JP2013049761A - Powdery anti-sagging agent for nonaqueous anticorrosive paint and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powdery anti-sagging agent to be added to a nonaqueous anticorrosive paint which exhibits excellent anti-sagging effect even when dispersed at relatively low temperature, does not impair storage stability of the paint, and does not contain harmful organic solvent, and a method of manufacturing the same.SOLUTION: The powdery anti-sagging agent for nonaqueous anticorrosive paint contains: (A) diamide compound obtained by a condensation reaction between a mixture of hydrogen-added castor oil aliphatic acid and one or more aliphatic monocarboxylic acids having a carbon number of 2-22 other than hydrogen-added castor oil aliphatic acid (mixing ratio of hydrogen-added castor oil aliphatic acid and aliphatic monocarboxylic acid is in a range of 10:0 to 2:8 by the molar ratio) and diamine; (B) diamide compound other than (A) obtained by the condensation reaction between one or more aliphatic monocarboxylic acids having the carbon number of 2-22 and diamine; and (C) carboxyl-containing polyolefin wax, wherein, with reference to the total weight of the diamide compound (A), the diamide compound (B), and the carboxyl-containing polyolefin wax (C), it contains 40-90 wt.% diamide compound (A), 0-50 wt.% diamide compound (B), and 10-60 wt.% carboxyl-containing polyolefin wax (C). The powdery anti-sagging agent for nonaqueous anticorrosive paint is obtained by heating and melting (A), (B), and (C), uniformly mixing them and then cooling them, and finely grinding the cooled substance.

Description

  The present invention relates to a powdery sag-preventing agent for non-aqueous anti-corrosion paints which can be prevented from sagging during coating by adding a small amount to the non-aqueous anti-corrosion paints.

  In order to prevent sagging when the coating composition is applied to the coated surface with a high film thickness or when it is applied to a vertical surface, the coating composition tends to flow in the high shear rate region at the time of painting. An anti-sagging agent (sometimes called a rheology control agent, a thixotropic agent, a thixotropic agent, or a viscosity modifier) that makes it difficult to flow in the low shear rate region is added.

  Conventionally, montmorillonite derivatives, polymerized oil, hydrogenated castor oil, emulsifiable polyethylene wax, polyester-based polymer, polyamide-based polymer, diamide compound and the like are known as anti-sagging agents for non-aqueous coatings.

  For example, in Patent Document 1, a hydrogenated castor oil fatty acid or an amide wax obtained from the reaction of an organic acid mixture containing at least 30 mole percent of a hydrogenated castor oil fatty acid with an amine and an emulsifying polyethylene wax are used in combination. It is disclosed that anti-sagging property is improved in a non-aqueous fluid system including finely divided solid particles. The combined method may be a method in which both are added individually, a method in which both are added simultaneously in the form of a mixture or a eutectic, and the shape may be in the form of powder or dispersed in a non-aqueous medium. It is said that the dispersion in a non-aqueous medium is the most practical method in that the kneading and dispersing machine and the kneading and dispersing temperature are not selected.

  In Patent Document 2, a polyester-based polymer obtained from a reaction between a polyol and a polycarboxylic acid and having at least two active hydrogen moieties at its end imparts anti-sagging properties to a non-aqueous composition containing a paint. It is disclosed.

  In Patent Document 3, an oligomeric polyamide obtained from hydroxystearic acid, primary diamine and dicarboxylic acid, and a powdered composition of hydrogenated castor oil improve the flow characteristics of the non-aqueous coating material and impart sag prevention properties. It is disclosed. In Patent Document 4, a polyamide wax obtained by reacting an aliphatic primary diamine having 2 to 6 carbon atoms with 12-hydroxystearic acid and an aliphatic dicarboxylic acid is pulverized and swollen in an organic solvent. It is disclosed that the composition imparts excellent anti-sag properties to non-aqueous paints. Further, in Patent Document 5, a low molecular weight amide compound obtained by condensing an aliphatic carboxylic acid including a hydroxy aliphatic monocarboxylic acid and a diamine, and a high molecular weight obtained by condensing the same kind of the carboxylic acid, the same kind of the diamine, and a carboxyl group-containing polymer. It is disclosed that a composition in which fine particles containing a molecular weight amide compound are swollen in an organic solvent imparts anti-sagging properties to non-aqueous paints.

