Aqueous dispersions containing at least one alkyd resin and at least one polymerisate having at least one (meth)acrylate segment

FIELD: chemistry.

SUBSTANCE: present invention relates to making coatings from aqueous dispersions and an aqueous dispersion containing at least one alkyd resin and at least one polymerisate having at least one (meth)acrylate segment. The (meth)acrylate segment contains 1-30 wt % of structural units derived from (meth)acrylates which in the alkyl residue have at least one double bond and 8-40 carbon atoms, 0.1-10 wt % of structural units derived from monomers containing acid groups, and 50-98.9 wt % of structural units derived from (meth)acrylates having 1-6 carbon atoms in the alkyl residue, based on the weight of the (meth)acrylate segment.

EFFECT: invention enables to obtain dispersions with prolonged storage stability and coatings with high mechanical strength.

39 cl, 2 tbl, 7 ex

 

This invention relates to aqueous dispersions that contain at least one alkyd resin and at least one polymerized at least one (meth)acrylate segment. Additionally, this invention concerns a method of obtaining these dispersions.

Means for creating coatings, in particular lacquers, for a long time produced synthetically. A large number of these funds to create coatings is based on the so-called alkyd resins, which are usually obtained with the use of polybasic acids, alcohols and fatty acids and/or derivatives of fatty acids. Separate groups of these alkyd resins under the action of an oxidising agent to form a crosslinked film, and this polymer cross-linking occurs through oxidation involving unsaturated groups. Many of these alkyd resins contain an organic solvent or dispersant, so that the resin can be applied to cover the product in a thin layer. However, from the use of this solvent should be abandoned for reasons of environmental protection, and safety. So I developed the corresponding resin-based aqueous dispersions, however, their storage stability is limited. In addition, many properties of alkyd resins are not optimal. For example, in many cases too the m high water absorption. In addition, for many applications the resistance to solvents or hardness is too low.

Accordingly, research studies were undertaken to replace the above classic lacquers based on alkyd. For example, the composition of the lacquer on the basis of the obtained solution polymers based on vinyl monomers is described in the German patent application DE-A-10106561. However, this composition contains a high proportion of organic solvents.

Additionally, also known aqueous dispersions of polymer-based (meth)acrylate. For example, in published German patent application DE-A-4105134 describes aqueous dispersions that can be used as binders in paints. This connecting means is carried out in several stages, and at first made polymerizate obtained in solution, which is used in emulsion polymerization after neutralization.

In addition, in the German patent application DE-A-2513516 describes aqueous dispersions, which contain polymers based on (meth)acrylates, and part of the (meth)acrylate contains unsaturated alcohol residues. The disadvantage of the described dispersion is, in particular, they are expensive to obtain, and polymers based on (meth)acrylates obtained through polymerization in RA the creators. However, these polymers have a high proportion of acidic groups, which is in the range from 5 to 20 wt.%, in terms of the polymer obtained in solution.

In the published German patent application DE-A-2638544 describes aqueous dispersions subjected to oxidative drying, which include emulsion polymers based on (meth)acrylate, and the part used (meth)acrylate contains unsaturated alcohol residues. However, to obtain emulsion polymer was used agents transfer circuit, so that the emulsion polymer exhibits high solubility.

Furthermore, aqueous dispersions, which contain polymers subjected to oxidative drying, presented in the publication F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation II", Journal of Applied Polymer Science, Vol.30, 4551-4570 (1985). These polymers contain from 2 to 8 wt.% structural units formed from (meth)acrylates with unsaturated long-chain alcohol residues. In addition, these polymers do not contain structural units which are obtained by polymerization of monomers containing acid groups. The stability of these dispersions, as well as the strength of varnishes are insufficient for many applications.

In addition, in the publications U.S. patent US 5750751, European patent application EP-A-1044993 and international application WO 2006/013061 describes means for creating n the floor, which contain polymers based on vinyl monomers, which can be crosslinked at room temperature. These polymers can be obtained as by polymerization in solution and in emulsion polymerization. A mixture of monomers, which should be subjected to polymerization, can, inter alia, contain (meth)acrylates, in which the alcohol residues modified with the use of unsaturated fatty acids. The disadvantage of the above varnishes that contain polymerizati-based (meth)acrylate, is their high cost. In addition, coatings that were obtained from the above funds to receive coatings often exhibit low strength. In these documents there are no indications for the use of these polymers in alkyd resins.

In addition, the prior art also known variance, which, in addition to polymers based on (meth)acrylates may also contain alkyd resins. For example, international application WO 98/22545 describes a polymer with structural units that are derived from (meth)acrylates with an unsaturated alcohol residues. These polymers can be used in combination with alkyd resins. However, to get from the described polymers, varnishes, solvents are used. Water dispersion in the international application WO 98/22545 not described. Matched with the public, these compositions are inherent in the above-mentioned disadvantages.

In addition, in the publication of Japanese patent JP 59011376 describes emulsion polymers based on (meth)acrylates. These polymers can have a very high content of (meth)acrylates, which contain unsaturated alcohol residues. Although it presents a mixture with other resins, however, are not explicitly represented by compositions that contain alkyd resin and polymerised at least one (meth)acrylate segment which contains from 1 to 30 wt.% structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms, from 0.1 to 10 wt.% structural units which are derived from monomers containing acid groups and 50 to the 98.9 wt.% structural units which are derived from (meth)acrylates having from 1 to 6 carbon atoms in the alkyl residue, in terms of the mass of the (meth)acrylate segment. The disadvantage of the compositions shown in Japanese patent JP 59011376, is their low stability during storage.

In addition, U.S. patent US 4010126 known compositions that include alkyd resin, modified polymers, (meth)acrylate, which is then used in the emulsion polymerization process. Getting HDMI described the operations carried out in several stages, so making this resin is very expensive.

In addition, in the publication of the European patent application EP-A-0267562 describes dispersions, which contain modified alkyd resin. To obtain an alkyd resin, in particular, copolymers are used, which is obtained by polymerization in solution (meth)acrylates and unsaturated fatty acids. While these fatty acids are incorporated into the copolymer by means of its double bonds. These resins is carried out in several stages, in particular, uses large amounts of solvents. In addition, requires a large number of simple glycol monobutyl ether, to obtain a dispersion. Similar dispersions are described in German patent application DE-A-3432482, and these dispersions have the same deficiencies as the variance, presented in European patent application EP-A-0267562.

Furthermore, from European patent application EP-A-1578864 known aqueous alkyd resins that have been modified (meth)acrylate polymers. To obtain (meth)acrylic polymers used large quantities of unsaturated fatty acids. However, the complicated process of obtaining these dispersions is a disadvantage. In addition, the described dispersion lead to coatings with relatively low what rochestie.

Thus, whereas the prior art, the objective of the invention is to obtain a tool for coatings and coatings with outstanding properties. In particular, the means for coatings should have a very low residual monomer content. Therefore, in addition, the objective of the invention was to obtain a dispersion, which is particularly long-term stability during storage and stability. In addition, the hardness of the coatings, which can be obtained from the means for coatings, would be varied within wide limits. According to a separate aspect of the present invention, in particular, would be of a composition that lead to a very hard, resistant to scratches coating.

In addition, the coating, which can be obtained from the means for coatings should have a high resistance to solvents. As another task you should consider obtaining means for coatings without volatile organic solvent. Coverage that can be obtained from aqueous dispersions should have a high resistance to external weather conditions, in particular high resistance to UV radiation. In addition, the film obtained from the means for coatings, would the region is to give low stickiness after a short time. In addition, tools for the manufacture of coatings according to the invention would be obtained easily and with minimal cost.

These and other tasks are not marked explicitly, which, however, can easily be identified and removed from discussed in the introductory part of this document relationships were solved by means of aqueous dispersions with all the hallmarks of paragraph 1 of the claims. Appropriate modification of the dispersions according to the invention is represented in the protected dependent claims. Regarding the method of obtaining the solution underlying the invention of the tasks is presented in paragraph 22 of the claims.

Therefore, the subject of this invention are aqueous dispersions containing

at least one alkyd resin, and

at least one polymerized at least one (meth)acrylate segment which contains

from 1 to 30 wt.% structural units derived from (meth)acrylates containing an alkyl residue, at least one double bond and 8 to 40 carbon atoms,

from 0.1 to 10 wt.% structural units derived from monomers containing acid groups, and

50 to the 98.9 wt.% structural units which are derived from (meth)acrylates having alkyl residue is t 1 to 6 carbon atoms, in each case, calculated on the weight of the (meth)acrylate segment.

In addition, using the methods according to the invention, among others, can be achieved the following benefits :

The dispersions according to the invention have a very low residual monomer content.

The hardness of the coatings, which can be obtained from the dispersions according to the invention can vary within wide limits. So can be obtained, in particular, solid, resistant to scratches coating. Coverage that can be obtained from the dispersions according to the invention show unexpectedly high resistance to solvents, which is manifested, in particular, in experiments with isobutyl ketone (MIBK) or ethanol. So, the resulting surfaces, in particular, in the case of the experiments according to tests for furniture surfaces according to DIN 68861-1 show exceptional characteristics. When this coating can also be cleaned using non-polar solvents, in particular, wash gasoline, except that the coating thus irreversibly damaged.

The dispersions according to the invention preferably do not contain volatile organic solvents. In addition, the dispersions according to the invention exhibit a high storage stability, high stability and very good p is edeleny shelf life. In particular, the formation of aggregates is detected with difficulty.

Coverage that can be obtained from aqueous dispersions that exhibit high resistance to external weather conditions, in particular high resistance to UV radiation. In addition, the films obtained from the aqueous dispersions have a low stickiness after a short time. In addition, means for coatings according to the invention exhibit high stability of the wet film, as well as the increased pot life.

In addition, the coating, which can be obtained from the dispersions according to the invention, many materials show a particularly high adhesive strength, abrasion resistance and ability to withstand load. In particular, the preferred coating, and materials coated with the surface coating according to the invention, can be subjected to high mechanical loads without the occurrence of cracking.

The dispersions according to the invention can be obtained in a large scale with the lowest cost. Dispersion and emulsion polymers according to the invention are environmentally friendly and can be recycled and can be safely and cost-effectively. When this dispersion according to the invention show a very high shear strength.

Water dispersion with the according to the invention contain, at least one alkyd resin. Alkyd resins known for a long time, and under them, as a rule, understand resins which are obtained by condensation of polybasic carboxylic acids and polyhydric alcohols, these connections are, as a rule, are modified with long-chain alcohols (fatty alcohols), fatty acids or compounds containing fatty acids, for example, fats or oils (according to DIN 55945; 1968). Alkyd resins represented, for example, information on the CD-ROM UIImann''s Encyclopedia of Industrial Chemistry 5. Edition. Along with these classic alkyd resins can also be used resins which possess similar properties. These resins also contain a high percentage of groups that are derived from the above-mentioned long-chain alcohols (fatty alcohols), fatty acids or compounds containing fatty acids, for example, fats or oils. However, these derivatives do not necessarily contain a polybasic carboxylic acid and can be obtained, for example, the interaction of polyols with isocyanates. Alkyd resins that can be used, preferably can be mixed or diluted with water.

