WO2006034070A1 - Formulations fluides de sulfopolyester et produits fabriqués à partir desdites formulations - Google Patents

Formulations fluides de sulfopolyester et produits fabriqués à partir desdites formulations Download PDF

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Publication number
WO2006034070A1
WO2006034070A1 PCT/US2005/033243 US2005033243W WO2006034070A1 WO 2006034070 A1 WO2006034070 A1 WO 2006034070A1 US 2005033243 W US2005033243 W US 2005033243W WO 2006034070 A1 WO2006034070 A1 WO 2006034070A1
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Prior art keywords
sulfopolyester
group
pourable
mixture
diol
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PCT/US2005/033243
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English (en)
Inventor
Thomas Hugh Williams
Terry Ann Oldfield
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Eastman Chemical Company
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Publication date
Priority claimed from US11/220,486 external-priority patent/US20060058438A1/en
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to EP05796760A priority Critical patent/EP1802679A1/fr
Priority to JP2007532519A priority patent/JP2008513581A/ja
Publication of WO2006034070A1 publication Critical patent/WO2006034070A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • 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
    • A61K8/85—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C09J167/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a composition having a sulfopolyester and an alcohol that is substantially fluid at temperatures above 25 0 C. More particularly, the present invention relates to a blended composition having from 65 to 95 weight % of a sulfopolyester and from 5 to 35 weight % of an alcohol.
  • Sulfopolyesters are well known to those skilled in the art. Generally, sulfopolyesters are water-dissipatable and essentially derived from the following components: A) at least one dicarboxylic acid; B) at least one diol where at least 20 mole percent of the diol is composed of an ethylene glycol having the formula
  • n is an integer of from two to about twenty; and C) at least one difunctional dicarboxylic acid sulfomonomer containing a -SO3M group attached to an aromatic nucleus, wherein M is hydrogen or an alkali metal salt Na + , Li + , K + , Mg " " " " , Ca + *, Cu +” * " , Fe +"1” , Fe +4"1” , or a combination thereof.
  • the sulfomonomer component of the polyester constitutes from about 8 mole percent to about 45 mole percent of the total moles in constituents A-C.
  • Such water-dissipatable polyesters are described in greater detail in U.S. Patent Nos.
  • the water-dissipatable sulfopolyesters may be branched or linear. Such sulfopolyesters have found widespread utility in such areas as personal care applications, adhesive formulations, coatings and other products that can be dissolved, dispersed or otherwise dissipated in aqueous solutions, preferably at temperatures of less than about 8O 0 C.
  • 6,346,234 discloses a hair styling composition wherein one component is a anionic fixative polymer.
  • Preferred fixative polymers are sulfopolyesters marketed by Eastman Chemical Company under the trade names of AQ 1045, AQ 1350 and AQ 14000.
  • Tg glass transition temperature
  • ambient temperature can be defined as a nominal room temperature of 25 0 C to a more climatic extreme of 50 0 C.
  • the solid sulfopolyesters when adding a solid sulfopolyester to an aqueous formulation, it must first be broken into small pieces by cryogenic grinding or by freezing the polymer below its Tg and then breaking it into pieces using a physical force. The ground or broken pieces must then be kept at a temperature below the Tg to keep them from agglomerating into a larger mass.
  • the solid sulfopolyesters are added in solid form as a block or slab to hot melt adhesive formulations that are heated to more than 150 0 C. The sulfopolyester softens enough at this temperature so that it can be blended with other components of the adhesive.
  • the sulfopolyester is made into an aqueous dispersion.
  • aqueous dispersion typically contains from 0.5 to 15 weight percent of the sulfopolyester and a significant amount of water. Over time, the sulfopolyester will hydrolyze, reducing the concentration of sulfopolyester. Additionally, the high concentration of water present in the dispersion adds to the cost of shipping.
  • the fluid sulfopolyester of the present invention is a mixture having: I) from 65 to 95 weight % of a branched water-dispersible polyester; and II) from 5 to 35 weight % of an alcohol.