  Patent Document 6 discloses that a diamide compound obtained by reacting a mixture of a hydrogenated castor oil fatty acid and a linear saturated fatty acid with xylylenediamine provides anti-sagging properties to an organic vehicle.

  In Patent Document 7, a urethane-modified amide compound obtained by reacting a reaction product of 12-hydroxystearic acid and castor oil fatty acid with a polyamine and a polyisocyanate suppresses dripping of the coating film of the non-aqueous paint. It is disclosed.

  Furthermore, in Patent Document 8, a fatty acid amide obtained by reacting a mixture of a linear saturated fatty acid having 3 to 4 carbon atoms with 12-hydroxystearic acid and primary diamine, and a linear saturated compound having 6 to 22 carbon atoms. A composition comprising a fatty acid amide obtained by reacting a mixture of a fatty acid and 12-hydroxystearic acid with a primary diamine is an anti-sagging agent having an excellent effect on anti-sagging agents for non-aqueous paints, particularly heavy anti-corrosion coatings. It is disclosed.

  However, non-aqueous anti-corrosion paints, especially non-aqueous high solid heavy-duty anti-corrosion paints with a reduced content of organic solvents that have been pointed out to be harmful to humans and the environment, or non-aqueous anti-corrosion paints that do not contain such organic solvents. When anti-sagging agent obtained by conventional technology is added to solvent-type heavy anticorrosive paint, the anti-sagging effect is insufficient, the organic solvent in the anti-sagging agent becomes a problem, There are problems such as large influence and poor storage stability of the paint, and an anti-sagging agent that solves these problems has been strongly desired.

Japanese Patent Publication No.51-48464 JP 2010-2442099 A JP-A-51-2750 JP-A-5-271585 JP 2008-260834 A Japanese Patent Laid-Open No. 60-223876 JP 2008-115199 A JP-A-63-235381

  An object of the present invention is to provide a non-aqueous anti-corrosion paint, in particular, a non-aqueous high solid heavy-duty anti-corrosion paint with a low content of organic solvents harmful to humans and the environment, or a non-aqueous solvent-free type that does not contain such an organic solvent. It is a powdery anti-sagging agent to be added to heavy anticorrosion paints, which exhibits excellent anti-sagging effects even when dispersed at relatively low temperatures, and does not impair the storage stability of the paints. An object of the present invention is to provide a powdery anti-sagging agent for non-aqueous anticorrosive paints which is not contained in an organic solvent and a method for producing the same.

  As a result of various studies to solve the above problems, the present inventors suitably used non-aqueous anticorrosion paints, particularly non-aqueous heavy anticorrosion paints with a low content of organic solvents harmful to humans and the environment. The present inventors have completed a powdery sag preventive agent for non-aqueous anticorrosive paints and a method for producing the same.

  That is, according to the present invention, a mixture of hydrogenated castor oil fatty acid and one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than hydrogenated castor oil fatty acid (hydrogenated castor oil fatty acid and aliphatic The mixing ratio of the monocarboxylic acid is in the range of 10: 0 to 2: 8 in terms of molar ratio) and the diamide compound (A) obtained by the condensation reaction of diamine and the aliphatic monocarboxylic acid having 2 to 22 carbon atoms. A diamide compound (B) other than (A) obtained by a condensation reaction of at least one carboxylic acid and a diamine, and a carboxyl group-containing polyolefin wax (C), the above-mentioned diamide compound (A), diamide compound (B) And 40 to 90% by weight of the diamide compound (A) based on the total weight of the carboxyl group-containing polyolefin wax (C), ) 0-50% by weight, and non-aqueous anticorrosive paint powdery anti-sagging agent is provided, characterized in that it contains 10 to 60% by weight of carboxyl group-containing polyolefin wax (C).

  In the above sag-preventing agent, the diamine is preferably ethylenediamine, 1,4-diaminobutane, hexamethylenediamine or xylylenediamine.

In the above sag-preventing agent, the carboxyl group-containing polyolefin wax (C) comprises an oxidized polyethylene wax (acid value of 3 to 70 mg KOH / g), an ethylene oxide-propylene copolymer wax (acid value of 3 to 70 mg KOH). / G) or ethylene-acrylic acid copolymer wax (acid value is 5 to 180 mg KOH / g).

