(19) United States
`(12) Patent Application Publication (10) Pub. No.: US 2001/0000468 A1
`(43) Pub. Date:
`Apr. 26, 2001
`Mak et al.
`
`US 20010000468A1
`
`(54) DERIVATIVES OF ARABINOGALACTAN
`AND COMPOSITIONS INCLUDING THE
`SAME
`
`Apr. 27, 1999, noW abandoned, Which is a non
`provisional of provisional application No. 60/083,
`110, ?led on Apr. 27, 1998.
`
`(76) Inventors: Chew-Hung Mak, Roseville, MN (US);
`Morton A. Westman, Oak Brook, IL
`(US); Michael Lynn Finney, Vadnais
`Heights, MN (US); Richard Dale
`Lamb, Oakdale, MN (US)
`
`Correspondence Address:
`MUETING, RAASCH & GEBHARDT, P.A.
`PO. BOX 581415
`MINNEAPOLIS, MN 55401 (US)
`
`(21) Appl. No.:
`
`09/727,035
`
`(22) Filed:
`
`Nov. 30, 2000
`
`Related US. Application Data
`
`(63) Continuation of application No. 09/300,150, ?led on
`
`Publication Classi?cation
`
`(51) Int. c1.7 ............................. .. A61K 7/06; A61K 7/11
`(52) US. Cl. .............. .. 424/401; 424/; 424/70.1; 424/47;
`424/706; 424/439; 424/70.13
`
`(57)
`
`ABSTRACT
`
`DerivatiZed Arabinogalactan can be utilized in a variety of
`compositions to impart functionality Without imparting
`negative rheological affects When the amount of the deriva
`tiZed Arabinogalactan is increased in the composition. This
`is particularly important in the personal care industry, Where
`it is desirable to have the ?exibility to adjust the amount of
`derivatiZed Arabinogalactan depending upon the results it is
`desired to deliver to the user Without negatively impacting
`the overall viscosity of the personal care composition.
`
`

`
`Patent Application Publication
`
`Apr. 26, 2001
`
`Sheet 1 0f 7
`
`US 2001/0000468 Al
`
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`
`Patent Application Publication
`
`Apr. 26, 2001
`
`Sheet 2 0f 7
`
`US 2001/0000468 A1
`
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`—<>- 20°C
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`

`
`Patent Application Publication
`
`Apr. 26, 2001
`
`Sheet 3 0f 7
`
`US 2001/0000468 A1
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`

`
`Patent Application Publication
`
`Apr. 26, 2001
`
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`
`Patent Application Publication
`
`Apr. 26, 2001
`
`Sheet 5 0f 7
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`US 2001/0000468 Al
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`

`
`Patent Application Publication
`
`Apr. 26, 2001
`
`Sheet 6 0f 7
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`US 2001/0000468 A1
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`

`
`Patent Application Publication
`
`Apr. 26, 2001
`
`Sheet 7 0f 7
`
`US 2001/0000468 A1
`
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`

`
`US 2001/0000468 A1
`
`Apr. 26, 2001
`
`DERIVATIVES OF ARABINOGALACTAN AND
`COMPOSITIONS INCLUDING THE SAME
`
`CROSS-RELATED APPLICATIONS
`
`[0001] This application claims bene?t from US. Provi
`sional Patent Application Serial No. 60/083,110, ?led Apr.
`27, 1998.
`
`FIELD OF THE INVENTION
`
`[0002] The present invention relates to Arabinogalactan
`(AG) and in particular the present invention relates to
`Arabinogalactan derivatives and compositions including the
`same.
`
`BACKGROUND OF THE INVENTION
`
`[0003] Polymers, Whether naturally occurring or synthetic,
`are generally included in personal care products, including
`hairsprays, shampoos, hair conditioners, skin creams, skin
`lotions, cosmetic products, antiperspirants, deodorants,
`shaving creams, topic drug compositions, sunscreen prod
`ucts, and the like, because of their Theological, holding, and
`?lm-forming properties.
