JPS6232154A - Maleinized alkyd resin emulsion paint composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which does not cause environmental pollution and has excellent flow-out, by blending a maleinized alkyd resin obtd. by maleinizing a condensate of an acid component and an alcohol component, a pigment and an alcoholic org. solvent. CONSTITUTION:An acid component (A) consisting of 45-68pts.(by weight, the same applies hereinbelow) (semi) drying oil and/or fat contg. at least 60wt% fatty acid thereof and/or said fatty acid (a), 8-25pts. arom. dibasic acid (anhydride) (h), 0-30pts. monobasic acid (c) other than component (a) and 0-20pts. polybasic acid (anhydride) (d) other than component (h) and an alcohol component (B) consisting of 5-25pts. tri-to hexahydric alcohol (e) (e.g. glycerol) and a dihydric alcohol component (f) are condensed.The condensate is maleinized to obtain a maleinized alkyd resin (C) having a fatty acid content of 50-70% and an acid value of 10-60. A mixture of 100pts. component C and a pigment (D) (e.g. titanium white) is mixed with an alcoholic org. solvent (E) to obtain the titled compsn. contg. not more than 5wt% component E.

Description

[Detailed Description of the Invention] A zero-invention maleated alkyd F'0 that is non-polluting, large, and excellent in flow development! %work! The present invention relates to a Rushosi paint composition.

Conventionally, water-soluble alkyd resin paints have been widely used because they are inexpensive and have excellent coating performance.

1. During the storage of the paint, the water-soluble alkyd resin of the vehicle component is easily hydrolyzed with water due to the antimeritic effect, and the ester bonds in the main chain are also hydrolyzed with water and a neutralizing agent. However, it becomes insoluble in water, causing sedimentation and aggregation, resulting in poor storage stability, and the coating film obtained by applying this paint has small irregularities on the surface of the object to be coated (for example, crystals from surface treatment, after etching, and from sandpaper). Because it picks up sanding marks (hereinafter simply referred to as "sanding"), it has the disadvantage of poor paint film appearance (texture, blurred gloss, etc.).

As for the storage stability, the method to improve these drawbacks is to make acid groups constituting the parent xylem exist on the surface of the emulsion particles, and the surface of the emulsion particles is composed of a lipophilic component. It can be improved by using The ability to pick up the substrate can be improved by incorporating a large amount of organic solvent into the maleated alkyd resin emulsion. However, objects coated using the former emulsion have a high surface tension and poor wettability to the coated object, resulting in poor substrate pick-up properties, and the latter emulsion suffers from organic solvents that remove emulsion particles during storage. Swelling causes water and neutralizing agents to be drawn into the inside of the emulsion particles, which accelerates the hydrolysis of the fat.As a result, the storage stability of the oil solution becomes poor, making it difficult to obtain an emulsion that satisfies both of these conditions. Deah nine.

Therefore, the inventors of the present invention have developed a method that has excellent storage stability, and that the coating film formed therefrom has excellent surface pick-up and coating properties! As a result of intensive research aimed at obtaining an excellent maleated alkyd resin emulsion paint composition, the emulsion particles themselves have strong lipophilic properties, and the inside of the particles contains specific alcohol and acid components. The emulsion has properties such as excellent storage stability, no tropism, and low surface tension by making it into a maleated resin with a compact structure with strong cohesive force. It was discovered that the material has excellent substrate pick-up properties9, and the present invention was completed.

That is, the present invention provides a (semi-)drying oil and/or its fatty acid (hereinafter referred to as "(semi-)drying oil fatty acid").
Fats and oils and/or their fatty acids (hereinafter referred to as "fatty acids") containing at least 60% by weight of 45-68
7 parts by weight, 8 to 25 parts by weight of an aromatic (anhydrous) dibasic acid, and 1 part by weight of a monobasic acid other than the above-mentioned fatty acids.

an acid component consisting of 0 to 30 parts by weight and 20 to 20 parts by weight of (anhydrous) polybasic #O other than the aromatic (anhydrous) dibasic acid; glycerile, trimethylolethane, trimethylolpropane, tris(2-hydroxyethyl); ) At least 1 s of tri- to hexa-hydric alcohol dissolved from isocyanurate, becitaerythritol, sorbitol (hereinafter referred to as "polyhydric alcohol") 5 to 25 times thick tooth shape dihydric alcohol 0 Fat made by maleating 12 of a condensation reaction product with an alcohol component consisting of 12 parts by weight #containing 150-7G, maleicized alkyd m fat 100] with an acid value of 10-60
The present invention relates to a malicated alkyd resin emulsion coating composition, which contains 150-toothed resin as a main component and contains an alcohol-based organic solvent in the coating composition in an amount of 5% by weight or less.