  According to the present invention, the diamide compound (A), the diamide compound (B) and the carboxyl group-containing polyolefin wax (C) are heated and melted, uniformly mixed and then cooled, and the cooled product is pulverized. Provides a method of obtaining each of the above-mentioned powdery sag-preventing agents for non-aqueous anticorrosive paints.

  The powder sag prevention agent for non-aqueous anticorrosion paints of the present invention is added to non-aqueous anticorrosion paints, particularly non-aqueous anticorrosion paints with a reduced amount of organic solvents that have been pointed out to be harmful to humans and the environment. Even if the conventional anti-sagging agent for non-aqueous paints does not provide satisfactory results, it provides an excellent anti-sagging effect and good storage stability without increasing harmful organic solvents. can do.

  The powder sag preventive agent of the present invention comprises non-aqueous epoxy resin paint, urethane resin paint, chlorinated rubber paint, tar epoxy resin paint, tar urethane resin paint, non-tar epoxy resin paint, modified epoxy resin paint, phthalate Contains anti-sagging effects in anti-corrosion paints such as acid resin-based paints and phenolic resin-based paints, and contains organic solvents that have been pointed out to be harmful to humans and the environment, especially because of the large amount of inorganic pigments. When added to high-solid-type epoxy resin paints or solvent-free epoxy resin paints with a small amount, the paint exhibits excellent dripping prevention effects that could not be achieved with conventional technology under relatively low temperature dispersion conditions. Has little adverse effect on storage stability.

As described above, the present invention is a mixture of hydrogenated castor oil fatty acid and one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than hydrogenated castor oil fatty acid (hydrogenated castor oil fatty acid and aliphatic The mixing ratio of the monocarboxylic acid is in the range of 10: 0 to 2: 8 in terms of molar ratio) and the diamide compound (A) obtained by the condensation reaction of diamine and the aliphatic monocarboxylic acid having 2 to 22 carbon atoms. A diamide compound (B) other than (A) obtained by a condensation reaction of at least one carboxylic acid and a diamine, and a carboxyl group-containing polyolefin wax (C), the above-mentioned diamide compound (A), diamide compound (B) And 40 to 90% by weight of the diamide compound (A) based on the total weight of the carboxyl group-containing polyolefin wax (C), ) 0-50% by weight, and to a non-aqueous anticorrosive paint powdery anti-sagging agent and a production method characterized by containing carboxyl group containing 10 to 60 wt% polyolefin wax (C).
Hereinafter, specific requirements necessary for carrying out the present invention will be described in detail.

1. 1. Powdery sagging inhibitor composition for non-aqueous anticorrosive paint 1-1. Diamide compound (A)
The diamide compound (A) (hereinafter also referred to as component (A)) is obtained by hydrogenating castor oil using a catalyst and hydrolyzing hydrogenated castor oil substantially free of unsaturated bonds. By a condensation reaction of a castor oil fatty acid and a diamine, or a mixture of a hydrogenated castor oil fatty acid and one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than the hydrogenated castor oil fatty acid and the diamine It is obtained by a condensation reaction.

  The hydrogenated castor oil fatty acid is generally a complex mixture containing 12-hydroxystearic acid as a main component and additionally containing stearic acid and unsaturated fatty acid. The product called 12-hydroxystearic acid distributed in the market is the same in composition as the hydrogenated castor oil fatty acid, and the hydrogenated castor oil fatty acid is easily available from the market.

  Examples of aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than hydrogenated castor oil fatty acid include acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid And behenic acid. These may be used alone or in a mixture. In addition, unsaturated aliphatic monocarboxylic acids and branched aliphatic monocarboxylic acids such as oleic acid and ricinoleic acid can also be used, but the pulverizability of the composition of the present invention deteriorates as the content in the total fatty acid increases. Since there is a possibility, it is desirable to use in the range which does not inhibit grindability.

  The mixing ratio of each component in the mixture of hydrogenated castor oil fatty acid and one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than hydrogenated castor oil fatty acid is a molar ratio of 10: 0 to 2: 8 Range. When the mixing ratio of hydrogenated castor oil fatty acid is less than 20%, the sagging prevention effect decreases.

