RU2320691C1 - Universal pigment coloring paste - Google Patents

Abstract

FIELD: paint and varnish materials.

SUBSTANCE: invention relates to coloring pastes designated for using in ready basic pant and varnish materials that are soluble in organic solvents. Universal pigment coloring paste comprises pigment, film-forming agent, disperser, thickening agent and organic solvent. Alkyd glyphtal resin based on flax oil, glycerol and phthalic anhydride is used as a filling agent taken in the ratio, wt.-%: 45-47; 17-19 and 34-38, respectively, with viscosity index 60 measured at temperature 20.0 ± 0.5°C by viscosimeter device VZ-246 as 50% resin solution in xylene and having acid number 17-19 mg of KOH/g taken in the amount 30-40 wt.-%. Thickening agent Clayton AF is used a thickening agent taken in the amount 0.3-0.5 wt.-%. Xylene is used as an organic solvent taken in the amount 34-45 wt.-%. Disperser is used in the amount 0.9-2 wt.-%, and pigment, the balance. Invention provides expanding assortment of coloring pigment pastas, their using in different basis of dyes in organic solvents, providing stability of dyes and without unfavorable effect of properties of paint and varnish covers.

EFFECT: improved and valuable properties of paste.

4 tbl

Description

The invention relates to tinting pastes intended for use in finished base paints and varnishes (LKM), soluble in organic solvents.

Their use as part of a tinting system containing a set of tinting pastes allows you to diversify the base paints of various types, both at the manufacturer and in wholesale warehouses, points of sale, etc. It is recommended to use a tinting system consisting of a paint base, tinting pastes, equipment for feeding and mixing components, as well as color matching software. The use of this system reduces costs, provides high quality, improves the level of customer service.

Pigment tinting pastes are pigment dispersions with a high solids content, controlled by color, its saturation and certain rheological properties.

The color of the paintwork can be changed by adding intensely colored tinting pastes to the finished paint bases, white or painted.

Known tinting paste, for example, European patent EP 448347. 1991, in which 100 parts of the film-forming accounts for 1-1000 parts of pigment. Use alkyd, acrylic, epoxy resins.

Known tinting composition for paint products, including ketone aldehyde, ketone, aldehyde resin, soluble in organic solvents: 70-100 wt.% Of the total film-forming mass, 2-75 wt.% - pigment component, 10-60 wt.% Diluent in the form biodegradable ester of lactic acid and alcohol C ₁ -C ₁₀ (RU 2157395, 1996). The specified composition is selected as a prototype.

An object of the invention should be considered the possibility of expanding the range of tinting pigment pastes, using them in various paint bases on organic solvents, ensuring the stability of paints, while not adversely affecting such properties of coatings as gloss, drying, etc.

Universal pigment tinting paste containing pigment, film-forming, dispersant, thickener, organic solvent, characterized in that the film-forming using alkyd glyphthalic resin based on linseed oil, glycerin and phthalic anhydride in the ratio, wt.%: 45-47; 17-19; 34-38, with a viscosity of 60 s, measured at a temperature of (20.0 ± 0.5) ° C with a VZ-246 viscometer, in the form of a 50% solution of this resin in xylene with an acid number of 17-19 mgKOH / g, Clayton AF thickener is used as a thickener, xylene is used as an organic solvent, in the following ratio of components, wt.%:

indicated 50% alkyd glyphthalic resin solution - 30-40 xylene - 34-45 dispersant - 0.9-2 thickener Clayton AF - 0.3-0.5 pigment - the rest

To select a film-forming paste, a wide selection of existing resin brands was carried out that could satisfy the following requirements: be compatible with a wide range of bases of organically soluble paints, because most film-forming agents have high viscosity and low dispersibility (wetting pigment).