The maleated alkyd resin of the present invention contains fatty acids, aromatic (
Anhydrous) dibasic acids, polyhydric alcohols, and if necessary monobasic acids other than fatty acids, (anhydrous) polysalts, tea drinks, and dihydric alcohol components are combined and reacted with dehydration, followed by further maleation. Examples of the (semi)11F oil fatty acids that can be obtained include, for example, linseed oil,
7. Lawer oil, soybean oil, sesame oil, poppy seed oil, eno oil, hemp seed oil, budok kernel oil, sorghum oil, hi! Examples include those having an iodine value of 100 or more, such as warp oil, cottonseed oil, walnut oil, rubber seed oil, tung oil, tung oil, dehydrated castor oil, and fatty acids thereof and tall oil fatty acids. Among them, it is preferable to use linseed oil and its fatty acids, which are easily maleated and have good water dispersibility. These (half) $t'
The fatty acids within the scope of the present invention can be obtained by using drying oil fatty acids alone or in combination with (non-)drying oils and/or their fatty acids. The (semi)drying oil fatty acid amount in the fatty acid is 60
The content is more than 65% by weight, preferably more than 65% by weight.

If the content of the (semi-)drying oil fatty acid is less than 60% by weight, the addition reaction with maleic anhydride will be insufficient, making it impossible to obtain a stable emulsion, and the drying properties of the final coating will also be poor. . ! In addition, the amount of fatty acid added is 45 to 68
Parts by weight, preferably in the range of 50 to 65 parts by weight, 4
If the amount is less than 5 parts by weight, the pick-up of the substrate will be insufficient
If the amount is more than 8 parts by weight, the physical and chemical properties of the final coating film will be poor.

Non-drying oils and/or fatty acids thereof include, for example, coconut oil, rice bran oil, olive oil, palm oil, fallen main oil, rapeseed oil, and these fatty acids.

The monobasic acids other than fats and oils or fatty acids may be those used in the production of general alkyd resins, such as benzoic acid, P-tert-butylbenzoic acid, methylbenzoic acid, nonasic acid, and decanoic acid.

The monobasic acid can be used in an amount of 0 to 30 parts by weight.

The aromatic (anhydrous) dibasic acid has a molecular weight of 180 or less and is not hydrogenated, for example, (anhydrous) 7
Examples include tarric acid, isophthalic acid and terephthalic acid. The blending amount of the aromatic (anhydrous) dibasic acid is in the range of 8 to 25 parts by weight, preferably 10 to 20 parts by weight, and if it is less than 8 parts by weight, the drying properties and physical properties of the final coating film will be affected. It has poor physical and chemical properties, and if it exceeds 25 parts by weight, it has poor substrate pick-up properties. The effect of blending the aromatic (anhydrous) dibasic acid is obtained by combining the above-mentioned fatty acid and the following polyhydric alcohol. In other words, the emulsion obtained by combining these components has strong lipophilic properties, and the particle surface has a soft structure. Furthermore, the inside of the particles has a compact structure consisting mainly of aromatic dibasic acids and polyhydric alcohols, which has a strong cohesive force and is compact, which has a positive effect on coating drying properties and coating performance. It is something.

As the (anhydrous) polybasic acid, the above-mentioned aromatic (anhydrous) 2
Polybasic acids other than basic acids and/or their anhydrides, such as (anhydrous) maleic acid, (anhydrous) succinic acid, itaconic acid, adivicic acid, sepaticic acid, azelaic acid, (anhydrous) hymic acid, tetrahydro( Examples include 7-talic acid anhydride, trimellitic anhydride, methylcyclohexene tricarboxylic acid anhydride, and pyromellitic acid anhydride.