`[0004] Derivatives of naturally occurring polymers can
`provide chemical and physical properties that differ from the
`naturally occurring polymer. For example, cellulose and
`guar derivatives have been derived from chemical reaction
`With a variety of compounds, including ethylene or propy
`lene oxide, sodium monochloroacetate, and quaternary
`reagents. Some of these derivatives produce substances that
`are solvent compatible, have greater clarity in solution as
`compared With the non-derivatiZed form, hydrate faster and
`have greater temperature stability. As a result these deriva
`tives have improved use for liquid formulations. For
`example, cationic starch derivatives are important in the
`paper industry as Wet-end additives Where they act to
`increase dry strength. The chemical properties of the deriva
`tives depend upon the base material being derivatiZed and
`upon the derivatiZing reagent With Which they are reacted.
`DerivatiZation With a cationic reagent can lend charge to a
`base polymer, providing the efficacy in the application that
`Would otherWise be absent, e.g. cationic groups improve
`adhesion to polar substrates. DerivatiZation With a cationic
`reagent generally involves the use of either Water-based or
`solvent-based, hydroxide catalyZed reactions, as described
`in the technical literature available from the suppliers of
`such reagents.
`[0005] Quaternary ammonium (also referred to as “quat
`erniZed”) derivatives of a number of commercially available
`polymers are knoWn in the personal care industry to enhance
`substantivity (i.e., cling and resistance to removal upon
`rinsing With Water) to anionic sites Within hair or skin.
`QuaterniZed derivatives of cellulose, guar, and starch, for
`example, can be found in many personal care products.
`[0006] The degree of substitution (D.S.), of derivatiZed
`polysaccharide polymers generally ranges from 0.05 to 0.25.
`The mode of reaction for polysaccharide polymers is typi
`cally through the hydroxyl groups associated With the sugar
`rings on the polysaccharide polymers. In one example,
`derivatiZation of polysaccharide polymers With ethylene or
`propylene oxide is catalyZed by a base hydroxide to yield
`polymer derivatives With a substitution level of one to ?fty
`
`percent by Weight of ethylene or propylene oxide. Ethylene
`or propylene oxide derivatiZed polysaccharide polymers
`have been used in the personal care area. In another
`example, double derivatives of starch, cellulose or guar can
`also be prepared, for example, using a quaternary amine.
`
`[0007] In the industrial arena, hydroxypropyl cellulose
`and/or guar have been used as viscosifying agents for oil
`Well drilling, oil Well stimulation, ?re ?ghting, textiles,
`paints and other applications. DerivatiZation of sugar con
`taining polymers With sodium monochloroacetate (for
`example, to produce carboxymethyl derivatives) yields
`anionic polymers that are also useful in industrial applica
`tions. For example these derivatives function as Wet strength
`additives in papermaking or in textile siZing. Hydroxypropyl
`methylcellulose has also been used in the cosmetic and
`personal care industries.
`
`[0008] Typically, a derivatiZed polysaccharide polymer
`can also function as a viscosifying agent. Very loW concen
`trations of any of the above derivatives can impart a high
`viscosity to a solution to Which the derivatives are added.
`This is particularly true for solutions have some starting
`measurable viscosity. As a result of the added viscosity
`imparted by the derivatiZed polysaccharide polymer there is
`generally a loW upper limit to the amount of derivatiZed
`polysaccharide polymer that can be added to these solutions.
`In addition, derivatiZed polysaccharide (including sugar and
`starch polymers) are typically salt and pH sensitive. There
`fore, solutions containing these polymers are stable over
`limited salt concentration ranges and over narroW pH ranges.
`In addition, the derivatiZed polymers are often shear sensi
`tive and generally non-NeWtonian in that their apparent
`viscosity is loWer With increased shear. When these polysac
`charide polymers are added to an existing composition, the
`rheology of the composition typically increases and the
`solution also becomes shear sensitive. Adding functionality
`(i.e., substantivity, solvent compatability, pH comparability,
`or the like) through the addition of a derivatiZed polymer,
`therefore, typically has a potential negative Theological
`effect upon the entire composition.