We tested a wide range of alkyd resins, especially glyphthalic resins, which are most suitable for the intended purpose, such as GF-01, GF-0174, GF-064, GF-066 (TU 6010-612-72), GF-046, GF- 050

Alkyd glyphthalic resins form solutions of low viscosity, which allows to achieve a high concentration of pigment.

Based on the results of the tests, an alkyd glyphthalic resin based on linseed oil, glycerin, phthalic anhydride was specially synthesized in a ratio of 45-47, respectively; 17-19; 34-38 wt.% With the following technical indicators:

- conditional viscosity at a temperature of (20.0 ± 0.5) ° С VZ-246 viscometer with a nozzle diameter of 4 mm, s, not less - 60 - acid number mg KOH / g, not more than - 17-19 - mass fraction of non-volatiles,% - 50-52 - Color of iodine scale mg J _2/100 cm ^3, which is darker than - 80

The synthesis of the resin is carried out in the traditional azeotropic manner.

Resin synthesis

Before loading into the reactor, linseed oil is heated to 100 ° C for 1 hour. Next is the loading of glycerin, the heating of the reactor is turned on, the inert gas is supplied. The temperature in the reactor is increased to 200 ° C, the catalyst for loading the alcoholysis reaction of soda ash is loaded. Next, the temperature is increased to 235-245 ° C. Samples are taken every 30 minutes. The process of alcoholysis is considered complete when the solubility of the sample in ethanol is achieved in a ratio of at least 1: 1 at a temperature of 20 ± 2 ° C. Next, the inert gas supply to the reactor is stopped, the temperature is reduced to 180-200 ° C, phthalic anhydride is charged and 3-4% of the xylene charge is charged. The temperature in the reactor was raised to 255 ± 5 ° C, the polycondensation reaction was carried out, more xylene was added, and the freed mixture of water in xylene was removed from the reactor as an azeotropic mixture. The reaction mass is maintained at a temperature of 255 ± 5 ° C until the desired viscosity and acid number values are achieved. Next, the heating is turned off and the resin is cooled to 180 ° C.

When using tinting pastes, problems arise with obtaining a certain shade of color, gloss, color purity, reproducibility.

Therefore, an important component of the pigment paste is a dispersing agent. The dispersion medium (dispersing agent, solvent) should provide good wetting and stability of the paste.

To overcome these problems, in addition to the solvent and the film-forming, dispersants, thickeners and other additives are introduced.

As a dispersing agent, a dispersing and wetting agent from TROY, USA, is included in the composition of the pigment paste.

The chemical composition of TROYSOL 98 C:

Fatty amine based surfactant. 95% solids in N-butyl alcohol. Dark viscous amber-colored liquid.

Gardner viscosity (25 ° C) Z3 MAX density (25 ° C), g / cm ³ - 0.90-0.92 % non-volatile substances - 95 min

It has advantages: it allows to obtain a paste with a high pigment filling, reduces viscosity, improves bottling, increases gloss. Into the pigment paste is introduced at the stage of dispersion in an amount of 0.9-2% by weight of the pigment.

Actively used dispersant for the paint and varnish and printing industry DP-TU 2484-005-23431487-2004. It is a salt of a quaternary ammonium base based on a high molecular weight ester, the content of the basic substance,% - 48-52,

acid number 2-4 mgKOH / g solvent alkylbenzenes amine number 0-2 mgKOH / g

Clayton AF rheological additive (Larchfield Ltd., Great Britain) is used as a thickener for pigment paste. This is organically modified alumina, which is obtained by reacting reactive organic cations, such as quaternary ammonium chloride, with bentonite. As a result, the nature of bentonite changes from hydrophilic to oleophilic. It is self-dispersing, prevents the deposition of pigments. The amount of additive is 0.3-0.5% by weight of the product.

One of the indispensable conditions for obtaining universal pigment tinting paste was the use of a specific, only one solvent, since pigment pastes are mixed with basic paints on any film-forming and various solvents. Xylene is selected as an organic solvent.

