WO1994022937A1 - Oligomeres d'ester sulfone pouvant etre utilises comme agents dispersants dans des compositions detersives - Google Patents

Oligomeres d'ester sulfone pouvant etre utilises comme agents dispersants dans des compositions detersives Download PDF

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Publication number
WO1994022937A1
WO1994022937A1 PCT/US1994/003740 US9403740W WO9422937A1 WO 1994022937 A1 WO1994022937 A1 WO 1994022937A1 US 9403740 W US9403740 W US 9403740W WO 9422937 A1 WO9422937 A1 WO 9422937A1
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units
weight
formula
fabrics
esters
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PCT/US1994/003740
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English (en)
Inventor
Randall Alan Watson
Eugene Paul Gosselink
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP94912958A priority Critical patent/EP0698049A4/fr
Priority to JP6522475A priority patent/JPH08511285A/ja
Priority to BR9405863A priority patent/BR9405863A/pt
Publication of WO1994022937A1 publication Critical patent/WO1994022937A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates

Definitions

  • the present invention relates to anionic ester compositions useful as soil dispersing agents in fabric care compositions, especially liquid and granular laundry detergent compositions and synthetic laundry bar detergents.
  • a number of dispersing or antiredeposition compounds are known to be effective in detergent compositions, particularly for inorganic particulates such as clay. However, to date, these compounds have not been found to be effective under conditions of heavy, organic soiling wherein the soils become highly concentrated in the laundry liquor.
  • soil release agents s.r.a.'s
  • s.r.a.'s deposit on the fabric surface, particularly polyester fabrics, during the laundry cycle. As the fabrics are used or worn, soils collect on the treated fabric surface. When the fabric is re-laundered, the s.r.a.'s aid in the removal of these soils from the fabric's surface.
  • soil release agents for use in in-home fabric treatment processes are known in the art.
  • Various s.r.a.'s have been commercialized and are currently used in detergent compositions and fabric softener/antistatic articles and composi ⁇ tions.
  • Anionic s.r.a.'s typically comprise an oligoester backbone, which may itself optionally contain various anionic substituents, and will usually terminate with one or more end-capping units which are also anionic.
  • various oxyalkylene/terephtha- late/sulfoisophthaloyl oligomers end-capped with sulfoaroyl substi ⁇ tuents comprise a known and important class of s.r.a.'s for use in laundry detergents.
  • s.r.a.'s require multi-cycle laundering to provide benefits. Through multiple launderings the s.r.a.'s are deposited onto the fabric surface. It is only after the s.r.a.'s have been deposited onto the fabric that the s.r.a.'s aid in the cleaning process. In contrast, the dispersing agents of this invention are not required to deposit on the fabric surface; cleaning benefits are, therefore, provided even during the first laundry cycle before the fabrics have been previously contacted with the dispersing agent.
  • oligomer compositions similar to those employed as s.r.a.'s, especially those of low molecular weight and incomplete oligo erization can be employed as dispersing agents.
  • Such dispersing agents have been found to be especially effective under conditions of heavy fabric soiling.
  • the oligomer compositions disperse and suspend the soil in the laundry liquor and prevent the soil from redepositing onto the fabric surface. Accordingly, the laundered fabrics have a brighter, less dingy appearance, even after the first laundry cycle.
  • the present invention thus solves the long-standing need for an effective dispersing agent which provides a novel method of brightening fabrics by suspending organic soils in the laundry liquor and preventing their redeposition onto the fabric surface.
  • the dispersing agents are particularly effective in liquid or granular detergent compositions and synthetic detergent bars for use in hand-wash, or under other circumstances where low water to fabric ratios are used in a laundering operation.
  • U.S. Patent 4,702,857, Gosselink issued October 27, 1987, discloses block polyester esters and mixtures thereof useful as soil release agents in detergent compositions. See also U.S. Patent 4,861,512.
  • Polyesters have also been disclosed for use in rinse-added consumer laundry products, in dryer-added products, and in certain built liquid detergents. See Canadian Patent 1,100,262, Becker et al, Issued July 8, 1975; U.S. Patent 3,712,873, Zenk, issued January 23, 1973; U.S. Patent 4,238,531, Rudy et al , issued December 9, 1980; and British Patent Application 2,172,608, Crossin, published September 24, 1986.
  • the present invention encompasses a method for cleaning fabrics, said method comprises contacting said fabrics in an aqueous liquor comprising conventional detergent ingredients and oligo eric, substantially linear ester compositions useful as dispersing agents.
  • the detergent ingredients can optionally comprise detergent builders and other conventional detersive adjuncts in a liquid, granular or laundry bar detergent composi ⁇ tion.
  • the method also encompasses presoaking soiled fabrics before washing.
  • the detergent compositions employed in the present invention may even be used for overnight soaking of the laundry. Therefore, the preferred method of laundering involves contacting fabric or textiles with an aqueous laundry liquor comprising a detergent composition which comprises at least about 300 ppm, preferably from about 300 ppm to about 20,000 ppm, of conventional detersive ingredients and at least about 1 ppm, preferably from about 1 ppm to about 50 ppm, of said dispersing agent for about 5 minutes to about 15 hours.
  • the detersive ingredients comprise a detersive surfactant
  • the ratio of dispersing agent to surfactant should preferably be below about 1:10.
  • the washing operation preferably employs agitating the fabrics with an aqueous liquor containing the compositions herein.
  • the fabrics can then be rinsed with water and line or tumble dried.
  • the dispersing agents are especially effective under typical hand-wash conditions or in low water to fabric load laundering situations wherein the ratio of fabricrwater (kg:liters) ranges from about 1:15 to about 1:0.5, especially from about 1:7 to about 1:1.
  • a typical ratio under hand-wash conditions is about 1:5.
  • the dispersing agents herein comprise ester compositions with relatively low Completion Indices and relatively low molecular weights (i.e., below the range of fiber-forming polyesters).
  • Typical dispersing agents of the present invention have a number average molecular weight ranging from about 400 to about 3,000.
  • Said ester compositions employed herein comprise oxyethyleneoxy or oxy-l,2-propyleneoxy units and terephthaloyl units.
  • Preferred ester compositions additionally comprise sulfoisophthalate and sulfonated end-capping units. (Mixtures of such esters with reaction by-products and the like retain their utility as soil dispersing agents when they contain a minimum of doubly end-capped esters.)
  • the ester compositions provided by this invention encompass a mixture of oligomeric esters comprising "backbones" which are optionally end-capped on one or both ends of the backbone by end-capping units.
  • the esters are not fully oligomerized, i.e., doubly end-capped.
  • the relative ratio of fully oligomerized to partially oligomerized ester molecules in a given composition can be related to its Completion Index (defined hereinafter).
  • the end-capping units herein are anionic sulfonated hydro- philes and connected to the esters by an ester linkage.
  • the pre ⁇ ferred end-capping units are selected from the group consisting of: a) M ⁇ 3S(CH2)m( H2CH2 ⁇ )(RO) n -, wherein M is a salt-forming cation such as sodium or tetraalkylammonium, R is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 0 to 4; b) sulfobenzoyl units of the formula (M ⁇ 3S)(C6H )C(0)-, wherein M is a salt-forming cation; and c) mixtures of a) and b).
  • noncharged, hydrophobic aryldicarbonyl units are essential in the backbone unit of the oligoesters herein. Preferably, these are exclusively terephthaloyl units. Other noncharged, hydrophobic aryldicarbonyl units, such as isophthaloyl or the like, can also be present if desired, provided that the soil dispersing benefits of the esters are not significantly diminished.
  • anionic hydrophilic units capable of forming two ester bonds may be used.
  • Suitable anionic hydrophilic units of this specific type are well illustrated by sulfonated dicarbonyl units, such as sulfoisophthal- oyl, i.e., -(0)C(C6H3)(S ⁇ 3M)C(0)-, wherein M is a salt-forming cation such as an alkali metal or tetraalkylammonium ion.
  • preferred dispersing agents herein comprise mixtures of:
