JPH11279489A - Aqueous wax dispersion, and its production and aqueous coating containing the aqueous wax dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous wax dispersion capable of stably maintaining the dispersion states of aqueous coating compositions and not deteriorating the water resistance of dried coating films by compounding a specific resin, a wax, a volatile amine and an aqueous medium. SOLUTION: This aqueous wax dispersion comprises (A) a resin having an acid value of 100-500 and a number-average mol.wt. of 2,000-50,000, (B) at least one kind of wax selected from (i) natural waxes and (ii) synthetic waxes, (C) a volatile amine, and (D) an aqueous medium. The component A comprises at least one kind of resin selected from carboxyl group-containing acrylic resins and carboxyl group-containing polyester resins. The component A and the component B are contained in amounts of 1-50 pts.wt. and 50-99 pts.wt., respectively, wherein the total amount of the components A and the component B is 100 pts.wt. The photocurable coating composition is preferably obtained by mixing the component A with the component B in a mixture liquid state, and subsequently adding the component C and the component D to the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous wax dispersion obtained by dispersing waxes in an aqueous medium mainly composed of water using a small amount of emulsifier having good water resistance, and a method for producing the same. Further, the present invention relates to an aqueous coating agent comprising the aqueous wax dispersion. The aqueous wax dispersion obtained by the present invention is used as a water-based paint, a water-based ink or other various water-based compositions, or by being mixed with a water-based paint or a water-based ink for various water-based compositions to be used. It is suitably used as a material which imparts lubricity, water repellency and the like to the dried film, facilitates transportation in a can-making process, and imparts performance such as prevention of damage in the transportation process.

[0002]

2. Description of the Related Art Conventionally, carnauba wax, candelilla wax, rice wax, lanolin wax, montan wax, white wax, polyethylene wax, polypropylene wax, poly (ethylene-propylene) copolymer wax, Teflon wax, microcrystalline wax Animal and plant-based waxes, mineral-based waxes, synthetic waxes, and the like are widely used as lubricity-imparting paints, anti-scratch paints, anti-adhesion paints, thermal transfer inks, water-repellent paints, release agents, and the like.

[0003] Conventionally, solvent-based paints are generally used as lubricity-imparting and scratch-proof paints applied to cans. Depending on the purpose, the wax described above is dissolved or dispersed in the paint as it is, or Such a wax was obtained by previously dissolving or dispersing in an aromatic solvent or the like and then adding it to the coating after adding it to the coating.In recent years, solvent-based coatings discharge organic solvents and emit carbon dioxide by combustion.
From the viewpoint of protection of the global environment, there has been a demand for a water-based paint in which the content of an organic solvent is reduced as much as possible. However, the wax may be directly dissolved or dispersed in the aqueous paint in the same manner as in the solvent paint described above, or the wax may be dissolved or dispersed in an aromatic solvent or the like beforehand in the aqueous paint. Even when added, it was difficult for the wax to aggregate and to stably exist in the water-based paint. On the other hand, there is a method of increasing the amount of the organic solvent in order to allow the wax to be stably present in the water-based paint. Further, a method of dispersing a wax in water using a surfactant has also been proposed, but in the case of an aqueous coating composition containing an aqueous wax dispersion obtained by such a method, the water resistance of the obtained coating film is remarkable. Will drop.

[0004]

SUMMARY OF THE INVENTION The present invention solves the various problems of the above-mentioned conventional wax dispersion, can maintain the dispersion state of the aqueous coating composition stably, and can improve the water resistance of the dried coating film. The aim is to obtain an aqueous wax dispersion which does not impair.

[0005]

That is, the first invention has an acid value of 100 to 500 and a number average molecular weight of 2000 to 2000.
50,000 or more of a resin (A), a natural wax (b1) or a synthetic wax (b2), a volatile amine (C), and an aqueous medium (D). Aqueous wax dispersion.

According to a second invention, the resin (A) comprises at least one of an acrylic resin (a1) having a carboxyl group or a polyester resin (a2) having a carboxyl group.
The aqueous wax dispersion according to the first invention, which is a seed.

The third invention is characterized in that the resin (A) and the wax (B) each contain 1 to 50 parts by weight of the resin (A) and 50 to 99 parts by weight of the wax (C) in a total of 100 parts by weight. The aqueous wax dispersion according to the first or second aspect of the present invention.

The fourth invention relates to a resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2000 to 50,000.
And at least one kind of wax (B) among natural wax (b1) and synthetic wax (b2), and then mixed with volatile amine (C) and aqueous medium (D). ) Is added.

The fifth invention relates to a resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2,000 to 50,000.
And at least one kind of wax (B) among natural wax (b1) and synthetic wax (b2), and then mixed with volatile amine (C) and aqueous medium (D). ) Is added.

