JPS6136372A - Water-dispersible resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved water dispersibility, storage stability, and little coloring of film of coating, obtained by reacting an alkyd resin modified with fats and oils having a specific iodine value with maleic anhydride to give a maleinized alkyd resin, neutralizing it, and dispersing it into water. CONSTITUTION:(A) (i) Fats oils having 135-175 iodine value and/or fatty acid, containing 0-30wt%, preferably 1.5-25wt% linoleic acid is reacted with (ii) a polybasic acid (phthalic acid, etc.), (iii) a monobasic acid (e.g., benzoic acid, etc.), and (iv) a polyhydric alcohol (e.g., ethylene glycol, etc.) to give an alkyd resin having 35-80 oil length, which is reacted with (B) maleic anhydride, to give the prepared maleinized alkyd resin having 10-70 acid value, which is neutralized, and dispersed into water, to give the aimed composition. EFFECT:A film of coating having improved water and corrosion resistance is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION A maleated alkyd resin emulsion composition has been invented, which has excellent water dispersibility, extremely good storage stability, and its application WI! This invention relates to a maleated alkyd resin emulsion composition that has little coloration and excellent properties such as water resistance and corrosion resistance.

In recent years, water-soluble alkyd resins have been widely used as vehicle components for general and industrial paints due to their low cost and non-polluting properties.

Conventionally, the water-soluble alkyd resin W& has been generally converted into a halfester using phthalic anhydride, trimellitic anhydride, etc. as a method of introducing an acid necessary for making the alkyd resin water-soluble.

The water-soluble alkyd resin thus obtained is easily hydrolyzed due to the achymeric effect, and the water-soluble alkyd resin becomes insolubilized, resulting in poor storage stability. Furthermore, since the main chain of the water-soluble alkyd resin also has an ester bond, it is hydrolyzed by water and a neutralizing agent, and the main chain of the water-soluble alkyd resin is severed, resulting in poor storage stability.

As an attempt to improve these drawbacks, there is a method of introducing an acid by maleation. The maleated alkyd resin emulsion obtained by this method has acid groups constituting the parent xylem on the particle surface, and the particle interface is composed of a highly lipophilic oily component, so it is difficult to absorb water and neutralizing agents. It is stable against In addition, in order to easily increase the water content of maleated alkyd resin, conventional methods have used a large amount of amphipathic organic solvent for maleated alkyd resin, but this method generally involves a large amount of contact with the maleated alkyd resin, resulting in hydrolysis and the maleated alkyd resin. Poor storage stability due to insolubilization. Furthermore, even if the aqueous dispersion is in the emulsion range, the amphiphilic organic solvent swells the maleated alkyd resin emulsion particles during storage, and furthermore, water and neutralization occur inside the maleated alkyd resin emulsion particles. Storage stability is poor because the agent is drawn in. When maleating alkyd resins, alkyd resins modified with linseed oil fatty acids containing a large amount of unsaturated fatty acids (especially 1-lyluic acid) having three active double bonds in one molecule will not undergo maleation reaction. The obtained linseed oil fatty acid-modified maleated alkyd resin has excellent water dispersibility, but the coating film obtained from this aqueous dispersion is colored, which limits its use. there were.

Therefore, the present inventors conducted intensive research with the aim of obtaining a maleated alkyd resin emulsion composition that has excellent water dispersibility, little coloring of the coating film formed therefrom, and excellent water resistance. As a result, the present invention was completed.

That is, the present invention provides oils and/or fatty acids modified with an iodine value of 135 to 175 (hereinafter sometimes referred to as mono-Kr dry (semi-) fatty acids), and
Alternatively, a maleated alkyd resin with an acid value of 10 to 70 obtained by reacting maleic anhydride to an alkyd resin with an oil length of 35 to 80 containing 30% by weight or less of liluic acid in the fatty acid component is neutralized and dispersed in water. The present invention relates to a maleated alkyd resin emulsion composition comprising No. 17.

