WO2014151439A1 - Polymères d'acide itaconique pour applications de soin oral - Google Patents

Polymères d'acide itaconique pour applications de soin oral Download PDF

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Publication number
WO2014151439A1
WO2014151439A1 PCT/US2014/025730 US2014025730W WO2014151439A1 WO 2014151439 A1 WO2014151439 A1 WO 2014151439A1 US 2014025730 W US2014025730 W US 2014025730W WO 2014151439 A1 WO2014151439 A1 WO 2014151439A1
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Prior art keywords
oral care
care composition
polymer
mole
acid
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PCT/US2014/025730
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English (en)
Inventor
Krishnan Tamareselvy
John Ta-Yuan Lai
Hong Luo
Roger W. Day
Elena S. Draganoiu
Naser Pourahmady
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Lubrizol Advanced Materials, Inc.
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Publication of WO2014151439A1 publication Critical patent/WO2014151439A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • 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
    • A61K8/91—Graft copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid

Definitions

  • the disclosed technology relates to an oral care composition
  • an oral care composition comprising a pure polyitaconic acid homo- or co-polymer free of the less reactive tri- substituted vinyl monomers (e.g., citraconic acid or mesaconic acid) .
  • WO 2001 /2 1677 describes an itaconic acid polymerization comprising a free radical generator (persulfate) and a phosphorous-containing reducing agent.
  • US 4,485,223 teaches an "essentially homogenous" (meth)acrylic acid/itaconic acid copolymer.
  • the process taught in the '223 patent teaches a post-neutralization step, and process temperatures ranging from 80 to 120°C, as well as an initiator amount of from 5 to 20 mole%.
  • the level of initiator required in the post-neutralization step of the '223 process results in a corrosive copolymer solution (pH ⁇ 1), which has significant safety concerns from a handling point of view that would make scale-up difficult.
  • the high initiator level used in the polymerization step taught in the '223 patent gives a dark colored copolymer with a strong unpleasant sulfur odor that would not be suitable for use in the personal care or homecare market.
  • the high temperatures used in the '223 process causes the initiator to decompose quickly, causing oxidized and/ or sulfurized itaconic acid impurities resulting in poor performance and potential health concerns with use in the final application.
  • Itaconic acid polymers and co-polymers having improved purity, and being free of tri-substituted vinyl monomer isomerization that provide improved stain resistant capabilities in dental care applications, along with methods of preparing the same would be desirable.
  • the disclosed technology therefore, solves the problem of inefficient stain prevention capability in current dental care applications by providing polymers or co-polymers, that are derived from substantially pure itaconic acid and that are free of tri-substituted vinyl monomers.
  • an oral care composition including a safe and effective amount of a homopolymer or copolymer or salts thereof.
  • the copolymer can contain from about 10 mole percent to about 90 mole percent itaconic acid derived monomer groups.
  • the copolymer can also contain from about 10 mole percent to about 90 mole percent of at least one of: (meth)acrylic acid derived monomer groups, poly unsaturated monomer groups, and combinations thereof.
  • the oral care formulations include dentifrice or gel and mouthwash (e.g., spray, rinse, solutions and suspensions).
  • Other types of oral care formulations include denture adhesives, denture cleaning products, dental composites, tooth whiteners, tooth varnishes, lozenges and chewing gum.
  • the copolymer will be transparent, or substantially transparent.
  • the copolymer included in the oral care composition can be prepared at a reaction temperature of between about 60 to about 85°C in the presence of from about 0.01 to about 5 mole percent polymerization initiator, based on the total amount of said monomer groups, and less than 5 equivalent% of a neutralizer per total itaconic acid monomer acid group.
  • the oral care composition can contain from about 0.01% to about 20.0% by weight of the copolymer.
  • a method of preventing stains on hydroxyapatite which is considered as a model compound of enamel due to the chemical similarity.
  • the method can include the step of applying to the hydroxyapatite surface a safe and effective amount of a copolymer as described above, or salts thereof.
  • a first aspect of the invention is an oral care composition including a safe and effective amount of a homopolymer or copolymer or salts thereof.
  • the copolymer can be a homogenous or substantially homogenous polymer, or a random or block copolymer or terpolymer or crosslinked polymer ("improved polymers") providing improved stain prevention for oral care applications.
  • the improved polymers can comprise, consist essentially of, or consist of itaconic acid derived monomer groups.
  • the improved polymer may be a homopolymer of itaconic acid wherein the polymer backbone comprises structural units derived from itaconic acid, or an anhydride or salt thereof (collectively referred to as itaconic acid) .
  • the improved polymer can contain monomer units derived from itaconic acid.
  • the improved polymer can contain greater than about 10 mole%, or 50 mole%, preferably greater than 70 mole%, or from about 60 mole% to about 65 or 70 mole% monomer units derived from itaconic acid.
