RU2303615C2 - Water-dispersed lacquer composition - Google Patents

Abstract

FIELD: paint-and-varnish industry.

SUBSTANCE: invention relates to polymer compositions to prepare biocidally active lacquer coatings. Composition proposed by invention contains nonionic water-dilutable film-forming component in the form of aqueous polymer dispersion, aqueous solution of biocide additive(polyhexamethylene-guanidine), and polymer paste. The latter is prepared from pigment, filler, and dispersing solution containing water, anionic polymeric disperser, nonionic cellulose thickener, emulsifier, and organic solvent, weight ratio of nonionic cellulose thickener to anionic polymeric disperser ranging from 2.0:1.0 to 1.0:2.0. In particular, nonionic cellulose thickener is a hydrocellulose derivative in amount 0.5=1.0%, anionic polymeric disperser is represented by sodium and ammonium salts of polycarboxylic acids (0.17-0.55%), and anionic polymeric disperser is sodium polyphosphate.

EFFECT: increased resistance of coating to water in cases where humidity is present under indoor conditions and ensured bactericidal effect when dry surface is wiped with wet cloth.

4 cl, 2 tbl

Description

The invention relates to the chemistry of polymers, namely to polymer compositions for the production of biocidal coatings.

In conditions of high air pollution in enclosed spaces and in crowded places (hospitals, public institutions and organizations, schools, kindergartens, military barracks, etc.), the role of nonspecific prevention of infectious diseases - the use of biocidal materials for painting walls and other surfaces.

In addition to health care, biocidal coatings can be demanded by educational and cultural institutions (libraries, museums), defense, food industry - to avoid mold in wet rooms (cold stores, flour, grain, cereals), in public utilities (pools, baths, basements).

Known polymer composition for coating bactericidal action, which as a bactericidal component contains a low-toxic, water-soluble polymer with a wide spectrum of biocidal action - polyhexamethylene guanidine (PHMG) of the formula

where R is OH, Cl, PO ₃ ; n = 2-60 (ed. certificate of the USSR No. 1728264, class C08L 15/02, 1992, BI No. 151).

Known biocidal paint "Biokrapag", which in the amount of 3-7% as a biocide introduced salts of PGMG (US Pat. RU 2131897, CL C09D 5/14, 1999, BI No. 17).

Due to their polymeric nature, the compounds of PHMG are low toxic and possess a wide spectrum of biocidal action against various microorganisms, i.e. They have bactericidal, virucidal, fungicidal, pesticidal, insecticidal, and algicidal effects.

However, the introduction of PHMG compounds in the composition of paints and coatings presents significant difficulties, since the salts of PHMG are polycationic products and even if they are introduced in small amounts into the composition of paint compositions they cause precipitation.

Known water-dispersed paint composition, including water-borne film-forming, pigments, thickener, surfactant, biocidal additive and water (US Pat. RU 2059673, 1996, BI No. 13).

Known water-borne composition for bactericidal coatings based on water-based paints with the addition of PGMG derivatives in the form of 0.3-30% aqueous emulsion solution in an amount of 0.5-9 wt.h. per 100 parts by weight compositions (US Pat. RU 2189999, C09D 5/14, 2002, BI No. 27).

The disadvantage of these compositions is the low resistance of the coating to water and film washability, which excludes frequent wet cleaning of rooms, the walls of which are coated, including this composition.

The closest known polymer compositions by composition is a water-dispersed paint composition comprising a water-borne film-forming, pigments, a thickener, a surfactant, a biocidal additive, an alkyd emulsion with a nonionic and / or anionic emulsifier and water (US Pat. RU 2154078, class C09D 5/02, 2000).

However, this water-dispersed paint composition as a biocidal additive contains toxic substances (tetramethylthiuram disulfide of the Tiuram D brand, isothiazoline with halogenated derivatives of alkanol of the Metatin brand K 520, 2 n-octyl-4-isothiazolin-3-one of the Skane brand 8) and is insufficient water resistance and storage stability.

An object of the invention is:

- obtaining a polymer composition on available raw materials, including as a biocidal additive derivatives of PHMG;

- development of conditions to prevent them from precipitating by selecting dispersion emulsifiers;

- increase the resistance of the coating to water in the presence of humidity in rooms whose walls are covered with this composition, and providing bactericidal action when wiping a dry coating with a damp cloth.

