JPH0139466B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an anti-sag agent for non-aqueous paints.
More specifically, the present invention relates to anti-sagging agents for non-aqueous paints such as alkyds, aminoalkyds, unsaturated polyesters, and acrylic paints using organic solvents. Conventional anti-sagging agents for non-aqueous paints include polymerized oil or polyamide wax synthesized from polymerized oil and ethylene diamine, metal soap (aluminum distearate, etc.), hydrogenated castor oil, organic benzinite, oxidized polyethylene wax, and sulfuric acid. Polymerized or phosphorylated castor oil is known.
However, these anti-sag agents often have insufficient anti-sag effects, and even when they are sufficient, other paint properties such as dispersibility, gloss retention, color toning, and paint stability are affected. etc. were often damaged. The present inventors have conducted intensive studies on anti-sag agents that do not have the above-mentioned problems, and as a result, have arrived at the present invention. That is, the present invention provides a polyamide (A) of a (poly)alkylene polyamine and a higher fatty acid, and a sulfonate type surfactant (B) [the weight ratio of (A) and (B) is 70:30 to 97: 3] is an anti-sagging agent for non-aqueous paints. In the polyamide (A) of (poly)alkylene polyamine [referred to as alkylene polyamine and/or polyalkylene polyamine] and higher fatty acids, the (poly) alkylene polyamine is
general formula [In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently H, -(AO)pH (wherein A is an alkylene group having 2 to 3 carbon atoms, such as an ethylene group or a propylene group;
P is an integer of 1 to 10) or a _C1 to ₄ alkyl group, m is an integer of 0 to 4, n is an integer of 2 to 12, and at least 2 of R ₁ , R ₃ and R ₅ is H]. Specifically, examples of the alkylene polyamine include ethylene diamine, propylene diamine, hexamethylene diamine, and β-hydroxyethyl ethylene diamine. Examples of polyalkylene polyamines include diethylenetriamine and triethylenetetramine. Among the (poly)alkylene polyamines, preferred are ethylenediamine and those containing ethylenediamine as a main component (50% by weight or more), and particularly preferred is ethylenediamine. Examples of higher fatty acids include fatty acids having 12 to 22 carbon atoms and/or hydroxyl group-containing fatty acids having 12 to 22 carbon atoms. Examples of the fatty acids include palmitic acid, oleic acid, stearic acid, linoleic acid, erucic acid, and mixed fatty acids such as beef tallow fatty acid, tall oil fatty acid, and linseed oil fatty acid. Examples of the hydroxyl group-containing fatty acids include ricinoleic acid, hydroxystearic acid, castor oil fatty acid, and hydrogenated castor oil fatty acid. Among these, preferred are those containing hydroxystearic acid, the content of which is 35 to 35%.
90% by weight, especially 45-85% by weight is preferred. When the hydroxystearic acid content is 35% by weight or more, excellent preventive properties are exhibited, and when it is 90% or less, the dispersibility and gloss retention properties are excellent. In the polyamide (A), the ratio of the (poly)alkylene polyamine to the higher fatty acid is usually such that the equivalent ratio of the sum of the primary and secondary amino groups contained in the polyamine to the carboxyl group in the higher fatty acid is 1:
The ratio is 0.9 to 1.2, preferably 1 for practical purposes. Polyamide (A) is made by combining (poly)alkylene polyamine and higher fatty acids, lower alkyl ( _C1-4 alkyl: methyl, _ethyl , propyl, etc.) esters thereof, or fats and oils that are their esters with glycerin in a non-catalyzed manner, or Catalyst (acid or alkali)
in the presence of usually 120-270℃, preferably 160-250℃
It can be obtained by reacting at ℃. In the above reaction, depending on whether the partner of the (poly)alkylene polyamine is a higher fatty acid or an ester thereof, the reaction is a dehydration reaction, a lower alcohol removal reaction, or an ester-amidation exchange reaction. In particular, when the resin is an ester of higher fatty acids with glycerin, it is not necessary to remove glycerin by-produced by the ester-amidation exchange reaction or glycerides by-produced by the partial reaction from the reaction system. On the contrary, glycerides may have positive effects on dispersibility, etc.
