WO1993022413A1 - COMPOSITION COMPRENANT UN COPOLYMERE SE DISPERSANT DANS L'EAU CONTENANT DES MONOMERES ABSORBANT LA LUMIERE UVA et UVB - Google Patents

COMPOSITION COMPRENANT UN COPOLYMERE SE DISPERSANT DANS L'EAU CONTENANT DES MONOMERES ABSORBANT LA LUMIERE UVA et UVB Download PDF

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Publication number
WO1993022413A1
WO1993022413A1 PCT/GB1993/000081 GB9300081W WO9322413A1 WO 1993022413 A1 WO1993022413 A1 WO 1993022413A1 GB 9300081 W GB9300081 W GB 9300081W WO 9322413 A1 WO9322413 A1 WO 9322413A1
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WIPO (PCT)
Prior art keywords
alkyl
composition according
group
acid
absorbing
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PCT/GB1993/000081
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English (en)
Inventor
Matthew Evan Langer
Ferial Khorshahi
Katherine Lee
John Frederick Hessel
Dennis Sinfield
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Unilever Plc
Unilever Nv
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Application filed by Unilever Plc, Unilever Nv filed Critical Unilever Plc
Publication of WO1993022413A1 publication Critical patent/WO1993022413A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • 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
    • A61K8/88—Polyamides
    • 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
    • A61K8/90—Block copolymers
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • 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
    • 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
    • C11D3/3719—Polyamides or polyimides

Definitions

  • the subject invention relates to compositions comprising novel water-dispersible copolymers which contain a UVA
  • copolymers may optionally contain a hydrophobic monomer component. Because of their broad range of UV absorbency, the copolyesters may be used in fabric care compositions, personal product compositions, and in other applications recognized by those skilled in the art.
  • UVB 290-320 nm
  • erythema unsunburn
  • cancer M.M. Rieger
  • UVA 320-400 nm
  • the UVA (320-400 nm) portion of the solar spectrum is believed to be responsible for skin aging and premature wrinkling (L.H. Kligman, F.J. Akin, and A.M. Kligman, J. Invest. Dermatol., 84:272 (1985)).
  • UV light is also known to fade garments, especially in areas of high solar intensity.
  • This problem has been partially addressed via the application of various monomeric chromophores to garment surfaces (U.S. Patent 4,153,744 to K.H. Remley; U.S. Patent 4,788,054 to R.J. Bernhardt et. al; P.C.
  • U.S. Patent 3,864,473 to Ciaudelli teaches the use of 4-dimethylaminobenzoate-grafted poly (ethyleneimine) as a polymeric UV light absorber.
  • the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
  • 4-aminobenzoate) copolymer as a polymeric UV light absorber.
  • the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
  • cinnamate-grafted poly(dimethylsiloxanol) as a polymeric UV light absorber.
  • poly(glycidol)/poly(4-glycidylaminobenzoate) copolymer as a polymeric UV light absorber.
  • German Patent 2,726,568 to Jacguet et al. teaches the use of cyanodiphenylacrylic acid-grafted poly(vinyl acetate) as a polymeric UV light absorber.
  • U.S. Patent 4,839,160 to Forestier et al. teaches the use of benzylidenecamphor-grafted poly (aerylamide) as a polymeric sunscreen.
  • the use of either a hydrophobic or hydrophilic component to control the dispersibility and adsorption properties of the polymer is not taught.
  • the polymers used differ from the copolymers used in the compositions of the subject invention both in that there is no teaching of the use of both a UVA and a UVB light-absorbing monomer to selectively filter out both UVB and UVA light at ⁇ max; and that there is no teaching or suggestion that the UVA and UVB light-absorbing polymer can be hydrophilicly or hydrophobicly modified to control the
  • compositions comprising a water-soluble ox or water dispersible copolymer containing a UV-absorbing monomer. It is not clear from this reference, however, that the polymers must contain both a
  • UVA-absorbing and a UVB-absorbing monomer to provide the broad spectrum absorbing alcohols obtained with the polymers used in the present invention.
  • compositions comprising novel copolymers comprising both a UVB light-absorbing monomer and a UVA light-absorbing monomer.
  • compositions comprising polymers having a hydrophilic monomer which allows the polymer to be solvated in aqueous media, and optionally a hydrophobic monomer to fine-tune the polymer's ability to adhere to a desired surface.
  • compositions comprising novel water dispersible or water soluble copolymers which contain at least one UVA light-absorbing monomer, one UVB light-absorbing monomer, one hydrophilic monomer, and optionally one hydrophobic monomer component.
  • compositions may be in fabric care compositions, personal product compositions and other applications recognized by those skilled in the art.
  • compositions comprising novel water-dispersible or water-soluble copolymers which contain at least one UVA light-absorbing monomer, one UVB light-absorbing monomer, one hydrophilic monomer, and optionally one hydrophobic monomer component.
  • the optional hydrophobic monomer may be used to fine-tune the copolymer's ability to adsorb onto a desired surface.
  • compositions of the invention are intended to absorb a broad spectrum of ultraviolet radiation (ie., both UVA and UVB light) at maximum wavelength.
  • the copolymers used in the compositions of the invention are intended to achieve a balance in water-solubility such that they are soluble enough to be able to deliver normally insoluble UVA and UVB monomers to a desired surface but sufficiently insoluble such that the UVA and UVB light absorbing polymer can adhere or adsorb onto the desired surface.
  • compositions of the invention may be fabric care compositions, skin care compositions, or in other applications recognized by those skilled in the art.
  • compositions of the invention may be fabric care compositions (i.e., cleansing or detergent compositions) such as heavy duty liquid detergents (generally enzyme containing) or powdered detergents.
  • fabric care compositions i.e., cleansing or detergent compositions
  • heavy duty liquid detergents generally enzyme containing
  • powdered detergents are described in U.S. Patent No. 4,959,179 to Aronson (for liquid detergent compositions) and U.S. Patent No. 4,929,379 to Oldenburg et al. (for powdered detergent compositions), both of which are incorporated herein by reference.
  • Liquid detergent compositions may be built or unbuilt and may be aqueous or nonaqueous.
  • the compositions generally comprise about 5%-70% by weight of a detergent active material and from 0% to 50% of a builder.
  • the liquid detergent compositions of the invention may further comprise an amount of electrolyte (defined as any water-soluble salt) whose quantity depends on whether or not the composition is structured.
  • structured is meant the formation of a lamellar phase sufficient to endow solid suspending capability.
  • the water-soluble electrolyte salt may be a detergency builder, such as the inorganic salt sodium tripolyphosphate or it may be a non-functional electrolyte such as sodium sulphate or chloride.
  • whatever builder is used in the composition comprises all or part of the electrolyte.
  • the liquid detergent composition generally further comprises enzymes such as proteases, lipases, amylases and cellulases which, when present, may be used in amounts from about 0.01 to 5% of the compositions.
  • enzymes such as proteases, lipases, amylases and cellulases which, when present, may be used in amounts from about 0.01 to 5% of the compositions.
  • Stabilizers or stabilizer systems may be used in conjunction with enzymes and generally comprise from about 0.1 to 15% by weight of the composition.
  • the enzyme stabilization system may comprise calcium ion, boric acid, propylene glycol and/or short chain carboxylic acids.
  • the composition preferably contains from about 0.01.to about 50, preferably from about 0.1 to about 30, more preferably from about 1 to about 20 millimoles of calcium ion per liter.
  • the level of calcium ion should be selected so that there is always some minimum level available for the enzyme after allowing for complexation with builders, etc., in the composition.
  • Any water-soluble calcium salt can be used as the source of calcium ion, including calcium chloride, calcium formate, calcium acetate and calcium propionate.
  • a small amount of calcium ion is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • Another enzyme stabilizer which may be used is propionic acid or a propionic acid salt capable of forming propionic acid. When used, this stabilizer may be used in an amount from about 0.1% to about 15% by weight of the composition.