  • i) (CAP) represents sulfonated end-capping units selected from the group consisting of: (a) M ⁇ 3S(CH 2 ) m (CH 2 CH2 ⁇ )(RO) n -, wherein M is a salt-forming cation, R is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 0 to 4;
  • v is determined by the formula v - y+z to y+z-1.
  • v is determined by the formula v « y+z+1, and when the (CAP) units are i)(c) » v is determined by the formula v ⁇ y+z+1.
  • the preferred esters have a number average molecular weight of no more than 70%, preferably from about 10% to about 60%, of the formula weight of the fully oligomerized or "target" structure. In calculating the number average molecular weight of the compositions only the ester components are included and not any residual free glycols which may also be present.
  • the degree of oligomerization necessary to achieve the desired percent of target formula weight can be related to a Completion Index.
  • Ester compositions of the invention will comprise at least about 5%, preferably at least about 10% and most preferably at least about 50%, of partially oligomerized esters. A fully oligomerized ester will be doubly end-capped and will have a Completion Index of infinity.
  • the ester "backbone” of the present compositions comprises all the units other than the end-capping units. All the units incorporated into the esters being interconnected by means of ester bonds.
  • the ester "backbones” comprise only terephthaloyl units and oxyethyleneoxy units.
  • the ester "backbone” comprises terephthaloyl units, oxyethyleneoxy, and oxy-l,2-propyleneoxy units.
  • hydrophilic units such as 5-sulfo- isophthalate are present in the backbone wherein the preferred ratio of terephthaloyl to 5-sulfoisophthaloyl units is determined by the formula y/(z+l) » 2 to 4, wherein y and z are defined above.
  • the ester compositions herein comprise at least 50% by weight of said ester oligomers having a number average molecular weight ranging from about 400 to about 3,000.
  • the invention also encompasses the preparation of dispersing agents characterized in that they consist essentially of the oligomeric product of reacting dimethyl terephthalate or terephthalic acid, ethylene glycol, propylene glycol or a mixture thereof, a compound selected from the group consisting of monovalent cation salts of sulfonated end-capping monomers and, optionally, dimethyl sodiosulfoisophthalate or sulfoisophthalic acid, monosodium salt.
  • the resulting water-soluble oligomeric products are useful for dispersing soils in an aqueous laundry liquor.
  • a preferred dispersing agent is prepared by reacting 1 mole of monovalent cation salts of sulfonated end-capping monomers, 5 moles of dimethyl terephthalate, 1 mole of dimethyl sulfoisophthalate, and 12 moles of ethylene glycol, propylene glycol or mixtures thereof.
  • the conventional detergent ingredients used in the present invention comprise from about 1% to about 99.9%, preferably from about 5% to about 80%, of a detersive surfactant.
  • the detergent ingredients comprise from about 5% to about 80% of a detergent builder.
  • Other optional detersive adjuncts can also be included in such compositions, at conventional usage levels.
  • the dispersing agents will typically constitute from about 0.1% to about 10%, preferably from about 0.25% to about 5%, by weight of detergent composition.
  • the essential component of the compositions employed in the present invention is a dispersing agent comprising a mixture of fully and partially oligomerized esters characterized by certain essential backbone units and optional end-capping units, all in particular proportions and having structural arrangements as described hereinafter.
  • the target structure of a fully oligomerized ester has the formula:
  • the preferred partially oligomerized ester employed in the present invention will have about 50% of the formula weight of the above target ester and a Completion Index of about 6.
  • the target structure is:
  • the preferred partially oligomerized ester employed in the present invention will have about 40% to 50% of the formula weight of the above target ester and a Completion Index of about 3.
  • the target structure is:
  • the preferred partially oligomerized ester employed in the present invention will have about 20% of the formula weight of the above target ester and a Completion Index of about 1.8.
  • esters herein can be simply characterized as oligomers which comprise a substantially linear ester "backbone” and, optionally, one or more kinds of end-capping units, especially 2-(2-oxyethoxy)ethanesulfonate or sulfobenzoyl.
  • compositions herein are not resinous, high molecular weight, macromolecular or fiber-forming polyesters but, instead, are relatively low molecular weight and contain species more ap ⁇ intestinaltely described as oligomers rather than as polymers.
  • Ester molecules herein, including the end-capping units can have number average molecular weights ranging from about 400 to about 3,000. Relevant for purposes of comparison with glycol-terephthalate fibrous polyesters (typically averaging 15,000 or more in molecular weight) is the molecular weight range of from about 500 to about 1,100, within which preferred molecules of the esters of the invention which incorporate the essential units are generally found. Accordingly, the compositions of this invention are referred to as "oligomeric esters" rather than "polyester” in the colloquial sense of that term as commonly used to denote high polymers such as fibrous polyesters.
  • esters of the invention are all "substantially linear" in the sense that they are not significantly branched or crosslinked by virtue of the incorporation into their structure of units having more than two ester-bond forming sites.
  • no cyclic esters are essential for the purposes of the invention but may be present in the compositions of the invention at low levels as a result of side-reactions during ester synthesis.
  • cyclic esters will not exceed about 2% by weight of the compositions; most preferably, they will be entirely absent from the compositions.
  • the term "substantially linear” as applied to the esters herein does, however, expressly encompasses materials which contain side-chains which are unreactive in ester-forming or transesterification reactions.
  • oxy-1,2- propyleneoxy units are of an unsy metrically substituted type; their methyl groups do not constitute what is conventionally regarded as "branching" in polymer technology (see Odian, Principles of Polymerization, Wiley, N.Y., 1981, pages 18-19, with which the present definitions are fully consistent) and are unreactive in ester-forming reactions.
  • Optional units in the esters of the invention can likewise have side-chains, provided that they conform with the same nonreactivity criterion.
  • esters of this invention comprise end-capping units and repeating backbone units.
  • molecules of the ester are comprised of three kinds of units, namely: i) sulfonated end-capping units selected from, the group consisting of:
  • esters herein also contain anionic hydrophilic units in the backbone. These units most preferably are: iv) 5-sulfoisophthaloyl backbone units of the formula -(0)C(C6H3)(S03M)C(0)-, wherein M is a salt-forming cation.
  • siinnggTlyy end-capped ester molecule comprised of units i), ii) and iii);
  • ester molecule singly end-capped ester molecule, (termed a "hybrid backbone” ester molecule herein) comprised of units i), ii) and ill).
  • Units ii) are a mixture of oxyethyleneoxy and oxy-1,2- propyleneoxy units, in the example shown below at a 3:1 mole ratio;
  • the present invention encompasses not only the arrangement of units at the molecular level, but also the gross mixtures of esters which result from the reaction schemes herein and which have the desired range of composition and properties. Accordingly, when the number of monomer units or ratios of units are given, the numbers refer to an average quantity of monomer units present in oligomers of the composition.
  • the backbone is formed by oxyethyleneoxy and/or oxypropyleneoxy and terephthaloyl units connected in alternation.
  • the backbone is formed by
  • esters employed herein is a term which encompasses the doubly and singly end-capped compounds disclosed herein, mixtures thereof, and mixtures of said end-capped materials with non-capped species.
  • ester when referring simply to an "ester” herein it is intended to refer, by definition, collectively to the mixture of sulfonated capped and uncapped ester molecules resulting from any single preparation.
  • ester molecules which are present in compositions of the invention which are not fully, i.e., doubly, end-capped by the end- capping units must terminate with units which are not sulfonated end-capping units.
  • These termini will typically be hydroxyl groups or other groups attributable to the unit-forming reactant.
  • a chain terminal position to which is attached -H forms a hydroxyl group.
