Phosphoric esters and their use as dispersants
Patent References 3076011 3112335 Manufacture of low molecular weight block copolymers of vinyl or diene monomers and alkylene oxides Pigment concentrates for resins Pigment dispersions, processes for their preparation and their use Aqueous, hard water-resistant wetting agent and detergent composition, and the preparation and use thereof in textile pretreatment Dyeable BMC molding compounds Polyadducts of alkylene oxide and styrene oxide with aryl alkanols Phosphoric acid esters, method of producing them, and use thereof as dispersants Phosphoric acid esters, method of producing them, and use thereof as dispersants Inventors
AssigneeApplicationNo. 10853763 filed on 05/25/2004US Classes:106/476, Organic material containing, e.g., wax, paraffin, etc.106/503, Sulfur or phosphorus containing516/33, The material primarily contains inorganic material (e.g., chrome yellow, sodium nitrite)516/34, The inorganic material primarily contains compounds containing both silicon and oxygen, or both aluminum and oxygen, or combinations thereof (e.g., silica (SiO2) organosol*, silica alcosol, talc, clay)516/77, Aqueous continuous liquid phase and discontinuous phase primarily solid (e.g., water based suspensions, dispersions, or certain sols*, of natural or synthetic ester-wax, beeswax, carnauba wax; or latex dispersion)516/81, The material is substantially pure silica sol516/90, The metal present in the greatest amount is titanium, zirconium, or hafnium516/93, The metal present in the greatest amount is aluminum516/199, The agent contains organic compound containing phosphorus516/908, The compound contains repeating -(OCnH2n)- (i.e., repeating unsubstituted oxyalkylene)524/141, Aryl group524/513, With polycarboxylic acid or derivative and a polyol at least one of which is saturated or with solid polymer thereof524/522, Solid polymer derived from carboxylic acid-containing monomer524/115, Phosphorus organic compound DNRM524/136, Pentavalent phosphorus atom directly bonded to at least one oxygen atom525/333.3, Polymer derived from aromatic hydrocarbon monomer, e.g., styrene, etc.525/340, Chemical treating agent contains a phosphorus atom558/186, Plural ether oxygens or thioether sulfurs attached indirectly to the phosphorus by acyclic nonionic bonding526/932THICKENER OR DISPERSANT FOR AQUEOUS SYSTEMExaminersPrimary: Metzmaier, Daniel S.Attorney, Agent or FirmForeign Patent References
International ClassesC08K 5/372C08K 5/52 B01F 17/14 B01F 3/12 C07F 9/09 DescriptionFIELD OF THE INVENTION The present invention relates to phosphoric esters a) obtainable by reacting an ω-hydroxy-functional oligo- or poly(alkyl)styrene with an alkylene oxide to give a poly(alkyl)styrene-block(b)-polyalkylene oxide copolymer and then convertingsaid copolymer into the corresponding phosphoric esters with a phosphorus compound which forms phosphoric esters, up to 100% of the terminal hydroxyl groups of said poly(alkyl) styrene-block(b)-polyalkylene oxide copolymer being reacted to givephosphoric ester groups and the phosphorus atoms, depending on the chosen stoichiometric proportions, being mono- and/or diesterified, or b) based on polystyrene oxide-block(b)-polyalkylene oxide copolymers obtainable starting from a mono-functionalstarter alcohol by sequential addition of styrene oxide and of an alkylene oxide in accordance with the desired sequence and chain length of the individual segments and subsequently by reaction to give the corresponding phosphoric esters, in the mannerdescribed in a). The invention relates, furthermore, to the preparation of these phosphoric esters and to their use as dispersants for pigments and fillers. BACKGROUND OF THE INVENTION For the dispersion of fillers and pigments in liquid media it is common to operate with the aid of dispersants in order to reduce the mechanical shear forces required for effective dispersion of the solids and at the same time to obtain very highdegrees of filling. The dispersants support the disruption of agglomerates, wet and/or cover, as surface-active materials, the surface of the particles to be dispersed, and stabilize the particles against unwanted reagglomeration. Dispersants have become indispensable for the preparation, for example, of highly concentrated color pastes for the paints and coatings industry, for the preparation of pigment concentrates (masterbatches) for the coloring of articles made ofplastic, and for the processing of unsaturated polyester resins (UP resins) which comprise large amounts of calcium carbonate or aluminum hydroxide (ATH) as fillers. The combination of very high degrees of filling in association with a very low viscosity is of particular interest for the producers and users of these products on primarily economic grounds. In the case of the fillers, these commonly constitutethe least expensive formulating component; pigment concentrates are intended by the plastics processor to be used for coloring in very highly concentrated form--that is, as far as possible without additional carrier materials. Phosphoric esters and their use as dispersants are known and can be found in the prior art. For instance, U.S. Pat. No. 4,720,514 describes phosphoric esters of a range of alkylphenol ethoxylates, which can be used with advantage to formulateaqueous pigment dispersions. Phosphoric esters for similar use are described in EP-A-0,256,427, U.S. Pat. No. 5,130,463 and U.S. Pat. No. 5,151,218 report phosphoric esters based on hydroxy-terminated polyaddition products and polycondensationproducts, which are used for the preparation of highly filled polyester molding compounds, especially for SMC and BMC formulations (SMC=sheet molding compounds; BMC=bulk molding compounds). Bifunctional phosphoric esters prepared by theMannich-Moedritzer reaction, and their adsorption characteristics on calcium carbonate, are described in J. Appl. Polym. Sci. 65, 2545 (1997). The known phosphoric esters, however, have the disadvantage that in general they are not universally applicable since there is in many cases a lack of adequate compatibility between the dispersing additive and binder or between the dispersingadditive and the surrounding medium (aqueous or solvent-containing formulations). The chemical composition of the phosphoric esters also has a large part to play: in aqueous formulations it is preferred to use only those phosphoric esters whose moleculecarries no additional hydrolyzable functional groups, such as ester or urethane groups. Frequently, high levels of dispersing additives are required in order to suppress the incidence of agglomerates; the degrees of filling which can be achieved areunsatisfactorily low, the stability of the dispersions and thus the permanence of the viscosity is often inadequate, and flocculation and aggregation cannot always be avoided, possibly resulting in visible separation and in flow defects and surfacedefects. BRIEF SUMMARY OF THE INVENTION It is therefore an object of the present invention to overcome a large number of the above disadvantages and in so doing to achieve not only the viscosity reduction of highly filled dispersions that is important for processability but alsoimproved compatibility with the surrounding medium. This object is surprisingly achieved through the use of phosphoric esters of amphiphilic block copolymers having the characteristic structural feature of a poly(alkyl)styrene segment and/or a polystyrene oxide segment to which a polyalkyleneoxide segment is attached. The invention accordingly provides phosphoric esters of the general formula I ##STR00002## x is 1 or 2, n is a number from 2 to 18, m and o are each a number from 2 to 100, k is a number from 2 to 4, R'' is H or a linear or branched alkyl radicalwhich may if desired be substituted by additional functional groups, and R' is an alkyl, alkaryl, alkenyl or sulfopropyl radical. DETAILED DESCRIPTION OF THE INVENTION Preferably R''=H. R' is commonly derived from an alcohol R'OH which functions as the starter alcohol for the polymerization of the styrene oxide and alkylene oxide. Examples of the radicals R' are the methyl, butyl, stearyl, allyl, hexenyl, nonylphenyl and oleyl radicals. Methyl and butyl radicals are preferred for R'. Where n=2 the polyether radical contains exclusively ethylene oxide units. Where n>2, the polyether radical consists of ethylene oxide units and, proportionally, of oxyalkylene units whose carbon number is between 3 and 18. In this case ncan adopt the value of a fractional number between 2 and 18. Preferably, the oxyalkylene block consists of ethylene oxide units, with the additional presence if desired of oxybutylene units in addition to the oxypropylene units. Oxyalkylene unitshaving a carbon number of from 4 to 18 are preferred when, in addition, it is desired for the product to have oleophilic properties. The average molecular weight of the phosphoric esters of the invention lies within the range from 300 to about 15,000 g/mol, preferably from 500 to 5000 g/mol. It can be determined with great ease by the customary methods of polymer analysis,both for the phosphoric esters and for the amphiphilic