  • polyols containing only carbon, hydrogen and oxygen atoms are preferred. They preferably contain from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples include propylene glycol (especially 1,2-propane diol which is preferred), ethylene glycol, glycerol, sorbitol, mannitol and glucose.
  • the polyol generally represents from about 0.5% to about 15%, preferably from about 1.0% to about 8% by weight of the composition.
  • the composition herein may also optionally contain from about 0.25% to about 5%, most preferably from about 0.5% to about 3% by weight of boric acid.
  • the boric acid may be, but is preferably not, formed by a compound capable of forming boric acid in the composition. Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g. sodium ortho-, meta- and pyroborate and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid and a p-bromo
  • phenylboronic acid can also be used in place of boric acid.
  • One especially preferred stabilization system is a polyol in combination with boric acid.
  • the weight ratio of polyol to boric acid added is at least 1 to 1, more preferably at least about 1.3 to 1.
  • the detergent active material may be an alkali metal or alkanolamine soap or a 10 to 24 carbon atom fatty acid, including polymerized fatty acids, or an anionic, a nonionic, cationic, zwitterionic or amphoteric
  • anionic synthetic detergents examples include salts (including sodium, potassium, ammonium and substituted ammonium salts) such as mono-, di- and triethanolamine salts of 9 to 20 carbon alkylbenzenesulphonates, 8 to 22 carbon primary or
  • secondary alkanesulphonates 8 to 24 carbon olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Patent specification, 1,082,179, 8 to 22 carbon alkylsulphates, 8 to 24 carbon alkylpolyglycol-ether-sulphates, -carboxylates and -phosphates (containing up to 10 moles of ethylene oxide); further examples are described in
  • nonionic synthetic detergents which may be used with the invention are the condensation products of ethylene oxide, propylene oxide and/or butylene oxide with 8 to 18 carbon alkylphenols, 8 to 18 carbon fatty acid amides; further examples of nonionics include tertiary amine oxides with 8 to 18 carbon alkyl chain and two 1 to 3 carbon alkyl chains. The above reference also describes further examples of nonionics.
  • the average number of moles of ethylene oxide and/or propylene oxide present in the above nonionics varies from 1-30; mixtures of various nonionics, including mixtures of nonionics with a lower and a higher degree of alkoxylation, may also be used.
  • cationic detergents which may be used are the quaternary ammonium compounds such as alkyldimethylammonium halogenides.
  • amphoteric or zwitterionic detergents which may be used with the invention are N-alkylamine acids,
  • sulphobetaines condensation products of fatty acids with protein hydroiysates; but owing to their relatively high costs they are usually used in combination with an anionic or a nonionic
  • detergent Mixtures of the various types of. active detergents may also be used, and preference is given to mixtures of an anionic and a nonionic detergent active. Soaps (in the form of their sodium, potassium and substituted ammonium salts) of fatty acids may also be used, preferably in conjunction with an anionic and/or nonionic synthetic detergent.
  • Builders which can be used according to this invention include conventional alkaline detergency builders, inorganic or organic, which can be used at levels from 0% to about 50% by weight of the composition, preferably from 1% to about 20% by weight, most preferably from 2% to about 8%.
  • Suitable inorganic alkaline detergency builders are water-soluble alkalimetal phosphates, polyphosphates, borates, silicates and also carbonates.
  • Specific examples of such salts are sodium and potassium triphosphates, pyrophosphates, orthophosphates, hexametaphosphates, tetraborates, silicates and carbonates.
  • suitable organic alkaline detergency builder salts are: (1) water-soluble amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetracetates, nitrilotriacetates and N-(2-hydroxyethyl)-nitrilodiacetates; (2) water-soluble salts of phytic acid, e.g., sodium and potassium phytates (see U.S. Patent No. 2,379,942); (3) water-soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of
  • potassium and lithium salts of methylene diphosphonic acid and sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid.
  • Other examples include the alkali methyl salts of ethane-2-carboxy-1,1-diphosphonic acid hydroxymethanediphosphonic acid, carboxy lidiphosphonic acid,
  • Patent No. 3,308,067 is a patent No. 3,308,067.
  • polycarboxylate builders can be used satisfactorily, including water-soluble salts of mellitic acid, citric acid, and carboxymethyloxysuccinic acid and salts of polymers of itaconic acid and maleic acid.
  • polycarboxylate builders include DPA (dipicolinic acid) and ODS (oxydisuccinic acid).
  • DPA dipicolinic acid
  • ODS oxydisuccinic acid
  • Certain zeolites or aluminosilicates can be used. One such aluminosilicate which is useful in the
  • compositions of the invention is an amorphous water-insoluble hydrated compound of the formula Na x ( y AlO 2 .SiO 2 ), wherein x is a number from 1.0 to 1.2 and y is 1, said amorphous material being further characterized by a Mg++ exchange capacity of from about 50mg eq. CaCO 3 /g. and a particle diameter of from about 0.01 micron to about 5 microns.
  • This ion exchange builder is more fully described in British Pat. No. 1,470,250.
  • a second water-insoluble synthetic aluminosilicate ion exchange material useful herein is crystalline in nature and has the formula Na z [(AlO 2 ) y .(SiO 2 )]xH 2 O, wherein z and y are integers of at least 6; the molar ratio of z and y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264; said aluminosilicate ion exchange material having a particle size diameter from about 0.1 micron to about 100 microns; a calcium ion exchange capacity on an anhydrous basis of at least about 200 milligrams equivalent of CaCO 3 hardness per gram; and a calcium exchange rate on an anhydrous basis of at least about 2
  • the preferred compositions herein frequently contain a series of optional ingredients which are used for the known functionality in conventional levels. While the detergent compositions are generally premised on aqueous, enzyme-containing detergent compositions, it is frequently desirable to use a phase regulant. This component together with water constitutes then the solvent matrix for the liquid compositions.
  • phase regulants are well-known in liquid detergent technology and, for example, can be represented by hydrotropes such as salts of alkylarylsulfonates having up to 3 carbon atoms in the alkylgroup, e.g., sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-, ethylbenzene-, cumene-, and isopropylbenzene sulfonic acids. Alcohols may also be used as phase regulants. This phase regulant is frequently used in an amount from about 0.5% to about 20%, the sum of phase regulant and water is normally in the range from 35% to 65%.
  • hydrotropes such as salts of alkylarylsulfonates having up to 3 carbon atoms in the alkylgroup, e.g., sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-, ethylbenzene-, cumene-
  • compositions herein can contain a series of further optional ingredients which are mostly used in additive levels, usually below about 5%.
  • additives include: polyacids, suds regulants, opacifiers, antioxidants, bactericides, dyes, perfumes, brighteners and the like.
  • compositions under various usage conditions can require the utilization of a suds regulant. While generally all detergent suds regulants can be utilized, preferred for use herein are alkylated polysiloxanes such as dimethylpolysiloxane, also frequently termed silicones. The silicones are frequently used in a level not exceeding 0.5%, most preferably between 0.01% and 0.2%.
  • opacifiers include: polystyrene commercially known as LYTRON 621 manufactured by Monsanto Chemical Corporation. The opacifiers are frequently used in an amount from 0.3% to 1.5%.
  • the compositions herein can also contain known antioxidants for their known utility, frequently radical
  • scavengers in the art established levels, i.e., 0.00 to 0.25% (by reference to total composition) These antioxidants are frequently introduced in conjunction with fatty acid
  • liquid detergent compositions of the invention may also contain deflocculating polymers such as described in U.S. Patent No. 5,071,586, hereby incorporated by reference.
  • the liquid composition is an aqueous composition
  • the balance of the formulation consists of an aqueous medium.
  • the above ingredients make up for the whole formulation (a nonaqueous composition may contain up to 5% water
  • An ideal liquid detergent composition might contain (all percentages by weight
  • the detergent composition of the invention might also be a powdered detergent composition.