  • Another aspect of the present invention is an adhesive formulation incorporating from 0.5 to 80 weight % of the fluid sulfopolyester.
  • Yet another aspect of the present invention is a personal care product, such as a hair styling composition that includes the pourable branched sulfopolyester of the present invention.
  • a pourable, water-dispersible, branched sulfopolyester composition that can be used in a variety of applications, such as adhesive compositions and personal care products, can be prepared by mixing:
  • R 1 in the reactant is a hydrogen atom, an alkyl of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms;
  • R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms
  • the polyester, component (I) of the present invention contains substantially equal mole proportions of acid equivalents (100 mole %) and diol or diol and diamine equivalents (100 mole %), wherein at least 20 weight percent of the groups linking the moieties of the monomeric units are ester linkages.
  • the inherent viscosity of the polyester, component (I) is at least 0.1 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25 0 C and at a concentration of 0.5 g of polymer in 100 ml of the solvent, the glass transition temperature Tg is no greater than 20°C.
  • component (I) of the present invention can be a blend of two different polyesters comprising: (A) 20 to 80 weight percent of the linear water-dispersible polyester composition made of the residues or moieties of reaction products;
  • component (I) contains substantially equal mole proportions of acid equivalents (100 mole %) and diol or diol and diamine equivalents (100 mole %), wherein at least 20 weight percent of the groups linking the moieties of the monomeric units are ester linkages and wherein the inherent viscosity is at least 0.1 dL/g measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25 0 C and at a concentration of 0.25 g of polymer in 100 ml of the solvent, and (B) 20 to 80 weight percent of the branched water-dispersible polyester made of the moieties of reaction products;
  • At least one difunctional dicarboxylic acid which is not a sulfomonomer (2) 1 to 20 mole percent, based on the total of acid, hydroxyl and amino equivalents, of residues of at least one difunctional sulfomonomer containing at least one sulfonate group bonded to an aromatic ring wherein the functional groups are hydroxyl, carboxyl, or amino; (3) at least one difunctional reactant selected from a glycol or a mixture of glycol and diamine having two -NRH groups, the glycol containing two — C(R 1 ) 2 OH groups wherein R in the reactant is hydrogen or an alkyl group of 1 to 6 carbon atoms, and R 1 in the reactant is a hydrogen atom, an alkyl of 1 to 5 carbon atoms, or an aryl group of 6 to 10 carbon atoms; (4) 0 to 40 mole % of a difunctional reactant selected from hydroxycarboxylic acids having one -C(R-) 2
  • the branched, sulfonate-containing, water-dispersible polyesters, component (I) of the present invention comprise polyesters, including polyesteramides, having repeating, alternating residues or moieties of one or more dicarboxylic acid which is not a sulfomonomer and one or more diols or a combination of one or more diols and one or more diamines wherein the mole percentages are based on 100 mole percent dicarboxylic acid residues and 100 mole percent diol or diol and diamine residues, for a total of 200 mole percent.
  • the polyesters can include residues of monomers having mixed functionality such as hydroxycarboxylic acids, aminocarboxylic acids and/or aminoalkanols.
  • suitable difunctional dicarboxylic acid monomers used include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, or mixtures of two or more of these acids.
  • preferred suitable dicarboxylic acids include succinic; glutaric; adipic; azelaic; sebacic; fumaric; maleic; itaconic; 1,4- cyclohexanedicarboxylic; 1,3-cyclohexanedicarboxylic; phthalic; terephthalic; and isophthalic.
  • terephthalic acid is used as the dicarboxylic acid component of the polyester, superior results are achieved when at least 5 mole percent of one of the other acids is also used. It should be understood that the use of the corresponding acid anhydrides, esters, and acid chlorides of these acids is included in the term "dicarboxylic acid".
  • the difunctional sulfomonomer residue or reactant is preferably a dicarboxylic acid or ester thereof containing a metal sulfonate group or a glycol containing a metal sulfonate group or a hydroxy acid containing metal sulfonate group -SO 3 M attached to an aromatic nucleus, wherein M is hydrogen, NH 4 + , or a metal ion selected from the group ions Li + , Na + , K + , Mg 1+ , Ca ++ , Cu +4 , Nf + , Fe "1+ , and Fe + ⁇ .