  Examples of diamines include ethylene diamine, trimethylene diamine, 1,4-diaminobutane, hexamethylene diamine, octamethylene diamine, 1,10-decamethylene diamine, 1,11-undecamethylene diamine, 1,12-dodecamethylene. Examples include diamine, phenylenediamine, xylylenediamine, diaminodiphenyl ether, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, ethylenediamine, 1,4- Diaminobutane, hexamethylenediamine or xylylenediamine is preferred. These diamines may be used alone or in combination of two or more.

  As the component (A) in the composition of the present invention, a diamide compound (A ′) obtained by a condensation reaction of a hydrogenated castor oil fatty acid and a diamine may be used alone, or a hydrogenated castor oil fatty acid and hydrogenated. A diamide compound (A ″) obtained by a condensation reaction of a mixture of the above-mentioned molar ratio with one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than castor oil fatty acid and a diamine, alone. However, both the diamide compound (A ′) and the diamide compound (A ″) may be contained.

  Component (A) is the component that contributes most to the sag prevention effect in the composition of the present invention. The component (A) content range is 40 to 90% by weight, preferably 50 to 80% by weight, based on the total weight of the diamide compound (A), diamide compound (B) and carboxyl group-containing polyolefin wax (C). It is. When the content of the component (A) is less than 40% by weight and exceeds 90% by weight, the sagging prevention property is lowered.

1-2. Diamide compound (B)
The diamide compound (B) (hereinafter also referred to as component (B)) is obtained by a condensation reaction of one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms with a diamine. A) is not included in the diamide compound (B).

  Examples of aliphatic monocarboxylic acids having 2 to 22 carbon atoms include acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, as in the case of diamide compound (A). Palmitic acid, stearic acid, behenic acid and the like can be mentioned, but besides these, hydrogenated castor oil fatty acid can be used as long as it does not overlap with the case of diamide compound (A). The aliphatic monocarboxylic acids may be used alone or in a mixture. In addition, unsaturated aliphatic monocarboxylic acids and branched aliphatic monocarboxylic acids such as oleic acid and ricinoleic acid can also be used, but the pulverizability of the composition of the present invention deteriorates as the content in the total fatty acid increases. Since there is a possibility, it is desirable to use in the range which does not inhibit grindability.

  Examples of diamines are ethylene diamine, trimethylene diamine, 1,4-diaminobutane, hexamethylene diamine, octamethylene diamine, 1,10-decamethylene diamine, 1,11- as in the case of the diamide compound (A). Undecamethylenediamine, 1,12-dodecamethylenediamine, phenylenediamine, xylylenediamine, diaminodiphenyl ether, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, etc. Of these, ethylenediamine, 1,4-diaminobutane, hexamethylenediamine or xylylenediamine are preferred. These diamines may be used alone or in combination of two or more.

The purpose of blending the diamide compound (B) is to improve the compatibility between the diamide compound (A) and the carboxyl group-containing polyolefin wax (C), improve the grindability of the composition according to the present invention, and low-temperature dispersion. This is to improve the swelling property of the powdery anti-sagging agent at the time, but since it has an amide bond, some anti-sagging effect can be expected. Due to the relationship between these purposes and the sagging prevention effect of the diamide compound (A) and the carboxyl group-containing polyolefin wax (C), the content range of the diamide compound (B) is as follows: diamide compound (A), diamide compound (B) and It is 0 to 50% by weight, preferably 0 to 40% by weight, based on the total weight of the carboxyl group-containing polyolefin wax (C). When the content of the component (B) exceeds 50% by weight, the sag prevention property is lowered.
In the composition of the present invention, the component (B) may contain only one kind or two or more kinds.

1-3. Carboxyl group-containing polyolefin wax (C)
The carboxyl group-containing polyolefin wax (C) used in the present invention is not particularly limited as long as it is a polyolefin wax having a carboxyl group.