Preferred polybasic carboxylic acid to produce alkyd resins, which preferably should in order to emanate in the dispersions according to the invention, among other things, are di - and tricarboxylic acids, such as phthalic acid, isophthalic acid, 5-(netresult)-isophthalic acid, terephthalic acid, trimellitate acid, 1,4-cyclohexanecarbonyl acid, butandikislota acid, maleic acid, fumaric acid, sabotinova acid, adipic acid and azelaic acid. These acids can also be used to obtain in the form of anhydrides. Especially it is preferable to obtain alkyd resins are aromatic dicarboxylic acids. The share of polybasic carboxylic acids is preferably in the range from 2 to 50 wt.%, particularly preferably from 5 to 40 wt.%, in terms of the mass of the starting compounds to obtain the resin in the reaction mixture.

In addition, to obtain alkyd resins are used polyhydric alcohols. Such alcohols include, among others, trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylacetyl, neopentylglycol, ethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetrahydrofuran, polycaprolactone, polycaprolactone, simple monoallelic ether trimethylol, simple dellroy ether trimethylol, simple trailerby ether of pentaerythritol, simple dellroy ether foams is of eritria, simple monoallelic ether of pentaerythritol, 2-ethyl-2-hydroxymethyl-1,3-propandiol, 2-methyl-1,3-propandiol, 2,2,4-trimethylpentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2'-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol a), propylene glycol, dipropyleneglycol, polypropyleneglycol, glycerin, and sorbitol. Of them, preferred are, in particular, trimethylacetyl, trimethylolpropane, pentaerythritol and sorbitol. According to a separate aspect, preferred are, in particular, alcohols with three or more hydroxyl groups. The proportion of polyhydric alcohols is preferably in the range from 2 to 50 wt.%, particularly preferably from 5 to 40 wt.%, in terms of the mass of the starting compounds to obtain the resin in the reaction mixture.

In addition, to obtain the above-mentioned alkyd resins can be used, in particular, fatty acids. In this case, first of all, can be used saturated and unsaturated fatty acids, and, above all, preferred are mixtures which contain unsaturated fatty acids. Preferred acids contain from 6 to 30, particularly preferably from 10 to 26, and most preferably from 12 to 22 carbon atoms. The proportion of fatty acid is preferably in the range from 2 to 90 wt.%, particularly preferably from 10 to 70 wt.%, in terms of the mass of the starting substances for the doctrine of the resin in the reaction mixture.

Suitable saturated fatty acids include, among others Caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, arachnid acid, Bekenova acid, Ognianova acid, zerotinova acid, palmarola acid and stearic acid.

To the preferred unsaturated fatty acids include, among others undecylenoyl acid, palmitoleic acid, oleic acid, elaidic acid, Aksenova acid, Aksenova acid, catolina acid, erucic acid, Neronova acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, kopandanova acid and/or cervanova acid.

In addition, the above fatty acids can also be used in the form of their esters, for example, in the form of triglycerides.

In addition, the above-mentioned alkyd resin can contain other components. These include, for example, monobasic carboxylic acids, monohydroxy alcohols or compounds that lead to the inclusion in resin emulsifying groups, such as, for example, the oxides. In addition, the alkyd resin may contain hydroxycarbonate acid, such as, for example, 2-, 3-, 4-hydroxybenzoic acid, oksolinova acid, dihydroxy who Rodionova acid, dihydroxyethane acid, dihydroxybenzoic acid, 2,2-dimethyllysine acid, 2,2-dimethylolpropionic acid, 2,2-dimethylaniline acid, and 2,2-dimethylamphetamine acid.

In addition, can also be used modified alkyd resins which are modified resins, in particular, rosin, polymers of styrene, acrylic polymers, epoxies, urethanes, polyamides and/or silicones. These modifications among other things, provided in the quotation above patent literature, as well as information on the CD-ROM Ullmann''s Encyclopedia of Industrial Chemistry 5. Edition. With these improvements of the invention may vary, in particular, drying, adhesion strength, resistance to exterior weathering, age limit, resistance to chemicals, full cure, resistance to spreading of the wet film, and abrasion resistance.

For example, can preferably be used alkyd resins which are modified with polymers obtained by radical polymerization. Resins of this type are known, inter alia, from publications, U.S. patent US 5538760, US 6369135, and from German patent application DE-A-19957161.

According to publications of the U.S. patents US 5538760 and US 6369135 modified alkyd resins, among other things, can be obtained p the fact that, the mixture of monomers subjected to polymerization in the presence of alkyd resins. The mass ratio of the mixture of monomer and alkyd resin thus preferably is in the range from 100:1 to 1:4, preferably from 5:1 to 1:1.

Among other particularly suitable are modified acrylates alkyd resin described in the German patent application DE-A-19957161. These alkyd resins, along with basic alkyd component, contain groups which are obtained by polymerization of (meth)acrylates.

These modified acrylates alkyd resins can be obtained due to the fact that in the presence of at least one miscible with water diol

(1) was dispersed in water at least one alkyd resin, which. in terms of its total weight, contains from 0.1 to 10 wt.% alliancegroup located in the side chain and/or which is the end, thanks to what is obtained dispersion 1,

(2) is subjected to graft copolymerization in dispersion 1 mixture of methacrylic acid and at least one additional olefinic unsaturated monomer containing no carboxyl groups, allowing obtained dispersion 2, and

(3) one or n times.

(3.1) at least one olefinic unsaturated monomer containing no carboxyl groups, and/or

(3.2) at least one mixture of men is our least one olefinic unsaturated monomer, containing carboxyl groups, and at least one olefinic unsaturated monomer containing no carboxyl groups, is subjected to graft copolymerization in the dispersion 2 or dispersion from 2 to n-1, resulting in corresponding the above stages of the process (2) or (2) to (n-1), with the condition that at the stage of process (3) or his reps from (3) to (n) introduces acid groups in an amount which in total corresponds to at most 90 mol.% the number of acid groups introduced at the stage of process (2).

The above alliancegroup located in the side chain and/or which limit may be contained in the alkyd resin in amounts of, in each case in terms of alkyd resin, from 0.1 to 10, mostly from 0.2 to 9, preferably from 0.3 to 8, particularly preferably from 0.4 to 7, extremely preferably from 0.5 to 6 and in particular from 0.6 to 5 wt.%. The oxygen atom of alliancegroup may be part of a urethane group, an ester group or a fragment of a simple ester, which connect allyl balance with the main chain alkyd resin.

Examples of suitable compounds for introducing alliancegroup located in the side chain and/or which end are allyl alcohol, a simple 2-hydroxyethylcellulose ether, a simple 3-hydroxypropylcellulose the IDF, simple trimethylolpropane or diallylamine esters, simple glycerine or diallylamine esters, simple pentaerythritol-, di -, or-triallylamine esters, simple manamana-, di-, or three - or-tetraethylene ethers, allyl complex esters dihydroxypropane acid, dihydroxystearic acid, dihydroxybenzoic acid, 2,2-dimethylisoxazol acid, 2,2-dimethylolpropionic acid, 2,2-dimethylamylamine acid or 2,2-dimethylaminoethanol acid or allylurea, of which preferred is a simple monoallelic ether trimethylolpropane. For modification of the acrylate dispersion 1 in stage (2) can be subjected to graft copolymerization with methacrylic acid and at least one additional olefinic unsaturated monomer. Additional olefinic unsaturated monomers in addition to the olefinic unsaturated double bonds may contain reactive functional groups other than carboxyl groups, for example, groups are active towards isocyanates, carbamates, N-methylol or a simple N-myelolipomas groups or active against alkoxycarbonylmethyl. It is important that these reactive functional groups under the given reaction conditions and subsequent storage of the dispersions according to the invention does not reacts with carboxyl what groups of methacrylic acid or other reactive functional groups, present if necessary. Examples of reactive functional groups that satisfy these requirements is a hydroxyl group. These monomers are known, and examples are presented in German patent DE 19957161. These include, above all, complex hydroxyalkyl esters of acrylic acid, methacrylic acid or other alpha, beta-unsaturated olefinic carboxylic acids, esters of acrylic acid, methacrylic acid, crotonic acid or metacrilato acid containing alkyl residue with up to 20 carbon atoms.

In addition, the preferred alkyd resins are those which can be obtained according to the publication of U.S. patent US 5096959. These alkyd resins modified cycloaliphatic polycarboxylic acids, and suitable for modification are, in particular, cyclohexanecarbonyl acid and cyclopentanecarbonyl acid.

In addition, there may be used an alkyd resin that is modified with polyethylene glycol. In a large number of patent publications described getting able to give an aqueous emulsion of alkyd resins by modification with polyethylene glycol (PEG). In most ways directly in alkyd resin through reaction of transesterification or esterification approx implement the RNO from 10 to 30% PEG (see, among other things, U.S. patent US 2634245; 2853459; 3133032; 3223659; 3379548; 3437615; 3437618; 10 3442835; 3457206; 3639315; German open description 14 95 032 or British patents number 1038696, and the number of 1044821).

The preferred alkyd resins which are modified with polyethylene glycol, among others, are known from the published German patent application DE-A-0029145. According to this document it may be the interaction of polyethylene glycol with a carboxylic acid containing an epoxy group. Thus obtained reaction product can then be used in the reaction mixture to obtain an alkyd resin. Preferred glycols for modification of alkyd resins have srednekamennogo molecular weight, for example, from 500 to 5000 g/mol.

Especially preferably an alkyd resin, modified polyethylene glycol, can be further modified using copolymerization, which can be obtained by polymerization of methacrylic acid, unsaturated fatty acids, as well as vinyl and/or vinylidene connections.

Also suitable are the alkyd resins which are modified with urethane groups. Alkyd resins of this type, among other things, presented in the international application WO 2006/092211 and European patent application EP-A-1533342.

According to worthwhile improvement can be used in Atsa uretonimine resin, described in European patent application EP-A-1533342, which contain structural elements that are derived from unsaturated fatty acids A1, aliphatic, or aromatic, or aromatic-aliphatic monocarboxylic acids A2, which do not contain olefinic double bonds, a cycloaliphatic dicarboxylic acids A3 or their anhydrides, at least triatomic, preferably at least chetyrehtomnik alcohols A4, as well as aromatic or aliphatic multifunctional primarily difunctional isocyanates A5. Uretonimine resin is preferably obtained in the two-stage reaction, with the first stage components A1 to A4 are subjected to esterification, while the acid number of the product of the first stage is preferably a maximum of 10 mg/g, particularly preferably 5 mg/g In the second stage, the product of the first stage containing a hydroxyl group interacts with the isocyanate A5 with increasing molecule by adding a small amount (up to 1% by weight of the product obtained in the first stage, preferably up to 0.5% of its weight) of the tertiary amine. Preferred uretonimine resins have an index of Staudinger, measured in chloroform at 23°C of at least 9 cm3/g, preferably at least 11 cm3/year

Preferably can use Atsa uretonimine resin, which are obtained by the interaction of polyhydric alcohols And'modified fatty acids In'fatty acids' and multifunctional isocyanates D'. Modified fatty acids' can be obtained by the interaction of unsaturated fatty acids B1' with unsaturated carboxylic acids B2'. These Ratanakiri, among other things, known from international application WO 2006/092211.

