United States Patent (19)
`Trandai et al.
`
`||||||IIII
`USO05585092A
`5,585,092
`11
`Patent Number:
`Dec. 17, 1996
`45 Date of Patent:
`
`54) GEL DEODORANT COMPOSITIONS
`(75) Inventors: Angie Trandai, West Chester; Milan
`M. Jevtitch, Cincinnati; Dean W. Phan,
`West Chester; Paulette L. Warner,
`Cincinnati, all of Ohio
`Assignee: The Procter & Gamble Company,
`Cincinnati, Ohio
`
`(73
`
`(21) Appl. No.: 421,644
`22 Filed:
`Apr. 13, 1995
`(51
`int. Cl. ....................... A61K 7/32
`52 U.S. Cl. ..................... 424/65; 424/78.02; 424/78.08;
`424/78.18; 424/401; 424/407; 514/944;
`514/946; 512/1
`58 Field of Search .............................. 424/65, 400, 401,
`424/407, 78.02, 78.08, 78.18; 512/1; 514/944,
`946
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`Re. 33,993 7/1992 Grollier et al. ........................... 424f74
`4,205,062 5/1980 Daahn ....................................... 424f66
`4,219,540 8/1980 Soldati et al.
`... 424f65
`4,229,432 10/1980 Geria ......................................... 424f68
`4,264,586 4/1981 Callingham et al. ..................... 424/68
`4,278,655 7/1981 Elmi....................
`424/47
`4.278,658 7/1981 Hooper et al.
`... 424f65
`4,280,994 7/1981 Turney .....
`... 424/68
`4,338,294 7/1982 Mast .....
`... 424/68
`4,346,079 8/1982 Roehl ...
`... 424/65
`4,369,173
`1/1983 Causland et al.
`... 424/35
`4,511,554 4/1985 Geria et al. ......
`... 424/65
`4,678,663 7/1987 Scott et al. ...
`... 424/62
`4,695,452 9/1987 Gannis et al.
`424/59
`4,708,863 11/1987 Bews et al. ............................... 424/47
`4,774,079 9/1988 Shin et al. ................................ 424f66
`4,814,165 3/1989 Berg et al. ...
`... 424/63
`4,870,010 9/1989 Hayes..........
`. 424/114
`4,921,694 5/1990 Hoppe et al. ............................. 424f65
`5,013.473
`5/1991 Norbury et al. .
`252A17413
`5,120,541
`6/1992 Macaulay et al. ...................... 424,401
`
`
`
`7/1992 Brewster et al. ......................... 424f65
`5,128,123
`5,162,378 11/1992 Guthauser ............................... 54f785
`5,194,249 3/1993 Drucker et al. ........................... 424f68
`5, 198,218 3/1993 Kuznitz et al. .
`. 424/401
`5,221,529 6/1993 Tansley ..................................... 42465
`5,252,711 10/1993 Rogers et al.
`530/388.2
`5,258,174 11/1993 Schebece .................................. 424f65
`5,271,930 12/1993 Walele et al. ........................ 424f78.08
`5,286,755 2/1994 Kauffmann et al. .................... 514f.944
`5,292,503 3/1994 Raleigh et al. ....
`... 424/59
`5,316,761
`5/1994 Brazinsky ......
`... 424/65
`5,338,541
`8/1994. Matz et al. ..
`... 424/7
`5,364,625 11/1994 Sebag et al. ...
`. 424/40
`5,374,614 12/1994 Behan et al. ................................ 512/3
`5,378,468
`1/1995 Sufis et al. ............................. 424/401
`5,385,729
`1/1995 Prencipe et al. ..................... 424f70.11
`Primary Examiner-Terressa Mosley
`Attorney, Agent, or Firm-Carl J. Roof; William J. Winter;
`David K. Dabbiere
`ABSTRACT
`(57)
`The present invention relates to a gel deodorant composition
`comprising: (a) from about 0.001% to about 50%, by weight
`of the composition, of deodorant active, fragrance, or com
`bination thereof; (b) from about 0.01% to about 15%, by
`weight of the composition, of a soap gelling agent selected
`from the group consisting of salts of C-Cofatty acids, and
`combinations thereof; (c) from about 3% to about 50%, by
`weight of the composition, of glycerol, a polymer of glyc
`erol, wherein said polymer has a weight average molecular
`weight of about 800 or less, or combinations thereof; (d)
`from about 5% to about 70%, by weight of the composition,
`of one or more low molecular weight polyoxyethylene
`compounds having a structure according to Formula (I):
`R-(-OCH2CH2OR
`(I)
`wherein n is the interger 2, 3, 4, 5, 6, 7, or 8; R and R' are,
`independently, hydrogen; alkyl; or-C(=O)R’, where R is
`hydrogen or alkyl; and (e) from about 8% to about 75%, by
`weight of the composition, of water; wherein said compo
`sition contains no more than about 15% propylene glycol, by
`weight of the composition.