`
`SUMMARY OF THE INVENTION
`
`[0009] There remains a need for polymer additives in the
`personal care and industrial markets that can impart func
`tionality (that is, a functional bene?t to the polymer such as,
`but not limited to, substantivity, solvent compatability, salt
`comparability, NeWtonian rheology, non-pseudoplastic
`behavior, pH compatability, compatability With other addi
`tives, loWering irritation to skin, shear thinning, pourability,
`and the like) Without imparting negative rheological affects
`to the composition. The addition of a polymer to a compo
`sition Without increasing the viscosity of the product, induc
`ing salt and pH incompatibilities, or causing the system to
`become shear sensitive or unstable With time, Would be of
`bene?t beyond polymers that are currently available. This is
`true Whether the properties being sought are characteristic of
`the speci?c polymer being added, characteristic of hydro
`colloids in general, or characteristic of the functional group
`derivatiZed With the polymer.
`
`[0010] For example, in the hair care area, there is a
`continuing need for hair manageability and style retention.
`Many styling enhancing aids, including certain shampoo
`formulations, certain conditioning formulations, gels,
`
`

`
`US 2001/0000468 A1
`
`Apr. 26, 2001
`
`mousses, and hair holding sprays, typically include a deriva
`tiZed polymer, generally a quaterniZed polymer, or gum for
`coating the hair ?bers and/or bonding them together. Some
`of these styling aids require additional application steps and
`time once styling is completed and, thus, can be inconve
`nient for the user. Some of these styling aids may deliver
`style enhancement in the form of a “rinse-off” product, such
`as a shampoo and/or conditioner. HoWever, rinse-off prod
`ucts typically require styling agents that are substantive to
`the hair and are not readily removed during rinsing. For
`eXample, a conventional styling enhancing polymer used in
`rinse-off products resists removal as the result of Water
`rinsing by bonding to anionic sites Within the hair. Such
`materials may cause a build-up of a visible residue on the
`hair With repeated usage that can difficult to remove With
`conventional shampooing.
`
`[0011] This invention provides polymer compositions that
`have little or no negative impact upon the personal care or
`industrial product properties While delivering the desired
`functional performance aspects.
`
`[0012] As used herein, the term “Arabinogalactan,” unless
`otherWise speci?ed, includes naturally occurring or syn
`thetic Arabinogalactan, portions of Arabinogalactan, such as
`degradation products, and chemically or biochemically
`modi?ed Arabinogalactan or portions thereof Which have
`been modi?ed using methods available in the art.
`
`[0013] As used herein, “ultrare?ned Arabinogalactan”
`refers to Arabinogalactan, preferably isolated from a plant
`source such as trees of the genus LariX, With a purity greater
`than 95%.
`
`[0014] As used herein, “derivatiZed” or a “derivative” of
`Arabinogalactan refers to a product of a chemical reaction
`betWeen Arabinogalactan and a derivatiZing reagent result
`ing in the attachment of at least one chemical moiety on the
`Arabinogalactan, preferably by attaching to a reactive site on
`the Arabinogalactan.
`
`[0015] As used herein, the term “substantivity” describes
`a propensity of a compound to adhere to a given substrate
`and to resist removal by a typical Water rinse procedure that
`generally folloWs application of a hair shampoo and/or
`conditioner.
`
`[0016] One aspect of the present invention provides a
`composition including a derivatiZed Arabinogalactan. In one
`embodiment, the derivatiZed Arabinogalactan includes at
`least one cationic moiety. In another embodiment, the
`derivatiZed Arabinogalactan is selected from the group con
`sisting of a single derivatiZed Arabinogalactan, a double
`derivatiZed Arabinogalactan, and a combination thereof.
`Preferably, the derivatiZed Arabinogalactan is selected from
`the group consisting of hydroXypropyl Arabinogalactan,
`carboXymethyl hydroXypropyl Arabinogalactan, quaternary
`ammonium Arabinogalactan, carboXymethyl Arabinogalac
`tan, and a combination thereof.