Examples of the component (C) include polyethylene oxide wax obtained by contacting polyethylene wax with oxygen and the like, ethylene oxide-propylene copolymer wax obtained by contacting ethylene-propylene copolymer wax with oxygen and the like, Polypropylene oxide obtained by contacting polypropylene wax with oxygen, etc., ethylene-acrylic acid copolymer wax, ethylene-methacrylic acid copolymer wax, hydrolyzate of ethylene-maleic anhydride copolymer wax, propylene-anhydrous Mention may be made, for example, of hydrolysates of maleic acid copolymer wax, such as oxidized polyethylene wax (acid value 3 to 70 mg KOH / g), ethylene oxide-propylene copolymer wax (acid value 3 to 70 mg). KOH / g) or ethylene-acrylic acid copolymer (Acid value is 5 to 180 mg KOH / g) is particularly preferable.
In the composition of the present invention, the component (C) may contain only one type or two or more types.

  When component (C) is an oxidized polyolefin wax, the acid value is preferably in the range of 2 to 80 mg KOH / g, and the softening point is preferably in the range of 85 to 130 ° C. Commercially available products include AC polyethylene manufactured by Honeywell and Mitsui High Wax manufactured by Mitsui Chemicals.

  When component (C) is an ethylene-acrylic acid copolymer wax, the acid value is preferably in the range of 5 to 200 mg KOH / g. Specific examples include commercially available products such as A-C 580 and A-C 5120 manufactured by Honeywell.

  When component (C) is an ethylene-ethylenically unsaturated dicarboxylic acid copolymer wax, the acid value is preferably in the range of 5 to 200 mg KOH / g. Specific examples include those obtained by hydrolyzing commercial products such as A-C 575A and A-C 907A manufactured by Honeywell.

  Component (C) forms a structure by adsorbing to a powdery substance such as an inorganic pigment in the paint, but mainly contributes to the sag-preventing property by a synergistic effect with a strong network structure by the diamide compound (A). It is thought that there is. The content range of the component (C) is 10 to 60% by weight based on the total weight of the diamide compound (A), the diamide compound (B) and the carboxyl group-containing polyolefin wax (C), preferably 15 to 40%. % By weight. If the content of component (C) is less than 10% by weight, problems such as an increase in the optimum swelling temperature, a decrease in sag prevention or a decrease in the storage stability of the paint occur. Problems such as reduced pulverization and sag prevention occur.

1-4. Other components The composition of the present invention comprises 40 to 90% by weight of component (A) based on the total weight of diamide compound (A), diamide compound (B) and carboxyl group-containing polyolefin wax (C). In the case where (B) is contained in an amount of 0 to 50% by weight and component (C) is contained in an amount of 10 to 60% by weight. One or more kinds of added castor oil, polyamide polymer, or polyester polymer can be further included.

2. Method for producing powder sag preventive agent for non-aqueous anticorrosive paint The powder sag preventive agent of the present invention is prepared by mixing and grinding an amide compound and an emulsifiable polyethylene wax as described in Example 1-4 of Patent Document 1. Unlike the method, the diamide compound (A), the diamide compound (B) and the carboxyl group-containing polyolefin wax (C) are heated and melted, mixed uniformly by stirring, and after cooling, an appropriate pulverizer is used. And then pulverized. This will be described in more detail below.

  The production method of the present invention comprises a mixture of hydrogenated castor oil fatty acid and one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than hydrogenated castor oil fatty acid (hydrogenated castor oil fatty acid and aliphatic monocarboxylic acid). The mixing ratio of the carboxylic acid is in the range of 10: 0 to 2: 8 in terms of molar ratio) and a diamine reaction step (S1) in which a diamine is reacted to form a diamide compound (A); A diamide compound synthesis step (S2) in which one or more of aliphatic monocarboxylic acids 22 is reacted with a diamine to form a diamide compound (B), and the diamide compound (A), the diamide compound (B) and a carboxyl group; The mixing polyolefin wax (C) is heated and melted and mixed uniformly by stirring, and finely pulverized using an appropriate pulverizer after cooling. And a grinding step.

  The reaction conditions in the above-mentioned diamide synthesis step (S1) and diamide synthesis step (S2) are not particularly limited. For example, 2 mol equivalents of the above-mentioned aliphatic monocarboxylic acid and 1 mol equivalent of diamine are solvent-free or condensed. A diamide compound (A) and a diamide compound (B) are obtained by reacting for 2 to 10 hours while heating at 150 to 220 ° C. using an appropriate organic solvent for the purpose of easily removing water generated in the reaction. Can do.