The maleated alkyd resin used in Kihatsu MK is obtained mainly by reacting dry (semi) oil fatty acids, polybasic acids, -basic acids, and polyhydric alcohols, and further by reacting maleic anhydride. .

Typical dry (semi-) fatty acids used include, for example, linseed oil, soybean oil, soybean oil, horse sorghum oil, cottonseed oil, grape kernel oil, hemp oil, eno oil, poppy seed oil, and sugarcane oil. Examples include fatty acids such as oil, rice bran oil, and tall oil fatty acids, and these are used alone or in combination of two or more so that the iodine value falls within the range of 135 to 175.

The dry (raw) oil fatty acid has an iodine value of 135 to 175,
Good maneuverability 140-170, even better trench maneuverability 145-
It is necessary that the iodine value is 165, and those with an iodine value lower than 135 will become maleic and difficult to disperse in water, and the coating film obtained from the aqueous dispersion will not be sufficiently cured. Poor coating performance. On the other hand, if the iodine value is higher than 175, there is a drawback that the resulting coating film is markedly colored. Furthermore, the amount of riluic acid that can be contained as a component of the dry (semi-) fatty acid is 0 to 3.
0% by weight, preferably about 1.5 to about 2 in terms of water dispersibility
It is 5%. The content of riluic acid can be changed as required, but if the amount of riluic acid exceeds 30% by weight, there is a drawback that the resulting coating film will be significantly colored. In addition, it is necessary that the content of the 9,11-linoleic acid component having a conjugated double bond in the dry (raw) external fatty acid is less than 10% by weight, and if it exceeds 10% by weight, the maleation reaction There is a risk of gelation during resin synthesis.

Polybasic acid I7 is a compound having 2 to 4 carboxyl groups in one molecule. Specifically, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid,
Tetrahydrophthalic acid, cono-phosphoric acid, maleic acid, adipic acid, yapatic acid, azelaic acid, hymic acid, itaconic acid, methylcyclohexane tricarboxylic acid, crotonic acid, pyromellitic acid and their anhydrides, etc. may be used. I can do it. Among these, phthalic acid, isophthalic acid, and terephthalic acid are preferred.

Examples of the monobasic acid include benzoic acid, paratertiary glutyl benzoic acid, methylbenzoic acid, non-drying oil fatty acids and synthetic fatty acids, which do not contain the above-mentioned fatty acids and are generally used in the production of alkyd resins. Among these, benzoic acid is preferred because it is low cost and has high coating film hardness.

The polyhydric alcohol is an alcohol having 2 to 6 hydroxyl groups in one molecule, and specifically includes ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, bucundiol, decanediol, diethylene glycol, bentanediol, Examples include neopentyl glycol, chrycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, 1.4 cyclohexane dimetatool, tricyclodecane dimetatool, and tris isocyanurate. Furthermore, in addition to polyhydric alcohols, epoxy resins can also be used as alkyd resin components. The alkyd m fat components described above can be used alone or in combination of two or more.

Alkyd resin GL! The above-mentioned components were mixed in an inert gas atmosphere in accordance with a synthetic method known per se to about 150%
This can be carried out by carrying out a dehydration condensation reaction at ~250°C for about 3 to 10 hours.

Next, to synthesize the maleated alkyd resin, the mixture of the above-mentioned alkyd resin ♂ ruic anhydride is heated at about 150 to about 230°C.
This is carried out by reacting for about 1 to about 5 hours. The acid value Fi of the maleated alkyd resin thus obtained
It should be in the range 10-70, preferably in the range 20-55.

When the acid value is less than 10, water dispersion becomes difficult, and when it is more than 70, the water resistance of the coating film is impaired.