The (anhydrous) polybasic acid can be used in an amount of 0 to 20 parts by weight.

Polyhydric alcohols have relatively small molecular weights and are trivalent to hexavalent alcohols, such as glycerin, trimethylolethane, trimethylolethane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, cichentaerythritol, and Sorbitol etc. The amount of the polyhydric alcohol blended is in the range of 5 to 25 parts by weight, preferably 8 to 20 parts by weight. If the blending amount of the polyhydric alcohol is outside the range of 5 to 25 parts by weight, it will not be possible to obtain an emulsion composition having the structure described for the (anhydrous) aromatic dibasic acid, and as a result, the storage stability will be poor.
The balance between coating drying properties and coating performance will be poor.

The dihydric alcohol may be one that is used in the production of general alkyd resins, such as ethylene glycol 1,1 alcohol, polyethylene glycol, phlopyrecylic alcohol I, polypropylene glycol I, butanediol, decanediol, Diethylene crico I, hentanedio-
1, neopentyl glycol, 1,4-cyclohexane dimetatool, tricyclodecane methanol and the like. The dihydric alcohol can be used in an amount of 0 to 12 parts by weight, preferably 1 to 10 parts by weight. When the amount of dihydric alcohol 11 is more than 12 parts by weight, the coating film has excellent substrate pick-up properties and coating film additivity, but is poor in coating film hardness, water resistance, and salt spray resistance, and cannot be used practically.

The maleated alkyd resin is prepared by mixing each of the above components in an inert gas atmosphere for about 1 hour
A dehydration condensation reaction is carried out at 50 to about 250°C for about 3 to about 15 hours to synthesize an alkyd resin, and then maleic anhydride is added to the alkyd resin and the reaction is carried out at about 150 to about 220°C for about 1 to about 15 hours.
This can be carried out by carrying out a maricization reaction for about 5 hours.

The maleated alkyd resin thus obtained has a fatty acid content [the fatty acid content is determined by the formula: fatty acid amount (converted to fatty acid if oil is used) x 100/maleated alkyd resin solid content] of 50 to 70. range of,
The fatty acid content is in the range of 55 to 65, and if the fatty acid content is less than 50, the final coating film has poor substrate pick-up properties, and if it is greater than 70, the coating film performance is poor. No. 1. <No. The acid value of the resin is in the range of 10 to 60, preferably 15 to 50. If the acid value is less than 10, the water dispersibility is poor, and if it is greater than 70, the resin is water soluble. This is undesirable because it tends to be easily hydrolyzed, resulting in poor storage stability and impairing the water resistance of the final coating film.Also, the viscosity of the resin is not limited; Foam viscometer value is in the range of E-z, preferably H-22
range. When the Gardner foam viscometer value is E, water dispersion is easy, but the stability of the emulsion is poor and it is difficult to balance the two, and the water resistance of the coating film is also poor. Conversely, if the value is greater than 25,
Water education becomes difficult.

To prepare the maleated alkyd resin emulsion coating composition of the present invention, the maleated alkyd resin is preferably neutralized with a neutralizing agent and diluted with an alcoholic organic solvent if necessary after or before neutralization. If it has not been neutralized, after neutralization, add deionized water to the resin solution to form an emulsion, then remove the solvent from the resulting emulsion by vacuum distillation, and then add the pigment or make it into a mosuke emulsion. This can be done by blending a pigment and then removing the solvent by distillation under reduced pressure so that the content of the alcoholic organic solvent in the emulsion coating composition is 5% by weight or less.

The neutralizing agents used are ammonia and organic amines to hydrate the maleated alkyd resin;
For example, primary, secondary, or tertiary alkylamines, representative examples include methifuramine, ethylamine,
Propylamine, spotted.

l Reamine, amylamine, diptylamin, diptylamin, diprobi! Raamine, diptylamine, trimethylamine, triethylamine, triethylamine, morpholine; primary, secondary, or tertiary alkanolamines; representative examples include monoethanolamine;
These include jetanolamine, dimethylethanolamine, and diethylethanolamine. Among these neutralizing agents, ammonia, diptylamine, triethylamine, and dimethylethanolamine are preferred because they have good dispersibility and are highly volatile and do not easily remain in the coating film.