  • the aromatic nucleus to which the metal sulfonate group -SO 3 M can be attached include benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl, and methylenediphenyl.
  • the cationic portion of a nonmetallic sulfonate group optionally present in the reactant can be a nitrogen-based cation derived from nitrogen-containing bases which may be aliphatic, cycloaliphatic or aromatic basic compounds that have ionization constants in water at 25°C of 10 "3 to 10 "10 , and preferably from 10 ⁇ 5 to 10 "8 .
  • nitrogen-containing bases are ammonia, dimethylethanolamine, diethanolamine, triethanolamine, pyridine, morpholine, and piperidine, due to availability, cost, and usefulness.
  • Such nitrogen-containing bases and cations derived therefrom are described in U.S. Pat. No. 4,304,901, the disclosure of which is incorporated herein by reference in its entirety.
  • difunctional sulfomonomer residue or reactant be present in a concentration of 4 to 12 mole percent, more preferably 6 to 10 mole percent, with a mole percent of 8 being most preferred based on total acid equivalents.
  • preferred diols include diethylene glycol, triethylene glycol, and mixtures thereof. The preferred diol concentration is 10 to 80 mole percent, however, and more preferably 20 to 80 mole percent.
  • the moieties of (C)(U) and (3)(i) are preferably at a concentration of 1 to 5 mole percent, particularly when n is 10 to 30, due to the preferably higher softening points.
  • the remaining portion of the glycol component of (C), and (B)(3) can consist of aliphatic, alicyclic, and aralkyl glycols.
  • glycols examples include neopentyl glycol; ethylene glycol; propylene glycol; 1,3-propanediol; 2,4-dimethyl-2-ethylhexane-l,3-diol; 2,2-dimethyl-l,3-propanediol; 2-ethyl-2-butyl-l,3-propanediol; 2-ethyl-2-isobuty 1-1,3 - propanediol; 1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 2,2,4- trimethyl-l,6-hexanediol; thiodiethanol; 1,2-cyclohexanedimethanol; 1,3- cyclohexanedimethanol; 1,4-cyclohexanedimethanol; 2,2,4,4-tetramethyl-l,3-
  • Copolymers may be prepared from two or more of the above glycols.
  • Preferred glycols due to availability, cost, and usefulness, include neopentyl glycol, ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,6-hexane diol and cyclohexane dimethanols.
  • the amount of the moieties (C)(Ui) present in the polyester is preferably a minor amount up to 99 mole percent, more preferably 20 to 80 mole percent with a mole percent of 30 to 70 being more preferred due to the preferred balance between the desired low Tg and the desired high softening point.
  • advantageous difunctional components include 5-ammopentanol-l,4-aminomethylcyclohexanemethanol, 5-amino-2- ethyl-pentanol- 1 , 2-(4- ⁇ -hydroxyethoxyphenyl)- 1 -aminoethane, 3 -amino-2,2- dimethylpropanol, and hydroxyethylamine.
  • aminoalcohols contain from 2 to 20 carbon atoms, one -NRH group and one -CR 2 -OH group.
  • Advantageous difunctional monomer components which are aminocarboxylic acids include aromatic, aliphatic, heterocyclic, and other types in regard to component (D), (A)(4), and (B)(4) and include lactams.
  • Specific examples include 6-aminocaproic acid, its lactam known as caprolactam, omega aminoundecanoic acid, 3-amino-2- dimethylpropionic acid, 4-( ⁇ -aminoethyl)benzoic acid, 2-( ⁇ -aminopropoxy)benzoic acid, 4-aminomethylcyclohexanecarboxylic acid, and 2-( ⁇ -aminopropoxy) cyclohexanecarboxylic acid.
  • these compounds contain from 2 to 20 carbon atoms.
  • these moieties, component (D), (A)(4), and (B)(4) are less preferred, but they can be present.