If its content is 50% by weight or less based on polyamide (A), it can be used without any problem. It is also possible to convert by-produced glycerin into mono- or diglyceride using higher fatty acids. In addition, if the (poly)alkylene polyamine has a hydroxyl group such as β-hydroxyethyl or ethylenediamine, or if the higher fatty acid has a hydroxyl group such as hydroxystearic acid, the required amount of higher fatty acid is added. These hydroxyl groups can also be esterified. It is preferable that 50% or more of the hydroxyl groups remain unesterified. In particular, those containing 35% by weight or more of hydroxystearic acid whose hydroxyl group is not esterified based on the total amount of higher fatty acids are preferred. During the production of polyamide (A), the end point of the reaction can be controlled by measuring the amine value and acid value. The polyamide (A) thus obtained is a white to yellow solid, and the amine value and acid value are each usually 15 or less, preferably 10 or less. The melting point shows a wide range of values, usually 70 to 150℃,
Preferably it is 80-140°C. In the sulfonate type surfactant (B) in the present invention, examples of the salt include salts of alkali metals (Na, K, etc.), alkaline earth metals (Ca, Mg, etc.), amines (triethanolamine, etc.), etc. It will be done. Examples of sulfonate type surfactants include dialkyl sulfosuccinates (where the alkyl group usually has 6 to 18 carbon atoms, such as sodium dioctyl sulfosuccinate, sodium didecyl sulfosuccinate, etc.), alkylbenzene sulfonates [where the number of carbon atoms in the alkyl group is Usually has one and/or more than one alkyl group having a straight chain and/or branched chain of 8 to 22 (preferably 10 to 18), such as calcium dodecylbenzenesulfonate, triethanol pentadecylbenzenesulfonate. aion, etc.] alkanesulfonic acid (alkanesulfonate having an alkyl group usually having 8 to 20 carbon atoms, such as potassium octadecylsulfonate), α
-Olephin sulfonate (usually 10-22 carbon atoms)
(alpha-olefin sulfonic acid triethanolamine, etc.) and mixtures of two or more thereof. Among these sulfonate type surfactants, dialkyl sulfosuccinates (especially alkali metal salts) and alkybenzenesulfonic acids (especially alkaline earth metal salts) are preferred. These sulfonate type surfactants are typically
It is used as a surfactant itself, but it may also be commercially available as a solution in water, alcohol, methyl isobutyl ketone, xylene, etc. If these solvents inhibit the solubility of the paint resin, they should be removed. Can be done. In particular, in the case of an aqueous solution, the amount of water is preferably 10% by weight or less, particularly 6% by weight or less, based on the total amount of polyamide (A) and sulfonate type surfactant (B). In the present invention, the ratio (weight ratio) of (A) and (B) is 70:
The ratio is 30-97:3, preferably 75:25-95:5.