  • Such powdered compositions generally comprise from about 5-40% of a detergent active system which generally consists of an anionic, a nonionic active, a fatty acid soap or mixtures thereof; from 20-70% of an alkaline buffering agent; up to about 40% builder and balance minors and water.
  • the alkaline buffering agent may be any such agent capable of providing a 1% product solution with a pH of above 11.5 or even 12.
  • Advantageous alkaline buffering agents are the alkalimetal silicates, as they decrease the corrosion of metal parts in washing machines, and in particular sodium orthometa- or di-silicates, of which sodium metasilicate is preferred.
  • the alkaline buffering agent is present in an amount of from 0 to 70% by weight, preferably from 0 to 30% by weight.
  • powdered detergent compositions of the invention can and normally will contain detergency builders in an amount of up to 40% by weight and preferably from 5 to 25% by weight of the total composition.
  • Suitable builders include sodium, potassium and ammonium or substituted ammonium pyro- and tri-polyphosphates, -ethylene diamine tetraacetates, -nitrilotriacetates,
  • -etherpolycarboxylates -citrates, -carbonates, -orthophosphates, -carboxymethyloxysuccinates, etc.
  • Specific builders include DPA and ODS. Also less soluble builders may be included, such as e.g., an easily dispersible zeolite. Particularly preferred are the polyphosphate builder salts, nitrilotriacetates, citrates, carboxymethyloxysuccinates and mixtures thereof.
  • sequestering agents such as ethylenediamine tetraphosphonic acid
  • soil-suspending agents such as
  • sodiumcarboxymethylcellulose polyvinylpyrrolidone or the maleic anhydride/ vinylmethylether copolymer, hydrotropes; dyes;
  • perfumes such as: perfumes; optical brighteners; alkali-stable enzymes; germicides; anti-tarnishing agents; lather depressants; fabric softening agents; oxygen- or chlorine-liberating bleaches, such as
  • the remainder of the composition is water.
  • An ideal powdered detergent composition might contain the
  • UVA and UVB copolymers described herein may also be used in personal product compositions such as, for example, soap bar compositions, facial or body cleansing compositions, shampoos for hair or body, conditioners, cosmetic compositions or sunscreen compositions.
  • the copolymers may be used, for example, in a toilet bar (i.e., soap and/or detergent bar) formulation.
  • a toilet bar i.e., soap and/or detergent bar
  • Typical toilet bar compositions are those comprising fatty acid soaps used in combination with a detergent other than fatty acid soap and free fatty acids. It should be noted that the composition may comprise no fatty acid soap and may be based on actives other than fatty acid soap. Mildness improving salts, such as alkali metal salt or isethionate, are also typically added. In addition other ingredients, such as germicides, perfumes, colorants, pigments, suds-boosting salts and
  • anti-mushing agents may also be added.
  • Fatty acid soaps are typically alkali metal or alkanol ammonium salts of aliphatic alkane or alkene monocarboxylic acids. Sodium, potassium, mono-, di- and tri-ethanol ammonium cations, or combinations thereof, are suitable for purposes of the invention.
  • the soaps are well known alkali metal salts of natural or
  • fatty acid soaps will generally comprise greater than 25% of the composition, generally from 30-95%.
  • the amount of soap will range from 40% to 70% by weight of the composition.
  • soap may comprise 0-50% by weight.
  • C 8 to C 24 fatty acid comprises 5-60% of the composition.
  • compositions will also generally comprise a non-soap detergent which is generally chosen from anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent materials or mixtures thereof. These surfactants are all well known in the art and are described, for example, in U.S. Patent Nos. 4,695,395 and 4,260,507 discussed above.
  • a non-soap anionic is a C 8 -C 22 acyl isethionate. These ester may be prepared by the reaction between alkali metal isethionate and mixed aliphatic fatty acids having from 8 to 22 carbons.
  • the non-soap actives may comprise from 0 to 50% of the composition.
  • a certain amount of free fatty acids of 8 to 22 carbons are also desirably incorporated into soap compositions to act as superfatting agents or as skin feel and creaminess enhancers. If present, the free fatty acids comprise between 1 and 15% of the compositions.
  • a preferred mildness improving salt which may be added to soap compositions is a simple unsubstituted sodium isethionate. This may be present as 0.1 to 50% of the composition, preferably .5% to 25%, more preferably 2% to about 15% by weight.
  • Other mildness co-actives which may be used include betaine compounds or ether sulphates. These also may be present at 0.1 to 50% of the composition, preferably 0.5% to 25%.
  • the sulfate ester surfactant may comprise .01 to 45% by weight of the composition (as the monoester), preferably 25% to 40%, and .01% to 10% of the composition (as the diester),
  • moisturizers such as glycerin, propylene glycol, sorbitol, polyethylene glycol, ethoxylated or methoxylated ether of methyl glucose etc; water-soluble polymers such as collagens, modified celluloses (such as Polymer JR (R) ), guar gums and polyacrylates; sequestering agents such as citrate, and emollients such as silicones or mineral oil.
  • moisturizers such as glycerin, propylene glycol, sorbitol, polyethylene glycol, ethoxylated or methoxylated ether of methyl glucose etc
  • water-soluble polymers such as collagens, modified celluloses (such as Polymer JR (R) ), guar gums and polyacrylates
  • sequestering agents such as citrate
  • emollients such as silicones or mineral oil.
  • Another useful set of ingredients are various co-surfactants and non-soap detergents.
  • the copolymers may be present in a facial or body cleansing composition.
  • a facial or body cleansing composition composition.
  • cleaning compositions are examples of such cleaning compositions.
  • cleansing compositions will comprise a fatty acid soap together with a non-soap surfactant, preferably a mild synthetic surfactant.
  • Cleaning compositions will also generally include a moisturizer or emollient and polymeric skin feel and mildness aids.
  • the compositions may further optionally include thickener (e.g. magnesium aluminum silicate, Carbopol),
  • water soluble polymers e.g. carboxymethyl
  • the fatty acid soaps used are such as those described above in uses in toilet bar formulations. These soaps are typically alkali metal or alkanol ammonium salts of aliphatic or alkene monocarboxylic salts. Sodium, potassium, mono-, di- and triethanol ammonium cations, or combinations thereof are suitable. Preferred soaps are 8 to 24 carbon half acid salts of, for example, triethanolamine.
  • Surfactants can be chosen from anionic, nonionic, cationic, zwitterionic or amphoteric materials or mixtures thereof such as are described in U.S. Patent No. 4,695,395 mentioned above, or in U.S. Patent No. 4,854,333 to Inman et al, hereby incorporated by reference.
  • Moisturizers are included to provide skin conditioning benefits and improve mildness. This term is often used as
  • Nonocclusive hygroscopic substances to the stratum corneum which will retain water, and make this water available to the stratum corneum to alter its physical properties and produce a cosmetically desirable effect.
  • moisturizers also function by improving the lubricity of the skin.
  • moisturizers can work in the present invention.
  • Some examples of moisturizers are long chain fatty acids, liquid water-soluble polyols, glycerin,
  • ethoxylated/propoxylated ethers of methyl glucose eg., methyl gluceth-20
  • ethoxylated/-propoxylated ethers of lanolin alcohol e.g., Solulan-75
  • Preferred moisturizers are coco and tallow fatty acids. Some other preferred moisturizers are the nonocclusive liquid water soluble polyols and the essential amino acid compounds found naturally in the skin.
  • nonocclusive moisturizers are compounds found to be naturally occurring in the stratum corneum of the skin, such as sodium pyrrolidone carboxylic acid, lactic acid, urea, L-proline, guanidine and pyrrolidone.