block copolymers. The ratio of m to o is from 1:50 to 50:1, preferably from 1:10 to 10:1 and, with particular preference, from 1:2 to 10:1. Examples of suitable phosphoric esters are: ##STR00003## Starting materials used to prepared the phosphoric esters of the invention are, accordingly, amphiphilic block copolymers of the general structures: ##STR00004## respectively, where the radicals R'' and R' and the indices m, k, n and o are asdefined above. These block copolymers are prepared by reacting the terminal hydroxyl group with a phosphorus compound which forms phosphoric esters, to give the phosphoric esters of the invention. Block copolymers of this kind are described, for example, in DE-A-41 34 967. The polystyrene-b-polyalkylene oxide copolymers of type A-B are prepared by first subjecting styrene to free-radical polymerization in the presence of sufficientamounts of an initiator and of an amount, corresponding to the desired chain length, of a chain regulator which carries not only a mercapto group but also another functional group having an active hydrogen radical, generally a hydroxyl group, andsubjecting the resulting polymer to an addition reaction at temperatures from 20 to 180° C. with alkylene oxide until the desired molecular weight in the block B is reached. The corresponding polystyrene oxide-b-polyalkylene oxide copolymers are prepared, starting from the starter alcohol R'OH, by subjecting the corresponding alkylene oxides to a sequential addition reaction in accordance with the desired sequenceand chain length of the individual segments so as to give a blocklike structure. Both synthetic routes lead to a amphiphilic block copolymers having a terminal hydroxyl group, both including, as an additional, characteristic structural element, a hydrophobic segment composed of aromatic groups. The processes described makeit possible in a simple manner to adapt the chain lengths m and o of the individual segments, the overall molecular weight and the ratio m/o of aromatic to nonaromatic segments to the technical requirements of the particular application. For instance,products employed for applications in aqueous systems are preferably those whose polyalkylene oxide segment is composed of ethylene oxide units. Conversely, products having a relatively high proportion of styrene units and/or styrene oxide units haveproven particularly suitable for dispersion processes in a very hydrophobic environment, such as, for example, paraffin oils, or in a polyolefin melt. The reaction to give the phosphoric esters of the invention takes place by reaction of the terminal hydroxyl groups with a phosphorus compound which forms phosphoric esters, in a manner known per se. Examples of suitable phosphorus compounds arephosphorus pentoxide, phosphoryl chloride or polyphosphoric acids of the general formula Hn 2PnO.sub.3n 1. For the preparation of the phosphoric esters it is particularly preferred to employ a commercially available polyphosphoric acid (Merck)having a content of about 85% P4O.sub.10. The reaction generally takes place without solvent at temperatures from about 80 to 100° C. To remove any traces of moisture present it is possible first of all to remove residues of water from thesystem using an inert solvent, such as toluene or xylene, for example, prior to the reaction with the polyphosphoric acid. Alternatively, in principle, the reaction can be carried out in the presence of solvents or solvent mixtures. This is alwaysadvantageous when the phosphoric esters of the invention have to be formulated in inert solvents or solvent mixtures in accordance with their subsequent use. The extent of esterification of the terminal hydroxyl group of the amphiphilic block copolymers which is the target of esterification in the esterification reaction is preferably from 50 to 100%; with particular preference, esterification isquantitative. Depending on the amount of phosphorus compound which forms phosphoric esters, employed relative to the hydroxyl equivalent of the block copolymers, the products of the esterification are alternatively preferably monoesters, diesters, ormixtures of monoesters and diesters. Depending on the pH of the medium employed, the phosphoric esters of the invention may also be present in partially or fully neutralized form. The dispersants can either be applied directly to the solids that are to be dispersed or else can be added to the aqueous and/or organic medium. They can be distributed in pure form or as a masterbatch in relatively high concentration in anorganic medium. It is of course