The mixing step of heating and melting the diamide compound (A) and the diamide compound (B) and the carboxyl group-containing polyolefin wax (C) and mixing them uniformly by stirring can be performed by the following method.
[1] A method in which component (A), component (B) and component (C) are placed in a container, and all components are melted by heating from the outside and stirred to mix uniformly.
[2] One component in component (A), component (B) and component (C) was put in a container and melted by heating from the outside, and the other two components were added to melt all components. After that, stirring is performed to make it uniform. In this method, at the end of the synthesis of the diamide synthesis step (S1) or the diamide synthesis step (S2), the other two components are added to the component (A) or the component (B) in a molten state to add all the components. After melting, the method includes stirring to make it uniform.
[3] Two components in component (A), component (B) and component (C) were put in a container and melted by heating from the outside, and another component was added to melt all components. After that, stirring is performed to make it uniform. When the composition of the present invention does not contain the component (B), the method [3] is not applied.

  The temperature at which the component (A), the component (B) and the component (C) are melted is not particularly limited, but is preferably 140 to 180 ° C. from the viewpoint of stirring efficiency and a method for cooling the mixture.

  In the mixing step, the composition comprising the component (A), the component (B) and the component (C) needs to be uniform, but it is not an essential condition that the composition is completely compatible and transparent. The powdery anti-sagging agent of the present invention exhibits the expected effect even in a uniformly dispersed state unless the separated state is intense and non-uniform.

  Although the method of cooling and solidifying the composition comprising the component (A), the component (B) and the component (C) that has become uniform in the mixing step is not limited, for example, cooling is performed using a cooling device such as a belt flaker. By doing, it can be set as a flaky solid. The shape of the flaky solid material is suitable for the pulverization step which is the next step.

  In the pulverization process, in order to use the flaky solid as a fine powder sag-preventing agent, it is usually made into a coarse powdery substance using a mechanical pulverizer such as a pin-type pulverizer or a hammer mill pulverizer, and then jetted. A method of making a fine powdery substance using an airflow type pulverizer such as a mill pulverizer is used. In consideration of the sagging prevention effect and the storage stability of the paint, the average particle size of the powdery sagging agent is preferably in the range of 5 to 30 microns, more preferably in the range of 5 to 20 microns. When the average particle size is less than 5 microns, the pulverization efficiency tends to decrease. When the average particle size exceeds 40 microns, the sag prevention effect decreases and the storage stability of the paint tends to deteriorate.

  Hereinafter, the present invention will be described more specifically and in detail by way of amide synthesis examples, blending examples, blending comparative examples, and test examples, but the present invention is not limited thereto. In each example, “part” indicates “part by weight”, and “%” indicates “% by weight”.

Preparation of Diamide Compounds (A) and (B) Amide Synthesis Example 1
622 parts (2.0 mol) of hydrogenated castor oil fatty acid was weighed and heated to 100 ° C. in a four-necked flask having a 1-liter internal volume equipped with a stirrer, a condenser, and a thermometer. Next, 116 parts (1.0 mol) of hexamethylenediamine melted by heating was gradually added and stirred, and then gently heated to 175 ° C. for dehydration reaction. By reacting for 4 hours, a synthetic amide A-1 was obtained as the diamide compound (A).

Amide Synthesis Examples 2-4
Synthesis was performed at the blending ratio shown in Table 1 using the same method as in Example 1 for amide synthesis, and synthetic amide A-2 to 3 as diamide compound (A) and synthetic amide B-1 as diamide compound (B) were obtained. .

Production formulation example 1 of powdery anti-sagging agent for non-aqueous anticorrosive paint
In a container having an internal volume of 0.5 liter, 120 parts of synthetic amide A-1, 40 parts of synthetic amide B-1 and ethylene-acrylic acid copolymer AC 5120 (Honeywell, acid value: 120) 40 parts were weighed and heated to 180 ° C. for mixing. After cooling the resulting mixture, coarse pulverization and fine pulverization using a research compact jet mill (device name “CO-JET SYSTEMα MARK III”, manufactured by Seishin Enterprise Co., Ltd.) has an average particle size of 10 μm. A powdery anti-sagging agent for a non-aqueous anticorrosive paint was obtained.

Formulation Examples 2-13
Using the same method as in Blending Example 1, the components were mixed at the blending ratios shown in Table 2 to obtain a powdery sag-preventing agent for non-aqueous anticorrosive paints.