The technical result is achieved by the fact that the water-dispersion paint composition with a biocidal action contains a non-ionic water-borne film-forming - an aqueous polymer dispersion, an aqueous solution of a biocide additive - a derivative of polymesamethylene guanidine and a pigment paste obtained from a pigment and a filler and dispersant solution containing an anionic polymer non-ionic cellulose thickener, emulsifier, organic solvent in the following ratio, wt.%.

pigment paste 63.0 - 92.0 aqueous polymer dispersion 5.0 - 30.0 25% aqueous solution of biocidal additives 3.0 - 7.0

The combination of a non-ionic system of emulsifiers in a polymer aqueous dispersion, a non-ionic thickener with anionic dispersants in a pigment paste in the above ratios ensures the introduction of a biocidal additive without precipitation, and the monomeric composition of the aqueous polymer dispersion and the composition of emulsifiers give the necessary water resistance to biocidal coatings.

Water-dispersion paint may additionally contain a neutralizing base in an amount of 0.1-0.2 wt.%, Antifoam in an amount of 0.2-0.6%, a coalescing solvent in an amount of 0.3-1.0 wt.%, A preservative in an amount of 0.1-0, 15 wt.%.

Applied using the proposed composition of water-dispersion paint, the coating dries in natural conditions.

As a water-borne film-forming, in particular, apply: non-ionic dispersion FINNDisp company Forsyth (Finland); copolymer dispersions based on acrylate-vinyl acetate grades K-65, K-23, K-30; homogeneous dispersion based on H-22 brand vinyl acetate: a number of Lenkhoztorg water dispersions (dispersions of a copolymer of vinyl acetate with dibutyl maleate of grades DPM 5035 according to TU 2241-039-00203521-98, dispersions of copolymers of vinyl acetate with esters of acrylic acid, grades A30, A50 according to TU 2241-002 -47923137-2001).

As pigments, any neutral or slightly basic pigments are used, for example, titanium dioxide (GOST 9808-84), chalk (TU 5743-002-2956580-96, GOST 12085-88), yellow iron oxide pigment (GOST 18172-72), red iron oxide pigment for the rubber industry (TU 6-10-602-77), ground mica for the rubber industry (GOST 855-74), omiakarb, which is a fine marble powder of high purity with a calcium carbonate content of at least 98% (Omia company), blue pigment phthalocyanine (GOST 6220-76), carbon technical grade P-803 (GOST 7985-86), microtalc for la paint industry (GOST 19284-79), kaolin (GOST 19608-84), zeolite and others.

As thickeners, for example, Hercules cellulose derivatives are used; hydroxyethyl cellulose, grade Natrosol-250, grades HHBR, H4BR, HBR, MHBR, methyl hydroxyethyl cellulose CULMINAL HEC various brands, methylhydroxypropyl cellulose CULMINAL HEC various brands.

In addition to the above, you can use hydroxypropyl cellulose brands Methocel from Dow Chemical.

As an emulsifier, an auxiliary substance OP-7 or OP-10 (GOST 8433-81), triton CF-10 (Union Carbide company), a block copolymer of ethylene oxide with propylene oxide GDPE-108 (TU 38-407219-82) are used.

The dispersant used is the sodium and ammonium salts of polycarboxylic acids of the brand, for example, Orotan-731 K, Orotan 850-K, Orotan-165 from Rohm and Haas; Ciba Dispexs products; sodium polyphosphate (GOST 20291-86) and others.

Ethylene glycol (GOST 19710), propylene glycol (TU 6-01-4639387-88), diethylene glycol (GOST 10136-77), white spirit (GOST 3134-78) and others are used as organic solvents.

Organosilicon compounds, for example, Agitan-731 from Munzing Chemie; a mixture of aliphatic hydrocarbons and emulsifiers NOPKO NXZ (HENKEL NOPCO Germany), a polyester fatty acid derivative of Lumiten EL from BASF and others.

As a preservative, Parmethol A-26 from Schuike Mayr is used.

As a coalescing solvent, coalescent Lusolvan FBH (diisobutyl ester of a mixture of dicarboxylic acids) from BASF Eastman Texanol.

As a biocidal additive, a 25% aqueous solution of polyhexamethylene guanidine derivatives (PHMG) of the formula is used

where R is OH, Cl, PO ₃ ; n = 2-60.5.

The proposed composition is prepared as follows. A dispersing solution is prepared in the mixer by loading, according to the recipe, water, a thickener, a neutralizer, a dispersant, an emulsifier, glycols and a preservative. The mixture is stirred until a homogeneous solution with a viscosity of 60-200 s is determined, determined by a B3-4 funnel with a nozzle diameter of 4 mm and a pH of 7-9.

Dispersing solution can be prepared as an independent semi-finished product, stored and used as necessary. It can be prepared in a dissolver for each subsequent operation for the manufacture of pigment paste.

Then, a dispersing solution is placed in a high-speed dissolver, and with continuous stirring, according to the formulation, pigments, fillers (talc, chalk, barite, etc.), a coalescing solvent, and antifoam are loaded. Mixing is continued until a homogeneous kneading is formed.