  • the monomer units derived from itaconic acid can be from about 1 to about 99 mole%, or about 5 to about 95 mole%, or even about 10 to about 90 mole%, and in some instances from about 20 to about 80 mole%, or about 30 to about 70 mole %, or even from about 40 to about 60 mole %.
  • the improved polymer can also comprise, consist of, or consist essentially of (in addition to itaconic acid derived monomer groups) at least one of: C1-C18 alkyl (meth)acrylates where the alkyl group may be a straight chain group or branched chain group.
  • the alkyl group may be substituted with one or more hydroxyl groups, alkoxy groups, or a mixture thereof.
  • the monomers that may be used may include methyl acrylate, ethyl acrylate, butyl acrylate, 2- hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, phosphate containing monomers, stearyl acrylate, polyethyleneglycol monomethylether acrylate, acrylamide, C1-C18 N-alkyl
  • the amount of co-monomer in the copolymer may be up to about 50% by weight of the copolymer or up to 90% by weight, or from about 5 to about 50%, or from 10% to about 40%, or from about 15% to about 20 or 30% by weight of the copolymer.
  • the amount of itaconic acid is desirably at least 50, more desirably at least 70, and preferably at least 80% by weight of said polymer or copolymer derived from itaconic acid.
  • the improved crosslinked itaconic acid copolymers may comprise ethylenically polyunsaturated compounds containing at least two polymerizable ethylenically unsaturated moieties.
  • Exemplary polyunsaturated crosslinking monomer components include di(meth)acrylate compounds such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1 ,3-butylene glycol di(meth)acrylate, 1 ,6- butylene glycol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, 2,2'-bis(4-(acryloxy-propyloxyphenyl)propane, and 2,2'-bis(4- (acryloxydiethoxy-phenyl)prop
  • Non limiting examples of crosslinking monomers derived from ethoxylated polyols are acrylate and methacrylate esters of polyols having at least two acrylate or methacrylate ester groups, such as polyethylene glycol diacrylate, polyethylene glycol di- methacrylate, trimethylolpropane ethoxylated ( 15) triacrylate (TMPEO 15TA) and ethoxylated (30) bisphenol A dimethacrylate (EOBDMA), and the like.
  • the polymer may comprise a grafted polymer or copolymer wherein one or more polyols are grafted to the polymer backbone.
  • the polyol may comprise any polyol with a molecular weight of up to about 10000, or in the range from about 50 to about 5000, or from about 50 to about 1000, that contains 2 or more hydroxyl groups, or from 2 to about 6 hydroxyl groups, or from 2 to about 4 hydroxyl groups.
  • polyols examples include polyalkylene glycol, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, glycerol, 1 ,3-propanediol, starch, pentaerythritol, trimethylolpropane, sorbitol, sucrose, xylitolglu- cose, resorcinol, catechol, pyrogallol, glycollated ureas, 1 ,4- cyclohexanediol, diethanolamine, triethanolamine, or a mixture of two or more thereof. In one embodiment it is preferred that at least 50 wt.% of the polyols be glycerol.
  • the number of structural units derived from itaconic acid, or anhydride or salt thereof, and/ or the one or more co- monomers referred to above in the polymer backbone that may be grafted with a polyol may be up to about 30% of the structural units, or from about 1 % to about 30%, or from about 1% to about
  • 20% of the structural units may be grafted with a polyol.
  • the num- ber of structural units derived from itaconic acid, or anhydride or salt thereof, in the polymer backbone that may be grafted with a polyol may be up to about 30% of the structural units, or from about 1 % to about 30%, or from about 1% to about 20% of the structural units may be grafted with a polyol.
  • the monomers in the improved polymers may be in the form of salts, such as, for example, sodium, potassium or ammonium salts and alkylated ammonium salts such as triethyl ammonium salt, and alkylated hydroxyl ammonium salts such as triethanol ammonium salt, and the like.
  • salts such as, for example, sodium, potassium or ammonium salts and alkylated ammonium salts such as triethyl ammonium salt, and alkylated hydroxyl ammonium salts such as triethanol ammonium salt, and the like.
  • the AMPS can be present from about 0. 1 to about 10 mole%, or about 0.5 to about 5 mole%, or about 1 to about 2.5 mole% of the copolymer and/ or terpolymer, in which case the other co-monomers in the improved polymer will be in the range of about 90 to about 99.9 mole%, or about 95 to about 99.5 mole%, or about 97.5 to about 99% of the copolymer and/ or terpolymer.
  • the improved polymers are free of, or substantially free of moieties of tri- substituted vinyl monomer isomers of itaconic acid, such as citriconic acid and mesaconic acid.
  • substantially free of moieties of tri-substituted vinyl monomer isomers it is meant that there is an insufficient amount of the isomer moieties present in the improved polymer to effect the efficacy of the improved polymer, such as, for example, less than 0.5 mole %, or 0. 1 mole %, or less than 0.05 mole %, or less than 0.01 mole %, based on the number of monomer units in the improved polymer.