The sixth invention relates to a resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2,000 to 50,000.
And at least one kind of wax (B) among natural wax (b1) and synthetic wax (b2), and then a volatile amine (C) is added to the mixture (E).
Obtaining a mixture (F) of a resin (A), a wax (B) and a volatile amine (C), and then adding an aqueous medium (D) to the mixture (F). It is.

The seventh invention relates to a resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2000 to 50,000.
And at least one kind of wax (B) among natural wax (b1) and synthetic wax (b2), and then a volatile amine (C) is added to the mixture (E).
A method for producing an aqueous wax dispersion, comprising obtaining a mixture (F) of a resin (A), a wax (B) and a volatile amine (C), and then adding the mixture (F) to an aqueous medium (D). It is.

An eighth invention provides a resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2000 to 50,000,
At least one wax (B) of a natural wax (b1) or a synthetic wax (b2), a volatile amine (C)
And a mixture (G) of an aqueous medium (D) and a wax (B)
A method for producing an aqueous wax dispersion comprising stirring at a temperature not lower than the melting point of the wax.

A ninth invention is a resin (A) obtained by adding a volatile amine (C) and an aqueous medium (D) to a resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2000 to 50,000. At least one of natural wax (b1) and synthetic wax (b2)
A method for producing an aqueous wax dispersion, comprising adding a kind of wax (B) in a molten or dissolved state.

According to a tenth aspect, the acid value of the wax (B) is at least 100 in a melt or a melt of at least one of the natural wax (b1) and the synthetic wax (b2).
500, wherein an aqueous solution or aqueous dispersion of the resin (A) obtained by adding a volatile amine (C) and an aqueous medium (D) to the resin (A) having a number average molecular weight of 2,000 to 50,000 is added. This is a method for producing an aqueous wax dispersion.

An eleventh invention is characterized in that the resin (A) is at least one of an acrylic resin (a1) having a carboxyl group and a polyester resin (a2) having a carboxyl group. The method for producing an aqueous wax dispersion according to any one of the inventions.

A twelfth invention is an aqueous coating agent comprising the aqueous wax dispersion according to any one of the first to third inventions.

A thirteenth invention is an aqueous coating composition comprising the aqueous wax dispersion obtained by the method for producing an aqueous wax dispersion according to any one of the fourth to eleventh inventions.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous wax dispersion of the present invention comprises
The wax (B) is dispersed in the aqueous medium (D) by using a neutralized product of the resin (A) as an emulsifier.

The resin (A) used in the present invention comprises:
Acid value is 100-500, number average molecular weight is 2000-50
000, the acid value is more preferably 100 to 400, and the number average molecular weight is more preferably 2,000 to 20,000. When the acid value of the resin (A) is less than 100, the emulsifying function after neutralization is small, and it becomes difficult to stably disperse the wax (B), and an aggregate of the wax (B) is formed in the aqueous dispersion. It will be easier. On the other hand, if the acid value exceeds 500, the water resistance of the coating film obtained from the aqueous coating composition to which the aqueous wax dispersion has been added tends to decrease. Therefore, it is important that the acid value is 100 to 500. Further, even if the number average molecular weight of the resin (A) is less than 2,000 or more than 50,000, the neutralized product is difficult to disperse the wax (B), so that the number average molecular weight is 2,000 to 50,000, and 2,000 to 50,000. 2000
More preferably, it is 0. The resin (A) is preferably at least one of an acrylic resin (a1) having a carboxyl group and a polyester resin (a2) having a carboxyl group, and a part or all of the carboxyl group is a volatile amine described later. By neutralizing with (C), an emulsifying function can be exhibited.

Further, in the present invention, the resin (A) is added to the resin (A) in a total of 100 parts by weight of the resin (A) and the wax (B).
It is preferable to contain 50 to 99 parts by weight of the wax (C). If the amount of the resin (A) is less than 1 part by weight, it is difficult to emulsify the wax (B), and it is easy to generate aggregates in the aqueous dispersion. On the other hand, if it exceeds 50 parts by weight, the aqueous wax dispersion is added. Not only does the water resistance of the coating film obtained from the aqueous coating composition tend to decrease, but also the lubricity tends to decrease due to the decrease in the buoyancy of the wax in the coating film. It is preferably 50 parts by weight, more preferably 2 to 20 parts by weight.

Among the resins (A) used in the present invention, the acrylic resin (a1) having a carboxyl group is
Acrylic acid, methacrylic acid, maleic acid, itaconic acid,
Α, β-unsaturated carboxylic acids such as crotonic acid and fumaric acid and monomers copolymerizable with these α, β-unsaturated carboxylic acids, for example, styrene, vinyltoluene, 2-methylstyrene, t-butylstyrene , Styrene-based monomers such as chlorostyrene; methyl (meth) acrylate,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
N-Amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, (meth)
2-ethylhexyl acrylate, n- (meth) acrylate
(Meth) acrylate-based monomers such as octyl, decyl (meth) acrylate, dodecyl (meth) acrylate, and lauryl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate , Hydroxyl-containing monomers such as hydroxymethyl (meth) acrylate; N-methylol (meth)
N-substituted (meth) acrylic acid monomers such as acrylamide and N-butoxymethyl (meth) acrylamide;
It is obtained by copolymerization of one or more species.