Preferably the modified fatty acids In' have an acid number of at least 80 mg/g, Especially preferably an increase of the acid number due to the graft polymerization is in the range from 80 mg/g to 250 mg/g and highly preferably in the range from 100 mg/g to 150 mg/g, and an acid number may be determined in accordance with DIN EN ISO 2114. Iodine number of fatty acids With'used to obtain Ratanakiri resin, is mainly of at least 80 g/100 g, and preferably at least 120 g/100 g To obtain Ratanakiri resins described in the international application WO 2006/092211, as a rule, the components interact And',' With', and the condensation product preferably has a hydroxyl functionality of at least 1.9 to, particularly preferably at least 2. In addition, the condensation product may contain groups which are derived from polybasic CT is nowych acids, in particular, the above di - and tricarboxylic acids. This condensation product is then interacts with a multifunctional isocyanate. To the preferred multifunctional isocyanates include 2,4 - and 2,6-toluylenediisocyanate, as well as their technical mixtures, bis-(4-isocyanatophenyl)methane, isophorondiisocyanate, bis-(4-isocyanatophenyl)methane, and 1,6-diisocyanatohexane, and formed of them isocyanurate, allophanate and biuret.

Along with the above classic alkyd resins, for which, as a rule, are polycarboxylic acids can also be used with other resins, such as those that have already been mentioned above. These primarily include urethane resin, which can be obtained by the reaction of polyhydric alcohols with multifunctional isocyanates. Preferred urethane resins are known, for example, from European patent application EP-A-1129147. They can be obtained, for example, in the interaction of esters of aminodiol with polyols and multifunctional isocyanates. Esters of aminodiol, which should be used according to European patent application EP-A-1129147, can be obtained by the reaction of vegetable oils with N,N-dialkanolamine.

According to a preferred aspect of this and is gaining alkyd resin may have an iodine number, determined according to DIN 53241, at least 1 g of iodine/100 g, preferably at least 10 g iodine/100 g, particularly preferably at least 15 g iodine/100 g According to a separate aspect of the present invention iodine number alkyd resin may be in the range from 2 to 100 g iodine per 100 g of alkyd resin, particularly preferably from 15 to 50 g of iodine per 100 g of alkyd resin. Iodine number can be defined for a variance, its value refers to the solids content.

It is advisable, when the alkyd resin may have an acid number in the range from 0.1 to 100 mg KOH/g, preferably from 1 to 40 mg KOH/g and most preferably in the range from 2 to 10 mg KOH/g Acid number can be determined for a variance in accordance with DIN EN ISO 2114, its value refers to the solids content.

The hydroxyl number of the alkyd resin may preferably be in the range from 0 to 400 mg KOH/g, particularly preferably from 1 to 200 mg KOH/g and most preferably in the range from 3 to 150 mg KOH/g hydroxyl number can be determined for dispersion according to the standard ASTM E222, its value refers to the solids content.

The production of alkyd resins known for a long time and is carried out by condensation of the above-mentioned alcohols and acids, and modificat what I may be in the process of this condensation, and at the end of this condensation. In this regard, refer, in particular, cited above literature.

Furthermore, aqueous dispersions according to the invention contain at least one polymerized at least one (meth)acrylate segment which contains from 1 to 30 wt.% structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms, from 0.1 to 10 wt.% structural units which are derived from monomers containing acid groups and 50 to the 98.9 wt.% structural units which are derived from (meth)acrylates having from 1 to 6 carbon atoms in the alkyl residue, in terms of the mass of the (meth)acrylate segment.

The term "polymerized at least one (meth)acrylate segment" means that the dispersion contains particles, which were obtained by polymerization of a mixture of monomers that include at least one (meth)acrylate, and the polymerization may be conducted in one stage or in several stages. Thus polymerizat may contain one or more polymers, which can be separated, for example, using a suitable solvent. The term "segment" means that polymerizat includes at least one segment with duplicate (meth)acrylic the structural units. Thus polymerizat may consist of one segment, thus constructed, or contain other segments. Mass fraction of (meth)acrylate segment, in terms of weight polymerizate, is preferably at least 10 wt.%, particularly preferably at least 20 wt.%. Polymerizat preferably contains at least 40 wt.%, particularly preferably at least 60 wt.% and highly preferably at least 90 wt.% (meth)acrylate.

(Meth)acrylate segment polymerizate, which should be used according to the invention, contains from 1 to 30 wt.%, preferably from 5 to 25 wt.% and particularly preferably from 10 to 20 wt.% structural units which are derived from (meth)acrylates having an alkyl residue with at least one double bond and 8 to 40 carbon atoms, calculated on the total weight of (meth)acrylate segment. Preferably polymerized can be obtained by radical polymerization. Accordingly, the mass fraction of structural units derived from the mass fractions of the respective monomers used for obtaining the (meth)acrylate segment.

The expression "(meth)acrylate" includes methacrylates and acrylates, and mixtures of both. (Meth)acrylates, which contain in the alkyl residue, at least one double bond and 8 is about 40 carbon atoms, are esters of (meth)acrylic acid in which the alcohol residue contains at least one double bond and 8 to 40 carbon atoms. Alkyl or alcohol residue may preferably contain from 10 to 30, and particularly preferably from 12 to 20 carbon atoms, and the remainder may contain heteroatoms, in particular oxygen atoms, nitrogen or sulfur. Alcohol residue may contain one, two. three or more double bonds. The conditions of the polymerization, which is obtained this emulsion polymer, preferably chosen so that when the polymerization is maintained to the maximum possible proportion of double bonds in the alcohol residue. This can be done, for example, using the spatial shielding double bonds contained in the alcohol residue.

Iodine number (meth)acrylate, which should be used for emulsion polymer containing an alcohol residue of at least one double bond and 8 to 40 carbon atoms, is preferably at least 40, particularly preferably at least 80 and most preferably at least 140 g of iodine/100 g of (meth)acrylate.

(Meth)acrylates of this type, generally, correspond to the formula (I),

in which the residue R is predstavljaet a hydrogen atom or methyl, a R1denotes a linear or branched residue containing from 8 to 40 carbon atoms, which contains at least one double bond.

(Meth)acrylates, which contain at least one double bond and 8 to 40 carbon atoms, can be obtained, for example, esterification of (meth)acrylic acid, the conversion of (meth)acryloylmorpholine or transesterification of (meth)acrylates under the action of alcohols that contain at least one double bond and 8 to 40 carbon atoms. These reactions are represented, for example, information on the CD-ROM Ullmann''s Encyclopedia of Industrial Chemistry 5. Edition or publication F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation I", Journal of Applied Polymer Science, Vol.30, 4571-4582 (1985).

Suitable for this purpose are alcohols, among others, include octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecane, eicosanol, docosanol, octadienal, nonadienal, decadienal, undecadienal, dodecadienol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecadiene, octadecatrienoic, noneducational, eicosadienoic and/or docosanol. These so-called fatty alcohols are partly commercially available or can be obtained from fatty acids, and this prevremeni is presented, for example, F.-B. Chen, G. Bufkin, Journal of Applied Polymer Science, Vol.30, 4571-4582 (1985).

For the preferred (meth)acrylates, which can be obtained by this method are, first of all, octadecadienyl(meth)acrylate, octadecadienyl(meth)acrylate, hexadecyl(meth)acrylate, octadecenyl(meth)acrylate, and hexadecanediol(meth)acrylate.

In addition, (meth)acrylates, which contain in the alkyl residue with at least one double bond and 8 to 40 carbon atoms, can also be obtained by the reaction of an unsaturated fatty acid with (meth)acrylates, in which the alcohol residue containing reactive group. To reactive groups include, in particular, hydroxyl groups and epoxy groups. Accordingly, as the source materials for the production of the above (meth)acrylates can be used, for example, hydroxyalkyl(meth)acrylates, such as 3-hydroxypropyl(meth)acrylate, 3,4-dihydroxybutyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2,5-dimethyl-1,6-hexanediol(meth)acrylate, 1,10-decanediol(meth)acrylate or (meth)acrylate containing an epoxy group, for example, glycidyl(meth)acrylate.

Suitable fatty acids for interaction with the abovementioned (meth)acrylates are widely available commercial products and are obtained from natures is on raw. Among others, these include undecylenoyl acid, palmitoleic acid, oleic acid, elaidic acid, Aksenova acid, Aksenova acid, catolina acid, erucic acid, Neronova acid, linoleic acid, linolenic acid, arachidonic acid, timnodonic acid, kopandanova acid and/or cervanova acid.

For the preferred (meth)acrylates, which can be obtained in this way are, in particular, complex (meth)acryloyloxy-2-hydroxypropionic ether of linoleic acid complex (meth)acryloyloxy-2-hydroxypropionic ester of linolenic acid, as well as complex (meth)acryloyloxy-2-hydroxypropionic ester of oleic acid.

The interaction of an unsaturated fatty acid with (meth)acrylates, which contain an alcohol residue of a reactive group, is known and is represented, for example, in German patent applications DE-A-4105134, DE-A-2513516, DE-A-2638544, as well as U.S. patent US 5750751.

The above (meth)acrylates containing at least one double bond, can be used individually or as mixtures of two or more (meth)acrylates.

Unexpected benefits demonstrate, in particular, polymerizate, which include a large proportion of structural units derived complex (meth)acryloyloxy-2-hydroxypropyl what about the ether of linoleic acid. It may turn out, in particular, coatings, are relatively resistant to scratching and solvents, and means for obtaining coatings can be processed particularly easily and have unexpectedly high stability during storage.

These advantages, in particular, can be achieved in the case of (meth)acrylate segments that include at least 20 wt.%, preferably at least 40 wt.% and most preferably at least 50 wt.% structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of linoleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms. Preferably (meth)acrylate segment contains from 45 to 80 wt.%, particularly preferably from 55 to 70 wt.% structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of linoleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

According to another aspect of the present invention are preferred polymerizate that on the receive at least 5, preferably at least 10 wt.% and particularly preferably at least 15 wt.% structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of oleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms. Preferably such polymerizate contains from 15 to 45 wt.%, particularly preferably from 20 to 35 wt.% structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of oleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

In addition, special improvement can be achieved due to the fact that the mass ratio of structural units which are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of linoleic acid, and structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of oleic acid, greater than or equal to 1, and this mass ratio preferably lies in the range from 8:1 to 1:1, particularly preferably from 5:1 to 3:2.

In addition, (meth)acrylic is hydrated segment polymerizate according to the invention contains from 0.1 to 10 wt.%, preferably from 0.5 to 8 wt.% and especially preferably from 1 to 5 wt.% structural units which are derived from monomers containing acid groups, in terms of the total weight of (meth)acrylate segment.

The monomers containing acid groups, are compounds, which preferably can react radical copolymerization with the above-mentioned (meth)acrylates. Preferably the monomers containing acid groups have from 2 to 7 carbon atoms, and an end of the double bond. These include, for example, monomers with acid sulfopropyl, as, for example, vinylsulfonic acid; monomers with a phosphonic acid group, such as, for example, vinylphosphonic acid, and unsaturated carboxylic acids, such as methacrylic acid, acrylic acid, fumaric acid and maleic acid. Especially preferred are methacrylic acid and acrylic acid. The monomers containing acid groups can be used individually or as mixtures of two, three or more monomers containing acid groups.

In addition, (meth)acrylate segment used polymerizate according to the invention contains from 50 to the 98.9 wt.%, preferably from 60 to 95 wt.% and particularly preferably from 70 to 90 wt.% structural units that t is Auda derivatives of (meth)acrylates with the number of carbon atoms in the alkyl residue of 1 to 6, in terms of the total weight of (meth)acrylate segment.