Further, the above neutralizing agents can be used alone or in combination of two or more. The amount of neutralizing agent used is generally 0.1 to 2.0 equivalents, preferably 0.1 to 2.0 equivalents, based on the carboxyl group in the resin.
It is 3 to 1.0 equivalent.

The alcohol-based organic solvent is one that helps the dispersion of the maleated alkyd resin in water, and is an organic solvent that can be removed under reduced pressure and has a polar group that dissolves the maleated alkyd resin and is miscible with water. It is a solvent.

Examples of such organic solvents include those having the formula HO-CmH2m+
1 (wherein m is an integer of 2 to 6), such as ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, iso-butyl alcohol, 5eC-butyl alcohol, tert
-7' thyl alcohol, isoamyl alcohol, 5eC
-amyl alcohol, tert-amyl alcohol, etc. 2
Formula HO-CoH2n-0-CpH2,+1 (wherein,
n#-i2-4 and p represent an integer of 1-4. ), such as ethylene glycol monomethyl ether monoethyl ether, glycol 7-methyl ether 3-methoxy-3-methyl-butanol,
Examples include ethylene glycol motubutyl ether.

Among the above alcohol-based organic solvents, Mononoke is preferable,
It is an alcohol having HO-CmH2m+1. The amount of the alcoholic organic solvent used may be 1,100 parts by weight or less, preferably 20 to 60 parts by weight, based on 100 parts by weight of the solid content of the maleated alkyd resin. If the amount of the organic solvent is more than 5% by weight based on the final emulsion coating composition, it is removed to 5% by weight or less. The temperature at which the neutralized resin solution is water-edified and the organic solvent removed from the emulsion under reduced pressure are preferably in the range of about 20 to about 60°C. In addition, high boiling point alcoholic organic solvents other than those listed above may also be present in an amount of 5% by weight or less based on the emulsion coating composition.
It can be contained preferably within a range of 2% by weight or less.

The solid fraction of the thus obtained daleinated resin emulsion coating composition is, but not limited to, in the range of 20 to 65% by weight, preferably in the range of 25 to 55% by weight, and the following average as measured by a turbidity method: The particle diameter value is 0.6μ or less, preferably #-i0.3μ or less. If the average particle size is larger than 0.6 μm, the sedimentation stability of the maleated alkyd resin (Emarunyo) will be poor, and the water resistance and corrosion resistance of the coating film will also be poor. The turbidity method referred to here is based on the literature (Bull, Indus), in which a water-diluted clear emulsion is measured with a spectrophotometer and the absorbance ratio is calculated using the following formula.
trial.

Chemical, Research VoL, 4
2 P. 145-152 (1964)) to determine the average particle diameter.

The pigment used in the present invention is preferably a commonly used inorganic or organic pigment dispersed with a known aqueous dispersion stabilizer. As inorganic pigments, (1)
Oxide-based (zinc white, titanium dioxide, red iron oxide, chromium oxide, cobalt flue, iron black, etc.): (2) Hydroxide-based (alumina white, yellow iron oxide, etc.): (3) Sulfide, selenide-based ( (zinc sulfide) vermilion, cadmicum yellow, cadmicum red, etc.); (4) 7erocyanide type (prussian blue, etc.):
(5) Chromate-based (yellow, zinc chromate, molybdenum red, etc.); (6) Sulfate-based (precipitated Paricum sulfate, etc.); (7) Carbonate-based (Precipitated Paricum sulfate, etc.); (
8) Silicate base (hydrated silicate, clay, ultramarine, etc.): (9)
Phosphate type (manganese bioleft etc.): (10) i
iM (carbon black, etc.); (11) metal powder-based materials (aluminum powder, bronze powder, lead powder, etc.), and organic materials include (1) nitroso@t+-based materials (Narlatol Green B, etc.); ): (2) Nitroso pigment type (
7 Tall Yellow 549): (3) Azo pigment type (litho-
/L/ L/Rat Lake Red C1 Fast Yellow,
Naphthol Red, Red, etc.): (4) Dyeing Lake Pigment System (Alkali Blue Lake, Roguemin Lake '41-
): (5) Phthalocyanine pigments (phthalocyanine blue, 7 ast sky blue, etc.): (6) Condensed polycyclic pigment yarns (perylene red, quinacridone red, dioxadithi violet, iso-f-nitrinone yellow, etc.)
Examples include.