`20 Claims, No Drawings
`
`Petitioner Dr. Squatch
` Ex. 1025
`
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`5,585,092
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`porating into the soap-based product both glycerol and low
`molecular weight polyethylene glycol as solvents. The com
`bination of these two mild solvent materials allows for
`compositions which contain minimal to essentially no pro
`pylene glycol. The combination also allows for reduction or
`elimination of dipropylene glycol, a common solvent used in
`deodorant compositions that is not as skin compatiable as
`the solvents used in the present invention. As a result of this
`invention, gel deodorant compositions having improved skin
`compatibility but still retaining overall gel rheology can be
`provided.
`The compositions of the invention will contain no more
`than about 15% propylene glycol. More preferably they will
`contain no more than about 10% propylene glycol, still more
`preferably less than about 5%, most preferably less than
`about 2%.
`In addition to reducing to minimal levels, or eliminating,
`propylene glycol and reducing the amount needed of other
`polyhydric alcohols, inclusion of the glycerol and low
`molecular weight polyoxyethylene components provides
`other benefits. Specifically, the glycerol component provides
`humectant properties desirable in deodorant compositions.
`The polyoxyethylene component eliminates the need to use
`excessively high levels of glycerol; use of such high levels
`results in undesirable tackiness to many users. Moreover,
`Applicants have discovered that low molecular weight poly
`oxyethylene provides theological properties that allow
`smooth application and efficient delivery of the gel deodor
`at.
`Deodorant compositions comprising-glycerol and poly
`oxyethylene are described in co-pending application U.S.
`Ser. No. 08/307/951, filed Sep. 16, 1994, by Trandai and
`Phan. The compositions described in this co-pending appli
`cation also contain a polymeric gelling agent and a high
`level of water. Applicants have discovered that the compo
`sitions of the present invention, which do not contain such
`a gelling agent, are also useful as deodorant gels.
`In particular, this invention provides a gel deodorant
`composition comprising:
`(a) from about 0.001% to about 50%, by weight of the
`composition, of deodorant active, fragrance, or combi
`nation thereof;
`(b) from about 0.01% to about 15%, by weight of the
`composition, of a soap gelling agent selected from the
`group consisting of salts of C2-Cao fatty acids, and
`combinations thereof;
`(c) from about 3% to about 50%, by weight of the
`composition, of glycerol or a polymer of glycerol,
`wherein said polymer has a weight average molecular
`weight of about 800 or less, or a combination thereof;
`(d) from about 5% to about 70%, by weight of the
`composition, of one or more low molecular weight
`polyoxyethylene compounds having a structure accord
`ing to Formula (I):
`R-(-OCH2CH2OR
`
`(I)
`
`1.
`GEL DEODORANT COMPOSITIONS
`FIELD OF INVENTION
`This invention relates to gel deodorant compositions
`containing glycerol and low molecular weight polyethylene
`glycol. These compositions provide enhanced skin compat
`ibility compared with known gel deodorant products.
`BACKGROUND OF THE INVENTION Human body
`malodors are generally believed to be caused in part by
`microbial interaction with sweat gland secretions which
`produces pungent fatty acids. Aside from cleansing, one way
`such odors are controlled is by the use of deodorant prod
`ucts, particularly in the underarm area of the body.
`Deodorant products generally contain a safe and effective
`level of perfume or other odor masking ingredients, an
`antimicrobial active ingredient, or a combination thereof,
`incorporated into a vehicle from which the active ingredients
`may be deposited on the skin. Gel deodorant compositions
`have several advantages over other types of stick formula
`tions. For example, they usually leave no more than a
`minimal amount of residue on the skin, and they glide easily
`over the skin when applied. Deodorant compositions of the
`gel type generally incorporate three key ingredients: a
`material known to have deodorant efficacy, a gelling agent,
`and a polar solvent system.