(Meth)acrylates of this type, generally, correspond to the formula (II)

in which the residue R represents a hydrogen atom or methyl, a, R2denotes a linear or branched residue containing from 1 to 6, preferably from 1 to 4 carbon atoms.

These include, first of all, (meth)acrylates which derive from saturated alcohols, such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, tertbutyl(meth)acrylate, and pentyl(meth)acrylate, hexyl(meth)acrylate;

cycloalkyl(meth)acrylates, such as cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate; and

(meth)acrylates which derive from unsaturated alcohols, such as 2-PROPYNYL(meth)acrylate, allyl(meth)acrylate and vinyl(meth)acrylate.

Particularly preferred mixtures are used, which include methacrylates and acrylates. Thus, in particular, can be applied to a mixture of methyl methacrylate and acrylates with the number of carbon atoms from 2 to 6, such as acrylate, butyl acrylate and hexidecimal.

Along with the above structural units (meth)acrylate segment of the emulsion polymer according to the invention may contain structural units which are derived from the monomers. These comonomers different from the above structural units of the emulsion polymer, however, can copolymerisate with the above monomers.

These include, for example, (meth)acrylates containing at least 7 carbon atoms in the alkyl residue, which derive from saturated alcohols, such as, for example, 2-ethylhexyl(meth)acrylate, heptyl(meth)acrylate, 2-tertbutylphenyl(meth)acrylate, octyl(meth)acrylate, 3-isopropylphenyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, undecyl(meth)acrylate, 5-methylundecyl(meth)acrylate, dodecyl(meth)acrylate 2-methyldecyl(meth)acrylate, tridecyl(meth)acrylate, 5-methyldecyl(meth)acrylate, tetradecyl(meth)acrylate, pentadecyl(meth)acrylate, hexadecyl(meth)acrylate, 2-methylhexane(meth)acrylate, heptadecyl(meth)acrylate, 5-isopropylimidazole(meth)acrylate, 4-tributylstannyl(meth)acrylate, 5-atelectasis(meth)acrylate, 3-isopropylthiazole(meth)acrylate, octadecyl(meth)acrylate, monodecyl(meth)acrylate, eicosyl(meth)acrylate, tetracosyl(meth)acrylate, saarilahti(meth)acrylate, docosyl(meth)acrylate and/or anotherattribute(meth)acrylate; cycloalkyl(meth)acrylates, such as 3-vinylcyclohexane(meth)acrylate, bornyl(meth)acrylate, cycloalkyl(meth)acrylates, such as 2,4,5-titlebuy-3-vinylcyclohexane(meth)acrylate, 2,4,5-tetrametyl-3-vinylcyclohexane(met)and is relat, 2,3,4,5-tetratriacontane(meth)acrylate; NITRILES of (meth)acrylic acid and other nitrogen-containing (meth)acrylates, such as N-(methacryloyloxyethyl)diisobutylamine, N-(methacryloyloxyethyl)directdetection, methacryloyloxyethyl, 2-methacryloyloxyethyl, cyanomethylation; aryl(meth)acrylates such as benzyl(meth)acrylate or phenyl(meth)acrylate, and aryl residues in each case may be unsubstituted or may contain up to four substituents; (meth)acrylates, which contain two or more (meth)acrylic group, glycolide(meth)acrylates, such as etilenglikoli(meth)acrylate, diacylglyceride(meth)acrylate, triethyleneglycol(meth)acrylate, Tetra -, polietilenglikoli(meth)acrylate, 1,3-butanediol(meth)acrylate, 1,4-butanediol(meth)acrylate, 1,6-hexanediol(meth)acrylate, glycerine(meth)acrylate; di(meth)acrylates of ethoxylated bisphenol a; (meth)acrylates with three or more double bonds, such as, for example, glycerine(meth)acrylate, trimethylolpropane(meth)acrylate, pentaerythrityl(meth)acrylate and dipentaerythritol(meth)acrylate;

vinylchloride, such as, for example, vinyl chloride, viniferin, vinylidenechloride and vinylidenefluoride; heterocyclic (meth)acrylates, such as 2-(1-imidazolyl)ethyl(meth)acrylate, 2-(4-morpholinyl)ethyl(meth)acrylate and 1-(2-methacryloyloxyethyl)-2-pyrrol the don;

complex vinyl esters such as vinyl acetate;

styrene, substituted styrene with one alkyl substituent in the side chain, such as, for example, α-methylsterols and β-atillery, substituted styrene with an alkyl substituent in the ring, such as vinyltoluene and p-methylsterol, halogenated styrene such as, for example, monochlor-sterols, dichlorostyrene, dibromostyrene and tetrabromoethane;

heterocyclic vinyl compounds such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyridine, vinylpyridine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinyl pyrrolidone, 2-vinyl pyrrolidone, N-vinylpyrrolidone, 3-vinylpyrrolidone, N-vinylcaprolactam, N-vinylboronate, vinyloxy, viniferin, Venitian, vinylsilane, and vinylthiazole hydrogenated vinylthiazole, vinylacetal and hydrogenated vinylacetal;

vinyl and izoprenil ethers;

derivatives of maleic acid, such as, for example, maleic acid anhydride, esters of maleic acid, for example, a complex of dimethyl ether maleic acid anhydride methylmaleimide acid, maleinimide, methylmaleimide; and fumaric acid derivatives, such as dimethyl ether complex fumaric acid.

the Olya structural units, which are derived from comonomers can vary depending on the use and profile of properties of the polymer. Typically, this percentage may be in the range from 0 to 45 wt.%, preferably from 2 to 30 wt.% and particularly preferably from 3 to 10 wt.%, in terms of the total weight of (meth)acrylate segment.

The resistance of the coatings to the external atmospheric influences can be improved, for example, by reducing the proportion of monomers of styrene in the tool for creating coatings or respectively in the emulsion polymer, so that is extremely resistant to UV coatings can be obtained from the means for creating coatings that do not contain sterols. According to a separate modification of this invention polymerizate containing at least one (meth)acrylate segment comprises at most 30 wt.%, particularly preferably at most 15 wt.% structural units which are derived from styrene, substituted styrene with an alkyl substituent in the side chain, substituted styrene with an alkyl substituent in the ring and/or halogenated styrene, calculated on the total weight of (meth)acrylate segment.

The coating is extremely resistant to scratching and solvents can be obtained, in particular, due to the fact that polymerizate containing at meredin (meth)acrylate segment, includes at most 10 wt.% structural units which are derived from (meth)acrylates obtained by the interaction of saturated fatty acids with at least one (meth)acrylate that contains an alcohol residue of a reactive group, calculated on the total weight of (meth)acrylate segment. Unexpected improvements in these coatings demonstrate, first of all, in the case of emulsion polymers, which include preferably from 0.05 to 5, particularly preferably from 0.1 to 3 wt.% structural units which are derived from (meth)acrylates which are obtained by the interaction of saturated fatty acids with at least one (meth)acrylate containing an alcohol residue of a reactive group, calculated on the total weight of (meth)acrylate segment. As the (meth)acrylate with a reactive group in the alcohol residue may preferably be used glycidyl(meth)acrylate. Saturated fatty acids that can interact with (meth)acrylate containing at least one reactive group in the alcohol residue, preferably glycidyl(meth)acrylate, preferably contain from 10 to 26, particularly preferably from 12 to 22 carbon atoms. To saturated fatty acids with the number of carbon atoms from 10 to 26 include, in particular, Kapralova the acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, arachnid acid, Bekenova acid, Ognianova acid, zerotinova acid, palmarola acid and stearic acid.

Preferably polymerizate containing at least one (meth)acrylate segment may contain component from 2 to 60 wt.%, particularly preferably from 10 to 50 wt.% and most preferably from 20 to 40 wt.%, in terms of weight polymerizate containing at least one (meth)acrylate segment, the portion which is soluble in tetrahydrofuran (THF) at 20°C. For determination of the soluble portion of the sample polymerizate containing at least one (meth)acrylate segment, dried in the absence of oxygen at 20°C for 4 hours and placed in a 200-fold amount of solvent, based on the weight of the sample. To ensure the absence of oxygen, the sample can be dried, for example, in nitrogen atmosphere or in vacuum. Then the solution is separated from nerastvorimaya part, for example, by filtration. After evaporation of the solvent is determined by the mass of the solid residue. For example, the sample is dried in vacuum emulsion polymer weight of 0.5 g can be drawn in 150 ml of THF for 4 hours.

According to a preferred modification of this invention polymers is t, containing at least one (meth)acrylate segment may have swelling in tetrahydrofuran (THF) at 20°C of at least 1000%, especially preferably at least 1400% and most preferably at least 1600%. The upper bound value is not critical, and the swelling is preferably not more than 5000%, particularly preferably not more than 3000% and highly preferably no more than 2500%. To determine the swelling of the sample polymerizate containing at least one (meth)acrylate segment, dried in the absence of oxygen at 20°C for 4 hours and placed in a 200-fold amount of THF. When this occurs swelling of the sample. The sample subjected to the swelling thus separated from the rest of the free solvent. Then from the sample to remove the solvent. For example, most of the solvent can evaporate at room temperature (20°C). Remaining solvent can be removed in a drying Cabinet (140°C), and, as a rule, this can be done within 1 hour. From the mass of solvent absorbed by the sample, and the dry weight of the sample is obtained, the amount of swelling. In addition, by using the difference in mass of the sample before the experiment with the swelling and the mass of dried sample after the experiment with swelling is determined by the soluble fraction of emulsion floor the measure.

The radius of the particles polymerizate containing at least one (meth)acrylate segment can be in a wide range. So can be used polymerizate, in particular, with the radius of the particles in the region of from 10 to 500 nm, preferably from 10 to 100 nm, particularly preferably from 20 to 60 nm. First of all, the radius of the particles less than 50 nm may be favorable for the formation of films and properties of coatings.

According to a separate aspect of the present invention polymerizate containing at least one (meth)acrylate segment may have a particle radius of at least 50 nm. Preferably the radius of the particles is in the range from 60 to 500 nm, particularly preferably from 70 to 150 nm and highly preferably from 75 to 100 nm. The radius of the particles can be determined using the method of the FCC (photon correlation spectroscopy), and these data refer to the value of d50 (50% of the particles are smaller and 50% are larger). For this purpose can be used, for example, the analyzer of submicron size particles of the company Beckman Coulter - N5 Submicron Particle Size Analyzer. When using polymerization with the above particle sizes can be unexpectedly improved stability of the dispersions during storage.

The transition temperature in the glassy state (meth)acrylate segment is preferably in the range from -30°C to 70°C, the OS is especially preferably in the range from -20 to 40°C and highly preferably in the range from 0 to 25°C. On the transition temperature in the glassy state can influence the type and proportion of monomers used for obtaining the (meth)acrylate segment. The temperature of the transition polymerizate in the vitreous state of the Tg can be determined by a known method, by the method of differential scanning calorimetry (DSC). In addition, the transition temperature in the glassy state can also be pre-approximately determined using equation Fox. According to Fox, T.G. Fox, Bull. Am. Physics Soc. 1, 3, page 123 (1956) we have the following relation:

in which xnrepresents a mass ratio (wt.%/100) of the monomer n and Tgndenotes the transition temperature in the glassy state for homopolymer of the monomer n, measured in degrees Kelvin. Other useful guidance a specialist can learn from the publication Polymer Handbook, 2ndEdition, J. Wiley & Sons, New York (1975), which shows the values of Tg for the most common homopolymerization.