  • the concentration of these moieties is preferably from 0 to 20 mole percent and more preferably less than 10 mole percent.
  • Preferred water dispersible linear polyesters of component (A) in the polyester blend contain diacid monomer residues that are 75 to 90 mole percent isophthalic acid residues, and 10 to 25 mole percent 5-sodiosulfoisophthalic acid monomer residues; and diol monomer residues of 45 to 100 mole percent diethylene glycol monomer residues and 0 up to 55 mole percent 1,4-cyclohexanedimethanol.
  • the more preferred water dispersible linear polyesters of component (A) in the polyester blend have an inherent viscosity of 0.1 to 0.6, preferably 0.2 to 0.5, and a Tg range of 25° to 88°C, preferably 29° to 55°C.
  • Related branched water-dispersible polyesters of component (B) of the polyester blend are disclosed in U.S. Pat. No. 5,218,042, the disclosure of which is incorporated herein by reference in its entirety.
  • the dispersible linear polyester composition of component (A) is blended with the branched water-dispersible polyester composition of component (B) at temperatures greater than 200°C, preferably 225°C, for at least one hour.
  • the relative amounts of the two polyesters vary from 20 to 80 weight percent of the polyester of (A) and 20 to 80 weight percent of the polyester of (B).
  • the water-dispersible polyesters described herein have an inherent viscosity of at least 0.1 dL/g, preferably 0.2 to 0.5 dL/g, measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25°C. and at a concentration of 0.25 g of polymer in 100 ml of solvent.
  • the preferred Tg of component I of the present polyester mixture according to the present invention is less than 1O 0 C, and more preferably may vary from 4° to -20°C, with a Tg of 4° to -13 0 C being most preferred.
  • the second component (II) of the sulfopolyester mixture is an alcohol.
  • the alcohol can have from 1 to 9 carbon atoms and can include linear, branched, cyclic, and aromatic alcohols which may be substituted with one or more moieties having from 2 to 6 carbon atoms. Desirably, the alcohol has a boiling point of less than 200 0 C.
  • the alcohol is a linear or branched alcohol having from 1 to 4 carbon atom, and most preferably the alcohol is selected from methanol, ethanol, isopropanol and mixtures thereof.
  • the amount of alcohol present in the pourable mixture is from 5 to 35 weight %, preferably from 5 to 30 weight %.
  • the ranges of such components, moieties or compounds expressed herein further includes all ranges therebetween and that the ranges expressed are for the sake of brevity of description.
  • the pourable, water-dispersible, branched sulfopolyester composition of the present invention can be prepared by stirring or otherwise agitating the mixture of alcohol and sulfopolyester as it is heated.
  • the mixture is heated to at least 60 0 C with stirring until it becomes very liquid or homogeneous.
  • the maximum temperature at which the pourable polyester can be prepared is the boiling point of the alcohol.
  • the pourable branched sulfopolyester mixture can be incorporated into liquid formulations at room temperature, i.e., at temperatures of from 20° to 5O 0 C and more preferably from 25° to 45 0 C.
  • Such coatings include personal care products and cosmetics where adhesion to the hair, skin, or nails is desirable.
  • An advantage of the present invention is that a pourable, branched sulfopolyester can be prepared substantially without the presence of water.
  • substantially without the presence of water means that less than 30 weight % water can be added to mixture to make it pourable at room temperature.
  • less than 20 weight % water can be added to mixture to make it pourable at room temperature, more preferably, less than 10 weight % water can be added to the mixture and most preferably, less than 0.5 weight % water can be added to mixture to make it pourable at room temperature.
  • the pourable form of branched sulfopolyester of the present invention are suitable for use as adhesives for many substrates including non woven assemblies (such as non woven polypropylene), paper products (such as paper and paperboard), and wood pulp.
  • An adhesive composition according to the present invention can be applied as a liquid in a solvent or in an aqueous solution at a concentration of 0.5 to 80 weight percent with the remainder being solvent or water or mixtures thereof.
