RU2418815C2 - Polyurethane dispersing resin - Google Patents

Abstract

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

Description

The invention relates to a polyurethane dispersant resin having a polyurethane backbone containing hydrophilic polyalkylene oxide side chain groups, the side chain groups being attached to the main polyurethane chain via covalent bonds. In addition, the invention relates to compositions containing a polyurethane dispersant resin, a method for producing these compositions and the use of a polyurethane dispersant resin.

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

WO 03/046038 describes a polyurethane polymer containing from 35% to 90% by weight. poly (C _2-4 alkylene oxide) based groups on the total weight of the polymer, and where at least 5% of the poly (C _2-4 alkylene oxide) based groups on the total weight of the polymer are contained in the side chains.

It was found that when using known polyurethane dispersant resins, the dispersion of pigment pastes and the flocculation stability of pigments in paints are further improved, especially when hard-dispersed pigments are used. Moreover, the known polyurethane dispersant resins are less suitable for the preparation of so-called mixing pigment compositions. Moreover, in particular, dry pigment compositions containing known polyurethane dispersant resins do not produce stably dispersed pigment paints. Compositions for mixing pigments are often dry, mainly powder pigment concentrates containing pigment and dispersing agent, which can be included in the matrix, such as in coating compositions, by simple mixing without the need for an additional dispersion step, hence the name - composition to mix the pigment. Compositions for mixing pigments of organic pigments are preferably obtained by treating the pressed pigment precipitate with dispersing agents, followed by drying. When the squeezed pigment precipitate is mixed with known polyurethane dispersant resins, the squeezed pigment precipitate cannot be fluidized into a pigment suspension, which is necessary for further processing steps to obtain a composition for mixing the pigment.

Thus, the present invention provides a polyurethane dispersant resin, which allows the creation of pigment concentrates that can be easily incorporated into coating compositions where the pigments are stably dispersed. In addition, the dispersant resin should be suitable for use with a wide range of pigments. Pigment concentrates should allow the production of paints having excellent quality and stability, especially in the case of hard to disperse and stabilize pigments.

The invention provides a polyurethane dispersant containing hydrophilic polyalkylene oxide side chain groups, wherein the side chain groups are attached to the main polyurethane chain by covalent bonds, and wherein the polyalkylene oxide content of the polyurethane dispersant resin is at least 45% by weight, characterized in that the polyurethane additionally contains hydrophobic side chain groups that are attached to the main polyurethane chain via covalent bonds.

The polyurethane dispersant resin according to the invention allows the creation of pigment concentrates that can be easily incorporated into coating compositions where the pigments are stably dispersed. In addition, the dispersant resin is suitable for use with a wide range of pigments. Pigment concentrates make it possible to obtain paints having excellent quality and stability, especially in the case of hard-to-disperse and stabilize pigments.

The polyurethane dispersant resin according to the invention can be obtained by reaction

(a) at least one di- or polyisocyanate,

(b) at least one compound having at least two groups capable of reacting with an isocyanate and a hydrophilic group of a polyalkylene oxide side chain,

(c) optionally one or more compounds capable of reacting with an isocyanate, having at least two groups capable of reacting with an isocyanate, and

(d) optionally, a compound capable of reacting with an isocyanate having one group capable of reacting with an isocyanate,

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

As suitable di- or polyisocyanates, aliphatic, cycloaliphatic or aromatic di-, tri- or tetraisocyanates may be mentioned. Examples of diisocyanates include 1,2-propylene diisocyanate, trimethylenediisocyanate, tetramethylenediisocyanate, 2,3-butylenediisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodiodido 2-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, 4-methyl-1,3-diisocyanate-cyclohexane, trans-vinylidene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (Desmodur ^® W), toluene diisocyanate, isocyanatomethyl) benzene , xylylene diisocyanate, α, α, α ', α'-tetramethylxylene diisocyanate (TMXDI ^® ), 1,5-dimethyl-2,4-bis (2-isocyanatoethyl) benzene, 1,3,5-triethyl-2,4-bis (isocyanatomethyl) benzene, 4,4'-diisocyanato-diphenyl, 4,4'-diisocyanate-3,3'-dichloro-diphenyl, 3,3'-diphenyl-4,4'-diisocyanato-diphenyl, 4,4 '-diisocyanate-3,3'-dimethoxy-diphenyl,4,4'-diisocyanate-diphenylmethane,4,4'-diisocyanate-3,3'-dimethyl-diphenylmethane and diisocyanate naphtholine. Examples of triisocyanates include 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene, 1,8-diisocyanate-4- (isocyanatomethyl) octane and lysine triisocyanate. Adducts and oligomers of polyisocinates also include, for example, biurets, isocyanurates, allophanates, uretdiones, urethanes, iminooxadiazinediones, and mixtures thereof. Examples of such oligomers and adducts are the adduct of 2 diisocyanate molecules, for example, hexamethylene diisocyanate or isophorone diisocyanate with a diol, such as ethylene glycol, the adduct of 3 hexamethylene diisocyanate molecules with 1 water molecule (available under the trade name Desmodur N from Byer 1) trimethylolpropane with 3 molecules of toluene diisocyanate (available under the trade name Desmodur L from Byer), adduct of the 1st molecule of trimethylolpropane with 3 molecules of isophorone diisocyanate, adduct of the 1st molecule of pentaerythrol with 4 molecules of toluene diiso ionate, adduct of 3 moles of m-α, α, α ', α'-tetramethylxylene diisocyanate with 1 mole of trimethylopropane, isocyanurate trimmer of 1,6-diisocyanatohexane, isocyanurate trimmer of isophorone diisocyanate, urethdione isomethane 1, 1,6-dihexane diurethate 1,6-diurethane 1-diurethane 1,6 6-diisocyanatohexane, 1,6-diisocyanatohexane alofanate and a mixture thereof.

Suitable compounds (b) can be prepared by reacting a polyalkylene glycol monoester with a diisocyanate, followed by reaction with a secondary amine having two hydroxyl groups. The preparation of such compounds is generally known. A detailed description of the receipt, for example, is presented in US 3905929.

Further examples of compounds having two groups capable of reacting with an isocyanate and a hydrophilic group of a polyalkylene oxide side chain are derived from triols in which one hydroxyl group is blocked by a polypropylene or polyethylene oxide segment ending in an ether group. A commercially available example 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 a mixture thereof,

where R is the residue of the monoepoxide compound after reaction with an amino group, R ^{1 is} selected from alkyl groups from C ₁ to C ₄ , n is from 0 to 25, m is from 1 to 50, and n + m ≤ 50. Obviously, (C ₃ H ₆ O) and (C ₂ H ₄ O) units may be present in the polymer chain as blocks of polypropylene oxide and polyethylene oxide or as a more or less random mixture of units formed from propylene oxide or ethylene oxide. Preferably, R contains a hydrocarbon group having from 4 to 30 carbon atoms. Compounds of formula (I) can be prepared by reacting 1 mole of a primary amine with 1 mole of a monoepoxide compound, compounds of formula (II) can be prepared by reacting 1 mole of a primary amine with 2 moles of a monoepoxy compound. The remainder of 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 of formula (I) contains a hydroxyl group and a secondary amino group as groups capable of reacting with an isocyanate. The compound of formula (II) contains two hydroxyl groups as capable of reacting with an isocyanate.

Examples of suitable starting monoepoxides for preparing compounds of formula (I) or (II) are epoxidized olefins, such as epoxidized α-olefins; glycidyl ethers of monohydroxyl compounds such as ethylhexyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether; and glycidyl esters of carboxylic acids, such as glycidyl ether of propionic acid, glycidyl ether of hexanoic acid, glycidyl ether of hexane, glycidyl ether of decanoic acid and glycidyl ether of versatic acid, commercially available from Resolution Performance Products under the name Cardura E 10.