The (meth) acrylate monomer is an acrylate monomer and / or a methacrylate ester monomer, and the 2-hydroxyethyl (meth) acrylate is 2-hydroxyethyl acrylate and / or methacrylic acid. 2-hydroxyethyl acid, and N-substituted (meth) acrylic acid monomer means N-substituted acrylic acid monomer and / or N-substituted methacrylic acid monomer.

The above monomer mixture is preferably polymerized in a suitable organic solvent. Examples of the polymerization catalyst include organic peroxides, persulfates, azobis compounds, and redox systems obtained by combining these with a reducing agent. Can be used. Specifically, benzoyl peroxide,
Perbutyl octate, t-butyl hydroperoxide, azobisisobutyronitrile, azobisvaleronitrile, 2,2′-azobis (2-aminopropane) hydrochloride and the like, and benzoyl peroxide, azobisiso Butyronitrile is particularly preferred. These are generally from 0.3 to 100 parts by weight of the polymerizable component.
It can be used in a proportion of 15 parts by weight.

Acrylic resin having carboxyl group (a
1) includes an α, β-unsaturated carboxylic acid such as (meth) acrylic acid in an amount such that the acid value after polymerization is 100 to 500, although the composition ratio and type of the monomer are not particularly limited. As the vinyl monomer copolymerizable with the α, β-unsaturated carboxylic acid, styrene, ethyl acrylate and methyl methacrylate are preferred.

Among the resins (A) used in the present invention, a polyester resin (a2) having a carboxyl group
Is ethylene glycol, propylene glycol, 1,
3-butylene glycol, 1,6-hexanediol,
Dihydric alcohols such as diethylene glycol, dipropylene glycol, neopentyl glycol, and triethylene glycol; Alcohol components such as the above alcohols, and (phthalic anhydride), isophthalic acid, terephthalic acid, (succinic anhydride), adipic acid, azelaic acid, sebacic acid, tetrahydro (phthalic anhydride) phthalic acid, hexahydro (phthalic anhydride), (Anhydrous) hymic acid, (anhydrous)
Polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, trimellitic anhydride (anhydride), methylene dichlorohexentricarboxylic acid (anhydride), (anhydride) pyromellitic acid or anhydrides thereof, and if necessary, used in combination. It is obtained by condensation with an acid component such as a monobasic acid such as benzoic acid or t-butylbenzoic acid.

As the polyester resin (a2) having a carboxyl group, an oil-free polyester resin obtained by condensing the above-mentioned alcohol component and acid component, or a castor oil, dehydrated castor oil, Tung oil, safflower oil, soybean oil, linseed oil, tall oil, coconut oil and the like, and an oil component that is a mixture of one or more of these fatty acids, in addition to the acid component and the alcohol component, An alkyd resin obtained by reacting three components is exemplified. Further, a graft-modified polyester resin obtained by modifying an acrylic resin to a polyester resin having an unsaturated bond by grafting may also be used.

Among the waxes (B) used in the present invention, the natural wax (b1) includes animal and plant-based substances such as beeswax, lanolin wax, spermaceti, candelilla wax, carnauba wax, rice wax, wood wax and jojoba oil. Wax, montan wax, ozogenite, ceresin,
Paraffin wax, microcrystalline wax,
Minerals such as petrolatum, petroleum-based wax and the like,
Carnauba wax, candelilla wax, rice wax, lanolin wax, and microcrystalline wax are preferred, and these can be used alone or as a mixture of two or more.

Among the waxes (B) used in the present invention, the synthetic wax (b2) includes synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene wax, polyethylene oxide wax and polypropylene oxide wax, montan wax derivatives, Modified waxes such as paraffin wax derivatives and microcrystalline wax derivatives, hydrogenated waxes such as hardened castor oil and hardened castor oil derivatives, Teflon wax, etc., and polyethylene wax, Teflon wax, and microcrystalline wax derivatives are preferable, and these are used alone. Alternatively, they can be used as a mixture of two or more.

The volatile amine (C) used in the present invention includes ammonia, ethylamine, diethylamine,
Examples include, but are not limited to, triethylamine, ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, cyclohexylamine, and the like. These volatile amines (C)
Is used to neutralize a part or all of the carboxyl groups in the resin (A), and by neutralizing, the resin (A) functions as an emulsifier for the wax (B). The wax (B) can be stably dispersed in the aqueous medium (D).