  • units such as -(0)CC6H4C(0)-0CH3 and -(0)CC ⁇ H4C(0)-0H may be found in terminal positions.
  • Anionic End-Capping Units The end-capping units used in the esters of the present invention are anionic sulfonated groups. These end-cap units provide anionic charged sites when the esters are dispersed in aqueous media, such as a laundry liquor. The end-caps serve to assist transport in aqueous media and to provide hydrophilic sites on the ester molecules.
  • esters herein are used as sodium salts, as salts of other alkali metals, as salts with nitrogen-containing cations (especially tetraalkylammonium), or as the disassociated ions in an aqueous environment.
  • anionic end-capping group monomers include sodium isethionate, sodium 2-(2-hydroxyethoxy)ethanesulfonate, sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate, sodium 5-hydroxy-4- methyl-3-oxapentanesulfonate, sodium alpha-3-sulfopropyl-omega- hydroxy-poly(oxy-l,2-ethanediyl), sodium 5-hydroxy-3-oxa-hexanesul- fonate, sodium 3-hydroxy-l-propanesulfonate, sulfobenzoyl and mixtures thereof.
  • the oxy-l,2-propyl- eneoxy units can have their methyl groups randomly alternating with one of the adjacent -CH2- hydrogen atoms, thereby lowering the symmetry of the ester chain.
  • the oxy-l,2-propyleneoxy unit can be depicted as having either the -0CH2CH(CH3)0- orientation" or as having the opposite -OCH(CH3)CH2 ⁇ - orientation.
  • Carbon atoms in the oxy-l,2-propylene units to which the methyl groups are attached are, furthermore, asymmetric, i.e., chiral; they have four nonequivalent chemical entities attached.
  • various optional units of a hydrophilicity- enhancing and nonpolyester substantive type can be incorporated into the esters.
  • the pattern of such incorporation will generally be random.
  • Preferred optional units are anionic hydrophiles, such as 5-sulfoisophthaloyl or similar units.
  • the essential non-charged aryldicarbonyl units herein need not exclusively be terephthaloyl units.
  • minor amounts of isomeric non-charged dicarbonyl units, such as isophthaloyl or the like, are acceptable for incorporation into the esters.
  • ester compositions of the present invention can be prepared using any one or combination of several alternative general reaction types, each being well-known in the art. Many different starting materials and diverse, well-known experimental and analytical techniques are 0 useful for the syntheses.
  • esters of the invention include those classifiable as:
  • reaction types 2-4 are highly preferred since 0 they render unnecessary the use of expensive solvents and halogenated reactants. Reaction types 2 and 3 are especially preferred as being the most economical.
  • Suitable starting materials or reactants for making the esters of this invention are any reactants (especially esterifiable or ⁇ transesterifiable reactants) that are capable of combining in accordance with the reaction types 1-4, or combinations thereof, to provide esters having the correct proportions of all the above-specified units (i) to (iv) of the esters.
  • Such reactants can be categorized as "simple" reactants, i.e., those that are singly capable of providing only one kind of unit necessary for making the esters, or as derivatives of the simple reactants which singly contain two or more different types of unit necessary for 5 making the esters.
  • Illustrative of the simple kind of reactant is dimethyl terephthalate which can provide only terephthaloyl units.
  • bis(2-hydroxypropyl)-terephthalate is a reactant that can be prepared from dimethyl terephthalate and 1,2-propylene glycol and which can desirably be used to provide two kinds of
  • containing cation provided that the latter does not overly promote crystallization of the oligomer and is unreactive during the synthesis, e.g. tetraalkylammonium. It is, of course, possible to subject any of the esters of the invention to cation exchange after the synthesis and, thereby, afford a means of introducing more
  • glycols or cyclic carbonate derivatives thereof can be used to provide oxy-l,2-alkyleneoxy units; thus,
  • Oxyethyleneoxy units are suitable sources of oxy-l,2-propyleneoxy units for use herein.
  • Oxyethyleneoxy units are most conveniently provided by ethylene glycol.
  • ethylene carbonate could be used when free carboxylic acid groups are to be esterified.
  • Aryldicarboxylic acids or their lower alkyl esters can be used to provide the essential aryldicarbonyl units; thus, terephthalic acid or dimethyl terephthalate are suitable sources of terephthal ⁇ oyl units. In general, it is preferred herein to use ester rather than acid forms of reactants to provide the aryldicarbonyl units.
  • esters will be provided by well-known and readily identifiable reagents; for example, dimethyl 5-sulfoiso- phthalate is an example of a reagent capable of providing 5-sulfo- isophthaloyl units for optional incorporation into the esters of the invention. It is generally preferred that all units of the type (iv) as defined hereinabove should be provided by reactants in ester or carboxylic acid forms.
  • the overall synthesis is usually multi-step and involves at least two stages, such as an initial esterification or trans- esterification (also known as ester interchange) stage followed by an o igomerization stage in which molecular weights of the esters are increased, but only to a limited extent as provided for by the invention.
  • an initial esterification or trans- esterification (also known as ester interchange) stage followed by an o igomerization stage in which molecular weights of the esters are increased, but only to a limited extent as provided for by the invention.
  • reaction 2 and 3 Formation of ester-bonds in reaction types 2 and 3 involves elimination of low molecular weight by-products such as water (reaction 2) or simple alcohols (reaction 3). Complete removal of the latter from reaction mixtures is generally somewhat easier than removal of the former. However, since the ester-bond forming reactions are generally reversible, it is necessary to "drive" the reactions forward in both instances by removing these by-products.
  • the reactants are mixed in appropriate proportions and are heated to provide a melt at atmospheric or slightly superatmospheric pressures (preferably of an inert gas such as nitrogen, or argon). Water and/or low molecular weight alcohol is liberated and is distilled from the reactor at temperatures up to about 200°C. (A temperature range of from about 150-200°C is generally preferred for this stage).
  • vacuum and temperatures somewhat higher than in the first stage are applied; removal of volatile by-products and excess reactants continues until the reaction is at the desired stage of completion, as monitored by conventional spectroscopic techniques.
  • Continuously applied vacuum typically of about 50 mm Hg or lower can be used.
  • a suitable temperature for oligomerization lies most preferably in the range of from about 150°C to about 260°C when higher ratios of EG/PG are present and in the range of from about 150°C to about 240°C when lower ratios of EG/PG are present (assuming that no special precautions, such as of reactor design, are otherwise taken to limit thermolysis).
  • condensation temperatures are preferably 150-240°C.
  • Catalysts and catalyst levels appropriate for esterification, transesterification, oligomerization, and for combinations thereof are all well-known in polyester chemistry, and will generally be used herein; as noted above, a single catalyst will suffice.
  • Catalytic metals are reported in Chemical Abstracts, CA83:178505v, which states that the catalytic activity of transition metal ions during direct esterification of K and Na carboxybenzenesulfonates by ethylene glycol decreases in the order Sn (best), Ti, Pb, Zn, Mn, Co (worst).
  • the reactions can be continued over periods of time sufficient to reach the desired level of oligomerization, or various conventional analytical monitoring techniques can be employed to monitor progress of the forward reaction.
  • Such monitoring makes it possible to speed up the procedures somewhat and to stop the reaction as soon as a product having the minimum acceptable composition is formed.
  • tetraalkylammonium cations 0 is is preferred to stop the reaction at less than full completion, relative to the sodium cation form, to reduce the possibility of thermal instability.
  • Appropriate monitoring techniques include measurement of relative and intrinsic viscosities, hydroxyl numbers, H and ⁇ 3 C 5 nuclear magnetic resonance (n.m.r) spectra, and liquid chroma- tograms.
  • sublimation-type losses such as of dimethyl terephthalate
  • sublimation-type losses may be minimized 1) by apparatus design; 2) by raising the reaction temperature slowly enough to allow a large proportion of dimethyl terephthalate to be converted to less volatile glycol esters before reaching the upper reaction temperatures; 3) by conducting the early phase of the transesterification under low to moderate pressure (especially effective is a procedure allowing sufficient reaction time to evolve at least about 90% of the theoretical yield of methanol before applying vacuum).