When (B) is in the range of 3 to 30, excellent anti-sag properties that cannot be obtained with (A) alone are exhibited. Furthermore, it has excellent dispersibility, gloss retention, color toning, and paint stability. On the other hand, if (B) is less than 3 or greater than 30, the anti-sagging effect is low and the dispersibility or color toning properties are poor. The anti-sagging agent of the present invention contains (A) and (B), and is preferably used by dispersing (A) and (B) in an organic solvent in the form of a paste. The solvents listed above include aromatic hydrocarbons (toluene, xylene, etc.), aliphatic or alicyclic hydrocarbons (mineral turpentine, etc.), ketones, esters, or alcohols with relatively high boiling points (methyl isobutyl ketone, butyl acetate,
isobutanol, etc.), and mixtures of two or more of these. When dispersed, the concentration is usually 8 to 40% by weight, preferably 10 to 30% by weight, based on the total amount of (A) and (B). If the concentration is less than 8% by weight, the amount added to the paint will inevitably be large, which tends to cause problems in terms of practicality, while if it is more than 40% by weight, the paste state of the product tends to be poor and workability decreases. As a method for dispersing (A) and (B) in an organic solvent, (A) is uniformly dissolved in an organic solvent at a temperature of 90°C or higher, and this is rapidly cooled into a paste under mixing and dispersion by stirring, etc., and then One method is to add (B) and mix uniformly. Methods for rapidly cooling into a paste include adding the high-temperature (A) solution to a low-temperature organic solvent below 90°C, or continuously and instantaneously mixing the high-temperature (A) solution and the low-temperature organic solvent. Examples include methods. Furthermore, the method of adding (B) is not particularly limited; for example, it may be added to the paste of (A), or preferably it is added in advance to a high temperature solution of (A) or a low temperature organic solvent. There is a way. The anti-sagging agent of the present invention is mainly composed of aromatic hydrocarbons (xylene, toluene, etc.), aliphatic or alicyclic hydrocarbons (minerals, turpentine, etc.), alcohols (isobutanol, etc.), ketones (methyl, isobutyl ketone, etc.), esters (butyl acetate, etc.), and mixed solvents of two or more of these to produce alkyd resins, aminoalkyd resins, unsaturated polyester resins, acrylic resins, polyurethane resins, epoxy resin paints, etc. It can be used as an anti-sag agent for non-aqueous synthetic resin paints. These paints are described in "Synthetic Resin Paints" (December 10, 1966, published by Kobunshi Kankankai). The amount of anti-sagging agent added to the paint can be varied depending on the type of paint and required performance, but the total amount of (A) and (B) is usually 0.15 to 3% by weight, preferably 0.2 to 2% by weight. be. The anti-sag agent is usually added during the pigment dispersion step of the paint, but the anti-sag agent can also be added after the dispersion step. When the anti-sag agent of the present invention is used as an anti-sag agent for the above-mentioned non-aqueous paint, it imparts a sufficient anti-sag effect to the paint. Furthermore, it provides excellent performance in other essential properties of paints, such as dispersibility, thickening properties, gloss retention, toning properties, and paint stability. The present invention will be further explained below using production examples, working examples, and test examples, but the present invention is not limited thereto. In the above examples, parts indicate parts by weight. The measurement methods for the test items in the test examples are as follows. Dispersibility A tube gauge (0 to 100μ, 10μ units) was used. The dispersibility indicates the numerical value (μ) at the point where the globules begin to be almost uniform. Thickening property A Stormer viscometer was used. Thickening property indicates the value of viscosity (KU, 25°C). Anti-sag property A sag tester (manufactured by Honfuji, film thickness 50 μm unit) was used. Adjust paint viscosity to 68KU (20℃) with mineral turpentine.
Measurements were made using a glass plate at room temperature (20°C). The anti-sag property is determined by measuring the blank area of the sag tester (width 3
It is expressed as the film thickness (μ) at which sagging occurs in approximately half of the thickness (mm). Gloss retention using a gloss meter. The paint was applied on a glass plate to a thickness of 100μ, dried at room temperature (20°C) for 24 hours, and measured. Gloss retention is expressed as a 60° gloss value. Toning property: Mix 100 parts of paint and 30 parts of commercially available black paint (elongated alkyd resin paint), apply it on a glass plate with a brush, and perform a spotting test to determine whether there is any color separation on the spotted surface. Determine defectiveness. Stability of paint: Seal the paint and leave it at 40°C for one month.