The aqueous medium (D) used in the present invention
In addition to water, a mixture of water and a hydrophilic organic solvent is used. Examples of the hydrophilic organic solvent include alcohols, glycols, diglycols, and acetates. Specifically, n-propanol,
Isopropanol, n-butyl alcohol, isobutyl alcohol, n-amyl alcohol, amyl alcohol, methyl amyl alcohol, ethylene glycol, diethylene glycol, 1,3-butylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, methyl propylene glycol, methyl propylene diglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate Tate, ethylene glycol monobutyl ether acetate, can be mentioned 3-methyl-3-methoxybutyl acetate and the like. However, it is desirable that these hydrophilic organic solvents be as small as possible. The amount of the aqueous medium (D) is not particularly limited as long as the wax (B) can be dispersed in the aqueous medium (D).
It may be appropriately selected in consideration of the desired nonvolatile content and viscosity of the aqueous wax dispersion.

The aqueous wax dispersion of the present invention can be obtained by the following various methods, but the production method is not limited thereto. (1) After the resin (A) and the wax (B) are in a mixed liquid state, the mixed liquid (E) is added to the volatile amine (C) and the aqueous medium (D). (2) After the resin (A) and the wax (B) are mixed, a volatile amine (C) and an aqueous medium (D) are added to the mixed liquid (E).

(3) After the resin (A) and the wax (B) are mixed, a volatile amine (C) is added to the mixed solution (E), and the resin (A), the wax (B) and A mixture (F) of volatile amines (C) is obtained, and to this mixture (F) is added an aqueous medium (D). (4) After the resin (A) and the wax (B) are in a mixed liquid state, a volatile amine (C) is added to the mixed liquid (E),
A mixture (F) of a resin (A), a wax (B) and a volatile amine (C) is obtained, and then the mixture (F) is added to an aqueous medium (D). In the case of the methods (1) to (4), the resin (A) and the wax (B) may be forcibly brought into a mixed liquid state using a kneader or a powerful stirrer. Or wax (B) and resin (A) in the molten state
May be mixed to form a mixed liquid state.

(5) Mixture (G) of resin (A), wax (B), volatile amine (C) and aqueous medium (D)
Is stirred at a temperature equal to or higher than the melting point of the wax (B). (6) While stirring the mixture (H) of the resin (A), the wax (B) and the aqueous medium (D) at a temperature not lower than the melting point of the wax (B), the mixture (H) is added to the volatile amine (C). ). (7) The mixture (H) of the resin (A), the wax (B) and the aqueous medium (D) is added to the volatile amine (C) while stirring the mixture (H) at a temperature not lower than the melting point of the wax (B). ).

(8) A volatile amine (C) is added to the resin (A).
The wax (B) is added in a molten or dissolved state to an aqueous solution or aqueous dispersion of the resin (A) to which the aqueous medium (D) is added. (9) In the melt or melt of the wax (B),
An aqueous solution or aqueous dispersion of resin (A) obtained by adding volatile amine (C) and aqueous medium (D) to resin (A),
Add.

The amounts of the resin (A), the wax (B), the volatile amine (C), and the aqueous medium (D), the neutralization ratio, and the mixing conditions (mixing speed, stirring conditions, temperature, etc.) are variously changed. Thereby, various aqueous wax dispersions having different sizes of dispersed particles can be obtained.

The organic solvent present in the process of dispersing the wax in the aqueous medium can be removed under reduced pressure if necessary. At this time, water and the organic solvent may be removed as an azeotropic mixture. In such a case, it is more preferable to use an organic solvent which can be easily deorganized, that is, an organic solvent having a relatively low boiling point.

The particle size of the aqueous dispersion of the wax of the present invention is not particularly limited as long as it can be stably present in the aqueous medium (D), but the wax dispersion is mixed with a water-soluble resin solution or an aqueous resin dispersion. In consideration of the stability of the water-based paint obtained by baking, and the surface condition, slipperiness, water resistance, etc. of the coating film obtained by baking and drying the water-based paint, the thickness is preferably 0.1 to 5 μm or less, more preferably 0.1 to 5 μm. 2-1 μm.

The aqueous wax dispersion of the present invention can be prepared by adding an appropriate amount to a water-soluble resin solution or an aqueous resin dispersion in consideration of required quality characteristics such as slipperiness and scratch resistance of the obtained dried coating film. However, since the aqueous wax dispersion of the present invention is an anionic dispersion, the aqueous resin solution or aqueous resin dispersion to be blended is preferably an anionic aqueous resin. If the amount of the wax (B) is less than 0.01% by weight based on the weight of the dried coating film, the properties substantially derived from the wax are hardly exhibited, so that the amount of the wax (B) in the dried coating film is 0.01%. It is preferable to add the aqueous wax dispersion to the water-soluble resin solution or the aqueous resin dispersion so that the amount becomes at least% by weight.

[0039]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but these do not limit the present invention at all. In the following Examples and Comparative Examples, “parts” means “parts by weight” or “% by weight” unless otherwise specified.