  • the "volatile" glycol components used herein must be truly volatile if an excess is to be used. In general, lower glycols or mixtures thereof having boiling points below about 350°C at atmospheric pressure are used herein; these are volatile enough to be practically removable under typical reaction conditions.
  • the generalized target structure is selected for a fully dicapped polymer consisting of units derived from the desired monomeric reactants.
  • the generalized target structure is: (CAP)2(EG/PG) x (T) y (SI) z , where the CAP units are derived from (A), the EG/PG units from (B) and (C), the T units from (D), and the SI units from (E);
  • the average number of terephthalate units desired for the target structure is selected; for the present example, the value of 5 is selected for y, which falls in the range of most highly preferred values according to the invention, is used;
  • the average number of " sulfoisophthalate units desired for the target structure is selected; for the present example, the value of 1 is selected for z, which falls in the range of the most highly preferred values according to the invention, is used;
  • glycols typically 2 to 10 times the sum of the number of moles of dimethyl terephthalate plus dimethyl 5-sulfoisophthalate is suitable; in this example, the glycols are ethylene glycol, (B) and propylene glycol, (C);
  • the target ratio of incorporated ethylene glycol :propylene glycol is selected; for the present example, the ratio of 2:1 is selected which is in the most highly preferred range according to the invention; typically, the EG/PG ratio incorporated is higher than the initial (B):(C) reactant ratio
  • Oliganeric esters useful as dispersing agents as disclosed in this invention may also be prepared from an oligomeric ester conprising the desired monomer units but with a higher Completion ndex than desired.
  • the oligomeric ester is mixed with ethylene glycol, or a mixture of ethylene glycol and propylene glycol, under heat to reverse the polymerization of the oligomer.
  • the glycol acts to cleave the oligomer and, thereby, provides a mixture of oliganeric esters with a lower average Completion Index.
  • the ratio of ethylene glycol to propylene glycol will be about the same as the ratio of the two glycols present in the oligomeric ester.
  • the amount of glycol to be mixed with the oligomeric ester is dependant upon the final Completion Index desired. Generally, a lower Completion Index will be achieved by using more glycol.
  • Dispersing agents which contain end-cap units having from 1 to
  • a sulfonate-type hydrotrope or stabilizer such as alkylbenzenesulf ⁇ nate, cumenesulfonate or toluenesulfonate, may be mixed with the reactants during synthesis of the ester to reduce the crystallization problem. Typically 0.5% to about 20%, by weight of the ester composition, of stabilizer is added to the opposition.
  • any sulfite residual may be oxidiz ⁇ ed after conversion to sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • the resulting isethi ⁇ nate solution may be used directly for conver ⁇ sion to modified isethionates. Conversion of the isethi ⁇ nate solution into sodium 2-(2-hydr ⁇ xyBtho ⁇ y)ethanesulf ⁇ nate is accomplished by adding sodium hydroxide (4.00g, 0.10 mol, Mallirkckrodt) and ethylene glycol (260g, 5.9 mol. Baker Chemical Co.). While maintaining the inert atmosphere, the pH probe is removed and replaced by a modified Claisen head to distill out the water. The temperature is gradually raised to ca.
  • modified isethi ⁇ nate is preferably conducted with an excess of polyol reactant to isethi nate.
  • a mole ratio of at least 2:1 polyol to isethionate is preferred.
  • a mole ratio of at least 5:1, most preferred from about 5:1 to about 10:1, is used.
  • Even higher ratios of polyol to isethionate can be used to insure predominate mono sulfonate product.
  • the excess polyol reactant provides the desired mono sulfonate product. Use of a 1:1 or lower ratio may lead to predominately disulf ⁇ nate product.
  • the preferred polyols include volatile diols, triols, and mixtures thereof, including ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentane- diol, 1,6-hexanediol, 2,2-dimethyl-l,3-propanediol, 2-methyl-l,3- propanediol,glycerin, diethylene glycol, triethylene glycol, and mixtures thereof.
  • the reaction may be conducted at any pressure, typically from about atmospheric to about 300 psig.
  • the temperature of the reaction should be below the temperature in which the polyol will distill off under the reaction conditions, and hi ⁇ gh enough to allow removal of the water formed, typically from about 150°c to about 250°C.
  • the reaction is preferably conducted in the presence of a base catalyst.
  • the base is present in an amount equal to from about 1 to about 25 mole percent of the isethionate reactant.
  • one or more of the hydroxyl sub ⁇ tituents of the polyol can be converted into an alkoxide.
  • Suitable reactants useful to farm the alkoxide of the polyol include alkali metals, alkali oxides, .alkali hydroxides. Particlularly prefered reactants include sodium metal and sodium hydroxide.
  • the completion of the reaction is dependent on the base used and the temperature at which the reaction is conducted. Typically the reaction is run until most of the theoretical water is dis ⁇ tilled from the reaction vessel. If a mixture of iethi ⁇ nate and modified isethionate is desired, the reaction can be conducted until the desired fraction of theoretical modified isethionate is produced. This can be estimated based on the fraction of theoretical water distilled from the reaction vessel.
  • the excess polyol should preferably be volatile to aid in its removal. Prior to removal of excess polyol by volatilization, it is preferable to neutralize the basic catalyst so that the pH of the system during the stripping be maintained near neutrality. To this end, it is often helpful to add a low level of a buffer, such as an alkali phosphate, to the system. Removal of excess polyol is preferably conducted under a vacuum of less than about 100 mm Hg.
  • a 1L stainless steel kettle is fitted with a three neck glass cover which is clamped in place. Through one neck of the lid is inserted a glass rod with a teflon stir paddle at one end. The glass rod is connected to a motor for stirring purposes.
  • the other necks of the lid are equipped with a thermocouple and temperature control device (Therm-0-Watch I2R) , and a modified Claisen head and condenser set for distillation.
  • Therm-0-Watch I2R thermocouple and temperature control device
  • Therm-0-Watch I2R thermocouple and temperature control device
  • a modified Claisen head and condenser set for distillation To this reaction flask is added the isethionic acid, sodium salt (Aldrich, 50.2g, 0.339 moles) and an equal weight of water. The mixture is allowed to stir until the isethionic acid, sodium salt is fully dissolved.
  • the pH of the solution is adjusted to neutral with methanesulfonic acid (Aldrich) .
  • the product mixture is new dissolved in deionized water to farm a 30% solution.
  • the solution is transferred to a 1L, single neck, round bottom flask.
  • a small amount of potassium phosphate, monobasic Aldrich, 2.6g, 0.019 moles, 6 mole% relative to amount of isethionic acid, sodium salt
  • the pH of the soution measures -5.5.
  • the pH is readjusted to 7 using IN NaOH solution and a pH meter.
  • EXAMPLE III An ester ⁇ c ⁇ position made from sodium 2-(2-hydroxyethoxy)- etnanesulfonate, monosodium salt, ethylene glycol, 1,2-propylene glycol, and dimethyl terephthalate.
  • the exa ⁇ ple illustrates an ester composition according to the invention wherein the backbone contains a mixture of essential ethylene glycol and nonessential 1,2-propylene glycol.
  • a 1L, three neck, round bottom flask is equipped with a magnetic stir bar, a modified Claisen head, a thermometer, a temperature control device (Therm-O-Watch , IT*) , and a condenser set for distillation.
  • hydrotropes sodium cumenesulfonate, sodium toluenesulfonate, and sodium xylenesulfonate (all from Ruetgers- Nease, 4.8g each, each is 4% of final polymer weight).
  • the reaction mixture is heated at a constant temperature of 180°C under an argon environment for a period of one day as methanol and water distill frcm the reaction vessel to give a prepolymer reaction product.
  • An 81.7g portion of this prepolymer solution is poured in a 1L, single neck, round bottom flask and placed in a Kugelrohr apparatus (Aldrich) under a 2 mmHg vacuum. The temperature of the Kugelrohr is raised to 240°C and maintained at this temperature for 6 minutes. At this time, the heating element is switched off, and the flask is allowed to cool to room temperature under continuous vacuum for thirty minutes.