The principle of construction of polymerizate is not critical for many applications and properties. Accordingly, polymerizat may include random copolymers, gradient copolymers, block copolymers and/or graft copolymers. Block copolymers or, respectively, the gradient copolymers can be obtained, for example, the R, due to the fact that during the growth of the chain continuously change the composition of the Monomeric composition. According to a preferred aspect of this invention, polymerized contains statistical copolymer for which the composition of the monomer composition in the polymerization process is basically constant. However, since the monomers may have different copolymerization parameters, the exact composition can vary throughout the polymer chain polymerizate.

Polymerizate can be a homogeneous polymer which, for example, forms a water dispersion of particles remaining constant composition. In this case, polymerizat may consist of one or more (meth)acrylate segments, which include from 1 to 30 wt.% structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms, from 0.1 to 10 wt.% structural units which are derived from monomers containing acid groups and 50 to the 98.9 wt.% structural units which are derived from (meth)acrylates having from 1 to 6 carbon atoms in the alkyl residue, in terms of the mass of the (meth)acrylate segment.

According to another embodiment of the invention polymerizate may be a polymer type poison the on-shell", which may contain one, two, three or more shells. This (meth)acrylate segment preferably forms the exterior of the shell polymer of the type "core-shell". The shell may be associated with the nucleus or inner shells by means of covalent bonds. In addition, the shell can also dry out the core or inner shell. This embodiment of the invention the polymers of the outer shell can repeatedly be separated from the kernel and to be isolated using an appropriate solvent.

Preferably the mass ratio of the (meth)acrylate segment and the core lies in the range from 2:1 to 1:6, particularly preferably from 1:1 to 1:3.

The core may preferably be formed from polymers which comprise from 50 to 100 wt.%, preferably from 60 to 90 wt.% structural units derived from (meth)acrylates. While preferred are esters of (meth)acrylic acid in which the alcohol residues preferably contain from 1 to 30 carbon atoms, particularly preferably from 1 to 20 carbon atoms and most preferably from 1 to 10 carbon atoms. These include, in particular, (meth)acrylates which derive from saturated alcohols, such as methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, t is edbutil(meth)acrylate, and pentyl(meth)acrylate, hexyl(meth)acrylate.

According to the specific improvement of the present invention to obtain a kernel can be used with a mixture that includes methacrylates and acrylates. So, may apply, in particular, mixtures of methacrylate and acrylate with a number of carbon atoms in the alkyl residue of from 2 to 6, such as acrylate, butyl acrylate and hexidecimal.

In addition, the polymer core may include the above comonomers. According to a preferred modification of the invention the core may be crosslinked polymer. This polymer cross-linking can be achieved through the use of monomers with two, three or more double bonds capable of radical polymerization.

The outer shell of polymer type a "core-shell" preferably ranges from 15 to 28 wt.% structural units which are derived from (meth)acrylates which in the alkyl residue containing at least one double bond and 8 to 40 carbon atoms.

According to a separate aspect of the invention the core may preferably have a transition temperature in the glassy state in the region from -30°C to 200°C, particularly preferably in the range from -20 to 150°C. the Membrane, which is preferably formed of (meth)acrylate segment polymerizate, preferably may have a transition temperature steklovidne state in the region from -30°C to 70°C, particularly preferably in the range from -20 to 40°C and highly preferably in the range from 0 to 25°C. According to a separate aspect of the present invention, the temperature of transition to the glassy state of the core may be greater than the transition temperature in the glassy state of the shell. It is advantageous if the temperature of transition to the glassy state of the nucleus lies at least 10°C., preferably at least 20°C above the temperature of transition to the glassy state of the shell.

Iodine number for polymerizate, which should be used according to the invention, measured according to DIN 53241-1, preferably is in the range from 1 to 150 g of iodine per 100 g of polymerizate, particularly preferably in the range from 2 to 100 g iodine per 100 g of polymerizate and most preferably from 5 to 40 g iodine per 100 g of polymerizate. Iodine number can be measured, in particular, for dispersion according to the invention.

It is expedient if polymerizate containing at least one (meth)acrylate segment can have an acid number in the range from 0.1 to 40 mg KOH/g, preferably from 1 to 20 mg KOH/g and most preferably in the range from 2 to 10 mg KOH/g Acid number may be determined in accordance with DIN EN ISO 2114 for dispersion.

The hydroxyl number for polymerizate, which should be applied according to izaberete the Oia, preferably may be in the range from 0 to 200 mg KOH/g, particularly preferably from 1 to 100 mg KOH/g and most preferably in the range from 3 to 50 mg KOH/g hydroxyl number can be determined for dispersion according to the standard ASTM E222.

The above polymerizate based on (meth)acrylates can be obtained by known methods, for example, by polymerization in solution, in bulk or emulsion polymerization, while preferably the receiving is carried out by emulsion polymerization, and these ways, among others, presented in the publication Ullmann''s Encyclopedia of Industrial Chemistry, Fifth Edition.

To obtain polymerizate by the method of emulsion polymerization, as a rule, is preparing the aqueous phase, which in addition to water may contain conventional additives, in particular, emulsifiers and protective colloids to stabilize emulsions.

To this aqueous phase is then added monomers, and are subjected to polymerization in the aqueous phase. When obtaining a homogeneous polymer particles of the mixture of monomers may be added during the period of time in a continuous mode or in smaller portions.

The dispersion phase containing the monomer in the aqueous phase can be carried out using known means. These include, in particular, mechanical methods, and the use of ultraslo the A.

The mixture of monomers to obtain emulsion polymerizate according to the invention preferably includes

from 1 to 30 wt.% (meth)acrylate containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms,

from 0.1 to 10 wt.% monomers containing acid groups, and

50 to the 98.9 wt.% of methacrylates having alkyl residue of 1 to 6 carbon atoms.

Particularly preferably, the mixture of monomers contains from 1 to 5 wt.% monomers containing acid groups.

When obtaining a homogeneous emulsion polymerization may preferably be used a mixture of monomers, which contains from 10 to 20 wt.% (meth)acrylates having an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

Upon receipt of polymers of type "core-shell" composition of the mixture of monomers may change periodically, and before changing the composition of the polymerization preferably is carried out to achieve the degree of conversion of at least 80 wt.%, especially preferably, at least. 95 wt.% in each case, calculated on the total weight of used monomer mixture. In this case, the polymer-type "core-shell" is polymerizat, which was obtained by emulsion polymerization carried out in two or more stages, butobarbitone structures of type "core-shell", for example, using the method of electron microscopy. Tracking the completion of the polymerization reaction at each stage may be conducted by known methods, for example, gravimetrically or by using gas chromatography.

The mixture of monomers to obtain a core preferably comprises from 50 to 100 wt.% (meth)acrylate, and particularly preferably uses a mixture of acrylates and methacrylates. After receipt of the nuclei on the surface is preferably grafted copolymerization or polymerization mixture of monomers, which comprises from 15 to 28 wt.% (meth)acrylate containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

Emulsion polymerization is carried out at a temperature preferably in the range from 0 to 120°C, particularly preferably in the range from 30 to 100°C. the most favorable temperature was conducting the polymerization in the range from more than 60 to less than 90°, the most suitable in the range from more than 70 to less than 85°C., preferably in the field from more than 75 to less than 85°C.

The process of initiating polymerization using initiators used for emulsion polymerization. Suitable organic initiators are, for example, hydroperoxides such as tertBUTYLPEROXY Il is cumonherface. Suitable inorganic initiators are hydrogen peroxide, and salt peroxidizing acid with alkali metals and ammonia, in particular, peroxodisulfate ammonium, sodium and potassium. Suitable redox system initiators are, for example, combinations of tertiary amines with peroxides or disulfit sodium and salts peroxidizing acid with alkali metals and ammonia, in particular, peroxodisulfate sodium and potassium. Additional details can be found in the literature, in particular in the publications N. Raum-Puntigam, Th. An active part, "Acryl - und Methacrylverbindungen", Springer, Heidelberg, 1967 or Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.1, pages 386 and forth, J. Wiley, New York, 1978. In the framework of this invention, especially preferred is the use of organic and inorganic initiators.

Given the initiators may be used either individually or as mixtures. They are used preferably in amounts of from 0.05 to 3.0 wt.%, in terms of the total weight of the monomer at an appropriate stage. Preferably, the polymerization can also be carried out with a mixture of different polymerization initiators having different half-life, so that in the course of polymerization, and at different temperatures of polymerization to maintain the flow of radicals is as constant.

Stabilizirovannye original compositions preferably carried out with the aid of emulsifiers and protective colloids. Preferably the emulsion is stabilized by emulsifiers, in order to provide a low viscosity dispersion. The total amount of emulsifier is preferably from 0.1 to 15 wt.%, first of all, from 1 to 10 wt.% and especially preferably from 2 to 5 wt.%, in terms of the total weight of monomer used. According to a separate aspect of the present invention a portion of the emulsifier may be added during polymerization.

Particularly suitable emulsifiers are anionic and nonionic emulsifiers or mixtures thereof, in particular

the alkyl sulphates, preferably the alkyl sulphates with the number of carbon atoms in the alkyl residue of from 8 to 18, ethers, alkyl - and alkylarylsulfonates with the number of carbon atoms in the alkyl residue of from 8 to 18 and the number ethylenoxide structural units from 1 to 50;

- sulfonates, preferably the alkyl sulphonates with the number of carbon atoms in the alkyl residue of from 8 to 18, alkylarylsulfonate with the number of carbon atoms in the alkyl residue of from 8 to 18, complex di - or monetary sulfonterol acid with a monohydroxy alcohols or alkyl phenols with the number of carbon atoms in the alkyl residue of from 4 to 15; if necessary, these alcohols or ALKYLPHENOLS may also be this is calirovance and contain from 1 to 40 units of ethylene oxide;

partial esters of phosphoric acid and their salts with alkali metals and ammonia, preferably alkyl and alkylaromatic containing from 8 to 20 carbon atoms in the alkyl or respectively alcylaryl residue and 1 to 5 units of ethylene oxide;

- simple alkylpolyglycoside esters, preferably containing from 8 to 20 carbon atoms in the alkyl residue and from 8 to 40 units of ethylene oxide;

- simple alkylarylsulphonate esters, preferably containing from 8 to 20 carbon atoms in the alkyl or respectively alcylaryl residue and from 8 to 40 units of ethylene oxide:

- copolymers of ethylene oxide/propylene oxide, preferably block copolymers, preferably containing from 8 to 40 units of ethylene oxide or of propylene oxide, respectively.

Particularly preferred anionic emulsifier is referred, in particular, the sulfate ethers of fatty alcohols, diisooctylphthalate, lauryl,- parafusulina containing 15 carbon atoms, and, as a rule, these compounds may be used in the form of salts of alkali metals, in particular, in the form of sodium salts. These compounds, in particular, may be commercially available under the trade names of Disponil® FES 32, Aerosol® 75, Texapon® K1296 and Statexan® K1 manufacturers Cognis GmbH, Cytec Industrie, Inc., a Bayer AG.