Production Example 1 Production of acrylic resin (a1-1) solution (1) 105.0 parts of styrene (2) 105.0 parts of ethyl acrylate (3) 90.0 parts of methacrylic acid (4) benzoyl peroxide 6 0.0 part (5) n-butanol 100.0 parts (6) n-butanol 592.8 parts (7) benzoyl peroxide 0.6 part (8) benzoyl peroxide 0.6 part The above four-necked flask (6) And 1 under nitrogen flow
The mixture was heated and stirred at 10 ° C, and the mixture of (1) to (5) was
3 hours after the addition, (7) was added 1 hour after the addition, (8) was added 1 hour later, the mixture was maintained at the same temperature for 1 hour, and solid content 30%, acid value 196, Number average molecular weight 10
000 acrylic resin (a1-1) solution was obtained.

Production Example 2 Production of Acrylic Resin (a1-2) Solution (1) 90.0 parts of styrene (2) 60.0 parts of ethyl acrylate (3) 150.0 parts of methacrylic acid (4) Benzoyl peroxide 3 0.0 part (5) n-butanol 100.0 parts (6) n-butanol 595.8 parts (7) benzoyl peroxide 0.6 part (8) benzoyl peroxide 0.6 part Reaction in the same manner as in Production Example 1 And an acrylic resin (a1) having a solid content of 30%, an acid value of 326, and a number average molecular weight of 15,000.
-2) A solution was obtained.

Production Example 3 Production of Polyester Resin (a2) Solution (1) Ethylene glycol 50.9 parts (2) Neopentyl glycol 85.1 parts (3) Adipic acid 88.6 parts (4) Terephthalic acid 100.7 Part (5) 99.7 parts of trimellitic anhydride (6) 345.0 parts of ethylene glycol monobutyl ether (7) 230.0 parts of n-butanol The above-mentioned (1) to (4) were charged into a four-necked flask, and a nitrogen gas flow was conducted. Then, the mixture was heated and stirred at 230 ° C., and reacted until the acid value became 5 or less, then cooled to 170 ° C., (5) was added, and the reaction was further continued when the acid value became 135 or less. Then, (6) to (7) were added, and the solid content was 40% and the acid value was 1
33, a polyester resin having a number average molecular weight of 3000 (a
2) A solution was obtained.

Production Example 4 Production of aqueous resin dispersion (1) 93.3 parts of ethylene glycol monobutyl ether (2) 140.0 parts of epicoat 1009 (3) 200.0 parts of acrylic resin (a1-2) solution (4) Dimethylethanolamine 13.0 parts (5) Ion-exchanged water 553.7 parts The above (1) and (2) were charged into a four-necked flask, and heated and stirred at 100 ° C. under a nitrogen stream to dissolve (2). Next, (3) was charged, and (4) was further charged at 80 ° C.
, And then cooled to 60 ° C. (5)
Was gradually added to obtain a milky white dispersion having a solid content of 20%. A part of the solvent was removed under reduced pressure, and the mixture was adjusted with ion-exchanged water to obtain a milky white dispersion having a solvent of 10% (ethylene glycol monobutyl ether 9%, n-butanol 1%) and a solid content of 20%. The obtained dispersion was stored at 50 ° C. for one month, and no abnormality was observed.

[0044]

Example 1 (1) Purified Carnauba No. 1 (mp. 82 ° C.) 100.0 parts (2) Acrylic resin (a1-1) solution 16.2 parts (3) Dimethylethanolamine 3.1 parts (4) 863.6 parts of ion-exchanged water The above (1) and (2) were charged into a four-necked flask (F1), and the mixture was heated to 90 ° C. while stirring under a nitrogen stream to dissolve and mix. In another four-necked flask (F2), the above (3)-
(4) was charged and heated to 90 ° C., and the stirring speed was 600 RPM.
The solution in the flask (F1) was gradually added to another flask (F2) while stirring with. After completion of the addition, the mixture is cooled to 40 ° C. or less while stirring, and the solid content is reduced to about 1%.
A 0.7% aqueous wax dispersion was obtained. The average particle size of the dispersed particles of the aqueous wax dispersion by a light scattering method is 30.
It was 0 nm. When the obtained dispersion was stored at 50 ° C. for 3 months, no abnormality was observed.

[0045]

Embodiment 2 ~

Example 8 According to the formulation shown in Table 1, a wax aqueous dispersion was obtained in the same manner as in Example 1. Table 1 shows the average particle size of the dispersed particles of each of the obtained aqueous wax dispersions by a light scattering method and the storage stability. In the case of the fourth embodiment,
In the flask (F1), purified carnauba wax and lanolin wax were charged, and in the case of Example 5, the flask (F1) was charged with purified carnauba wax and microcrystalline wax.