`The gelling agents used most often in deodorant gel
`compositions are of the fatty acid soap type. The gelling
`agents used in these compositions include, for instance, the
`sodium or potassium salts of C-C fatty acids. These
`types of gel compositions most often utilize a highly polar
`alcohol solvent as the primary polar solvent ingredient,
`which is necessary to form the gel structure with the gelling
`agent. Monohydric and dihydric alcohols, especially, pro
`pylene glycol and dipropylene glycol, are typically used for
`this purpose.
`Although alcohol/soap gel deodorants are quite popular
`and commonly used, it is desirable to provide an improved
`deodorant gel composition that exhibites improved mildness
`to the user. It is an object of the present invention to provide
`such a composition. It is also an object of the present
`invention to provide gel deodorant compositions having
`reduced levels of polar solvents that can be relatively
`irritating to the skin, e.g., mono- and dihydric alcohols such
`as propylene glycol and dipropylene glycol, and to replace
`them with other ingredients. It is also an object of the present
`invention to provide gel deodorant compositions having
`minimal to essentially no propylene glycol. These and other
`benefits of the present invention as may be disclosed or
`become apparent to those skilled in the art can be obtained
`according to the invention described below.
`All percentages herein are by weight of the compositions
`unless otherwise indicated, All ratios are weight ratios
`unless otherwise indicated.
`All percentages, ratios, and levels of ingredients referred
`to herein are based on the actual amount of the ingredient,
`and do not include solvents, fillers, or other materials with
`which the ingredient may be combined as commercially
`available products, unless otherwise indicated.
`The invention hereof can comprise, consist of, or consist
`essentially of the essential elements described herein as well
`as any of the preferred or optional ingredients also described
`herein.
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`SUMMARY OF THE INVENTION
`It has now been found that gel deodorant compositions
`with improved skin compatibility can be obtained by incor
`
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`wherein n is the interger 2, 3, 4, 5, 6, 7, or 8; R and R'
`are, independently, hydrogen; alkyl; or -C(=O)R’,
`where R is hydrogen or alkyl; and
`(e) from about 8% to about 75%, by weight of the
`composition, of water,
`wherein said composition contains no more than about 15%,
`by weight of the composition, propylene glycol.
`The deodorant products of the present invention relate to
`gel deodorant compositions. These gel products may be in
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`3
`the form of solid sticks, semi-solid sticks, or other softer, gel
`products. Most preferred is where the gel products are in the
`form of a solid stick.
`The present invention is described in more detail below.
`
`DETALLED DESCRIPTION
`The essential ingredients as well as a variety of preferred
`and optional ingredients for the compositions of the present
`invention are described below.
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`ESSENTIAL INGREDIENTS
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`Active Ingredients
`The deodorant compositions hereof preferably comprise
`from about 0.001% to about 50%, by weight, of a deodorant
`active, fragrance, or combination thereof, preferably from
`about 0.01% to about 20%, more preferably from about
`0.1% to about 10%. Higher or lower levels are also con
`templated and intended to be encompasses as long as they
`are safe and effective for topical application to the skin to
`control malodor. For purposes hereof, a deodorant active
`shall be defined as an ingredient which prevents or elimi
`nates malodors from perspiration, as opposed to a fragrance
`which covers or masks odors.
`a. Deodorant Active Ingredients
`Suitable types of deodorant actives include antimicrobial
`ingredients such as bactericides and fungicides. Exemplary
`deodorant actives include quaternary ammonium com
`30
`pounds such as cetyl-trimethylammonium bromide, cetyl
`pyridinium chloride, benzethonium chloride, diisobutylphe
`noxy ethoxy ethyl dimethyl benzyl ammonium chloride,
`sodium N-lauryl sarcosine, sodium N-palmethyl sarcosine,
`lauroyl sarcosine, N-myristoyl glycine, potassium N-lauryl
`sarcosine, stearyl, trimethyl ammonium chloride, sodium
`aluminum chlorohydroxy lactate, tricetylmethyl ammonium
`chloride, 2,4,4'-trichlorio-2'-hydroxy diphenyl ether, diami
`noalkyl amides such as L-lysine hexadecyl amide, heavy
`metal salts of citrate, salicylate, and piroctose, especially
`zinc salts, and acids thereof, heavy metal salts of pyrithione,
`especially zinc pyrithione and zinc phenolsulfate. Still other
`antimicrobial ingredients include farnesol.