  • the pourable, branched sulfopolyester of the present invention comprises from 0.5 to 35 weight % of an adhesive composition.
  • the adhesive compositions When applied as a solution, the adhesive compositions are generally applied by conventional processes, such as extrusion coating, spray coating, roll coating, brush coating, dip coating, etc.
  • the adhesive composition according to the present invention may be used as a hot melt adhesive or a pressure sensitive adhesive as described in U.S. Patent Nos. 6,642,304 issued to Hansen et al. on November 4, 2003; 6,162,890 issued to George et al., and 6,293,037 issued to Spada et al. on September 25, 2001, the entire disclosures of which are incorporated herein by reference.
  • the pourable sulfopolyester of the present invention may be used as an emulsifier as is known to those skilled in the art and be present in an amount of from 0.5 to 15 weight %.
  • the adhesive compositions of the present invention are preferably not cross-linked since that would impair the water-dispersibility of the sulfopolyester. However, they may be cross-linked, to a certain extent with diisocyanates to improve strength and heat resistance although this is less preferred.
  • An adhesive composition according to the present invention may further contain from 0.1 to 0.5 weight % stabilizers.
  • Suitable stabilizers include the antioxidant type and generally consist of sterically hindered phenols, or sulfur or phosphorous substituted phenols.
  • An especially useful antioxidant is Irganox 1010 (from Ciba-Geigy, Hawthorne, N.Y.) which is a pentaerythritol tetrakis-3(3,5-di-tertiarybutyl-4- hydroxyphenyl)propionate.
  • Tackifiers may also be added to the polyester composition. Tackifiers are typically selected from at least one of the groups consisting of hydrocarbon resins, synthetic polyterpenes, functional copolymers, and rosin esters. Hydrocarbon resins are disclosed in U.S. Pat. No. 3,850,858 and functional copolymers, such as styrene-co-maleic anhydride, are well known in the art. Hydrocarbon resins, prepared according to U.S. Pat. No.
  • polyterpenes can be used alone or in combinations.
  • tackifying resins which preferably have softening points of at least 100° C and most preferably 120 0 C, can be used in amounts of 10% to 50% by weight of the adhesive composition, and preferably is 25% to 40% by weight.
  • Suitable resins and rosin esters are the terpene polymers such as the polymeric, resinous materials including the dimers as well as higher polymers obtained by polymerization and/or copolymerization of terpene hydrocarbons such as the alicyclic, monocyclic, and bicyclic monoterpenes and their mixtures, including allo-ocimene, carene, isomerized pinene, pinene, dipentene, terpinene, terpinolene, limonene, turpentine, a terpene cut of fraction, and various other terpenes.
  • Commercially available resins of the terpene type include the Zonarez terpene B-series and 7000 series from Arizona Chemical.
  • rosin esters with acid numbers above 5 such as the Zonatac resins from Arizona Chemical.
  • Particularly useful materials are terpene mixtures containing a mixture of sulphate terpene, and at least 20% of at least one other terpene selected from the group consisting of pinene, limonene, or dipentene.
  • the pourable sulfopolyester of the present invention may also be used in a hair styling composition that includes from 0.5 to 50 weight %, preferably from 0.5 to 15 weight % of the pourable branched sulfopolyester mixture described above wherein the polymer after being applied to keratinous fibers and dried, provides a styling material having a glass transition temperature (Tg) of less than +10 0 C and a detachment profile defined by: a) a maximum detachment force F max of greater than 1 newton and b) a separation energy E S(m/g) of the styling material placed in contact with a glass surface of less than 300 ⁇ J when the glass temperature Tg is less than -15°C.
  • Tg glass transition temperature
  • F max maximum detachment force
  • E S(m/g) separation energy
  • F max denotes the maximum tensile force, measured using an extensometer, required to detach the respective 38 millimeter square surfaces of two rigid, inert and non-absorbent substrates (A) and (B) placed opposite one another.
  • the surfaces are coated beforehand with the composition at a rate of 53/c ⁇ g/mm 2 where "c" is the dry matter concentration in the composition (in grams per gram of composition), i.e. the ratio of the mass of dry matter in the composition to the total mass of the composition.