  • nonocclusive moisturizers include hexadecyl, myristyl, isodecyl or isopropyl esters of adipic, lactic, oleic, stearic, isostearic, myristic or linoleic acids, as well as many of their corresponding alcohol esters (sodium isostearoyl-2 lactylate, sodium capryl lactylate), hydrolyzed protein and other collagen-derived
  • Some occlusive moisturizers include petrolatum, mineral oil, beeswax, silicones, lanolin and oil-soluble lanolin
  • saturated and unsaturated fatty alcohols such as behenyl alcohol, squalene and squalane, and various animal and vegetable oils such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil, poppyseed oil, pine oil, castor oil, soybean oil, avocado oil, safflower oil, coconut oil, hazelnut oil, olive oil, grape seed oil and sunflower seed oil.
  • saturated and unsaturated fatty alcohols such as behenyl alcohol, squalene and squalane
  • various animal and vegetable oils such as almond oil, peanut oil, wheat germ oil, linseed oil, jojoba oil, oil of apricot pits, walnuts, palm nuts, pistachio nuts, sesame seeds, rapeseed, cade oil, corn oil, peach pit oil
  • the polymeric skin feel and mildness aids useful in the present invention are the cationic, anionic, amphoteric, and the nonionic polymers used in the cosmetic field. Reduced skin irritation benefits as measured by patch testing of cationic and nonionic types of polymers are set out in "Polymer JR for Skin Care” Bulletin, by Union Carbide, 1977. The cationics are preferred over the others because they provide better skin feel benefits.
  • the amount of polymeric skin feel and mildness aids found useful in the composition of the present invention is from about 0.01% to about 5%, preferably from about 0.3% to about 4%. In bar compositions with less than 5.5% soap, the polymer is used at a level of 2% to 5%, preferably 3% or more.
  • polymeric skin feel and skin mildness aids such as nonionic guar gums, Merquats 100 and 550, made by Merck & Co, Inc.; Jaguar C-14-S made by Stein Hall; Mirapol A15 made by Miranol Chemical Company, Inc.; and Galactasol 811, made by Henkel, Inc.; plus others, are usable.
  • the polymer also provides enhanced creamy lather benefits.
  • nonionic polymers found to be useful include the nonionic polysaccharides, e.g., nonionic hydroxypropyl guar gums, offered by Celanese Corp.
  • a .preferred nonionic hydroxypropyl guar gum material is Jaguar (R) HP-60 having molar substitution of about 0.6.
  • Another class of useful nonionics is the cellulosic nonionic polymers, e.g., HEC and CMC.
  • the cationic polymers employed in this invention also provide a desirable silky, soft, smooth in-use feeling.
  • the preferred level for this invention is 0.1-5% of the composition.
  • Suitable cationic polymers are copolymers of dimethylaminoethylmethacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride and acrylamide in which the ratio of the cationic to neutral monomer units has been selected to give a copolymer having a cationic charge.
  • suitable types of cationic polymers are the cationic starches, e.g., Sta-Lok R 300 and 400 made by Staley, Inc.
  • the UVA plus UVB copolymers may be used, for example, in a shampoo.
  • a shampoo examples of such compositions are described in U.S. Patent No. 4,854,333, to Inman and U.S. Patent No. 4,526,710 to Fujisawa, both of which are hereby incorporated by reference.
  • the shampoo compositions which may be used typically comprise a surfactant selected from any one of a wide variety of surfactants known in the art (such as those described in U.S.
  • the shampoo compositions may additionally comprise a compound
  • dandruff e.g. selenium sulfide.
  • compositions all may also optionally comprise a suspending agent, for example, any of several acyl derivative materials or mixtures thereof.
  • a suspending agent for example, any of several acyl derivative materials or mixtures thereof.
  • these are ethylene glycol esters of fatty acids having 16 to 22 carbons.
  • suspending agents include ethylene glycol stearates, both mono-and distearate.
  • Preferred alkanol amides are stearic
  • long chain acyl derivatives include long chain esters of long chain fatty acids (e.g., stearyl stearate, cetyl palmitate), glyceryl esters (e.g. glyceryl distearate), and long chain esters of long chain alkanol
  • amides e.g., stearamide DEA distearate, stearamide MEA stearate.
  • suspending agents are alkyl (16 to 22 carbon) dimethyl amine oxides, such as stearyl dimethyl amine oxide. If the compositions contain an amine oxide or a long chain acyl derivative as a surfactant, these components may also provide the suspending function and additional suspending agent may not be needed.
  • Xanthan gum is another agent used to suspend, for example, selenium sulfide which may be in the present
  • This biosynthetic gum material is commercially available and is a heteropolysaccharide with a molecular weight of greater than 1 million. It is believed to contain D-glucose, D-mannose and D-glucuronate in the molar ratio of 2.8:2.0:2.0. The polysaccharide is partially acetylated with 4.7% acetyl.
  • Kelco a Division of Merck & Co., Inc., offers xanthan gum as Keltrol (R) .
  • a particularly preferred suspending system comprises a mixture of xanthan gum, present at a level of from about 0.05% to about 1.0%, preferably from about 0.2% to about 0.4%, of the compositions, together with magnesium aluminum silicate
  • Magnesium aluminum silicate occurs naturally in such smectite minerals as colerainite, saponite and sapphire. Refined magnesium aluminum silicates useful herein are readily available, for example as veegum, manufactured by R.T. Vanderbilt Company, Inc. Mixtures of suspending agents are also suitable for use in the compositions of this invention.
  • thickening agents are the cross-linked polyacrylates such as those manufactured by B. F. Goodrich and sold under the Carbopol (R) tradename.
  • Another optional component for use in the present compositions is an amide.
  • compositions can be any of the alkanolamides of fatty acids known for use in shampoos. These are generally mono- and
  • diethanolamides of fatty acids having from about 8 to 24 carbon atoms Preferred are coconut monoethanolamide, lauric
  • diethanolamide and mixtures thereof.
  • the amide is present at a level of from about 1% to about 10% of the compositions.
  • compositions may also contain nonionic polymer material which is used at a low level to aid in dispersing particles.
  • the material can be any of a large variety of types including cellulosic materials such as hydroxypropyl methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose and sodium carboxymethyl cellulose as well as mixtures of these materials.
  • the nonionic polymer is used at a level of from about 0.001% to about 0.1%, preferably from about 0.002% to about 0.05%, of the composition.
  • Hydroxypropyl methyl cellulose is the preferred polymer.
  • Another suitable optional component useful in the present compositions is a nonvolatile silicone fluid.
  • the nonvolatile silicone fluid may be either a polyalkyl siloxane, a polyaryl siloxane, a polyalkylarly siloxane or a polyether siloxane copolymer and is present at a level of from about 0.1% to about 10.0%, preferably from about 0.5% to about 5.0%. Mixtures of these fluids may also be Used and are preferred in certain executions.
  • the dispersed silicone particles should also be insoluble in the shampoo matrix. This is the meaning of "insoluble" as used herein.
  • the essentially nonvolatile polyalkyl siloxane fluids that may be used include, for example, polydimethyl siloxanes with viscosities ranging from about 5 to about 600,000 centistokes at 25° C.
  • siloxanes are available, for example, from the General Electric Company as the Viscasil series and from Dow Corning as the Dow Corning 200 series.
  • the siloxane viscosity can be measured by means of a glass capillary viscometer as set forth in Dow Corning Corporate Test Method CTM0004, July 20, 1970.
  • the viscosity of the these siloxanes range from about 350 centistokes to about 100,000 centistokes.
  • the essentially nonvolatile polyether siloxane copolymer that may be used is, for example, a polypropylene oxide modified dimethylpolysiloxane (e.g., Dow Corning DC-1248), although ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
  • a polypropylene oxide modified dimethylpolysiloxane e.g., Dow Corning DC-1248
  • ethylene oxide or mixtures of ethylene oxide and propylene oxide may also be used.
  • Suitable silicone fluids are described in U.S. Pat. No. 2,826,551, Green; U.S. Pat. No. 3,946,500, June 22, 1976,
  • Silicone gums are described by Petrarch and others including U.S. Pat. No. 4,152,416, May 1, 1979, Spitzer, et al., and Noll,
  • polydiorganosiloxanes having a mass molecular weight of from about 200,000 to about 1,000,000. Specific examples include
  • polydimethylsiloxane (polydimethylsiloxane) (methylvinylsiloxane) copolymer, poly(dimethylsiloxane) (diphenyl) (methylvinylsiloxane) copolymer, and mixtures thereof.