Homogeneous kneading from a high-speed dissolver is sent to a continuously working bead mill. The feed rate of the batch is controlled so that during the stay of the paste in the dispersion zone, the degree of milling along the wedge would be 40-60 microns. Then, the obtained pigment paste having the required dispersion is sent to a mixer for making paint.

An aqueous polymer dispersion, for example FINN DCSP K-65, is added to the pigment paste obtained in the mixer with moderate stirring, mixed until homogeneous, and an aqueous solution of the bactericidal additive is added. The resulting finished paint is checked according to quality indicators. The composition, if necessary, is diluted to a working viscosity with water and applied by pneumatic spraying or by brush.

Indicators of properties in comparison with the prototype are given in table 1, indicators of bactericidal activity in table. 2. The data in the tables show that the quality of the coating using the proposed composition of the water-dispersion paint composition is higher than that of the prototype, and the bactericidal properties are at the level of known biocidal paints.

The following are examples of formulations of the main components of the water-dispersion paint of the proposed composition.

Dispersion solution formulation:

drinking water 94.55-97.3 wt.% thickener-hydroxyethyl cellulose, e.g. Natrosol-259 HHBR 0.5-1.0 wt.% ammonia water converter 25% 0.1-0.2 wt.% dispersant - sodium polyphosphate or polycarboxylic acid salts, for example CiBa Dispexs products, Orotan 731 K, Stamp Orotan 165 m. Rohm and haas 0.5-1.0 wt.% emulsifier - GDPE-108, or auxiliary substance OP-7 or OP-10 0.5-1.0 wt.% an organic solvent, ethylene, or propylene glycol 1.0-2.0 wt.% preservative - Parmetol A-26 0.1-0.15 wt.%

Pigment paste recipe:

dispersing solution 35.0-55.0 wt.% pigments and fillers (talc, chalk, barite, etc.) 43.7-65.5 wt.% coalescing solvent 0.3-1.0 wt.% antifoam 0.2-0.3 wt.%

The composition of the input dispersion paint:

pigment paste 63.0-92.0 wt.% aqueous polymer dispersion 5.0-30.0 wt.% 25% aqueous solution of biocidal additives 3.0-7.0 wt.%

Table 1
Indicators of the properties of a water-dispersion paint composition and coatings based on it The name of indicators According to the prototype (US Pat. RU 2154078) According to the proposed composition Mass fraction of nonvolatile substances,% There is no data 63 The appearance of the coating Smooth, homogeneous surface Smooth, homogeneous surface Conditional viscosity on a viscometer of the B3-46 type with a nozzle diameter of 6 mm twenty thirty Drying time to degree 3 at a temperature of (20 ± 2) ° C, h one one Spreading rate of the dried film, g / m ² 96 97 The film washability, g / m ² There is no data 2.15 Resistance to static exposure to water at a temperature of (20 ± 2) ° С, h 48 120 Storage stability There is no data 6 months without change

table 2
Inactivation of various forms of microorganisms with a water-dispersion paint composition,% Biotest Contact time The claimed composition Paint "Bikrapag" (US Pat. RU 2131897) Composition according to (Pat. RU 2189999) E.Coil 30 minutes. one hundred one hundred 95.4 Bac.cereus 24 hours one hundred There is no data 75.1 Penicillium chry- sogenum 24 hours one hundred 96.0 90.0 30 minutes. 99.97 C. albicans 1 hour 100.0 4 hours 100.0 There is no data There is no data 24 h 100.0 S. aureus 1 hour 99.93 2 hours 100.0 There is no data There is no data 4 hours 100.0 Mycobacterium b5 2 hours 99.94 4 hours 100.0 There is no data There is no data 24 h 100.0

Claims (4)

1. A water-dispersion varnish-and-paint composition with a biocidal action, including a nonionic water-borne film-forming - an aqueous polymer dispersion, an aqueous solution of a biocidal additive - a derivative of polyhexamethylene guanidine and a polymer paste obtained from a pigment and a filler and a dispersant solution containing water, an anionic non-polymer dispersant , emulsifier, organic solvent in the following ratio of components, wt.%: pigment paste 63.0 - 92.0 aqueous polymer dispersion 5.0 - 30.0 25% aqueous solution of biocidal additives 3.0 - 7.0 wherein the weight ratio of the nonionic cellulose thickener to the anionic polymer dispersant in the pigment paste is 2.0: 1.0-1.0: 2.0. 2. The composition according to claim 1, in which a hydrocellulose derivative introduced into the dispersing solution in an amount of 0.5-1.0 wt.% Is used as a nonionic cellulose thickener. 3. The composition according to claim 1, in which the sodium and ammonium salts of polycarboxylic acids used in the pigment paste in an amount of 0.17-0.55 wt.% Are used as an anionic polymer dispersant. 4. The composition according to claim 3, in which sodium polyphosphate is used as the anionic polymer dispersant.