  • the yield of the desired oligomer is
  • a Ti-NMR (in EMSO-dg) shows a resonance at -7.9 ppm for the aromatic protons in the terephthalate groups, and a resonance at -2.8 ppm for the proton adjacent to the sulfur (-CH-SO Na) in the capping groups derived from 2-(2-hydroxyeth ⁇ xy)ethane-sulf ⁇ nate.
  • the ratio of the area of the peak for protons in the methylene group of diesters of ethylene glycol at -4.7 ppm to the area of peak for the methyne proton of diesters of propylene glycol at -5.4 ppm is measured.
  • EG/PG ratio molar ratio of incorporated ethylene/propylene glycols
  • An ester composition made from m-sulfobenzoic acid, monosodium salt, ethylene glycol, propylene glycol, dimethyl 5-sulfoisophtha ⁇ late, sodium salt, and dimethyl terephthalate.
  • the example illus ⁇ trates an ester composition according to the invention wherein the ester molecules have a backbone incorporating sulfonated units.
  • This mixture is heated to 180°C and maintained at that temperature for 2 nights under argon as methanol and water distill from the reaction vessel.
  • a -224g portion of the material (prepolymer) is transferred to a IL, single neck, round bottom flask and heated gradually over about 20 minutes to 240°C in a Kugelrohr apparatus (Aldrich) at about 2mm Hg and maintained there for 10 min.
  • the reaction flask is then allowed to air cool quite rapidly to near room temperature under vacuum (-30 min.)
  • the reaction affords 139g of the desired oligomer as a yellow crunchy glass.
  • a 13 C-NMR(DMSO-d 6 ) shows a resonance for - fOJCOL ⁇ O ⁇ OfOJC- at -63.2 ppm (diester) and a resonance for -CfOJCCH-OLOH at 59.4 ppm (m ⁇ noester) .
  • the ratio of the diester peak to the m ⁇ noester peak is measured to be 1.4:1.0 for a Completion Index [C.l. (63/60) ] of 1.4.
  • the solubility is tested by weighting a small amount of material into a vial, adding enough distilled water to make a 35% by wei t solution, and agitating the vial vigorously.
  • the material is mostly soluble under these conditions.
  • the milky solution which forms gels after a few hours.
  • EXAMPLE V An ester composition made from m-sulfobenzoic acid monosodium salt, ethylene glycol, dimethyl 5-sulfoisophthalate, sodium salt, and dimethyl terephthalate.
  • the example illustrates an ester c ⁇ mposition according to the invention with low completion index.
  • a 13 C-NMR(OlS0-d 6 ) shows a resonance for -C(0) 0Ckl tl 2 0(0) C- at -63.2 ppm (diester) and a resonance for at -59.4 ppm (monoester) .
  • the ratio of the heights of the diester to monoester peaks is measured to be 6.8:1 for a Corpletion Index of 6.8.
  • a H-NMR(CMSO-d 6 ) shews a resonance at -8.4 ppm representing the sulfois ⁇ phthalate aromatic hydrogens and a resonance at -7.9 ppm representing terephthalate aromatic hydrogens.
  • the solubility is tested by weighing small amounts of material into 2 vials, crushing it, adding enough distilled water to make 5% and 10% by weight solutions, and agitating the vials vigorously. The material dissolves under these conditions.
  • EXAMPLE VT An ester composition made from sodium 2-(2-hydroxyethoxy)- ethanesulf ⁇ nate, dimethyl terephthalate, dimethyl 5-sulfoiso ⁇ phthalate, sodium salt, ethylene glycol, and propylene glycol with mixed hydr ⁇ trope stabilizer.
  • the example illustrates an ester composition according to the invention with a lew Corpletion Index.
  • a IL, three neck, round bottom flask is equipped with a magnetic stir bar, a modified Claisen head, a thermometer, a
  • sodium acetate (Baker, 0.320g, 2 mole% of dimethyl 5-sulfoisophthalate, sodium salt)
  • catalyst titanium(TV) propoxide Aldrich, 0.126g, 0.02% of total reaction weight
  • hydr ⁇ tropes sodium cumenesul- fonate, sodium toluenesulfonate, and sodium xylenesulfonate all from Ruetgers-Nease, 12.9 g each, each is 4% of final polymer weight
  • the reaction mixture is heated at a constant 180 C under an argon environment for a period of two days as methanol and water distill from the reaction vessel to give a prepolymer reaction product.
  • the ratio of the area of the peak for protons in the methylene group of diesters of ethylene glycol at -4.7 ppm to the area of the peak for the methyne proton of diesters of propylene glycol at -5.4 ppm is measured and fund to be 1.7:1. From this, the molar ratio of incorporated ethylene/pro- pylene glycols (EG/PG ratio) is calculated to be 1.7.
  • a small sample of the finished polymer is placed into a screw cap, glass vial for solubility testing. It is crushed, and enough deionized water is added to make a 35% solution by weight. The polymer initially dissolves to form a clear solution, but after 3 hours the solution is milky white in color. The solution gels after two days.
  • a second portion of the prepolymer (80.5g) is added to a IL, single neck, round bottom flask and is placed on the Kugelrohr under vacuum as above. However, this proton is heated for only five minutes at 240°C.
  • An 18.5g portion of this polymer is added to a 500mL, single neck, round bottom flask and is placed back on the Kugelrohr apparatus under vacuum. Again, the temperature of the Kugelrohr is allowed to rise to 240°C, and is maintained at this temperature for only 30 seconds.
  • the yield of this desired polymer is 17.5g of translucent, light yellow, glassy material.
  • a 35% by wei t solution of this polymer is made up in deionized water. The solution is initially clear, but becomes cloudy within an hour, and gels within 5 hours.
  • a third portion of prepolymer (81.3g) is added to a IL, single neck, round bottcm flask, and is heated under the same temperature and pressure conditions as above. The 240°C temperature is maintained for 3 minutes and 30 seconds.
  • the extent of oligomerization can be estimated from the
  • Completion Index which is proportional to the diester:monoester ratio for ethylene glycols incorporated into the oligomeric structure.
  • An oligomer with a low Completion Index will have a relatively low proportion of diesters of ethylene glycol and therefore have a low degree of oligomerization.
  • An oligomer with a high Cc ⁇ pleti ⁇ n Index will have a relatively high proportion of diesters of ethylene glycol and therefore have a high degree of oligomerization.
  • a fully dicapped oligomer will have all diesters and no monoesters of ethylene glycol and will have an infinite Completion Index.
  • test method can be used to determine the "O ⁇ spleti ⁇ n Index" of the dispersing agents of the invention.
  • the dispersing agent is well mixed as a melt to ensure representative sampling and is cooled rapidly from a temperature above the melting-point to well below the vitrification temperature, e.g., 45°C or lower. 2. A solid sample of the bulk dispersing agent is taken.
  • the height of the tallest resonance observed in the 63.0-63.8 ppm region (referred to as "the 63 peak” and associated with diesters of ethylene glycol) is measured. (This is often observed as a single peak under the specified conditions but may appear as a poorly resolved multiplet) .
  • the height of the tallest resonance observed in the 59-59.7 ppm region (referred to as "the 60 peak") and associated with monoesters of ethylene glycol is measured. (When this is large enough to distinguish from the baseline, it normally appears to be a single peak under the specified conditions.) 8.
  • the Completion Index is calculated as the height ratio for the "63 peak” over the "60 peak". In the special case where the dispersing agent comprises oxy-l,2-oxvpropyleneoxy units but very little or no oxyethyleneoxy units, the measurement of Cc ⁇ pletion Index based on di- and monoesters of ethylene glycol is not feasible.
  • Dispersing Agents in Detergent campositions - Esters of the invention are especially useful as dispersing agents of a type compatible in the laundry with conventional detersive ingredients such as those typically found in liquid detergents, granular laundry detergents or laundry bars. Additionally, the esters are useful in laundry additive or pretreatment compositions comprising the essential ester compositions and conventional detergent ingredients.
  • the amount of detersive surfactant included in the fully-formulated detergent compositions afforded by the present invention can vary from about 1% to about 99.9% by weight of the composition depending upon the particular surfactants used and the effects desired.
  • the detersive surfactants comprise from about 5% to about 80% by weight of the composition.
  • the detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic, or cationic. Mixtures of these surfactants can also
  • Preferred detergent compositions of the present invention combine the cost-effectiveness of anionic surfactants with the increased compatibility of the anionic oligomeric esters of the invention with such surfactants.
  • Preferred detergent compositions comprise anionic detersive surfactants or mixtures of anionic