Examples of suitable starting amines for the preparation of compounds of formula (I) or (II) are polyalkylene oxide based amines on, which are commercially available from Huntsman under the trade designation Jeffamine ^® M.

By using compounds (b) according to formulas (I) and / or (II), pigment dispersions with a polyurethane dispersant resin can be obtained with particularly good stability.

Alternatively or in addition to at least one compound having at least two groups capable of reacting with an isocyanate and hydrophilic polyalkylene oxide side chain groups, it is also possible to introduce hydrophilic polyurethane into the polyurethane when preparing the polyurethane dispersant resin polyalkylene oxide side chain groups using at least one compound having at least two isocyanate groups and a polyalkylene oxide based side chain hydrophilic group.

Upon receipt of the polyurethane dispersant resin, the number of compounds having at least two groups capable of reacting with an isocyanate and a hydrophilic group of a polyalkylene oxide side chain is selected so as to provide a polyalkylene oxide content in the polyurethane dispersant resin of at least 45% the weight. Preferably, the amount of polyalkylene oxide in the polyurethane dispersant resin should not exceed 80% by weight. Most preferably, the amount of polyalkylene oxide is in the range of 50% to 70% by weight. The polyurethane dispersant resin preferably contains at least two, more preferably at least three hydrophilic polyalkylene oxide side chain groups per molecule.

Examples of suitable alkylene oxides are ethylene oxide, propylene oxide and butylene oxide. Preferably, the polyalkylene oxide-based groups are based on ethylene oxide or propylene oxide or mixtures thereof. At this time, very good results have been obtained with polyalkylene oxide based side groups, 50% by weight, preferably 70% by weight. which is based on ethylene oxide, calculated on the total weight of the side group based on polyalkylene oxide.

Examples of compounds capable of reacting with an isocyanate having at least two groups that are capable of reacting with an isocyanate include di- and polyamines, di- and polythiols, amino alcohols, aminothiols and, in particular, polyols. Suitable polyols that can be used in the preparation of polyurethanes include diols and triols and mixtures thereof, however, polyols with a large number of functional groups can also be used. Examples of low molecular weight polyols include ethylene glycol, diethylene glycol, tetraethylene glycol, propane-1,2- and -1,3-diol, butane-1,4- and -1,3-diol, hexane-1,6-diol, octane -1,8-diol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A and tetrabromobisphenol A, diol-based fatty acid dimer, glycerol, pentaerythritol, trimethylolpropane, dithrimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, quinitol, mannitol , sorbitol, methyl glycoside, 1,4,3,6-dianhydrohexitols, monoesters of neopentyl alcohol and hydroxypival acid, bis (hydroxyethyl) terephthalate, furandimethanol and reaction products with a molecular weight of up to 400 of these polyols with propylene oxide and / or ethylene oxide.

Organic polymer polyols that can be used in the preparation of polyurethane include diols and triols, and mixtures thereof, however, polyols with a large number of functional groups, for example, as minor components, in addition to diols, can also be used. Suitable polymer polyols are selected from the group consisting of polyesters, polyesters of amides, polyesters, polythioesters, polycarbonates, polyacetates, polyolefions and polysiloxanes.

The polyesters of the polyols that can be used include hydroxyl terminated reaction products of polyhydric alcohols, such as ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, furandimethanol, dimethylol cyclohexane, glycerolpentol mixtures thereof with polycarboxylic acids, in particular dicarboxylic acids or their derivatives, giving esters, for example succinic, glutaric and adipic acids and their dimethyl complex esters, phthalic anhydride, hexahydrophthalic anhydride, dimethyl terephthalate and mixtures thereof. Amide polyesters can be prepared by incorporating amino alcohols, such as ethanolamine, in a polyesterification mixture.

Suitable polyester polyols include polyalkylene oxide glycol, where the alkylene oxide may be selected from ethylene oxide and / or propylene oxide units. In this case, polyalkylene oxide glycols introduce hydrophilic groups into the main chain of the polyurethane resin. Too much polyalkylene oxide glycol in the backbone of the polyurethane resin reduces its lipophilic character. Preferably, the amount of polyalkylene oxide glycol is limited to the extent that the main polyurethane chain remains highly lipophilic. Thus, the preferred amount of polyalkylene oxide glycol is below 25% by weight. based on the total weight of the compounds (c) reacting with the isocyanate, more preferably below 10% by weight. and most preferably below 5% weight.

Polythioether polyols that can be used include products obtained by condensation of both the thioglycol ether itself and other glycols, dicarboxylic acids, formaldehyde, amino alcohols or amino acids.

Polycarbonate polyols include products obtained by the reaction of diols, such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol or tetraethylene glycol, with diaryl carbonates, for example diphenyl carbonate or phosgene. Polyurethane resins that contain carbonate groups are described in detail in WO 01/48106, and are incorporated herein by reference. Suitable polyolefin polyols include hydroxyl-terminated butadiene homo- and copolymers.

According to the prior art, in dispersant resins containing hydrolysis-prone ester bonds in the polymer backbone, disturbances in the long-term stability of the aqueous dispersions containing them and a pH shift are observed. It is believed that these phenomena, at least partially, occur due to hydrolysis of ester bonds in the main chain of the dispersant resin, causing the destruction of the dispersant resin. It was found that dispersion instability and a pH shift are virtually absent if the polyurethane dispersant resin of the invention is used that does not contain ester groups prone to hydrolysis in the polymer backbone. Therefore, in a preferred embodiment, the polyurethane dispersant resin comprises a polyurethane resin backbone that is substantially free of ester bonds prone to hydrolysis. This means that preferably polyester polyols are not used as building blocks for the polyurethane dispersant of the invention. Such dispersant resins give stable aqueous dispersions even with a long storage period.

Compounds having one isocyanate-reactive group may possibly be used in the preparation of polyurethane as a chain terminating agent to limit the molecular weight of the polyurethane. Suitable compounds are well known in the art and include mono alcohols, monoamines and monothiols.

As indicated, the polyurethane dispersant of the present invention further comprises hydrophobic side chain groups attached to the polyurethane backbone via covalent bonds. The hydrophobic groups of the side chain are different from the hydrophilic groups of the side chain. The term "hydrophobic" describes the tendency of a molecule or molecular group not to penetrate water or leave the aqueous phase, as defined in DIN EN ISO 862: 1995-10. The hydrophobic properties of molecules or groups are mainly associated with the presence of hydrocarbon groups. Therefore, in an embodiment of the invention, the hydrophobic side groups contain hydrocarbon groups having at least 4, or at least 6, or at least 8 carbon atoms.

Hydrocarbon groups can have a large number of carbon atoms, for example, when hydrocarbon groups 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, hydrocarbon groups have up to 50, or 30, or 20 carbon atoms. Hydrocarbon groups may be saturated. However, unsaturated hydrocarbon groups and aromatic hydrocarbon groups are also suitable. Hydrocarbon groups may be linear, cyclic or branched. Branched hydrocarbon groups are preferred. Hydrophobic side groups may also contain ester and ether groups. As an example, mention may be made of caprolactone or higher fatty acid ester side groups.

The number and molecular weight of the hydrophilic and hydrophobic groups of the side chain is determined by the hydrophilic / hydrophobic balance of the polyurethane of the present invention. The polyurethane dispersant resin preferably contains at least two, more preferably at least three hydrophobic side chain groups per molecule. In one embodiment, the number of hydrophobic side groups attached to the backbone of the polyurethane polymer is equal to the number of hydrophilic side groups based on polyalkylene oxide attached to it.