Suitable nonionic emulsifiers, among others, are tertoctylphenol containing 30 units of ethylene oxide and simple polietilenglikolya ethers of fatty alcohols, preferably containing from 8 to 20 carbon atoms in the alkyl residue and from 8 to 40 units of ethylene oxide. These emulsifiers are commercially available under the trade names Triton® X-305 (Fluka), Tergitol® 15-S-7 (Sigma-Aldrich Co.), Marlipal® 1618/25 (company Sasol Germany), and Marlipal® O 13/400 (company Sasol Germany).

Preferably can be used a mixture of anionic emulsifier and a nonionic emulsifier. Suitable mass ratio of anionic emulsifier and a nonionic emulsifier may be in the range from 20:1 to 1:20, preferably from 2:1 to 1:10 and particularly preferably from 1:1 to 1:5. The most well-proven mixtures that contain sulfate, in particular, the simple sulfate ester, fatty alcohol, lauryl, or sulfonate, in particular, diisooctylphthalate or parafusulina as anionic emulsifier, and alkylphenolethoxylate or simple polietilenglikolya ether fatty alcohol, respectively, contain from 8 to 20 carbon atoms in the alkyl residue and from 8 to 40 units of ethylene oxide, as the nonionic emulsifier is.

If necessary, the emulsifiers can also be used in a mixture with protective colloids. Protective colloids include, among others, partially milennia the polyvinyl acetate, polyvinylpyrrolidone, carboxymethyl-, methyl-, hydroxyethyl-, hydroxypropylcellulose, starches, proteins, poly(meth)acrylic acid. poly(meth)acrylamide, polyphenylsulfone acid, melamineformaldehyde, naphthalenedisulfonate, copolymers of styrene with maleic acid and simple vinyl ether with maleic acid. If used protective colloids, they are used in quantities of from 0.01 to 1.0 wt.%, in terms of the total weight of the monomers. Protective colloids may be present in the mixture prior to the polymerization or added in the process. The initiator may be present in the mixture prior to the polymerization or added in the process. In addition, it is also possible that the part of the initiator was already present in the mixture, and the residue was added in the process.

Preferably the polymerization is started by heating the initial mixture to the polymerization temperature and adding the initiator, preferably in aqueous solution. The addition of emulsifier and monomer can be carried out individually or in a mixture. When adding a mixture of emulsifier and monomer are received so that the emulsifier and mo is Omer pre-mixed in the mixer, in front of the reactor for polymerization. Preferably the remains of the emulsifier and monomer that has not been paid in advance, after the start of polymerization is added separately from each other. Preferably start with a dosage in the range from 15 to 35 minutes after the start of polymerization.

Polymerizate that contain at least one (meth)acrylate segment, with a high content of insoluble polymers can be obtained by the above method, and the parameters of the reaction required to obtain high molecular weight are known. Thus, it is possible, in particular, to renounce the use of molecular weight regulators.

To obtain aqueous dispersions according to the invention the aqueous alkyd resin may be mixed with the above polymerization.

Mass fraction of alkyd resins and polymerisate based on (meth)acrylates may lie within wide limits, and, as a rule, it can be aligned with the desired profile of properties. Preferably the mass ratio of alkyd resin and polymerizate-based (meth)acrylate is in the range from 20:1 to 1:20, particularly preferably from 5:1 to 1:5 and most preferably from 3:1 to 1:3, in terms of the dry mass of the respective components.

Water dispersion, which can be what Holocene using the method according to the invention, can be used as a means to create coatings. Preferably these aqueous dispersions have a solids content in the range from 10 to 70 wt.%, particularly preferably from 20 to 60 wt.%.

To obtain the dispersion according to the invention preferably can be used variance polymerizate, which has a dynamic viscosity in the range from 0.1 to 180 MPa·s, preferably from 1 to 80 MPa·s and most preferably from 5 to 20 MPa·s, measured according to DIN EN ISO 2555 at 25°C (Brookfield viscometer).

Along with water, as well as the above alkyd resin and polymerizate-based (meth)acrylate dispersions according to the invention can contain additives or additional components in order to tailor the properties of tools for creating coatings to specific requirements. Such additives include, first of all, substances that accelerate the drying, the so-called driers, fluidity improvers, pigments and dyes.

Especially preferably to aqueous dispersions can be added driers. These include, in particular, ORGANOMETALLIC compounds, for example, metallic Soaps are based on transition metals, such as, for example, cobalt, manganese, lead, zirconium; alkali and alkaline earth metals, such as, for example, lithium, potassium is calcium. As an example, mention should be made of, for example, naftalin cobalt and cobalt acetate. Driers can be used individually or as mixtures, and particularly preferred are mixtures, in particular, those which contain salts of cobalt, zirconium, and lithium.

Preferably the means for coatings according to the invention have a minimum film forming temperature, which can be measured in accordance with DIN ISO 2115, at most 50°C., particularly preferably at most 35°C. and most preferably at most 25°C.

According to a preferred aspect of this invention, the aqueous dispersion according to the invention may have an iodine number according to DIN 53241 at least 1 g of iodine/100 g, preferably at least 10 g iodine/100 g, particularly preferably at least 15 g iodine/100 g According to a separate aspect of the present invention iodine number water dispersion may be in the range from 2 to 100 g iodine per 100 g of the aqueous dispersion, particularly preferably from 15 to 50 g of iodine per 100 g of the aqueous dispersion. Iodine number can be determined for dispersion, its value refers to the solids content.

It is advisable, when the aqueous dispersion may have an acid number in the range from 0.1 to 100 mg KOH/g, preferably from 1 to 40 mg KOH/g and most before occhialino in the region from 2 to 10 mg KOH/g Acid number can be determined for a variance in accordance with DIN EN ISO 2114, and its value refers to the solids content.

Hydroxyl number water dispersion according to the invention may preferably be in the range from 0 to 400 mg KOH/g, particularly preferably from 1 to 200 mg KOH/g and most preferably in the range from 3 to 150 mg KOH/g hydroxyl number can be determined for dispersion according to the standard ASTM E222, its value refers to the solids content.

Aqueous dispersions according to this invention can be used, in particular, as a means to create coatings or as additives for them. These include, first of all, lacquers, impregnations, adhesives and/or primers. Particularly preferably aqueous dispersions can be used for the manufacture of varnishes or means for impregnation for use on the surface of the wood and/or metal.

The coatings produced from the means for coatings according to the invention exhibit high resistance to solvents, in particular, only a small portion of the coating may be dissolved by action of the solvent. Preferred coatings show high stability, in particular in relation to the isobutyl ketone (MIBK). So, last the processing MIBK losing weight is preferably at most 50 wt.%, preferably at most 35 wt.%. Absorption MIBK is preferably at most 300 wt.%, particularly preferably at most 250 wt.% in terms of weight used coatings. These values are measured at a temperature of approximately 25°C and reaction time of at least 4 hours, and measurements are conducted to fully dried coatings. It has been drying in the presence of oxygen, such as air, to make possible the polymer stitching.

Coatings, which are obtained from the means for coatings according to the invention, exhibit high mechanical stability. Preferably pendulum hardness, measured according to DIN ISO 1522, is at least 20, preferably at least 25 C.

Below the invention is explained in more detail based on examples, which however does not limit the claims.

Example 1

First in a beaker made of polyethylene with a volume of 2 l by means of the device Ultra Turrax for 3 minutes at 4000 rpm was emulsiable 180 g of butyl acrylate (BA), 156 g of methyl methacrylate (MMA), 60 g of complex methacryloyloxy-2-hydroxypropionic ester of linoleic acid, 4 g of methacrylic acid (MAC), 1.2 g of peroxodisulfate ammonium (APS), 12.0 g Disponil FES 32 (30%), and 359,18 g of water. Complex methacryloyloxy-2-hydroc profilemy ether of linoleic acid were obtained using the reaction of linoleic acid with glycidylmethacrylate.

In a glass reactor with a volume of 2 liters, which had the possibility of a temperature in a water bath and was equipped with paddle stirrer, were placed 230 g of water and 0.3 g of Disponil FES 32 (30%), was heated up to 80°C and was added 0.3 g of peroxodisulfate ammonium (APS)dissolved in 10 g of water. After 5 minutes after addition of APS this was added a pre-obtained emulsion within 240 minutes (with the following intervals: add in for 3 minutes, pause for 4 minutes, adding the remaining part for 237 minutes).

Then after the addition was stirred at 80°C for 1 hour. Then cooled to room temperature and the dispersion was filtered through a cloth sieve of vinyl acetate with a cell size of 0.09 mm

The resulting dispersion had a solids content equal to 40±1%, the value of pH of 2.6, the viscosity of 17 MPa·s and a value of rN575 nm.

Mixed 117,15 g obtained above water emulsion from 33.7 g of the polyurethane-alkyd resin (commercially available under the trade name Worlée E150W company Worlée).

Properties of tools for creating coatings thus obtained were tested using different experiments. For this purpose with the dried films was carried out experiments on the resistance to solvents, water absorption and resistance to scratching.

The definition of sustainability the spine to the action of solvents was carried out using isobutyl ketone (MIBK), moreover, the sample was subjected to swelling under the action of MIBK at room temperature for 4 hours. Then, the sample was removed from the solvent and the excess solvent was removed. Thereafter, the sample was dried for 1 hour at approximately 140°C. From the weight loss was calculated the proportion of the sample that is removed under the action of the solvent. The values presented in Table 1, relate to the weight of the coating after processing MIBK, here indicated as well as the "true swelling". The magnitude of swelling in MILK that are related to the mass of the used coatings are lower.

To determine the water absorption can be used to sample for testing of raw pine wood (about the size of 45-50 mm × 45-50 mm × 17 mm). The sample for testing was covered with a layer of varnish and placed in water at room temperature so that in contact with water was only the surface with the coating. From the weight increase of the sample for testing is calculated absorption of water.

Resistance to scratching was investigated using test method paint film hardness when scratching pencils of varying hardness, and using the pendulum test. In addition, conducted the test processing solvent with acetone and purifying gasoline ASTM D 4752. The results obtained is shown in Table 1.

Example 2

Basically echoed the example 1, however, used 117,15 g water emulsion which was obtained with a complex 2-methacryloyloxy-2-hydroxypropylamino ester of oleic acid instead of complex 2-methacryloyloxy-2-hydroxypropionic ester of linoleic acid. This emulsion was mixed from 33.7 g of the polyurethane-alkyd resin (commercially available under the trade name Worlée E150W company Worlée). The results obtained with this tool for creating coatings are shown in table 1.

Example 3

Basically echoed the example 1, however, used 117,15 g water emulsion which was obtained by ineliminability instead of complex 2-methacryloyloxy-2-hydroxypropionic ester of linoleic acid. This emulsion was mixed from 33.7 g of the polyurethane-alkyd resin (commercially available under the trade name Worlée E150W company Worlée). Linolelaidic was obtained by transesterification of methyl methacrylate linoleic alcohol (compare F.-B. Chen, G. Bufkin, "Crosslinkable Emulsion Polymers by Autooxidation II", Journal of Applied Polymer Science, Vol.30, 4551-4570 (1985)). The results obtained with this tool for creating coatings are shown in table 1.