  • Nonlimiting examples of surfactants useful herein include the conventional C..-C. D alkyl benzene sulfonates and primary and
  • adjunct nonionic surfactants especially useful herein comprises the polyhydroxy fatty acid amides of the formula:
  • R is H, C.-C 8 hydrocarbyl, 2-hydroxyethyl, 2-hydroxy- propyl, or a mixture thereof, preferably C -C. alkyl, more prefer ⁇ ably C. or C- alkyl, most preferably C. alkyl (i.e., methyl); and R is a C 5 - __ hydrocarbyl moiety, preferably straight chain C_-
  • alkyl or alkenyl more preferably straight chain C-- .- alkyl or alkenyl, most preferably straight chain alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z.
  • Z preferably will be selected from the group consisting of -CrL- (CHOH)-CH-OH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -Cr -(CHOH) -CH OH.
  • R can be, for example, N-methyl, N-ethyl, N-prcpyl, N-is ⁇ propyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydr ⁇ xy pr ⁇ pyl.
  • R is preferably methyl or hydroxyalkyl.
  • R is preferably C_-Cg alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pe ⁇ tyl, hexyl and 2-ethyl hexyl.
  • R -co* can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Detergent Builders - Optional detergent compositions of the present invention contain inorganic and/or organic detergent builders to assist in mineral hardness control. If used, these builders ⁇ c ⁇ prise from about 5% to about 80%, preferably from about 10% to about 50% by weight of the compositions.
  • Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium ' and alkanolammonium salts of polyphos- phates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates) , phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbon- ates) , sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • silicate builders are the alkali metal silicates, particularly those having a Sio :Na 0 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, available from Hoechst under the trademark "SKS"; SKS-6 is an especially preferred layered silicate builder.
  • aluminosilicate builders are especially useful in the present invention.
  • Preferred aluminosilicates are zeolite builders which have the formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be raturally-occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B) , and Zeolite X.
  • Organic builders include, but are not limited to polvcarb ⁇ xylate ccmpounds such as ether polycarboxylates and ether hvdr ⁇ xypolvcarb ⁇ xylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulph ⁇ nic acid, carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar- b ⁇ xylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • polvcarb ⁇ xylate ccmpounds such as ether polycarboxylates and
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt)
  • citric acid and soluble salts thereof are preferred polycarboxylate builders that can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders.
  • Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related ⁇ mpounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • Useful succinic acid builders include the C 5 -C 2 o alkyl and alkenyl succinic acids and salts thereof.
  • Fatty acids e.g., C - monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a reduction of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-kncwn sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphorate builders such as ethane-l-hydroxy-l,l-diphosphonate and other known phosphorates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • compositions herein can optionally include one or more conventional detergent adjunct materials or other materials for assisting ⁇ r enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent co ⁇ position.
  • detergent compositions of the present invention include solvents, hydrotropes, solubilizing agents, soil release agents, chelating agents, clay soil removal/anti-redeposition agents, polymeric dispersing agents, processing aids, antitarnish and/or anti-cor ⁇ rosion agents, dyes, fillers, optical brighteners, germicides, pH-adjusting agents (monoethanolamine, sodium carbonate, sodium hydroxide, etc.), perfumes, fabric softening components, static control agents, bleaching agents, bleach activators, bleach stabilizers, suds suppressors, suds boosters, and the like.
  • the compositions employed in the present invention comprise detersive enzymes.
  • Detersive enzymes are included for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer.
  • the enzymes to be incorporated include proteases, a ylases, lipases, cellulases, and pero ⁇ idases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to abcut 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1%, by weight of a commercial enzyme preparation. Enzymes are usually present in such ccmmercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of co ⁇ position.
  • AU Anson units
  • the dispersing agents of the invention at cxincentrations in an aqueous fabric laundering liquor of at least about 1 ppm, preferably from about l to about 50 ppm, and most preferably about 5 to about 30 ppm, provide effective, combined cleaning and soil dispersing treatments for fabrics washed in an aqueous, preferably alkaline (pH range about 6.5 to about 11, more preferably about 7 to about 10.5) environment, in the presence of typical detergent ingredients.
  • all of the above-identified detergent ingredients can be present in the wash water at their art disclosed levels to perform their conventional tasks, e.g., for cleaning and softening fabrics or the like, without ill-effects on the soil dispersing properties of the esters.
  • the method of washing fabrics with the dispersing agents si ⁇ ply comprises contacting said fabrics with an aqueous laundry liquor containing the conventional detersive ingredients described hereinabove, as well as the above-disclosed effective levels of dispersing agent.
  • this method is not especially limited in terms of factors such as pH and surfactant types present, it should be appreciated that for best cleaning of fabrics, it is often especially desirable to make use in the laundry process of anionic surfactants, such as conventional linear alkylbenzene sulfonates and also to use higher pH ranges as defined above.
  • a preferred method for an optimized combination of cleaning and soil dispersing constitutes using all of the following: the preferred levels of dispersing agent (5-30ppm) ; anionic surfactant; pH of from about 7 to about 10.5.
  • Cleaning benefits are surprisingly obtainable after a single use/laundry cycle comprising the following steps: a) exposing said fabrics to soiling through normal wear or use; b) contacting said fabrics with said aqueous laundry liquor by soaking or by hand-washing or in an automatic washing machine far periods ranging from about 5 minutes to about
  • step (b) includes both hand-washing and typical U.S., Japanese, or European washing machines operating under their conventional conditions of time, temperature, fabric load, amounts of water and laundry product concentrations.
  • the detergent can be introduced to the system either by liquid or granular detergent or by synthetic detergent bar.
  • step (d) the "txmtole-drying" to which is referred involves use of conventional brands of programmable laundry dryers (these are occasionally integral with the washing machine) using their conventional fabric loads, temperatures and operating times.
  • EXAMPLE VII A granular detergent composition is prepared comprising the following ingredients and an ester composition prepared following the procedures set forth in Example IV.
  • the following test method is used: White 100% cotton fabric, white polycotton fabric (50%/50% T-Shirt material) , and an all synthetic material (81% acrylic, 15% nylon, 4% Lycra) are used in the testing.
  • the fabrics are desized with a ccmmercial granular detergent (DASH) .
  • the washing is conducted in 0 grains per gallon (gpg) water at a temperature of 120°F (48.8°C) for 12 minutes, with subsequent rinsing in 0 gpg water at a temperature of 120°F (48.8°C).
  • This desizing step is done twice and is followed by two additional wash cycles using only water.
  • the desized fabrics are formed into swatches (5 inches square) .
  • AMW Automatic Mini-Washer
  • the wash cycle consists of a 30 minute soak followed by 10 minute agitation. After the wash cycle, there is a 2 minute spin cycle, followed by two 2-minute rinse cycles using 8 gpg water at a temperature of 77°F (25°C) .
  • the wash cycle consists of a 30 minute soak followed by 10 minute agitation. After the wash cycle, there is a 2 minute spin cycle, followed by two 2-minute rinse cycles using 8 gpg water at a temperature of 77°F (25°C) .
  • the test swatches are dried and the above steps repeated using the same test swatches and new dirty consumer bundles.
  • a laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following: Component Weight %