Hydrophobic side chain groups can be introduced into the polyurethane dispersant, similarly to the hydrophilic polyalkylene oxide side groups described above. Suitable building blocks for introducing hydrophobic side chain groups into the polyurethane dispersant are compounds having two groups capable of reacting with an isocyanate and at least one hydrophobic side chain group. Such compounds can be prepared, for example, by reacting a hydrophobic epoxy-functionalized compound with an amino group-containing compound. It is also possible to obtain such compounds by the reaction of a non-hydrophobic epoxy-functionalized compound with an amine having a hydrophobic group. Also suitable are the reaction products of a hydrophobic epoxy-functionalized compound and an amine having a hydrophobic group. In this case, a compound is formed having two groups capable of reacting with an isocyanate and two hydrophobic side chain groups. In another embodiment, it is possible to use the reaction products of a hydrophobic epoxy-functionalized compound and an amine having a hydrophilic polyalkylene oxide group. Such a reaction product has two groups capable of reacting with an isocyanate, a hydrophobic side chain group and a polyalkylene oxide side chain group. In addition, very good results were obtained with versatic acid glycidyl ester (a synthetic branched chain fatty acid), commercially available under the name Cardura E 10, as a hydrophobic epoxy-functionalized compound.

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

A polyurethane dispersant resin can be obtained in the usual way by reacting an organic polyisocyanate with other reagents under completely anhydrous conditions at a temperature between about 30 ° C and about 130 ° C until the reaction between the isocyanate groups and groups capable of reacting with the isocyanate in to a large extent does not end. The reaction may possibly be catalyzed by a catalyst such as dibutyl tin dilaurate. The reagents are mainly used in proportions according to the ratio of isocyanate groups to groups capable of reacting with an isocyanate (usually hydroxyl), from about 1: 1 to about 6: 1, preferably about 1: 1. If an excess of organic polyisocyanate is used, an isocyanate-terminating prepolymer may be prepared in the first step. In a second step, at least one compound containing a group capable of reacting with an isocyanate may be added.

The molar ratio and functionality of the starting compounds used to prepare the polyurethane dispersant resin is suitable if selected in such a way as to avoid solidification of the polyurethane and to achieve an average molecular weight of the polyurethane in the range of 800 to 100,000. Preferably, the average molecular weight is in the range of 1000 up to 50,000, more preferably 2,000 to 20,000. Typically, the polyurethane resin backbone is generally linear and preferably lipophilic, having polyalkes enoksidnye hydrophilic side chain group. Such polymers may also be described as comb polymers. They can be obtained from difunctional and possibly monofunctional starting compounds. Alternatively, isocyanates and / or compounds capable of reacting with an isocyanate having more than 2 functional groups may be included in the process for producing a polyurethane dispersant resin, resulting in a branched polyurethane.

When a molar excess of the starting compounds capable of reacting with the isocyanate is used to produce a polyurethane dispersant resin, polyurethane is formed ending in groups capable of reacting with the isocyanate, such as hydroxyl groups. Preferred is a polyurethane dispersant resin having hydroxyl groups, for example, a polyurethane dispersant having a hydroxyl value in the range of 2 to 100 mg KOH / g, preferably in the range of 5 to 50 mg KOH / g.

The polyurethane dispersant may contain tertiary amino groups. A suitable value of the tertiary amine of the polyurethane dispersant should not exceed 50 mg KOH / g. Preferably, the tertiary amine value is in the range of 2 to 30 mg KOH / g based on the non-volatile matter of the polyurethane dispersant resin. The tertiary amino groups are suitably introduced into the polyurethane using di- or polyisocyanates functionalized with a tertiary amine or using amino-functionalized compounds capable of reacting with an isocyanate. Particularly suitable tertiary amino-functionalized compounds capable of reacting with an isocyanate are compounds of formula (II). However, other tertiary amino functionalized compounds capable of reacting with an isocyanate, such as, for example, diols functionalized with a tertiary amine, can be used.

In addition, it is preferable that at least part of the tertiary amino groups present in the polyurethane dispersant resin is neutralized with an acid neutralizing agent. Suitable acid neutralizing agents are both mineral acids and organic acids, with carboxylic acids being preferred. A particularly 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 carboxylic acid groups, sulfonic acid groups, and phosphate or phosphorous groups. Such groups can be introduced into the polyurethane dispersant resin using a compound capable of reacting with an isocyanate containing anionic groups or groups capable of forming anions. As typical examples, dimethylolpropionic acid and sulfonate functionalized diols can be mentioned. The formation of anionic groups can be carried out before or after the production of polyurethane. Typically, anionic groups are formed by treating the groups capable of forming anions with a basic neutralizing agent, such as ammonia or an amine, or with alkali metal hydroxides.

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

The invention also relates to a composition comprising a polyurethane dispersant resin and particles.

In one embodiment of the composition, the particles are pigment particles. Preferred are compositions containing a large amount of pigment, i.e. pigment concentrates, since such compositions are particularly effective in transmitting color and coating paints. Pigment concentrates typically contain from 5% to 85% by weight, preferably from 20% to 75% by weight. pigment based on the total weight of the pigment concentrate.

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

The compositions may be liquid compositions containing an organic diluent and / or a water-based diluent. In addition, dry pigment concentrates can be used, for example in the form of powder, granules or tablets.

The pigment concentrate may be part of a modular system for producing pigment coating compositions. Such a modular system may, for example, contain one or more pigment concentrates in the form of a coloring module, a binding module, and a reducing module. The primer compositions indicated below can be suitably prepared by mixing the modules of such a modular system.

Pigment concentrates or coloring pastes can be obtained during the process where a liquid mixture containing a pigment, a polyurethane dispersant resin according to the invention and, possibly, a liquid diluent, is subject to shear. The pigmented dispersant resin of the invention can be used in combination with one or more other pigment dispersion aids and / or surfactants. Examples of suitable process equipment are ball mills, vortex mills, ultrasonic mills, basket mills, roller mills and high speed dissolvers. Inorganic or organic pigments or mixtures thereof can be used. Preferably, water is used as the liquid diluent. Instead of water or in addition to water, organic solvents such as glycol ethers, for example ethylene glycol, or higher homologues thereof, or ethylene glycol mono-n-butyl ether can be used.

The 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 contains at least 35% by weight, at least one pigment and more than 65% by weight. dispersing resin, calculated on the total weight of the pigment and dispersing resin.

The pigment composition of the invention can be used as a composition for mixing a pigment, leading to coating compositions with stably dispersed pigments. The pigment composition can be easily incorporated into coating compositions in which the pigments are stably dispersed. In addition, it is possible to obtain pigment compositions with a wide range of pigments. Pigment compositions make it possible to obtain paints having excellent properties and stability, especially in the case of difficult to disperse and stabilize pigments.

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

Mostly, the pigment particles in the composition exist in finely divided form. Thus, pigments typically have an average particle size in the range of 50 nm to 5000 nm. Preferably, the average particle size is not less than 80 nm, more preferably not less than 100 nm. Preferably, the average particle size is not 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 particles of the composition, for example, can be determined using electron microscopy. Since the average particle size of the pigments in the composition is actually the same as the average particle size of the pigments after they are suspended in the liquid, it is also possible to mix the pigment composition with the liquid medium and determine the average size of the pigment particles using dynamic light scattering.