`
`[0017] The composition can be an ink, a paint or a coating.
`The composition can also be an adhesive. The composition
`can also be used in paper manufacturing. Additionally, the
`composition can be a personal care composition. The com
`position can also be a rheology control additive, an emul
`si?cation additive, a food additive, a formulation aid, a
`release agent or a processing aid. The composition can also
`
`be a food, or a pharmaceutical composition. The composi
`tion may also be a drilling ?uid or a fracturing ?uid.
`
`[0018] In one embodiment, the personal care composition
`can be selected from the group consisting of a hair care
`composition, a skin care composition, a cosmetic, and a
`fragrance.
`[0019] The derivatiZed Arabinogalactan is preferably
`derivatiZed With a derivatiZing reagent that is present in an
`amount from about 1% to about 200% of a Weight of
`Arabinogalactan.
`[0020] Also provided is a method for making derivatiZed
`Arabinogalactan. The method preferably includes combin
`ing Arabinogalactan in a reaction solution With a derivatiZ
`ing reagent selected from the group consisting of ethylene
`oxide, propylene oXide, a quaternary amine, sodium
`monochloroacetate, dimethylsulfate, methyl chloride,
`ketene, vinyl acetate, and a combination thereof to form a
`reaction product; and heating to a temperature of at least 37°
`C. for a time to produce a derivatiZed Arabinogalactan.
`Preferably, the reaction product is selected from the group
`consisting of quaternary ammonium Arabinogalactan, car
`boXymethylate Arabinogalactan, hydroXypropyl Arabinoga
`lactan, carboXymethyl hydroXypropyl Arabinogalactan, and
`hydroXypropyl quaternary ammonium Arabinogalactan.
`Preferably, the reaction solution includes about 10% to about
`20% by Weight of Arabinogalactan. Preferably, the tempera
`ture is at least about 48° C. and is preferably less than about
`82° C. The derivatiZing reagent is preferably present in an
`amount of about 200% or less of a Weight of Arabinogalac
`tan.
`
`[0021] Yet another aspect provides a derivatiZed Ara
`binogalactan produced by combining Arabinogalactan With
`a derivatiZing reagent selected from the group consisting of
`ethylene oxide, propylene oXide, a quaternary amine,
`sodium monochloroacetate, dimethylsulfate, methyl chlo
`ride, ketene, vinyl acetate, and a combination thereof.
`[0022] A further aspect of the present invention provides
`a composition comprising derivatiZed Arabinogalactan, the
`derivatiZed Arabinogalactan produced by combining Ara
`binogalactan With a derivatiZing reagent selected from the
`group consisting of ethylene oXide, propylene oXide, a
`quaternary amine, sodium monochloroacetate, dimethylsul
`fate, methyl chloride, ketene, vinyl acetate, and a combina
`tion thereof.
`
`[0023] Yet a further aspect of the present invention pro
`vides a personal care composition including a derivatiZed
`Arabinogalactan and a diluent. Preferably, the derivatiZed
`Arabinogalactan includes at least one cationic moeity. The
`derivatiZed Arabinogalactan can be selected from the group
`consisting of a single derivative of Arabinogalactan, a
`double derivative of Arabinogalactan, and a combination
`thereof.
`[0024] Preferably, the derivatiZed Arabinogalactan is
`selected from the group consisting of hydroXypropyl Ara
`binogalactan, carboXymethyl hydroXypropyl Arabinogalac
`tan, quaternary ammonium Arabinogalactan, carboXymethyl
`Arabinogalactan, and a combination thereof. The derivatiZed
`Arabinogalactan is preferably quaterniZed ammonium Ara
`binogalactan.