The oil strength of the maleated alkyd resin used in the present invention,
The range is 35-80, preferably 40-65. If the oil length is less than 35, the amount of maleic anhydride added will be small, making it impossible to obtain a stable maleated alkyd resin emulsion composition, and the number of active double bonds required for curing one coating film will be small, resulting in sufficient curing. No coating film can be obtained. On the other hand, if it is more than 80, the amount of maleic anhydride necessary for water solubilization increases, the acid value of the maleated alkyd resin becomes high, and the water resistance of the resulting coating film is poor.

The viscosity of the maleated alkyd resin used in the present invention,
Although not limited to, a 60% by weight diluted butyl cellosorg solution has a Gardner foam viscometer value in the range of 0-ZS, preferably in the range of Q=Z3, more preferably in the range of T-22.

When the Gardner foam viscometer value is less than 0, water dispersion becomes easy, but the stability of the emulsion deteriorates, making it difficult to maintain a balance between the two, and the water resistance of the coating film is also poor.

Conversely, if the value is greater than 25, water dispersion becomes difficult.

Neutralizing agents used in the present invention include ammonia and organic amines for water dispersing the maleated alkyd resin, such as Fi primary, secondary or 41FJ tertiary alkyl amines, representative ones. Methylamine,
Ethylamine, glutylamine, glutylamine, amylamine, dimethylamine, diethylamine, dipropylamine, digtylamine, trimethylamine, triethylamine tripropylamine, morpholine; No. 19.32
Typical examples include monoethanolamine, jetanolamine, dimethylethanolamine, and diethylethanolamine. Among these neutralizing agents, ammonia diethylamine, triethylamine, and dimethylethanolamine are preferred because they have good dispersibility, remain in the coating film, and are highly volatile. Further, the above neutralizing agents can be used alone or in combination of two or more. The amount of neutralizing agent used is generally 1,0.1 to 2.0 per carboxyl group in the resin.
equivalent, preferably 0.3 to 1.0 equivalent.

Further, in the present invention, an alcohol-based organic solvent can be used as a water dispersion aid. The alcoholic organic solvent has the following formulas (1), (2) and (3) HO-R1 (1) HO-C, IH21-OR2 (2) HO-cnazn-'o cnH2n-o Rz
(3) In each of the above formulas, R1 represents an alkyl group having 2 to 16 longitudinal atoms, Rzu represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer from 2 to 5. These are alcohol-based solvents, cellosolve-based solvents, and carpitol-based solvents shown in 1. Such an organic solvent is an organic solvent for hydrating the maleated alkyd resin, and there is a polar group that has an affinity for the maleated alkyd resin and has a coarse affinity for water, and the balance between the two is For example, the alcohol-based organic solvent and [7 are ethyl alcohol, n-propyl alcohol, isoamyl alcohol, n-butyl alcohol, isobutyl alcohol, w-7'1000 alcohol, tert
-Butyl alcohol, isoamyl alcohol, di-amyl alcohol, tert-anyl alcohol, propylene glycol motsubutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol motsubutyl ether, propylene glycol Monomethyl ether, propylene glycol ethyl ether, propylene glycol motsubutyl ether, propylene glycol motsubutyl ether, 3-methoxy-3-methylbutanol, diethylene glycol motsubutyl ether, diethylene glycol motsubutyl ether, diethylene glycol motsubutyl ether, diethylene glycol motsubutyl ether , diglopylene glycol monoethyl ether and diethylene glycol motsubutyl ether. Among the above alcohol-based organic solvents, alcohols having a C2-6 alkyl group are preferred. The amount of the alcoholic organic solvent is 25% based on the solid content of the maleated alkyd resin.
It is used in an amount of less than 10% by weight, preferably less than 10 quadrats, more preferably less than 5% by weight. When the amount of the alcohol-based organic solvent is more than 25% by weight, as the temperature changes during storage of the maleated alkyd resin emulsion, the SL fat constituting the parent wood on the particle surface is redissolved, and the particle surface and The barrier of fatty acid groups constituting the inside of the particles is destroyed, and as a result, the hydrolysis of the emulsion is promoted, resulting in poor storage stability, and the coating film formed from the ruinated alkyd fat emulsion has poor water resistance and corrosion resistance. Such characteristics are poor and unsatisfactory. In addition, as a method of using the alcoholic organic solvent in the present invention, it is particularly preferable to use the alcoholic organic solvent in an amount greater than 25 deuterium based on the solid partial pressure of the maleated alkyd resin. This method further facilitates the removal of the alcohol-based organic solvent to 25% by weight or less based on the solid content of the resin. The maleated alkyd m thus obtained
The fat emulsion composition has a small particle size and good storage stability, and the coating film formed therefrom has good properties such as water resistance and corrosion resistance.