`Other deodorant actives include odor absorbing materials
`such as carbonate and bicarbonate salts, e.g. as the alkali
`metal carbonates and bicarbonates, ammonium and tet
`raalkylammonium carbonates and bicarbonates, especially
`the sodium and potassium salts.
`Mixtures of deodorant actives are also contemplated and
`intended to be encompassed herein.
`b. Fragrance
`The compositions of the present invention can contain a
`fragrance, or perfume, to impart a desired aroma, or to mask
`odors that may be associated with other components of the
`compositions. In the present invention the fragrance is
`generally used at a level from about 0.01% to about 10%.
`Any fragrance suitable for application to the skin can be
`used herein including a wide variety of fragrances and
`perfumes that are known to those skilled in the art. The
`particular fragrance used is largely a matter of choice;
`however, the fragrance should be used at a level effective for
`providing a noticeable aroma to the composition, or for
`masking undesired aroma of the composition. Also, the
`fragrance and whatever carriers accompany it should not
`impart excessive stinging to the skin, especially broken or
`irritated skin, at the levels previously disclosed. The fra
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`grance can be water soluble or water insoluble; however it
`generally will be soluble in the composition hereof, typically
`in either water or the polar solvent system.
`Fragrances are made by those skilled in the art in a wide
`variety of fragrances and strengths. Typical fragrances are
`described in Arctander, Perfume and Flavour Chemicals
`(Aroma Chemicals), Vol. I and II (1969); and Arctander,
`Perfume and Flavour Materials of Natural Origin (1960).
`U.S. Pat. No. 4,322,308, Hooper et al., issuedMar. 30, 1982,
`and U.S. Pat. No. 4,304,679, Hooper et al., issued Dec. 8,
`1981, both incorporated herein by reference, disclose fra
`grance components as generally including, but are not
`limited to, volatile phenolic substances (such as iso-amyl
`salicylate, benzyl salicylate, and thyme oil red), essence oils
`(such as geranium oil, patchouli oil, and petitgrain oil);
`citrus oils; extracts and resins (such as benzoin siam resinoid
`and opoponax resinoid); "synthetic' oils (such as Bergamot
`37 and 430, Geranium 76 and Pomeransol 314); aldehydes
`and ketones (such as B-methyl naphthyl ketone, p-t-butyl
`A-methyl hydrocinnamic aidehyde and p-t-amyl cyclohex
`anone); polycyclic compounds (such as Coumarin and
`B-naphthyl methyl ether); esters (such as diethyl phthalate,
`phenylethyl phenylacetate, non-anolide-1:4). Fragrances
`also include esters and essential oils derived from floral
`materials and fruits, citrus oils, absolutes, aldehydes, res
`inoides, musk and other animal notes (e.g., natural isolates
`of civet, castoreum and musk), balsamic, etc. and alcohols
`(such as dimyrcetol, phenylethyl alcohol and tetrahydromu
`guol). Examples of such components useful in fragrances
`herein include decyl aidehyde, undecyl aidehyde, unde
`cylenic aidehyde, lauric aidehyde, amyl cinnamic aidehyde,
`ethyl methyl phenylglycidate, methyl nonyl acetaldehyde,
`myristic aidehyde, nonalactone, nonyl aidehyde, octyl aide
`hyde, undecalactone, hexyl cinnamic aidehyde, benzalde
`hyde, vanillin, heliotropine, camphor para-hydroxy phe
`nolbutanone,
`6-acetyl
`1,1,3,446
`hexamethyl
`tetrahydronaphthalene, alpha-methyl ionone, gamma-me
`thyl ionone, and amyl-cyclohexanone and mixtures of these
`components.
`Fragrance used in the present invention may also contain
`solubilizers, diluents, or solvents which are well known in
`the art. Such materials are described in Arctander, Perfume
`and Flavour Chemicals (Aroma Chemicals), Vol. and II
`(1969). These materials typically include dipropylene gly
`col, diethylene glycol, C-C alcohols, and benzyl alcohol.