also possible to employ the dispersants to be used in accordance with the invention together with further auxiliaries or dispersants, such as, for example, with the stearates known as dispersants. Appropriate solids are mineral fillers, such as talc, calcium carbonate, dolomite, mica, wollastonite, kaolin, and mineral flame retardants, such as aluminum hydroxide or magnesium hydroxide. Suitable pigments are carbon black or titaniumdioxide, the latter also being employable in finely divided form as a UV protectant in cosmetic formulations. Further dispersible solids are chemical blowing agents, such as azodicarbonamide, or mixtures of solid acids and carbonates. The dispersants to be used in accordance with the invention can also be employed for dispersing ceramic materials in organic media, such as, for example, finely divided alumina, silicon carbide or silicon nitride. Suitable organic media include polyethylene, polypropylene, polystyrene, polyamides, polyesters, poly (meth)acrylates, polyvinyl chloride, unsaturated polyesters, and liquid paraffins. The dispersants of the invention are particularly suitable for enhancing the distribution of finely divided solids in elastomers, thermoplasts, thermosets and polymer blends. The phosphoric esters of the invention have proven particularly suitable as dispersants for the preparation of highly filled SMC and BMC molding compounds. SMCs (sheet molting compounds) and BMCs (bulk molding compounds) consist of unsaturatedpolyester resins, a thermoplastic component, glass fibers, and fillers. The unsaturated polyester resin and the thermoplastic component (polystyrene is frequently used as the thermoplastic component) are usually dissolved in monomeric styrene which, inthe course of processing by compression or injection molding, cures and forms a three-dimensional network structure with the unsaturated polyester resin. The addition of glass fibers leads to high tensile strength and rigidity; the fillers guaranteehigh compressive strength and are responsible, moreover, for good dimensional stability and low thermal expansion. With the phosphoric esters of the invention a very low viscosity is achieved even at very high degrees of filling. The formulations feature absolute freedom from inhomogeneities and a high level of stability on storage. In addition, the phosphoric esters of the invention can be used to prepare aqueous pigment pastes. For this purpose, use is made of from 0.1 to 200% by weight of the phosphoric esters, preferably from 0.5 to 100% by weight (based on the weightof the pigments). In the case of use in accordance with the invention the phosphoric esters can either be mixed beforehand with the pigments to be dispersed or else can be dissolved directly in the aqueous or solvent-containing dispersion medium priorto or simultaneously with the addition of pigments and any other solids. Examples of pigments which can be mentioned in this context are organic and inorganic pigments, including carbon blacks. As inorganic pigments mention may be made by way of example of titanium dioxides and iron oxides. Examples of organic pigments which may be considered are azo pigments, metal complex pigments, anthraquinonoid pigments, phthalocyanine pigments,polycyclic pigments, especially those of the thioindigo, quinacridone, dioxazine, pyrrolopyrrole, naphthalenetetracarboxylic acid, perylene, iso-amidolin(on)e, flavanthrone, pyranthrone or isoviolanthrone series. With particular preference, thedispersing additives of the invention are suitable for preparing aqueous carbon black (gas black) pastes. Examples of fillers which can be dispersed in aqueous coating materials are those, for example, based on kaolin, talc, other silicates, chalk, glass fibers, glass beads, or metal powders. Suitable coating systems in which the pigment pastes of the invention can be incorporated are any desired aqueous 1- or 2-component coating materials. Examples which may be mentioned are aqueous 1-component coating materials, such as those basedon alkyd, acrylate, epoxy, polyvinyl acetate, polyester or polyurethane resins, or aqueous 2-component coating materials, examples being those based on hydroxyl-containing polyacrylate or polyester resins with melamine resins or, if desired, blockedpolyisocyanate resins as crosslinkers. Similarly, polyepoxy systems may also be mentioned. In the examples below, the preparation of the compounds to be used in accordance with the invention is described first of all. This is followed by performance examples demonstrating the properties of the compounds to be