Tinting pigment pastes are characterized by a high concentration of pigments, so the pigments selected for this purpose must meet a number of requirements: compatibility of two or more pigments, reactivity in an acidic and alkaline environment.

Organic and inorganic pigments (based on iron oxides, lead crown, azo pigments, phthalocyanine pigments, and also carbon blacks) are used as pigments.

The technology of manufacturing tinting pigment paste

The manufacture of tinting pigment paste is carried out according to reliable technology and consists of the following stages:

- manufacture of a pigment suspension,

- dispersion.

The pigment suspension is made in a bowl using a disolver. A 50% solution of alkyd glyphthalic resin and a dispersant are loaded into a bowl, transported to a disolver, a stirrer is turned on, and mixed for 5-10 minutes at a stirrer speed of 500 rpm. Then proceed to download the pigment and thickener. The contents of the bowl are mixed until smooth for 20 minutes at a stirrer speed of 500 rpm. Then the rotation speed of the mixer is increased to 1250 rpm and stirred for 40 minutes. The readiness of the suspension is checked by the uniformity of the sample when pouring onto glass.

The finished suspension is fed to a bead mill. Dispersed to a milling degree of not more than 10 microns.

According to the above, 3 samples of pigment paste were made on the basis of alkyd glyptal resin of different formulations (Table 1), for comparison, the resin resin analogue of Resin 135 (TU 2311-032-72311668-2006) is given.

Table 2 shows the possible formulations of tinting pastes and similar. The prototype is not presented, because due to the impossibility of identifying the components of the tinting pastes, the comparison was carried out with an analog.

Table 3 shows the properties of the obtained tinting pastes.

Table 4 shows the test results obtained after the introduction of tinting pastes in the amount of 10% in the composition of the white bases of paints. The thickness of the paint layer is 150 mkm.

Table 3 shows the properties of the universal pigment tinting pastes obtained according to the invention. The tests were carried out according to the indicators of the degree of grinding and viscosity immediately after the manufacture of pastes and after 6 weeks. Reduced or increased indicators within the established limits. The table shows that the performance of sample 4b (analogue) inferior to the samples according to the invention.

Table 4 shows the results of tests for flocculation, gloss and hardness of the coatings obtained by introducing the universal pigment paste according to the invention into enamel bases.

Tests were carried out by introducing tinting paste (blue phthalcyanine pigment paste) into enamel bases (alkyd, alkyd-urethane, acrylic) in an amount of 10% and mixing in a mixer for 2 minutes.

The flocculation test was carried out by adding 9.5 ml of tinting composition to 250 ml of enamel base. Enamel layer after tinting with a thickness of 160 mm is applied using a applicator to a special filter paper. When this layer is almost completely dry, a drop of fresh enamel is added to it and a moist portion of the enamel is rubbed into the first layer with circular finger movements until the layers adhere. After that, the test sample is allowed to dry, and then the shade of the rubbing area is compared with the shade of the rest of the film. The appearance of a difference in shades indicates the presence of flocculation. Assessments are carried out visually using a 4-point system, where 0 - flocculation is absent, 3 - strong flocculation: the less flocculation, the easier it is to achieve reproducibility of the hue.

As in the patent RU 2157395 for testing for flocculation in alkyd paints with tinting pastes, and in table 4 in samples with tinting pastes according to the invention, the flocculation rate is "0". While in the examples with the analogue flocculation takes place.

The gloss index in the samples on white enamel bases (alkyd, alkyd-urethane, acrylic) with the addition of 10% tinting paste of blue phthalcyanine pigment remained at the same level as in the control samples (without tinting).

In the samples of analogues, a slight change in brightness was observed towards deterioration.

The gloss of the coatings was determined on an FB-2 photoelectric device on samples dried at t = 20 ± 2 ° C.

The hardness of the coating was determined on an M-3 pendulum instrument on samples with a layer thickness of 150 mkm after 48 hours and 5 days after application. As can be seen from table 4, tinting practically does not affect the hardness index in all coating samples.

