KR100254385B1 - Method for preparing thixotropic agent - Google Patents

Abstract

PURPOSE: Provided is a method for preparing thixotropic agent which shows excellent heat-resistant stability, low viscosity change in storing, flow prevention effect and brilliance effect. CONSTITUTION: The method for preparing thixotropic agent comprises the steps of: (i) mixing 1 equivalent of one or two species of organic acid having 2-22 carbon numbers and 1-2 carboxyl groups with 0.5-1.1 equivalent of metal, metal oxide or metal hydroxide to prepare reactant A; (ii) mixing 1 equivalent of one or two species of organic acid with 2-22 carbon numbers and 1-2 carboxyl groups having 0.9-1.1 equivalent of one or two species of amines with 1-2 amine groups to prepare reactant B; (iii) mixing reactant A and reactant B at 5-50:95-50 weight ratio to prepare composition C; (iv) crushing the composition to be less than 50 micrometer; and (v) keeping weight ratio between the crushing materials of the composition C and organic solvent in 10-30:90-70 and swollen ripening.

Description

Method for preparing a viscoelastic modulator {Method for preparing thixotropic agent}

The present invention relates to a method for preparing a viscoelastic modulator (THIXOTROPIC AGENT OR RHEOLOGY MODIFIER) used to control the flow characteristics of a fluid containing water-insoluble suspension or fine solid particles.

In general, the rate at which solid particles settle in the fluid system can be expressed by the formula of stoke, which is briefly described as follows.

The settling velocity is reduced by decreasing the radius of the particles, by reducing the density difference between the solid particles and the liquid, or by increasing the viscosity of the liquid. However, if the viscosity of the liquid is increased, the viscosity is high at the time of work, and thus a smooth surface cannot be obtained due to poor workability and poor leveling after work. In addition, it is practically difficult to reduce the radius of the particles in the case of a coating material in which several kinds of particles are mixed rather than one kind of particles.

In general, fluids to which viscoelastic modifiers are applied are collapsed due to external stress, and the viscosity is rapidly lowered to a sol state, and when the stress is removed, a gel structure is formed again to increase the viscosity. Such a reversible fluid of gel and sol The flow characteristic is called thixotropy. Viscoelasticity modifier is added to paints, varnishes, printing inks, adhesives, laminates, enamels, etc., to reduce the viscosity during the operation, improve the flow characteristics, reduce the flow after the operation, suppress the flow phenomenon, and settle and Suppresses the hard cake phenomenon.

Many types of viscoelastic modifiers have been used to obtain thixotropic properties, but conventional viscoelastic modulators have the following disadvantages.

1) Metal salts such as aluminum stearate have the disadvantage of easily precipitated in polar solvents such as water or alcohol when used alone, precipitation nuclei are generated, water resistance decreases, and gloss is poor.

2) Montmorillonite derivatives have a disadvantage in that poor state is easily generated when swelling and dispersing is reduced.

3) The viscoelastic regulator of fatty acid crab has disadvantages such as gloss deterioration and precipitation nuclei when using pigments such as zinc oxide, chromium yellow and calcium carbonate.

4) Viscoelastic modifiers based on hydrogenated castor oil have good flow protection but poor thermal stability, making precipitation seed even at 50 ℃ or 40 ℃, making it difficult to control the temperature during dispersion such as milling or grinding.

5) The emulsifiable polyethylene wax has a good flow prevention effect and precipitation nucleation effect, but has a disadvantage in that the flow prevention effect does not immediately occur when external stress is removed.

In addition, Japanese Patent Publication No. 63-235381, Japanese Patent Publication No. 56-112977, and British Patent No. 1,454, 388 disclose a method of preparing a viscoelastic modifier by reacting a saturated fatty acid or an isocyanate compound with an amine. Due to the lack of heat resistance, there was a limitation in the use temperature and the flow prevention effect was inferior.

It is an object of the present invention to provide a manufacturing method of viscoelasticity for solving the above problems.

The production method of the present invention for achieving the above object 1) a reactant by reacting a metal, an oxide of a metal or a metal hydrate with one or two or more kinds of organic acids having 2 to 22 carbon atoms having one or two carboxyl groups in a molecule A was prepared, and 2) a reaction product B was prepared by reacting an amine containing one or two or more amine groups in a molecule with one or two or more organic acids having 2 to 22 carbon atoms having one or two carboxyl groups. After the preparation, (3) the composition A is prepared by melting and mixing the reactant A and the reactant B, and (4) swelling and aging the organic solvent after grinding to prepare the desired viscoelastic regulator D. Viscoelasticity modulator according to the present invention has excellent heat stability, viscosity change according to the temperature at the time of storage, compared to the existing amide wax-based viscoelasticity modifier, good flow prevention effect during standing, good gloss and solid particles precipitate during long-term storage Viscoelasticity regulators with very little hardening are possible, leading to the present invention.