The blending amount of Sunta@ can vary within a wide range depending on the S@ of the pigment and the degree of coloring required for the final coating f+4, but it is 3 to 150 parts by weight per 100 parts by weight of maleated alkyd 111t greasy round part. This is within the scope of the department. If the amount of pigment is less than 3 V silver parts, it becomes meaningless as it becomes difficult to stand out when picking up the base material, whereas if it is more than 150 M parts, the smoothness of the final coating film will be poor, which is not preferable.

As the aqueous pigment dispersion stabilizer, conventionally known ones can be used. Nonionic-aniosylic surfactants such as sodium lafricate: Carboxylate-type anionic surfactants such as sodium lafricate and sodium stearate: β-nafucrene sulfosic acid formalin conjugate, sodium frecy maleic acid polymer Examples include oligomer or polymer type surfactants such as salts, copolymers of acrylic monomers and di- or vinyl monomers, and the like.

Preparation of pigments in aqueous pigment dispersants can be carried out by mixing together the above components in a suitable dispersion apparatus; fractional apparatuses that can be used include:
Examples include ball mills, roll mills, homomixers, sand grinders, shakers, and attritors that are commonly used in the paint industry.

The maleated alkyd resin emulsion composition of the present invention may further contain optionally a plasticizer, a dryer, an antifoaming agent, a thickener, a preservative, an emulsion or an aqueous resin other than those mentioned above, and the like.

The coating film formed from the composition of the present invention is sufficiently crosslinked and cured at room temperature, but when heated in the presence or absence of an amino resin, etc., it cures in a short time and provides a coating film with good water resistance, corrosion resistance, etc. is obtained.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Hereinafter, parts and % indicate parts by weight and % by weight.

In a reaction vessel for producing maleated alkyd resin (2), 727 parts of linseed oil and 165 parts of pentaerythritol were added with 0.4 part of lead oxide, and while stirring under nitrogen atmosphere, 230 parts of lead oxide was added.
The esterification reaction was carried out for 40 minutes at −40°C, and then the temperature was increased to 200°C.
The temperature was lowered to 24°C, and 249 parts of isophthalic acid, 196 parts of benzoic acid, an esterification catalyst, a color inhibitor, and an antifoaming agent were added.
Dehydration was carried out at 0°C for 10 hours to obtain an alkyd resin with an acid value of 4.1. Subsequently, the alkyd resin was cooled to 200°C, 53 parts of maleic anhydride and a color inhibitor were added,
Maleation reaction was carried out at 200°C for 3 hours. Next, water was added to the obtained nine maleate to perform a ring-opening reaction, resulting in a resin acid value of 44.8, fatty acid content of 53, and a Gardner viscosity (resin of 6
0 part was dissolved with 23 parts of butyl cellosolve and 17 parts of isopropyl alcohol to obtain a maleated alkyd resin (up to 1) with a Gardner viscosity and a color number of less than 1, and the measurement of Gardner viscosity and color number also showed the same meaning.

! 374 parts of linseed oil fatty acid 221 parts of isophthalic acid were added to the reaction vessel on the production side of the rained alkyd resin (■).
parts, 246 parts of pentaerythritol and 182 parts of benzoic acid.
of the mixture, and further added an esterification catalyst, a color inhibitor, and an antifoaming agent, and the mixture was heated for 240 min with stirring under a nitrogen atmosphere.
The dehydration condensation reaction was carried out for 40 minutes at ℃, and then the temperature was lowered to 20℃.
The temperature was lowered to 0°C, 269 parts of soybean oil fatty acid and 134 parts of linseed oil fatty acid were added, and then the temperature was further raised to 240°C and dehydration condensation was carried out for 10 hours to obtain an alkyd resin with an acid value of 5. Subsequently, the alkyd resin was cooled to 200°C, 53 parts of maleic anhydride and a coloring inhibitor were added, and the mixture was heated at 200°C.
Be sure to carry out the maleation reaction for some time.