Typically, organic pigments are organic color pigments and black pigments. Inorganic pigments can likewise be colored pigments (color, black and white pigments), as well as shiny pigments and inorganic pigments, which are commonly 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. The pigment is yellow 1, 3, 62, 65, 73, 74, 97, 120, 151, 154, 168, 181, 183 and 191; C.I. Pigment Purple 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, 180 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. Brown pigment 23 and 41;

antrantron pigments:

C.I. Pigment red 168;

anthraquinone pigments:

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

anthrapyrimidine pigments:

C.I. Pigment Yellow 108;

quinacridone pigments:

Pigment Orange 48 and 49; C.I. Pigment red 122, 202, 206 and 209; C.I. Pigment Purple 19;

chinophthalone pigments:

C.I. Pigment Yellow 138;

diketopyrrolopyrol 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;

flavantrone pigments:

C.I. Pigment Yellow 24;

indantrone 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;

isoindolinone pigments

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

isoviolantrone pigments:

C.I. Pigment Purple 31;

metal complex pigments:

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

perinone pigments:

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

perylene pigments:

C.I. Pigment black 31 and 32; C.I. Pigment red 123, 149, 178, 179, 190 and 224; C.I. Pigment violet 29;

phthalocyanine pigments:

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

pyrantron pigments:

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

pyrazoloquinazolone 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;

triarylcarboxylic 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 (Aldazine Yellow); C.I. Brown pigment 22.

Suitable examples of inorganic color pigments are:

white pigments:

titanium oxide (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);

color pigments:

chromium oxide; green chromium oxide hydrate; 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; blue manganese; ultramarine violet; cobalt violet, manganese violet; red iron oxide (C.I. Pigment red 101); cadmium sulfoselinide (C.I. Pigment red 108); cerium sulfide (C.I. Pigment red 265); molybdate red (C.I. Pigment red 104); ultramarine red; brown iron oxide (CI Pigment brown 6 and 7), mixed brown, spinel phases and diamond spar (CI Pigment brown 29, 31, 33, 34, 35, 37, 39 and 40), chromium titanium yellow (CI 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); chrome titanium yellow; spinel phases (C.I. Pigment yellow 119); cadmium sulfide and zinc cadmium sulfide (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 commonly used as fillers are transparent silica, silica flour, alumina, aluminum hydroxide, natural mica, natural and precipitated chalk and barium sulfate.

Shiny pigments are pigments coated with a metal having a monophasic or polyphase structure, the play of color of which is due to phenomena of interference, reflection and absorption. Examples are aluminum plates and aluminum, iron oxide and mica plates bearing one or more coatings, mainly metal oxides.

As indicated above, as the necessary ingredients, the pigment composition of the present invention contains a pigment and a dispersing resin. In the case of a solid, a suitable composition contains at least 35% by weight of at least one pigment and not more than 65% by weight. dispersing resin, calculated on the total weight of the pigment and dispersing resin. If the composition of the pigment is carbon black, it is preferable that the carbon black content of the pigment composition is in the lower part of the described range. So, if the pigment is carbon black, then the pigment composition preferably contains at least 40% by weight, more preferably at least 45% by weight. carbon black and not more than 60% by weight., preferably not more than 55% by weight. dispersing resin, calculated on the total weight of the pigment and dispersing resin. With other pigments, the pigment composition mainly contains at least 60% by weight, preferably at least 64% by weight, more preferably at least 68% by weight. and most preferably at least 70% by weight of at least one pigment and not more than 40% by weight, preferably not more than 36% by weight, more preferably not more than 32% by weight. and most preferably not more than 30% by weight. dispersing resin, calculated on the total weight of the pigment and dispersing resin. In an extremely preferred embodiment, the aforementioned weight ratios of the pigment and the dispersing resin are also applicable when calculating the total weight of the pigment composition.

The pigment composition may also contain other ingredients, additives or adjuvants commonly used in pigment formulations, such as organic solvents, wetting agents, anti-foaming agents, heat stabilizers, light stabilizers, antioxidants and other pigment dispersion adjuvants and / or surfactants.

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

The invention also relates to a method for producing a pigment composition comprising the steps of

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

b) optionally grinding the suspension and

c) drying the suspension.

As indicated above with respect to the pigment composition, the pigment used in the process may be an 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 pigments, or a mixture of inorganic and organic pigments. It is possible to use a wide variety of pigments in the process. Pigments can be introduced into the process as standard dried pigments. The grinding step serves to break down the agglomerates and to achieve the desired pigment particle size. Organic pigments are also available as so-called squeezed sediments. In the synthesis, organic pigments are formed in the form of very small crystals, called primary particles. The purpose of the synthesis of pigments is to obtain primary particles with a size that optimizes the properties of the application of the pigment, such as color strength, tone and brightness, transparency and turbidity and fluidity. The squeezed precipitate contains pigment, mainly in a disaggregated form. However, less energy is required to break down the agglomerates and to achieve the desired pigment particle size. In the process of drying the pressed pigment precipitate in the absence of a dispersing resin, the primary particles will join together to form aggregates and agglomerates. Therefore, when using an organic pigment in a process, it is possible and preferable to use an organic pigment in the form of a squeezed pigment deposit. When using a squeezed pigment precipitate, the usual mixing of a fluidized pigment suspension may be sufficient to achieve the desired particle size. In such cases, the step of grinding the suspension may not be necessary.

If additional liquid is needed to fluidize the mixture of pigment and dispersant resin, it is preferred that the liquid is water. Instead of water or in addition to water, organic solvents such as glycols or glycol ethers, for example ethylene glycol, or higher homologs thereof, or ethylene glycol mono-n-butyl ether can be used.

Optionally, the grinding step can be carried out using well-known grinding devices commonly used for grinding the particle size of pigments. Examples of suitable process devices are ball mills, vortex mills, ultrasonic mills, basket mills, roller mills and high-speed dissolvers. Mostly, grinding continues until the average particle size is in the range of 50 nm to 5000 nm. Preferably, the average particle size is at least 80 nm, more preferably at least 100 nm. Preferably, the average particle size is not more than 3000 nm, more preferably not more than 1500 nm, and most preferably not more than 1000 nm.

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

Spray drying and fluidized bed drying can produce rough, crushed coarser particles having an average particle size of from 50 to 5000 μm and, in particular, from 100 to 1000 μm. Depending on the process conditions, spray drying may also produce finely divided pigment compositions. Spray drying typically gives granules having an average particle size of <20 μm. Finely ground formulations are also obtained by drying in a paddle dryer and by evaporation followed by grinding.

The residual moisture content of the obtained dried pigment composition can vary significantly, while ensuring that the dried composition is a solid composition. The residual moisture content, for example, may be 15% by weight, calculated on the total weight of the pigment composition. In general, the residual moisture content should not exceed 15% by weight, preferably should not exceed 12% by weight. In many cases, the residual moisture content is even less than 5% by weight. If the pigment composition is intended for use in anhydrous systems, then preferably a low residual moisture content, for example, less than 2% by weight.

The pigment compositions of the present invention are outstanding in use because of their excellent color properties, especially with regard to color strength, brightness, tone and coating ability, and especially because of their mixing characteristics, i.e. they can be dispersed in the medium used with minimal 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, exhibit very good storage stability, are both economically and environmentally friendly with respect to packaging, storage and transportation, and they are universal in use.

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

Examples of materials that can be pigmented with the pigment compositions of the present invention include coatings, for example architectural coatings, industrial coatings, automotive coatings, radiation curable coatings, powder coatings; paints, including paints for the exterior of buildings and for building interiors, for example, wood paints, lime whitewash, adhesive paints, emulsion paints; solvent-resistant inks, such as offset printing inks, gravure toluene printing inks, textile printing inks, radiation-curable printing inks, water-resistant inks, including inkjet inks; color filters; building materials (water is usually added only after the building material and the pigment mixture were mixed dry), for example plaster, cement, concrete, cement mortar, gypsum, bitumen, sealants; cellulosic materials, for example paper, cardboard, thin cardboard, wood, and wood material that may be coated or otherwise finished; adhesives forming films protective colloidal substances that are used, for example, in the pharmaceutical industry; cosmetic products; plastics and detergents.