  • the improved polymer solution will include less than 0.5% w/w unreacted monomer and co-monomer based on the total weight of the polymer present in the solution, or less than 0.25% w/w, or free or substantially free of unreacted monomer and co-monomer.
  • substantially free of unreacted monomer it is meant that there is an insufficient amount of unreacted monomer present in the improved polymer solution to affect the efficacy of the solution, such as, for example, less than 0.5 mole %, or 0.
  • w/w 1% w/w, or less than 0.05% w/w, or less than 0.01% w/w, or less than 0.001% w/w, based on the weight of the improved polymer in the solution, or from less than 2.5 or 2.0 wt%, or 1 wt%, or less than 0.5 wt%, or less than 0. 1 wt.%.
  • the improved polymers can have number average molecular weights (Mn) of from about 500 to 10,000,000, preferably from about 1000 to 1 ,000,000, more preferably from about 2500 to about 500,000. In some embodiments the Mn of the improved polymers can be from about 500 to about 100,000 or 1000 to about 50,000. Likewise, the improved polymer can have a polydispersity of from about 1 to 60, more preferably 1 to 30, or 1 to 20 or 10, or 8.
  • the improved polymers can be prepared by polymerizing itaconic acid on its own, or a major amount of itaconic acid monomer with at least one comonomer.
  • the polymerization process can provide homogenous, substantially homogenous, random or block polymers and copolymers and/ or crosslinked polymers.
  • Block copolymer are defined by the art as polymers derived from two or more different monomers in which multiple sequences, or blocks, of the same monomer alternate in series with the different monomer blocks.
  • Block copolymers can contain two blocks (di-block), three blocks (tri-block), or more than three blocks (multi-block).
  • Block copolymers can be alternating copolymers with the two or more different monomers along the polymer backbone at regularly alternating intervals. There are also periodic copolymers in which the two or more monomers are arranged in a regularly repeating sequence, and statistical copolymers in which the sequence of the two or more different monomers repeat based on a statistical rule.
  • the block copolymer created according to the process of the invention is an alternating multi-block copolymer.
  • the improved polymers of the invention can be synthesized by free radical polymerization of the monomer mixture described above.
  • the polymers can be prepared via solution, dispersion, precipitation, mass or emulsion (or inverse emulsion) polymerization techniques that are well-known in the polymer art.
  • the present polymers are prepared by solution polymerization in solvents, preferably in water, isopropyl alcohol and their mixtures thereof.
  • the polymerization process is completed in an aqueous medium in the presence of a polymerization initiator and at lower temperatures than taught in the prior art.
  • the co- monomers and the initiator are added separately from the itaconic acid, but they can also be added simultaneously with the itaconic acid.
  • Certain co-monomers, such as acrylic acid, methacrylic acid and AMPS copolymerize in essentially the same manner with itaconic acid, and may therefore be interchanged or mixed in the process to give products with essentially the same molecular weight and improved metal ion-binding characteristics for a copolymer of given AMPS or (meth)acrylic acid/itaconic acid mole ratio.
  • the process can include a pre-neutralization step in which the pH of the polymerization solution is neutralized with a neutralizer, (i.e. a source of sodium, potassium or ammonium and alkylated ammonium such as triethyl ammonium, and alkylated hydroxyl ammonium such as triethanol ammonium, and the like) to a pH of greater than about 1 .8, or greater than about 2 or 3.
  • a neutralizer i.e. a source of sodium, potassium or ammonium and alkylated ammonium such as triethyl ammonium, and alkylated hydroxyl ammonium such as triethanol ammonium, and the like
  • a neutralizer i.e. a source of sodium, potassium or ammonium and alkylated ammonium such as triethyl ammonium, and alkylated hydroxyl ammonium such as triethanol ammonium, and the like
  • the closer the pH to neutral i.e., 7) the less corro
  • the neutralizer is added in an amount suitable to achieve a pH of greater than 1.8 but less than the critical threshold at which itaconic acid will isomerize.
  • the neutralizer can be added during the pre-neutralization step at a dosage to neutralize no more than 20 mole % of the carboxylic acid groups from the itaconic acid monomers.
  • the neutralizer can be added during the pre- neutralization step at a dosage to neutralize no more than 20 mole %, 15 mole %, or 10 mole % of the total carboxylic acid groups from all monomers, more preferably no more than 5 mole %.
  • the neutralizer can be added during the pre- neutralization step at a dosage to neutralize from about 0.01 to about 20 mole % of the carboxylic acid groups from all monomers, more preferably from about 0. 1 to about 15 mole %, or from about 0.5 to about 10 mole %, or even 1 to about 5 mole % of the carboxylic acid groups from all monomers.
  • the neutralizer can be an alkali metal base, ammonium, and/or amine base.
  • Alkali metal bases suitable for the neutralization include sodium hydroxide, potassium hydroxide and lithium hydroxide, while suitable ammonium and amine bases include ammonia, ammonium hydroxide, mono-, di-and trialkyl amines having 1 to 5 carbon atoms in each alkyl group, pyridine, morpho- line and lutidine.
  • the neutralizer can also be a base with carboxylic acid functionality, although it is preferred that such a neutralizer has less than 25 mole % carboxylic acid functionality.
  • neutralizers having carboxylic acid functionality include, but are not limited to, amino acids, peptides, polypeptides, and their derivatives.
  • the amino acid can be chosen from alanine, arginine, aspara- gine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.
  • Any water-soluble, free-radical initiator may be used as the polymerization initiator of this process.
  • Suitable initiators include persulfates such as sodium and potassium persulfate as well as redox systems.
  • Other initiators such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide, cumene hydroperoxide and t-butyl hydroperoxide; organic peracids, such as peracetic acid; and oil and water soluble free radical producing agents, such as 2,2'-azobisisobutyronitrile, and the like, and mixtures thereof can also be used in combination with water soluble initiators.
  • Suitable reducers for the redox system include sulfur compounds, such as, for example, the sodium salt of hy- droxymethanesulfinic acid, a mixture of a disodium salt of 2- hydroxy-2-sulfinatoacetic acid and sodium sulfite, BruggolitTM FF6 and FF7, sodium sulfite, sodium disulfite, sodium thiosulfate, and acetone-bisulfite adduct.
  • a typical redox system can include, consist essentially of, or consist of, for example, sodium persulfate type oxidizers with sodium bisulfite type reducers, such as BruggolitTM FF6.
  • the reaction mixture is free of metal promoters, such as copper and the like.
  • polymerization additives and processing aids which are well known in the solution polymerization art, such as, chain transfer agents, solvents, emulsifiers, processing aids, defoamers, buffering agents, chelating agents, inorganic electrolytes, polymeric stabilizers, biocides, and pH adjusting agents can be included in the polymerization system.
  • the polymerization can be carried in a variety of solvents, such alcohols, ethers, esters, aromatic solvents, glycols, glycol ethers, glycerol and glycol esters.
  • solvents include ethyl alcohol, isopropyl alcohol, t-butyl alcohol, ethyl acetate, me- thyl acetate, butyl acetate, benzene, toluene, and methylene cho- ride.
  • solvents can be used also in combination with hydrocarbon solvents such as hexane, cyclohexane, mineral spirits, and the like.
  • Glycerol, isopropyl alcohol, water, or a mixture of two or more thereof are preferred.
  • the polymerization initiator should be present in an amount of less than about 5 mole % based on the total amount of the monomers, such as from about 0.01 to about 5 mole %, or 0. 1 to about 4.95 mole %, and even about 1 to about 4.9 mole % based on the total amount of the monomers. All or at least half of the initiator can be added separately from the itaconic acid monomer. In one embodiment, the initiator can be added essentially continuously throughout the polymerization period. The initiator can also be added in discreet amounts at various times through the polymerization period.
  • the initiator charge is dissolved along with the itaconic acid in the aqueous medium and the remainder of the initiator is then introduced, preferably as an aqueous solution, over the polymerization period or with the co-monomers.
  • concentration of the initiator in the aqueous addition solution is normally from about 0.5 to 10 weight%.
  • the temperature and duration of the polymerization are influential in determining the nature of the resulting copolymer.
  • the polymerization is therefore limited to temperatures of from about 55 to 90°C, or from 60 to 85°C, or even from 60 to 80°C.
  • the polymerization period can be sustained at from about 2 to about 8, 12, or 16 hours.
  • the final polymerization solution is generally maintained at the polymerization temperature until reaction is completed following the completion of the co-monomers and initiator addition period.
  • homogeneous or substantially homogeneous polymers, or random or block copolymers and/ or terpolymers of itaconic acid, (meth)acrylic acid and/or AMPS can be prepared with number average molecular weights (Mn) of from about 500 to 100,000, preferably from about 1000 to 50,000, more preferably 1000 to 10,000.
  • the improved polymer, copolymers, terpolymers and/ or crosslinked polymers produced according to the above process will be free of or substantially free of moieties of tri- substituted vinyl monomer isomers of itaconic acid, such as citri- conic acid and mesaconic acid.
  • the resulting polymer solution will include less than 0.5% w/w unreacted monomer based on the total weight of the polymer present in the solution, or less than 0.25% w/w, or free or substantially free of unreacted monomer.
  • the polymer solution will be transparent or substantially transparent. Transparency of a solution can be measured in terms of the turbidity of the solution; that is the cloudiness or haziness of the solution. Turbidity is measured on a nepholometer in nephelometric turbidity units ("NTU"). By transparent it is meant that the solution has a turbidity of less than 5 NTUs. Substantially transparent means the polymer solution has a turbidity of between about 5 and 100 NTUs, or more preferably 5 and 50 NTUs, 5 to 25 NTUs, or 5 to 15 NTUs.
  • Preferred embodiments of the instant process include those in which from about 30 to 40 mole % acrylic acid is copoly- merized with from about 60 to 70 mole % itaconic acid.
  • about 30 to 40 mole % acrylic acid, 1 to 2 mole % sodium persulfate and 1 to 2 mole % BruggolitTM FF6 are added separately over a period of about 3 to 5 hours to an aqueous solution of about 60 to 70 mole % itaconic acid at a temperature of between about 60° to 80°C, and the polymerization solution is held at temperature for an additional 4 hours following the addition.
  • the improved polymers consisting essentially of from about 30 to 40 mole % co-monomer and from about 60 to 70 mole % itaconic acid derived monomer units, and having a number average molecular weight of from about 500 to 100,000, preferably from about 1000 to 50,000, more preferably 1000 to 10,000.
  • the copolymer will normally be added to aqueous systems.
  • the final polymerization solution as such, diluted or concentrated as desired, will generally be used without isolation of the copolymer product.
  • Liquid polymers can also be dried using various drying techniques as known in the prior art [Handbook of Industrial Drying, by Arun S. Mujumdar, Third Edition, 2007] .
  • Some commonly used polymer dryers are rotary dryer, flash dryer, spray dryer, fluidized bed dryer, vibrated fluidized bed dryer, contact fluid-bed dryer, paddle dryer, plate dryer, and DRT spiral dryer.
  • the improved polymers of the present invention are especially useful in the prevention of stains on the surface of hy- droxyapatite surface, such as teeth.
  • the copolymer is normally added to an oral care formulation in an effective amount to bring the effects to the oral care formulation, normally at a level from about 0.01 to 20 weight % active, and preferably from about 0.05 to 10 weight %, or about 0. 1 to about 5 weight %, or about 0.25 to about 2.5 weight percent. Evaluation of these improved polymers has shown them to be superior to the itaconic acid polymers of the prior art.
  • the improved polymers can therefore be employed in a method of preventing stains on a hydroxyapatite surface, such as teeth.
  • the method can comprise adding to an oral care formulation the improved polymers or solutions thereof.
  • Preferred oral care formulations include dentifrice or gel and mouthwash (e.g., spray, rinse, solutions and suspensions) .
  • Other types of oral care formulations include denture adhesives, denture cleaning products, dental composites, tooth whiteners, tooth varnishes, lozenges and chewing gum.
  • the oral care formulation may be substantially solid or pasty in character, such as tooth- powder, a dental tablet, toothpaste, gel or dental cream.
  • the vehicle of such solid or pasty oral preparations generally contains a polishing material.
  • polishing materials are water-insoluble sodium metaphosphate, potassium metaphosphate, tricalcium phosphate, dehydrated calcium phosphate, anhydrous dicalcium phosphate, calcium pyrophosphate, magnesium orthophosphate, trimagnesium phosphate, calcium carbonate, sodium bicarbonate, aluminum silicate, zirconium silicate, silica, bentonite, and mixtures thereof.
  • Other suitable polishing materials include the particulate thermosetting resins described in U.S. Pat. No.
  • polishing materials include crystalline silica having particle size of up to about 5 microns, a mean particle size of up to about 1. 1 microns, and a surface area of up to about 50,000 cm 2 /gm, silica gel or colloidal silica, and complex amorphous alkali metal aluminosilicate.
  • a polishing agent of colloidal silica and alkali metal aluminosilicate complexes are particularly useful since they have refractive indices close to the refractive indices of the liquid gelling agent.
  • linear, molecularly dehydrated polyphosphate salts operative herein as abrasive dental additives are well known, being generally employed in the form of their wholly or partially neutral- ized water soluble alkali metal or ammonium salts and mixtures thereof.
  • Representative examples include sodium hexametaphos- phate, sodium tripolyphosphate, disodium diacid, trisodium mono- acid, and tetrasodium pyrophosphates, and the like.
  • Linear polyphosphates correspond to (NaPO3)n where n is about 2 to about 125. They are generally employed in the instant oral care compositions in approximate weight amounts of 0. 1 to 7%, preferably 1 to 5%.
  • the polishing material or dental abrasive is generally present in the solid or pasty compositions in weight concentrations of about 1 % to about 99% preferably, it is present in amounts ranging from about 3 or 5% to about 75% in toothpaste, and from about 70% to about 99% in toothpowder.
  • Toothpastes, creams and gels typically contain a natural or synthetic thickener or gelling agent in proportions of about 0. 1 to about 15, preferably about 0.5 to about 10 weight percent and even from 1 to 5 weight percent.
  • a suitable thickener can be cellulosic polymers, natural gums, semi-synthetic gum, synthetic hectorite, silica, a synthetic colloidal magnesium, alkali metal silicate complex clay, and carboxyvinyl polymer or polyacrylic acid of intermediate molecular weight.
  • the oral care compositions of this invention can contain a variety of optional conventional oral ingredients.
  • Such optional ingredients include surface active agents, flavoring agents, sweetening agents, binding agents, coloring agents, humectants, and pigments.
  • a preferred optional ingredient is a surface acting agent.
  • Suitable surfactants are those which are reasonably stable and form suds throughout a wide pH range, i.e. , non-soap anionic, cationic, zwitterionic and amphoteric organic synthetic detergents. Surface acting agents of these types, are described more fully in Agricola et al U.S. Pat. Nos. 3,959,458 and in Haefele 3,937,807. [0057] Flavoring agents can also be added to the instant compositions. Suitable flavoring agents include oil of wintergreen, oil of peppermint, oil of spearmint, oil of sassafras, menthol, cinnamon, and oil of clove and other volatile oils.
  • Sweetening agents which can be used include sorbitol, glycerin, saccharin, dextrose, levulose, aspartame, D-tryptophan, dihydrochalcones, acesulfame, xylitol, mannitol and sodium cyclamate and the like. Flavoring agents are generally used in the compositions at levels of from about 0.4% to about 10% by weight and sweetening agents at levels of from about 0. 1% to about 65% or 75 % by weight.
  • the oral care formulations can also include coloring agents.
  • Suitable coloring agents can include, for example, titanium dioxide, FD&C colors and any colorant used for food and pharmaceutical products and the like.
  • Binders can also be used with the toothpastes of the present inventions.
  • Such binders include, for example, cellulosic polymers, xanthan gum, carrageenan (Irish moss), natural and semi-synthetic gums, and carboxyvinyl polymers or polyacrylic acids of intermediate molecular weight, and the like. These binders are generally present at a level of from about 0. 1 % to 5%.
  • humectant Another optional component of the compositions herein is a humectant.
  • the humectant serves to keep the toothpaste compositions from hardening upon exposure to air and in mouthwashes, give a moist feel to the mouth.
  • Certain humectants can also impart desirable sweetness or flavor to mouthwash and toothpaste compositions.
  • the humectant, on a pure humectant basis generally comprises from about 0% to 70%, preferably from about 5% to 55%, by weight of the compositions herein.
  • Suitable humectants for use in this invention include edible polyhydric alcohols such as glycerine, sorbitol, xylitol, poly- ethylene glycol, propylene glycol and other glycols. Sorbitol is frequently employed as a 70% aqueous solution.
  • the mouthwashes herein may also contain ethanol in an amount of from about 0 to about 30%, preferably 5 to 25%, as a germicide.
  • the pH of the compositions herein is in the range of 3 to 10, preferably from 4 to 8.
  • the pH is preferably achieved through a proper balancing of the ingredients listed above or by the addition of an alkaline or acidic agent.
  • Other optional ingredients can include film forming polymers, such as polyvinyl acetate, acrylics, cellulosics and the like, bleaches, including peroxide, fixatives, and dental composite ingredients.
  • film forming polymers such as polyvinyl acetate, acrylics, cellulosics and the like, bleaches, including peroxide, fixatives, and dental composite ingredients.
  • Water employed in the preparation of commercially suitable oral care compositions should preferably be of low ion content and free of organic impurities. Water comprises from about 2% to about 95%, preferably from about 20% to about 95% of the compositions of this invention. When in the form of toothpastes, the amount of water is preferably from about 2% to about 45%, while mouthwashes preferably contain from about 45% to about 95%.
  • each chemical component described is presented exclusive of any solvent or diluent, which may be customarily present in the commercial material, that is, on an active chemical basis, unless otherwise indicated.
  • each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade.
  • Brookfield rotating spindle method (all viscosity measurements reported herein are conducted by the Brookfield method whether mentioned or not): The viscosity measurements are calculated in mPa-s, employing a Brookfield rotating spindle viscometer, Model RVT (Brookfield Engineering Laboratories, Inc.), at about 20 revolutions per minute (rpm), at ambient room temperature of about 20 to 25°C (hereafter referred to as viscosity). Spindle sizes are selected in accordance with the standard operating recommendations from the manufacturer. Generally, spindle sizes are selected as follows:
  • spindle size recommendations are for illustrative purposes only. The artisan of ordinary skill in the art will select a spindle size appropriate for the system to be measured.
  • NTU Nephelometric Turbidity Units
  • the weight average molecular weights referenced herein are measured by GPC using a Waters Model 515 pump, Waters Model 717 WISP autosampler with Waters Model 2410 Refractive Index @ 40°C.
  • Approximately 0.01 g polymer sample is dissolved in 10 ml of 97.5% O.
  • I M Sodium Nitrate with 2.5% tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the test sample solution is gently shaken for about two hours and filtered by passing the sample solution through a 0.45 ⁇ PTFE disposable disc filter.
  • the chromatographic conditions are: Mobile phase: 97.5% O.
  • IM Sodium Nitrate/ 2.5% THF (pH 10), 0.7 ml/min.
  • Sample size ⁇ Column set: TOSOH Guard + 2 x TSKgel GMPWxl ( 13u), 300 x 7.8 mm, @ 35°C. Waters Empower Pro LC / GPC software is used to analyze the results and to calculate M w of the polymers of the invention.
  • J H NMR spectra referenced herein are measured by dissolving the samples in D2O solvent in 5mm NMR tubes and observed by J H NMR on the Bruker AV500.
  • Residual monomers such as, itaconic acid, acrylic acid and AMPS are measured by HPLC using a Varian 5020 with UV detector, Spectra-Physics 4100 data analyzer and column C- 18 modified silica such as Phenomenex Jupiter 5u C- 18 300A, 4.6 mm
  • the calcium chelating capacity of the polymers is measured using Thermo Orion Calcium Ion Selective Electrode (ISE) connected to an Orion Start Plus Meter.
  • ISE Thermo Orion Calcium Ion Selective Electrode
  • the instrument is calibrated using four standard(Calcium chloride (CaC ) solutions with concentrations of 0.0001 M, 0.001 M, 0.01 M and 0. 1 M.
  • 1% chelator solution is prepared in DI water and its pH is adjusted to desired value using NaOH solution.
  • Burette is filled with 1% chelator solution.
  • 100 mL of 0.01 M CaC solution is taken.
  • 2 mL of Ionic Strength Adjuster (ISA) is added.
  • the ISE and reference electrodes are rinsed with distilled water, wiped and placed in the solution.
  • the chelator solution is titrated from the burette and the Ca 2+ concentration is monitored in the Orion Star Plus meter.
  • the chelator solution is added gradually until the meter shows 0.00 M concentration of Ca 2+ .
  • the end point of the titration is used to calculate the Calcium binding capacity of the polymer in mg of CaCO3/g of polymer using the following equation: / c l 0.100087*Mschreib _ _ 1000
  • HAP HAP Disc Dense (sintered) Hydroxyapatite (HAP) disc
  • Sample 1 is repeated to make Samples 2-4 with pre- neutralized itaconic acid as mentioned in Table 1 to investigate the effect of neutralization on IA isomerization as well as its conversion.
  • a neutralizing solution of 50% NaOH at different percent based on the acid groups of the IA monomer is added along with IA and is referred to as the percent degree of neutralization (%DN).
  • Samples 2-4 contain 5, 10 and 20% DN neutralizing solution respectively.
  • a polyitaconic acid polymer is prepared in water using the procedure of Example I in US Patent No. 7,910,676 at 50% DN using 70% tBHP initiator at reflux condition.
  • Polymers 6 through 12 are also synthesized as set forth in Sample 5.
  • a neutralizing solution of 50% NaOH at 5 percent based on the acid groups of the total monomers (5% DN) is added along with IA in Samples 1 1 and 12.
  • the monomer components for these Samples are set forth in Table 2 below.
  • a copolymer of 90/ 10 mole % of IA/ AA is prepared using the procedure of Example 2B in US Patent No. 4,485,223 at reflux condition with about 20 wt% (0. 1 mole %) initiator.
  • Polymers 13 through 22 are also synthesized as set forth in Sample 5 (e.g., at a reaction temperature of 85°C and with 0% DN) except a sodium salt of AMPS monomer is used in place of AA or in combination with AA.
  • the monomer components for these Samples are set forth in Table 3 below.
  • reaction is heated at 75°C for another 30 minutes before cooling to 60°C when a redox of 0.6g SPS in 4g DM water is followed by 0.6g BurgolitTM FF-6 in l Og DM water. The reaction is then cooled down and poured into a jar.
  • the reaction was heated at 75°C for another 30 minutes before cooling to 60°C when a redox of 0.6g SPS in 4g DM water is followed by 0.6g BurgolitTM FF-6 in lOg DM water. The reaction is then cooled down and poured into a jar.
  • the reaction was heated at 75°C for another 30 minutes before cooling to 60°C when a redox of 0.6g SPS in 4g DM water is followed by 0.6g BurgolitTM FF-6 in lOg DM water. The reaction is then cooled down and poured into a jar.
  • HAP hydroxyap- atite
  • HAP Hydroxyapatite
  • Color meter Portable Spectrophotomete: Color-Guide Gloss Model 683 by BYK Gardner (Catalogue #SP6831 ; 1997 version 3.26 D65/ 10 0 )
  • Polymer solutions (3 or 10 w/w) were prepared by diluting the polymer with deionized water. • Final pH of the polymer solution was adjusted with 18% NaOH solution to a target pH 6.5 (similar to pH environment in oral).
  • the discs are rinsed with deionized water for 5 seconds to remove excess polymer solution and then dried with a paper towel.
  • HAP discs treated with polymer solution (3 or 10% w/w) and un-coated (as control) were immersed in tea solution and shaken for 24 hours at 200 rpm.
  • the HAP discs were removed from the tea solution, and rinsed with D.I. water for ⁇ 30 seconds to clear any residual tea solution, dried with paper towel, and further dried in the air.
  • the stain test results are rated on a visual scale of 1 to 5, where 1 represents no stain (HAP discs before staining) and 5 represents intense staining (HAP discs without polymer treatment and stained for 24h). A color reading was also measured on using the color meter, which measures a ⁇ value. The lower the ⁇ value the better.
  • both porous and sintered HAP discs coated with itaconic- containing polymers used as example polymers for this invention showed superior performance on stain prevention as compared to the discs coated with comparative polymers (Comparative Example II, Carbopol® 907, and Gantrez® S-97 BF). Better stain prevention was observed for porous discs.
  • the transitional term "comprising,” which is synonymous with “including,” “containing,” or “characterized by,” is inclusive or open-ended and does not exclude additional, un-recited elements or method steps.
  • the term encompass, as alternative embodiments, the phrases “consisting essentially of and “consisting of,” where “consisting of excludes any element or step not specified and “consisting essentially of permits the inclusion of additional un-recited elements or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cosmetics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une composition de soin oral comprenant un homo- ou un copolymère d'acide polyitaconique pur exempt des monomères vinyliques trisubstitués moins réactifs (par exemple, acide citraconique ou acide mésaconique).
PCT/US2014/025730 2013-03-15 2014-03-13 Polymères d'acide itaconique pour applications de soin oral WO2014151439A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015138872A1 (fr) * 2014-03-14 2015-09-17 Lubrizol Advanced Materials, Inc. Polymères et copolymères d'acide itaconique
WO2016075498A1 (fr) * 2015-02-27 2016-05-19 Revolymer (U.K.) Limited Polymères d'acide itaconique et utilisations de ceux-ci en tant qu'agent filmogène dans un produit cosmétique ou de soins personnels
CN115105463A (zh) * 2022-07-27 2022-09-27 上海交通大学医学院附属第九人民医院 一种用于修复皮肤损伤的软膏

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138477A (en) * 1976-05-28 1979-02-06 Colgate Palmolive Company Composition to control mouth odor
US4206292A (en) * 1978-03-09 1980-06-03 Kureha Kagaku Kogyo Kabushiki Kaisha Vinyl chloride resin composition containing polymeric processing aid
EP0079165A2 (fr) * 1981-10-29 1983-05-18 Pfizer Inc. Copolymères d'acide acrylique et itaconique, leur préparation et leur usage comme antitartre
EP0506246A1 (fr) * 1991-03-27 1992-09-30 Rohm And Haas Company Préparation de polymères d'acide itaconique
WO2006073822A1 (fr) * 2004-12-30 2006-07-13 Colgate-Palmolive Company Composition de blanchiment des dents contenant un polymere reticule et des peroxydes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4138477A (en) * 1976-05-28 1979-02-06 Colgate Palmolive Company Composition to control mouth odor
US4206292A (en) * 1978-03-09 1980-06-03 Kureha Kagaku Kogyo Kabushiki Kaisha Vinyl chloride resin composition containing polymeric processing aid
EP0079165A2 (fr) * 1981-10-29 1983-05-18 Pfizer Inc. Copolymères d'acide acrylique et itaconique, leur préparation et leur usage comme antitartre
EP0506246A1 (fr) * 1991-03-27 1992-09-30 Rohm And Haas Company Préparation de polymères d'acide itaconique
WO2006073822A1 (fr) * 2004-12-30 2006-07-13 Colgate-Palmolive Company Composition de blanchiment des dents contenant un polymere reticule et des peroxydes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015138872A1 (fr) * 2014-03-14 2015-09-17 Lubrizol Advanced Materials, Inc. Polymères et copolymères d'acide itaconique
US20170022451A1 (en) * 2014-03-14 2017-01-26 Lubrizol Advanced Materials, Inc. Itaconic acid polymers and copolymers
CN106574018A (zh) * 2014-03-14 2017-04-19 路博润先进材料公司 衣康酸聚合物和共聚物
EP3116924B1 (fr) 2014-03-14 2020-08-19 Lubrizol Advanced Materials, Inc. Polymères et copolymères d'acide itaconique
US11214758B2 (en) 2014-03-14 2022-01-04 Lubrizol Advanced Materials, Inc. Itaconic acid polymers and copolymers
WO2016075498A1 (fr) * 2015-02-27 2016-05-19 Revolymer (U.K.) Limited Polymères d'acide itaconique et utilisations de ceux-ci en tant qu'agent filmogène dans un produit cosmétique ou de soins personnels
CN107405288A (zh) * 2015-02-27 2017-11-28 伊塔康尼克（英国）有限公司 衣康酸的聚合物及其在化妆品产品或个人护理产品中作为成膜剂的用途
CN115105463A (zh) * 2022-07-27 2022-09-27 上海交通大学医学院附属第九人民医院 一种用于修复皮肤损伤的软膏

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