  • Example VII In testing the soil dispersing performance of the dispersing agents, the test method used in Example VII is followed. All fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the esters of the invention.
  • a liquid detergent composition is prepared comprising the following ingredients and an ester composition prepared following the procedures set forth in Example IV.
  • fr ⁇ ti convenient materials such as CaCO , talc, clay, silicates, and the like.
  • Example VII In testing the soil dispersing performance of the dispersing agents, the test method used in Example VII is followed. All fabrics display significantly improved whiteness after laundering compared with fabrics which have not been exposed to the esters of the invention.
  • a concentrated liquid detergent composition is prepared comprising the following ingredients and an ester composition prepared following the procedures set forth in Example III.
  • Component Weight % is set forth in Example III.
  • Example VII In testing the soil dispersing performance of the dispersing agents, the test method used in Example VII is followed. All fabrics display significantly ijrproved whiteness after laundering compared with fabrics which have not been exposed to the esters of the invention.
  • compositions and processes of the present invention are especially useful in hand-wash fabric laundering cperations, it is to be understood that they are also useful in any cleaning system which involves low water:fabric ratios.
  • One such system is disclosed in U.S. Patent 4,489,455, Spendel, issued Dec. 25, 1984, which involves a washing machine apparatus which contacts fabrics with wash water containing detersive ingredients using a low water: fabric ratio rather than the conventional method of immersing fabrics in an aqueous bath.
  • the ratio of water:fabric ranges from about 0.5:1 to about 6:1 (liters of waterrkg of fabric) .
  • Example VTI a composition according to Example VTI herein are used to launder fabrics. If desired, sudsing of the composition can be minimized by incorporating therein from 0.2% to 2% by weight of a fatty acid, secondary alcohol, or silicone suds controlling ingredient.
  • Dishwashing Compositions Another aspect of the present invention relates to dishwashing compositions, in particular automatic and manual dishwashing compositions, especially manual liquid dishwashing compositions.
  • Liquid dishwashing compositions according to the present invention preferably comprise from at least about 0.1%, more preferably from about 0.5% to about 30%, most preferably frcrn about
  • Liquid dishwashing compositions according to the present invention may comprise any of the ingredients listed herein above. in addition the dishwashing compositions may comprise other ingredients such as bactericides, chelants, suds enhancers, opacifiers and calcium and magnesium ions.
  • Hydrotropes - A hy ⁇ rotrope is typically added to the compositions of the present invention, and may be present at levels of from about 0% to about 10%, preferably from about 1% to about 5%, by weight.
  • Useful hydrotropes include sodium, potassium, and ammonium xylene sulph ⁇ nates, sodium, potassium, and ammonium toluene sulph ⁇ nate, sodium, potassium and ammonium cumene sulphonate, and mixtures thereof.
  • Other compounds useful as hydrotropes herein include polycarboxylates. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties.
  • An example of a commercially available alkylpolyethoxy polycarboxylate which can be employed herein is POLY-TERGEMT C, Olin Corporation, Cheshire, CT.
  • Another compound useful as a hydrotrope is alkyl a phodi- carboxylic acid of the generic formula:
  • R is a C. to C 8 alkyl group
  • x is from 1 to 2
  • M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions.
  • the preferred alkyl chain length (R) is a C.. to C alkyl group and the dicarboxylic acid functionally is diacetic acid and/or dipropionic acid.
  • a suitable example of an alkyl amphodicarboxylic acid is the amph ⁇ teric surfactant Miranol R 2CM Gone, manufactured by Miranol, Inc., Dayton, NJ.
  • Organic solvent The compositions of the invention will most preferably contain an organic solvent system present at levels of from about 1% to about 30% by wei «ght, preferably from abcut 1% to about 20% by weight, more preferably from about 2% to about 15% by weight of the composition.
  • the organic solvent system may be a mono, or mixed solvent system.
  • at least the major component of the solvent system is of low volatility.
  • Suitable organic solvents for use herein has the general formula: R' RO(Oi CHO) n ⁇ wherein R is an alkyl, alkenyl, or alkyl aryl group having from about 1 to about 8 carbon atoms, R' is either H or Ctr, and n is an integer from 1 to 4.
  • R is an alkyl group containing l to 4 carbon atoms, and n is 1 or 2.
  • Especially preferred R groups are n-butyl or iso- butyl.
  • solvents useful herein include the water soluble CARBITOL or CELLOSOLVE solvents. These solvents are compounds of the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived fr ⁇ n ethyl, propyl or butyl.
  • Suitable solvents are benzyl alcohol, and diols such as 2-ethyl-l,3-hexanediol and 2,2,4-trimethl-l,3-pentanediol.
  • diols such as 2-ethyl-l,3-hexanediol and 2,2,4-trimethl-l,3-pentanediol.
  • the low molecular weight, water-soluble, liquid polyethylene glycols are also suitable solvents for use herein.
  • alkane mono and diols especially the C1-C6 alkane mono and diols are suitable for use herein.
  • C1-C4 monohydric alcohols especially the C1-C6 alkane mono and diols are suitable for use herein.
  • ethanol eg: ethanol, propanol, isopropanol, butanol and mixtures thereof
  • ethanol particularly preferred
  • C1-C4 dihydric alcohols including propylene glycol, are also preferred.
  • compositions acx ⁇ rding to the present invention may additionally comprise thickening agents, such as polyquateriura cellulose cationic polymer, for example QuatrisoftR available from the Americhol Corporation.
  • thickening agents such as polyquateriura cellulose cationic polymer, for example QuatrisoftR available from the Americhol Corporation.
  • Calcium - Compositions according to the present invention may optionally comprise from about 0.01% to about 3%, more preferably from about 0.15% to about 0.9% of calcium ions.
  • the calcium ions can, for example, be added as a chloride, hydroxide, oxide, formate or acetate, or nitrate salt. If the anionic surfactants are in the acid farm, the calcium can be added as a calcium oxide or calcium hydroxide slurry in water to neutralise the acid.
  • the calcium ions may be present in the compositions as salts.
  • the amount of calcium ions present in compositions of the invention nay be dependent upon the amount of total anionic surfactant present herein.
  • the molar ratio of calcium ions to total anionic surfactant is preferably from about 1:0.1 to about 1:25 more preferably from about 1:2 to about 1:10, for compositions of the invention.
  • Calcium stabilising agent - In order to provide good product stability, and in particular to prevent the precipitation of insoluble calcium salts malic, maleic or acetic acid, or their salts, or certain lime soap dispersant compounds may be added to the composition of the present invention comprising calcium .
  • malic, maleic or acetic acid, or their salts can be added at levels of from about 0.05% to about 10% of the composition and a molar ratio with calcium of from about 10:1 to about 1:10.
  • Magnesium - From about 0.01% to about 3%, most preferably from about 0.15% to about 2%, by weight, of magnesium ions are preferably added to the liquid detergent compositions of the invention for improved product stability, as well as improved sudsing.
  • the magnesium can be added by neutralisation of the acid with a magnesium oxide or magnesium hydroxide slurry in water. Calcium can be treated similarly. This technique minimizes the addition of chloride ions, which reduces corrosive properties.
  • the neutralized surfactant salts and the hydrotrope are then added to the final mixing tank and any optional ingredients are added before adjusting the pH.
  • pH of the Oumnositions - The composition according to the present invention formulated for use in manual dishwashing applications are preferably formulated to have a pH at 20°C of from about 3 to about 12, preferably from about 6 to about 9, most preferably from about 7 to about 8.5.
  • the dishwashing composition may be formulated for use as in pre-treatment applications whereby the composition is applied in essentially the concentrated farm onto the dishes. Preferably the composition is ⁇ allowed to remain on the dishes for a period of time.
  • Compositions for use in such .applications preferably have a pH of from about 3 to about 14, more preferably from about 3 to about 5 or greater than about 8.
  • the dispersing agent used in the above examples may be replaced by any of the dispersing agents described herein.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Detergent Compositions (AREA)