The pigment compositions of the present invention are very useful as miscible components in mixing or color matching systems. Based on their mixing characteristics for these purposes, they can be used directly in solid form. However, if necessary, they can be first converted to background paint, varnish mixes and coating paints (especially paints having a high solids content, “HS paints”), or even to highly pigmented coating pastes, which then form the components of the mixing system . The selection of the desired shade and, consequently, the mixing of paint components can be effectively visually controlled using a card paint system in a wide range of shades, based on color standards such as RAL, BS and NCS, or, preferably, with computer control, in which an unlimited range is achievable shades ("computer color matching"). The invention also relates to a coating composition containing at least one film-forming substance that is different from a polyurethane dispersant resin, at least one pigment and a pigment dispersant resin, where the pigment dispersant resin is a polyurethane dispersant resin, as described above. Preferably, the coating composition is an aqueous coating composition. For example, the coating composition may be a basic coating composition, preferably an aqueous base coating composition. The main coating composition is a color- and / or effect-transmitting coating composition, which is used in multilayer varnish systems having a transparent outer coating. Such multi-layer varnish systems are often used to protect and decorate automobiles and large vehicles. Also, the coating compositions may contain other ingredients, additives or adjuvants commonly used in coating compositions, such as dyes, leveling agents, organic solvents, wetting agents, anti-scratch agents, anti-foam agents, anti-deformation agents, heat stabilizers, light stabilizers, UV absorbers rays, antioxidants and fillers. It is also possible to use the pigment dispersant resins of the invention in combination with one or more other pigment excipients and / or surfactant.

The polyurethane dispersant resin of the invention is also suitable for dispersing hydrophobic resins in aqueous systems. Therefore, the invention also relates to the use of a dispersant in the dispersion process of hydrophobic resins in aqueous systems and aqueous compositions containing a polyurethane dispersant resin and at least one dispersed hydrophobic resin. Such compositions can advantageously be used as binders in aqueous two-component coating compositions.

Also, a polyurethane dispersant resin can be used to disperse other hydrophobic and / or difficult to disperse materials in water. Examples of such materials are additives and auxiliary substances, such as catalysts, ultraviolet absorbers, and light stabilizers.

Examples

Used raw materials:

Huntsman's Jeffamine M 1000 Polyalkylene Oxide Amine

Cardura E10 Glycidyl ester versatic acid from Resolution Performance Products

Tegomer D 3403 Diol containing polyalkylene oxide side groups from Tego Chemie Service GmbH

Tegomer D 3123 Diol containing polyalkylene oxide side groups from Tego Chemie Service GmbH

Pripol 2033 Uniqema Diol Based Higher Fatty Acid Dimer

Autowave Akzo Nobel Car Refinishes Modular Water Coating System

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

Autowave 666 Pure Autowave Module Containing Akzo Nobel Car Refinishes Acrylic Dispersion

Autowave 357 Akow Nobel Car Refinishes Autowave Red Toner Module

Autowave 00 Autowave White Toner Module by 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.

Viscosities are determined using a Brookfield viscometer.

Molecular weight is determined by gel permeation chromatography using polystyrene as a standard.

The dispersion of pigment dispersions is determined using a Hegman instrument.

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

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

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

Gloss is determined using a Byk-Garden gloss meter, and the results are presented in gloss units.

The color intensity values (C *) are determined according to the CIE LCh system.

Example 1

Obtaining a polyurethane dispersant resin according to the invention

347.5 g of Jeffamine M 1000 are placed in a reaction vessel equipped with a stirrer, thermocouple, heating jacket, reflux condenser and dropping funnel. The contents of the reaction vessel are heated to 120 ° C. under a layer of nitrogen, and 138.5 are added through a dropping funnel over 30 minutes. g Cardura E 10. The content of the reaction vessel is maintained at a temperature of 120 ° C for 4 hours, after which it is allowed to cool to room temperature. Then, the following components are added to the reaction vessel:

20.2 g 1,4-cyclohexanedimethanol

7.3 g neopentyl glycol

62.0 g 2-butanone

104.8 g of 4,4`-diisocyanate dicyclohexylmethane.

The reaction mixture is heated to 120 ° C and maintained at this temperature for 2 hours. 4 drops of dibutyl tin dilaurate are added 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 13.1 g of 10% by weight are added at this temperature. aqueous solution of acetic acid. Then, over 3 hours, while gradually cooling to room temperature, 1.575 g of demineralized water are added. A clear solution of a polyurethane dispersant resin in water is obtained. The alkylene oxide content in the resin is 56.2% by weight, the ethylene oxide content is 48.5% by weight. The tertiary amine content is 0.38 mmol / g.

Example 2

Obtaining a polyurethane dispersant resin according to the invention

The polyurethane resin is obtained according to the procedure described above in Example 1, using as starting compounds:

710.8 g Jeffamine M 1000

302.2 g Cardura E 10

58.1 g 1,4-cyclohexanedimethanol

125.0 g 2-butanone

187.0 g isophorondiisocyanate

8 drops of dibutyl tin dilaurate

3.082 g of demineralized water.

Acetic acid is not added to the polyurethane. A clear non-ionic solution of a polyurethane dispersant resin in water is obtained. The alkylene oxide content in the resin is 56.3% by weight, the ethylene oxide content is 48.8% by weight. The tertiary amine content is 24.7 mg KOH / g.

Example 3

Obtaining a polyurethane dispersant resin according to the invention

The polyurethane resin is obtained according to the procedure described above in Example 1, using as starting compounds:

726.2 g Jeffamine M 1000

253.4 g Cardura E 10

66.2 g 1,4-cyclohexanedimethanol

125.0 g 2-butanone

204.0 g isophorondiisocyanate

8 drops of dibutyl tin dilaurate

3.082 g of demineralized water

25 g 10% by weight. aqueous solution of acetic acid.

A clear solution of a polyurethane dispersant resin in water is obtained. The alkylene oxide content in the resin is 58.1% by weight, the ethylene oxide content is 50.2% by weight. The tertiary amine content is 15.1 mg KOH / g.

Example 4

Obtaining a polyurethane dispersant resin according to the invention

In a reaction vessel equipped with a stirrer, a thermocouple, a heating jacket, a reflux condenser and a dropping funnel, 778.8 g (0.74 mol) of Jeffamine M 1000 are placed. The contents of the reaction vessel are heated to 120 ° C. under a layer of nitrogen, and through a dropping funnel for 181.1 g (0.74 mol) of Cardura E 10 was added over 30 minutes. The contents of the reaction vessel were then kept at 120 ° C for 4 hours, after which they were allowed to cool to room temperature. Then, the following components are added to the reaction vessel:

71.0 g 1,4-cyclohexanedimethanol

125.0 g 2-butanone.

The reaction mixture is heated to 65 ° C. and 218.0 g of isophorone diisocyanate are added at this temperature. The reaction mixture is heated to 120 ° C and maintained at this temperature for 2 hours. Then 4 drops of dibutyl tin dilaurate are added and the reaction mixture is left at 120 ° C. for the next 2 hours. After that, 2-butanone was evaporated under reduced pressure, and 3.060 g of demineralized water was added over 3 hours while gradually cooling to room temperature. A clear non-ionic solution of a polyurethane dispersant resin in water is obtained. The alkylene oxide content in the resin is 62.3% by weight, the ethylene oxide content is 53.8% by weight. The tertiary amine content is 5.6 mg KOH / g.