`
`Soap Gelling Agent
`The compositions hereof will comprise from about 0.01%
`to about 15%, by weight, of a soap gelling agent, preferably
`from about 0.1% to about 10%, more preferably from about
`1% to about 8%, most preferably from about 3% to about
`7%.
`The soap gelling agents hereof are salts of fatty acids
`containing from about 12 to about 40 carbon atoms
`(C-C), preferably salts of C-C fatty acids, more
`preferably C-Clo, most preferably Co-Cio Suitable salt
`forming cations for use in these gelling agents include metal
`salts such as alkali metals, e.g. sodium and potassium,
`alkaline earth metals, e.g. magnesium, and aluminum. Pre
`ferred are sodium and potassium salts.
`Examples of fatty acids useful in synthesizing the gel
`forming agents herein include myristic, palmitic, stearic,
`oleic, linoleic, linolenic, margaric and mixtures of such
`acids. Naturally occurring sources of such fatty acids include
`coconut oil, beef tallow, lanolin, fish oil, beeswax, palm oil,
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`peanut oil, olive oil, cottonseed oil, soybean oil, corn oil,
`rapeseed oil, rosin acids, and greases.
`Preferred fatty acid soap type gel forming agents include
`sodium stearate, sodium palmitate, potassium Stearate,
`potassium palmitate, sodium myristate, and aluminum
`monostearate. The most preferred gel forming agent is
`Sodium stearate.
`Mixtures of Soap gelling agents can also be used.
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`Gycerol Component
`The compositions of the present invention will comprise
`from about 3% to about 50%, by weight, of glycerol or
`polyglycerol, preferably from about 6% to about 40%, more
`preferably from about 8% to about 35%, most preferably
`from about 8% to about 20%.
`(i.e.,
`glycerol
`is
`The
`glycerol
`component
`HOCHCH(OH)CHOH); a polymer of glycerol having a
`weight average molecular weight of about 800 or less; or
`mixtures thereof. Where a polyglycerol is used, preferred is
`where the weight average molecular weight is about 500 or
`less, more preferably 300 or less.
`References herein to the glycerol component shall be
`understood to include derivatives of glycerol. Suitable
`25
`derivatives are alkyl ether derivatives (preferably C-Cs.
`more preferably C-C most preferably C-C). Exem
`plary alkyl ether derivatives include ethyl, propyl, and butyl
`ether derivatives.
`Also useful in the present compositions are the propoxy
`late glycerols described in U.S. Pat. No. 4,976,953, issued
`Dec. 11, 1990 to Orr and Sabatelli, which is incorporated by
`reference herein.
`Most preferred are compositions that contain glycerol, per
`se, not glycerol derivatives or polyglycerols.
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`Polyoxyethylene Component
`The compositions of the present invention will comprise
`from about 5% to about 70%, by weight, of a polyoxyeth
`ylene (hereafter "POE') component, preferably from about
`10% to about 50%, more preferably from about 15% to
`about 35%, most preferably from about 15% to about 30%.
`The polyoxyethylene compounds used herein are low
`molecular weight polyethylene glycols (hereafter "PEGS"),
`or full or partial ethers or esters thereof. These compounds
`have a structure according to the following formula:
`(I)
`R-(-OCH2CH2OR
`wherein R and R' are, independently, hydrogen; alkyl; or
`-C(=O)R’, wherein R is hydrogen or alkyl. When R is
`alkyl or -C(=O)R’, both R and R are the same. This is
`where the POE is a PEG-diether derivative or a PEG-diester
`derivative. When R is hydrogen, R' can be hydrogen (a
`PEG), alkyl (PEG-monoether), or -C(=O)R’ (PEG-mo
`noester).
`Particularly preferred are compostions wherein both R
`and R' are hydrogen.
`In this formula, n is an interger from 2 to 8, which relates
`to PEGs having an average degree of ethoxylation of 2 to 8.
`Preferred is where n is from 2 to 6, more preferably 2 to 5,
`most preferably 4.
`The total combined amount of glycerol and POE, by
`weight of the composition, is from about 8% to about 70%.
