SUBSTANCE: invention relates to a self-crosslinking binder for coating compositions containing an aqueously dispersed polymer component A having at least one carbonyl group of the ketone or aldehyde type per molecule, and a component B having at least two hydrazine or hydrazide groups per molecule, and at least one structural unit -NR1-NR2-CHR3-CHR4-NH-R5 (I), where the radicals R1, R2, R3 and R4 are each individually selected from a group consisting of a hydrogen radical and a linear or branched alkyl radical having from 1 to 10 carbon atoms, R3 and R4 may additionally be selected from a group consisting of aryl and alkylaryl radicals having from 6 to 15 carbon atoms, and from oxyalkyl radicals with 1 to 10 carbon atoms, where oxy groups may be inserted into the alkyl chain or at the end of an alkyl chain, and R5 is selected from a group consisting of a hydrogen radical, alkyl radicals which may be linear, branched or cyclic and may have from 1 to 10 carbon atoms, and residues of formula -(CH2)n-CO-O-X, where n is an integer of from 1 to 6, and X is a residue of a polyatomic alcohol or phenol. A method of producing such a binder is also described.
EFFECT: producing a coating binder which is self-crosslinking when drying, having fast drying properties and improved chemical resistance and weather resistance.
17 cl, 5 ex, 5 tbl
The present invention relates to samoszhimayuschimsya binder. It also relates to a method for obtaining such samoszhimayuschihsya binders, as well as how they can be applied to obtain coating films.
Smossyvesa polyurethane dispersions are described inter alia in EP 0649865 B1. They contain a mixture of modedesignerin metafunctional polyurethane resins and polyhydrazides, such as adiposogenital.
It was found that chemical resistance and mechanical strength of the coating films obtained from such dispersions, still require improvement. On the other hand, although smossyvesa acrylic resin-based carbonylations acrylic dispersions and dihydrazide as bridges (such as described in EP 0995780 B1) lead to rapid drying, paint solvent, which have good chemical resistance, their wetting properties in wood coatings still require improvement, and resistance to stains from red wine and coffee is not satisfactory. Polyurethane-acrylic hybrid system, such as known from EP 0332326 B1, have better wetting properties of wood, but the drying time is significantly longer, and these systems usually contain a coalescing solvent (n-organic).
Therefore, the aim of the present invention I have is the creation of a binder cover, which is samoszhimayuschimsya drying properties quick drying and superior chemical resistance and resistance to the environment.
This goal is achieved by creating samoszhimayuschegosya binders for coating compositions as claimed in claim 1 of the claims.
The present invention therefore relates to water-dispersible samoszhimayuschegosya binders for coating compositions containing polymer component And having at least one carbonyl group of the ketone or aldehyde-type molecule, and component having at least two hydrazine or hydrazide groups per molecule, and at least one structural unit of the formula
where the radicals R1, R2, R3and R4each separately selected from the group consisting of a hydrogen radical and a linear or branched alkyl radical having from 1 to 10 carbon atoms, R3and R4can be optionally selected from the group consisting of aryl - and alkylaryl radicals having from 6 to 15 carbon atoms, and from oxyalkyl radicals having from 1 to 10 carbon atoms, where the hydroxy group can be introduced in the alkyl-C is ro or at the end of the alkyl chain, and where the radical R5selected from the group consisting of hydrogen radicals, alkyl radicals, which may be linear, branched or cyclic and may have from 1 to 10 carbon atoms, polyvalent aliphatic radicals, which are, preferably, branched, and of polyvalent cycloaliphatic radicals, and each has at least two and up to six of the connecting parts, and from the remnants of the formula
where n is an integer from 1 to 6, and X represents the residue of a polyhydric alcohol or phenol having, preferably, at least two, particularly preferably at least three and up to six hydroxyl groups.
Another objective of the present invention is a method of obtaining the specified water-dispersible samoszhimayuschegosya binder by providing a polymer component having at least one carbonyl group of the ketone or aldehyde-type molecule, which is dispersed in water or in a mixture, containing a mass fraction of at least 30% of water, and the interaction of the compounds B1 having at least two hydrazide or hydrazine groups on the molecule, and multifunctional aziridine B2, having at least two, preferably at least three aziridine GRU is dust on the molecule, preferably, in the presence of a water dispersion of the polymer component A.
Hydrazide group means a group of the structure R-CO-NH-NH2and hydrazine group means a group of the structure R-NH-NH2where R represents any organic residue.
Another objective of the present invention to provide coating compositions containing smossyvesa binder according to claim 1 of the claims.
A polymeric component And, preferably, selected from the group consisting of polyurethanes, polyesters, complex polyetherimides, polyamides, alkyd resins, epoxy resins, and polymers of vinyl type. The polymer component a is a water-dispersible. This can be accomplished in a known manner with the introduction of emulsifiers in part a or in water, or an aqueous mixture, which should dispergirujutsja component And, before or during dispersion of the component in the aqueous phase. Preferred are mixtures of at least two emulsifiers, which contain at least one reinacting emulsifier and at least one inactively emulsifier. Another preferred way of stabilizing aqueous dispersions of the polymeric component is to ensure that the specified component And a sufficient number of hydrophilic groups, which can be neionoaktivnye, such as groups, produced the water from oligomeric oxyethylene residues, or, preferably, inactivity or ionic, which means groups which dissociate in alkaline aqueous solutions, preferably in the formation of anions that combine with the polymer chains of the polymer component A.
Polymer component And is characterized by the content of carbonyl groups of the ketone or aldehyde type. Obviously, resins And modified by the introduction of suitable comonomers or other selected substances (raw materials), which provide the resin And the required carbonyl functional groups, namely aldehyde or ketone groups, as described above. In the context of the present invention carbonyl group of ketone type represents a group >C=O, where both the remaining connection of the carbon atom indicated carbonyl group connected to the carbon atoms, whereas the carbonyl group of the aldehyde type has a carbon atom of the carbonyl group, which is connected with one carbon and one hydrogen atom. Especially preferred that these carbonyl group connected to the polymer main chain by a sequence of at least two adjacent carbon atoms. This means that the polymeric component And, preferably, contains a structure of type
where the wavy line on the means of the polymer main chain, the remains of Raand Rbmay be the same or different in each case and can be hydrogen or, less preferably, halogen, or lower alkyl having up to 4 carbon atoms, and n is an integer of at least 2. You can also enter an oxygen atom or oxyalkylene group between the carbon atom forming part of the polymer main chain, and at least two carbon atoms in brackets in the above formula. In the preferred embodiment, has a carbonyl group originating from the polymer chain as the structure-CH2-CH2-CO-R, where R is preferably methyl or ethyl.