Example 5

Obtaining a polyurethane dispersant resin according to the invention

The polyurethane resin is obtained according to the procedure described above in Example 1, using as starting compounds:

711.1 g Jeffamine M 1000

302.3 g Cardura E 10

50.8 g 1,4-cyclohexanedimethanol

6.7 g dimethylopropionic acid

125.0 g 2-butanone

179.0 g isophorondiisocyanate

8 drops of dibutyl tin dilaurate

3.060 g of demineralized water.

Acetic acid is not added to the polyurethane. A clear solution of a polyurethane dispersant resin in water is obtained. The alkylene oxide content in the resin is 56.9% by weight, the ethylene oxide content is 49.1% by weight. The tertiary amine content is 2.24 mg KOH / g, the carboxylic acid / carboxylate content is 0.04 mmol / g.

Example 6

Obtaining a polyurethane dispersant resin according to the invention

The polyurethane resin is obtained according to the procedure described above in Example 5, using as starting compounds:

711.4 g Jeffamine M 1000

302.4 g Cardura E 10

43.5 g 1,4-cyclohexanedimethanol

13.5 g dimethylopropionic acid

125.0 g 2-butanone

179.1 g of isophorondiisocyanate

8 drops of dibutyl tin dilaurate

3.060 g of demineralized water.

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

Example 7

Obtaining a polyurethane dispersant resin according to the invention

The polyurethane resin is obtained according to the procedure described above in Example 5, using as starting compounds:

707.0 g Jeffamine M 1000

300.6 g Cardura E 10

108.2 g. Hemp 2033

125.0 g 2-butanone

133.5 g of isophorondiisocyanate

8 drops of dibutyl tin dilaurate

3.060 g of demineralized water.

A clear solution of a polyurethane dispersant resin in water is obtained. The alkylene oxide content in the resin is 56.6% by weight, the ethylene oxide content is 48.9% by weight. The tertiary amine content is 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, 686.4 g of Tegomer D 3403, 348.4 g of the reaction product of 1 mole of cyclohexylamine and 2 moles of Caruda E 10, 125.0 g of 2-butanone are placed. These components are mixed until homogeneous and 215.2 g of isophorone diisocyanate are added. The reaction mixture is heated to 120 ° C under a layer of nitrogen and kept at this temperature for 2 hours. Then 8 drops of dibutyl tin dilaurate are added and the reaction mixture is left at 120 ° C. for the next 2 hours. After that, 2-butanone was evaporated under reduced pressure, and 2,331 g of demineralized water was added over 3 hours while gradually cooling to room temperature. A clear non-ionic solution of a polyurethane dispersant resin in water is obtained. The ethylene oxide content in the resin is 54% by weight. The tertiary amine content is 25.8 mg KOH / g.

Comparative Example A

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

368.8 g Tegomer D 3403, 507.5 g oleyl alcohol, 456.9 g diol sulfosuccinate, which is the reaction product of 1 mole of maleic acid, 2 moles of Caruda ^® E 10 and 1 mole of NaHSO are placed in a reaction vessel equipped as described above ₃ and 196.0 g of 2-butanone. The components are mixed and 420.5 g of isophorondiisocyanate are added via a dropping funnel. The reaction mixture is heated to 120 ° C and maintained at this temperature for 2 hours. Then, 0.5 g of dibutyl tin dilaurate was added and the reaction mixture was left at 120 ° C for the next 2 hours. The temperature is then lowered to 90 ° C. and evaporation is carried out under reduced pressure until all volatile solvents are completely removed. Then, over 3 hours, while gradually cooling to room temperature, 6.746 g of water are added. An aqueous solution of a polyurethane dispersant resin is obtained. The ethylene oxide content in polyurethane is 18.7% by weight.

Comparative Example B

Obtaining a polyurethane dispersant resin containing hydrophobic side chain groups.

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

354.0 g Tegomer D 3123

40.5 g Pripol 2033

43.5 g 1,4-cyclohe

26.0 g 2-ethylhesanol

90.0 g 2-butanone.

These components are mixed until homogeneous and 122.1 g of isophorone diisocyanate are added. The reaction mixture is heated to 110 ° C under a layer of nitrogen and maintained at this temperature for 2 hours. Then, 2 drops of dibutyl tin dilaurate were added to the reaction mixture, and the reaction mixture was left at 110 ° C. for the next 2 hours. After which, 2-butanone was evaporated under reduced pressure, and 1.328 g of demineralized water was added over 3 hours while gradually cooling to room temperature. A clear non-ionic solution of a polyurethane dispersant resin in water is obtained. The alkylene oxide content in the resin is 65% by weight, the ethylene oxide content is 55% by weight.

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

Table 1 Example The solids content in% weight. Viscosity in Pa · s pH Mn Mw one 26.8 0.24 7.2 4,700 8,050 2 28.3 0.50 9.7 4,140 6,280 3 28,4 0.21 7.7 4,420 7,060 four 29.3 0.42 9.8 4,690 6,550 5 28.5 0.98 8.3 4,060 5,950 6 29.7 1,08 7.2 3,810 5,940 7 27.8 0.60 9.9 3,400 5,450 8 34.2 1.30 7.4 6,050 10,050 BUT 26.0 0.55 6.9 1,760 2,850 AT 28.8 0.64 5.5 6,400 13,330

Example 9

Obtaining aqueous dispersions of hydrophobic polysyloephrine resins

The hydrophobic ester resin I is prepared by a standard etherification process from 134 g of trimethylolpropane, 282 g of cyclohexadimethanol and 308 g of hexahydrophthalic anhydride. An ester polysilane resin I is obtained having an OH value of 251 mg KOH / g and an acid value of 8.6 mg KOH / g.

The hydrophobic ester resin II is prepared by a standard etherification process from 141 g of trimethylolpropane, 249 g of 1,6-hexanediol and 324 g of hexahydrophthalic anhydride. An ester polysilane resin II is obtained having an OH value of 266 mg KOH / g and an acid value of 3.9 mg KOH / g.

Hydrophobic polysilicon ester resins I and II are mixed with the polyurethane dispersant resin from Example 4, obtaining a mixture of A, B and C:

Mixture A: 80 g of polystyrene ester resin I

20 g of the polyurethane dispersant resin of Example 4

25 g of 2-methoxypropyl acetate (diluent)

Mixture A has an OH value of 164 mg KOH / g

Mixture B: 90 g of polysilicon ester resin I

10 g of a polyurethane dispersant resin from Example 4

33 g of 2-methoxypropyl acetate (diluent)

Mixture A has an OH value of 171 mg KOH / g

Mixture C: 90 g of polysilicon ester resin I

10 g of a polyurethane dispersant resin from Example 4

25 g of 2-methoxypropyl acetate (diluent)

Mixture A has an OH value of 193 mg KOH / g

Mixtures A to C are mixed with commercially available polyisocyanate resins to give prototypes of clear coating compositions.

Isocyanate 1: Desmodur N 3600, 80% by weight. solution in 2-methoxypropyl acetate

Isocyanate 2: Bayhydur N 3100, 70% by weight. solution in 2-methoxypropyl acetate

Isocyanate 3: Bayhydur LS2150, 70% by weight. solution in 2-methoxypropyl acetate.

In a glass beaker mix such an amount of polysilicon resin that corresponds to 0.1 mol of OH and such an amount of isocyanate that corresponds to 0.1 mol of NCO.

Under stirring with a spatula, demineralized water is added until the viscosity is from 15 to 18 s (DIN cup 4).