Next, 545 parts of linseed oil and 124 parts of pentaerythritol were added to the reaction vessel for producing maleated alkyd resin (0) to obtain a maleated alkyd resin (Peng) by adding water to the maleated product and carrying out a ring-opening reaction. After adding 0.4 parts of lead oxide, an esterification reaction was carried out at 230°C for 40 minutes while stirring under a nitrogen atmosphere, and then the temperature was lowered to 200°C and 249 parts of isophthalic acid, 41 parts of pentaerythritol, and 19 parts of glycerin were added. , 196 parts of benzoic acid, 174 parts of rice bran oil fatty acid, an esterification catalyst, a color inhibitor and an antifoaming agent were added.
Dehydration condensation was carried out at 0'C for 10 hours to obtain an alkyd resin with an acid value of 6.9. Subsequently, the alkyd resin was heated to 200°C.
53 parts of maleic anhydride and a color inhibitor were added.
The maleation reaction was then carried out at 200°C for 3 hours. Next, water is added to the maleated product to perform a ring-opening reaction to obtain a maleated alkyd resin (O).

675 parts of linseed oil fatty acid, 209 parts of isophthalic acid, 234 parts of pentaerythritol, and 205 parts of benzoic acid were added to the reaction vessel for the production of maleated alkyd resin (g), and then an esterification catalyst and an antifoaming agent were added. A dehydration bonding reaction was carried out at 240° C. for 8 hours while stirring in an atmosphere to obtain an alkyd resin with an acid value of 1.7. The temperature of the alkyd resin was then lowered to 200°C, 52 parts of maleic anhydride was added, and a maleation reaction was carried out at 200°C for 3 hours. Next, water was added to the maleated product to perform a ring-opening reaction to obtain a maleated alkyd resin.

After adding 720 parts of linseed oil fatty acid, 256 parts of isophthalic acid, 165 parts of pentaerythritol, 113 parts of trimethylolpropane, and 175 parts of benzoic acid to a reaction vessel on the production side of maleated alkyd resin (El), and adding an esterification catalyst and an antifoaming agent, nitrogen 240℃-1 while stirring under atmosphere
A partial dehydration condensation reaction was carried out to obtain an alkyd resin with an acid value of 1.4. Subsequently, the alkyd resin was cooled to 200°C, 55 parts of maleic anhydride was added, and a maleation reaction was carried out at 200°C for 3 hours. Next, water was added to the maleated product to perform a ring-opening reaction to obtain a maleated alkyd resin (E).

Maleated alkyd resin (696 parts of linseed oil fatty acid, 826 parts of isophthalic acid in the reaction vessel on the production side of E)
3. Add 165 parts of pentaerythritol, 76 parts of glycerin and 176 parts of benzoic acid, and further add an esterification catalyst,
After adding the antifoaming agent, it was heated to 240°C while stirring under a nitrogen atmosphere.
A dehydration condensation reaction was then carried out at -9 hours to obtain an alkyd resin with an acid value of 2.3.

Subsequently, the alkyd resin was lowered to 200'C, 53 parts of maleic anhydride was added, and a maleation reaction was carried out at 200C for 3 hours. Next, water was added to the maleated product to perform a ring-opening reaction to obtain a maleated alkyd resin (F).

Add 727 parts of linseed oil and 165 parts of pentaerythritol to a reaction vessel on the production side of maleated alkyd resin (Q), add 0.4 parts of lead oxide, and then esterify at 230°C for 40 minutes with stirring under nitrogen atmosphere. The reaction was carried out, and then the temperature was lowered to 200°C, 249 parts of isophthalic acid, 450 parts of soybean oil fatty acid, an esterification catalyst and an antifoaming agent were added, and dehydration condensation was carried out at 240°C for 1 part hour to obtain an acid value of 2.8. The alkyd resin was then cooled to 200°C and maleic anhydride 6 was added.
3 parts and a coloring inhibitor were added and the maleation reaction was carried out at 200°C for 3 hours. Next, water was added to the maleated product to perform a ring-opening reaction to obtain a maleated alkyd resin (Q).