Component a can be any resin containing at least one ketone carbonyl group or aldehyde carbonyl group in the molecule, which (resin) can be dispersed in water or aqueous phase or in the introduction of at least one emulsifier (so-called external emulsification)or component And can be self emulsifiable. Preferably, component a is selected from the group consisting of polyurethanes, poliuretanowy, vinyl polymers, in particular polymers or copolymers of derivatives of acrylic or methacrylic acids, such as complex alkalemia esters, complex hydroxyalkyl esters and NITRILES where the acid and styrene and nesennye styrene are preferred as comonomers, and polyesters, alkyd resins, complex polyetherimides and epoxy resins. Especially preferred are polyurethanes, vinyl resin type and polyurethane or alkyd resins, which are grafted or otherwise modified, for example, by etherification, acrylic residues. Also preferred are hybrid polymers containing polyurethane and/or difficult-polyester resins, on the one hand, and polymers of vinyl type, on the other hand. They can be preferably synthesized using one or more monomers of the vinyl type, such as styrene or methyl methacrylate, as solvents in the formation of polyurethane or hard-polyester resins. After the formation of the above resin mixture was then dispersed in water, the resin acts as an emulsifier and, optionally, enter additional emulsifier and then carry out emulsion polymerization of monomers of the vinyl type. In the scope of the present invention can also use a mixture of resin And having at least one carbonyl group per molecule, with other resins And which are miscible with the resin And without phase separation at normal application temperatures, preferably of the same chemical class, but does not contain the carbonyl group. Under exp is feared "the same chemical class" means, what, for example, both resins are epoxy resin, or both resins are alkyd resin, or both resins are polyurethane resin type.
Also as a component And you can use the product of the condensation of the ester type, which is obtained by reaction of esterification hydrophobic hydroxyquinoline polymer compound A1 and hydrophilic colorfunction polymer compound A2, where ideally, at least one molecule each of A1 and A2 are connected together ester bond, and at least one of the polymer compound (A1 and A2) further comprises at least one carbonyl functionality. Such polymeric compounds A1 and A2, in turn, selected from the group consisting of polyurethanes, polyesters, alkyd resins, epoxy resins and vinyl polymers of the type having, in turn, hydroxyquinolinato and acid functionality and at least one of A1 and A2 also has a carbonyl functional group.
As is known in the art, the polyurethane is produced by interaction of oligomeric or polymeric multifunctional organic hydroxycodone with multifunctional isocyanates, optionally comprising low molecular weight organic multifunctional hydroxycodone. The term "multi is material in the context of the present invention relates to compounds, have a functionality of at least 2. As is also known in the technique, self emulsifiable polyurethane receive when introduced into the reaction mixture of compounds having acid functionality and at least one functional group which is reactive towards isocyanate groups. In addition, it is known in the art, that the water-dispersible polyurethanes, preferably, obtained when synthesizing the first stage of prepolymer A having the isocyanate functional groups, which are dispersed in an aqueous mixture containing the so-called chain extension A compound having at least two groups, which interact with isocyanate groups faster than water. On average, at least two molecules of prepolymer A' interact with at least one of the extension chain A” in the polyaddition reaction in the lengthening of the chain, forming, thus, more high molecular weight polyurethane (or poliuretanovomu in the case when A contains at least one primary or secondary amino group).
Carbonyl functionality is introduced into the polyurethane-isocyanate, polymeric or oligomeric multifunctional hydroxidealuminum, optional low molecular weight multifunctional hydroxidealuminum or a low-single the purpose ground receiving stations hydroxy - or aminoguanidinium. Such reactions are used in the case of polymer compounds And having different chemical nature, and carbonylation molecule is always chosen so that it contains at least one carbonyl group and at least one group which communication occurs in the polymer main chain between Monomeric residues. In the case of a vinyl polymer it can be an aldehyde or ketone with the olefinic unsaturation, or in the case of epoxy resin, it can be simple diglycidyl ester of an aliphatic or aromatic aldehyde or ketone, such as, for example, a simple diglycidyl broadcast dihydroxybenzaldehyde or simple diglycidyl ether dihydroxybenzophenone.
Component having at least two hydrazine or hydrazide group and at least one structural unit of formula I (see above) on the molecule, can be obtained by the interaction of the compounds B1 having at least two hydrazide or hydrazine groups on the molecule, and multifunctional aziridine B2, having at least two aziridine group in the molecule, preferably in the presence of a water dispersion of the polymer component A.
Multifunctional aziridine B2 has at least two aziridine group, a higher degree of crosslinking can be realized by the use of the implement multi aziridine B2, have at least three or more aziridine groups on the molecule.
The method used to obtain water samoszhimayuschihsya binder of the present invention, includes the following stages:
a) obtaining a polymer compound And,
b) dispersing polymer compound And water,
C) introduction of a dispersion of multi-functional compounds of aziridine having at least two aziridine group in the molecule, preferably at least three aziridine group in the molecule, and homogenization of the mixture, and
d) introduction to the specified mixture of hydrazine or hydrosalpinges compounds having at least two hydrazine or hydrazide groups per molecule.
In order to achieve a higher degree of crosslinking, it is preferable to use in this way multi-aziridine B2, which have three or more aziridine groups.
In the case when a is a polyurethane or poliuretanovomu, preferably, a polymeric compound which is injected into the water in the second stage (b)is isocyanatobenzyl polyurethane prepolymer A', and the molecule so-called chain extension A” is injected into the water in which the dispersed prepolymer A', before or during dispersion A' stage b), and A' and A” interact in vodeistages with the formation of polyurethane or poliuretanoviy with a long chain A.
If a is a self emulsifiable resin, it is sufficient to disperse the specified resin And, preferably, under high shear in the water at the stage b). This can be done using commercially available dispersant, such as a paddle stirrer, impeller stirrer or Ultra-Turrax.
If a is not self emulsifiable resin, emulsifying agents administered either in the water used in stage b), or A resin, which are dispersed in stage b). Commonly used emulsifiers are molecules that have both hydrophilic and hydrophobic part. These molecules form aggregates in the intermediate layer between the aqueous and non-aqueous phases and stabilize the dispersed droplets in the continuous phase.
Preferred are mixtures of at least two emulsifiers, which contain at least one reinacting emulsifier and at least one inactively emulsifier.
At the stage (C) a multifunctional compound containing at least two hydrazine or hydrazide groups per molecule, is injected into the dispersion And the water formed in stage b)so that, preferably, is formed of a homogeneous mixture. Also, preferably, after this stage of mixing the pH of the aqueous mixture is set higher than the value 6, more preferably above 7. Optimalen the first result is if the pH is in the range of from 8.0 to 10.5.
In the fourth stage (d) a multifunctional compound of aziridine injected into the mixture of stage (C), and "multifunctional" means here a compound, which has at least two aziridine group on the molecule, where the ratio of the number of substances aziridine groups to the amount of matter hydrazide-functional molecules is preferably in the range from 0.8 mol/mol to 1.0 mol/mol, and especially preferably from 0.9 mol/mol to 0.99 mol/mol. The ratio of the amounts of carbonyl groups in And to the quantity of substance remaining hydrazine or hydrazide groups after is stage d), and the reaction goes to weight, is then, preferably, from 1.0 mol/mol to 1.5 mol/mol, particularly preferably from 1.05 mol/mol to 1.2 mol/mol.
Interval quantities of carbonyl groups in the polymer component And, hydrazide or hydrazine groups in component B1 and aziridine groups in component B2 before any interaction of these groups among them
is preferably 1 mol:(1.0 mol to 2.2 mol):(0.2 mol-1.1 mol) in case trifunctional of aziridine and the bifunctional hydrazine or hydrazide.
Smossyvesa binder of the present invention can pre-emption is about to be used to obtain the compositions of coatings for wood and drevesinovedeniya materials. They are also suitable for coating other temperature-sensitive materials, such as paper and cardboard, leather and textile materials.
In the examples, as well as in the preceding text, all of the physical quantity with the unit of "%" or "IG/g" - related solutions or mixtures are mass fractions (mass of solute or a separate component divided by the mass of the solution or mixture), unless otherwise specified.
Acid number is determined according to DIN EN ISO 3682 (DIN 53402) as the ratio of the mass mKOHpotassium hydroxide required to neutralize the sample in the study, and the mass mBthis sample or mass of solids in the sample in the case of a solution or dispersion; its customary unit is "mg/g".
Amine number is defined according to DIN 53176 as the ratio of the mass mKOHpotassium hydroxide, which consumes the same amount of acid for neutralization, as the sample in the study, and the mass mBof this sample, or the mass of solids in the sample in the case of solutions or dispersions; commonly used unit is "mg/g".
Obtaining polymer component polyurethane
In a three-neck vessel equipped with a reflux condenser and a dropping funnel, a load of 900 g of castor oil, 16 g dimethylolpropionic acid, 272 g of 3-acetylphenol, 100 g of neopentyl glycol and 178 g simple dimethyl ether dipropyleneglycol and heated with stirring at 120°C to obtain a homogeneous solution. Slowly add 369 g colordistance with maintaining the reaction temperature at 124°C. After the introduction of the total diisocyanate stirring is continued at a temperature of from 115°C to 120°C until the mass fraction of isocyanate groups will not be reduced to less than 0.04%. Then add 632 g isophorondiisocyanate and the reaction mixture is again stirred at the specified temperature up until the mass fraction of isocyanate groups again drops below 0.6%. Type 59 g of fully demineralized water to reduce the temperature to about 97°C. There is a slight foaming. Then add a mixture of 52 g of aqueous ammonia solution of 25% concentration and 59 g of water and homogeneous mix. Neutralized resin solution is then dispersed in 2800 g of fully demineralized water for 30-45 minutes
The introduction of hydrazide
The dispersion of the resin from example 1 is heated with stirring at a temperature in the range from 70°C to 80°C. Add 176 g adipic hydrazide and the mixture is stirred for 30 min to obtain a homogeneous mixture. This mixture is cooled to room temperature and filtered through a 25 micron filter is C textiles with fleece to remove any sediment. The resulting dispersion has an average particle size of 73 nm, mass fraction of solids 43%, an acid number of 26.6 mg/g, dynamic viscosity of 2300 MPa·s and a pH (1 g dispersion, diluted with 9 g of water) of 7.7. The ratio of the amount of substance of hydrazide groups to the amount of substance of carbonyl groups is 0.8:1.
Getting samoszhimayuschegosya binder
In a vessel load of 800 g of the dispersion from example 2. At a temperature from 25°C to 30°C, slowly add 240 g polyaniline (crosslinking agent brand SH, DSM NeoResins B.V.) maintaining the temperature below 45°C. In the process of adding greatly increases the viscosity. After complete addition, stirring is continued for another 1 h, after which the vessel is left to stand for 15 hours at ambient temperature. During this period, the viscosity is reduced slowly and evenly. Get a fine dispersion, which is finally filtered through a filter fabric with fleece with 25 μm pores. The obtained dispersion is determined by the following data: dynamic viscosity of 1200 MPa·s, the mass fraction of solids of 45%, an amine number of 12.2 mg/g and an acid number of 17.7 mg/g Acid number increases when stored for one week (168 hours) at ambient temperatures up to 29.6 mg/g (approximately the original value, see example 2).
Dispersions of examples 2 and 3 are used for the formulation of non-pigmented coating compositions C2 and C3 for wood substrates. As comparative examples use industrial smeshivaemost polyurethane-acrylic hybrid resin (C4) together with samoszhimayuschimsya binder based on acrylic copolymers (according to example 4 of EP 0995780 B1; the composition of the coating C1). Table 1 shows the composition of the coating agents:
|The composition of the coatings|
|Designation||C1 Example 4 of EP 0995780 B1||C2 Dispersion from example 2||C3 Dispersion from example 3||C4 Industrial polyurethane-acrylic hybrid resin|
|Mass fraction of solids||43%||43%||43%||35%|
|Binder (see name)||100||100||100||100|
|Total weight in grams||109,8||106,8||106,8||109,8|
|Use the following additions:|
Protivovospalitel: Simple politicaleconomy copolymer trademark Tego-Foamex 805, Degussa AG
Solvent 1: a Mixture of equal mass fractions of butylglycol (simple monobutyl ether of ethylene glycol) and water
Solvent 2: a Mixture of equal mass fractions of butylglycol (simple monobutyl ether of ethylene glycol) and butyldiglycol (p is hostoi monobutyl ether of diethylene glycol)
Thickener: 2.5% aqueous solution (easy polyester)-mochevinoformaldegidnogo thickener brand Rheolat 278, supplier - Rheox, Inc., Houston, new Jersey, USA
The wetting agent is a trademark of Additol VXW 6503.
The coating composition obtained by mixing a binder, adding protivovospalitel and solvent and mixing for ten minutes by a high speed stirrer. Then add the thickener and lubricant and mix well for another ten minutes. Then add additional water to adjust the viscosity after a time of thirty seconds (DIN 4 Cup according to DIN EN ISO 2431). Thus obtained coating composition is applied on a glass plate and maple boards. Get the following results:
|Characterization of coatings|
|Composition of coating||C1||C2||C3||C4|
|Mass fraction of solids||45%||43%||43%||35%|
|The content of the process is Italia||no||DPGDME, 3%||NMP, 6,7%|
|Drying time - "from dust"||30 min||25 min||26 min||45 min|
|to "tack-free"||45 min||40 min||43 min||>180 min|
|Hardness by pendulum device - 24 hours||90||120||115||83|
|- 7 days (168 h)||115||150||147||149|
|Resistance on glass plates - acetone||26||30||60||20|
|- water||80 min||8 h||20 h||80 min|
|Resistance on the maple Board - ethanol||5||2-3||5||5|
|- ammonia solution||5||5||5||5|
|- instant coffee||3||5||5||4|
|- red wine||3||4-5||5||5|
|- Wetting wood||poor||very good||very good||very good|
Drying time "from dust" and "tack-free" is defined on a wet film thickness of 150 microns. Hardness by pendulum device (König) determine to 150 μm wet film on glass plates. The same samples used for assessment of resistance to water and solvents. Maple boards are covered twice 200 μm wet film, resistance to these agents evaluated after three weeks (504 hours) drying at room temperature according to DIN 68861/1. Wetting the wood is evaluated on an empirical basis on a scale range from 1=very good to 5=bad.
When compared with known smeshivayushchimisya binder based on acrylic copolymer (composition of coating C1) and urethane-acrylic hybrids (composition of coating C4) of the binder of the present invention show a faster drying time, a more rapid increase in hardness and improved resistance to water and solvents. Although you can see a slight deviation resistance coated plates is always on a par with systems prototypes.
Obtaining polymer component based on acrylic copolymer
Acrylic copolymer containing carboxylic acid and carbonyl functionality ketone type, is obtained using the monomial is different mixtures, as detailed in table 3.
|Getting carbonyl - and carboxylterminal acrylic copolymer (weight chemicals in g)|
|Ingredient||mass in g|
|Fully deionized water||1108|
|The regulator polymerization degree4||8,4|
|1Matricariifolium (30% solution in water, brand Disponil SDS, Cognis Deutschland GmbH & Co. KG)|
2Mixture this is Filatov fatty alcohol, Disponil SDS, Cognis Deutschland GmbH & Co. KG)
With dispersion of acrylic copolymer obtained as described above, mixing 18 g of fully deionized water, 12 g of aqueous ammonia solution of 25% concentration, 9 g of Acticide MBS (bactericidal substance, a mixture of methyl-4-isothiazoline and 1,2-benzisothiazolin-3-one, Thor Specialities Ltd.), 108 g of adipic dihydrazide and an additional 111 g of fully deionized water with the formation of a homogeneous dispersion.
This mixture is divided into 4 equal parts, each of the fourth portion (example 5.4) added 27 g of adipic dihydrazide and homogenized, and then add different amounts presidedover bridge trademarks SH:
|Getting samoszhimayuschihsya binder|
|Weight entered polyaniline||0 g||3.75 g||7.5 g||15 g|
Homogenized mixture is applied to glass the e plates in a wet film thickness of 150 μm each. The film is dried under standard conditions (23°C; 50% relative humidity) for one week (168 hours). Resistance to the acetone determine when applying drops of acetone on the coating film and determining the time when the coating may be removed in the experiment on scratching. Get the following results:
|The test results of the coatings|
|Resistance to acetone (C)||30||33||40||55|
The ratio of n(>C=O):n(-CO-NH-NH2):n(aziridine) (measured in mol:mol:mol) sets how many carbonyl groups, hydrazide groups (two for adipic dihydrazide) and aziridine groups (three for each 1 mol of the CX-100) are present in the mixture before interaction with each other. 1 mol of hydrazide groups RA is hochetsja when interacting with each 1 mol aziridine groups. In example 5.1 clossiana is only the interaction of ketone carbonyl groups of the acrylic copolymer with hydrazide groups adipic hydrazide. The degree of clossiana is on par with the results obtained in accordance with the description of the EP W. With the introduction of aziridine in example 5.2 part of hydrazide groups (25%) is spent in the interaction with aziridines that leaves only 75% of hydrazide groups to interact with the carbonyl groups in the copolymer. The degree of crosslinking is therefore reduced, but the density of crosslinking increases with education trifunctional bridge that leads to a small overall improvement in resistance to solvent. In example 5.3 50% of hydrazide groups consumed when interacting with aziridines, which leaves even less of hydrazide groups to interact with the carbonyl groups in the copolymer. Another small improvement in resistance to solvent may be due to the increase in the density of crosslinking, which compensates for the loss of the degree of crosslinking. The best value as the degree and density of crosslinking, however, observed in example 5.4, when the reaction trifunctional of aziridine used in the example, with the hydrazide may go to the weight, but still leaves a stoichiometric amount of hydrazide groups for crosslinking, when arr is the reattaching trifunctional lengthening chain of hydrazide bridge which interacts with the copolymer in the formation Gerasimovich structures. As shown by this example and confirmed by additional experiments performed in the course of research that led to the present invention, the optimum interval for the ratio of the quantities of substances for carbonyl groups, hydrazide groups and aziridine groups before any interaction from the specified group among themselves
1 mol:(1.0 mol to 2.2 mol):(0.2 mol to 1.1 mol, preferably 1 mol:(1.5 mol-2.1 mol):(0.5 mol-1.05 mol), and, particularly preferably, 1 mol:(1.8 mol-2.05 mol):(0.5 mol-1.05 mol).
1. Smossyvesa binder for coating compositions containing water-dispersible polymer component And having at least one carbonyl group of the ketone or aldehyde-type molecule, and component having at least two hydrazine or hydrazide groups per molecule, and at least one structural unit of the formula:
where the radicals R1, R2, R3and R4each separately selected from the group consisting of a hydrogen radical and a linear or branched alkyl radical having from 1 to 10 carbon atoms, R3and R4can be optionally selected from the group consisting of aryl - and Alki the aryl radical, having from 6 to 15 carbon atoms, and from oxyalkyl radicals having from 1 to 10 carbon atoms, where the hydroxy group can be introduced in the alkyl chain or at the end of the alkyl chain, and R5selected from the group consisting of hydrogen radicals, alkyl radicals, which may be linear, branched or cyclic and may have from 1 to 10 carbon atoms, and from the remnants of the formula
where n is an integer from 1 to 6, and X represents the residue of a polyhydric alcohol or phenol.
2. Smossyvesa binder according to claim 1, in which the polymer component a selected from the group consisting of polyurethanes, polyesters, complex polyetherimides, polyamides, alkyd resins, epoxy resins and vinyl polymers.
3. Smossyvesa binder according to claim 2, in which the vinyl polymers are poly(meth)acrylates or copolymers having a mass fraction of at least 30%, derived from (meth)acrylic monomers, which are derivatives of acrylic or methacrylic acid.
4. Smossyvesa binder according to claim 1, in which the polymer component a is a polymer with a non-branched chain, and the polymer chain is at least one carbonyl group.
5. Smossyvesa binder according to claim 1, in which the polymer component a is a polymer clay is, having at least one point of branching in the molecule, and at least one chain has a chain length of not more than twenty atoms forming at least one circuit and at least one carbonyl group is at least one chain having not more than twenty epioblasma atoms.
6. Smossyvesa binder according to claim 5, in which at least one circuit has at least three and not more than fifteen epioblasma atoms.
7. Smossyvesa binder according to claim 1, in which the polymer component a is a polyurethane having at least one side of the carbonyl group chain ketone or aldehyde type, where the carbonyl group is separated from the main chain, at least two adjacent carbon atoms.
8. Smossyvesa binder according to claim 1, in which the polymer component a is a poly(meth)acrylate having at least one side of the carbonyl group chain ketone or aldehyde type, where the carbonyl group is separated from the main chain, at least two adjacent carbon atoms.
9. Smossyvesa binder according to claim 1, in which the polymer component a is a complex polyester having at least one side of the carbonyl group chain ketone or aldehyde type, where the carbonyl group of the Department is on from the main circuit, at least two adjacent carbon atoms.
10. Smossyvesa binder according to claim 1, in which the polymer component a is a product of the interaction hydroxyquinoline hydrophobic polymer compound A1 and colorfunction polymer compound A2, at least one of which contains at least one carbonyl group chain ketone or aldehyde type, and in which A1 and A2 are connected together ester bond.
11. Smossyvesa binder according to claim 1, in which component has at least two structural element of formula I.
12. Smossyvesa binder according to claim 1, in which the polymer component a is a hydrophilic modified by the presence in the specified component And groups that make the specified component And samoszhimayuschimsya that group selected from the group consisting of oligomeric oxyethylene residues consisting of at least three consecutive oxyethylene groups, anionic groups and acidic groups which form an acid anions by neutralizing bases selected from the group consisting of carboxylic groups, sulfonic, phosphoric and phosphonic acids, and cationic groups, which form cations by neutralizing acids selected from the group consisting of primary, secondary and tertiary amines, the ri condition, that anionic and cationic groups are present simultaneously in the component A.
13. Smossyvesa binder indicated in paragraph 12, in which the polymer component a is a water-dispersible polyurethane and a hydrophilic modification is the presence of at least three consecutive oxyethylene groups in the polymer chain or the presence of remnant bishydroxamic acid in the polymer chain, or by the presence of both.
14. Smossyvesa binder indicated in paragraph 12, in which the polymer component a is a water-dispersible poly(meth)acrylate and hydrophilic modification is the presence in the polymer chain of the residue of poly(oksietilenom)-(meth)acrylate having at least three consecutive oxyethylene group, or the presence in the polymer chain of the residue colorfunction monomer with the olefinic unsaturation, or by the presence of both.
15. Smossyvesa binder according to claim 1, which contains an effective amount of at least one emulsifier and emulsifier selected from the group consisting of reinacting, anionic and zwitterionic emulsifiers and mixtures reinacting emulsifiers with any of these anionic and zwitter-ionic emulsifiers.
16. The method of obtaining samoszhimayuschihsya binder according to claim 1, the soda is containing the following stages:
a) obtaining a polymer compound And having the carbonyl group of the ketone or aldehyde-type
b) dispersing polymer compound And water,
c) introducing the dispersion of the hydrazine - or hydrosalpinges connection B1 having at least two hydrazine or hydrazide groups per molecule, and homogenization of the mixture, and
d) the introduction to this mixture multifunctional compounds of aziridine B2, having at least two aziridine group in the molecule, and the interaction of the mixture with the education component, having at least two hydrazine or hydrazide groups per molecule and at least one structural unit:
where abbreviations and R1-R5have the same meanings as in claim 1.
17. The method according to clause 16, in which the interval for the ratio of the quantities of substances for carbonyl groups in the polymer component And, hydrazide or hydrazine groups in component B1 and aziridine groups in component B2, where B1 is bifunctional, and B2 is trifunctionally, before any interaction of these groups with each other
1 mol:(1.0 mol to 2.2 mol):(0.2 mol - 1.1 mol).
SUBSTANCE: invention represents an emulsion, in which oligomers with terminal isocyanate groups are a dispersion medium, and a disperse phase is a solution or a dispersion produced as a result of mixing a lime solution with calcium hydroxide content of 10-70 wt % with glycerine in the amount of 1-250 wt parts per 100 wt parts of calcium hydroxide, besides, the disperse phase content in the composition makes 1-55 wt %.
EFFECT: development of a cheap and easy to apply composition, coatings from which have high adhesion to moist metal or concrete surfaces, have proper adhesion to concrete applied onto them, are hardened with specified speed at temperature from zero and above, inhibit processes of metal corrosion and have low elasticity module.
SUBSTANCE: coating has surface tension less than 20 mN/m, wherein the coating material used is hydrolysis-resistance lacquers, and where the hydrolysis-resistant lacquers are selected from a group consisting of polyurethanes, acryl and silicones, where the coating has a random topography with roughness of less than 500 nm, preferably less than 300 nm.
EFFECT: coating prevents deposit of bacteria and improves thermal conduction of the coated material.
19 cl, 4 dwg, 2 ex
SUBSTANCE: invention relates to aldimines of formula (I)
where A does not contain active hydrogen and a primary amine group, or together with R7 denotes a (n+2)-valent hydrocarbon radical containing 3-20 carbon atoms and, if necessary, at least one heteroatom in form of oxygen of an ether group or nitrogen or a tertiary amine group; n equals 1, 2, 3 or 4; m equals 0,1, 2, 3 or 4; R1 and R2 each denotes a univalent hydrocarbon residue with 1-12 carbon atoms or together denote a divalent hydrocarbon radical which is part of a carbocyclic ring with 5-8 carbon atoms; R3 denotes H or alkyl; R4 and R5 independently denote CH3 or a univalent aliphatic radical containing 2-12 carbon atoms and optionally hydroxy groups; X denotes O, S, N-R6, or N-R7, where R6 denotes a univalent hydrocarbon radical containing 1-20 carbon atoms and having at least one hydroxy group; as well as curable compositions containing such aldimines and use of said compositions.
EFFECT: obtaining novel aldimines which can be used as curing agents in curable compositions.
22 cl, 18 ex, 6 tbl
SUBSTANCE: powder coating is obtained from a composition containing at least one binding material (A) from polyester resin with a hydroxyl functional group and at least one polyurethane resin (B) as a cross-linking agent containing blocked isocyanate groups. At least one binding material from the polyester resin (A) with a hydroxyl functional group and at least one polyurethane resin (B) have melting point of 60-180°C, specifically 60-160°C. The powder composition is deposited on a substrate and cured. The substrate can be metal, plastic, wood, paper or glass.
EFFECT: obtaining coatings with the required processing properties, specifically obtaining thin films and high flexibility combined with excellent mechanical coating properties.
11 cl, 2 tbl
SUBSTANCE: paint with thermo-, fire-protective properties contains (wt %): binder based on acrylic (co)polymers and/or silicone resins and organosoluble polyurethanes - (20-40), filler in form of a mineral component - (10-30), antipyrene additive - (10-20), modifying additive in form of ceramic and/or glass microspheres with diameter of 20-150 mcm -(10-30) and an organic solvent - the rest. The paint composition additionally contains bentonite powder, intercalated with cobalt Co2+ ions and/or cerium Ce3+ ions in amount of 3-7 wt %.
EFFECT: invention increases stability of the formed protective paint coating to thermal-oxidative reactions, improves environmental safety, fire-resistance of the protective coating and endows said coating with bactericidal properties.
7 cl, 2 dwg, 1 tbl
SUBSTANCE: invention relates to a method of producing microporous coatings, wherein a composition is foamed and dried, said composition containing an aqueous, anionically hydrophilised polyurethane dispersion (I) and a cationic coagulant (II), wherein the cationic coagulant (II) is a polymer with number-average molecular weight ranging from 500000 to 50000000 g/mol, which has structural links of general formulae and ,
where R denotes C=O, -COO(CH2)2- or -COO(CH2)3- and X- denotes a halide ion. The invention also describes a microporous coating obtained using said method, a composition for producing microporous coatings and a substrate coated with said microporous coating.
EFFECT: production of microporous coatings using a novel method, having good mechanical properties and a thin microporous structure.
10 cl, 9 ex, 1 tbl
SUBSTANCE: polyacrylic (co)polymer which is curable under the effect of atmospheric moisture and having elastometic properties is a plurality of acrylic prepolymer segments interlinked by urea or urethane links caused by moisture curing. Each of the plurality of prepolymer segments is a homopolymer or a copolymer of methylmethacrylate, C1-C16-alkylacrylate and C1-C16-alkylmethacrylate as the predominant monomer group. The moisture-curing method involves formation of a plurality of segments of an acrylic prepolymer, obtaining isocyanate-functionalised segments of the acrylic prepolymer, storing the isocyanate-functionalised segments in anhydrous state, followed by deposition thereof onto a substrate and moisture-curing to form a polyacrylic polymer.
EFFECT: obtaining polyacrylic (co)polymers cured under the effect of atmospheric moisture and having elastomeric properties, which retain resistance to UV rays, optical transparency, wear and physical properties of conventional thermoplastic acrylic polymers.
14 cl, 5 ex
SUBSTANCE: invention relates to a method of producing dispersions of blocked polyurethane prepolymers, use of dispersions obtained using said method to produce coating agents, adhesive substances and sealants and elastomers, said application products themselves, as well as substrates provided with coating agents. The method involves the following: I) a blocked polyurethane prepolymer is obtained first by reacting a) 100 equivalent % of at least one polyisocyanate with b) 50-90 equivalent %, in terms of isocyanate reactive groups, of a thermally split blocking agent, c) 5-45 equivalent %, in terms of isocyanate reactive groups, monohydroxycarboxylic acid as a hydrophilic agent and d) 0-25 equivalent %, in terms of isocyanate reactive groups, of polyhydroxycarboxylic acid as a hydrophilic agent and e) 0-15 equivalent %, in terms of isocyanate reactive groups, of at least one, in terms of isocyanate reactive groups, di- or polyfunctional component of a chain extender with molecular weight from 32 to 350 g/mol, where i) this takes place using (partially) water-miscible organic solvents which are inert to NCO-groups and have boiling point lower than 120°C (at 1013 mbar), ii) and they are used in such an amount that the polyurethane prepolymer contained in the reaction solution after complete conversion ranges from 70 to 98 wt %. Further, II) the polyurethane prepolymer solution obtained at step (I) is dispersed in water, where before, during or after dispersion, deprotonation of carboxylic acid groups with a base takes place at least partially, and then III) if needed, the contained organic solvent is completely removed during dispersion via distillation.
EFFECT: obtaining polyurethane dispersions which are stable during storage, endow said products of their application with good optical properties, high resistance to chemical reagents and pendulum hardness.
13 cl, 10 ex, 1 tbl
SUBSTANCE: invention relates to an actinic radiation cured coating composition containing a compound which contains at least two isocyanate groups, a compound which contains at least two hydroxyl groups, a sensitising agent and a photolatent catalyst for an isocyanate-hydroxl coupling reaction, where the photolatent catalyst is an organometallic compound, containing tin as a catalytically active metal, and where the atom of the catalytically active metal in the organometallic compound is not bonded to atoms of other metals. The invention also describes a method of coating a substrate, involving a step for applying said composition onto the substrate, as well as a set of parts for preparing said actinic radiation cured coating composition.
EFFECT: obtaining an actinic radiation cured coating composition having a good balance of long life and fast curing after application and irradiation, and leads to formation of cured coatings, the colour of which is not affected by coloured residues or photolatent catalyst fragments.
13 cl, 6 ex, 4 tbl
FIELD: textile industry.
SUBSTANCE: fabric is of polyester or polyetheretherketone type. The fabric coating is produced by way of cross-linking anionic aliphatic dispersion with OH-number < 0.5 with hydrophilous aliphatic polyisocyanate, preferably, based on hexamethylenediisocyanate with NCO value 17-18. The fabric may be woven of already coated fibres or filament yarns. The coating is applied on the fabric by way of its contacting with a gluing compound containing a gluing substance activated to perform cross-linking when heated. Then the fabric is ironed at a temperature of 95-100°C. The fabric is pitched on structures at a surface temperature, with the seams and laps not heated over 100°C. The invention excludes the necessity of further application of coating on the fabric after application the coating which ensures application of a significantly less weight in the process of coating.
EFFECT: one eliminates application of any organic solvents in the gluing compounds providing for tension of oil varnishes, liquifiers, fillers or coloured oil varnishes and offers an environmentally safe method for application of coating on an aircraft.
9 cl, 3 ex
SUBSTANCE: invention relates to compositions for extreme media used in agriculture, cosmetology and everyday life. The compositions contain a surfactant based on an organosilicon compound of the formula: MM', where M=R1R2R3SiO1/2; M'=R4R5R6SiO1/2; where R1 is selected from a group consisting of a branched monovalent hydrocarbon radical containing 3-6 carbon atoms, and R7, where R7 has the formula: R8R9R10SiR12, R8, R9 and R10 are each independently selected from monovalent hydrocarbon radicals containing 1-6 carbon atoms and monovalent aryl or alkylaryl hydrocarbon radicals containing 6-13 carbon atoms, and R12 is a divalent hydrocarbon radical containing 1-3 carbon atoms, R2 and R3 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R1, with R4 in form of alkyl polyalkylene oxide of general formula: R13(C2H4O)a(C3H6O)b(C4H8O)cR14, where R13 is a divalent straight or branched hydrocarbon radical, having the structure: -CH2-CH(R15)(R16)dO-, where R15 is H or methyl; R16 is a divalent alkyl radical with 1-6 carbon atoms, where the subscrip d is equal to 0 or 1; R14 is selected from a group consisting of H, monovalent hydrocarbon radicals with 1-6 carbon atoms and acetyl, where subscripts a, b and c are equal to zero or positive numbers and satisfy the following relationships: 2≤a+b+c ≤20 for a≥2, and R5 and R6 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R4. The compositions have hydrolysis resistance in a wide pH range.
EFFECT: invention increases hydrolytic stability of the compositions.
65 cl, 21 tbl, 13 ex
SUBSTANCE: invention relates to compositions for extreme media used in agriculture, cosmetology and everyday life. The surfactant compositions for extreme media contain organically modified hydrolysis-resistant disiloxane surfactants which are based on an organosilicon compound of formula: MM', where M = R1R2R3SiO1/2; M' = R4R5R6SiO1/2; where R1 is selected from a group consisting of a branched monovalent hydrocarbon radical containing 3-6 carbon atoms, and R7, where R7 has the formula: R8R9R10SiR12, R8, R9 and R10 are each independently selected from a group of monovalent hydrocarbon radical containing 1-6 carbon atom and monovalent aryl or alkylaryl hydrocarbon radical containing 6-13 carbon atoms, and R12 is a divalent hydrocarbon radical containing 1-3 carbon atoms, R2 and R3 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R1, with R4 in form of alkylpolyalkylene oxide of general formula: R13(C2H4O)a(C3H6O)b (C4H8O)cR14, where R13 is a divalent straight or branched hydrocarbon radical, having the structure: -CH2-CH(R15)(R16)dO-, where R15 is H or methyl; R16 is a divalent alkyl radical consisting of 1-6 carbon atoms, where the subscript d can be equal to 0 or 1; R14 is selected from a group consisting of H, monovalent hydrocarbon radicals consisting of 1-6 carbon atoms and acetyl, where subscripts a, b and c are equal to zero or positive numbers and satisfy the following relationships: 2≤a+b+c≤20 for a ≥2, and R5 and R6 are each independently selected from a group of monovalent hydrocarbon radicals containing 1-6 carbon atoms or R4. The compositions are resistant to hydrolysis in a wide pH range.
EFFECT: invention increases hydrolytic stability of the compositions.
65 cl, 21 tbl, 13 ex
FIELD: process engineering.
SUBSTANCE: invention relates to laminate used in glass panels, lenses etc. Proposed laminate comprises base made up of polycarbonate resin, first layer resulted from hardening acrylic resin hardening, second layer produced by thermal hardening of organosiloxane resin. Acrylic resin composition comprises (A) acrylic copolymer containing at least 70 mol % of repeating link of formula (A)
where X is hydrogen or methyl, Y is methyl, ethyl, cycloalkyl or hydroxyalkyl with the number of atoms of 2 to 5, or residue of UV radiation absorber based on triazine; blocked polyisocyanate compound; hardening catalyst; and (D) UV radiation absorber based on triazine. Note here that total content of UV radiation absorber based on triazine in formula (A) and as component (D) varies from 1 to 40 wt %. Composition of organosiloxane resin in proposed laminate comprises (E) colloidal silicon dioxide and (F) hydrolytic condensate of alkoxy silane. Invention covers also window glass made based on said laminate.
EFFECT: higher strength and longer life.
25 cl, 15 tbl, 50 ex
SUBSTANCE: disclosed aqueous dispersion of copolymerisation products containing A) one or more hydroxy-functional copolymerisation products, obtained from the following (wt %): non-hydroxyl containing ester of (meth)acrylic acid and/or vinylaromatic compounds (53.5-87), hydroxy-functional ester of (meth)acrylic acid (2.5-45.9), ionic and/or potentially ionic monomers (0.6-19) capable of radical copolymerisation, as well as, if necessary, other monomers capable of radical copolymerisation which are different from compounds of components a)-c) (0-43.4) and B) at least one hydroxy-functional polycarbonate-polyol as a reactive diluent. Disclosed also is an aqueous coating agent which contains one or more of the disclosed aqueous dispersions of copolymerisation products and at least one cross-linking agent which interacts with hydroxyl groups.
EFFECT: disclosed aqueous dispersions have low solvent content and enable to obtain coatings with high level of resistance of lacquer films, with high scratch resistance and acid resistance.
5 cl, 1 tbl, 12 ex
SUBSTANCE: road marking paint contains an acrylic film-forming agent - copolymer of methylmethacrylate and butylmethacrylate - DIANAL BR-116 resin, calcite filler - finely ground white marble Omicarb and micronised calcite filler MK, barite filler - fractionated microbarite Mibari, plasticiser - chloroparaffin KP-470, organic solvent - toluene and ethylacetate, pigment - titanium dioxide, thickener - organic derivative of montmorillonite Bentone SD-2, dispersing agent - mixture of natural phospholipids Soya lecithin, anti-sedimentation agent - 20% solution of emulsion polyethylene resin in xylene M-P-A 2000X, with components in a defined ratio. Chrome yellow and/or technical carbon can also be contained as pigment.
EFFECT: maintaining high level of the rest the of factors.
3 cl, 2 tbl, 11 ex
SUBSTANCE: powdered UV-curable composition contains 89.5-96.5 pts. wt oligoether(meth)acrylate, 1.0-2.7 pts. wt benzoyl-type photoinitiator, 1.0-1.5 pts. wt flow agent, 0.5-0.7 pts. wt degassing agent and a fluorine-containing modifying additive in form of a solid unsaturated compound with molecular weight of 850-2700 g/mol, obtained through synthesis from p-hydroxyethoxystyrene, diisocyanate in form of 1,6-hexamethylenediisocyanate or isophorone diisocyanate, and perfluorinated oligoester alcohol or oligoester diol with molecular weight of 500-2000 g/mol in amount of 1.0-5.6 pts. wt.
EFFECT: good physical and mechanical properties and obtaining coatings having high wear resistance, low dirt holding, good decorative and protective properties.
2 tbl, 16 ex
SUBSTANCE: acrylic paint composition in the first version contains an acrylic film-forming - acrylic organosoluble copolymer Polyform and a copolymer of p-butylmethacrylate with methylmethacrylate, silica filler, thickener - benton or pangel, plasticiser - phthalic ester, pigment and organic solvent. In the second version the acrylic paint composition contains an acrylic film-forming - acrylic organosoluble copolymer Polyform and a copolymer of p-butylmethacrylate with methylmethacrylate and additionally a polyorganosiloxane resin, silica filler, thickener - benton or pangel, plasticiser - phthalic ester, pigment and organic solvent.
EFFECT: improved physical and mechanical properties.
2 cl, 2 tbl
SUBSTANCE: road marking paint contains an acrylic filming agent, inorganic filler, a plasticiser, a mixed organic solvent, a pigment - titanium dioxide, a thickener based on organobentonite and a dispersing agent based on lecithin. The inorganic filler used is acid plagioclase in form of particle with size ranging from 12 to 60 mcm with sodium content ranging from 10.50 to 10.60 wt % in terms of Na2O. The paint additionally contains microtalc.
EFFECT: increased resistance of the road mark to prolonged effect of water, salt and alkali.
2 tbl, 3 ex
SUBSTANCE: method is described for preparing gelcoat composition which involves mixing unsaturated styrene polyester resin Kamfest-01 with a surfactant OP-10 and a hardening accelerator NK-2 - cobalt naphthenate in a styrene solution, addition of a soot paste based on unsaturated styrene polyester resin Kamfest-01 and filler Aerosil into the mixture, with subsequent curing and mastication of the obtained mass, obtaining the end product.
EFFECT: obtaining a stable gelcoat which provides for making an opaque decorative layer of high uniformity and opaqueness.
1 cl, 1 tbl
SUBSTANCE: invention relates to cleaning of surfaces made from natural and artificial stones, ceramic materials and may be used for cleaning buildings faces and interiors from atmospheric contamination and for maintenance activities. Method of buildings faces and interiors cleaning includes cleaning with water, drying and applying hydrophobisated compositions in two layers. As soon as the first layer is applied, it is exposed before the second layer application during the time needed for complete hydrophobisated composition absorption. Polysiloxane resin emulsion Tego Phobe 6600 is dissolved in water at ratio 1:4-5 and used as hydrophobisated composition for the first layer. As hydrophobisated composition in the second layer, a composition is used, that contains styrene-acryl dispersion, silicon resin or silicon resins mixture, pigments, disperser, thickener, emulsifier, foam killer, preserving agent, coalescent and water at the stated ratio of components.
EFFECT: cleaning of surfaces and protection from recontamination.
1 tbl, 3 ex