used in accordance withthe invention and, for comparison, properties obtainable with some prior art products. It is obvious and conventional to the skilled worker that these examples represent merely a selection of the possibilities which exist and are in no way to be regarded as a limitation. PREPARATION EXAMPLES 1) Preparation of polystyrene-b-polyalkylene oxide copolymers (in analogy to DE-A-41 34 967, not in accordance with the invention) as starting materials for the preparation of the corresponding phosphoric esters of the invention a) Preparation of a polystyrene-b-polyalkylene oxide copolymer (in analogy to DE-A-41 34 967) 100 g of xylene are heated to 120° C. under a nitrogen atmosphere in a reactor which is fitted with a stirrer. Over the course of 3 hours, while maintaining the temperature of 120° C., a mixture of 1350 g (about 13 mol) ofstyrene, 78.1 g (1 mol) of 2-mercaptoethanol, 4.1 g of azodiisobutyronitrile and 310 g of xylene is added. After the end of the addition, reaction continues for about 15 minutes; subsequently, 0.16 g of methylhydroquinone is added. Excess monomer, xylene and residues of 2-mercaptoethanol are removed by distillation in vacuo and the colorless, viscous liquid which remains is finally diluted with xylene to a solids content of about 80%. The molecular weight Mn determined from the hydroxyl number is 700 g/mol. The value for the molecular weight as determined by vapor pressure osmometry is 720 g/mol. The solution of 700 g (about 1 mol) of the ω-hydroxy-functional polystyrene in 175 g of xylene and 35.0 g of potassium methylate (about 0.5 mol) are placed in a thoroughly dried stainless steel reactor which is additionally fitted with astirrer. Azeotropic distillation is used to remove both traces of water and methanol together with xylene. Subsequently, a temperature of 80° C. is established and about 2000 g of ethylene oxide (about 45.5 mol) are added with stirring at arate such that the internal reactor temperature does not exceed 85° C. and the pressure does not exceed 6 bar. After all of the ethylene oxide has been introduced, the temperature is held at 80° C. until a constant pressure indicates theend of the subsequent reaction. 100 g of water are added to the resulting product, which is then brought to a pH of from 6 to 7 with 30% phosphoric acid. The water is removed by azeotropic distillation in vacuo, and the salt which precipitates isremoved by filtration. The molecular weight determined from the hydroxyl number, at an assumed functionality of 1, is 2650; the gel permeation chromatogram shows only one maximum and gives a value of 3100 for Mn (calibration against PS); a value of 1.14 is obtained forthe ratio Mw/Mn. b) Preparation of the phosphoric ester 2650 g (corresponding to 1 OH equivalent) of the block copolymer are placed in the reactor, about 50 ml of toluene are added, and this initial charge is heated to 120° C. A vacuum is applied to remove all of the volatile fractions,especially water which may be present in the product, from the reaction chamber by distillation. After blanketing with nitrogen, the temperature of the contents is stabilized at 80° C. and 85 g of liquid polyphosphoric acid (0.25 molP4O.sub.10; manufacturer: Merck; purity calculated as P4O10: about 85%) are added. After 2 hours the reaction is at an end. The acid number of the resulting material is 41 mg of KOH/g. An aliphatic hydroxyl group can no longer be detected in the 1H-NMR spectrum. Table 1 shows examples of some phosphoric esters based on some polystyrene-b-polyalkylene oxide copolymers, as obtained by the above preparation process. The table indicates the molecular weights of the polystyrene segment and the chemicalnature and molecular weight of the corresponding alkylene oxide. TABLE-US-00001 TABLE 1 Mn Mn Phosphoric (polystyrene (polyalkylene Alkylene ester segment)1 oxide segment)1 oxide 1A 700 2000 EO2 2A 700 1000 EO 3A 1000 1000 EO 4A 1000 1000 EO/PO3 (1:1)4 5A 1000 4000 EO 6A 400 1000 EO7A 400 1800 EO 1The molecular weight is calculated from the determination of the hydroxyl number 2EO = ethylene oxide 3PO = propylene oxide 4Addition of a mixture of EO and PO; 1:1 denotes the molar ratio of EO to PO 2) Preparation of polystyrene oxide-b-polyalkylene oxide copolymers (not in accordance with the invention) as starting materials in the preparation of the corresponding phosphoric esters of the invention 128 g (1.72 mol) of butanol and 12.2 g (0.17 mol) of potassium methylate are placed in a reactor under a nitrogen atmosphere. After careful flushing with ultrapure nitrogen, this