Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/37—Esters of carboxylic acids
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/87—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
  • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/43—Thickening agents
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
• • 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
  • C11D3/3726—Polyurethanes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/48—Thickener, Thickening system

Definitions

• the present invention is directed to liquid thickeners for aqueous systems containing polyurethane associative thickeners and ethoxylated glycerides and to their use in the preparation of thickened aqueous systems, such as cosmetics, latex paints, water-based inks and printing pastes, paper coatings agents, detergents.
• liquid thickeners of the invention advantageously, contain neither an organic solvent, nor volatile organic compounds, nor other viscosity suppressing agents, they can be easily incorporated into aqueous systems and are acceptable for cosmetic use.
• Polyurethane associative thickeners are well known and described in many publications (such as in US 4,079,028 and US 4,155,892, both assigned to Rohm and Haas).
• Certain surfactants such as alkoxylated phenols, are toxicologically objectionable; others are not so efficient in reducing the viscosity of the thickener, especially in the case of highly active, extremely pseudoplastic thickeners, or they give rise to unstable compositions, or they adversely affect some properties in applications.
• a liquid thickener for aqueous systems containing, as viscosity suppressing agent, from 5 to 40% wt of ethoxylated mono- and/or di- glycerides of carboxylic acids having from 6 to 18 carbon atoms, from 15 to 40% wt of a polyurethane associative thickener, obtained from the reaction of at least one organic polyisocyanate, at least one water soluble polyether diol and at least one hydrophobic capping agent containing from 10 to 24 carbon atoms, from 20 to 80% wt of water, and which is devoid of organic solvents, volatile organic compounds and other viscosity suppressing agents, exhibits the characteristics mentioned in the above paragraph.
• the above described ethoxylated mono and/or di-glycerides are also effective as stabiliser of the liquid thickeners.
• the mono and/or di-glycerides useful for the realisation of the present invention are known and described for example in US 3,934,003. They can be prepared, for example, by reacting ethylene oxide with partial glycerides, which can be obtained by fractionating natural oil fatty acids, or by ethoxylation of glycerine followed by ester- ification of the resulting product with fatty acids.
• ethoxylated mono- and/or di-glycerides of fatty acids are particularly appreciated, as they also act as emollient components.
• the mono and/or di-glycerides of the invention are water soluble, and are ethoxylated with from 4 to 12 moles of ethylene oxide.
• the liquid thickener comprises an associative polyurethane obtained from the reaction of at least one organic poly- isocyanate, at least one water soluble polyether diol and at least one hydrophobic capping agent containing from 12 to 24 carbon atoms.
• Examples of utilisable polyurethanes are linear or branched polyurethanes obtained from the reaction of polyethylene glycol or polypropylene glycol (having an average molecular weight of 4,000 to 14,000), linear or branched monohydric alcohols containing from 10 to 24 carbon atoms and of one ore more isocyanates selected from hexamethylene- 1 ,6-diisocyanate, l-isocyanatomethyl-5-isocyanato-l,3,3-trimethylc ⁇ clohexane, 4,4'-dic ⁇ clohexyl methane diisocyanate, l,6-diisocyanato-2,4,4-trimethylhexane, 2,6- and
• the liquid thickeners of the invention are devoid of solvents, volatile organic compounds and other viscosity suppressing agents, i.e. they contain less than 1% wt of the sum of said substances.
• the associative polyurethane contained in the liquid thickener of the invention may be newtonian, i.e. highly effective at mid-high shear rate, or even pseudoplastic, i.e.
• Liquid thickeners comprising associative compounds are normally used to thicken binder-containing compositions, sirh as water-based paper coating agents and water based varnish and paints.
• Suitable binders are emulsion binders, sirh as alkyd resins, and latex binders, such as polyvinyl acetate, copolymers of vinyl acetate and acrylate, and/or ethylene, and/or vinyl chloride, and/or styrene, polyacrylates.
• the liquid thickeners of the invention have proven to be suited to thicken aqueous based binder-containing compositions.