`Where a higher level of this combination is used, the
`compositions provide decreased performance, and reduced
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`end-user satisfaction. The total combined amount is prefer
`ably from about 15% to about 50%, more preferably about
`23% to about 45%, most preferably from about 25% to about
`40%.
`The weight ratio of the glycerol component to the POE
`component is from about 1:10 to about 5:1, preferably about
`1:5 to about 2:1, more preferably about 1:3 to about 1:1;
`most preferably from about 1:2 to about 1:1.
`Other polar solvents may be used in the present compo
`sitions as optional ingredients. These include, for example,
`monohydric C-C alkyl alcohols, dihydric C-C alkyl
`alcohols other than propylene glycol, alkyl ethers thereof
`(preferably C-C alkyl ethers), and mixtures thereof.
`Examples of such optional solvents include dipropylene
`glycol, tripropylene glycol, ethanol, n-propanol, n-butanol,
`t-butanol, 2-methoxyethanol, 2-ethyoxyethanol, ethylene
`glycol, isopropanol, isobutanol, 1,4-butylene glycol, 1,2-
`butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol,
`2,4-dihydroxy-2-methylpentane; trimethylene glycol, 1,3-
`butane diol, 1,4-butane diol, and the like, and mixtures
`thereof.
`Monohydric alcohols used herein not only provide sol
`vency, but also provide certain cosmetic advantages such as
`cool feel to the skin and a strong scent which confirms the
`deodorant's presence to the user. Preferred monohydric
`alcohols for such purpose include, for example, methanol,
`ethanol, isopropanol, and mixtures thereof, most preferred is
`ethanol.
`The level of mono- and di- hydric C-C alcohols,
`especially the C-C alcohols, in the present compositions
`should generally be no more than about 50%, by weight of
`the composition, preferably no more than about 35%, more
`preferably no more than about 30%, even more preferably
`no more than about 25%, and most preferably from 0% to no
`more than about 15%.
`Optional polar solvents useful in the present invention
`also include, for example, propylene carbonate and 3-me
`thyl-2-oxazolidinone.
`
`Water
`The compositions of the present invention will comprise
`from about 8% to about 75%, by weight, water, preferably
`from about 10% to about 60%, more preferably from about
`15% to about 50%, most preferably from about 15% to about
`30%.
`
`NON-ESSENTIAL INGREDIENTS
`
`Hydrogel Forming Polymeric Gelling Agent
`The deodorant compositions of the present invention may
`comprise aqueous gel formed from a highly absorbent
`hydrogel forming polymeric gelling agent. As discussed
`above, such compositions are described in co-pending appli
`cation U.S. Ser. No. 08/307,951. An advantage provided by
`inclusion of a hydrogel forming polymeric gelling agent is
`that increased levels of water can be included in the com
`positions.
`The compositions may contain from about 0.001% to
`about 5%, by weight of the composition, preferably from
`about 0.01% to about 5%, more preferably from about
`0.05% to about .1%, most preferably from about 0.1% to
`about 0.75% of such hydrogel forming polymeric gelling
`agent, calculated based on the dry weight of the hydrogel
`forming polymeric gelling agent.
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`The optional hydrogel forming polymeric gelling agent
`hereof is highly absorbent of water, and will generally be
`able to absorb at least about 40g water (deionized) per gram
`of gelling agent, preferably at least about 60 g/g, more
`preferably at least about 80 g/g. These values, referred to as
`"Absorptive Capacity' herein can be determined according
`to the procedure in the Absorptive Capacity "Tea Bag" test
`in the Experimental Section below.
`The hydrogel forming polymeric gelling agent hereof will
`also preferably be characterized by an extractable polymer
`content of (e) of no more than about 20%, more preferably
`no more than about 12%, most preferably no more than
`about 10%. The extractable polymer content (e) is deter
`mined according to the procedures set forth in the Experi
`mental Section, below.
`The hydrogel forming polymeric material, when in dry
`form, will generally be in the form of particles or fibers.