initial charge is heated to 110° C. and 854 g (7.1 mol) ofstyrene oxide are added over the course of one hour. After a further two hours the addition reaction of the styrene oxide is at an end, evident from a residual styrene oxide content of less than 0.1% (GC). Subsequently, 2847 g (64.6 mol) of ethyleneoxide are metered into the reactor at a rate such that the internal temperature does not exceed 120° C. and the pressure does not exceed 6 bar. After all the ethylene oxide has been introduced, the temperature is held at 115° C. until aconstant manometer pressure indicates the end of the subsequent reaction. Finally, the unreacted monomers are removed in vacuo at from 80 to 90° C. The resulting product is neutralized using phosphoric acid and the water is removed by distillation, and the resultant potassium phosphate is removed by filtration together with a filtering aid. The molecular weight determined from the hydroxylnumber (Mn/OH number), at an assumed functionality of 1, is 1950. b) Preparation of the phosphoric ester The preparation of the phosphoric ester takes place as described under 1b). Table 2 shows examples of some phosphoric esters based on polystyrene oxide-b-polyalkylene oxide copolymers, as obtained by the above preparation process. The table indicates the molecular weights of the polystyrene segment and the chemicalnature and molecular weight of the corresponding alkylene oxide. TABLE-US-00002 TABLE 2 Phosphoric Mn (polystyrene Mn (polyalkylene Alkylene ester oxide segment)1 oxide segment)1 oxide 1B 450 1500 EO2 .sup. 2B3 450 1500 EO 3B 630 1100 EO/BO4 (3:1)51The molecular weight iscalculated from the determination of the hydroxyl number 2EO = ethylene oxide 3Block structure by way of 1. ethylene oxide, 2. styrene oxide 4BO = butylene oxide 5Addition of a mixture of EO and BO; 3:1 denotes the molar ratio of EOto BO Performance Examples The effectiveness of the dispersants to be used in accordance with the invention is examined in accordance with various methods which describe typical applications in the plastics or coatings sector. Method 1: The fillers (or pigments) are treated with a solution of the test dispersant in toluene. The toluene is then distilled off and the surface-treated material is dried in vacuo. The solids coated in this way are ground in an ultracentrifugal mill(screen size 0.5 mm) in each case to the same agglomerate size. Subsequently, the ground solids are dispersed in liquid paraffin (30 cP) using a mizer disk first for 2 minutes at 2000 rpm and then 3 minutes at 4000 rpm. For the experiments inaccordance with Method 1 calcium carbonate and aluminum hydroxide are coated, specifically calcium carbonate (CaCO3) with 2% by weight of dispersant and aluminum hydroxide (ATH) with 1% by weight of dispersant. The viscosities are measured with a Brookfield spindle viscometer (model LVT) at 23° C. and a rotary speed of 30 rpm with spindles of size No. 3 or No. 4. Table 3 indicates the viscosities of the liquid paraffin dispersions filled withthe corresponding solids. TABLE-US-00003 TABLE 3 Level of Phosphoric ester Filler filling, % Viscosity/mPas -- ATH/CaCO3 45 n.d. 1A CaCO3 55 720 3A CaCO3 55 410 3A ATH 65 660 6A CaCO3 55 520 Stearic acid CaCO3 55 6900 1B CaCO3 55 560 3BCaCO3 55 820 n.d. = not determinable: dispersion highly viscous to solid Method 2: The fillers are added to a defined mixture which comprises not only the other formulating constituents but also the dispersant, using a stirring motor with a dispersing disk (φ50 mm) at a speed of rotation of about 1000 (rpm). For theperformance experiments, mixtures are chosen comprising: 60 parts of unsaturated polyester resin (Palapreg P 17-02 or Palapreg P 14-01; manufacturer: BASF) 40 parts of thermoplastic component (Palapreg H 814-01: polystyrene, dissolved in styrene, orPalapreg H 850-01: polymethyl methacrylate, dissolved in styrene; manufacturer: BASF) 4.5 parts of zinc stearate 1.5 parts of t-butyl perbenzoate 180 parts of filler (calcium carbonate/Millicarb OG, manufacturer: Omya or aluminum hydroxide/Martinal ON310; manufacturer: Martinswerke) and X parts of phosphoric esters of the invention. In this case the viscosities are measured with a Brookfield spindle viscometer (model DV-I) at 23° C. and a rotary speed of 50 rpm with a spindle of type RVT-7. The viscosities are measured after a storage period of 10 minutes. Tables 4to 7 show the viscosities of the various formulations, corresponding to the above formulation variants. In all cases the extent of reduction in viscosity obtainable with the dispersion