The paint viscosity (cps) before and after standing was measured using a B-type viscometer (measurement temperature 20°C), and the respective viscosity index (the value obtained by dividing the viscosity at 6 rpm by the viscosity at 60 rpm) is shown. Production Example 1 Hydroxystearic acid (0.6 equivalent) and tall oil fatty acid (0.4 equivalent) were placed in a reaction vessel, and after uniformly dissolving, ethylenediamine (1 equivalent) was added. Next, the temperature was gradually raised under a nitrogen stream, and the amide reaction proceeded at 205°C to obtain a polyamide. The analysis values showed an amine value of 6, an acid value of 5, and a melting point of about 105 to 130°C. Production example 2 Hydrogenated castor oil (0.75 equivalent), rapeseed oil fatty acid (0.51 equivalent), and NaOH (0.01 equivalent) as a catalyst
was charged into a reaction vessel and after homogeneous dissolution, ethylenediamine (1 equivalent) was added. Next, in the same manner as in Production Example 1, an ester-amide exchange reaction, an amidation reaction, and an esterification reaction of by-produced glycerin were carried out to obtain a polyamide. The analytical values showed an amine value of 8, an acid value of 2, and a melting point of about 95-120°C. Production Examples 3 to 8 Table 1 was prepared in the same manner as in Production Example 1 or 2.
Polyamide was manufactured using the raw materials shown in .

[Table] Example 1 250 parts of mineral turpentine was added to 225 parts of the polyamide of Production Example 1 and uniformly dissolved at about 130°C. This solution was continuously added to 400 parts of mineral turpentine at a temperature of about 60° C. under stirring to obtain a polyamide paste. To this paste, 35 parts of sodium dioctyl sulfosuccinate solution (commercial product, concentration 70%, solvents are equal amounts of water and propylene glycol) were uniformly mixed, and mineral turpentine was added to make a total of 1000 parts.
A paste-like anti-sagging agent with a concentration of 25% by weight was obtained. Examples 2 to 9 Anti-sag agents having the compositions shown in Table 2 were obtained in the same manner as in Example 1.

[Table] Example 8 250 parts of mineral turpentine was added to 225 parts of the polyamide obtained in Production Example 2, and uniformly dissolved at about 120°C. Add this solution to mineral turpentine at a temperature of approximately 60℃.
400 parts and calcium dodecylbenzenesulfonate solution (commercial product, concentration 70%, solvent is xylene)
The mixture was continuously added to 35 parts of the mixture with stirring, and mineral turpentine was added to make a total of 1000 parts to obtain a paste-like anti-sagging agent with a concentration of 25% by weight. Example 9 and Comparative Examples 4 and 5 In the same manner as in Example 8, anti-sag agents having the compositions shown in Table 3 were obtained.

[Table] Test Example 1 A test example is shown when applied to alkyd resin paint, which is a typical non-aqueous paint. Composition of paint (a) Dispersion process oil-based alkyd resin solution (concentration 65%, solvent mineral turpentine) 150 parts Mineral turpentine 35 Anti-sag agent (concentration 25% by weight) 50 Titanium white (rutin type) 230 Calcium carbonate 120 (subtotal 585 ) (b) Dissolution process length oil-based alkyd resin solution 330 Mineral turpentine 20 Stand oil 30 Dryer 20 Anti-skinning agent 5 (Total 990) Charge each raw material into a magnetic pole mill in the proportions shown in (a) above, and premix at a temperature of 25 Allowed to split for 15 hours at ~30°C. Take out 585 parts of this into a container,
The raw materials shown in (b) were blended and uniformly dispersed using a lab disper to produce 990 parts of paint. The dispersibility and thickening properties of this finished paint were measured. Then use mineral turpentine to maintain a constant viscosity (80KU, 25
After adjusting to
The toning properties and stability of the paint were examined. The results are shown in Table 4.

[Table] There it was.

Claims (1)

[Claims] 1. Polyamide (A) of (poly)alkylene polyamine and higher fatty acids and sulfonate type surfactant (B) [weight ratio of (A) and (B) is 70:30 to 97 :3] A drip-preventing agent for non-aqueous paints. 2 Higher fatty acids convert hydroxystearic acid into
The inhibitor according to claim 1, which contains 35 to 90% by weight. 3. The prevention according to claim 1 or 2, wherein (B) is selected from the group consisting of dialkyl sulfosuccinates, alkylbenzene sulfonates, alkanesulfonates, and α-olefin sulfonates. agent. 4 (A) and (B) as the total amount of (A) and (B) 8 to 40
The inhibitor according to any one of claims 1 to 3, which is contained in a dispersed state in an organic solvent in weight percent.