the acrylic resin to the water-soluble aminoplast resin is 1 by weight.
18. The coating composition according to claim 17, which has a molecular weight of 0.0070.5 to 100/100. 27 The above (oral) component contains 0.5 to 30% by weight of a glycidyl group-containing α,β monoethylenic monomer segment in the molecule.
Resin particles containing 30 to 100% by weight of an acrylic polymer containing acrylic acid, methacrylic acid, itaconic acid,
At least one member of the group consisting of crotonic acid and maleic anhydride
The particles contain a carboxyl group-containing acrylic copolymer containing 0.5 to 30% by weight of a monomer segment in the molecule.
0 to 100% by weight of resin particles, and the ratio of the glycidyl group-containing acrylic copolymer to the carboxyl group-containing acrylic copolymer is 99/1 to 1/99 by weight. The coating composition according to either item 17 or 18. 28 The inocyanate equivalent of the blocked isocyanate resin is 100 to 2000, and the mixing ratio with the acrylic resin is the functional group ratio of isocyanato groups/hydroxyl groups of 0.4 to 1.
2. The coating composition according to claim 19, which is 29 The aminoplast resin is one or more of a methylolated product of urea, penzoguanamine or melamine, a methyl ether or butyl ether of the methylolated product, and a condensate thereof, and the acrylic resin and the amineplast resin The weight ratio is 9/1 to 5/
21. The coating composition according to claim 20, which is No. 5. () The above-mentioned blocked isocyanate group-containing α,β-ethylenic monomer segment is contained in the molecule in an amount of 0.5 to 30% by weight.
The isocyanate equivalent of the acrylic copolymer containing 100
~2000, and the mixing ratio with the polyhydric alcoholic hydroxyl group-containing compound is 0.0.
23. The coating composition according to claim 22, which has a molecular weight of 4 to 1.2. 31 The blocked isocyanate is a resin having an incyanate equivalent of 100 to 2000, and the mixing ratio with the polyester resin is 0.4 in terms of the functional group ratio of isocyanate groups/hydroxyl groups.
25. The coating composition according to claim 24, which has a molecular weight of 1.2 to 1.2.