• a particularly preferred liquid thickener according to the present invention which, unexpectedly, has been found well suited for use even in binder-free aqueous com- positions, contains from 5 to 30% wt of mono and/or di-gl ⁇ cerides of caprylic and capric acids ethoxylated with about 6 moles of ethylene oxide, from 15 to 30% wt of an associative polyurethane obtained from the reaction of polyethylene glycol, 4,4'-dic ⁇ clohexyl methane diisocyanate and/or l-isocyanatomethyl-5-isocyanato-l,3,3-trimethylc ⁇ clohexane and C 16 -C 2 ⁇ branched monohydric alcohol, preferably C 16 or C 20 Guerbet abohol, and having a molecular weight of about 6,000 to 20,000, and from 40 to 80% wt of water; this preferred liquid thickener is colourless, transparent, remarkably stable over time and can be advantageously used to obtain thickened,
• the liquid thickeners of the invention can be prepared by reacting at least one organic polyisocyanate, at least one water soluble polyether diol and at least one hydrophobic capping agent to obtain an associative polyurethane, and then mixing the polyurethane with the proper amount of ethoxylated mono- and/or di-gly_-erides of carboxylic acids having 6 to 18 carbon atoms and adjusting the amount of water prior or after the mixing step.
• the associative polyurethanes are prepared according to techniques generally known for the synthesis of urethanes, preferably in sirh a way that no isocyanate remains unreacted.
• Anhydrous conditions are achieved by preliminary drying of reactants.
• reaction is run preferably without any solvent.
• reaction temperature should be selected in order to obtain reasonably fast reaction and polymer viscosity while avoiding undesirable side reactions.
• the liquid thickener according to the invention is prepared by adding the ethoxylated mono and/or di-gl ⁇ ceride immediately after the preparation of the associative polyurethane, while still in molten form.
• the polygl ⁇ col is placed in a mixer, heated and de-watered for several hours.
• the polyisocyanate and catalyst are added and after a suitable reaction time, the capping agent is added and allowed to react.
• the ethoxylated mono and/or di-gly_-eride is then preferably added to the molten polyurethane and then the polyurethane is dispersed in water.
• the liquid thickener of the invention can be obtained by mixing the proper amounts of associative polyurethane in dry form, of ethoxylated mono- and/or di-gl ⁇ cerides of carboxylic acids having from 6 to 18 carbon atoms and the proper amount of water.
• It is another object of the present invention a process for the preparation of liquid thickeners, comprising the following steps: a) reacting at least an organic poly- isocyanate, at least a water soluble polyether diol and at least a hydrophobic capping agent containing from 10 to 24 carbon atoms, to obtain an associative polyurethane, preferably in molten form; b) mixing the polyurethane, preferably in molten form, with from 0.1 to 2.7 parts by weight of ethoxylated mono and/or di-gly_-erides of carboxylic acids having from 6 to 18 carbon atoms and with from 0.5 to 5.3 parts by weight of water.
• the liquid thickener according to the invention are particularly suited for the preparation of cosmetics, sirh as shampoos, hair lotions and creams, masks; latex paints; water-based paper coatings; cleaners, in particular household cleaners containing acids as the active ingredients, sirh as metal cleaners, de-scalant, toilet bowl cleaners, automatic dishwasher rinse additives, and the like.
• liquid thickeners of the invention are characterised by an exceptionally low viscosity combined with high thickening efficiency, even when they contain highly active associative polyurethanes.
• the ethoxylated gly_-erides of the invention permit to obtain stable aqueous compositions that do not separate during stock at room temperature and are easy to handle during synthesis of the thickener.
• Example 1-6 Viscosity of liquid thickeners prepared from a molten polyurethane.
• a reaction vessel equipped with internal thermometer, stirrer and cooler, is filled, under nitrogen atmosphere and at room temperature with 254.3 g of a 4,000 average molecular weight poryethyleneglyxjl.
• the polyethylenegly_-ol is melted, heated to 110 0 C and dehydrated for 3 hours under vacuum; the temperature is then stabilised at 75 0 C and the reactor content placed under a nitrogen blanket.
• the molten polymer is diluted with 300 g of Sterol CC 595 (PEG-6 capric- caprylic gl ⁇ ceride, from Cesalpinia Chemicals) and 400 g of demineralized water to give a solvent free liquid thickener made of about 30% polyurethane/30% Sterol CC 595 / 40% water, having Brookfield Viscosity at 20 0 C of 7,320 mPa*s (S06; 50 rpm).
• Sterol CC 595 PEG-6 capric- caprylic gl ⁇ ceride, from Cesalpinia Chemicals
• the obtained liquid thickener is transparent and colourless.
• Example 1 The procedure of Example 1 was repeated with the exception that Sterol CC 595 was replaced by the nonionic viscosity suppressing agents listed below, to obtain liquid thickeners having the composition and Brookfield viscosity at 20 0 C reported in Table 1.