of the invention is significant. TABLE-US-00004 TABLE 4 (UP resin: Palapreg P 17-02/thermoplastic component: polystyrene/filler:calcium carbonate) Phosphoric ester Amount/X parts Viscosity (mPas) -- -- 81000 2A 1.8 29000 3A 1.8 44500 5A 1.8 51500 6A 1.8 21000 7A 0.9 28500 7A1.8 18000 7A 2.7 16000 1B 1.8 18500 TABLE-US-00005 TABLE 5 (UP resin: Palapreg P 14-01/thermoplastic component: polystyrene/filler:calcium carbonate) Phosphoric ester Amount/X parts Viscosity (mPas) -- -- 120000 4A 1.8 28500 7A 1.8 21000 7A 2.7 18000 1B 1.8 19500 2B 1.8 19000 TABLE-US-00006 TABLE 6 (UP resin: Palapreg P 17-02/thermoplastic component: polystyrene/filler:ATH Phosphoric ester Amount/X parts Viscosity (mPas/10 rpm) -- -- 240000 4A 1.8 50500 7A 1.8 33000 .sup. 7A1 5.2 255000 1B 2.7 19000 3B 1.821000 1Formulation contains 350 parts of ATH/5.2 parts correspond in this way to 1.5% based on filler TABLE-US-00007 TABLE 7 (UP resin: Palapreg P 17-02/thermoplastic component: polymethyl methacrylate/filler:ATH) Phosphoric ester Amount/X parts Viscosity (mPas) -- -- 54000 1A 1.8 30000 7A 1.8 27000 2B 1.8 19000 Method 3: Preparation of pigment pastes To prepare the pigment pastes, the dispersing additives are dissolved beforehand 40% strength in water, mixed with water and, if desired, with antifoams, and then the pigments are added. The dispersion takes place following the addition ofgrinding media (glass beads 2 to 3 mm, same volume as the pigment paste) for one (titanium dioxide) or two hours (other pigments) in a Skandex vibrator with air cooling. Formulation of the white pastes The white pastes are formulated as follows (amounts in % by wt.): 16.4 Water 12.3 Additive solution, 40% strength 1.0 Defoamer (e.g., Tego Foamex 810, Tego Chemie Service GmbH) 70.0 Titanium dioxide 2160 (Kronos) 0.3 Aerosil A 200 (fumed silica,Degussa) Formulation of the black pastes The black pastes are formulated as follows (amounts in % by wt.): 60.3 Water 22.3 (Dispersing) additive solution, 40% strength 1.0 Defoamer (e.g., Tego Foamex 810, Tego Chemie Service GmbH) 1.4 2-Amino-2-methylpropanol (Angus) 15.0 Pigmentarycarbon black FW 200 (Dugussa) Test coating materials Transparent stoving enamel based on a modified alkyd resin (amounts in % by wt): 70.88 Alkyd resin Resydrol VWA 5477, 40% strength (Hoechst) 0.14 Defoamer (e.g. Byk 020, Byk-Chemie) 0.68 Thickener Bentone SD 1 (Rheox) 8.24 Melamine resin MaprenalMF 900 (Hoechst) 0.14 Triethanolamine 19.10 Water 0.68 Defoamer Additol XW 395 (Hoechst) 0.14 Leveling agent Additol XW 329 (Hoechst) Introduce item 1 and add the other components with stirring. Transparent emulsion varnish 97.0 Acrylate dispersion Neocryl XK 90 (Zeneca) 3.0 Texanol (ester alcohol, Eastman) To prepare paints with gray pigmentation, 40.0 g of transparent enamel or varnish, respectively, 14.2 g of white paste and 2.65 g of black paste are added, and the mixture is homogenized at 1500 rpm for 5 minutes. The samples are knife-coatedonto aluminum panels in a wet film thickness of 100 μm and are either stoved at 150° C. for 15 minutes following a flash-off time of 20 minutes (stoving enamel) or dried at room temperature (emulsion paint). Test of paste stabilities To determine the paste stabilities, the achievable initial viscosities and the viscosities after storage at 50° C. for four weeks are determined at two different shear rates (20 l/s and 1000 l/s). TABLE-US-00008 White pastes Viscosity/ Viscosity/ Viscosity/ Viscosity/ dPas dPas dPas dPas after 4 wk after 4 wk immediate immediate 50° C. 50° C. Sample at 20 l/s at 1000 l/s at 20 l/s at 1000 l/s 1A 3.0 0.6 3.4 0.7 2A 3.1 0.53.3 0.4 3A 3.3 0.7 3.5 0.7 4A 3.0 0.5 3.2 0.5 5A 3.6 0.6 3.8 0.7 6A 3.1 0.4 3.2 0.4 7A 3.3 0.5 3.4 0.6 1B 3.6 0.5 3.8 0.5 2B 3.5 0.6 3.6 0.6 3B 3.4 0.4 3.3 0.5 Polystyrene-b- 3.3 0.4 3.7 0.4 polyalkylene oxide copolymer precursor to 1A Polystyrene-b- 3.50.6 3.8 0.7 polyakylene oxide copolymer precursor to 3A Fatty acid 2.8 0.5 5.5 1.0 alkoxylate Modified 4.2 1.3 6.8 1.5 acrylate polymer Black pastes Viscosity/ Viscosity/ Viscosity/ Viscosity/ dPas dPas dPas dPas after 4 wk after 4 wk immediate immediate50° C. 50° C. Sample at 20 l/s at 1000 l/s at 20 l/s at 1000 l/s 1A 2.2 0.6 2.3 0.6 2A 2.3 0.6 2.5 0.7 3A 2.0 0.5 2.1 0.6 4A 2.4 0.7 2.4 0.7 5A 2.3 0.5 2.5 0.6 6A 1.9 0.5 2.0 0.6 7A 2.0 0.6 2.1 0.6 1B 2.3 0.7 2.4 0.7 2B 2.2 0.6 2.3 0.7 3B2.0 0.6 2.2 0.7 Polystyrene-b- 2.0 0.6 2.2 0.7 polyalkylene oxide copolymer precursor to 1A Polystyrene-b- 2.1 0.5 2.3 0.6 polyaklyene oxide copolymer precursor to 3A Fatty acid 1.8 0.4 2.5 0.6 alkoxylate Modified acrylate 3.7 0.8 