The transparent composition is applied to the glass plates with a rod, obtaining films after drying with a thickness of about 60 microns. Transparent coating compositions and properties are shown below in table 2. VOC is the theoretical amount of volatile organic compounds in a transparent coating composition. The hardness of Persosa is expressed in seconds and is determined after 5 days at room temperature. In all cases, transparent films are obtained.

table 2 Mixture Isocyanate The solids content in% weight. VOC in g / l Watch stability Hardness Persosa BUT one 45 200 2 190 BUT 2 42 250 2 114 BUT 3 40 260 four 276 AT one 45 230 1,5 299 AT 2 42 280 1,5 200 AT 3 40 280 3 320 FROM one 45 200 one 150

The above results show that the dispersant resin of the invention is suitable for preparing aqueous dispersible hydrophobic resin compositions.

Example 10

Use of a dispersant resin to disperse pigments and coating compositions.

The following pigments were investigated:

Pigment 1: White - Kronos 2310 by Kronos

Pigment 2: Red - Ciba's Irgazin DPP Red Bo

Pigment 3: Cyan - Basi Heliogene Blue L7101F

Pigment 4: Purple - Bayer Quindo Violet RV6926

Mixtures of solutions of these pigments are prepared with the above-described aqueous pigment dispersant resins. The mixtures were dispersed in a Red Devil shaker. The results are shown below in table 3.

In addition, an aqueous coating composition for a primer is obtained.

Pigment plates with pigment 1 are obtained by grinding the following components:

11.86 g of a solution of polyurethane dispersant resin, as indicated in Table 3

5.97 g Water

0.28 g Propylene glycol

2.40 g Commercially available dispersant

70.02 g Pigment 1

9.46 g Water

Compositions for coating with pigment 1 are obtained by mixing the following components:

20.80 g of an aqueous binder dispersion containing polyacrylate and polyurethane, solids content of 42% by weight.

7.35 g Aqueous polyacrylate dispersion, solids content 40% by weight.

0.08 g of amine

13.09 g Water

3.17 g Co-solvent

0.30 g Clay thickener

14.62 g Water

1.06 g Thickener HEUR

1.75 g Water

30.43 g Pigment paste with pigment 1

1.95 g Co-solvent

5.40 g Water

Pigment plates with pigment 2 are obtained by grinding the following components:

33.51 g Polyurethane dispersant resin solution as indicated in Table 3

1.44 g Propylene glycol

0.18 g Commercially available dispersant

0.45 g Antifoam

46.12 g Pigment 2

18.29 g Water

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

19.94 g of an aqueous binder dispersion containing polyacrylate and polyurethane, solids content of 42% by weight.

7.05 g Aqueous polyacrylate dispersion, solids content 40% by weight.

0.08 g of amine

12.56 g Water

3.04 g Co-solvent

0.29 g Clay thickener

14.02 g Water

1.02 g Thickener HEUR

1.68 g Water

14.59 g Pigment paste with pigment 2

1.19 g Co-solvent

24.54 g Water

Pigment plates with pigment 3 are obtained by grinding the following components:

22.19 g of a solution of polyurethane dispersant resin, as indicated in Table 3

1.42 g Propylene glycol

0.44 g Antifoam

35.19 g Pigment 3

40.76 g Water

Compositions for coating with pigment 3 are obtained by mixing the following components:

25.21 g of an aqueous binder dispersion containing polyacrylate and polyurethane, solids content of 42% by weight.

8.91 g Aqueous polyacrylate dispersion, solids content 40% by weight.

0.10 g Amine

15.87 g Water

3.84 g Co-solvent

0.36 g clay thickener

17.72 g Water

1.28 g Thickener HEUR

2.12 g Water

11.13 g Pigment paste with pigment 3

0.98 g Co-solvent

12.48 g Water

Pigment plates with pigment 4 are obtained by grinding the following components:

21.51 g Polyurethane dispersant resin solution as indicated in Table 3

1.50 g Propylene glycol

4.00 g Commercially available dispersant

0.50 g Antifoam

40.00 g Pigment 4

32.49 g Water

Compositions for coating with pigment 4 are obtained by mixing the following components:

27.66 g of an aqueous binder dispersion containing polyacrylate and polyurethane, solids content of 42% by weight.

9.78 g Aqueous polyacrylate dispersion, solids content 40% by weight.

0.11 g of Amine

17.43 g Water

4.22 g Co-solvent

0.40 g Clay thickener

19.44 g Water

1.41 g HEUR Thickener

2.33 g Water

17.00 g Pigment paste with pigment 4

Thus, table 3 shows the properties of the obtained pigment plates and coating compositions.

From the data shown in table 3, we can conclude that the dispersion resins according to the invention of Examples 1 to 8 give pigment pastes and soil coating compositions having less flocculation and better dispersion than the pigment dispersion based on the comparative dispersant resin from comparative Example A, having a low content of polyalkylene oxide. Also with the hard-dispersed Quindo Violet (pigment 4), using the dispersant resin of the invention, excellent dispersion and flocculation stability were obtained.

In the case of the transparent pigment Heliogene Blue (pigment 3), using the dispersant resin of the invention, good transparency of the pigment paste was achieved. When used with this pigment, the comparative dispersant resin of Example A, the pigment paste was opaque. The comparative dispersing resin of Example B does not have hydrophobic side chain groups. Very low quality pigment paste was obtained with this resin in combination with a white pigment, which is usually easily dispersible. The paste showed strong flocculation, contained many lumps, and the dispersion of the paste was unsatisfactory. In the case of the dispersant resin of the invention from Examples 1 and 2, these problems were not encountered in combination with white pigment.

Example 11

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

17.566 parts by weight of Jeffamine M 1000 are placed in a reaction vessel equipped with a stirrer, thermocouple, heating jacket, reflux condenser and dropping funnel. The reactor is purged with nitrogen, and the contents are heated to 120 ° C. Then, over a period of 15 minutes, 4.083 parts by weight of Cardura E 10 was added to the reactor, after which the contents of the reactor were heated to 130 ° C and held at this temperature for 4 hours. After that, the contents of the reactor are cooled to 65 ° C.

Then, 1.604 parts by weight of 1,4-cyclohexanedimethanol are added to the reactor, after which 4.948 parts by weight of isophorone diisocyanate are added over 5 minutes. An exothermic reaction occurs. Washing the tubes, 2.790 parts by weight of methyl ethyl ketone are added to the reactor. The contents of the reactor are heated to boiling, about 120 ° C, and kept at boiling for 2 hours. The contents of the reactor are cooled to 115 ° C., 0.006 parts by weight of dibutyl tin dilaurate are added, and the reaction is continued for 2 hours at 120 ° C. The isocyanate content is below 0.1% by weight. The solvent, methyl ethyl ketone, is first evaporated at atmospheric pressure. The pressure is gradually reduced by evaporation to about 100 mbar in order to completely evaporate the methyl ethyl ketone.

The temperature of the contents of the reactor was lowered to 100 ° C. and 71.499 parts by weight of water were added over 2.5 hours. In the process of adding, the temperature of the contents of the reactor is gradually reduced to 30 ° C. After that, the contents of the reactor were cooled to room temperature and an aqueous solution of a dispersing resin was obtained.

The dispersant resin has a hydroxy value of 29.3 mg KOH / g, Mn 4.150, an alkylene oxide content of 62.2% by weight, an ethylene oxide content of 51.5% by weight, all properties are based on a dispersant resin that does not contain volatile components.

Comparative Example C

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

368.8 g of Tegomer D 3403, 507.5 g of oleyl alcohol, 456.9 g of diol sulfosuccinate, which is the reaction product of 1 mole of maleic acid, 2 moles of Caruda ^® E 10 and 1 mole of NaHSO are placed in a reaction vessel equipped as described above ₃ and 196.0 g of 2-butanone. The components are mixed and 420.5 g of isophorondiisocyanate are added via a dropping funnel. The reaction mixture is heated to 120 ° C and maintained at this temperature for 2 hours. Then, 0.5 g of dibutyl tin dilaurate was added and the reaction mixture was left at 120 ° C for the next 2 hours. The temperature is then lowered to 90 ° C. and evaporation is carried out under reduced pressure until all volatile solvents are completely removed. Then, over 3 hours, while gradually cooling to room temperature, 6.746 g of water are added. An aqueous solution of a polyurethane dispersant resin is obtained. The ethylene oxide content in polyurethane is 18.7% by weight.

Example 12

Obtaining a pigment composition according to the invention

Pressed precipitate pigment Ciba Irgazin Red BO containing 38% by weight. pigment, mixed with a solution of dispersing resin of Example 11 and fluidized in a dissolver, obtaining a liquid suspension of pigment. The amount of dispersant resin solution is calculated so as to achieve 17% weight. dispersing resin, calculated on the sum of the pigment and dispersing resin. The suspension was pulverized on a 7 liter scale using a pilot ECM mill and a pigment dispersion was obtained after 20 passes using 0.7-0.9 mm beads. The pigment suspension shows good grinding characteristics. The dispersion of the ground composition achieved after fluidization in a dissolver shows good pigment wettability. A low viscosity value is associated with a high water content in the suspension. Samples are spray dried in a Buchi mini-spray dryer with an inlet temperature of 132 ° C and an outlet temperature of 85 ° C. Feed 0.2 kg / h. No visible clogging of the valve and pressure increase was noted. The powder is dried to about 1% residual moisture. The final pigment composition is free-flowing powder.

Comparative Example D

Obtaining a comparative pigment composition

Example 12 is repeated, except that the dispersant resin solution of Example 11 is replaced with the dispersant resin solution of Comparative Example C. The pigment cake which has been squeezed out cannot be fluidized, which indicates unsatisfactory wetting of the pigment. Even when using an additional amount of a dispersing resin solution suitable for grinding, a pigment suspension did not form.

Examples 13 to 16 and Comparative Examples E and F

Obtaining compositions for coating

The pigment composition of Example 12 is examined as a mixing pigment in two different aqueous binder coating systems, Autowave 665 (Example 13) and Autowave 666 (Example 14). For research, an IKA RW20 stirrer with a 4 cm blade operating at 750-760 rpm was used. The pigment composition of Example 12 is added with stirring and maintaining the set speed for all 30 minutes. A sufficient amount of pigment composition is added to obtain a coating composition having a pigment content of 6.6% by weight. It is identical to the Autowave 357 toner used as a comparison (Comparative Example E).

The final coating composition has excellent fineness of the grinding value, and particles are not observed in the Hegman measurement test.

White concentrates are prepared by mixing coating compositions with a white Autowave 00 toner module.

Example 15

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

Example 16

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

Comparative Example F

The comparative coating composition of Example E is mixed with a white Autowave 00 toner module so that the ratio of the weight of the red pigment to the white pigment in the final mixture is 50:50.

Coating compositions were applied to Leneta 2A light transmittance cards using a K-Control coating machine and allowed to dry at room temperature overnight.

The paint depth properties of the Examples 13 and 14 are excellent. Compared to Comparative Example E, the gloss level is higher and has a bright, smooth looking color. The color purity value of the white concentrate is good.

The results are shown in Table 4.

Example Mixing properties Gloss (60 °) Gloss (20 °) Color tone (C ^* ) 13 excellent 72.9 36.9 72.06 fourteen excellent 71.3 32,7 71.72 E not applicable 64,2 14,4 69.45 fifteen not applicable 65,4 22.3 60.57 16 not applicable 71.0 29.7 60.75 F not applicable 65.8 18.9 63.24

Claims (24)

1. A polyurethane dispersant resin having a polyurethane backbone containing hydrophilic polyalkylene oxide side chain groups, the side chain groups being attached to the main polyurethane chain by covalent bonds, and wherein the polyalkylene oxide content of the polyurethane dispersant resin is at least 45 weight. % and not more than 80 wt.%, characterized in that the polyurethane additionally contains hydrophobic groups of the side chain, which are attached to the main polyurethane chain by forging the covariant relations. 2. The polyurethane dispersant resin according to claim 1, characterized in that the polyalkylene oxide is based on ethylene oxide, propylene oxide or a mixture thereof. 3. The polyurethane dispersant resin according to claim 1, characterized in that the hydrophobic groups of the side chain contain hydrocarbon groups having at least 4 carbon atoms. 4. The polyurethane dispersant resin according to claim 3, characterized in that the hydrophobic groups of the side chain contain hydrocarbon groups having no more than 30 carbon atoms. 5. The polyurethane dispersant resin according to claim 3 or 4, characterized in that the hydrocarbon groups are branched. 6. The polyurethane dispersant resin according to claim 1, characterized in that the polyurethane dispersant resin contains tertiary amino groups. 7. The polyurethane dispersant resin according to claim 6, characterized in that the tertiary amino groups are at least partially neutralized by an acid neutralizing agent. 8. The polyurethane dispersant resin according to claim 1, characterized in that the main chain of the polyurethane resin practically does not contain ester bonds capable of hydrolysis. 9. The polyurethane dispersant resin according to claim 1, characterized in that the hydrophilic groups of the side chain based on polyalkylene oxide were introduced into the polyurethane using a compound having at least two groups capable of reacting with isocyanate and a side polyalkylene oxide group. 10. The polyurethane dispersant resin according to claim 9, characterized in that the compound having at least two groups capable of reacting with an isocyanate and a side polyalkylene oxide group is a compound of formula (I), or (II), or a mixture thereof ,

where R is the residue of the monoepoxide compound after reaction with an amino group, R ¹ is selected from C ₁ to C ₇ alkyl groups, n is from 0 to 25, m is from 1 to 50, and n + m≤50. 11. The polyurethane dispersant resin of claim 10, characterized in that R contains a hydrocarbon group having from 4 to 30 carbon atoms. 12. A coating composition comprising a polyurethane dispersant resin according to any one of the preceding claims 1 to 11 and particles. 13. The composition according to p. 12, characterized in that the particles are pigment particles. 14. The composition according to p. 12 or 13, characterized in that the composition is liquid. 15. The composition according to item 13, wherein the composition is solid. 16. The composition according to p. 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 the pigment and 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 further comprises
a) at least one organic film-forming binder that is different from the polyurethane dispersant resin according to claims 1 to 11, and,
b) at least one pigment. 19. The method of obtaining a composition according to item 13, comprising the steps for shearing the liquid mixture containing the pigment, at least one dispersing agent and, optionally, a liquid diluent, characterized in that the polyurethane dispersing resin according to any one of the preceding paragraphs. 1-11 is used as a dispersing agent. 20. The method according to claim 19, characterized in that the liquid diluent is water. 21. The method of obtaining the composition according to clause 15, comprising the following stages:
a) mixing the composition containing the pigment and dispersing agent, possibly with the addition of water or an organic diluent, with the formation of a fluidized suspension of the pigment,
b) optionally grinding the suspension and
c) drying the suspension,
characterized in that the polyurethane dispersant resin according to any one of the preceding claims 1 to 11 is used as a dispersing agent. 22. The method according to item 21, wherein the pigment is an organic pigment, presented in the form of a pressed precipitate. 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 a dispersant resin according to one of the preceding claims 1 to 11 to obtain a composition for mixing pigment.