  • the surfaces are dried for 24 hours at 22°C. at a relative humidity of 50%.
  • the surfaces are then subjected for 20 seconds to a compressive force of 3 newtons and finally subjected for 30 seconds to tension at a rate of 20 mm/minute.
  • E S(m/g) denotes the energy supplied by the extensometer in order to bring about the "separation" of the respective 38mm 2 surfaces of two rigid, inert and non- absorbent substrates (C) and (D) placed opposite one another; one of the substrates consisting of polished glass and the other substrates being identical in nature to the above- defined substrates (A) and (B).
  • the substrates have a surface which is coated with the composition at a rate of 53/c ⁇ g/mm 2 , where "c" is as defined above.
  • the two surfaces of the substrates (C) and (D) are subjected subsequently for 20 seconds to a compressive force of 3 newtons and finally subjected for 30 seconds to tension at a rate of 20 mm/minute.
  • the solid, rigid, inert and non-absorbent substrates can be selected from those consisting of polyethylene, polypropylene, metal alloy and, more preferably, glass.
  • composition according to the invention can comprise other constituents which are conventional in cosmetics, especially preservatives, perfumes, UV filters, and active hair care agents. It is understood that the person skilled in the art will know how to select these constituents and their amount in the composition according to the invention so as not adversely to affect its styling properties.
  • compositions according to the invention can be provided in any form known from the prior art which is appropriate for their application to the hair, in particular in the form of a vaporizable composition, mousse, gel, or lotion.
  • the appropriate cosmetically acceptable vehicle is adapted to the method of application selected.
  • the vehicle consists preferably of an appropriate solvent to which may be added additives such as gelling agents, foaming agents, and silicones.
  • the composition is vaporizable either by means of a pump or is a pressurized aerosol composition which are well known in the art.
  • the vaporizable composition according to the invention is a solution or dispersion comprising at least one fixative polymer according to the invention and an appropriate solvent selected from water, an alcohol having from 1 to 4 carbon atoms or an aqueous- alcoholic mixture.
  • Branched sulfopolyesters (as taught in U.S. Patent No. 5,543,488, are available from Eastman Chemical Company under the trade names AQ 1045, AQ 1350, and AQ 1950) were frozen, and broken into pieces having an average diameter of less than about
  • pourable branched sulfopoyesters in accordance with the present invention were prepared by adding 200.0 grams of the specified branched sulfopolyester and 56.4 grams of anhydrous ethanol to a 500-ml mixing vessel equipped with a paddle stirrer and condenser.
  • each of the sulfopolyesters had dispersed in the ethanol to form a homogeneous liquid.
  • the mixtures were translucent and remained homogenous after 2 weeks at room temperature. Based on the weight of ingredients added to the mixtures, these mixtures contain 78 wt% sulfopolyester solids.
  • the viscosity of the pourable sulfopolyester mixtures was measured at 25°, 45°, and
  • Branched sulfopolyester AQ 1350 was frozen, and then broken up into small pieces having an average diameter of less than about 1 inch and were kept cold on dry ice until use.
  • Pourable branched sulfopoyesters in accordance with the present invention were prepared by adding 200.0 g AQ 1350 and 80.0 g ethanol (Example 4) and 133.3 g ethanol (Example 5) to a 500-ml mixing vessel equipped with a paddle stirrer and condenser.
  • Example 4 The ingredients of each were heated with stirring to 75 0 C. After 30 minutes total mixing time, the AQ 1350 of both Example 4 and Example 5 had dispersed in the ethanol to form a homogeneous, translucent mixture. Based on the weight of ingredients added to the mixtures, these mixtures contain 71 weight % solids (Example 4) and 60 weight % solids (Example 5).