[0046]

Example 9 (1) Purified Carnauba No. 1 (mp. 82 ° C.) 100.0 parts (2) Acrylic resin (a1-1) solution 16.2 parts (3) Dimethylethanolamine 3.1 parts (4) 863.6 parts of ion-exchanged water The above (1) and (2) were charged into a four-necked flask (F1), and the mixture was heated to 90 ° C. while stirring under a nitrogen stream to dissolve and mix. In another four-necked flask (F2), the above (3)-
(4) was charged and heated to 90 ° C., and the stirring speed was 600 RPM.
The solution in the flask (F2) was gradually added to another flask (F1) while stirring with. After completion of the addition, the mixture is cooled to 40 ° C. or less while stirring, and the solid content is reduced to about 1%.
A 0.7% aqueous wax dispersion was obtained. The average particle size of the dispersed particles of the aqueous wax dispersion measured by a light scattering method is 42.
It was 0 nm. When the obtained dispersion was stored at 50 ° C. for 3 months, no abnormality was observed.

[0047]

Example 10 (1) Purified Carnauba No. 1 (mp. 82 ° C.) 100.0 parts (2) Acrylic resin (a1-1) solution 16.2 parts (3) Dimethylethanolamine 3.1 parts (4) 863.6 parts of ion-exchanged water The above-mentioned (1) and (2) are charged into a four-necked flask (F1), heated to 90 ° C. while stirring under a nitrogen stream, mixed and dissolved, and (3) is added to the mixed solution. Addition, then stirring speed 600R
While stirring with PM, (4) heated to 90 ° C. was gradually added. After completion of the addition, the mixture was cooled to 40 ° C. or lower with stirring as it was to obtain an aqueous wax dispersion having a solid content of 10.7%. The average particle diameter of the dispersed particles of the aqueous wax dispersion measured by a light scattering method was 400 nm. When the obtained dispersion was stored at 50 ° C. for 3 months, no abnormality was observed.

[0048]

Example 11 (1) Purified Carnauba No. 1 (mp. 82 ° C.) 100.0 parts (2) Acrylic resin (a1-1) solution 16.2 parts (3) Dimethylethanolamine 3.1 parts (4) 863.6 parts of ion-exchanged water The above-mentioned (1) and (2) are charged into a four-necked flask (F1), heated to 90 ° C. while stirring under a nitrogen stream, mixed and dissolved, and (3) is added to the mixed solution. added. Another flask (F2)
And heated to 90 ° C., stirring speed 600RP
While stirring at M, the mixture of the above (1) to (3) was gradually added. After completion of the addition, the mixture was cooled to 40 ° C. or lower while stirring to obtain an aqueous wax dispersion having a solid content of about 10.7%. The average particle size of the dispersed particles of the aqueous wax dispersion measured by a light scattering method was 380 nm. When the obtained dispersion was stored at 50 ° C. for 3 months, no abnormality was observed.

[0049]

Example 12 (1) Purified Carnauba No. 1 (mp. 82 ° C.) 100.0 parts (2) Acrylic resin (a1-1) solution 16.2 parts (3) Dimethylethanolamine 3.1 parts (4) 863.6 parts of ion-exchanged water The above (1) to (4) were charged into a four-necked flask (F1), and heated to 90 ° C. while stirring under a nitrogen stream to dissolve and mix. While maintaining 90 ± 5 ° C, stirring speed 1000RP
After stirring for 1 hour at M, when the average particle diameter of the wax dispersion reached the target particle diameter, the wax dispersion was cooled to 40 ° C. or lower while stirring to obtain an aqueous wax dispersion having a solid content of about 10.7%. The average particle diameter of this aqueous wax dispersion as measured by a light scattering method was 350 nm. Further, the obtained dispersion was
After storage at ℃ for 3 months, no abnormalities were observed.

[0050]

Example 13 (1) Acrylic resin (a1-1) solution 16.2 parts (2) Dimethylethanolamine 3.1 parts (3) Deionized water 863.6 parts (4) Purified Carnauba No. 1 (mp. (82 ° C.) 100.0 parts The above (1) to (3) were charged into a four-necked flask (F1), and heated and mixed at 90 ° C. while stirring under a nitrogen stream. The above (4) was charged into another four-necked flask (F2) and heated to 90 ° C. to be completely melted. Flask (F1)
The mixed solution of (1) to (3) was stirred at a stirring speed of 600 RP.
With stirring at M, the wax melt in the flask (F2) was gradually added to another flask (F1). After completion of the addition, the mixture is cooled to 40 ° C. or less while stirring,
An aqueous wax dispersion having a solid content of about 10.7% was obtained. The average particle diameter of this aqueous wax dispersion was 31 by a light scattering method.
It was 0 nm. When the obtained dispersion was stored at 50 ° C. for 3 months, no abnormality was observed.