Formulation Comparative Examples 14, 16-17
Using the same method as in Blending Example 1, the components were mixed at the blending ratios shown in Table 2 to obtain a powdery sag-preventing agent for non-aqueous anticorrosive paints.

Formulation Comparative Example 15
Weigh 60 parts of synthetic amide A-1 and 140 parts of oxidized polyethylene A-C 629 (Honeywell, acid value: 16, softening point: 101 ° C.) in a container with an internal volume of 0.5 liter, and bring it to 180 ° C. Mix by heating. The obtained mixture was coarsely pulverized after cooling, and pulverization was attempted using a research compact jet mill. However, since the pulverization was poor, a powdery anti-sagging agent for non-aqueous anticorrosive paints could not be obtained.

Test Test Example 1 Using Nonaqueous Solventless Epoxy Resin Paint
[Contains paint]
Using the non-aqueous solventless epoxy resin coating composition having the composition shown in Table 3, a performance test of a powdery sag-preventing agent (hereinafter also referred to as an additive) for a non-aqueous anticorrosive coating was performed.

[Preparation method of paint]
168 parts of bisphenol A type epoxy resin Epicoat 828, 24 parts of reactive diluent SY-40M, 48 parts of non-reactive diluent Neciles EPX-L2, 48 parts of benzyl alcohol, sulfuric acid 160 parts of barium BA, 160 parts of talc # 1, 136 parts of nepheline sianite MINEX7 and 56 parts of titanium oxide R-820 were charged. The contents are stirred (1000 rpm × 2 minutes) with a cowless dissolver (device name “TK auto homomixer”, blade diameter 6 cm, manufactured by Primix Co., Ltd.), and 4 parts of the additive are added and further stirred (4000 rpm × 20 minutes). )did. 100 parts of the obtained dispersion was weighed, 10.9 parts of modified polyamine sunmide X-4150 was added and stirred uniformly to prepare a non-aqueous solventless epoxy resin coating.

[Viscosity and TI value of paint]
For the paint described above, a viscosity at 60 rpm (P: poise, the same applies hereinafter) and a viscosity (P) at 6 rpm at 25 ° C. were measured using a B-type viscometer, and the TI value (thixotropic index) was a viscosity at 6 rpm. Was calculated by dividing by the viscosity at 60 rpm.

[Evaluation of sag prevention]
Using a sag tester ("Drip Tester" manufactured by Dazai Equipment Co., Ltd.), paint is applied to the drip test paper ("All Black Measurement Paper" manufactured by Dazai Equipment Co., Ltd.) at a thickness of 100 microns, and the test paper is thin. The coating thickness is one step thinner, with the coating strips standing vertically and air-dried at room temperature for the first time to hang down beyond the spacing between the coatings, and the part that touches the lower coating strips is recognized. Membrane pressure was determined to determine sag prevention. Table 4 shows the results of the initial evaluation.

[Evaluation of storage stability]
The dispersion of the main agent and additive was sealed and stored in a thermostatic bath at 50 ° C. for 2 weeks, and then the anti-sagging property was evaluated again by the same method as described above. Table 4 shows the evaluation results after the storage stability test.

  As is clear from the results in Table 4, the non-aqueous solventless epoxy resin paint added with the powdery sag preventive agent for non-aqueous anticorrosive paints of the present invention is compared with the paint (blank) to which no sag-preventing agent is added. It was confirmed that the anti-sagging property on the vertical surface was excellent, and the storage stability at 50 ° C. was good as compared with the paint to which the additive of the formulation comparative example was added.

Test Test Example 2 Using Nonaqueous High Solid Type Epoxy Resin Paint
[Contains paint]
Using the non-aqueous high solid type epoxy resin coating composition having the composition shown in Table 5, the performance test of the powder sag prevention agent for non-aqueous anti-corrosion coating was conducted.