Example 4

Basically echoed the example 1, however, 66,29 g water dispersion which was obtained in example 1 was mixed from 57.2 g of the polyurethane-alkyd resin (commercially available under the trade n the naming Worlée E150W company Worlée). For dried films were conducted experiments on the resistance to solvents, water absorption and resistance to scratching. The results are shown in table 1.

The example for comparison 1

In another experiment alkyd resin used in example 1 was investigated without mixing with the described above polymerization based on (meth)acrylates. For dried films were conducted experiments on the resistance to solvents, water absorption and resistance to scratching. In addition, conducted the test processing solvent with acetone and purifying gasoline. The results are shown in table 1.

The example for comparison 2

First in a beaker made of polyethylene with a volume of 2 l by means of the device Ultra Turrax for 3 minutes at 4000 rpm was emulsiable 216 g of butyl acrylate (BA), 180 g of methyl methacrylate (MMA), 4 g of methacrylic acid (MAC), 1.2 g of peroxodisulfate ammonium (APS), 12.0 g Disponil FES 32 (30%). and 359,18 g of water.

In a glass reactor with a volume of 2 liters, which had the possibility of a temperature in a water bath and was equipped with paddle stirrer, were placed 230 g of water and 0.3 g of Disponil FES 32 (30%), was heated up to 80°C and was added 0.3 g of peroxodisulfate ammonium (APS)dissolved in 10 g of water. After 5 minutes after addition of APS this was added a previously received the second emulsion in the course of 240 minutes (with the following intervals: add in for 3 minutes, pause for 4 minutes, adding the remaining part for 237 minutes).

Then after the addition was stirred at 80°C for 1 hour. After this was cooled to room temperature and the dispersion was filtered through a cloth sieve of vinyl acetate with a cell size of 0.09 mm

For dried films were conducted experiments on the resistance to solvents, water absorption and resistance to scratching.

Table 1
The results of investigations of the properties
Example 1Example 2Example 3Example 4The example for comparison 1The example for comparison 2
Pendulum hardness [s]53,249,741,825,213,37
The hardness scratching pencils of varying hardness3H3H2H 3H<6B-
True swelling in MIBK [%]306438522374391dissolve
The loss of mass under the action of MIBK [%]27,6to 33.8of 37.930,147,7dissolve
The water absorption of 6 h (amendment of 37.8%) [%]9,914,613,512,114,0-
Test processing solvent with acetone [the number of ticks for rinsing the film]2527
Test processing by solvent cleaning with gasoline [the number of ticks for rinsing the film]>50 21

Example 5

Basically echoed the example 1, however, 117,15 g water dispersion which was obtained in example 1 was mixed with 33,7 g modified urethane, not containing co-solvent skinny alkyd emulsion. For dried films were conducted experiments on the resistance to solvents, water absorption and resistance to scratching.

In this case, an additional test was performed for furniture surfaces according to DIN 68861-1.

The results are shown in table 2.

Example 6

Basically echoed example 5, however, 66,29 g water dispersion which was obtained in Example 1 was mixed with 57,2 g modified urethane, not containing co-solvent skinny alkyd emulsion. For dried films were conducted experiments on the resistance to solvents, water absorption and resistance to scratching. The results are shown in table 2.

Example 7

Basically echoed example 5, however, 33,7 g water dispersion which was obtained in example 1 was mixed with 117,15 g modified urethane, not containing co-solvent skinny alkyd emulsion. For dried films were conducted experiments on the resistance to solvents, absorption the structure of water and resistance to scratching. The results are shown in table 2.

The example for comparison 3

In another experiment alkyd resin used in example 5 was investigated without mixing with the described above polymerization based on (meth)acrylates. For dried films were conducted experiments on the resistance to solvents, water absorption and resistance to scratching. The results are shown in table 2.

Table 2
The results of investigations of the properties
Example 5Example 6Example 7The example for comparison 3
Pendulum hardness [s]14,215,118,212.6
True swelling in MIBK [%]3684032411024
True swelling in ethanol [%]123154170 281
Test for furniture surfaces DIN 68861-1/48% EtOH5553
Test for furniture surfaces DIN 68861-1/15% SPLA5553

1. Aqueous dispersion comprising at least one alkyd resin and at least one polymerized at least one (meth)acrylate segment which contains from 1 to 30 wt.% structural units derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms, from 0.1 to 10 wt.% structural units derived from monomers containing acid groups and 50 to the 98.9 wt.% structural units which are derived from (meth)acrylates having alkyl residue of 1 to 6 carbon atoms, in each case calculated on the weight of the (meth)acrylate segment.

2. Aqueous dispersion according to claim 1, characterized in that the alkyd resin can be obtained by interaction of a polyhydric alcohol with a multifunctional isocyanate.

3. Aqueous dispersion according to claim 1, characterized in that the alkyd resin contains structural units which are derived from aromatic dicarboxylic acids.

4. Aqueous dispersion according to claim 1, characterized in that the alkyd resin contains structural units which are derived from alcohols containing three or more hydroxyl groups.

5. Aqueous dispersion according to claim 1, characterized in that the alkyd resin contains structural units which are derived from fatty acids containing from 6 to 30 carbon atoms.

6. Aqueous dispersion according to claim 5, characterized in that the alkyd resin contains structural units which are derived from unsaturated fatty acids containing from 6 to 30 carbon atoms.

7. Aqueous dispersion according to claim 1, wherein the alkyd resin has an iodine number of at least 10 g iodine per 100 g

8. Aqueous dispersion according to claim 1, wherein the alkyd resin has an acid number in the range from 0.1 to 100 mg KOH per one g of alkyd resin.

9. Aqueous dispersion according to claim 1, wherein the alkyd resin has a hydroxyl number in the range from 1 to 200 mg KOH per one g of alkyd resin.

10. Aqueous dispersion according to claim 1, wherein the alkyd resin is retinancing resin, which can be obtained by reacting polyhydric alcohols And'modified fatty acids In'fatty acids' and multifunctional isocyanates D'.

11. Aqueous dispersion according to claim 1, characterized in that polymerizate containing less than the least one (meth)acrylate segment, has a particle radius of at least 50 nm.

12. Aqueous dispersion according to claim 1, characterized in that the (meth)acrylates, which contain in the alkyl residue with at least one double bond and 8 to 40 carbon atoms, obtained by the interaction of at least one unsaturated fatty acid with at least one (meth)acrylate that contains an alcohol residue of at least one reactive group.

13. Aqueous dispersion according to item 12, wherein the (meth)acrylate that contains an alcohol residue of at least one reactive group is hydroxyalkyl(meth)acrylate or (meth)acrylate with at least one epoxy group.

14. Aqueous dispersion according to item 12, wherein the (meth)acrylates, which contain in the alkyl residue with at least one double bond and 8 to 40 carbon atoms, obtained by the interaction of unsaturated fatty acids with glycidyl(meth)acrylate.

15. Aqueous dispersion according to claim 1, characterized in that polymerizat at least one (meth)acrylate segment contains structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of linoleic acid complex (meth)acryloyloxy-2-hydroxypropionic ester of linolenic acid and/or complex (meth)acryloyloxy-2-hydroxypropylamino EPE is and oleic acid.

16. Aqueous dispersion according to item 15, wherein the mass ratio of structural units which are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of linoleic acid and structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of oleic acid, greater than or equal to 1.

17. Aqueous dispersion according to item 15, wherein polymerizat at least one (meth)acrylate segment contains at least 40 wt.% structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of linoleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

18. Aqueous dispersion according to 17, characterized in that polymerizat at least one (meth)acrylate segment contains from 45 to 80 wt.% structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of linoleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

19. Aqueous dispersion according to item 15, wherein polymerizat on ENISA least one (meth)acrylate segment contains at least 10 wt.% structural units, which are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of oleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

20. Aqueous dispersion according to claim 19, characterized in that polymerizat at least one (meth)acrylate segment contains from 15 to 45 wt.% structural units that are derived complex (meth)acryloyloxy-2-hydroxypropionic ester of oleic acid, calculated on the weight of structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

21. Aqueous dispersion according to claim 1, characterized in that polymerizat at least one (meth)acrylate segment contains from 2 to 30 wt.% structural units which are derived from comonomers, in terms of the mass of the (meth)acrylate segment.

22. Aqueous dispersion according to claim 1, characterized in that polymerizat at least one (meth)acrylate segment contains at most 30 wt.% structural units which are derived from styrene, substituted styrene with an alkyl substituent in the side chain, substituted styrene with an alkyl substituent in the ring and/or the halo is animowany styrene, in terms of the mass of the (meth)acrylate segment.

23. Aqueous dispersion according to claim 1, characterized in that polymerizat at least one (meth)acrylate segment contains at most 10 wt.% structural units which are derived from (meth)acrylates obtained by the interaction of saturated fatty acids with at least one (meth)acrylate that contains an alcohol residue of at least one reactive group, in terms of the mass of the (meth)acrylate segment.

24. Aqueous dispersion according to item 23, wherein polymerizat at least one (meth)acrylate segment contains from 0.1 to 3 wt.% structural units which are derived from (meth)acrylates obtained by the interaction of saturated fatty acids with at least one (meth)acrylate that contains an alcohol residue of a reactive group, in terms of the mass of the (meth)acrylate segment.

25. Aqueous dispersion according to item 23, wherein the saturated fatty acid containing from 10 to 26 carbon atoms.

26. Aqueous dispersion according to item 23, wherein the (meth)acrylates can be obtained by the reaction of saturated fatty acids with glycidyl(meth)acrylate.

27. Aqueous dispersion according to claim 1, wherein from 2 to 60 wt.% polymerizate containing at least one (meth)acrylate segment is UNT, soluble in tetrahydrofuran (THF) at 20°C.

28. Aqueous dispersion according to claim 1, characterized in that polymerizate containing at least one (meth)acrylate segment has a structure of type "core-shell".

29. Aqueous dispersion for p, wherein the core contains from 50 to 100 wt.% structural units which are derived from (meth)acrylates.

30. Aqueous dispersion for p, characterized in that the core contains structural units that are derived from acrylates, as well as the structural units that are derived from methacrylates.

31. Aqueous dispersion for p, characterized in that the shell contains from 15 to 28 wt.% structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

32. Aqueous dispersion according to claim 1, characterized in that polymerizate containing at least one (meth)acrylate segment contains from 10 to 20 wt.% structural units which are derived from (meth)acrylates containing an alkyl residue with at least one double bond and 8 to 40 carbon atoms.

33. Aqueous dispersion according to claim 1, characterized in that polymerizate containing at least one (meth)acrylate segment has an iodine number in the range from 5 to 40 g per 100 g of polymerizate.

34. Water disperse who according to claim 1, characterized in that it has an iodine number in the range from 2 to 100 g per 100 g of dispersion, calculated on the solids content.

35. Aqueous dispersion according to claim 1, characterized in that the aqueous dispersion has an acid number in the range from 0.1 to 100 g per 100 g of dispersion, calculated on the solids content.

36. Aqueous dispersion according to one of claims 1 to 35, characterized in that the mass ratio of alkyd resin and polymerizate containing at least one (meth)acrylate segment is in the range from 20:1 to 1:20 in terms of the dry mass of the respective components.

37. A method of obtaining a water dispersion according to one of claims 1 to 36, characterized in that the receiving water dispersion of polymerizate containing at least one (meth)acrylate segment, and mix it with alkyd resins.

38. The method according to clause 37, wherein polymerizate containing at least one (meth)acrylate segment is an emulsion polymer.