• Rolfor 123/6.5 C 12 -C 13 alcohol 6.5 OE, Cesalpinia Chemicals
• Rolfor TR/40 Isotridecyl Alcohol 40 OE, Cesalpinia Chemicals;
• Rolfor TR8/L Isotridecyl Alcohol 8 OE, Cesalpinia Chemicals ;
• Borchigen DFN Benzyl p-hydroxy biphenyl ethoxylated, Borchers.
• Viscosity Stability Foam Appearance Viscosity suppressing persistence (mPa*s) agent transparent
• Example 16-20 [0102] 1.2 g of liquid thickener of, respectively, Example from 7 to 11 were added to 98.8 g of Rolflex D148.
• a reaction vessel equipped with internal thermometer, stirrer and cooler, is filled, under nitrogen atmosphere and at room temperature with 221.4 g of a 4,000 average molecular weight poryethyleneglyxjl.
• the polyethylenegl ⁇ col is melted, heated to 110 0 C and dehydrated for 3 hours under vacuum; the temperature is then stabilised at 75 0 C and the reactor content placed under a nitrogen blanket.
• Polyurethane B Preparation of the polyurethane (Polyurethane B): [0118] Polyurethane B was prepared as described in Example 21, except that neither Sterol CC 595 nor water were added and the polyurethane was isolated as a solid, easily friable wax. [0119] Preparation of the liquid thickeners: [0120] 25 g of Polyurethane B were added to a mixture of 25 g of viscosity suppressing agent (see Table 4) and 50 g of water under vigorous stirring for one hour and then the liquid thickener was stored at 20 0 C.
• Example 28-31 Preparation of liquid thickeners.
• Example 28 [0141] A reaction vessel, equipped with internal thermometer, stirrer and cooler, is filled, under nitrogen atmosphere and at room temperature with 214.4 g of a 4,000 average molecular weight poryethyleneglyxjl.
• the polyethylenegl ⁇ col is melted, heated to 110 0 C and dehydrated for 3 hours under vacuum; the temperature is then stabilised at 75 0 C and the reactor content placed under a nitrogen blanket.
• IPDI isophoronediisocyanate
• dibutyltin dilaurate as catalyst
• the molten polymer is diluted with 20Og of Sterol CC 595, 550 g of dem- ineralized water to give a liquid thickener made of 25% polyurethane CZ20% Sterol CC 595/55% water, having a Brookfield viscosity of 5620 mPa*s (S05; 50 rpm)
• liquid thickeners of the present invention are the only able to appreciatively thicken water and to give a transparent and colourless aqueous solution.
• a soft and silky shower cream is obtained with physiological pH.
• a Newtonian shower gel is obtained, delicate on skin thanks to the presence of a detoxifying surfactant sirh as cocopolyghrose tartrate.
• a detoxifying surfactant sirh as cocopolyghrose tartrate.
• the addition of the liquid thickener does not alter the pH of the formulation.
• [0190] [0191] Preparation of an after-shampoo balm.
• [0192] The ingredients listed in Table 11 are mixed.
• An after-shampoo balm is obtained with both the conditioning power of the wheat proteins and of guar and the soft toirh of the liquid thickener of the invention.
• the thickener of the invention gives protection to the hair thanks to a delicate film.
• the formulate is highly transparent.
• the thickener gives viscosity to the product and stabilises the less water soluble components.
• a product is obtained that, spread on skin, forms a light protective film.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Epidemiology (AREA)
• Veterinary Medicine (AREA)
• Birds (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Materials Engineering (AREA)
• Emergency Medicine (AREA)
• Cosmetics (AREA)
• Detergent Compositions (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paints Or Removers (AREA)
• Sorption Type Refrigeration Machines (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Publications (3)

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• 2005
  • 2005-10-27 IT IT000058A patent/ITVA20050058A1/it unknown
• 2006
  • 2006-10-23 AT AT06807464T patent/ATE494339T1/de not_active IP Right Cessation
  • 2006-10-23 JP JP2008537068A patent/JP2009513763A/ja active Pending
  • 2006-10-23 EP EP06807464A patent/EP1940978B1/en not_active Not-in-force
  • 2006-10-23 WO PCT/EP2006/067654 patent/WO2007048766A2/en not_active Ceased
  • 2006-10-23 US US12/091,508 patent/US20090209659A1/en not_active Abandoned
  • 2006-10-23 DE DE602006019461T patent/DE602006019461D1/de active Active

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