`Particles will preferably have a weight average particle size
`(diameter, or equivalent diameter in the case of non-spheri
`cal particles) of from about 5 to about 500 microns, pref
`erably from about 10 to about 60 microns, more preferably
`from about 10 to about 50 microns. Fibrous hydrogel
`forming polymeric gelling agent preferably have diameters
`(or equivalent diameters in the case of non-round fibers) of
`from about 5 to about 100 microns, preferably from about 15
`to about 50 microns, and lengths of from about 0.1 mm to
`about 5 mm more preferably from about 0.5 mm to about 2
`mm. It is contemplated that larger or smaller particles or
`fibers can be used, although they are not preferred, as larger
`particles or fibers may provide a grainier or a more string
`like product feel, and smaller particles may result in pro
`cessing difficulties. If relatively large particles or fibers are
`used during manufacture, improved finished product aes
`thetics can be obtained by sheer mixing the compositions or
`other mixing operations during processing of the composi
`tions.
`In general, the hydrogel forming polymeric gelling agent
`materials optionally used in the present invention are at least
`partially crosslinked polymers prepared from polymeriz
`able, unsaturated acid-containing monomers which are
`water-soluble or become water-soluble upon hydrolysis.
`These include monoethylenically unsaturated compounds
`having at least one hydrophilic radical, including olefinically
`unsaturated acids and anhydrides which contain at least one
`carbon-carbon olefinic double bond.
`With respect to these monomers, water-soluble means that
`the monomer is soluble in deionized water at 25 C. at a
`level of at least 0.2%, preferably at least 1.0%.
`Upon polymerization, monomeric units as described
`above will constitute from about 25 mole percent to 99.99
`mole percent, more preferably from about 50 mole percent
`to 99.99 mole percent, most preferably at least about 75
`mole percent of the polymeric gelling agent material (dry
`polymer weight basis). Two or more different monomer
`types of the previously described acid group-containing
`monomers may be copolymerized in order to provide the
`hydrogel-forming polymeric gelling material. Exemplary
`types of such acid groups and other hydrophilic groups
`include carboxyl, carboxylic acid anhydride, carboxylic salt,
`sulfonic acid, sulfonic acid salt, hydroxyl, ether, amide,
`amino and ammonium salt groups.
`Hydrogel forming polymeric gelling agents suitable for
`use herein are well known in the art, and are described, for
`example, in U.S. Pat. No. 4,076,663, Masuda et al., issued
`Feb. 28, 1978; U.S. Pat. No. 4,062,817, Westerman, issued
`Dec. 13, 1977; U.S. Pat. No. 4,286,082, Tsubakimoto et al.,
`
`45
`
`50
`
`55
`
`60
`
`65
`
`8
`issued Aug. 25, 1981; U.S. Pat. No. 5,061,259, Goldman et
`al., issued Oct. 29, 1991, and U.S. Pat. No. 4,654,039,
`Brandt et al., issued Mar. 31, 1987 all of which are incor
`porated herein in their entirety.
`Hydrogel forming polymeric gelling agents suitable for
`use herein are also described in U.S. Pat. No. 4,731,067,
`Le-Khac, issued Mar. 15, 1988, U.S. Pat. No. 4,743,244,
`Le-Khac, issued May 10, 1988, U.S. Pat. No. 4,813,945,
`Le-Khac, issued Mar. 21, 1989, U.S. Pat. No. 4,880,868,
`Le-Khac, issued Nov. 14, 1989, U.S. Pat. No. 4,892,533,
`Le-Khac, issued Jan. 9, 1990, U.S. Pat. No. 5,026,784,
`Le-Khac, issued Jun. 25, 1991, U.S. Pat. No. 5,079,306,
`Le-Khac, issued Jan. 7, 1992, U.S. Pat. No. 5,151,465,
`Le-Khac, issued Sep. 29, 1992, U.S. Pat. No. 4,861,539,
`Allen, Farrer, and Flesher, issued Aug. 29, 1989, and U.S.
`Pat. No. 4,962,172, Allen, Farrer, and Flesher, issued Oct. 9,
`1990, all incorporated herein by reference in their entireties.