478 parts of linseed oil fatty acid and 21 parts of isophthalic acid were added to the reaction vessel for the production of maleated alkyd resin (■).
8 parts, 263 parts of pentaerythritol and 37 parts of benzoic acid.
After adding 5 parts of esterification catalyst, anti-coloring agent and antifoaming agent, the mixture was heated to 240°C with stirring under nitrogen atmosphere.
- A dehydration condensation reaction was carried out for 10 hours to obtain an alkyd resin with an acid value of 4.6.

Subsequently, the temperature of the alkyd resin was lowered to 200°C, and 46 parts of maleic anhydride and a coloring inhibitor were added to carry out a raining reaction at 200°C for 3 hours. Next, water is added to the maleated compound to perform a ring-opening reaction to form a maleated alkyd resin (T).
Get the next one.

In a reaction vessel for producing maleated alkyd tree FNI (1), 675 parts of linseed oil fatty acid, 335 parts of isophthalic acid, 109 parts of pentaerythritol, and 19 parts of diethylene glycol were added.
5 parts of benzoic acid and 32 parts of benzoic acid were added, and then the esterification catalyst and antifoaming agent were added.
Dehydration M reaction was carried out at 0° C. for 10 hours to obtain an alkyd resin with an acid value of 1.8. Continue to add 200% of the alkyd resin.
℃ and added 53 parts of maleic anhydride to 200℃-3.
Next, carry out the maleation reaction for a time. Next, water is added to the maleated product to perform a ring-opening reaction, and the maleated alkyd resin (
I) was obtained.

Table 1 summarizes the raw material charging compositions of the maleated alkyd resins (4) to (I) of the above production examples and the characteristic values of the resins.

Example 1 126 parts of isopropyl alcohol (IO) was added to 420 parts of the nine-maleated alkyd resin powder obtained in the above production example, and 1.0 equivalent of triethylamine was added thereto.
Approximately 650 parts of deionized water was added dropwise at 50° C. over 2 hours to obtain an emulsion.

Subsequently, the emulsion was distilled under reduced pressure while being maintained at 40 to 50°C to remove isopropyl alcohol.

Next, the emulsion coating composition of Example 1 was obtained by blending the titanium self-dispersion described below into the emulsion.

Examples 2 to 8 Maleated alkyd resins (4) to (F
126 parts of isopropyl alcohol was added to 420 parts of each using 420 parts of triethylamine, and triethylamine was further neutralized with the neutralization equivalent shown in Table 2. After that, emulsification was carried out in the same manner as in Example 1, and decomposition was carried out by vacuum distillation. Next, a pigment-free emulsion was obtained by using a solvent.

Next, to the emulsion was added a reagent separation liquid according to the formulation shown in Table 2 to obtain emulsion coating compositions of Examples 2 to 8.

Comparative Examples 1 to 4 Maleated alkyd resins (Q to (1)
1 part of isopropyl alcohol to 420 parts of each
After adding 26 parts of triethylamine and neutralizing it with the neutralization equivalent shown in Table 2, emulsification was carried out in the same manner as in Example 1, and the solvent was removed by distillation under reduced pressure to obtain an emulsion that did not contain any additives. Just in case. Next, add the emulsion to the
Comparative Example 1 by adding face P + teaching liquid according to the formulation shown in 2.
~4 emulsion paints I got mine.

Tables 2 and 3 show the test results for the properties, storage stability, and coating performance of the emulsion paint compositions obtained in the above Examples and Comparative Examples.

Further, 30 parts of isopropyl alcohol (based on 100 parts of maleated alkyd resin) was added to the emulsion paints of Examples 1 to 8 and Comparative Examples 1 to 4, and after t, the temperature was 40°C.
Storage was carried out. As a result, the particle size increased by 3 to 6 times compared to the initial one within one month, and when continued for two months, all of the products became thickened and gelled, showing worse storage stability than those obtained by removing the solvent.