  • Example 4 The samples were allowed to sit overnight. A layer of ethanol was observed floating on top of the homogeneous mixtures. The ethanol top layer of Example 4 was less than that of Example 5. The sample of Example 4 was immediately stirred before measuring the viscosity. The results are shown in Table 2 below. The ethanol top layer of Example 5 was decanted. The percent solids of Example 5, with the top layer removed, was determined to be 78.5 weight %. This was determined gravimetrically by weighing the sample before and thereafter removing the volatile components by heating the sample overnight using a vacuum oven at a temperature of 100 0 C. EXAMPLE 6
  • the ingredients were heated with stirring to 66 0 C. After one hour total mixing time, the AQ 1350 had dispersed in the methanol to form a homogeneous, translucent mixture. The pourable mixture remained homogenous after 1 week. The mixture contained 78 weight % sulfopolyester solids, based on the weight of ingredients added to the mixture. The viscosity of this mixture over the shear rate range of 1.0 to 400 rad/s is shown in Table 2, and is compared to AQ 1350 in 56.4 g ethanol (Example 2). The viscosity of Example 6 was not determined at 6O 0 C because volatilization of the methanol at this temperature could cause the results to be inaccurate.
  • methanol and ethanol are the preferred alcohols for producing the pourable form of a branched sulfopolyester.
  • a linear sulfopolyester as taught in U.S. Patent Nos. 6,162,890 and 5,709,940 (available from Eastman Chemical Company under the trade name AQ 2350) was frozen, and then broken up into small pieces having an average diameter of less than about 1 inch and were kept cold on dry ice until use.
  • Two hundred grams of the linear sulfopolyester and 80.0 grams of anhydrous ethanol were charged to a 500-ml vessel equipped with a paddle stirrer and condenser.
  • the ingredients were heated with stirring to 78°C. After 30 minutes of mixing time it became apparent that the AQ 2350 was not dispersing in the liquid. An additional 130.0 grams of water and 50.0 grams of ethanol were added gradually over time until the AQ 2350 had dispersed. The total mixing time was 2 hours. Based on the weight of ingredients added to the mixture, the final mixture contains 42 weight % solids. After cooling to room temperature the viscous mixture was hazy. After sitting 4 weeks, the mixture showed slight separation of solids from the liquid.
  • the amount of ethanol in the final mixture was 200 g. Based on the weight of ingredients added to the mixture, the final mixture contains 31 weight % solids. After cooling to room temperature, the mixture was hazy. After sitting 5 weeks, there was evidence of slight settling of solids from the dispersion.
  • the ingredients were heated with stirring to 60 0 C. After one hour total mixing time, the AQ 1350 had solubilized in the ethanol-water blend to form a clear homogeneous mixture. After sitting 7 weeks, the mixture remained clear. Based on the weight of ingredients added to the mixture, the final mixture contains 50 weight % solids, 10 20 weight % ethanol, and 30 weight % water.
  • the viscosity of the sulfopolyester solution was measured at 25, 45, and 60 0 C and at shear rates ranging from 1.0 to 400 rad/s. Viscosities at 1.0 rad/s are given in Table 3 below. The viscosities for Example 2 are given for comparison.
  • Example 4 The purpose of this example is to show that the sulfopolyester-ethanol mixture of Example 4 can be diluted with water to achieve a homogeneous clear mixture, similar in appearance to the sample of Comparative Example 11.
  • Example 4 At room temperature, 13.44g of the sample of Example 4 was weighed into a vial. Water was added, 6.04 g, to achieve a final concentration of 50 weight % AQ 1350 sulfopolyester, 20 weight % ethanol, and 30 weight % water. The sample was mixed with a spatula. After sitting overnight to allow air bubbles to dissipate, the sample has the same appearance and viscosity as the sample of Comparative Example 11. There was no separation and no sedimentation after 4 weeks.
  • the branched sulfopolyester AQ 1350 was frozen and then broken up into small pieces having an average diameter of less than about 1 inch (2.54 cm) and were kept cold on dry ice until use. Two hundred grams of the AQ 1350 and 100.0 g of water were charged to a 500-ml mixing vessel equipped with a paddle stirrer and condenser.