`[0025] A personal care composition of the present inven
`tion preferably includes from about 0.05% to about 25% by
`
`

`
`US 2001/0000468 A1
`
`Apr. 26, 2001
`
`Weight derivatiZed Arabinogalactan. The personal care com
`position can further include at least one additive selected
`from the group consisting of a surfactant, an emulsi?er, a
`foam modi?er, a humectant, a moisturiZer, a thickener, an
`emollient, a conditioning agent, a specialiZed functional
`ingredient, a preservative, an antioxidant, a chelator, a
`sequestrant, and an aesthetic component. The personal care
`composition can further include a specialiZed active ingre
`dient in an amount of about 0.01% to about 10% by Weight
`of the composition.
`
`[0026] In one embodiment, the personal care composition
`is a hair care composition. Preferably, the hair care compo
`sition can be selected from the group consisting of a sham
`poo, a conditioner, a hair tonic, a setting lotion, a setting gel,
`a mousse, a hair spray, a permanent hair color treatment, a
`non-permanent hair color treatment, a permanent Wave
`treatment, a hair relaxer, and a pommade.
`
`BRIEF DESCRIPTION OF THE FIGURES
`
`[0027] FIG. 1 is a viscosity pro?le for Arabinogalactan as
`compared to gum arabic and guar.
`
`[0028] FIG. 2 illustrates one example of the salt compat
`ibility of Arabinogalactan at three temperatures and salt
`concentrations ranging from 0% to 16% NaCl.
`
`[0029] FIG. 3 illustrates another example of the salt
`compatibility of a 10% Arabinogalactan solution at three
`temperatures from 0% to 16% MgSO4.
`
`[0030] FIG. 4 illustrates the viscosity of a 10% Ara
`binogalactan solution measured from a pH of about 2 to
`about 11.
`
`[0031] FIG. 5 illustrates the shear stress versus shear rate
`for a 25% Arabinogalactan solution at tWo temperatures.
`
`[0032] FIG. 6 illustrates the shear stress versus shear rate
`in a Water-based ink system With and Without Arabinoga
`lactan.
`
`[0033] FIG. 7 illustrates the impact on viscosity of aque
`ous solutions of a derivatiZed Arabinogalactan as compared
`to other polymers.
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`[0034] Arabinogalactan is a Water-soluble polysaccharide
`that can be isolated from species of the genus Larix. Ara
`binogalactan can constitute up to 35% of the total heartWood
`of some species (Stout, “Larch Arabinogalactan” in Indus
`trial Gums, R. L. Whistler Ed., Academic Press, NeW York,
`pp. 307-310, 1959). Arabinogalactan is highly soluble and
`can be obtained at 95% purity from larch chips. In a
`preferred embodiment, ultrare?ned Arabinogalactan (i.e.,
`highly puri?ed) is used in this invention. One method for the
`preparation of ultrare?ned Arabinogalactan is disclosed in
`US. Pat. No. 5,116,969 (Adams et al.). Ultra-re?ned Ara
`binogalactan of greater than 95%, or optionally, greater than
`99.9% purity is preferably used. A suitable example is
`commercially available under the trade designations
`LAREX UF and LARACARE A200, both from Larex, Inc.,
`St. Paul, Minn. Ultrare?ned Arabinogalactan advanta
`geously makes little or no contribution to the osmolality of
`aqueous solutions in Which it is a solute. Ultrare?ned
`Arabinogalactan is highly stable, non-toxic and highly Water
`
`soluble. In another embodiment, Arabinogalactan material is
`used as produced and described in US. Pat. No. 5,756,098
`(Price et al.).
`[0035] A variety of Arabinogalactans can be used in this
`invention. In one embodiment, the molecular Weight of the
`Arabinogalactan ranges from about 6,000 Daltons to about
`2,500,000 Daltons. In another embodiment, the molecular
`Weight of the Arabinogalactan used is betWeen about 6,000
`Daltons to about 300,000 Daltons and in another embodi
`ment betWeen about 10,000 Daltons to about 30,000 Daltons
`as assessed by siZe exclusion liquid chromatography using
`Pullulan reference standards available from Millipore Cor
`poration (Milford, Mass.)