[0051]

Embodiment 14

Example 16 According to the formulation shown in Table 1, an aqueous wax dispersion was obtained in the same manner as in Example 13. Table 1 shows the average particle size of the dispersed particles of each of the obtained aqueous wax dispersions by a light scattering method and the storage stability. Example 14
Was charged with purified carnauba wax and lanolin wax in a flask (F2) and heated to 90 ° C. to be completely melted.

[0052]

Example 17 (1) Purified Carnauba No. 1 (mp. 82 ° C.) 100.0 parts (2) Acrylic resin (a1-1) solution 16.2 parts (3) Dimethylethanolamine 3.1 parts (4) 863.6 parts of ion-exchanged water The above (1) was charged into a four-necked flask (F1), and heated to 90 ° C. while stirring under a nitrogen stream to completely melt.
The above (2) to (4) were charged into another four-necked flask (F2) and heated to 90 ° C. to dissolve. While stirring the melt in the flask (F1) at a stirring speed of 600 RPM, the solution in the flask (F2) was gradually added to another flask (F1). After the addition is completed, stir at 40 ° C
By cooling to below, an aqueous wax dispersion having a solid content of 10.7% was obtained. The average particle size of the dispersed particles of the aqueous wax dispersion measured by a light scattering method was 310 nm. When the obtained dispersion was stored at 50 ° C. for 3 months, no abnormality was observed.

[0053]

Example 18 Purified carnauba wax and lanolin wax were charged into a flask (F1) and heated to 90 ° C. to be completely melted. Otherwise, according to the formulation shown in Table 1, a wax aqueous dispersion was prepared in the same manner as in Example 17. Obtained. Table 1 shows the average particle diameter of the dispersed particles of the obtained aqueous wax dispersion by a light scattering method and the storage stability.

[0054]

[Table 1]

[0055]

Comparative Example 1 Production of aqueous wax dispersion (1) Purified Carnauba No. 1 100.0 parts (2) Stearic acid 2.0 parts (3) Butyl cellosolve 10.0 parts (4) Dimethylethanolamine 5.0 parts ( 5) 830.0 parts of ion-exchanged water The above (1) to (3) were charged into a four-necked flask (F1), and heated and dissolved at 90 ° C. under a nitrogen stream. The above (4) to (5) were charged into another four-necked flask (F2) at 90 ° C., and the solution in the flask (F1) was gradually poured into another flask (F2) while stirring at a stirring speed of 600 RPM. Was added. After completion of the addition, the mixture was cooled to 40 ° C. or lower while stirring as it was to obtain an aqueous wax dispersion having a solid content of about 10.8%. Table 2 shows the average particle size of the dispersed particles of the obtained aqueous wax dispersion, and the storage stability.

[0056]

[Comparative Example 2] ~

Comparative Example 3 According to the formulation shown in Table 2, a wax aqueous dispersion was obtained in the same manner as in Comparative Example 1. Table 2 shows the average particle size of the dispersed particles of the obtained aqueous wax dispersion, and the storage stability.

[0057]

Comparative Example 4 (1) Purified Carnauba No. 1 100.0 parts (2) Butyl cellosolve 10.0 parts (3) Dimethylethanolamine 8.0 parts (4) Butyl cellosolve 410.0 parts (5) Deionized water 420. 0 parts The above (1) to (3) were charged into a four-necked flask (F1) and heated and dissolved at 90 ° C. under a nitrogen stream. The above (4) to (5) were charged into another four-necked flask (F2) at 90 ° C., and the solution in the flask (F1) was gradually poured into another flask (F2) while stirring at a stirring speed of 600 RPM. Was added. After completion of the addition, the mixture was cooled to 40 ° C. or lower while stirring as it was to obtain an aqueous wax dispersion having a solid content of about 10.7%. Table 2 shows the average particle size of the dispersed particles of the obtained wax dispersion, and the storage stability.

[0058]

[Table 2]

Storage stability of the wax dispersion composition: 50
The sample was stored in a thermostat at ℃ and periodically evaluated for appearance properties and presence or absence of aggregates over 3 months. ○: Good storage stability ×: Abnormalities such as gelation, sedimentation, separation, and generation of aggregates occurred during storage.

[0060]

Embodiment 19

Embodiment 36 and

Comparative Example 5

Comparative Example 8 4 parts by weight of the aqueous wax dispersions obtained in Examples 1 to 18 and Comparative Examples 1 to 4 were added to 100 parts by weight of the solid content of the aqueous resin dispersion obtained in Production Example 4. Was added to obtain an aqueous coating composition. Using each of the obtained aqueous coating agents, a test panel was prepared under the following conditions, and various physical properties of the coating film were evaluated. The results are shown in Tables 3 and 4. Various test methods in Tables 3 and 4 are as follows.