39. The method according to clause 37 or 38, characterized in that polymerizat mixed with the alkyd resin in the form of an aqueous dispersion of polymerizate, and aqueous dispersion of polymerizate has a dynamic viscosity in the range from 1 to 80 MPa·S.



 

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3 cl, 4 tbl, 70 ex

FIELD: chemistry.

SUBSTANCE: invention relates to preparation of surface coating solutions which contain boehmite. The surface coating solution is a latex paint and contains a trituration solution, a polymer emulsion and a solvent. The trituration solution is prepared using an active solution which contains a base in form of an aqueous solution and boehmite particles contained in the base. The boehmite particles are anisotropic moulded particles having mould ratio of 3:1 and are activated by substances selected from a group which includes ammonium hydroxide, alkali- or alkali-earth metal salt, nanoclay or colloidal silica. The surface coating solution has surface spreading and distribution with formation of a uniform film of at least 6 mil, and sag resistance of over 7 mil or surface spreading and distribution with formation of a uniform film of over 6 mil, and sag resistance of at least 7 mil. Described also is a method of preparing the surface coating solution involving the following operations: activation of boehmite particles with substances selected from a group which includes ammonium hydroxide, alkali- or alkali-earth metal salt, nanoclay or colloidal silica in order to form a water-based active solution; preparation of a trituration solution using the active solution; and preparation of a surface coating solution using the trituration solution, polymer emulsion and solvent.

EFFECT: solution enables to obtain coating with good technical properties.

42 cl, 2 tbl, 3 dwg, 2 ex

FIELD: transport, package.

SUBSTANCE: group of inventions relates to containers for food products and beverages and methods for applying coating on them. Containers for food products and beverages include metal substrate which has at least partially applied covering composite including water-dispersible system of resin and water carrier. Resin system includes epoxy component and acrylic component. Then composite is hardened and formed on metal substrate of hardened covering. In the preferable version of implementation, covering composite is at least minimally suitable for autoclaving in hardened condition.

EFFECT: elimination of covering corrosion, water absorption by covering and/or loss of adhesion to base substrate, as well as excluding influence of aggressive chemical properties of food product or beverage on the covering on water basis.

15 cl, 4 tbl, 14 ex

FIELD: metallurgy.

SUBSTANCE: invention relates to a composition for powder coating, which provides a special effect of the presence of metal on the substrate surface, as well as to a method for coating substrates for indoor and outdoor applications in the fields of architecture and industry. The composition contains well-mixed components (A), (B) and (C). Component (A) comprises 60-99 wt % of a mixture consisting of at least one polyester resin and at least one (meth)acrylate resin. Component (B) comprises 0-30 wt % of at least one crosslinking agent. Component (C) consists of 0.01-40 wt % of at least one pigment. Components (A), (B) and (C) are selected so that the composition provides the low dullness of curable coating in the range from 1 to 20 gloss units when considering the coating at an angle of 60° according to standard DIN 67530 (ISO2813). Simultaneously, the surface structure of the curable coating should have a value of the integral coefficient 1 of over 8.00 E+00, measured by Fourier analysis for mechanical profilometry.

EFFECT: composition for powder coating enables the formation of the desired special effect of the presence of metal on the covered surface, which corresponds to the effect of the presence of metal obtained from the use of anodised aluminium.

11 cl, 2 dwg, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: formulation composition contains: A) 5-95 wt % at least one radiation-curable resin, B) 5-25 wt % silicic acid, C) 0.1-10 wt % at least one adhesion promoter, D) 5-90 wt % at least one radiation-curable reactive diluent, E) 0.5-5 wt % at least one dispersant. The adhesion promoter is selected form phosphoric acid and/or phosphonic acid and/or products of reaction thereof with functionalised acrylates. The composition can additionally contain photoinitiators, pigments and additives, selected from diffusion promoting agents, delustering agents and degassing agents. The compositions are used as a primer, an intermediate layer, coating varnish and/or clear varnish, as well as for making coatings via a coil coating technique.

EFFECT: coatings have flexibility, thereby providing excellent protection of metal substrates from corrosion.

18 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: system based on a film-forming dispersion contains the following in wt %: 5-60 copolyether A, obtained using itaconic acid or a mixture of polyesters; 5-70 (meth)acrylate homo- and/or -copolymer B. Copolymer B consists of more than 50 wt % monomers of formula where R1 denotes hydrogen or methyl and R2 denotes an alkyl residue, an alphatic or aromatic residue with 1-5 carbon atoms. The film-forming dispersion also contains 5-60 graft copolymer from polymer A and polymer B (polymer AB). Copolyether A has a straight or branched structure with OH number from 5 to 150 mg KOH/g, and acid number less than 10 mg KOH/g, and number-average molecular weight 700-25000 g/mol. Content of itaconic links in the copolyether per total content of polycarboxylic acids ranges from 0.1 mol. % to 20 mol. %.

EFFECT: invention enables to obtain well compatible polymer structures which do not contain styrene or derivatives thereof, based on a polyether graft polymethacrylate copolymer.

16 cl, 3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: multicomponent aqueous composition contains an aqueous dispersion and a component containing a material having functional groups. The components are mixed with each other before applying the composition onto the substrate. The aqueous dispersion contains a polycarbonate-polyurethane polymer and an acrylic polyol. The aqueous dispersion also contains an organic solvent. The material having functional groups reacts with functional groups of the acrylic polyol and/or polycarbonate-polyurethane polymer. The acrylic polyol has number-average molecular weight from 500 to 4000. The polycarbonate-polyurethane polymer is obtained via a reaction between hydroxy-functional carbonate-containing material and polyisocyanate. The hydroxy-functional carbonate-containing material contains a product of reaction between carbonic acid or derivative thereof and a diol. The diol is hexane-1,6-diol.

EFFECT: composition has low content of volatile substances, as well as high water resistance and hardness.

20 cl, 3 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to varnish for heat transfer from lavsan to polyvinyl chloride (PVC) and can be used when depositing images on PVC followed by application of coating varnish. The varnish for heat transfer from lavsan to PVC contains vinyl resin with molecular weight 8000-20000 g/mol, thermoplastic acrylic resin with melting point 85-135°C and glass transition temperature 124°C, micronised polyethylene wax with antistatic effect with melting point between 40 and 260°C, an antistatic additive EFKA 6780, toluene solvents, methylethylketone or methylisobutylketone, ethylacetate.

EFFECT: high quality of varnish which reduces the volume of deposits in the ink box during printing, which lowers production losses, reduces heat transfer temperature, more uniform overlapping, prevention of fluffing and high wear resistance.

1 tbl

FIELD: chemistry.

SUBSTANCE: coating composition contains a polyvinyl chloride polymer, an acrylic resin which is preferably a polymer obtained from monomer acrylates or methacrylates, such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate resins, copolymer resins of said components or mixtures thereof, a cross-linking agent which is obtained from phenol, para-tert-butylphenol, xylenol or mixture thereof, and formaldehyde, an additive, a dye and a solvent component, and the composition essentially does not contain bisphenol A diglycidyl ether (BADGE) and bisphenol A resin. The coatings are suitable for containers made from three parts, as well as for metal cans made through deep-drawing. The coatings are particularly useful for covers which are torn in order to open due to their unusual flexibility and resistance to sterilisation.

EFFECT: composition provides coatings for metal cans which have suitable flexibility, resistance to scratching, adhesion and sterilisation during processing while in contact with food.

18 cl

FIELD: chemistry.

SUBSTANCE: packaging is suitable for sealing aluminium or polyethylene terephthalate films, as well as aluminium coated or polyethylene terephthalate coated films relative polypropylene, polystyrene or polyvinyl chloride substrates. The heat sealing system for coating consists of a film-forming dispersion of at least three different types of polymers A, B, AB and C, a system of organic solvents L containing the following mixture: L1) esters of aliphatic carboxylic acid with aliphatic alcohols and L2) aliphatic hydrocarbons. The weight ratio of L1 to L2 lies between 1 and 200 and the boiling point of the system of solvents under normal conditions is at most 105°C. Type A polymer is ethylene-propylene-diene rubber, type B polymer is a copolymer of (meth)acrylates, containing standard (meth)acrylates and a total of up to 15 wt % methacrylic acid and/or acrylic acid per type B polymer, type AB polymer is a graft polymer of type A and type B polymers and type C polymer is saturated polyester with hydroxyl number equal to 3-25 mg KOH/g.

EFFECT: heat sealing system is characterised by high heat resistance, good protective properties and short sealing time.

4 cl

FIELD: chemistry.

SUBSTANCE: invention relates to emulsion polymeric latex, particularly latex used in pressure-sensitive adhesives, paints and coatings. The paint composition contains at least one emulsion polymeric latex obtained from a surfactant composition containing at least one polystyryl phenol-based surfactant and synthetic monomers selected from a group consisting of at least one vinyl aromatic component, at least one acrylic acid component, at least one methacrylic acid component, at least one acrylic or methacrylic ester component, derivatives and combinations thereof. Surfactant compositions for use during synthesis of at least one emulsion polymeric latex contain at least one branched surfactant, at least one surfactant with a three-dimensional structure or a mixture of branched surfactant and a surfactant with a three-dimensional structure. One preferred surfactant composition contains at least one alkoxylated polyaryl-substituted aromatic compound. Another preferred surfactant composition contains at least one branched alkyl sulphate and at least one ethoxylated polystyryl phenol. Another preferred surfactant composition contains at least one sulphonated polystyryl phenol. Paint films made from latex have high resistance to wet cleaning with a brush, high adhesion and resistance to bubble formation.

EFFECT: adhesives are permanent at room temperature in dry form.

55 cl, 6 dwg, 7 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to an anti-fouling paint composition with high content of non-volatile components used for forming an anti-fouling coating film on the surface of a base such as underwater structures, outer sides of ships, fishing nets and fishing installations. The composition contains: (A) a carboxyl group-containing copolymer which has a structural unit obtained from a monomer (a1) of an unsaturated carboxylic acid and a structural unit obtained from another monomer (a2) of an unsaturated compound which copolymerises with monomers (a1) of the unsaturated carboxylic acid, and has average molecular weight of 1000-6000, measured using gel-penetrating chromatography, (B) a polyvalent metal compound capable of reacting with the carboxyl group of copolymer (A),and (C) an anti-fouling agent, where monomer (a1) of unsaturated carboxylic acid is (meth)acrylic acid, the other monomer (a2) is an unsaturated compound which is at least one type of monomer selected from a group consisting of alkyl(meth)acrylate and styrene and the polyvalent metal compound (B) is zinc oxide.

EFFECT: anti-fouling paint composition with high content of non-volatile components enables to obtain an anti-fouling coating film which has less effect on the environment and human body and has high resistance to fouling, retains these properties and has excellent mechanical strength.

62 cl, 22 dwg, 10 tbl, 4 ex

FIELD: thermosetting coating materials.

SUBSTANCE: claimed material contains polyester with carboxylic functional group and/or polyacrylate with carboxylic functional group, β-hydroxyalkylamide in which part of hydroxyls are chemically blocked, and/or fillers, and/or heat setting agent, and/or triboadditives, and/or additives such as flow controlling agent and degasification agent.

EFFECT: material of improved degasification and flow characteristics.

6 cl, 1 tbl, 3 ex

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