  • Mixtures of silicone fluids and silicone gums are also useful herein.
  • the shampoos herein can contain a variety of other nonessential optional components suitable for rendering such compositions more formulatable, or aesthetically and/or
  • Such conventional optional ingredients are well-known to those skilled in the art and include, e.g., preservatives, such as benzyl alcohol, methyl paraben, propyl paraben, and imidazolinidyl urea; cationic surfactants, such as cetyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, tricetyl methyl ammonium chloride, stearyldimethyl benzyl ammonium chloride, and di(partially hydrogenated tallow) dimethylammonium chloride; menthol; thickeners and viscosity modifiers, such as block polymers of ethylene oxide and propylene oxide such as Pluronic F88 offered by BaSa Wyandotte, sodium chloride, sodium sulfate, propylene glycol, and ethyl alcohol; pH adjusting agents, such as citric acid, succinic acid, phosphoric acid, sodium hydroxide, sodium carbonate; perfumes; dyes; and se
  • Such agents generally are used individually at a level of from about 0.01% to about 10%, preferably from about 0.5% to about 5.0%, of the composition.
  • a typical shampoo composition may comprise (percentages by weight):
  • the copolymer may be used in a conditioner composition such as is taught and described in U.S. Patent No. 4,913,828 to Caswell et al. which is hereby incorporated by reference.
  • conditioner compositions are those containing a conditioning agent (e.g. alkylamine compounds) such as those described in U.S. Patent 4,913,828.
  • a conditioning agent e.g. alkylamine compounds
  • the copolymer may be used in a cosmetic composition, such as is taught and is described in EP 0,371,803.
  • compositions generally comprise thickening agents, preservatives and further additions.
  • the composition may comprise polymer thickener in an amount sufficient to adjust the viscosity of the composition, so as to facilitate dispensing it conveniently onto the body surface.
  • polymer thickeners examples include: anionic cellulose materials, such as. sodium carboxy methyl cellulose;
  • anionic polymers such as carboxy vinyl polymers, for example, Carbomer 940 and 941; nonionic cellulose materials, such as methyl cellulose and hydroxy propyl methyl cellulose; cationic cellulose materials, such as Polymer JR 400; cationic gum materials, such as Jaguar C13 S; other gum materials such as gum acacia, gum
  • tragacanth locust bean gum, guar gum and carrageenan
  • proteins such as albumin and protein hydrolysates
  • clay materials such as bentonite, hectorite, magnesium aluminum silicate, or sodium magnesium silicate.
  • the thickening agent may comprise from 0.05 to 5%, preferably 0.1 to 1% by weight of the composition.
  • the composition according to the invention can also optionally comprise a preservative to prevent microbial spoilage.
  • preservatives examples include:
  • Chemical preservatives such as ethanol, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, sodium propionate and the methyl, ethyl, propyl and butyl esters of p-hydroxybenzoic acid, 2-bromo-2-nitropropane-1, 3-diol,
  • the amount of chemical preservative optionally to be incorporated in the composition according to the invention will generally be from 0.05 to 5%, preferably from 0.01 to 2% by weight, the amount chosen being sufficient to arrest microbial proliferation.
  • Water activity depressants such as glycerol, propylene glycol, sorbitol, sugars and salts, for examples alkali metal halides, sulphates and carboxylates.
  • glycerol propylene glycol
  • sorbitol propylene glycol
  • sugars and salts for examples alkali metal halides, sulphates and carboxylates.
  • composition can also contain other optional adjuncts, which are conventionally employed in compositions for topical application to human skin. These adjuncts, when present, will normally form the balance of the composition.
  • optional adjuncts include vehicles, the selection of which will depend on the required product form of the composition.
  • the vehicle when present will be chosen from diluents, dispersants or carriers for the dialkyl or dialkenyl phosphate salt so as to ensure an even distribution of it when applied to the skin.
  • compositions according to this invention can include water as a vehicle, usually with at least one other cosmetically-acceptable vehicle.
  • compositions according to the invention can include liquids or solids as
  • Emollients such as stearyl alcohol, glyceryl
  • stearate polyethylene glycol, triethylene glycol, lanolin, cocoa butter, corn oil, cotton seed oil, tallow, lard, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, soybean oil, sunflower seed oil, olive oil, sesame seed oil, coconut oil, arachis oil, castor oil, acetylated lanolin alcohols, petroleum, mineral oil, butyl myristate, isostearic acid, palmitic acid, isopropyl linoleate, lauryl lactate, myristyl lactate, decyl oleate, myristyl myristate;
  • Propellants such as trichlorofluoromethane
  • Solvents such as ethyl alcohol, methylene chloride, isopropanol, acetone, castor oil, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl sulphoxide, dimethyl formamide, tetrahydrofuran;
  • Humectants such as glycerin, sorbitol, sodium 2-pyrrolidone-5-carboxylate, soluble collagen, dibutyl phthalate, gelatin; Powders, such as chalk, talc, Fuller's Earth, kaolin, starch, gums, colloidal silicon dioxide, sodium polyacrylate, tetra alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminum silicate, organically modified montmorillonite clay, hydrated aluminum silicate, fumed silica, carboxyvinyl polymer, sodium carboxymethyl cellulose, ethylene glycol monostearate.
  • Powders such as chalk, talc, Fuller's Earth, kaolin, starch, gums, colloidal silicon dioxide, sodium polyacrylate, tetra alkyl and/or trialkyl aryl ammonium smectites, chemically modified magnesium aluminum silicate, organically modified montmorillonite clay, hydrated aluminum silicate, fu
  • the cosmetically acceptable vehicle when present, will usually form from 0.01 to 99.9%, preferably from 59 to 98% by weight of the composition, and can, in the absence of other cosmetic adjuncts, form the balance of the composition.
  • a wide variety of conventional sunscreening agents such as those described in U.S. Patent No. 4,919,934 to Deckner et al. hereby incorporated by reference, may also be used in the cosmetic compositions of the invention.
  • Such agents include, for example, p-aminobenzoic acid, its salts and its derivatives, anthranilates, salicylates, cinnamic acid derivatives, di- and trihydroxy cinnamic acid derivatives, hydrocarbons such as diphenylbutadiene and stilbene, dibenzalacetone and benzalacetophenone, naphthasulfonates, di-hydroxy naphthloic acid and its salts, hydroxy
  • diphenylsulfonates diphenylsulfonates, coumarin derivatives, diazoles, quinine salts, quinoline derivatives, hydroxy or methoxy substituted benzophenones, uric or vilouric acid, tannic acid and its derivatives, hydroquinone, and benzophenones.
  • the copolymer of the invention may be used in a light duty liquid detergent composition such as those taught in U.S. Patent No. 4,671,894 to Lamb et al. U.S. Patent No. 4,368,146 to Aronson et al. and U.S. Patent No. 4,555,366 to Bissett et al., all of which are hereby incorporated by reference into the subject application.
  • compositions comprise a mixture of sulphate and sulphonate anionic surfactants together with a suds stabilizing agent.
  • These compositions may also comprise nonionic surfactants designed to reduce the level of non-performing ingredients such as solvents and hydrotropes and zwitterionic surfactants for providing enhanced grease and particulate soil removal performance.
  • opacifiers e.g. ethylene glycol distearate
  • thickeners e.g., guar gum
  • antibacterial agents e.g., antitarnish agents
  • heavy metal chelators e.g. ETDA
  • the copolymers of the invention are sunscreen agents used in a sunscreen composition.
  • sunscreen compositions are preferably oil-in-water emulsions, wherein the emulsion is composed of an internal oil phase dispersed as spherical droplets in the external water phase.
  • An emulsifier surfactant or polymer is used to stabilize the droplets against phase separation.