4.4 1.0 polymer The good stability of the pigment pastes of the invention is readily evident from the rise in viscosity, which is small in each case. Test of dispersing properties Application of the test formulations in a wet film thickness of 100 μm; drying for 6 minutes, then rubout test over 1/3 of the surface; after stoving or overnight drying, calorimetric determination of the films by means of a XP 68spectrophotometer from X-Rite; determination of the degree of gloss and the haze by means of Haze-Gloss from Byk-Gardner. TABLE-US-00009 Stoving enamel based on Resydrol VWA 5477 Lightness Delta E after Degree of gloss Sample L rubout (60° angle) 1A 41.5 0.4 53 2A 42.3 0.3 51 3A 41.8 0.4 55 4A 43.2 0.4 53 5A 41.7 0.3 55 6A 40.9 0.5 54 7A 41.2 0.3 56 1B 42.20.3 54 2B 43.0 0.4 53 3B 42.8 0.3 53 Polystyrene-b-polyalkylene 44.0 0.6 51 oxide copolymer precursor to 1A Polystyrene-b-polyalkylene 44.2 0.5 52 oxide copolymer precursor to 3A Fatty acid alkoxylate 44.6 0.7 49 Modified acrylate 44.9 0.4 55 polymerEmulsion paint based on Neocryl XK 90 Delta E after Degree of gloss Sample Lightness L rubout (60° angle) Haze 1A 47.5 0.3 40.5 110 2A 47.6 0.4 42.0 115 3A 47.3 0.5 41.0 110 4A 47.9 0.3 39.0 120 5A 47.6 0.4 42.0 125 6A 47.7 0.5 41.5 115 7A 47.50.4 42.0 110 1B 48.0 0.4 40.5 120 2B 48.2 0.5 39.0 110 3B 48.1 0.4 42.5 125 Polystyrene-b- 48.3 0.7 39.0 120 polyalkylene oxide copolymer precursor to 1A Polystyrene-b- 48.4 0.8 39.5 125 polyalkylene oxide copolymer precursor to 3A Fatty acid 48.3 0.940.0 120 alkoxylate Modified acrylate 49.0 0.4 40.5 130 polymer The favorable development of color strength achievable through the use of the dispersing additives of the invention, and the rubout test, which is favorable in all cases, are evident. This also becomes particularly marked in comparison with the commercial examples not in accordance with the invention: a fatty acid alkoxylate (Tego dispers 740W, Tego Chemie Service) and a modified acrylate (Tego Dispers 745W). * * * * * Other References
Field of SearchPlural ether oxygens or thioether sulfurs attached indirectly to the phosphorus by acyclic nonionic bondingAnd reactant having alcoholic or phenolic -XH group, wherein X is chalcogen (and wherein H of -XH may be replaced by substituted or unsubstituted ammonium, or by a Group IA or IIA light metal) And reactant having alcoholic or phenolic -XH group, wherein X is chalcogen (and wherein H of -XH may be replaced by substituted or unsubstituted ammonium, or by a Group IA or IIA light metal) And reactant having alcoholic or phenolic -XH group, wherein X is chalcogen (and wherein H of -XH may be replaced by substituted or unsubstituted ammonium, or by a Group IA or IIA light metal) The agent contains organic compound containing phosphorus or silicon The agent contains organic compound containing phosphorus (e.g., lecithin) The inorganic material primarily contains compounds containing both silicon and oxygen, or both aluminum and oxygen, or combinations thereof (e.g., silica (SiO2) organosol*, silica alcosol, talc, clay) The compound contains repeating -(OCnH2n)- (i.e., repeating unsubstituted oxyalkylene) The agent contains organic compound containing phosphorus The compound contains repeating -(OCnH2n)- (i.e., repeating unsubstituted oxyalkylene) The material primarily contains inorganic material (e.g., chrome yellow, sodium nitrite) Aqueous continuous liquid phase and discontinuous phase primarily solid (e.g., water based suspensions, dispersions, or certain sols*, of natural or synthetic ester-wax, beeswax, carnauba wax; or latex dispersion) The solid is primarily inorganic material (e.g., mercurous halide) The metal present in the greatest amount is titanium, zirconium, or hafnium The metal present in the greatest amount is aluminum The material is substantially pure silica sol Organic material containing, e.g., wax, paraffin, etc. Sulfur or phosphorus containing Phosphorus organic compound DNRM Pentavalent phosphorus atom directly bonded to at least one oxygen atom Aryl group Material contains glass With polycarboxylic acid or derivative and a polyol at least one of which is saturated or with solid polymer thereof Solid polymer derived from carboxylic acid-containing monomer Chemical treating agent contains a phosphorus atom Polymer derived from aromatic hydrocarbon monomer, e.g., styrene, etc. At least one reactant contains a three-membered heterocyclic ring having two carbon and one oxygen atoms, e.g., oxirane, etc. THICKENER OR DISPERSANT FOR AQUEOUS SYSTEM |
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