Further, the alcohol-based organic solvent can be used alone or in combination of two or more. In addition, organic solvents and plasticizers other than those mentioned above may be used for purposes such as improving film-forming properties.

To prepare the maleated alkyd resin emulsion composition of the present invention, the maleated alkyd resin is neutralized with a neutralizing agent, and if necessary, the alcoholic organic solvent is added to the maleated alkyd resin with a solid content of 25%. If water is added to the neutralized resin solution containing less than 100% polytetra, or if the amount of the alcohol-based organic solvent is more than 25% by weight based on the solid content of the resin, the scope of the present invention may be reduced by adding water to the neutralized resin solution under reduced pressure. It is sufficient to remove up to 25% by weight or less. The temperature at which this product is dispersed in water is preferably 20 to 60°C. The solid content of the resulting maleated alkyd tH fat emulsion composition is not limited, but is from 10 to
The range is 65% by weight, and the range is 25-60% by weight for the trench. Moreover, the value of the average particle diameter measured by turbidity method is O,6
It is less than a, preferably less than 0.3μ. If the average particle size is larger than 0.6 fi, the sedimentation stability of the maleated alkyd resin emulsion will be poor, and the particles will not be stable, resulting in poor hydrolysis resistance, and the water resistance and corrosion resistance of the coating film will be poor. It also gets worse. The turbidity method referred to here is based on the literature (Bull, Ind.
strial, Chemical, Research
VOL.

42 P145-152 (1964)) K The average particle diameter was determined using the calibration curve described.

In the maleated alkyd resin emulsion composition of the present invention #i, a pigment, a pigment dispersant, a dryer, an antifoaming agent,
Thickeners, aqueous resins other than those mentioned above, etc. can also be optionally blended.

Coating Wl formed from the composition of the present invention! Although it is sufficiently crosslinked and cured at room temperature, it cures in a short time when heated in the presence or absence of an amino resin, etc., and a coating with good water resistance, corrosion resistance, etc. can be obtained.

The present invention will be explained in more detail with reference to the following KW examples and comparative examples. Hereinafter, parts and q6 are parts by weight and heavy responsibility%.
shows.

Example 1 Tall oil fatty acid (trade name: Kago Etol FAX manufactured by Arayo Forestry Industry Co., Ltd. 40% linoleic acid, 3.2% sulphur/lenic acid, 32% oleic acid, 24.8% others, iodine value 151)
599 parts of inphthalic acid, 218 parts of benzoic acid, and 245 parts of pentaerythritol were placed in a four-loaf flask equipped with a stirrer, a thermometer, and a branch tube condenser, and while stirring in the presence of the esterification catalyst, about 240 parts of pentaerythritol was added. ℃
A dehydration and binding reaction was carried out for about 8 hours to obtain an alkyd resin solution having a resin acid value of 2.7, a Gardner viscosity of W-X (75% butyl cellosolve solution), and a color of 'IIK7. Subsequently, the temperature was lowered to about 200° C., 50 parts of maleic anhydride was added, and the maleation reaction was carried out for about 3 hours. Total acid value 40
．． A maleated alkyd resin having a Gardner viscosity of 6, Z (60% butyl cellosolve solution) and a color number of 11 was obtained.