  • Such oil-in-water emulsions generally comprise:
  • sunscreen agent (1) 1-30% of the polymer of the invention as the sunscreen agent.
  • Other sunscreen agents which are well known in the art may be used in combination with the polymers.
  • alkyl amino benzoates such as octyl p-dimethyl amino-benzoate (Padimate O), PABA, and cinnamates (eg., ethylhexyl p-methoxy cinnamate);
  • anionic or nonionic emulsifier selected from the following groups: soaps, fatty acid amides, ethoxylated fatty acids, ethoxylated esters, ethoxylated ethers, ethoxylated alcohols, phosphated esters, polyoxyethylene fatty ether phosphates and acyl lactylates. These are used alone or in combination, preferably between 2 and 6%;
  • Film forming copolymers such as copolymers of PVP (i.e., eicosene-vinyl pyrrolidone copolymer, Ganex V-220 ex. GAF) and ethylene-vinyl acetate copolymers (AC-400A ex Allied-Signal) may be used;
  • PVP i.e., eicosene-vinyl pyrrolidone copolymer, Ganex V-220 ex. GAF
  • ethylene-vinyl acetate copolymers AC-400A ex Allied-Signal
  • oil soluble emollients such as lanolin, isopropyl myristate, glycerol stearate, cetyl alcohol, and dimethicone;
  • Synthetic polymers cross-linked acrylic acid polymer
  • natural polymers such as modified cellulosics (hydroxy ethyl cellulose) or nonionic gums (guar, xanthan, or arabic) may be used;
  • Optional ingredients include suspended particulate matter such as titanium dioxide, zinc oxide, talc, or kaolin, fragrances, and preservatives.
  • compositions are prepared by preblending the oil phase of emollients, oil soluble polymers and surfactant (i.e., fatty acid) at 70-110°C.
  • the oil phase is added to the preblend of the water phase (maintained at 70-95°C) and mixed until homogeneous.
  • the mixture is cooled to 65°C and the saponifying agent for the fatty acid is added.
  • the emulsion is cooled to 50°C and fragrance and preservatives added.
  • Steareth 2 (stearyl alcohol ethoxylated with 2 moles of ethylene oxide)
  • a third example of sunscreen composition is also shown below:
  • the UV polymers of the invention may also be used in other product such as water-in-oil emulsions, creams, polymer gels, and sunscreen oils.
  • the molecule of the invention may be used in underarm deodorant/antiperspirant compositions such as those taught in U.S. Patent No. 4,919,934 to Deckner, U.S. Patent No. 4,944,937 to McCall and U.S. Patent No. 4,944,938 to Patini, all of which patents are hereby incorporated by reference.
  • compositions generally comprise a cosmetic stick (gel or wax) composition which in turn generally comprises one or more liquid base materials (e.g., water, fatty acid and fatty alcohol esters, water-insoluble ethers and alcohols,
  • liquid base materials e.g., water, fatty acid and fatty alcohol esters, water-insoluble ethers and alcohols,
  • polyorganosiloxanes a solidifying agent for solidifying the liquid base
  • an active component such as bacteriostats or fungistats (for anti-deodorant activity) or astringent metallic salts (for antiperspirant activity).
  • compositions may also comprise hardeners, strengtheners, emollients, colorants, perfumes, emulsifiers and fillers.
  • copolymers of the invention may be defined by the following formula: I:
  • A is a monomer capable of absorbing UVA [320-400 nanometer (nm)] light at / ⁇ max and bearing the appropriate bifunctionality for copolymerization into the polymer main chain.
  • Such groups include planar aromatic moieties such as tetrahydroxybenzophenones; dicarboxydihydroxybenzophenones and alkane ester or acid halide derivatives thereof; dihydroxy-, dicarboxy-, and hydroxycarboxydibenzoylmethanes and alkane ester or acid halide derivatives thereof; dihydroxy-, dicarcarboxy-, and hydroxycarboxystilbenes and alkane ester or acid halide
  • B is a monomer capable of absorbing UVB [ 320-400
  • Such groups include planar aromatic moieties such as 4-aminobenzoic acid and alkane esters thereof ; anthranilic acid and alkane esters thereof ; salicylic acid and alkane esters thereof ; hydroxycinnamic acid and alkane esters thereof ;
  • C is a hydrophilic monomer incorporated to confer hydrophilicity to solvate the copolymer in aqueous media ;
  • D is an optional hydrophobic monomer incorporated to adjust the water-solubility or water-dispersibility and binding strength to hydrophobic surfaces ;
  • n is at least 1 and may range from 1 to 250, preferably 50 to 250, and most preferably 150-250;
  • m is at least 1 and may range from 1 to 250, preferably 50 to 250;
  • p is at least 5 and may range from 5 to 500; and
  • q may be zero and may range from 0 to 250.
  • q (defining the chain length of the hydrophobic monomer) should be at least 1 to ensure deposition of the copolymer onto the desired surface.
  • the length of the hydrophilic monomer (defined as C) or the percentage of C as the total percentage of the copolymer is such that the resulting copolymer is too water soluble to effectively adsorb onto the desired surface (ie., the copolymer preferentially rennains in the aqueous vehicle)
  • q must be greater than 0 and large enough to ensure that adsorption takes place while at the same time not so large as to preclude water solubility or dispersibility.
  • the level of p is chosen to balance the water solubility or dispersibility of the copolymer with its ability to adsorb onto a desired surface. In practice, a minimum value for p of approximately 10 is useful.
  • the UVA light-absorbing monomer A may comprise 1 to 99.9 mol % of the copolymer, preferably 10 to 80 mol %, and most preferably 25 to 75 mol %;
  • the UVB light-absorbing monomer B may comprise 1 to 99.9 mol % of the copolymer, preferably 10 to 80 mol%, and most preferably 25 to 75 mol %;
  • the hydrophilic monomer C may comprise 0.5 to 49.9 mol % of the copolymer, preferably 10 to 45 mol%, and most preferably 20 to 40 mol %; and the
  • hydrophobic monomer if present, may comprise 0.05 to 49.9 mol % of the copolymer, preferably 10 to 45 mol%, and most preferably 2 to 40 mol%.
  • A, B, C, and D are expressed above as a block copolymer, it is to be understood that the places of A, B, C, and D may be interchanged in random
  • copolymers of the subject invention may be further defined by the following formula II:
  • R is a difunctional aryl or alkyl group such as for example, difunctional benzene or naphthalene, preferably difunctional benzene or a difunctional straight or branched alkyl chain containing 4 to 16 carbon atoms;
  • R 1 is hydrogen or an aliphatic group having 1 to 20 carbons, preferably a straight-chained alkyl group having 1 to 12 carbons, most preferably 1 to 5 carbons, an aryl, an alkaryl, a secondary amine such as, for example, dialkylamine, an alkali metal sulfonate, an alkali metal carboxylate, an alkyl ether, or a halogen atom;
  • R 2 is a UVA light-absorbing monomer bearing the appropriate bifunctionality for incorporation into the main chain of the polymer.
  • bifunctional is meant any UVA light-absorbing monomer as defined above bearing at least the functional groups such as are well known to those skilled in the art. Examples include examples include amines, alkyl esters, carboxylic acids, carboxylic acid halides, hydroxyl groups, etc;
  • R 3 is a straight or branched chain alkyl group having 1 to 16 carbons, preferably 1 to 3 carbons;
  • R 4 is a UVB light-absorbing monomer bearing the appropriate bifunctionality for incorporation into the main chain of the polymer.
  • bifunctional is meant any UVB light-absorbing monomer as defined above bearing at least the functional groups such as are well known to those skilled in the art. Examples include amines, alkyl esters, carboxylic acids,
  • x which represents the number of monomeric units of the optional hydrophobic group, is selected such that the hydrophobe is present at 0 to 49.9 mol% of the polymer; y is selected such that the R 2 group, is present at 1 to 99.9 mol % of the polymer; z is selected such that the (OR 3 ) n O group is present at 0.05 to 49.9 mol% of the polymer wherein n is an integer between 2 and 200, preferably 10 to 25; and w is selected such that the R 4 group is present at 1 to
  • the UVA and UVB light-absorbing monomers are moieties bearing the appropriate bifunctionality for incorporation into the main chain of the polymer.
  • the UVA light-absorbing monomer should absorb at its A max ultraviolet light between 320 and 400 nm.
  • the UVB light-absorbing monomer should absorb at its A max ultraviolet light between 290 and 320 nm.
  • Preferred monomers are either highly conjugated and/or poly(ene)-based derivatives and/or aromatic-based derivatives bearing the appropriate difunctional group .
  • UVA absorbers examples include tetrahydroxybenzophenones, dihydroxydibenzoylmethanes,
  • dicarboxydibenzoylmethanes and alkane ester or acid halide derivatives thereof dihydroxystilbenes, dicarboxystilbenes and alkane ester or acid halide derivatives thereof,
  • UVA light-absorbers are 2,2',4,4'-tetrahydroxybenzophenone,
  • UVB absorbers examples include 4-aminobenzoic acid esters, anthranilic acid esters, salicylate esters, hydroxycinnamate esters, dihydroxybenzophenones,
  • UVB light-absorbers are methyl 4-aminobenzoate, methyl
  • the UVA light-absorbing monomer may be added as 1 to 99.9 mol% of the polymer, preferably 10 to 80 mol %, and most preferably 25 to 75 mol%.
  • the UVB light-absorbing monomer may be added as 1 to 99.9 mol% of the polymer, preferably 10 to 80 mol%, and most preferably 25 to 75 mol%.
  • the hydrophilic component (represented by (OR 3 ) n ) is incorporated to confer hydrophilicity to naturally hydrophobic surfaces such as soiled cotton or polyester as well as to
  • Hydrophilic monomers which may be used include, but. are not limited to the ⁇ , ⁇ -diols or alkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, and mixtures of the three.
  • Other hydrophilic monomers which may be used as (OR 3 ) n are based on simple sugars or poly(saccharide)s, or ⁇ , ⁇ -poly(ols) which may include glucose, sucrose, sorbitol, or glycerol.
  • (OR 3 ) n is a poly(ethylene glycol).
  • Suitable poly(ethylene glycol)s are those manufactured by Union Carbide and sold under the CARBOWAX (R) trade name. Examples include CARBOWAX (R) 300, 600, 1000, 3350, and the like.
  • the poly(ethylene glycol) unit must be present in at least sufficient quantity to ensure that the final copolymer may be delivered through an aqueous medium. In general, this monomer is present as 0 to 49.9 mol%, preferably 10 to 45 mol% of the reaction mixture.
  • UVA and UVB absorbing monomers could be used while still maintaining water dispersibility .
  • these monomers are are both hydrophobic hydrocarbon-based moities which would normally be more different to disperse in water.
  • hydrophobic monomer which may be optionally incorporated is used to adjust the water solubility and binding strength of the copolymer to hydrophobic surfaces.
  • Suitable hydrophobic monomers which may be used include long chain
  • hydrophobic monomers include the aromatic hydrophobic monomers, ⁇ , ⁇ -diols , ⁇ , ⁇ -diamines , or ⁇ , ⁇ -dicarboxylic acids or diester or diacid chloride derivatives thereof.
  • Another suitable class of hydrophobic monomers includes the aromatic hydrophobic monomers, ⁇ , ⁇ -diols , ⁇ , ⁇ -diamines , or ⁇ , ⁇ -dicarboxylic acids or diester or diacid chloride derivatives thereof.
  • the UVA light- absorbing monomer is a
  • the molecular weight of the copolymers of the invention may range from 3000 to 100,000, preferably 3000 to 25,000, and most preferably 3000 to 12,000.
  • the ratio of monomers can vary broadly depending upon the end use requirements such as whether the polymer is being used for UV light screening, soil release, anti-redeposition, or enzyme stabilization.
  • hydrophobic properties These can be fine tuned by those skilled in the art.
  • the copolymers of the present invention may be based upon the condensation product of 4,4'-bis(carbomethoxy)stilbene, poly(ethylene glycol), and methyl 4-aminobenzoate.
  • the poly(ethylene glycol) used will have a molecular weight ranging from about 200 to about 3400. These components may be combined via a 1-step transesterification reaction as set forth in Scheme 1 :
  • Scheme 1 the hydrophilic poly(ethylene glycol) monomer has been incorporated to facilitate polymer transfer through an aqueous medium.
  • the UVB light-absorbing methyl 4-aminobenzoate monomer has been incorporated to absorb at its ⁇ max ultraviolet light between 290 and 320 nm in wavelength.
  • the UVA light-absorbing 4,4'-bis(carbomethoxy)stilbene monomer has been incorporated to absorb at its ⁇ max ultraviolet light between 320 and 400 nm in wavelength.
  • the poly(ethylene glycol) and methyl 4-aminobenzoate were obtained commercially. The
  • 4,4'-bis(carbomethoxy)stilbene was prepared by a known route.
  • UVB 290-320 nm
  • UVA 320-400nm
  • the copolymers of the present invention may be based upon the condensation product of 4,4'-stilbenedicarboxylic acid chloride, poly(ethylene glycol), and 4,4'-dihydroxystilbene.
  • the poly(ethylene glycol) used will have a molecular weight ranging from about 200 to about 3400.
  • 4,4'-dihydroxybenzophenone monomer has been incorporated to absorb at its ⁇ max ultraviolet light between 290 and 320 nm in
  • the UVA light-absorbing 4,4'-stilbenedicarboxylic acid chloride monomer has been incorporated to absorb at its ⁇ max ultraviolet light between 320 and 400 nm in wavelength.
  • the poly(ethylene glycol) and 4,4'-dihydroxybenzophenone monomers were obtained commercially.
  • chlorinated aror ⁇ atics such as chlorobenzene or
  • Suitable bases include organic amines such as triethylamine, diethylamine,
  • alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate, lithium carbonate, and potassium carbonate
  • the cosolvent system may be used as 1-50% by weight of the solids content of the reaction.
  • chlorinated hydrocarbon may range from 1:10 to 10: 1, preferably 1:5 to 5:1, and most preferably 2:1 to 1:2.
  • Reaction temperatures may range from -78°C to reflux temperatures, preferably 0 to 50°C, and most preferably 25 to 50°C.
  • the time of reaction may range from 0.25h to 48h, preferably 0.5h to 24h, and most preferably 1h to 12h.
  • Trans-4,4'-stilbenedicarboxylic acid chloride was synthesized from trans-4,4'-stilbenedicarboxylic acid and thionyl chloride
  • Refractometer Chloroform eluent was used at a rate of 1 mL/min at 0.2 w/w % in sample and standard. The column and refractive index detector temperatures were 40°C. The standard calibration curve (peak position calibration curve) was constructed by narrow distribution poly(styrene) standards. UV absorbance data were obtained on a Beckman DU-65 Spectrophotometer at a concentration of 0.01 - 0.03g UV light-absorbing polymer/liter so that the absorbance was kept between 0.3 and 1.0 absorbance units.
  • Chloroform was used as the sample and reference solvent.
  • CD-SOCD 3 (as indicated) with tetramethylsilane as an internal standard.
  • UV Light-Absorbing Water Dispersible Copolymer Containing a UVA Light-Absorbing Stilbene Unit and a UVB
  • UV Light-Absorbing Water Dispersible Copolymer Containing a UVA Light-Absorbing Stilbene Unit and a UVB
  • UV Light-Absorbing Water Dispersible Copolymer Containing a UVA Light-Absorbing Stilbene Unit and a UVB
  • UV Light-Absorbing Water Dispersible Copolymer Containing a UVA Light-Absorbing Stilbene Unit and a UVB
  • UV Light-Absorbing Water Dispersible Copolymer Containing a UVA Light-Absorbing Stilbene Unit and a UVB
  • Premix A - Finsolv TN was heated to 80°C and stearic acid amphosol, and cetyl alcohol were added. The ingredients were mixed until clear and homogeneous. UV polymer was added. The premix was maintained at 80°C.
  • Premix B - Water was heated to 80° and triethanoline and Carbopol were added. Ingredients were mixed until clear gel formed and the premix was maintained at 80°C.
  • Premix C - Water was heated to 40°C and methyl paraban and propyl paraban were added.
  • Premix A was added to premix B and allowed to cool to 40°C under high shear, then premix C was added and allowed to cool to room temperature.
  • Finsolv TN Benzoic Acid Ester of C 12 -C 15 alcohol

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Abstract

L'invention concerne des compositions comprenant des nouveaux copolymères se dispersant ou se dissolvant dans l'eau qui contiennent au moins un monomère absorbant la lumière UVA, un monomère absorbant la lumière UVB, un monomère hydrophile et le cas échéant un monomère hydrophobe. Le monomère absorbant la lumière UVA a un maximum d'absorption dans l'ultraviolet à μmax dans la gamme de 320-400 nm. Le monomère absorbant la lumière UVB a un maximum d'absorption dans l'ultraviolet μmax dans la gamme de 290-320 nm.
PCT/GB1993/000081 1992-04-23 1993-01-15 COMPOSITION COMPRENANT UN COPOLYMERE SE DISPERSANT DANS L'EAU CONTENANT DES MONOMERES ABSORBANT LA LUMIERE UVA et UVB WO1993022413A1 (fr)

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US87287992A 1992-04-23 1992-04-23
US07/872,879 1992-04-23

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5487885A (en) * 1992-12-21 1996-01-30 Biophysica, Inc. Sunblocking polymers and their formulation
WO1996003492A1 (fr) * 1994-07-26 1996-02-08 The Procter & Gamble Company Produit de traitement du linge en sechoir contenant des antioxydants et des ecrans solaires protegeant le linge de la decoloration sous l'effet du soleil
WO1997023542A1 (fr) * 1995-12-21 1997-07-03 The Procter & Gamble Company Polymeres detachants avec proprietes de blanchiment fluorescent
WO1997042290A1 (fr) * 1996-05-03 1997-11-13 The Procter & Gamble Company Polyamines ameliorant avantageusement l'aspect des tissus
WO2000018863A1 (fr) * 1998-09-30 2000-04-06 Unilever Plc Composes polymeres et compositions a base de ceux-ci
EP0998900A1 (fr) * 1998-10-19 2000-05-10 Basf Aktiengesellschaft Utilisation de polymères cristaux liquides de type cholesterique comme filtre des UV dans des compositions cosmetiques et pharmaceutiques
US6123928A (en) * 1992-12-21 2000-09-26 Biophysica, Inc. Sunblocking polymers and their novel formulations
US9737471B2 (en) 2012-06-28 2017-08-22 Johnson & Johnson Consumer Inc. Sunscreen compositions containing an ultraviolet radiation-absorbing polymer
US9758618B2 (en) 2012-06-28 2017-09-12 Johnson & Johnson Consumer Inc. Ultraviolet radiation absorbing polyethers
US10596087B2 (en) 2016-10-05 2020-03-24 Johnson & Johnson Consumer Inc. Ultraviolet radiation absorbing polymer composition
US10874603B2 (en) 2014-05-12 2020-12-29 Johnson & Johnson Consumer Inc. Sunscreen compositions containing a UV-absorbing polyglycerol and a non-UV-absorbing polyglycerol

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US4524061A (en) * 1983-04-22 1985-06-18 Gaf Corporation Polymeric sunscreens
EP0165329A1 (fr) * 1982-05-06 1985-12-27 Soft Sheen Products, Inc. Détergent liquide avec un agent antisolaire
EP0255157A2 (fr) * 1986-06-27 1988-02-03 The Procter & Gamble Company Agents écrans solaires, compositions d'écran solaire et méthodes de prévention de l'érythème
US4913828A (en) * 1987-06-10 1990-04-03 The Procter & Gamble Company Conditioning agents and compositions containing same
US5134223A (en) * 1991-07-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Water dispersible or water soluble copolymer containing UV-absorbing monomer

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EP0165329A1 (fr) * 1982-05-06 1985-12-27 Soft Sheen Products, Inc. Détergent liquide avec un agent antisolaire
US4524061A (en) * 1983-04-22 1985-06-18 Gaf Corporation Polymeric sunscreens
EP0255157A2 (fr) * 1986-06-27 1988-02-03 The Procter & Gamble Company Agents écrans solaires, compositions d'écran solaire et méthodes de prévention de l'érythème
US4913828A (en) * 1987-06-10 1990-04-03 The Procter & Gamble Company Conditioning agents and compositions containing same
US5134223A (en) * 1991-07-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Water dispersible or water soluble copolymer containing UV-absorbing monomer

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DATABASE WPIL Derwent Publications Ltd., London, GB; AN 88-230562 [33] *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6123928A (en) * 1992-12-21 2000-09-26 Biophysica, Inc. Sunblocking polymers and their novel formulations
US5487885A (en) * 1992-12-21 1996-01-30 Biophysica, Inc. Sunblocking polymers and their formulation
US5741924A (en) * 1992-12-21 1998-04-21 Biophysica Inc. Sunblocking polymers and their formulation
WO1996003492A1 (fr) * 1994-07-26 1996-02-08 The Procter & Gamble Company Produit de traitement du linge en sechoir contenant des antioxydants et des ecrans solaires protegeant le linge de la decoloration sous l'effet du soleil
WO1997023542A1 (fr) * 1995-12-21 1997-07-03 The Procter & Gamble Company Polymeres detachants avec proprietes de blanchiment fluorescent
US6143713A (en) * 1996-05-03 2000-11-07 The Procter & Gamble Company Polyamines having fabric appearance enhancement benefits
WO1997042290A1 (fr) * 1996-05-03 1997-11-13 The Procter & Gamble Company Polyamines ameliorant avantageusement l'aspect des tissus
WO2000018863A1 (fr) * 1998-09-30 2000-04-06 Unilever Plc Composes polymeres et compositions a base de ceux-ci
EP0998900A1 (fr) * 1998-10-19 2000-05-10 Basf Aktiengesellschaft Utilisation de polymères cristaux liquides de type cholesterique comme filtre des UV dans des compositions cosmetiques et pharmaceutiques
US6159454A (en) * 1998-10-19 2000-12-12 Basf Aktiengesellschaft Use of cholesteric liquid-crystalline polymers as UV screens in cosmetic and pharmaceutical preparations
US9737471B2 (en) 2012-06-28 2017-08-22 Johnson & Johnson Consumer Inc. Sunscreen compositions containing an ultraviolet radiation-absorbing polymer
US9737470B2 (en) 2012-06-28 2017-08-22 Johnson & Johnson Consumer Inc. Sunscreen compositions containing an ultraviolet radiation-absorbing polymer
US9758618B2 (en) 2012-06-28 2017-09-12 Johnson & Johnson Consumer Inc. Ultraviolet radiation absorbing polyethers
US10278910B2 (en) 2012-06-28 2019-05-07 Johnson & Johnson Consumer Inc. Sunscreen compositions containing an ultraviolet radiation-absorbing polymer
US10874603B2 (en) 2014-05-12 2020-12-29 Johnson & Johnson Consumer Inc. Sunscreen compositions containing a UV-absorbing polyglycerol and a non-UV-absorbing polyglycerol
US10596087B2 (en) 2016-10-05 2020-03-24 Johnson & Johnson Consumer Inc. Ultraviolet radiation absorbing polymer composition
US10874597B2 (en) 2016-10-05 2020-12-29 Johnson & Johnson Consumer Inc. Ultraviolet radiation absorbing polymer composition

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