(1) Titanium self-dispersion liquid: Aqueous pigment dispersion liquid made by neutralizing a copolymer of fatty acid-modified glycidi, Remecrylate, acrylic acid, and vinylpyrrolidone, and titanium white pigment (manufactured by Sakai Kagaku Co., Ltd. - trade name Titanium White) R-5N) (in addition,
Titanium white pigment/resin content of aqueous pigment separation liquid l-136/1
A titanium white pigment liquid was obtained by adding water to the mixture (with a mixing ratio of The blending amount indicates the amount of titanium white pigment per 100 parts of solid content of emulsion.

Carbon black pigment dispersion 2 A mixture of the same aqueous pigment dispersion used in the above titanium self-teaching solution 9 (manufactured by Mitsubishi Kasei Corporation, trade name Carbon MA100) (The resin content of the carbon black pigment/aqueous pigment dispersion is Add water to the mixture (mixing ratio of 9/1) and use a Red Devi 1 minute teaching machine to mix it to 0.
A carbon black dynamic rod dispersion was obtained after 5 hours. The blending amount indicates the amount of carbon black pigment based on 100 parts of resin solid content of the emulsion.

(2) Solid content: In Examples 3 to 8 and Comparative Examples 1 and 4, the solid content was adjusted to 35.0% with deionized water. Initial characteristics and storage tests of emulsions were conducted using the prepared solid content Examples or Comparative Examples.

(3) Amount of residual solvent: Measured using a gas chromatograph, and the amount of isopropyl afrecol in the next emulsion was expressed in %.

(4) Viscosity Value of centivoise (rotation: 30 rpm) when measured using a Type 2 B viscometer.

[Coating film creation and coating film performance test]

In the Examples and Comparative Examples, 2% of the water-based dryer (product name: 1 Dekunate'', manufactured by Dainichi Ink Co., Ltd.) was added to the solid content of the nine emulsion compositions obtained in the Examples and Comparative Examples, and the mixture was polished with Sand Vapana 320 and painted on a mild steel plate. Drying was carried out in an atmosphere with a relative humidity of 75%.

The substrate pick-up properties and coating performance were compared using the following tests, which were dried for 7 days.

Ability to pick up the substrate: The outer coating (after polishing) was evaluated by 1 polishing. (○: Good, ■: Slightly inferior, Δ: Poor, ×: Significantly inferior) Adhesiveness: After making 100 1m-wide gopashi seams, pasting Seven Roaan adhesive tape on top of them and peeling them off vigorously, the following cutting was performed. Observe the number of pieces.

Processability A: Performed using an Elixessi extrusion tester. Extrusion that does not cause cracking of the coating film, & is shown below.

Workability B: Tested using a Dubosi impact tester. The number of heights at which the coating film does not crack under the conditions of rod diameter = 1/2 inch and load IKt (* indicates use at 500F) is shown.

Water resistance: The coated surface was immersed in tap water at 20° C. for 1 day and visually observed. (○: Good, Q: Whitening, △: Significant whitening, ×: Glossy fading) Salt water spray resistance: #t, Wk according to JIS K 5400 7.8. No from cross cut
The width of the crease (-number) is shown.

Claims (1)

[Claims] (semi) drying oil and/or fat containing at least 60% by weight of its fatty acids and/or its fatty acids 45 to 68 parts by weight, aromatic (anhydrous) dibasic acids 8 to 25 parts by weight, monobasic acids other than the above fatty acids an acid component consisting of 0 to 30 parts by weight, and 0 to 20 parts by weight of an (anhydrous) polybasic acid other than the aromatic (anhydrous) dibasic acid, glycerin, trimethylolethane,
5 to 25 parts by weight of at least one tri- to hexa-hydric alcohol selected from trimethylolpropane, tris(2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol and sorbitol, and 2
A fatty acid content of 50 to 50%, obtained by maleating a condensation reaction product with an alcohol component consisting of 0 to 12 parts by weight of a hydric alcohol.
70, maleated alkyd resin with acid value 10-60 100
1. A maleated alkyd resin emulsion coating composition, which contains 3 to 150 parts by weight of a pigment and an alcohol-based organic solvent in an amount of 5% by weight or less.