Table 1
The formulation of glyphthalic resins and varnishes based on them, wt.% №№ p.p. Name of components According to the invention Analogue one 2 3 four one Linseed oil 45 46 47 2 Castor oil 63 3 Glycerin, 100% 17 eighteen 19 13 four Phthalic anhydride 38 36 34 24 TOTAL: one hundred one hundred one hundred one hundred Characterization of resin solutions - conditional viscosity at a temperature of (20.0 ± 0.5) ° С according to the VZ-246 viscometer with a nozzle diameter of 4 mm, s 60 60 60 thirty - mass fraction of non-volatiles,% 52 51 51 fifty - acid number, mg KOH / g 19 eighteen 17 25

table 2
Recipes for tinting pigment pastes №№ p.p Name of components According to the invention Analogue 1a 2a 3a 4a one Alkyd Glyphthal Resin 50% solution, according to example No. 1, (table 1) 30,0 50% solution, according to example No. 2, (table 1) 40,0 50% solution, according to example No. 3, (table 1) 35.0 50% solution, according to example No. 4, (table 1) 31.5 2 Organic solvents Xylene 34.0 45.0 43,2 31.05 3 Dispersants Dispersant Troysol 98C 0.9 2.0 - 2.15 Dispersant DP - - 1,5 four Clayton AF Thickener 0.3 0.3 0.5 La tyix fb 0.3 5 Pigments - organic (blue phthalocyanine) 12.7 - inorganic (red iron oxide) 34.8 35 - carbon black P-803 19.8 TOTAL: one hundred one hundred one hundred one hundred

Table 3
Properties of tinting pastes Test Name 1b 2b 3b 4b 1. The degree of milling, mkm - immediately after cooking ≤10 ≤10 ≤10 ≤10 - after 6 weeks ≤10 ≤10 ≤10 12 2. Conditional viscosity at a temperature of (20.0 ± 0.5) ° С according to the VZ-246 viscometer with a nozzle diameter of 4 mm, s - immediately after cooking 64 103 90 75 - after 6 weeks b / rev 108 b / rev 115

Table 4
Test results of tinting paste based on blue phthalcyanine pigment in white enamel bases. Types of paints Indicators Flocculation, points Gloss,% Hardness units After 48 h After 5 days Alkyd enamel
TU 2312-056-49331636-2004 - blank sample - fifty 0.25 0.25 - with tinting paste according
example 3, table 3 0 fifty 0.24 0.26 - with tinting paste according to example 4, table 3 one 48 0.25 0.25 Alkyd-urethane enamel TU 2312-000-72322668-2006 - blank sample - fifty 0.4 0.45 - with tinting paste according to example 3, table 3 0 fifty 0.4 0.45 - with tinting paste according to example 4, table 3 one 45 0.4 0.4 Acrylic enamel TU 2313-008-49331636-98 - blank sample - 60 0.45 0.5 - with tinting paste according to example 3, table 3 0 59 0.4 0.5 - with tinting paste according to example 4, table 3 2 58 0.4 0.45

Claims (1)

Universal pigment tinting paste containing pigment, film-forming, dispersant, thickener, organic solvent, characterized in that as the film-forming use alkyd glyphthalic resin based on linseed oil, glycerol and phthalic anhydride in the ratio, wt.%: 45-47: 17- 19: 34-38, with a viscosity of 60 s, measured at a temperature of (20.0 ± 0.5) ° C with a VZ-246 viscometer, in the form of a 50% solution of resin in xylene with an acid number of 17-19 mgKOH / g , as a thickener use Clayton AF thickener, as an organic solution xylol is used in the creator, in the following ratio of components, wt.%: indicated 50% alkyd glyphthalic resin solution 30-40 xylene 34-45 dispersant 0.9-2 thickener Clayton AF 0.3-0.5 pigment rest