Hereinafter, the present invention will be described in detail. 1) 0.5 to 1.1 equivalents of a metal oxide, a metal hydrate or a metal is reacted with respect to one equivalent or two or more mixtures of organic acids having 2 to 22 carbon atoms having one or two carboxyl groups. Prepare reactant A, and 2) one or two or more amines having one or two amine groups in the molecule with respect to one or two or more equivalents of organic acids having 2 to 22 carbon atoms having one or two carboxyl groups in the molecule. Reaction B is prepared by reacting with 0.9 to 1.1 equivalents. 3) Composition C is prepared by melt-mixing reactants A and B. Preferably, the reactant A is prepared in a ratio of 5 to 50 parts by weight of reactant A and 95 to 50 parts by weight of reactant B. At this time, when the reactant A is more than 50 parts by weight, the flow-proof property is poor in the final paint properties, the precipitation nuclei are severely generated, and when the amount is less than 5 parts by weight, the water resistance is disadvantageous. When preparing the half-lump A, the reaction temperature is suitable in the range of 150 ~ 200 ℃, it is necessary to remove the condensation water generated sufficiently. The completion of the reaction is appropriate when the dehydration amount is more than 95% of theory. When preparing the reactant B, the reaction temperature is suitable in the range of 150 ~ 200 ℃ and the resulting condensate water needs to be sufficiently removed. The termination of the reaction is not particularly limited, but the time when the acid value and the amine value is 15 or less is appropriate.

Specific examples of the C2-C22 organic acid having one or two intramolecular carboxyl groups used to prepare Reactant A include palmitic acid, 12-hydroxy stearic acid, and oleic acid. ), Sebacic acid, adipic acid, succinic acid, hydrogenated dimer acid, 1,12-dodecanedioc acid, gluta Glutaric acid and the like can be used and these examples do not limit the scope of the present invention.

Specific examples of the metal used in the manufacture of reactant A include Pb, Co, Mn, Ca, Zn, Al, and the like, and specific examples of the metal oxides include SnO, CuO, PbO, Al ₂ O _3, and the like. ) _2, such as _{Co (OH) 2, Pb (} OH) 2, Zn (OH) 2, Al (OH) 3 can be used.

The reactant A between the organic acid and the metal, metal oxide, or metal hydrate contains metal in the molecule, and exhibits high thermal stability, forming micelles in a non-polar solvent and exhibiting high viscosity.

Organic acids having 2 to 22 carbon atoms having one or two intramolecular carboxyl groups used in the preparation of reactant B, 9-hydroxy stearic acid, 12-hydroxy stearic acid, sebacic acid, idipic acid, succinic acid, hydrogenated dimer acid, 1 , 12-dodecanedioic acid, glutaric acid and the like can be used.

Specific examples of the amine compound having one or two amine groups in the molecule used in the preparation of the reactant B include ethylene diamine, tetramethylene diamin, hexamethylene diamine, decadiamine, and xylene. Diamine and the like, and these examples do not limit the scope of the present invention.

The reactant A and the reactant B are melt-mixed at a temperature range of 100 to 250 ° C. to prepare a composition C, and then pulverized and swelled in an organic solvent to prepare a desired viscoelastic regulator D. At this time, the size of the pulverized product is suitable to 50㎛ or less, when the 50㎛ exceed the disadvantage of poor appearance of the coating film.

In the preparation of the viscoelastic modifier D, the mixing ratio of the pulverized product of the composition C and the organic solvent is preferably in the range of 10 to 30 parts by weight to 90 to 70 parts by weight. At this time, the preferred organic solvent is formulated as a mixed solvent of aromatic organic solvent and organic alcohol, and the mixing ratio of aromatic organic solvent (a) and organic alcohol (b) having 1 to 10 carbon atoms is 60 to 90 parts by weight to 40 to 10 parts by weight. The range is the most suitable.

Specific examples of the aromatic organic solvent (a) may include benzene, toluene, ortho-xylene (o-xylene), metha xylene, para xylene, and mixtures thereof.

The organic alcohol (b) having 1 to 10 carbon atoms is suitable for primary to secondary alcohols, and specific examples thereof include methanol, ethanol, isobutyl alcohol, isopropanol, normal butanol, octanol, normal propyl alcohol, and ethylene glycol. It is possible to use them by mixing them.

When the content of the organic alcohol (b) in the mixed solvent is excessively high, the effect of preventing flow after swelling aging may be lowered.

Through the following Preparation Examples and Examples will be described in more detail the specific manufacturing method and effect of the present invention. However, the following examples do not limit the scope of the present invention.

The preparation example of reaction A is as follows.

[Production Example 1]

1 mole of ZnO was added to 2 moles of 12-hydroxy stearic acid in a reactor equipped with a dehydration device, and the temperature was maintained at 160 ° C., and the reaction was completed at a time when the dehydration amount was 95% or more of theory.

At the end of the reaction, a vacuum was applied at 100 mm Hg to completely remove unreacted material and water, thereby preparing reactant A ₁ .