`[0036] Arabinogalactan has a number of bene?ts as com
`pared With other polysaccharide polymers. Arabinogalactan
`is Water-soluble, occurs naturally With a narroW molecular
`Weight distribution as compared to, for example, gum arabic
`and guar. As shoWn in FIG. 1, a concentration of Arabinoga
`lactan of about 55 W/W % results in a viscosity of a about
`1000 cps, While a viscosity of about 1000 cps is achieved
`With concentrations of about 40 W/W % and about 0.75 W/W
`% for guar and gum arabic, respectively. While not Wishing
`to be bound by any particular theory, it is believed that
`because Arabinogalactan is highly branched it is not subject
`to viscosity problems, as compared to other polymers.
`[0037] Arabinogalactan salt compatibility is unusually
`good. Unlike the phenomenon observed With most hydro
`colloids, increasing salt concentration has a very little
`impact on the apparent viscosity of an aqueous 10% Ara
`binogalactan solution. Referring to FIGS. 2 and 3, viscosity
`measurements Were taken for a 10% Arabinogalactan solu
`tion containing sodium chloride or magnesium sulfate,
`respectively, from Zero to ?fteen percent by Weight. Viscos
`ity measurements Were taken using a Brook?eld Viscometer
`at three different temperatures. As shoWn in FIG. 2, there is
`a negligible increase in viscosity of from about 0.7 cps to
`about 1.05 cps in the case of NaCl at 20° C. A similar effect
`Was observed in the case of MgSO4 at 20° C., Where there
`Was a negligible increase from about 0.7 cps to about 1.6
`cps. At 500 C., a negligible increase is again substantially
`linear from about 0.4 cps to about 0.7 cps for NaCl and to
`about 0.6 cps for MgSO4.
`[0038] Also, unlike other polysaccharide polymers, the
`response of a 10% Arabinogalactan solution With a pH
`increase from 2 to 11 results in a very small change in
`apparent viscosity, decreasing from about 0.75 cps at pH 2
`to about 0.65 cps at pH 11 (at 20°C.), as shoWn in FIG. 4.
`At 50° C., the relationship shoWs even less change, staying
`around 0.4 cps as the pH values increase from 2 to 11. In
`contrast, many conventional polysaccharide polymers are
`fairly sensitive to pH changes, Which results in a substantial
`change in viscosity.
`[0039] Arabinogalactan solutions are NeWtonian solutions
`(i.e., solutions in Which the relationship betWeen shear stress
`and shear rate is substantially linear). For a 25% Arabinoga
`lactan solution, increasing shear rate from Zero to sixty
`revolutions per minute (rpm) on a Brook?eld CP Viscometer
`increased shear stress linearly from Zero to forty ?ve cps (at
`35° C.), as shoWn in FIG. 5. This characteristic of Ara
`binogalactan transfers from a simple solution of the material
`to many complex systems containing Arabinogalactan. For
`example, a Water-based ink system, such as magenta ink
`
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`
`Without Arabinogalactan, exhibited a decrease in viscosity
`from about 9000 cps to about 3000 cps as the shear rate
`increased from ?ve and sixty rpm, as illustrated in FIG. 6.
`The same ink system With 2% Arabinogalactan had a ?at
`viscosity pro?le of about 1000 cps as the shear rate increased
`betWeen the same tWo rpm values.
`
`[0040] Arabinogalactan also stabilizes emulsions. It has
`been observed in photomicrographs of oil-in-Water systems
`containing Arabinogalactan, the oil-in-Water emulsion can
`be characteriZed as having smaller and more uniform oil
`droplets. The ability of Arabinogalactan to produce smaller,
`more uniform droplets tends to enhance the stability of
`Arabinogalactan-containing systems over time and is gen
`erally knoWn to enhance performance properties. These
`emulsions have application in cosmetic, personal care, food
`and industrial applications.