Next, 126 parts of Improvil alcohol was added to 420 parts of the maleated alkyd resin, and 1.0 parts of triethylamine was added.
After neutralization in an equivalent amount, 750 parts of deionized water was added dropwise over about 1 hour to effect emulsification and dispersion, and the isopropyl alcohol was distilled off from this aqueous dispersion at about 40° C. under reduced pressure. The properties of the obtained maleated alkyd mb emulsion and its ass properties t are shown in Table 2 below.

Examples 2 to 7 Maleated alkyd resins were obtained using the formulations shown in Table IK under exactly the same conditions as in Example 1. Further, 420 parts of the obtained maleated alkyd resin was added with the formulation shown in Table IK, and production was carried out under exactly the same conditions as in Example 1 to obtain a maleated alkyd resin emulsion. Got it
Further, the properties of the maleated alkyd resin emulsion and its coating performance are shown in Table 2 below.

Comparative Examples 1 and 2 Maleated alkyd resin emulsions were obtained using the formulations shown in Table IK under exactly the same conditions as in Example 1. Furthermore, the formulation shown in Table IK was added to 420 parts of the obtained maleated alkyd resin, and production was carried out under exactly the same conditions as in Example 1 to obtain a maleated alkyd resin emulsion. The properties of the resulting maleated alkyd resin emulsion and its coating performance are shown in Table 2 below.

Manufactured by Tall Fax Tall Oil Fatty Acid B: Manufactured by Harima Kasei Kogyo Co., Ltd., trade name Vertol FAI (48% linoleic acid, 52% others (oleic acid, stearic acid, palmitic acid), iodine value 133) (*2) Flaxseed Oil fatty acids: linoleic acid 21%, liluic acid 44%, other 35% (oleic acid, stearic acid, palmitic acid), iodine value 178 (*3) Safflower oil fatty acid dilinoleic acid 75%, liluic acid 1%, others 24% (oleic acid, stearic acid, palmitic acid)
, Iodine number (*4) Viscosity = Centivoise value when measured with a B-type viscometer at 6 rpm. 30rp
Centivoise value at m.

(*5) fi of isoproper tool: % of inproper tool to maleated alkyd resin solid content.

(*6) After clear coating is applied to a yellow glass plate to a dry film thickness of 40μ, a white plate with a yellow value (+b) = 0.51 is placed on the back of the clear glass plate to visually inspect it using a color difference meter (MA).
CHINE company 111! The yellow value (+b) was measured using model-CM2000).

(Incidentally, the larger the +b value, the stronger the yellow color.) [Applied odor performance test] Regarding the solid content of the maleated alkyd resin emulsion compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 2. Then, 2% of the water-based dryer (trade name: "Deiknate" cobalt metal manufactured by Dainippon Ink Co., Ltd.) was added, and the coating was applied to a mild steel plate so that the dry film thickness was about 45 μm.

After drying at 20° C. and 75% relative humidity, it was used for testing.

(In addition, the adhesion, workability and water resistance tests were performed using 14% paint.
This was done after drying in the sun. ) (urn 7) Adhesion: 1■
Make 100 wide gopans, put cellophane adhesive tape on top of them, and peel them off to show the number of bushes.

(*8) Workability: Cracking occurred using a DuPont impact tester, loft diameter = 1/2 inch, load = 50Of'.11. It shows a certain elegance.

Claims (1)

[Claims] Maleic anhydride is reacted with an alkyd resin having an oil length of 35 to 80 that has been modified with an oil and/or fatty acid having an iodine value of 135 to 175, and contains 30% by weight or less of linoleic acid in the oil and/or fatty acid component. Obtained acid value 10~
A maleated alkyd resin emulsion composition prepared by neutralizing a maleated alkyd resin of No. 70 and dispersing it in water.