Abstract

Esters anioniques entièrement et partiellement oligomérisés, pouvant être utilisés comme agents dispersants dans des compositions détersives. Ces esters comprennent des unités téréphtalate, des unités oxy-1,2-alkylèneoxy (les unités oxyéthylèneoxy sont de préférence utilisées), ainsi que des unités sulfo-isophtalate.
PCT/US1994/003740 1993-04-07 1994-04-05 Oligomeres d'ester sulfone pouvant etre utilises comme agents dispersants dans des compositions detersives WO1994022937A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP94912958A EP0698049A4 (fr) 1993-04-07 1994-04-05 Oligomeres d'ester sulfone pouvant etre utilises comme agents dispersants dans des compositions detersives
JP6522475A JPH08511285A (ja) 1993-04-07 1994-04-05 洗剤組成物の分散助剤として好適なスルホン化エステルオリゴマー
BR9405863A BR9405863A (pt) 1993-04-07 1994-04-05 Oligômeros éster sulfonatados adequados como agentes dispersantes em composições de detergentes

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US4499593A 1993-04-07 1993-04-07
US21044294A 1994-03-23 1994-03-23
US08/044,995 1994-03-23
US08/210,442 1994-03-23

Publications (1)

Publication Number Publication Date
WO1994022937A1 true WO1994022937A1 (fr) 1994-10-13

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PCT/US1994/003740 WO1994022937A1 (fr) 1993-04-07 1994-04-05 Oligomeres d'ester sulfone pouvant etre utilises comme agents dispersants dans des compositions detersives

Country Status (5)

Country Link
EP (1) EP0698049A4 (fr)
JP (1) JPH08511285A (fr)
BR (1) BR9405863A (fr)
CA (1) CA2159982A1 (fr)
WO (1) WO1994022937A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996018715A2 (fr) * 1994-12-14 1996-06-20 The Procter & Gamble Company Esters oligomeres convenant comme agents de lavage facilite dans des compositions detergentes
GB2307694A (en) * 1995-11-30 1997-06-04 Unilever Plc Detergent compositions containing soil release polymers
US5691298A (en) * 1994-12-14 1997-11-25 The Procter & Gamble Company Ester oligomers suitable as soil release agents in detergent compositions
US5789366A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
US5789367A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
US5789365A (en) * 1995-11-30 1998-08-04 Lever Brothers Division Of Conopco Inc. Detergent compositions containing soil release polymers
EP0776965A3 (fr) * 1995-11-30 1999-02-03 Unilever N.V. Compositions de polymères
AU731499B2 (en) * 1995-11-30 2001-03-29 Unilever Plc Polymer compositions
CN103773619A (zh) * 2014-02-20 2014-05-07 苏州龙腾万里化工科技有限公司 一种餐具洗涤剂
EP3222647A1 (fr) 2016-03-22 2017-09-27 WeylChem Wiesbaden GmbH Polyester, son procédé de fabrication et d'utilisation
JP2019127596A (ja) * 2018-01-25 2019-08-01 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 不透明な液体洗剤組成物を作製する方法
WO2022100876A1 (fr) 2020-11-13 2022-05-19 WeylChem Performance Products GmbH Compositions aqueuses de polyester, détergents et agents de nettoyage les contenant et leur utilisation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007038029A1 (de) * 2007-08-10 2009-02-12 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit polyesterbasiertem Soil-Release-Polymer

Citations (4)

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US4721580A (en) * 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
US4877896A (en) * 1987-10-05 1989-10-31 The Procter & Gamble Company Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US4976879A (en) * 1987-10-05 1990-12-11 The Procter & Gamble Company Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US5182043A (en) * 1989-10-31 1993-01-26 The Procter & Gamble Company Sulfobenzoyl end-capped ester oligomers useful as soil release agents in granular detergent compositions

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Publication number Priority date Publication date Assignee Title
CA2090236C (fr) * 1990-09-07 1998-09-29 Robert Y. L. Pan Agents detachants pour detergents a lessive en poudre

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Publication number Priority date Publication date Assignee Title
US4721580A (en) * 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
US4877896A (en) * 1987-10-05 1989-10-31 The Procter & Gamble Company Sulfoaroyl end-capped ester of oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US4976879A (en) * 1987-10-05 1990-12-11 The Procter & Gamble Company Sulfoaroyl end-capped ester oligomers suitable as soil-release agents in detergent compositions and fabric-conditioner articles
US5182043A (en) * 1989-10-31 1993-01-26 The Procter & Gamble Company Sulfobenzoyl end-capped ester oligomers useful as soil release agents in granular detergent compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0698049A4 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5691298A (en) * 1994-12-14 1997-11-25 The Procter & Gamble Company Ester oligomers suitable as soil release agents in detergent compositions
WO1996018715A3 (fr) * 1994-12-14 1996-08-22 Procter & Gamble Esters oligomeres convenant comme agents de lavage facilite dans des compositions detergentes
WO1996018715A2 (fr) * 1994-12-14 1996-06-20 The Procter & Gamble Company Esters oligomeres convenant comme agents de lavage facilite dans des compositions detergentes
US5789365A (en) * 1995-11-30 1998-08-04 Lever Brothers Division Of Conopco Inc. Detergent compositions containing soil release polymers
US5789366A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
US5789367A (en) * 1995-11-30 1998-08-04 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing soil release polymers
GB2307694A (en) * 1995-11-30 1997-06-04 Unilever Plc Detergent compositions containing soil release polymers
EP0776965A3 (fr) * 1995-11-30 1999-02-03 Unilever N.V. Compositions de polymères
AU731499B2 (en) * 1995-11-30 2001-03-29 Unilever Plc Polymer compositions
CN103773619A (zh) * 2014-02-20 2014-05-07 苏州龙腾万里化工科技有限公司 一种餐具洗涤剂
EP3222647A1 (fr) 2016-03-22 2017-09-27 WeylChem Wiesbaden GmbH Polyester, son procédé de fabrication et d'utilisation
DE102016003544A1 (de) 2016-03-22 2017-09-28 Weylchem Wiesbaden Gmbh Polyester, Verfahren zu deren Herstellung und deren Verwendung
JP2019127596A (ja) * 2018-01-25 2019-08-01 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ 不透明な液体洗剤組成物を作製する方法
WO2022100876A1 (fr) 2020-11-13 2022-05-19 WeylChem Performance Products GmbH Compositions aqueuses de polyester, détergents et agents de nettoyage les contenant et leur utilisation
DE102020006977A1 (de) 2020-11-13 2022-05-19 WeylChem Performance Products GmbH Wässrig-alkoholische Polyesterzusammensetzungen, Wasch- und Reinigungsmittel enthaltend diese und deren Verwendung

Also Published As

Publication number Publication date
BR9405863A (pt) 1995-12-26
EP0698049A4 (fr) 1998-04-29
JPH08511285A (ja) 1996-11-26
EP0698049A1 (fr) 1996-02-28
CA2159982A1 (fr) 1994-10-13

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