[Preparation method of paint]
In a 1 liter container, 320 parts of bisphenol A type epoxy resin Epicoat 828, 40 parts of non-reactive diluent Neciles EPX-L2, 280 parts of talc # 1, 80 parts of titanium oxide R-820, xylene 40 parts and 40 parts of n-butanol were charged. The contents were stirred with a cowless dissolver (device name “TK auto homomixer”, blade diameter 6 cm, manufactured by Primix Co., Ltd.) (1000 rpm × 2 minutes), added with 8 parts of additive, and further stirred (2000 rpm × 20 minutes) )did. 80 parts of the resulting dispersion was weighed, 16 parts of aminoamide resin versamide 140, 2 parts of xylene and 2 parts of n-butanol were added and stirred uniformly to obtain a non-aqueous high solid epoxy resin paint. Produced.

[Viscosity and TI value of paint]
About the coating material described above, a diluent (xylene / methyl amyl ketone (MAK) / n-butanol = 1/1/1) is used so that the viscosity at 60 rpm at 25 ° C. becomes 20 poises using a B-type viscometer. In addition, the TI value was calculated by adjusting and measuring the viscosity (P) at 6 rpm.

[Evaluation of sag prevention]
Using a sag tester ("Sag Tester" manufactured by Dazai Equipment Co., Ltd.), apply the paint prepared on the test paper ("All Black Measurement Paper" manufactured by Dazai Equipment Co., Ltd.) at a thickness of 50 microns or 100 microns. This test paper stands vertically so that the thin coating strip is on the top, and after air drying at room temperature, the coating film where the part contacting the lower coating strip is recognized for the first time when it hangs over the interval between each coating coating The coating pressure at which the thickness was one step thinner was judged to be a sag prevention property. The evaluation results are shown in Table 6.

[Evaluation of storage stability]
The dispersion of the main agent and additive was sealed and stored in a thermostatic bath at 50 ° C. for 2 weeks, and then the anti-sagging property was evaluated again by the same method as described above. Table 6 shows the evaluation results after the storage stability test.

  As is clear from the results in Table 6, the non-aqueous high solid type epoxy resin paint to which the powdery sag preventive agent for non-aqueous anticorrosive paint of the present invention is added is compared with the paint (blank) to which no sag-preventing agent is added. It was confirmed that the anti-sagging property on the vertical surface was excellent, and the storage stability at 50 ° C. was good as compared with the paint to which the additive of the formulation comparative example was added.

  As is apparent from the above results, the powdery anti-sagging agent for non-aqueous anticorrosion paints comprising the diamide compound / carboxyl group-containing polyolefin wax mixture of the present invention as a basic component is excellent when added to a non-aqueous anticorrosion paint. It is obvious that it has a dripping prevention effect and is excellent in storage stability.

Claims (4)

  A mixture of hydrogenated castor oil fatty acid and one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms other than hydrogenated castor oil fatty acid (the mixing ratio of hydrogenated castor oil fatty acid and aliphatic monocarboxylic acid is Diamide compound (A) obtained by condensation reaction of diamine and diamine in a molar ratio of 10: 0 to 2: 8, one or more aliphatic monocarboxylic acids having 2 to 22 carbon atoms and diamine A diamine compound (B) other than (A) obtained by a condensation reaction with the carboxylic acid group, and a carboxyl group-containing polyolefin wax (C). The diamide compound (A), diamide compound (B) and carboxyl group-containing polyolefin wax (C ) Based on the total weight of the diamide compound (A) 40 to 90% by weight, the diamide compound (B) 0 to 50% by weight, and Non-aqueous anticorrosive paint powdery anti-sagging agent characterized in that it contains 10 to 60% by weight of carboxyl group-containing polyolefin wax (C).   The powdery sag-preventing agent for non-aqueous anticorrosive paint according to claim 1, wherein the diamine is ethylenediamine, 1,4-diaminobutane, hexamethylenediamine or xylylenediamine.   The carboxyl group-containing polyolefin wax (C) is oxidized polyethylene wax (acid value is 3 to 70 mg KOH / g), ethylene oxide-propylene copolymer wax (acid value is 3 to 70 mg KOH / g) or ethylene-acrylic. The powdery sag prevention agent for non-aqueous anticorrosive paints according to claim 1 or 2, which is an acid copolymer wax (acid value is 5 to 180 mg KOH / g).   The non-condensed product according to claim 1, wherein the diamide compound (A), the diamide compound (B) and the carboxyl group-containing polyolefin wax (C) are heated and melted, uniformly mixed and then cooled, and the cooled product is finely pulverized. A method for obtaining a powdery anti-sagging agent for water-based anticorrosive paints.