`[0041] A variety of Arabinogalactan derivatives can be
`prepared using methods knoWn in the art, such as methods
`available for derivatiZing polysaccharides including cellu
`lose, guar, gum arabic, and the like (Gordon ToWle, Chemi
`cal Modi?cation of Gums, Industrial Gums, Roy Whistler,
`Ed., Academic Press, NeW York, 1993, pp 53-67). Typically,
`reactive sites on Arabinogalactan include primary and sec
`ondary hydroxyl groups that occur naturally as part of the
`sugar ring structure. Alternatively, reactive hydroxyl groups
`can be added as a result of a chemical modi?cation. Ara
`binogalactan can be chemically modi?ed prior to derivati
`Zation or simultaneously or sequentially as part of the
`derivatiZation reaction.
`
`[0042] In general, the derivatiZed Arabinogalactan is pre
`pared by dissolving or suspending the Arabinogalactan in a
`Water or solvent phase and combined With a derivatiZing
`reagent. The reaction can be catalyZed by a base hydroxide
`(typically KOH or NaOH) and can be either exothermic or
`endothermic, depending on the reagent used. The resulting
`derivatives can optionally be further re?ned and/or puri?ed
`to eliminate unWanted salts, impurities and/or reaction by
`products.
`[0043] DerivatiZed Arabinogalactan can be prepared by
`reacting Arabinogalactan With one or more of the folloWing
`derivatiZing reagents: ethylene oxide, propylene oxide, qua
`ternary amines, lauryl dimethyl quat, sodium monochloro
`acetate, dimethyl sulfate, methyl chloride, ketene, and vinyl
`acetate. The derivatiZed Arabinogalactan can be tested for
`use in particular compositions and for their composition
`altering properties such as, but not limited to, shear stress,
`viscosity, pH, salt sensitivity, and the like. The characteris
`tics of the derivatiZed Arabinogalactan Will depend on the
`type and extent of the degree of substitution. As Will be
`understood in the art, the degree of substitution can be
`controlled by limiting the amount of reagent or catalyst in
`contact With the polysaccharide.
`
`[0044] In addition to derivatiZation reactions Which result
`in chemical modi?cation by attachment of the reagent
`molecule to the polysaccharide, other derivatiZation reac
`tions exist that do not signi?cantly chemically modify the
`sugar structure but rather change the apparent viscosity of
`the resulting solutions, for example, by either depolymeriZ
`ing the polysaccharide or by complexing the material in
`solution or in use (termed depolymeriZed Arabinogalactan or
`complexed Arabinogalactan). These reactions can be carried
`out by oxidiZing the polysaccharide, for example, using
`
`hydrogen peroxide in the presence of a base, or by inclusion
`of a material such as a transition metal or borate ion, Which
`complexes the structure through hydroxyl crosslinking
`betWeen polymer chains. This technology is discussed in the
`art (Whistler, supra).
`[0045] Quaternary ammonium Arabinogalactan deriva
`tives can be prepared in an aqueous solution through the
`reaction of a quaternary reagent With Arabinogalactan, pref
`erably in the presence of a base. Suitable quaternary reagents
`include 3-chloro-2-hydroxypropyl trimethylammonium
`chloride, and those commercially available under the trade
`designations DOW QUAT 188, from DoW Corporation,
`Freeport, Tex., and DEGUSSA QUAB 188, from Degussa
`Corp., Ridge?eld Park, N]. One preferred base is sodium
`hydroxide. For example, a solution of Arabinogalactan, from
`about 10% to about 70% solids, is mixed With about 65%
`active quaternary reagent (about 10% to about 200% by
`Weight of Arabinogalactan) and a concentrated sodium
`hydroxide solution (about 20% to about 100% by Weight of
`Arabinogalactan) at room temperature. The reaction mixture
`is sloWly heated over a period of one hour to about 120° F.,
`and held at this temperature for about one hour, then cooled
`and either spray or drum dried. The resulting solid material
`can be used in the industrial market, such as for paper
`applications, including, but not limited to, inks, adhesives,
`and the like, or extensively Washed With a solvent, such as
`methanol or isopropanol to remove contaminants Where the
`derivates can be used in the personal care industry.