[Production Example 2]

1 mole of 12-hydroxy stearic acid and 1 mole of lauric acid CaO are added thereto, and the temperature is raised to 160 ° C., and the reaction is completed when the dehydration amount is 95% or more of theory.

At the end of the reaction, reactant A2 was prepared by completely removing unreacted material and water by vacuum at 100 mm Hg.

[Manufacture example 3]

1.2 moles of 9-hydroxy stearic acid and 1 mole of Al (OH) ₃ are added and the temperature is maintained at 160 ° C., and the reaction is completed when the dehydration amount is 95% or more of theory.

At the end of the reaction, vacuum was applied at 100 mm Hg to completely remove unreacted material and water, thereby preparing reactant A ₃ .

The preparation of reactant B is as follows.

[Production Example 4]

2 mol of 12-hydroxy stearic acid was heated to 120 ° C., melted, and then 1 mol of nucleomethylene diamine was added thereto, and the reaction product was heated to 180 ° C. and reacted for 5 hours, followed by reaction at 200 ° C. until the acid value and amine value were 5 or less. .

Production Example 5

2 mol of 12-hydroxy stearic acid was heated to 120 ° C., melted, hexamethylene diamine and ethylene diamine were added at 0.4: 0.6 molar ratio, and heated at 180 ° C. for 5 hours, followed by reaction at 200 ° C. until the acid value and amine value became 5 or less. Reactant B2 was prepared.

[Manufacture example 6]

2 mol of 12-hydroxy stearic acid was heated to 120 ° C., melted, and hexamethylene diamine and xylene diamine were added at a molar ratio of 0.8: 0.2. The mixture was heated to 180 ° C. and reacted at 200 ° C. until the acid value and amine value became 5 or less. Reactant B3 was prepared.

The preparation example and the comparative example of composition C are as follows.

[Production example: C1 ~ C4]

A1, A2, A3 and reactants B1, B2, and B3 prepared at the composition ratios shown in Table 1 were melt mixed at 150 ° C. to prepare compositions C1 to C4.

[Comparative Example: C5 ~ C8]

Compounds C5 to C8 were prepared by melt-mixing reactant A alone or B alone and a mixture of A and B at 150 ° C. in the composition ratios shown in Table 1 below.

Examples and Comparative Examples D1 to D8

The compositions C1 to C8 were pulverized to 50 µm or less, mixed well with the component ratios shown in Table 2 below, followed by swelling to obtain viscoelasticity regulators D1 to D4 of the examples of the pasty and viscoelasticity regulators D5 to D8 of the comparative example. .

[Examples and Comparative Examples E1 to E8]

The composition was mixed in the following component ratios of Table 3, and then stirred for 20 minutes at 2000 rpm using a high speed dissolver to compare the physical properties after dispersion, and the results are shown in Table 4 below.

Viscosity was measured by KS M 5000, flow resistance by ASTM D 4400, surface gloss by KS M 5000. The room temperature (25 ° C.) storage properties are shown in Table 5, and the high temperature (85 ° C.) storage properties are listed in Table 6.

* 1: Chlorinated rubber (SUPERCHLON # 507, manufactured by Sanyokoku Co., Ltd., Japan)

* 2: Chlorinated paraffin 45% Cl

* 3: Typeque R-820 (trade name of Chihara Sanyo)

* 4: Epoxy resin: YD 128 (trade name of Kukdo Chemical)

A high speed dissolver was used to stir at 2000 rpm for 20 minutes to compare physical properties after dispersion, and the results are shown in Table 4 below.

As a result, when the viscoelastic modulator according to the present invention is added to the paint, the viscosity change during storage is less than that of the conventional products, and the paint has excellent thermal stability and excellent gloss.

Claims (3)

(1) reactant A is prepared by reacting one or two or more organic acids having 2 to 22 carbon atoms with 1 or 2 carboxyl groups in a molecule with 0.5 to 1.1 equivalents of a metal, metal oxide or metal hydrate, 2) One equivalent or a mixture of two or more organic acids having 2 to 22 carbon atoms having one or two intramolecular carboxyl groups is reacted with one or two or more amine groups having 0.9 or 1.1 equivalents After the reactant B was prepared, (3) the reactant A and reactant B were melt-mixed at a weight ratio of 5 to 50: 95 to 50 to prepare a composition C, and (4) pulverized to 50 µm or less, and then (5) A method for producing a viscoelastic modifier comprising swelling and aging to make a weight ratio of the pulverized product of the composition C and the organic solvent of 10 to 30:90 to 70. The method of claim 1, wherein the organic solvent is a weight ratio of the aromatic organic solvent and the organic alcohol is 60 ~ 90: 40 ~ 10 characterized in that the manufacturing method of the viscoelastic modifier. The organic solvent according to claim 1, wherein benzene, toluene, o, m, p-xylene, which is an aromatic siliceous solvent, alone or in combination of two or more thereof, and the organic alcohol is used alone as a primary to secondary organic alcohol having 1 to 10 carbon atoms. Or a mixture of two or more thereof.