Test panel preparation conditions: Each aqueous coating was
It was coated on a 0.30 mm aluminum plate by a bar coater so as to have a dry film thickness of 5 μm, baked at 200 ° C. for 5 minutes, and dried to prepare a test panel. (1) Dynamic friction coefficient: 1 kg load supported by three steel balls
At a speed of 150 cm / min to determine the dynamic friction coefficient. (2) Scratch value: Tribogear manufactured by Shinto Kagaku Co., Ltd.
HEIDON-22H type used, Measurement conditions: Continuous weighting method Scratch speed: 300 mm / min Scratch needle: Sapphire 100μ Measurement temperature: 25 ° C (3) Water resistance test: Dipped in hot water at 130 ° C for 30 minutes, paint film The presence or absence of abnormality is visually determined.・ ・ ・: No abnormality ×: An abnormality such as retort whitening occurred.

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

According to the present invention, by using an acrylic resin and / or a polyester resin having a carboxyl group as a dispersant, wax can be stably dispersed in an aqueous medium with a very small amount of resin. And it became possible to obtain a coating film excellent in lubricity, water repellency, and scratch resistance from the aqueous coating agent containing the aqueous wax dispersion of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuto Nakano 2-3-1-13 Kyobashi, Chuo-ku, Tokyo Inside Toyo Ink Manufacturing Co., Ltd.

Claims (13)

[Claims] At least one of a resin (A), a natural wax (b1) or a synthetic wax (b2) having an acid value of 100 to 500 and a number average molecular weight of 2000 to 50,000.
An aqueous dispersion of wax, characterized in that it comprises a wax (B), a volatile amine (C) and an aqueous medium (D). 2. The aqueous wax dispersion according to claim 1, wherein the resin (A) is at least one of an acrylic resin (a1) having a carboxyl group and a polyester resin (a2) having a carboxyl group. body. 3. A total of 10 of resin (A) and wax (B)
The aqueous wax dispersion according to claim 1 or 2, wherein the aqueous dispersion contains 1 to 50 parts by weight of the resin (A) and 50 to 99 parts by weight of the wax (C) in 0 part by weight. 4. A resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2000 to 50,000, and at least one wax (B) of a natural wax (b1) or a synthetic wax (b2). A method for producing an aqueous wax dispersion, which comprises adding the mixed liquid (E) to the volatile amine (C) and the aqueous medium (D) after forming the mixed liquid. 5. A resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2,000 to 50,000, and at least one wax (B) of a natural wax (b1) or a synthetic wax (b2). A method for producing an aqueous wax dispersion, comprising: adding a volatile amine (C) and an aqueous medium (D) to the mixed liquid (E) after the mixture is in a mixed liquid state. 6. A resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2,000 to 50,000, and at least one kind of wax (B) among natural wax (b1) and synthetic wax (b2). After the mixture is in a mixed liquid state, a volatile amine (C) is added to the mixed liquid (E) to obtain a mixture (F) of a resin (A), a wax (B) and a volatile amine (C). A method for producing an aqueous wax dispersion, comprising adding an aqueous medium (D) to (F). 7. A resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2,000 to 50,000, and at least one wax (B) of a natural wax (b1) or a synthetic wax (b2). After the mixture is in a mixed liquid state, a volatile amine (C) is added to the mixed liquid (E) to obtain a mixture (F) of the resin (A), the wax (B) and the volatile amine (C). A method for producing an aqueous wax dispersion, comprising adding the mixture (F) to (D). 8. At least one of resin (A), natural wax (b1) or synthetic wax (b2) having an acid value of 100 to 500 and a number average molecular weight of 2000 to 50,000.
A method for producing an aqueous wax dispersion, comprising stirring a mixture (G) of a wax (B), a volatile amine (C) and an aqueous medium (D) at a temperature equal to or higher than the melting point of the wax (B). . 9. An aqueous or aqueous solution of the resin (A) obtained by adding a volatile amine (C) and an aqueous medium (D) to a resin (A) having an acid value of 100 to 500 and a number average molecular weight of 2,000 to 50,000. A process for producing an aqueous wax dispersion, comprising adding at least one kind of wax (B) of the natural wax (b1) or the synthetic wax (b2) to the dispersion in a molten or dissolved state. 10. An acid value of 100 to 500 and a number average molecular weight of 2,000 to 50,000 in a melt or a melt of at least one of the natural wax (b1) and the synthetic wax (b2). A method for producing an aqueous wax dispersion, comprising adding an aqueous solution or an aqueous dispersion of a resin (A) obtained by adding a volatile amine (C) and an aqueous medium (D) to a resin (A). 11. The resin according to claim 4, wherein the resin (A) is at least one of an acrylic resin (a1) having a carboxyl group and a polyester resin (a2) having a carboxyl group. A method for producing an aqueous dispersion of a wax. 12. An aqueous coating composition comprising the aqueous wax dispersion according to claim 1. Description: 13. An aqueous coating composition comprising the aqueous wax dispersion obtained by the method for producing an aqueous wax dispersion according to claim 4. Description: