Polyurethane dispersing resin

FIELD: chemistry.

SUBSTANCE: present invention relates to a polyurethane dispersing resin, primarily having a polyurethane chain which contains hydrophilic groups of the side chain based on polyalkylene oxide, where groups of the side chain are covalently bonded to the polyurethane backbone chain, and where content of polyalkylene oxide in the polyurethane dispersing resin is at least 45 wt % and not more than 80 wt %. Polyurethane also contains hydrophobic groups on the side chain, which are covalently bonded to the polyurethane backbone chain. The invention also describes a coating composition containing said polyurethane dispersing resin, methods of preparing said composition and use of the polyurethane dispersing resin to prepare a composition for mixing with a pigment.

EFFECT: providing a polyurethane dispersing resin which enables to prepare concentrates of pigments, which can be easily included in a coating composition, in which pigments are stably dispersed, as well as possibility of obtaining pigment compositions with a wide range of pigments and obtaining dyes having excellent properties and stability, especially hard-to-disperse and stabilised pigments.

24 cl, 16 ex, 4 tbl

 

The invention relates to a polyurethane dispersant resin with polyurethane main chain containing a hydrophilic group of the side chain on the basis of polyalkylated, and group of the side chain attached to the polyurethane main chain through covalent bonds. In addition, the invention relates to compositions containing a polyurethane dispersant resin, method for producing the compositions and polyurethane dispersant resin.

Polyurethane dispersant resin of the specified type is known from international application WO 97/19120. This document relates to dispersible in water unsaturated polyurethane. The polyurethane contains 10-40% by weight polyalkylbenzene groups of the side chain. Polyurethane is suitable for obtaining aqueous dispersions of hydrophobic polymers or dispersions of pigments.

WO 03/046038 describes a polyurethane polymer containing from 35% to 90% weight. groups based on poly(C2-4accelerated) of the total weight of the polymer, and where at least 5% of groups based on poly(C2-4accelerated) of the total weight of the polymer contained in the side chains.

It was found that when using the known polyurethane dispersant resin dispersion pigment pastes and flocculation stability of pigments in paints further improved, particularly with the learn the application trudnozapominaemyj pigments. Moreover, the known polyurethane dispersant resin is less suitable for obtaining the so-called compositions of pigments mixing. Moreover, in particular, compounds of dry pigments containing a known polyurethane dispersant resin, do not give the paint with a steadily dispergirovannykh pigments. Compositions for mixing pigments are often dry, mostly powder concentrates of pigments containing a pigment and a dispersing agent that can be included in the matrix, as for example, in compositions for coating, using a simple mixing without the need for additional phase dispersion, hence the name - composition for mixing pigment. Compositions for mixing pigments organic pigments are preferably obtained by treatment of pressed sludge pigment dispersing agents, followed by drying. When pressed the precipitated pigment is mixed with a known polyurethane dispersant resin, then pressed the precipitated pigment is impossible to fluidsurface in pigment suspension, which is necessary for the further processing stages with the purpose of obtaining a composition for mixing pigment.

Thus, the present invention provides a polyurethane dispersant resin, which allows you to create concentrates of pigments that may be what AGCO included in the composition for coating, where pigments stable of dispergirovany. In addition, dispersing resin shall be suitable for use with a wide range of pigments. Concentrates of pigments should allow obtaining paints with excellent quality and stability, especially in the case of trudnozapominaemyj and stabilized pigments.

The invention provides polyurethane dispersant containing the hydrophilic group of the side chain on the basis of polyalkylated, and group of the side chain attached to the polyurethane main chain through covalent bonds, and where the content of polyalkylated in the polyurethane dispersant resin, at least 45 wt%, characterized in that the polyurethane further comprises a hydrophobic group on the side chain, which is attached to the polyurethane main chain through covalent bonds.

Polyurethane dispersant resin according to the invention allows to create concentrates of pigments that can be easily incorporated into compositions for coating, where the pigment is stably dispersed. In addition, the dispersant resin is suitable for use with a wide range of pigments. Concentrates of pigments allow you to receive paint with excellent quality and stability, especially in the case of trudnozapominaemyj and stabilized pigments.

Polyurethanes which I dispersing resin according to the invention can be obtained by reaction

(a) at least one di - or MDI,

(b) at least one compound having at least two groups capable of reacting with isocyanates, and the hydrophilic group of the side chain on the basis of polyalkylated,

(C) possibly one or more compounds able to react with isocyanates having at least two groups capable of reacting with isocyanates, and

(d) may compound capable of reacting with isocyanates having one group capable of reacting with isocyanates,

where at least one of the components (a), (b) and (c) have a hydrophilic group in the side chain.

As a suitable di - or polyisocyanates can be mentioned aliphatic, cycloaliphatic or aromatic di-, tri - or territoriality. Examples of diisocyanates include 1,2-Propylenediamine, trimethylenediamine, tetramethyldisilane, 2,3-butylenediamine, hexamethylenediisocyanate, octamethyltrisiloxane, 2,2,4-trimethylhexamethylenediamine, dodecyltrimethoxysilane, ω,ω'- diisocyanate of DIPROPYLENE ether, 1,3-cyclopentanedione, 1,2-cyclohexanedione, 1,4-cyclohexanedione, isophorondiisocyanate, 4-methyl-1,3-diisocyanato-cyclohexane, TRANS-vinylidenechloride, dicyclohexylmethane-4,4'-diisocyanate (Desmodur®W), colorvision, 1,3-bis(isocyanate is Teal)benzene, xylylenediisocyanate, α,α,α',α'-tetramethylethylenediamine (TMXDI®), 1,5-dimethyl-2,4-bis(2-isocyanatomethyl)benzene, 1,3,5-triethyl-2,4-bis(isocyanatomethyl)benzene, 4,4'-diisocyanato-diphenyl, 4,4'-diisocyanato-3,3'-dichloro-diphenyl, 3,3'-diphenyl-4,4'-diisocyanato-diphenyl, 4,4'-diisocyanato-3,3'-dimethoxy-diphenyl, 4,4'-diisocyanato-difenilmetana, 4,4'-diisocyanato-3,3'-dimethyl-difenilmetana and disorientation. Examples of triisocyanate include 1,3,5-triisocyanate, 2,4,6-triisocyanate, 1,8-diisocyanate-4-(isocyanatomethyl)octane and disinclination. Adducts and oligomers of polyisocyanates include, for example, biuret, isocyanurate, allophanate, uretdione, urethanes, iminoimidazolidine and mixtures thereof. Examples of such oligomers and adducts is the adduct of 2 molecules of diisocyanate, for example hexamethylenediisocyanate or isophorondiisocyanate with diola, such as ethylene glycol, the adduct of 3 molecules hexamethylenediisocyanate with 1 molecule of water (available under the trade name Desmodur N from Byer), adduct 1 molecule of trimethylolpropane with 3 molecules colorvision (available under the trade name Desmodur L from Byer), adduct 1 molecule of trimethylolpropane with 3 molecules isophorondiisocyanate, adduct 1 molecule pentaerythrol with 4 molecules colorvision, the adduct of 3 moles of m-α,α,α',α'-tetramethyldisilane 1 m mol trimetroprim the Ana, which trimmer 1,6-diisocyanatohexane, which is trimmer isophorondiisocyanate, uretdione dimer of 1,6-diisocyanatohexane, biuret 1,6-diisocyanatohexane, Aliant 1,6-diisocyanatohexane and their mixture.

Suitable compounds (b) can be obtained by the reaction of monoether polyalkyleneglycol with diisocyanate, followed by reaction with a secondary amine having two hydroxyl groups. The receipt of such compounds, mainly known. Detailed description of obtaining, for example, presents US 3905929.

Further examples of compounds having two groups capable of reacting with isocyanates, and the hydrophilic group of the side chain on the basis of polyalkylated obtained from triolo, having one hydroxyl group blocked by segment based on polypropylene or polyethylene oxide, ending with simple ether group. Commercially available examples of such a diol is Tegomer D-3403 from Tego Chemie Service GmbH, Germany.

In a preferred embodiment, component (b) is a compound of formula (I)or (II), or mixtures thereof,

where R is the remainder monoepoxide compounds after reaction with the amino group, R1selected from alkyl groups from s1to C4n is from 0 to 25, m is from 1 to 50 and n+m ≤ 50. Obviously, (C3H6O) and (C2H4A) is incurred may be present in the polymer chain as blocks of polypropyleneoxide and polyethylene oxide or as a more or less random mixture of links, formed from propylene oxide or ethylene oxide. Preferably, R contains hydrocarbon group having 4 to 30 carbon atoms. Compounds according to formula (I) can be obtained by reaction of 1 mole of a primary amine with 1 mol monoepoxide compounds, compounds according to formula (II) can be obtained by reaction of 1 mole of a primary amine with 2 moles monoepoxides connection. The residue R contains a primary or secondary hydroxyl group and, preferably, R contains a hydrocarbon group having from 4 to 30 carbon atoms. Thus, the compound according to formula (I) contains a hydroxyl group and a secondary amino group as the groups capable of reacting with isocyanates. The compound according to formula (II) contains two hydroxyl groups as the groups capable of reacting with isocyanates.

Examples of suitable source monoepoxides for producing compounds according to formula (I) or (II) are epoxydecane olefins, such as epoxydecane α-olefins; glycidyloxy esters monohydroxylic compounds, such as Ethylhexylglycerin ether, butespecially ether, hexylpyridine ether, phenylglycidyl ether; and glycidyloxy esters of carboxylic acids, such as glycidyloxy ester propionic acid, glycidyloxy ester hexanoic acid, glycidyloxy ether ethylhexanoic acid, glycidyloxy the ether decanoas acid and glycidyloxy the ester versatic acid, commercially available from Resolution Performance Products under the name Cardura E 10.

Examples of suitable source amines to produce compounds according to formula (I) or (II) are amines based polyalkyleneglycol, which are commercially available from Huntsman under the trade designation Jeffamine®M

When using compounds (b) according to the formulas (I) and/or (II) can be obtained dispersion of pigments with polyurethane dispersant resin with a particularly good stability.

Alternatively or additionally, at least one compound having at least two groups capable of reacting with isocyanates, and the hydrophilic group of the side chain on the basis of polyalkylated, also, upon receipt of the polyurethane dispersant resin, polyurethane is possible to introduce the hydrophilic group of the side chain on the basis of polyalkylated using at least one compound having at least two isocyanate group and hydrophilic group in the side chain on the basis of polyalkylated.

Upon receipt of the polyurethane dispersant resin number of compounds having at least two groups capable of reacting with isocyanates, and the hydrophilic group of the side chain on the basis of polyalkylated, chosen in such a way as to ensure that the content of polyalkylated in polyurethane dis is argyroudis the resin, at least 45 wt%. Preferably, the number of polyalkylated in the polyurethane dispersant resin should not exceed 80% of the weight. Most preferably, the number of polyalkylated ranged from 50% to 70% weight. Polyurethane dispersant resin preferably contains at least two, more preferably at least three hydrophilic group of the side chain on the basis of polyalkylated per molecule.

Examples of suitable alkalisation are ethylene oxide, propylene oxide and butylenes. Preferably, the group-based polyalkylated was based on ethylene oxide or propylene oxide or their mixtures. At this time, very good results were obtained with the side groups on the basis of polyalkylated, 50 wt%, preferably 70 wt%. which is based on ethylene oxide, calculated on the total weight of the side groups on the basis of polyalkylated.

Examples of compounds able to react with isocyanates having at least two groups capable of reacting with isocyanates include di - and polyamine, di - and politiely, aminoalcohols, aminothiol and, in particular, the polyols. Suitable polyols that can be used to obtain polyurethanes include diols and trioli and their mixtures, however, can also be used polyols with most the number of functional groups. Examples of polyols with low molecular weight include ethylene glycol, diethyleneglycol, tetraethylene glycol, propane-1,2 - and -1,3-diol, butane-1,4 - and -1,3 - diol, hexane-1,6-diol, octane-1,8-diol, neopentylglycol, 1,4-bis-hydroxymethylcellulose, 2-methylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, dipropyleneglycol, polypropyleneglycol, dibutylamino, polietilenglikoli, bisphenol a and tetrabromobisphenol And, dimer fatty acid-based diols, glycerol, pentaerythritol, trimethylolpropane, detromethorphan, hexane-1,2,6-triol, butane-1,2,4-triol, henital, mannitol, sorbitol, methylglucoside, 1,4,3,6-diaminohexane, monetary neopentylene alcohol and hydroxypivalic acid, bis(hydroxyethyl)terephthalate, furandione and products of the reactions with the value of molecular weight up to 400 of these polyols with propylene oxide and/or ethylene oxide.

Organic polymeric polyols that can be used to obtain the polyurethane include diols, and trioli, and their mixtures, however, can also be used polyols with a large number of functional groups, for example, as secondary components, in addition to dilam. Suitable polymeric polyols selected from the group consisting of polyesters, polyester amides, polyethers, policyeview, polycarbonates, polyacetates, polyolefines and polysiloxanes.

the false polyether polyols, which can be used include hydroxyl-terminated group, the reaction products polimineralami alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, neopentylglycol, 1,4-butanediol, 1,6-hexanediol, furandione, dimethylcyclohexane, glycerol, trimethylolpropane, pentaerythritol and their mixtures with polycarboxylic acids, especially dicarboxylic acids or their derivatives, giving esters, for example succinic, glutaric and adipic acids and their dimethyl esters, phthalic anhydride, hexahydrophthalic anhydride, terephthalate, and mixtures thereof. Polyesters, amides can be obtained by the inclusion of aminoalcohols, such as ethanolamine, polyesterification mixture.

Suitable polyester polyols include polyalkyloxy glycol, where alkylenes may be selected from ethylenoxide and/or propylenoxide units. This polyalkylbenzene glycols introduce a hydrophilic group into the main chain of the polyurethane resin. Too many polyalkyleneglycol glycol in the main chain of the polyurethane resin reduces its lipophilic nature. Preferably, the number polyalkyleneglycol glycol is limited to the extent in which the polyurethane main chain remains highly lipophilic. Thus, preferred the number polyalkyleneglycol glycol below 25% weight. the total weight of compounds (C), reacting with isocyanates, more preferably below 10 wt%. and most preferably below 5 wt%.

Polythioether polyols that may be used include products obtained by the condensation of the ester thioglycolate, or with other glycols, dicarboxylic acids, formaldehyde, aminoalcohols or amino acids.

Polycarbonate polyols include products obtained by the reaction of diols, such as 1,3-propandiol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol or tetraethylene glycol, with dellcorporate, for example, diphenylcarbonate or with phosgene. Polyurethane resin containing a carbonate group, described in detail in WO 01/48106, and incorporated herein by reference. Suitable polyolefin polyols include hydroxyl-terminated group of Homo - and copolymers of butadiene.

According to the prior art, the dispersing resins containing prone to hydrolysis of ester bonds in the main chain of the polymer was observed violations of the long-term stability of the containing aqueous dispersions and offset pH. It is considered that this phenomenon is at least partially occur due to hydrolysis of ester groups in the main chain of the dispersant resin, causing the destruction of the dispersing resin. It was found that h is about dispersion instability and displacement of pH is actually absent, if you use a polyurethane dispersant resin according to the invention do not contain prone to hydrolysis of ester groups in the main chain of the polymer. Therefore, in a preferred embodiment, the polyurethane dispersant resin contains the main chain of the polyurethane resin, which contains almost no prone to hydrolysis of ester groups. This means that preferably the complex polyester polyols are not used as building blocks for polyurethane dispersant of the invention. Such dispersing resin to give a stable aqueous dispersion even after long period of storage.

Compounds having one group reactive isocyanates, may be used to obtain polyurethane as agent for breaking the circuit to limit the molecular weight of the polyurethane. Suitable connections are well known in the field of engineering and include monosperma, monoamines and monotony.

As mentioned, the polyurethane dispersant of the present invention further comprises a hydrophobic group on the side chain attached to the polyurethane main chain through covalent bonds. Hydrophobic group side chain different from the hydrophilic groups of the side chain. The term "hydrophobic" refers to the tendency of molecules or molecular groups do not penetrate into the ode or to leave the aqueous phase, as defined in DIN EN ISO 862: 1995-10. Hydrophobic properties of molecules or groups, mainly associated with the presence of hydrocarbon groups. Therefore, in the embodiment of the invention the hydrophobic side groups include hydrocarbon groups having at least 4, or at least 6, or at least 8 carbon atoms.

The hydrocarbon group may have a large number of carbon atoms, for example, when the hydrocarbon group to form polyolefins, such as polyethylene, polypropylene, polybutylene or polybutadiene. In such cases, the number of carbon atoms can be increased to several hundred, depending on the degree of polymerization. In other cases, the hydrocarbon groups have up to 50, or 30, or 20 carbon atoms. The hydrocarbon group may be saturated. However, also suitable are unsaturated hydrocarbon group and aromatic hydrocarbon group. The hydrocarbon group may be linear, cyclic or branched. Branched hydrocarbon groups are preferred. Hydrophobic side groups can also contain ester and ether groups. As an example we can mention the side groups on the basis of caprolactone or on the basis of esters of higher fatty acids.

The number and molecular weight of hydrophilic and hydrophobic groups, b is a similar circuit is determined by the hydrophilic/hydrophobic balance of the polyurethane of the present invention. Polyurethane dispersant resin preferably contains at least two, more preferably at least three hydrophobic groups of the side chain in the molecule. In one embodiment of the invention, the number of hydrophobic side groups attached to the main chain of the polyurethane polymer is equal to the number of hydrophilic side groups on the basis of polyalkylated attached to it.

The hydrophobic group on the side chain can be introduced into the polyurethane dispersant similar to hydrophilic side groups on the basis of polyalkylated described above. Suitable building blocks for the introduction of hydrophobic groups of the side chains in the polyurethane dispersant are compounds having two groups capable of reacting with isocyanates, and at least one hydrophobic group side chain. Such compounds can be obtained, for example, by the reaction of a hydrophobic epoxy-functionalized compound with a compound containing an amino group. It is also possible to obtain such compounds by the reaction dehydrogenase epoxy-functionalized compound with an amine having a hydrophobic group. Also suitable are the products of the reactions of hydrophobic epoxy-functionalized compound and an amine having a hydrophobic group. In this case a connection, imouse the two groups, capable of reacting with isocyanates, and two hydrophobic group side chain. Alternatively, you can use the reaction products of a hydrophobic epoxy-functionalized compound and an amine having a hydrophilic polyalkyleneglycol group. This reaction product has two groups capable of reacting with isocyanates, a hydrophobic group in the side chain and a group of the side chain on the basis of polyalkylated. Moreover, very good results were obtained with glycidyloxy ether acid versatic (synthetic fatty acid branched chain), commercially available under the name Cardura E 10, as hydrophobic epoxy-functionalized compounds.

Alternatively, it is possible to use compounds having two isocyanate functional group and at least one hydrophobic group side chain.

Polyurethane dispersant resin can be obtained in the usual way with the interaction of organic polyisocyanate with other reagents in completely anhydrous conditions at a temperature between about 30°and about 130°C until the reaction between isocyanate groups and groups capable of reacting with isocyanato largely will not end. The reaction may kataliziruetsa catalyst, such as dibutil tin, dilou is at. Mainly, reagents are being used in proportions according to the relation isocyanate groups to groups capable of reacting with isocyanates (usually hydroxyl), from about 1:1 to about 6:1, preferably about 1:1. If you are using an excess of organic polyisocyanate, in the first stage can be prepared isocyanate-termination prepolymer. In the second stage can be added, at least one compound containing a group capable of reacting with isocyanates.

The molar ratio and the functionality of the original compounds used to obtain the polyurethane dispersant resin, is suitable if selected in such a way as to avoid the solidification of the polyurethane and to achieve average molecular weight of the polyurethane in the range of from 800 to 100,000. Preferably, the average molecular weight is in the range of 1000 to 50000, more preferably 2000 to 20000. In a typical embodiment, the polyurethane main chain of the resin mainly linear and preferably lipophilic, having polyalkylbenzene hydrophilic group in the side chain. Such polymers can also be described as comb polymers. They can be obtained from difunctional and possibly monofunctional starting compounds. Alternatively, in the process of obtaining polyurethane dispersio the soup resin, leading to branched polyurethane may be included isocyanate and/or compounds capable of reacting with isocyanato with more than 2 functional groups.

When using a molar excess of the original compounds able to react with isocyanates, to obtain a polyurethane dispersant resin is polyurethane, ending with groups capable of reacting with isocyanates, such as hydroxyl groups. Preferred is a polyurethane dispersant resin having hydroxyl groups, for example, polyurethane dispersant having a hydroxyl value in the range from 2 to 100 mg KOH/g, preferably in the range of from 5 to 50 mg KOH/g

Polyurethane dispersant may contain tertiary amino groups. The appropriate value of the tertiary amine polyurethane dispersant should not exceed 50 mg KOH/g, Preferably, the value of the tertiary amine is in the range from 2 to 30 mg KOH/g, based on the nonvolatile matter of the polyurethane dispersant resin. The tertiary amino group suitably introduced into the polyurethane by using di - or polyisocyanates, functionalized tertiary amine or with amino-functionalized compounds able to react with isocyanates. Particularly suitable tertiary amino-functionalized soy is inanami, capable of reacting with isocyanates are compounds according to formula (II). However, there may be used other tertiary amino functionalityand compound capable of reacting with isocyanates, as well as for example, diols, functionalityand tertiary amine.

In addition, it is preferable that at least part of the tertiary amino groups present in the polyurethane dispersant resin was neutralized acid neutralizing agent. Suitable acid neutralizing agents include mineral acids and organic acids, and carboxylic acids are preferred. Especially preferred acid neutralizing agent is acetic acid.

In another embodiment, the polyurethane dispersant resin contains anionic groups or groups capable of forming anions. Typical examples of groups capable of forming anions are group carboxylic acid group, sulfonic acids, and phosphoric acid or phosphorylative group. Such groups can be introduced into the polyurethane dispersant resin with compounds capable of reacting with isocyanates containing anionic groups or groups capable of forming anions. As typical examples can be mentioned dimethylolpropionic acid and diols, functionalityof the data sulphonate groups. The formation of anionic groups may be conducted before or after receipt of the polyurethane. Usually anionic groups are formed by processing groups capable of forming anions, the basic neutralizing agent such as ammonia, or amine, or hydroxides of alkali metals.

Polyurethane dispersant resin can be used in various physical forms. If dispersing resin has a low molecular weight or low viscosity or used at elevated temperatures, it may be appropriate to use pure resin or to use a resin in the form of a melt or in powder form. Alternatively, the polyurethane dispersant resin can be used in the form of a solution in an organic solvent. It is preferable to use a polyurethane dispersant resin in environments aqueous media, for example in the form of a solution or dispersion. Aqueous solutions are particularly preferred.

The invention also relates to compositions containing the polyurethane dispersant resin and particles.

In one embodiment, the composition particles are pigment particles. Preferred are compositions containing a large amount of pigment, i.e., the pigment concentrates, as such compositions are particularly effective in the transfer of color and covered with paint. Concentrates pigmentation treatment is now usually contain from 5% to 85 wt%, preferably from 20% to 75% weight. pigment based on the total weight of the pigment concentrate.

Suitable compositions contain up to 150 wt%, preferably from 1% to 100 wt%, more preferably from 2% to 50% weight. polyurethane dispersant resin according to the present invention, calculated on the weight of pigment. Among other things, the most appropriate amount of the polyurethane dispersant resin depends on the specific type of pigment that must be atomized. The mixture may contain other known additives, such as additional dispersing agents, antifoaming agents and/or polymeric or oligomeric binders.

The compositions can be liquid compositions containing an organic solvent and/or diluent is water-based. In addition, can be applied dry concentrates of pigments, for example in the form of powder, granules or tablets.

The pigment concentrate can be part of a modular system for obtaining pigment compositions for coating. This modular system can, for example, contain one or more concentrates of pigments as coloring module, connecting module and a reducing module. Priming compositions, listed below, can be suitably prepared by mixing modules such modular systems.

The end of the spending pigments or coloring paste can be obtained in the course of the process, where the liquid mixture containing the pigment, polyurethane dispersant resin according to the invention and possibly liquid diluent exposed to shear force. Pigmentaria dispersing resin of the invention can be used in combination with one or more other pigment dispersion AIDS and/or surfactants. Examples of suitable equipment for performing the process are ball mills, jet mills, ultrasonic mills, basket mills, roller mills and high-speed dissolvers. Can be used inorganic or organic pigments or mixtures thereof. Preferably, as the liquid diluent is water. Instead of water, or in addition to water can be used organic solvents, such as glycol ethers, such as ethylene glycol, or their higher homologues, or mono-n-butyl ether of ethylene glycol.

Polyurethane dispersant resin according to the invention can also be used to obtain a composition for mixing pigments.

In one embodiment, the composition according to the invention is a solid pigment composition containing a pigment and a polyurethane dispersant resin, where the composition comprises at least 35 wt%, at least real the pigment and more than 65% of the weight. dispersing resin, calculated on the total weight of pigment and a dispersant resin.

Pigment composition of the invention can be used as a composition for mixing the pigment, resulting in compositions for coating with stable dispergirovannykh pigments. The pigment composition can be easily incorporated into compositions for coating in which the pigment stably dispergirovany. In addition, it is possible to obtain the pigment compositions with a wide range of pigments. Pigment compositions make it possible to obtain a paint having excellent properties and stability, especially in the case of hard dispersible and stabilized pigments.

Pigment composition of the invention may contain inorganic or organic pigments. Alternatively, the pigment composition may contain various pigments, for example, two or more inorganic pigment, two or more organic pigment or a mixture of one or more inorganic pigments and one or more organic pigments.

Mainly, the pigment particles in the composition are in finely divided form. Thus, the pigments typically have an average particle size in the range from 50 nm to 5000 nm. Preferably, the average particle size of not less than 80 nm, more preferably not less than 100 nm. Preferably, the average particle size would be the no more than 3000 nm, more preferably not more than 1500 nm, and most preferably not more than 1000 nm.

The average particle size of the pigment particle composition, for example, can be determined using electron microscopy. As the average particle size of the pigments in the composition is virtually the same as the average particle size of the pigments after suspending in a liquid, it is also possible to mix the pigment composition of the liquid medium and to determine the average size of the pigment particles using dynamic light scattering.

Usually organic pigments are organic colored pigments and black pigments. Inorganic pigments can also be colored by pigments (color, black and white pigments), and brilliant pigments and inorganic pigments which are usually used as filler.

Suitable examples of organic pigments are:

monoazo pigments:

C.I. Color indicator. Pigment brown 25; C.I. Pigment Orange 5, 13, 36, 38, 64, and C.I. Pigment red 1, 2, 3, 4, 5, 8, 9, 12, 17, 22, 23, 31, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 51:1, 52:2, 53, 53:1, 53:3, 57:1, 58:2, 58:4, 63, 112, 146, 148, 170, 175, 184, 185, 187, 191:1, 208, 210, 245, 247 and 251; C.I. Pigment yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191; C.I. Pigment violet 32;

diazo pigments:

C.I. Pigment Orange 16, 34, 44 and 72; C.I. Pigment yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176, 80 and 188:

diazo condensed pigments:

C.I. Pigment yellow 93, 95 and 128; C.I. Pigment red 144, 166, 214, 220, 221, 242 and 262; C.I. Pigment brown 23 and 41;

antiretrovi pigments:

C.I. Pigment red 168;

antrahinonovye pigments:

C.I. Pigment yellow 147, 177 and 199; C.I. Pigment violet 31;

intraperitonealy pigments:

C.I. Pigment yellow 108;

chinaredorbit pigments:

Pigment orange 48 and 49; C.I. Pigment red 122, 202, 206, and 209; C.I. Pigment violet 19;

chieftancy pigments:

C.I. Pigment yellow 138;

diketopiperazine pigments:

C.I. Pigment orange 71, 73 and 81; C.I. Pigment red 254, 255, 264, 270 and 272;

dioxazine pigments:

C.I. Pigment violet 23 and 37; C.I. Pigment blue 80;

flavanonol pigments:

C.I. Pigment yellow 24;

indanthrene pigments:

C.I. Pigment blue 60 and 64;

isoindoline pigments:

C.I. Pigment orange 61 and 69; C.I. Pigment red 260; C.I. Pigment yellow 139 and 185;

isoindoline pigments

C.I. Pigment yellow 109, 110 and 173;

isobilateral pigments:

C.I. Pigment violet 31;

metal complex pigments:

C.I. Pigment red 257; C.I. Pigment yellow 117, 129, 150, 153 and 177; C.I. Pigment green 8;

perinova pigments:

C.I. Pigment orange 43; C.I. Pigment red 194;

perylenebis pigments:

C.I. Pigment black 31 and 32; C.I. Pigment red 123, 149, 17, 179, 190 and 224; C.I. Pigment violet 29;

phthalocyanine pigments:

C.I. Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 and 16; C.I. Pigment green 7 and 36;

philanthropie pigments:

C.I. Pigment orange 51; C.I. Pigment red 216;

pyrazoloquinoline pigments:

C.I. Pigment orange 67; C.I. Pigment red 251;

thioindigo pigments:

C.I. Pigment red 88 and 181; C.I. Pigment violet 38;

triarylamine pigments:

C.I. Pigment blue 1, 61 and 62; C.I. Pigment green 1; C.I. Pigment red 81, 81:1 and 169; C.I. Pigment violet 1, 2, 3 and 27; C.I. Pigment black 1 (aniline black); C.I. Pigment yellow 101 (aldushin yellow; C.I. Pigment brown 22.

Suitable examples of inorganic color pigments are:

white pigments:

titanium dioxide (C.I. Pigment white 6), zinc white, pigment refined zinc oxide; zinc sulfide, lithopone;

black pigments:

iron oxide black (C.I. Pigment black 11), iron manganese black, spinel black (C.I. Pigment black 27) carbon black (C.I. Pigment black 7);

colored pigments:

the chromium oxide, chromium oxide hydrate green; chrome green (C.I. Pigment green 48); cobalt green (C.I. Pigment green 50), ultramarine green; cobalt blue (C.I. Pigment blue 28 and 36; C.I. Pigment blue 72); ultramarine blue; manganese blue; ultramarine violet; cobalt violet, manganese violet is new; red iron oxide (C.I. Pigment red 101); cadmium sulphoselenide (C.I. Pigment red 108); cerium sulfide (C.I. Pigment red 265); molybdate red (C.I. Pigment red 104); ultramarine red; brown iron oxide (C.I. Pigment brown 6 and 7), mixing brown, spinel phases and diamond spar (C.I. Pigment brown 29, 31, 33, 34, 35, 37, 39 and 40), chromium titanium yellow (C.I. Pigment brown 24), chrome orange; cerium sulfide (C.I. Pigment orange 75); yellow iron oxide (C.I. Pigment yellow 42); Nickel titanium yellow (C.I. Pigment yellow 53; C.I. Pigment yellow 157, 158, 159, 160, 161, 162, 163, 164 and 189); chromium titanium yellow; spinel phases (C.I. Pigment yellow 119); cadmium sulfide and cadmium sulfide zinc (C.I. Pigment yellow 37 and 35); chrome yellow ((C.I. Pigment yellow 34); bismuth Vanadate ((C.I. Pigment yellow 184).

Examples of inorganic pigments typically used as fillers, are transparent silicon dioxide, quartz powder, aluminum oxide, aluminum hydroxide, natural mica, natural and precipitated chalk and sulphate of barium.

Brilliant pigments are pigments coated with a metal having a monophase or pilifosova design, colors game which is due to the phenomena of interference, reflection and absorption. Examples are aluminum plates and aluminum, iron oxide and mica plate carrying one or more aircraft is s, mainly metal oxides.

As mentioned above, as necessary ingredients of the pigment composition of the present invention contains a pigment and a dispersant resin. In the case of solids suitable composition comprises at least 35 wt%, at least one pigment and not more than 65 wt%. dispersing resin, calculated on the total weight of pigment and a dispersant resin. If the composition of the pigment is carbon black, it is preferable that the content of carbon black in pigment composition was in the lower part of the described range. So, if the pigment is carbon black, the pigment composition preferably contains at least 40 wt%, more preferably at least 45 wt%. carbon black and not more than 60 wt%, preferably not more than 55 wt%. dispersing resin, calculated on the total weight of pigment and a dispersant resin. With other pigments pigment composition mainly contains at least 60 wt%, preferably not less than 64 wt%, more preferably not less than 68% of the weight. and most preferably at least 70 wt%, at least one pigment and not more than 40 wt%, preferably not more than 36 wt%, more preferably not more than 32% of the weight. and most preferably not more than 30 wt%. dispersing resin, calculated on the total weight of pigment and a dispersant resin. In chrisv the tea preferred embodiment, the above-mentioned weight ratio of pigment and a dispersant resin is also applicable when calculating the total weight of the pigment composition.

The pigment composition may also contain other ingredients, additives or auxiliary tools commonly used in pigment compositions, such as organic solvents, wetting means, protivoprilipajushchie agents, heat stabilizers, light stabilizers, antioxidants and other AIDS pigment dispersions and/or surfactants.

In one embodiment, the pigment composition of the invention is a granular powder that is suitable for use as a pigment mixing. In addition, a solid compact concentrates of pigments can be used, for example, in the form of granules or tablets.

The invention also relates to a method for producing a pigment composition, which includes stages

a) mixing the composition containing a pigment and a dispersant resin according to the invention, possibly with the addition of water or organic solvent, to form a fluidized suspension of pigment,

b) perhaps the grinding suspension and

C) drying of the suspension.

As indicated above with respect to the pigment composition, the pigment used in the process may be organic or inorganic pigment. It is also possible to use a mixture of pigments, for example a mixture of two or more inorganic pigments, a mixture of two or more organic is their pigments or a mixture of inorganic and organic pigments. You can use a wide variety of pigments in the process. The pigments can be introduced into the process in the form of standard dried pigments. Stage of grinding is used to break the agglomerates and in order to achieve the desired particle size of the pigment. Organic pigments are also available in the form of so-called pressed precipitation. In the synthesis of organic pigments are formed in the form of very small crystals, called primary particles. The aim of the synthesis of pigments is to obtain primary particles with a size that optimizes the properties of the application of pigment, such as the power of color, tone and brightness, transparency and turbidity, and flow. Pressed sludge contains pigment, mainly in disaggregated form. However, it requires less energy to break up the agglomerates and to achieve the desired particle size of the pigment. In the process of drying of pressed sludge pigment in the absence of a dispersing resin primary particle will be connected together to form aggregates and agglomerates. Therefore, when using the organic pigment in the process, it is possible and preferable to use an organic pigment in the form of pressed sludge pigment. When using pressed sediment pigment conventional mixing of the fluidized suspension of the pigment can be quite forachieve the desired particle size. In such cases, the stage of grinding the suspension may not be necessary.

If you need more liquid for fluidizable mixture of a pigment and a dispersant resin, it is preferable that the liquid was water. Instead of water, or in addition to water can be used organic solvents, such as glycols or glycol ethers such as ethylene glycol, or its higher homologues, or mono-n-butyl ether of ethylene glycol.

Perhaps the stage of grinding can be carried out using well-known grinding devices, commonly used for grinding particle size pigments. Examples of suitable devices for carrying out the process are ball mills, jet mills, ultrasonic mills, basket mills, roller mills and high-speed dissolvers. Mainly, the grinding continues until the average particle size is in the range from 50 nm to 5000 nm. Preferably, the average particle size was not less than 80 nm, more preferably not less than 100 nm. Preferably, the average particle size was not more than 3000 nm, more preferably not more than 1500 nm, and most preferably not more than 1000 nm.

Examples of suitable methods of drying is spray-granulation and drying in a fluidized bed, spray drying drying in a paddle dryer, evaporation and subsequent spray and freeze drying. The selected method of drying can affect the particle size of the pigment compositions of the present invention. Preferably, the stage drying is carried out using freeze drying or spray drying.

The spray drying and drying in a fluidized bed can give rough chopped granule having an average particle size of from 50 to 5000 μm and in particular from 100 to 1000 μm. Depending on the process conditions of the spray drying can also give finely ground pigment compositions. The spray drying usually give granules having average particle sizes of < 20 μm. Micronized compositions are also obtained when drying in a paddle dryer and upon evaporation with subsequent grinding.

The residual moisture of the obtained dried pigment composition may vary considerably, thus ensuring that the dried composition was solid composition. The content of residual moisture, for example, may be 15 wt%, calculated on the total weight of the pigment composition. Basically, the content of residual moisture should not exceed 15 wt%, preferably should not exceed 12% of the weight. In many cases, the content of residual moisture less than 5% weight. If the pigment composition is intended for use in dry systems, the pre is respectfully low content of residual moisture, for example, less than 2% of the weight.

The pigment compositions of the present invention are outstanding when used because of their excellent color properties, especially in regard to color strength, brightness, tone, and covering ability, and especially because of their characteristics of mixing, i.e. they can be dispersed in the environment with a minimum expenditure of energy, simply by stirring or shaking.

In addition, the pigment compositions of the present invention have the following advantages: they have a high pigment content, show a very good stability during storage, are both economically and environmentally advantageous with regard to packaging, storage and transportation, and they are versatile in use.

The pigment compositions of the present invention are very useful for pigmentation of macromolecular organic and inorganic materials of any kind. In this context, the liquid medium can be solely water, contain a mixture of water and organic solvents, for example alcohols, or solely based on organic solvents, such as alcohols, glycol ethers, ketones such as methyl ethyl ketone, amides such as N-organic and dimethylformamide, esters such as ethyl acetate, butyl acetate and methoxypropyl the tat, or aromatic or aliphatic hydrocarbons, for example xylene, mineral oil and mineral spirits.

Examples of materials which can be pigmented pigment compositions of the present invention include coatings such as architectural coatings, industrial coatings, automotive coatings, radiation curable coatings, powder coatings; paints, including paints for external areas of buildings and interiors of buildings, for example, paint on wood, lime plaster, glue, paint, emulsion paint, resistant to solvent printing ink, for example offset printing ink, toluene printing ink for gravure printing, textile printing ink, the radiation-curable printing inks, water resistant inks, including inks for ink-jet printing colour filters; construction materials (water is typically added only after the building material and pigment composition were mixed in a dry form, such as plaster, cement, concrete, cement mortar, plaster, bitumen, seals; cellulose materials such as paper, cardboard, thin cardboard, wood and woody material that can be coated or otherwise finished; adhesives, film forming protective colloid substances, which are used, for example, in the pharmaceutical industry the industry; cosmetic products; plastics and detergents.

The pigment compositions of the present invention are very useful as blending components in systems mixing or matching colors. On the basis of their characteristics stirring for these purposes they can be used directly in solid form. However, if necessary, they can be first translated into the background paint, varnish mixture and paint coatings (especially in paint having a high solids content, HS paint"), or even in highly pigmented pastes for coating, which then form the components of the mixing system. Selection of required shade and, therefore, the components are mixed paint can effectively visually adjusted using the card system paints in a large range of shades, standards-based colors, such as RAL, BS and NCS, or, preferably, under computer control, in which achievable unlimited number of shades ("computer color matching). The invention also relates to a coating composition containing at least one film forming agent, which is different from the polyurethane dispersant resin, at least one pigment and the pigment dispersing resin, where the pigment dispersing resin is a polyurethane dispersant resin, as indicated the above. Preferably, the coating composition was an aqueous coating composition. For example, the composition of the coating can be a primary coating composition, preferably water-based coating composition. The basic composition of the coating is color - and/or effectivedose composition of the coating, which is used in multi-layer lacquer systems with transparent outer coating. Such multi-layer lacquer systems are often used for protection and decoration of cars and larger vehicles. The coating composition can contain other ingredients, additives or auxiliary tools that are commonly used in coating compositions, such as colorants, leveling agents, organic solvents, wetting agents, protective agents against scratches, protivoprilipajushchie agents, agents against deformation, heat stabilizers, light stabilizers, absorbers of ultraviolet rays, antioxidants and fillers. You can also use pigment dispersing resins of the invention in combination with one or more other pigment auxiliary and/or surface-active agent.

Polyurethane dispersant resin according to the invention is also suitable for dispersing hydrophobic resins in aqueous systems. Therefore, the image is giving also refers to the use of dispersant in the process of dispersing hydrophobic resins in aqueous systems and water compositions, containing polyurethane dispersant resin and at least one dispergirovannoyj hydrophobic resin. Such compositions may preferably be used as a binder component in an aqueous two-component coating compositions.

Polyurethane dispersant resin can be used for other dispersion hydrophobic and/or trudnozapominaemyj materials in the water. Examples of such materials are additives and auxiliary substances such as catalysts, absorbents ultraviolet rays, and light stabilizers.

Examples

Used raw materials:

Jeffamine M 1000 amine-based polyalkylated from Huntsman

Cardura E10 Glycidyloxy ether acid versatic from Resolution Performance Products

Tegomer D-3403 Diol containing side groups on the basis of polyalkylated from Tego Chemie Service GmbH

Tegomer D 3123 Diol containing side groups on the basis of polyalkylated from Tego Chemie Service GmbH

Pripol 2033 Dimer, a higher fatty acid-based diol from Uniqema

Autowave Modular water system to cover from Akzo Nobel Car Refinishes

Autowave 665 Net module Autowave containing a mixture of polyurethane dispersions and acrylic resin from Akzo Nobel Car Refinishes

Autowave 666 Net module Autowave containing a dispersion of acrylic resin from Akzo Nobel Car Refinishes

Autowave 357 Module red toner Autowave from Akzo Nobel Car Refinishes

Autowave 00 Odul white toner Autowave from Akzo Nobel Car Refinishes

General methods.

The solids content of the compositions is determined by measuring the weight loss after heating the sample to 140°C for 30 minutes.

The viscosity is determined with a Brookfield viscometer.

The molecular weight determined using gel chromatography, using as the standard polystyrene.

The dispersion of dispersion of the pigments was determined by device Hagman.

The value of the specified dispersion in microns refers to the largest particles found in the sample.

Flocculation of pigments is determined using microscopy compared with reference samples of the same class of pigments. The results are presented in a scale from 0 to 10, where 0 indicates hard flocculation and 10 does not give flocculation.

The transparency of the samples determined by determining the light transmission through the samples in the cuvettes. The results are presented in % of light transmission.

The gloss was determined by Byk-meter Garden Shine, and the results are presented in units of glitter.

The intensity of staining (*) determined according to CIE LCh system.

Example 1

Obtaining a polyurethane dispersant resin according to the invention

Into a reaction vessel equipped with a stirrer, thermocouple, heating jacket, reflux condenser and addition funnel is placed to 347.5 g of Jeffamine M1000. The contents of the reaction vessel is heated to 120°C under a layer of nitrogen, and through the addition funnel over a 30 minute add on 138.5 g of Cardura E 10. The contents of the reaction vessel is maintained at a temperature of 120°C for 4 hours, then allowed to cool to room temperature. Then in the reaction vessel, add the following components:

20.2 g of 1,4-cyclohexanedimethanol

7,3 g neopentylglycol

62,0 g 2-butanone

to 104.8 g of 4,4`-diisocyanatohexane.

The reaction mixture is heated to 120°C and maintained at this temperature for 2 hours. Add 4 drops dibutil tin of dilaurate and the reaction mixture is left at 120°C for the next 2 hours. Then 2-butanone is evaporated under reduced pressure. The reaction mixture is cooled to 100°C. and at this temperature, added to 13.1 g of 10 wt%. an aqueous solution of acetic acid. Then for 3 hours while gradually cooling to room temperature, add 1,575 g of demineralized water. Get a clear solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 56,2% wt., the content of ethylene oxide to 48.5 wt%. The content of the tertiary amine 0.38 mmol/g

Example 2

Obtaining a polyurethane dispersant resin according to the invention

Polyurethane resin receive according to the procedure described above in Example 1, the use as starting compounds:

710,8 g Jeffamine M 1000

302,2 g of Cardura E 10

to 58.1 g of 1,4-cyclohexanedimethanol

125.0 g of 2-butanone

187,0 g isophorondiisocyanate

8 drops dibutil tin of dilaurate

3,082 g of demineralized water.

The polyurethane does not add acetic acid. Get transparent non-ionic solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 56.3% of the weight., the content of ethylene oxide to 48.8% weight. The content of the tertiary amine to 24.7 mg KOH/g

Example 3

Obtaining a polyurethane dispersant resin according to the invention

Polyurethane resin receive according to the procedure described above in Example 1, using as starting compounds:

us 726.2 g Jeffamine M 1000

253,4 g of Cardura E 10

66,2 g 1,4-cyclohexanedimethanol

125.0 g of 2-butanone

204,0 g isophorondiisocyanate

8 drops dibutil tin of dilaurate

3,082 g demineralized water

25 g of 10 wt%. an aqueous solution of acetic acid.

Get a clear solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 58.1% for weight., the content of ethylene oxide 50.2% of the weight. The content of the tertiary amine of 15.1 mg KOH/g

Example 4

Obtaining a polyurethane dispersant resin according to the invention

Into a reaction vessel equipped with a stirrer, thermocouple, heating jacket, reflux condenser and addition funnel is placed 778,8 g(0,74 mol) Jeffamine M 1000. The contents of the reaction vessel is heated to 120°C under a layer of nitrogen, and through an addition funnel over 30 minutes add 181,1 g (0,74 mol) Cardura E 10. Then the contents of the reaction vessel is maintained at a temperature of 120°C for 4 hours, then allowed to cool to room temperature. Then in the reaction vessel, add the following components:

71,0 g 1,4-cyclohexanedimethanol

125.0 g of 2-butanone.

The reaction mixture is heated to 65°C and at this temperature add 218,0 g isophorondiisocyanate. The reaction mixture is heated to 120°C and maintained at this temperature for 2 hours. Then add 4 drops dibutil tin of dilaurate and the reaction mixture is left at 120°C for the next 2 hours. Then, 2-butanone is evaporated under reduced pressure and for 3 hours while gradually cooling to room temperature, add 3,060 g of demineralized water. Get transparent non-ionic solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 62.3% of the weight., the content of ethylene oxide 53,8% weight. The content of the tertiary amine 5.6 mg KOH/g

Example 5

Obtaining a polyurethane dispersant resin according to the invention

Polyurethane resin receive according to the procedure described above in Example 1, using as starting compounds:

711,1 g Jeffamine M 1000

302,3 g Crdura E 10

50,8 g 1,4-cyclohexanedimethanol

6.7 g dimethylolpropionic acid

125.0 g of 2-butanone

179,0 g isophorondiisocyanate

8 drops dibutil tin of dilaurate

3,060 g of demineralized water.

The polyurethane does not add acetic acid. Get a clear solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 56.9% of the weight., the content of ethylene oxide 49.1% of the weight. The content of the tertiary amine 2,24 mg KOH/g, the content of carboxylic acid/carboxylate 0.04 mmol/g

Example 6

Obtaining a polyurethane dispersant resin according to the invention

Polyurethane resin receive according to the procedure described above in Example 5, using as starting compounds:

711,4 g Jeffamine M 1000

302,4 g of Cardura E 10

of 43.5 g of 1,4-cyclohexanedimethanol

13.5 g dimethylolpropionic acid

125.0 g of 2-butanone

179,1 g isophorondiisocyanate

8 drops dibutil tin of dilaurate

3,060 g of demineralized water.

Get a clear solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 56.9% of the weight., the content of ethylene oxide 49.1% of the weight. The content of the tertiary amine of 22.4 mg KOH/g, the content of carboxylic acid/carboxylate 4.5 mg KOH/g

Example 7

Obtaining a polyurethane dispersant resin according to the invention

Polyurethane resin receive according to% the fool, described above in Example 5, using as starting compounds:

707,0 g Jeffamine M 1000

300,6 g of Cardura E 10

to 108.2, PREPOL 2033

125.0 g of 2-butanone

133,5 g isophorondiisocyanate

8 drops dibutil tin of dilaurate

3,060 g of demineralized water.

Get a clear solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 56.6% of the weight., the content of ethylene oxide 48.9% of the weight. The content of the tertiary amine of 22.4 mg KOH/g

Example 8

Obtaining a polyurethane dispersant resin according to the invention

In a reaction vessel, equipped as in example 1, placed 686,4 g Tegomer D-3403, 348,4 g of the reaction product of 1 mole of cylohexane and 2 moles Caruda E 10, 125.0 g of 2-butanone. These components are stirred until a homogeneous state and add 215,2 g isophorondiisocyanate. The reaction mixture is heated to 120°C under a layer of nitrogen and maintained at this temperature for 2 hours. Then add 8 drops dibutil tin of dilaurate and the reaction mixture is left at 120°C for the next 2 hours. Then, 2-butanone is evaporated under reduced pressure and for 3 hours while gradually cooling to room temperature, add 2,331 g of demineralized water. Get transparent non-ionic solution of the polyurethane dispersant resin in water. The content of ethylene oxide in the resin 54% weight. The content of tertiary amine,8 mg KOH/g

Comparative Example a

Obtaining a polyurethane dispersant resin comparison according to WO 97/19120

In a reaction vessel, equipped as mentioned above, is placed 368,8 g Tegomer D-3403, are 507, 5 g olejowego alcohol, 456,9 g diol sulfosuccinate, which is the reaction product of 1 mole of maleic acid, 2 moles Caruda®E 10 and 1 mole NaHSO3and 196,0 g 2-butanone. Components are mixed and with the help of a dropping funnel add 420,5 g isophorondiisocyanate. The reaction mixture is heated to 120°C and maintained at this temperature for 2 hours. Then add 0.5 g dibutil tin of dilaurate and the reaction mixture is left at 120°C for the next 2 hours. Then lower the temperature to 90°C and carry out the evaporation under reduced pressure to remove all volatile solvents. Then, for 3 hours while gradually cooling to room temperature, add 6,746 g of water. Get a water solution of the polyurethane dispersant resin. The content of ethylene oxide in the polyurethane 18.7% of the weight.

Comparative Example

Obtaining a polyurethane dispersant resin containing a hydrophobic group on the side chain.

In a reaction vessel, equipped as described in example 1, is placed

354,0 g Tegomer D 3123

40,5 g Pripol 2033

of 43.5 g of 1,4-collage

26,0 g 2-ethylhexanol

90.0 g of 2-butanone.

These components are mixed is to a homogeneous state and add 122,1 g isophorondiisocyanate. The reaction mixture is heated to 110°C under a layer of nitrogen and maintained at this temperature for 2 hours. Then to the reaction mixture add 2 drops dibutil tin of dilaurate and the reaction mixture is left at 110°C for the next 2 hours. Then, 2-butanone is evaporated under reduced pressure, and within 3 hours with a gradual cooling to room temperature, add 1,328 g of demineralized water. Get transparent non-ionic solution of the polyurethane dispersant resin in water. The content of alkalinized in the resin 65 wt%, the content of ethylene oxide 55% of the weight.

Table 1 shows the following properties of the above-obtained polyurethane dispersant resin.

Table 1
ExampleThe solids content in % of weight.The viscosity in PA·spHMnMw
126,80,247,24,7008,050
228,30,50the 9.7 4,1406,280
328,40,217,74,4207,060
429,30,429,84,6906,550
528,50,988,34,0605,950
629,71,087,23,8105,940
727,80,609,93,4005,450
834,21,307,46,05010,050
And26,00,556,91,7602,850/td>
In28,80,645,56,40013,330

Example 9

Obtaining aqueous dispersions of hydrophobic polyclonally resins

Hydrophobic polyclonality resin I get through the standard process of etherification of 134 g of trimethylolpropane, 282 g of cyclohexanedimethanol and 308 g hexahydrophthalic anhydride. Get polyclonality resin I having the value HE 251 mg KOH/g and an acid value of 8.6 mg KOH/g

Hydrophobic polyclonality resin II get through the standard process of etherification of 141 g of trimethylolpropane, 249 g of 1,6-hexandiol and 324 g hexahydrophthalic anhydride. Get polyclonality resin II having the value HE 266 mg KOH/g and acid value of 3.9 mg KOH/g

Hydrophobic polyclonality resin I and II are mixed with polyurethane dispersant resin of Example 4, receiving a mixture of a, b and C:

Blend: 80 g prisonaires resin I

20 g of the polyurethane dispersant resin of Example 4

25 g of 2-methoxypropylacetate (diluent)

The mixture But the value HE 164 mg KOH/g

Mix In: 90 g policlonovmi resin I

10 g of the polyurethane dispersant resin of Example 4

33 g of 2-methoxypropylacetate (diluent)

The mixture But the value HE 171 mg KOH/g

Mixture: 90 g policlonovmi resin I

10 g of the polyurethane dispersant resin of Example 4

25 g of 2-methoxypropylacetate (diluent)

The mixture But the value HE 193 mg KOH/g

Mixture from a to C is mixed with commercially available polyisocyanate resins, getting prototypes transparent coating compositions.

Isocyanate 1: Desmodur N 3600, 80% weight. a solution of 2-methoxypropylacetate

Isocyanate 2: Bayhydur 3100 N, 70% weight. a solution of 2-methoxypropylacetate

Isocyanat 3: Bayhydur LS2150, 70% weight. a solution of 2-methoxypropylacetate.

In a glass beaker mix this amount of prisonaires resin, which corresponds to 0.1 pray HE and so many isocyanate, which corresponds to 0.1 pray NCO.

Under stirring with a spatula add demineralized water up until the viscosity will not be from 15 to 18 sec (DIN cup 4).

Transparent composition is applied on a glass plate by a rod receiving after drying, the film thickness of about 60 μm. The transparent coating composition and properties are shown below in table 2. VOC is theoretical amount of volatile organic compounds in the clear coating composition. The hardness of Persona expressed in seconds and is determined after 5 days of incubation at room temperature. In all cases receive transparencies.

Table 2
MixtureIsocyanatThe solids content in % of weight.VOC in g/lStability in hoursThe hardness of Persona
And1452002190
And2422502114
And3402604276
In1452301,5299
In2422801,5200
In340 2803320
1452001150

The above results show that the dispersion resin according to the invention is suitable for receiving water compositions dispersed hydrophobic resins.

Example 10

The use of dispersing resin for dispersion of pigments and coating compositions.

Were studied the following pigments:

Pigment 1: white - Kronos 2310 from Kronos

Pigment 2: red - Irgazin DPP Red Bo from Ciba

Pigment 3: blue - Heliogene Blue L7101F from Basf

Pigment 4: purple - Quindo Violet RV6926 from Bayer

Prepare a mixture of solutions of these pigments with the above aqueous pigment dispersing resins. Mixtures were dispergirovany apparatus for shaking Red Devil. The results are shown below in table 3.

In addition, receive water compositions for coatings for ground cover.

Plate pigments by pigment 1 is obtained by grinding the following components:

up 11,86 g of a Solution of a polyurethane dispersant resin, as shown in Table 3

5,97 g Water

0.28 g of Propylene glycol

2,40 g of a Commercially available dispersant

70,02 g of Pigment 1

9,46 g Water

the Composition for coating pigment 1 is produced by mixing the following components:

20,80 g Aqueous binder dispersion containing polyacrylate and polyurethane solids content of 42 wt%.

of 7.35 g of Aqueous polyacrylate dispersion, the solids content of 40 wt%.

0.08 g Amin

to 13.09 g of Water

3,17 g co-solvent

0,30 g Clay thickener

14,62 g Water

1.06 g HEUR Thickener

of 1.75 g of Water

30,43 g Pigment paste with pigment 1

1,95 g co-solvent

of 5.40 g of Water

Plate pigments by pigment 2 is obtained by grinding the following components:

33,51 g of a Solution of a polyurethane dispersant resin, as shown in Table 3

1.44 g Propylene glycol

0.18 g of a Commercially available dispersant

0.45 g of the Antifoam

46,12 g Pigment 2

18,29 g Water

Compositions for coating with pigment 2 is obtained by mixing the following components:

19,94 g Aqueous binder dispersion containing polyacrylate and polyurethane solids content of 42 wt%.

7,05 g Aqueous polyacrylate dispersion, the solids content of 40 wt%.

0.08 g Amin

12,56 g Water

3.04 from g the co-solvent

0.29 grams of Clay thickener

14,02 g Water

1,02 g HEUR Thickener

1.68 g of Water

14,59 g Pigment paste with pigment 2

1.19 g of the co-solvent

24,54 g Water

Plate pigments by pigment 3 is produced by grinding the following components:

22,19 g of a Solution of a polyurethane dispersant resin as Asano in Table 3

1.42 g Propylene glycol

of 0.44 g of Antifoam

35,19 g Pigment 3

40,76 g Water

Compositions for coating with pigment 3 is produced by mixing the following components:

25,21 g Aqueous binder dispersion containing polyacrylate and polyurethane solids content of 42 wt%.

8,91 g Aqueous polyacrylate dispersion, the solids content of 40 wt%.

0.10 g Amin

trend of 15.87 grams of Water

of 3.84 g of the co-solvent

0.36 g of a Clay thickener

17,72 g Water

1.28 g HEUR Thickener

2,12 g Water

11,13 g Pigment paste with pigment 3

0,98 g co-solvent

12,48 g Water

Plate pigments by pigment 4 is produced by grinding the following components:

21,51 g of a Solution of a polyurethane dispersant resin, as shown in Table 3

1.50 g Propylene glycol

of 4.00 g of a Commercially available dispersant

0.50 g of the Antifoam

40,00 g Pigment 4

32,49 g Water

Compositions for coating with pigment 4 is produced by mixing the following components:

27,66 g Aqueous binder dispersion containing polyacrylate and polyurethane solids content of 42 wt%.

9,78 g Aqueous polyacrylate dispersion, the solids content of 40 wt%.

0.11 g Amin

17,43 g Water

4,22 g co-solvent

0.40 g of a Clay thickener

19,44 g Water

1,41 g HEUR Thickener

2,33 g Water

17,00 g Pigment paste with pigment 4

Thus the m table 3 shows the properties of the resulting pigment plates and cover songs.

From the data presented in table 3, we can conclude that the dispersion resin according to the invention of Examples 1 to 8 give a pigment paste and the compositions of ground coverings, having smaller occulation and better dispersion than the pigment dispersion based on a comparative dispersant resin of comparative Example A, having a low content of polyalkylated. Also trudnoispolnimy Quindo Violet (pigment 4), using the dispersion resin according to the invention were obtained excellent dispersion and stability to flocculation.

In the case of transparent pigment Heliogene Blue (pigment 3), using the dispersion resin according to the invention was achieved a good transparency of the pigment paste. When using this comparative pigment dispersant resin of Example a pigment paste was opaque. Comparative dispersant resin of Example has no hydrophobic groups of the side chain. This resin was obtained pigment paste of very low quality in combination with a white pigment, which is usually easily dispersible. Pasta showed strong occulation, contained numerous lumps, and the dispersion paste was unsatisfactory. If var is shirouma resin according to the invention from Examples 1 and 2, these problems, in combination with a white pigment is not met.

Example 11

Obtaining a polyurethane dispersant resin for the pigment composition according to the invention

Into a reaction vessel equipped with a stirrer, thermocouple, heating jacket, reflux condenser and addition funnel is placed 17,566 parts by weight Jeffamine M 1000. The reactor is rinsed with nitrogen and the contents heated to 120°C. and Then for 15 minutes in a reactor add 4,083 parts by weight of Cardura E 10, after which the contents of the reactor are heated to 130°C and maintained at this temperature for 4 hours. Then, the reactor is cooled to 65°C.

Then, the reactor type 1,604 parts by weight of 1,4-cyclohexanedimethanol, then within 5 minutes add 4,948 parts by weight isophoronediisocyanate. Is exothermic reaction. Rinsing the tubes in the reactor add 2,790 parts by weight of methyl ethyl ketone. The reactor is heated to boiling, about 120°C., and maintained at boiling for 2 hours. The contents of the reactor is cooled to 115°C, add 0,006 parts by weight dibutil tin of dilaurate, and the reaction continued for 2 hours at 120°C. the Content of isocyanate below 0.1 wt%. The solvent, methyl ethyl ketone, first evaporated at atmospheric pressure. The pressure is gradually reduced by evaporation to about 100 mbar to full the nd evaporation of methyl ethyl ketone.

The temperature of the contents of the reactor is reduced to 100°C. and for 2.5 hours add 71,499 parts by weight of water. During the addition the temperature of the contents of the reactor was gradually reduced to 30°C. then the reactor is cooled to room temperature and obtain an aqueous solution of dispersant resin.

Dispersing resin is set hydroxy 29.3 mg KOH/g, Mn 4,150 content accelerated 62.2% of the weight., the content of ethylene oxide 51.5% of the weight., all properties based on dispersing resin that does not contain volatile components.

Comparative Example

Obtaining a polyurethane dispersant resin according to WO 97/19120 for comparative pigment composition.

In a reaction vessel, equipped as described above, is placed 368,8 g Tegomer D-3403, are 507, 5 g olejowego alcohol, 456,9 g diol sulfosuccinate, which is the reaction product of 1 mole of maleic acid, 2 moles Caruda®E 10 and 1 mole NaHSO3and 196,0 g 2-butanone. Components are mixed and with the help of a dropping funnel add 420,5 g isophorondiisocyanate. The reaction mixture is heated to 120°C and maintained at this temperature for 2 hours. Then add 0.5 g dibutil tin of dilaurate and the reaction mixture is left at 120°C for the next 2 hours. Then lower the temperature to 90°C and carry out the evaporation under reduced pressure to remove all volatile the solvent. Then, for 3 hours while gradually cooling to room temperature, add 6,746 g of water. Get a water solution of the polyurethane dispersant resin. The content of ethylene oxide in the polyurethane 18.7% of the weight.

Example 12

Obtaining the pigment composition according to the invention

The pressed residue of pigment Ciba Irgazin Red BO, containing 38 wt%. pigment is mixed with solution of dispersant resin of Example 11 and fluidizers in dissolvere receiving a liquid suspension of the pigment. The amount of solution dispersing resin expect in such a way as to achieve a 17% weight. dispersing resin, calculated on the amount of pigment and a dispersant resin. The suspension is milled in a scale of 7 liters, using ECM pilot mill, and was obtained pigment dispersion after 20 passages with the use of 0.7-0.9 mm balls. Suspension of the pigment shows good characteristics of grinding. Dispersment powdered composition, achieved after fluidizable in dissolvere shows good wetting of the pigment. Low viscosity is associated with a high water content in the suspension. The samples dried by spray mini-spray dryer Buchi with the inlet temperature of 132°C and outlet temperature of 85°C. the Flow of 0.2 kg/h Visible clogging of the valve and increase the pressure was not observed. The powder is dried to approximately % of residual moisture. The final pigment composition is engineering powder.

Comparative Example D

Comparative pigment composition

Example 12 is repeated, except that the solution of the dispersant resin of Example 11 is replaced by the solution of a dispersing resin of Comparative Example C. the Pressed residue of pigment cannot be fluidsurface, which indicates poor wetting of the pigment. Even when using additional quantities dispersing resin that is suitable for grinding the suspension of the pigment is not formed.

Examples 13 to 16 and Comparative Examples E and F

Obtaining compositions for coating

Pigment composition of Example 12 is investigated as a pigment mixture in two different water-binder coating system, Autowave 665 (example 13) and Autowave 666 (Example 14). For studies performed with stirrer IKA RW20 with 4 cm blade operating at to 750-760 rpm Pigment composition of Example 12 is added under stirring and maintaining the set speed for all 30 minutes. Add a sufficient amount of the pigment composition to obtain a coating composition having a pigment content of 6.6% by weight. It is identical to the toner Autowave 357, used as a comparison (Comparative Example E).

The final composition of the coating is prevoshodneishaia values grinding, and particles are not observed in the measurement test of Hagman.

White concentrates obtained by mixing the compositions of the coating with white toner module Autowave 00.

Example 15

A composition for coating of Example 13 is mixed with white toner module Autowave 00 so that the ratio of the weight in the final mixture of the red pigment to white pigment was 50:50.

Example 16

A composition for coating of Example 14 is mixed with white toner module Autowave 00 so that the ratio of the weight in the final mixture of the red pigment to white pigment was 50:50.

Comparative Example F

Comparative composition for coating of Example E is mixed with white toner module Autowave 00 so that the ratio of the weight of the red pigment to white pigment in the final mix was 50:50.

The composition of the coating applied on the card light transmission Leneta 2A, using the install K-Control, coating and left to be dried at room temperature overnight.

Properties depth of colour inks of Examples 13 and 14 taken excellent. Compared with Comparative Example E. the level of Shine above and has a bright, smooth type color. The value of the purity of the white color concentrate is good.

The results are shown in Table 4.

Example Properties mixingGloss (60°)Gloss (20°)The color tone (With*)
13superb72,936,972,06
14superb71,332,771,72
Enot applicable64,214.4V69,45
15not applicable65,422,360,57
16not applicable71,029,760,75
Fnot applicable65,818,963,24

1. Polyurethane dispersant resin with polyurethane main chain containing a hydrophilic group of the side chain on the basis of polyalkylated, and group side chain PR is connected to the polyurethane main chain through covalent bonds, and where the content of polyalkylated in the polyurethane dispersant resin is at least 45 wt.% and not more than 80 wt.%, characterized in that the polyurethane further comprises a hydrophobic group on the side chain, which is attached to the polyurethane main chain through covalent bonds.

2. Polyurethane dispersant resin according to claim 1, characterized in that polyalkylene based on ethylene oxide, propylene oxide or mixtures thereof.

3. Polyurethane dispersant resin according to claim 1, characterized in that the hydrophobic group side chain containing hydrocarbon group having at least 4 carbon atoms.

4. Polyurethane dispersant resin according to claim 3, characterized in that the hydrophobic group side chain containing hydrocarbon group having not more than 30 carbon atoms.

5. Polyurethane dispersant resin according to claim 3 or 4, characterized in that the hydrocarbon groups are branched.

6. Polyurethane dispersant resin according to claim 1, characterized in that the polyurethane dispersant resin contains tertiary amino groups.

7. Polyurethane dispersant resin according to claim 6, characterized in that the tertiary amino groups, at least partially neutralized acid neutralizing agent.

8. Polyurethane dispersant resin according to claim 1, characterized in that the main chain of the polyurethane resin contains almost no able to hydrolysis of ester groups.

9. Polyurethane dispersant resin according to claim 1, characterized in that the hydrophilic group of the side chain on the basis of polyalkylated were introduced into the polyurethane by using compounds having at least two groups capable to react with isocyanate, and side polyalkyleneglycol group.

10. Polyurethane dispersant resin according to claim 9, characterized in that the compound having at least two groups capable to react with isocyanate, and side polyalkyleneglycol group, is a compound of formula (I)or (II), or their mixture,

where R is the remainder monoepoxide compounds after reaction with the amino group, R1is selected from C1to C7alkyl groups, n is from 0 to 25, m is from 1 to 50 and n+m≤50.

11. Polyurethane dispersant resin according to claim 10, characterized in that R contains a hydrocarbon group having from 4 to 30 carbon atoms.

12. Composition for coatings containing polyurethane dispersant resin according to any of previous claims 1 to 11 and particles.

13. The composition according to item 12, wherein the particles are pigment particles.

14. The composition according to item 12 or 13, characterized in that the composition is a liquid.

15. The composition according to item 13, wherein the composition is a solid.

16. To the position indicated in paragraph 15 characterized in that the composition contains at least 35 wt.%, at least one pigment and not more than 65 wt.% polyurethane dispersant resin, calculated on the total weight of pigment and a polyurethane dispersant resin.

17. The composition according to 14, characterized in that the composition is an aqueous dispersion of a hydrophobic resin.

18. The composition according to 14, characterized in that the composition additionally contains
a) at least one organic film forming binder which is different from the polyurethane dispersant resin according to claims 1-11, and
b) at least one pigment.

19. The method of obtaining the composition according to item 13, which includes stages, designed to shift the impact of a liquid mixture containing a pigment, at least one dispersing agent and possibly a liquid diluent, wherein the polyurethane dispersant resin according to any one of the preceding claims 1 to 11 is used as a dispersing agent.

20. The method according to claim 19, wherein the liquid diluent is water.

21. The method of obtaining the composition according to item 15, comprising the following stages:
a) mixing the composition containing a pigment and a dispersing agent, possibly with the addition of water or organic solvent, with the formation of a fluidized suspension of pigment,
b) possibly grinding suspense and
c) drying of the suspension,
wherein the polyurethane dispersant resin according to any of previous claims 1 to 11 is used as a dispersing agent.

22. The method according to item 21, wherein the pigment is an organic pigment in the form of pressed sludge.

23. The method according to item 21 or 22, characterized in that stage C) is carried out using freeze drying or spray drying.

24. The use of dispersant resin according to one of the preceding claims 1 to 11 to obtain the composition for blending in a pigment.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a coating composition containing a) polyacrylate polyol obtained via polymerisation of unsaturated olefin monomers, where at least 40 wt % of the monomers include straight or branched alk(en)yl or alk(en)ylene groups, having at least 4 carbon atoms; b) polyether polyol obtained via esterification of component links having functional groups which form an ester, where at least 30 wt % of component links include straight or branched alk(en)yl or alk(en)ylene groups with at least 4 carbon atoms per functional group, which forms an ester, where he polyether polyol has hydroxyl number higher than 280 mg KOH/g and hydroxyl functionality of at least 2, and c) isocyanate-functionalised cross-linking agent. The invention also relates to a set of parts for preparing the coating composition and a method of applying the coating composition. The coating composition can be used as a top coating layer in multilayer paint coats, in finishing or reworking automobiles or large vehicles.

EFFECT: coating has high hardness, scratch resistance, lustre, longevity and wear resistance, chemical resistance and UV radiation resistance.

15 cl, 6 tbl

FIELD: chemistry.

SUBSTANCE: composition includes a polymer mixture which contains a) an aqueous dispersion of at least one polysiloxane and b) an aqueous dispersion of at least one polyurethane, in which content of the said at least one polysiloxane polymer varies from approximately 50 to 85 wt %, and content of the said at least one polyurethane varies from approximately 15 to 50 wt %, in terms of total weight of solid substances of the said at least one polysiloxane polymer and the said at least one polyurethane and c) polyolefin powder with ultrahigh molecular weight in amount of approximately 5-35 pts. wt per 100 total parts by weight of the said at least one or more polysiloxanes and the said one or more polyurethanes. The said polyurethane is obtained from at least one aliphatic or cycloaliphatic diisocyanate and at least one hydroxyl ending intermediate compound such as polycarbonate, polyester or polyether or combination thereof, and is heat-curable. The said aqueous dispersion contains approximately 7 wt % or less of an organic solvent in terms of total weight of the said dispersion composition, and the said polymer mixture contains from approximately less than 10 to 0 parts by weight of a substance for increasing adhesiveness per 100 total parts by weight of the said at least one polyurethane and the said at least one polysiloxane; and contains from approximately less than 10 to 0 parts by weight of a halogen-containing polymer per 100 total parts by weight of the said at least one polyurethane and the said at least one polysiloxane. The invention also describes versions of a polymer or rubber substrate and versions of a sealant for vehicles, at least partially coated with the dried composition described above.

EFFECT: low noise level when substrate coated with the said composition moves or is in contact with an article, as well as obtaining a surface with low coefficient of friction which does not increase with time.

17 cl, 14 ex, 10 tbl, 1 dwg

FIELD: chemistry.

SUBSTANCE: polyurethane material contains a first part of crystalline particles, having self-orientation and bonded so as to keep their orientation along a first crystallographic line at least in two directions, a second part of crystalline particles having self-orientation and bonded so as to keep their orientation along a second crystallographic line at least in two directions, wherein the first crystallographic line is different from the second crystallographic line and where the said crystalline particles constitute more than approximately 30% of the total volume of the polyurethane material, and where the polyurethane contains a product of reaction of components comprising: (a) approximately 1 equivalent of 4,4'-methylene-bis(cyclohexylisocyanate); (b) approximately 0.3 of a trimethylolpropane equivalent; and (c) approximately 0.7 of a butanediol or pentanediol equivalent, and where the polyurethane material undergoes thermal treatment at temperature ranging from approximately 35°C to approximately 150°C or holding.

EFFECT: production of polyurethane material, products of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

26 cl, 110 ex, 33 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: disclosed is an aqueous polyurethane dispersion which does not contain N-methylpyrrolidone and solvents and contains a product of reaction of a mixture of 1-isocyanate-3,3,5-trimethyl-5-isocyanatemethylcyclohexane and 4,4'-diisocyanatedicyclohexylmethane, one or more polyols with average molecular weight of 500-3000, one or more compounds with at least one OH- or NH- functional group, which contain a carboxyl and/or carboxylate group, where at least 50 mol % acid incorporated in the overall resin consists of dimethylol propionic acid, one or more polyols and/or polyamines with average molecular weight less than 500 and, if necessary, one or more monoalcohols and/or monoamines, as well as preparation method thereof and use thereof as an agent for coatings having good resistance characteristics.

EFFECT: obtaining a polyurethane dispersion which does not contain N-methylpyrrolidone and solvents, and contains a hydrophilization agent in form of dimethylol propionic acid, which can be stored for over 8 weeks and is suitable for making transparent shining coatings with high resistance to dyes.

8 cl, 2 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to aqueous coating compositions with low content of volatile organic compounds. The aqueous coating composition contains water, oxidative-curable resin, at least 1.5% of the weight of the composition of a non-structured alkali-soluble acrylate, having weight-average molecular weight Mw of 200000 g/mol or lower, and acid number of at least 15 mg KOH/g; and an emulsified second acrylate having Mw of at least 300000 g/mol. Content of the alkali-soluble acrylate in the composition is equal to at least 3 wt %. The weight ratio of the alkali-soluble acrylate to the second emulsified acrylate ranges from 1:0.5 to 1:5, and the weight ratio of the alkali-soluble acrylate to the oxidative-curable resin ranges from 1:0.5 to 1:10. The oxidative curable resin is an alkyd resin, alkyd-urethane resin. The second acrylate is cross-linkable, for example azomethine cross-linkable links.

EFFECT: aqueous coating composition has good physical and mechanical properties.

9 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethanes and articles made from said polyurethanes, as well as to laminated material and coating composition containing such polyurethanes. The polyurethane is a product of a reaction between components which contains less than approximately 10 wt % polyesterpolyol and/or polyetherpolyol, where the components are selected from: (a) approximately 1 equivalent of at least one polyisocyanate; (b) approximately 0.05-0.9 equivalent of at least one branched polyol which contains 3-18 carbon atoms and at least 3 hydroxyl groups; and (c) approximately 0.1-0.95 equivalent of at least one diol which contains 2-18 carbon atoms, where during mixing, the reaction components are held at reaction temperature of at least approximately 100°C for at least approximately 10 minutes.

EFFECT: production of polyurethanes, articles of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

37 cl, 113 ex, 82 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a moisture-curable composition for adhesive compounds, sealing compounds, coatings or linings, application thereof as an adhesive, sealing compound or coating, a cured composition obtained by reacting water with such a composition, methods of gluing bases and sealing using said composition, as well as adhesive and sealed articles made using said methods, respectively. The moisture-curable composition contains (i) at least one isocyanate-containing polyurethane polymer P, which is obtained from at least one polyisocyanate and at least one polyol, and (ii) at least one aldimine-containing compound of formula (I): .

EFFECT: preparation of compounds which are stable during storage, can be quickly moisture-cured without bubbles, do not cause smells during curing and are suitable for use as precursors of synthetic materials.

25 cl, 34 ex, 10 tbl

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to coating composition, applied, for instance, as transparent coatings, base coatings, pigmented coating layers, used, prime coatings, etc. Composition contains polyisocyanate, polyol, metal-based catalyst for carrying out reaction of addition reaction between isocyanate groups and hydroxyl groups, thiol-functioning compound and carboxylic acid, carbonyl group of carboxylic acid being in connection with π-electronic system.

EFFECT: creation of novel coating composition, demonstrating presence of favourable property balance, namely, low level of volatile organic solvent content with operation viscosity, high rate of hardening and long viability, which results in obtaining coatings, which demonstrate good outlook characteristics, in particular, low liability to formation of pinholes, and good hardness.

14 cl, 2 tbl

FIELD: construction.

SUBSTANCE: composition for coats contains isocyanate prepolymer produced by interaction of 4,4'-diphenylmethanediisocyanate and oligodiendiol with molecular weight of 2800-3200, content of hydroxyl groups 0.88-1.3% at the ratio of isolcyanate and hydroxyl groups of 4:1 with content of isocyanate groups in prepolymer of 8.0-9.7%, wt parts - 15-70, base - rubber composition from low-molecular hydroxyl-containing rubber, plasticiser, filler, anti-ageing agent and pigment - 100, catalyst of urethane production - 0.05-0.15 and glycerin 0.7-3.0.

EFFECT: higher strength, hardness and relative extension of coats.

2 tbl

FIELD: chemistry.

SUBSTANCE: woven belt is a coated belt made by depositing a urethane-based composition onto the surface of the said belt, where the said composition contains nanoparticles of filler selected from a group consisting of nanoparticles of clay, soot, silicon carbide, metal oxides and combinations of said nanoparticles. Content of nanoparticles of filler in the coating ranges from 0.01 to 10 wt %.

EFFECT: obtained belt increases resistance to bending fatigue, resistance to development of cracks, resistance to joining of grooves and wear resistance of urethane coatings of belts and shafts, increases water resistance and oil resistance of belts and shafts with urethane coating.

18 cl, 2 ex, 4 tbl, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention pertains to coloured finishing coatings, used, for example, in the motor car industry. Description is given of the coating, which has thickness of between 5 and 25 mcm. The coating contains a high-molecular organic binding substance and from 5 to 15 mass % of 3,6-di(4'-biphenyl)-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione in conversion to full content of non-volatile component, at least one extra colouring pigment and a compulsory additive of white pigments, black pigments or pigments which form special effects, which contain, in conversion to the quantity of colouring pigments, (a) from 30 to 90 % mass of 3,6-di(4'-biphenyl)-2,5-dihydropyrrole[3,4-c]pyrrole-1,4-dione, with specific surface area from 20 to 50 m2/g, and (b) from 10 to 70% mass of extra organic pigment, with surface area from 10 to 10 m/g, chosen from a group containing quinacridones, diketopyrrole[3,4-c]pyrrole dioxazines, indanthrones, perylenes, phtalocyanine and 3-amino-1H-isoindole-1-onoximate metal-complex pigments and their solid solutions and mixtures. Description is also given of a composition for external coating, method of depositing it and objects with the given coating.

EFFECT: invention provides for high quality non-transparent coating.

15 cl, 6 ex

FIELD: dyes and pigments.

SUBSTANCE: invention relates to a method for preparing an aqueous dispersion wherein water-insoluble dye is dispersed stable in an aqueous medium containing water and that is used as ink, respectively. Invention describes an aqueous dispersion comprising particles including water-insoluble dye and a polymeric compound or surface-active substance wherein its hydrophilic moiety is formed by at least one group taken among the group consisting of carboxyl, sulfonic, phosphorus, hydroxyl and alkylene oxide group. Particles are dispersed in water-containing medium and dispersion shows intensity of light scattering 30000 imp/s, not above, when it comprises sufficient amount of particles and to provides value of absorption peak with respect to visible light = 1 and particles give the same color as a water-insoluble dye in crystalline state. Also, invention relates to a method for its preparing involving the following stages: (1) preparing a solution containing water-insoluble dye and a dispersing agent dissolved in aprotonic water-soluble organic solvent in the presence of alkali; (2) mixing the solution with water and preparing the dispersion containing particles comprising water-insoluble dye and dispersing agent. Also, invention describes particles comprising water-insoluble dye and polymeric compound or surface-active substance wherein its hydrophilic moiety is formed by at least one group taken among the group consisting of carboxyl, sulfonic, phosphorus, hydroxyl and alkylene oxide group provides the same color as water-insoluble dye in crystalline state and having colored moiety with water-insoluble dye and non-colored moiety wherein non-colored moiety exists in the round region with radius 40 nm and wherein its center is the required point in a particle. Also, invention relates to a method for their preparing that involves the following stages: (A) preparing an aqueous dispersion; (B) formation of aggregate consisting of dispersion particles and isolation of aggregate from the dispersion; (C) conferring to particles in aggregate the capacity for repeated dispersing and wherein the stage (B) involves sub-stage of addition of acid to the dispersion to form aggregate, and the stage (C) involves sub-stage of treatment of aggregate with alkali to confer particle in aggregate the capacity for repeated dispersing, and ink containing particles described above. Proposed ink provides printing with excellent quality by color and clearness that are resistant to water and light.

EFFECT: improved preparing method, improved and valuable properties of dispersion and ink.

19 cl, 16 tbl, 1 dwg, 24 ex

The invention relates to the field of composite structures, mineral or organic fillers or pigments used in the paper industry for paper manufacturing, coating mastic

FIELD: chemistry.

SUBSTANCE: polyurethane material contains a first part of crystalline particles, having self-orientation and bonded so as to keep their orientation along a first crystallographic line at least in two directions, a second part of crystalline particles having self-orientation and bonded so as to keep their orientation along a second crystallographic line at least in two directions, wherein the first crystallographic line is different from the second crystallographic line and where the said crystalline particles constitute more than approximately 30% of the total volume of the polyurethane material, and where the polyurethane contains a product of reaction of components comprising: (a) approximately 1 equivalent of 4,4'-methylene-bis(cyclohexylisocyanate); (b) approximately 0.3 of a trimethylolpropane equivalent; and (c) approximately 0.7 of a butanediol or pentanediol equivalent, and where the polyurethane material undergoes thermal treatment at temperature ranging from approximately 35°C to approximately 150°C or holding.

EFFECT: production of polyurethane material, products of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

26 cl, 110 ex, 33 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to polyurethanes and articles made from said polyurethanes, as well as to laminated material and coating composition containing such polyurethanes. The polyurethane is a product of a reaction between components which contains less than approximately 10 wt % polyesterpolyol and/or polyetherpolyol, where the components are selected from: (a) approximately 1 equivalent of at least one polyisocyanate; (b) approximately 0.05-0.9 equivalent of at least one branched polyol which contains 3-18 carbon atoms and at least 3 hydroxyl groups; and (c) approximately 0.1-0.95 equivalent of at least one diol which contains 2-18 carbon atoms, where during mixing, the reaction components are held at reaction temperature of at least approximately 100°C for at least approximately 10 minutes.

EFFECT: production of polyurethanes, articles of which are made through casting or reaction injection moulding and have good optical properties, high resistance to impact loads, high impact resistance, high K-ratio, good ballistic stability, good resistance to solvents and good weather resistance.

37 cl, 113 ex, 82 tbl, 26 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to novel foam modifiers for producing flexible foam. Flexible foamed polyurethane with density of less than 128 kg/m3 is obtained by reacting an aromatic polyisocyanate component with functionality of at least approximately 2.0, with a component capable of reacting with isocyanate, which contains one or more polyoxyalkylenepolyester polyols having 2-8 hydroxyl groups with OH number between approximately 11 and approximately 280, and containing less than 30 wt % copolymerised oxyethylene from the weight of oxyethylene, and a foam modifier. The foam modifier contains 35-75 wt % of at least one low-molecular weight compound selected from a group consisting of 1,3-propanediol, 1,3-butanediol and 1,4-butanediol and their mixture, 20-60 wt % of one or more polyester polyols containing 2-8 hydroxyl groups per molecule with OH number from approximately 11 to approximately 280, and containing more than 50 wt % compolymerised oxyethylene from the weight of oxyethylene, and 5-25 wt % dipropylene glycol. The reaction takes place in the presence of one or more foaming agents, one or more catalysts and one or more surfactants.

EFFECT: improved operational characteristics and properties of flexible foam.

25 cl, 11 tbl

FIELD: organic chemistry, chemistry of polymers.

SUBSTANCE: invention relates to chemistry of polyurethans, namely, to spandex improved composition. Spandex is product of reaction of at least one polymeric glycol and at least one polyol comprising alkoxylated aromatic functional group with at least one organic diisocyanate followed by the polymerization process of synthesized protected glycol with at least one diamine. Alkoxylated diphenol or alkoxylated dihydrophenol is used as polyol comprising alkoxylated aromatic functional group. Also, invention describes a method for synthesis of spandex that comprises (with exception for steps in preparing isocyanate-protected polyols and their polymerization with diamines) molding steps from reaction mixture, molding from a melt, dry molding or wet molding of polyurethane also. Spandex possesses the best stability to high-temperature coloring and minimal loss of physical properties, such as elastic recovery of form.

EFFECT: improved method of synthesis.

16 cl, 4 tbl, 5 dwg

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to a method for preparing polyurethane material, and to material made of in relation with the indicated method. Invention describes a method for preparing polyurethane material showing the vitrification point 25°C, not below. Polymer is prepared by interaction of polyisocyanate component consisting of the following components: a) 80-100 wt.-% of diphenylmethane diisocyanate comprising 4,4'-diphenylmethane diisocyanate and/or variant of indicated diphenylmethane diisocyanate, 40 wt.-%, not less, and 0-20 wt.-% of another polyisocyanate with the isocyanate-reaction composition consisting of the following components: a) 80-100 wt.-% of simple polyetherpolyol with the average nominal polyfunctionality 3-8, average equivalent mass 200-2000 Da, average molecular mass 600-8000 Da, the oxyethylene content 50-100% and the content of primary hydroxyl groups 70-100%; b) reaction elongating agent and/or cross-linking agent taken in the amount wherein the ratio of hardness blocks = 0.60; and c) 0-20 wt.-% of one or some other isocyanate-reaction compounds but excluding water, and material made of the indicated method. Polyurethanes made of the proposed method show density value 957 kg/m3, the Shore hardness value 77 and the virtification temperature 87°C that can be used in making show footings, arm rests, door panels an car sun glass baffle plates.

EFFECT: improved preparing method.

5 cl, 1 tbl, 2 ex

FIELD: chemical industry; methods of production of a thermosetting elastomers.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of production of a thermosetting polyurethane elastomer and also to the elastomer produced according to the given method. The invention presents the method of production of the polyurethane elastomer having a total apparent density exceeding 150 kg/m3 and providing for an interaction of polyisocyanate and a reactive to isocyanate composition not necessarily at presence of water, according to which the reaction conduct at an isocyanate index of 85-120. At that the polyisocyanate component is composed of: al) 80-100 mass % of diphenylmethanediisocyanate containing at least 40 mass % of 4.4'- diphenylmethanediisocyanate and-or a derivative of the indicated diphenylmethanediisocyanate, which (the derivative) is a may be a liquid at the temperature of 25°C and has NCO value of no less than 20 mass % and a2) 20 mass % of the other polyisocyanate; the reactive to isocyanate composition b) consists of b1) 80-100 mass % of a simple polyol polyester having an average nominal functionality - 2-8, average reactive equivalent weight of 750-5000, an average molecular mass of 2000-12000, the share of oxyethylene - 60-90 mass % and the share of the primary hydroxyl groups of 70-100 mass % calculated for the total number of the primary and the secondary hydroxyl groups in polyol; b2) a reactive to isocyanate extender of the chain in such a quantity, that the ratio of the rigid block makes less than 0.45; and b3) - 20-0 mass % of one or more of other reactive to isocyanate composition excluding water. At that the amount of the polyol of 61) and the reactive to isocyanate composition 63) is calculated from the total amount of the indicated polyol 61) and the composition 63). The invention presents also description of the thermosetting elastomer produced according to the indicated method.

EFFECT: the invention ensures production of a thermosetting polyurethane elastomer.

10 cl, 2 ex

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