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Abstract

La présente invention a pour objet un mélange basé sur un sulfopolyester ramifié, utilisable dans des formulations de produits de type adhésifs ou de soins personnels. Le mélange basé sur un sulfopolyester ramifié comprend : I) entre 65 et 95 % en masse d’un polyester ramifié hydrodispersable ; et II) entre 5 et 35 % en masse d’un alcool. Le mélange basé sur un sulfopolyester ramifié est coulable à température ambiante.
PCT/US2005/033243 2004-09-16 2005-09-15 Formulations fluides de sulfopolyester et produits fabriqués à partir desdites formulations WO2006034070A1 (fr)

Priority Applications (2)

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EP05796760A EP1802679A1 (fr) 2004-09-16 2005-09-15 Formulations fluides de sulfopolyester et produits fabriques a partir desdites formulations
JP2007532519A JP2008513581A (ja) 2004-09-16 2005-09-15 流体状スルホポリエステル配合物及びそれから製造された製品

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US61049704P 2004-09-16 2004-09-16
US60/610,497 2004-09-16
US11/220,486 2005-09-07
US11/220,486 US20060058438A1 (en) 2004-09-16 2005-09-07 Fluid sulfopolyester formulations and products made therefrom

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939682A1 (fr) * 2008-12-17 2010-06-18 Oreal Compostion cosmetique comprenant un polyester sulfonoique ramifie, un polymere fixant additionnal et un epaississant particulier, utilisations en coiffage
US20120183861A1 (en) * 2010-10-21 2012-07-19 Eastman Chemical Company Sulfopolyester binders
US9598802B2 (en) 2013-12-17 2017-03-21 Eastman Chemical Company Ultrafiltration process for producing a sulfopolyester concentrate
US9605126B2 (en) 2013-12-17 2017-03-28 Eastman Chemical Company Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion
US9617685B2 (en) 2013-04-19 2017-04-11 Eastman Chemical Company Process for making paper and nonwoven articles comprising synthetic microfiber binders

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250296A (en) * 1977-08-18 1981-02-10 Cassella Aktiengesellschaft Levelling agent and process for the even dyeing of materials made of synthetic fibers
US5158762A (en) * 1992-03-09 1992-10-27 Isp Investments Inc. Water-based hair spray compositions containing multiple polymers
EP1103578A2 (fr) * 1999-11-26 2001-05-30 Eastman Chemical Company Feuilles et fibres dispersibles dans l'eau à base de sulfopolyesters
US6255366B1 (en) * 1999-10-01 2001-07-03 Eastman Chemical Company Sulfopolymers as emulsion stabilizers with improved coagulum level

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4250296A (en) * 1977-08-18 1981-02-10 Cassella Aktiengesellschaft Levelling agent and process for the even dyeing of materials made of synthetic fibers
US5158762A (en) * 1992-03-09 1992-10-27 Isp Investments Inc. Water-based hair spray compositions containing multiple polymers
US6255366B1 (en) * 1999-10-01 2001-07-03 Eastman Chemical Company Sulfopolymers as emulsion stabilizers with improved coagulum level
EP1103578A2 (fr) * 1999-11-26 2001-05-30 Eastman Chemical Company Feuilles et fibres dispersibles dans l'eau à base de sulfopolyesters

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939682A1 (fr) * 2008-12-17 2010-06-18 Oreal Compostion cosmetique comprenant un polyester sulfonoique ramifie, un polymere fixant additionnal et un epaississant particulier, utilisations en coiffage
US20120183861A1 (en) * 2010-10-21 2012-07-19 Eastman Chemical Company Sulfopolyester binders
US9617685B2 (en) 2013-04-19 2017-04-11 Eastman Chemical Company Process for making paper and nonwoven articles comprising synthetic microfiber binders
US9598802B2 (en) 2013-12-17 2017-03-21 Eastman Chemical Company Ultrafiltration process for producing a sulfopolyester concentrate
US9605126B2 (en) 2013-12-17 2017-03-28 Eastman Chemical Company Ultrafiltration process for the recovery of concentrated sulfopolyester dispersion

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