`
`[0046] Alternatively, quaternary ammonium Arabinoga
`lactan can be prepared in solvent reactions. In one example,
`about 10% to about 70% Arabinogalactan solids as a slurry
`in methanol, ethanol, IPA (isopropyl alcohol) or other appro
`priate solvent or aqueous solvent solution, in Which Ara
`binogalactan is only partially soluble or totally insoluble, is
`prepared. The quaternary reagent is added to the slurry or
`solution, either in concert With, before or after the addition
`of an hydroxide base such as sodium hydroxide or potassium
`hydroxide. The reaction mass is heated gradually to about
`120° F. (about 489° C.) over a period of one hour, held at
`that temperature for about one hour, then cooled and dis
`charged. The solid material is separated from the solvent
`using existing technology in the art, as for example With a
`solid boWl centrifuge, and then cake oven dried, ground in
`a pin or hammer mill and sifted to the desired mesh.
`Alternately, the solid material can be extensively Washed in
`solvent to remove reaction by-products and other contami
`nants and then dried.
`
`[0047] Production of a quaternary ammonium Arabinoga
`lactan compound is primarily targeted at, but not limited to,
`the personal care industry. Other potential compounds With
`Arabinogalactan for use in the personal care industry include
`stearyl or lauryl derivatives. These derivatives can be pro
`duced using the above chemical routes or modi?cations
`using quaternary ammonium reagents.
`
`[0048] Double derivatives of Arabinogalactan, i.e., Ara
`binogalactan including tWo chemical moieties, can be pre
`pared. For example, a double derivative of Arabinogalactan
`for inclusion in a personal care composition, can include
`Arabinogalactan having either a quaternary, lauryl or stearyl
`group and either a hydroxypropyl or hydroxyethyl group.
`Substitution levels can be about 1% to about 100% by
`Weight of Arabinogalactan for each reacted derivatiZing
`
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`reagent, but preferred in the range of about 1% to about 50%
`and most preferred in the range of about 1% to about 20%
`by Weight of Arabinogalactan.
`[0049] Single derivatives of Arabinogalactan With ethyl
`ene or propylene oxide can be produced in pressurized
`reaction vessels either in an aqueous or a solvent phase. As
`above, about 10% to about 70% solids solution or slurry is
`prepared and the reagents are added (about 10% to about
`200% by Weight of Arabinogalactan) together With, before
`or after the addition of the catalyZing base (typically about
`50% base solution at about 10% to about 20% by Weight of
`polysaccharide). The reaction mass is heated to a minimum
`of about 120° F. (about 48° C.), after Which the exothermic
`reaction is cooled and temperatures beloW about 180° F.
`(about 82° C.) are maintained. The reaction is carried out in
`an inert environment, such as a nitrogen atmosphere With or
`Without the addition of pressure. The resulting solution or
`solids are treated as above With the quaternary reaction
`products. The substitution levels of the resulting compounds
`can be in the range of about 1% to about 200% by Weight of
`Arabinogalactan.
`[0050] Carboxymethyl Arabinogalactans are produced by
`reacting Arabinogalactan, as above, With sodium monochlo
`roacetate. This reaction is typically endothermic and must be
`heated from about 150° F. (about 66° C.) to about 170° F.
`(about 77° C.) to achieve the desired reaction ef?ciencies
`and substitution levels. DerivatiZing reagent and base levels
`parallel that of the quaternary amine reactions, along With
`overall substitution levels.
`
`[0051] Other derivatiZing reagents as previously men
`tioned can be reacted With Arabinogalactan using methods
`similar to or identical to the above methods for quaternary
`amines, ethylene or propylene oxides or sodium monochlo
`roacetate.
`
`[0052] DerivativatiZed Arabinogalactan of this invention
`can be used for the same purposes as underivatiZed Ara
`binogalactan or for the same uses as other polysaccharides,
`natural, synthetic or derivatiZed, With the advantages that:
`(1) the derivatiZation adds functionality, including the addi
`tion of a charged group,