`Examples of suitable water-soluble monomers from
`which monomer units of the polymers hereof can be derived
`are as follows:
`1. Carboxyl group-containing monomers (carboxylic
`acid-containing): monoethylenically unsaturated mono or
`poly-carboxylic acids, such as (meth) acrylic acid (meaning
`acrylic acid or methacrylic acid; similar notations are used
`hereinafter), maleic acid, fumaric acid, sorbic acid, itaconic
`acid, citraconic acid, tricarboxy ethylene, and ethacrylic
`acid;
`2. Carboxylic acid anhydride group-containing mono
`mers: monoethylenically unsaturated polycarboxylic acid
`anhydrides, such as maleic anhydride;
`3. Carboxylic acid salt-containing monomers: water
`soluble salts 0 (alkali metal salts, ammonium salts, amine
`salts, etc.) of monoethylenically unsaturated mono- or poly
`carboxylic acids such as sodium (meth)acrylate, trimethy
`lamine (meth)acrylate, triethanolamine (meth) acrylate,
`sodium maleate, methylamine maleate;
`4. Sulfonic acid group-containing monomers: aliphatic or
`aromatic 5 vinyl sulfonic acids (such as vinylsulfonic acid,
`allyl sulfonic acid, vinyltoluenesulfonic acid, styrene sul
`fonic acid), (meth)acrylic sulfonic acids such as sulfopropyl
`(meth) acrylate, 2-hydroxy-3-(meth)acryloxy propyl sul
`fonic acid, 2-acylamido-2-methyl propane sulfonic acid);
`5. Sulfonic acid salt group-containing monomers: alkali
`metal salts, ammonium salts, amine salts of sulfonic acid
`group-containing monomers as mentioned above.
`6. Hydroxyl group-containing monomers: monoethyleni
`cally unsaturated alcohols such as (meth)allyl alcohol),
`monoethylenically unsaturated ethers or esters of polyols
`(alkylene glycols, glycerol, polyoxyalkylene polyols), such
`as hydroxethyl (meth)acrylate, hydroxypropyl (meth)acry
`late, triethylene glycol (meth)acrylate, poly(oxyethylene
`oxypropylene) glycol mono (meth)allyl ether (in which
`hydroxyl groups may be etherified or esterified).
`7. Amide group-containing monomers: (meth) acryla
`mide, N-alkyl (meth)acrylamides (such as N-methylacryla
`mide, N-hexylacrylamide), N,N-dialkyl (meth)acryl amides
`(such as N,N-dimethylacrylamide, N,N'-di-n-propylacryla
`mide), N-hydroxyalkyl (meth)acrylamides such as N-me
`thylol(meth)acrylamide, N-hydroxyethyl (meth)acryla
`mide), N,N-dihydroxyalkyl (meth)acrylamides such as
`N,N-dihydroxyethyl (meth)acrylamide), vinyl lactams (such
`as N-vinylpyrrolidone);
`8. Amino group-containing monomers: amino group
`containing esters (e.g. dialkylaminoalkyl esters, dihydroxy
`alkylaminoalkyl esters, morpholinoalkyl esters, etc. ) of
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`5,585,092
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`9
`monoethylenically unsaturated mono- or dicarboxylic acid
`such as dimethlaminoethyl (meth)acrylate, diethylaminoet
`hyl (meth)acrylate, morpholinoethyl (meth)acrylate, dim
`ethyl aminoethyl fumarate), heterocyclic vinyl compounds
`such as vinyl pyridines (e.g. 2-vinyl pyridine, 4-vinyl
`pyridine, N-vinyl pyridine), N-vinyl imidazol; and
`9. Quaternary ammonium salt group-containing mono
`mers: N,N,N-trialkyl-N-(meth)acryloyloxyalkylammonium
`salts such as N,N,N-trimethyl-N-(meth)acryloyloxyethy
`lammonium chloride, N,N,N-triethyl-N-(meth)acryloyloxy
`ethylammonium chloride, 2-hydroxy-3-(meth)-acryloylox
`ypropyl trimethyl ammonium chloride), and monomers as
`mentioned in British patent specification No. 1,034,296.
`Suitable monomers which become water-soluble by
`hydrolysis, for use in this invention instead of or in con
`junction with the water-soluble 5 monomers, include mon
`ethylenically unsaturated compounds having at least one
`hydrolyzable group, such as ester and nitrile groups. Such
`monomers having an ester group include for example, lower
`alkyl (C1-C3) esters of monoethylenically unsaturated car
`boxylic acids, such as methyl (meth)acrylate, ethyl (meth
`)acrylate and 2-ethylhexyl (meth)acrylate; and esters of
`monoethylenically unsaturated alcohols vinyl esters,
`(meth)-allyl ester, etc.), such as vinyl acetate and (meth)
`allyl