United States Patent
`
`[19]
`
`[11] Patent Number:
`
`4,746,690
`
`Busch et al.
`[45] Date of Patent: May 24, 1988
`
`
`[54] WATER-SOLUBLE POLYMER
`COMPOSITIONS
`
`[75]
`
`Inventors: Peter Busch, Erkrath; Klaus Thiele,
`Langenfeld, both of Fed. Rep. of
`Germany
`
`[73] Assignee:
`
`Henkel Kornmanditgesellschaft auf
`Aktien, Duesseldorf, Fed. Rep. of
`Germany
`
`[21] Appl. No.: 864,637
`
`[22] Filed:
`
`May 16, 1986
`
`[30]
`
`Foreign Application Priority Data
`
`May 24, 1985 [DE]
`
`Fed. Rep. of Germany ..... .. 3518673
`
`Int. Cl.4 ...................... .. A61K 7/06; A61K 31/74
`[51]
`[52] U.S. Cl. ...................................... .. 524/27; 524/55;
`527/312; 424/70; 424/489; 424/78
`[58] Field of Search .................. .. 524/27, 55; 527/312;
`536/30, 52; 424/70, 489, 78
`
`[56]
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`.................. 523/336
`Re. 28,474 7/1974 Anderson et al.
`3,472,840 10/1969 Stone et al.
`............................ 536/43
`
`............... .. 162/168.3
`8/1975 Sackman et al.
`3,901,857
`. . . .. .
`. . . . . .. 132/7
`4,240,450 12/1980 Grollier et al.
`..
`424/70
`4,273,760
`6/1981 Koehler et al.
`4,292,212
`9/1981 Melby .. . . . . . . . . . . ..
`. . .. . .. 424/70
`4,602,648
`7/1986 Syed et al.
`. . . . . . .
`. . . .. 424/70
`4,612,336
`9/1986 Yada et a1.
`.......................... .. 522/84
`
`
`
`FOREIGN PATENT DOCUMENTS
`
`1136842 12/1968 United Kingdom .
`
`Primary Examz'ner—De1bert R. Phillips
`Assistant Examiner-——Nathan M. Nutter
`Attorney, Agent, or Firm—Emest G. Szoke; Henry E.
`Millson, Jr.
`
`[57]
`
`ABSTRACT
`
`Cationic polymer - containing compositions in dry,
`powder form and having enhanced water-solubility are
`obtained by mixing (1) from about 5% to about 99% by
`weight of a solid, finely divided water-soluble cationic
`polymer and (2) from about 1.0% to about 95% by
`weight of a solid, finely divided, water-soluble anionic
`surfactant. The compositions are useful
`in cosmetic
`preparations and as flocculating agents, sludge dewater-
`ing agents and paper auxiliaries.
`
`12 Claims, No Drawings
`
`UNL ‘I053
`
`1
`
`

`
`1
`
`4,746,690
`
`WATER-SOI‘.UBLE POLYMER COMPOSITIONS
`
`. BACKGROUND OF THE INVENTION
`1. Field of the Invention
`
`This invention relates to compositions containing a
`mixture of a water-soluble, cationic polymer and an
`anionic surfactant. The compositions are characterized
`by their enhanced water-solubility.
`The compositions are used as flocculating agents,
`sludge dewatering agents, paper auxiliaries and as addi-
`tives in various cosmetic preparations applied to the
`skin and hair.
`
`2. Description of Related Art
`U.S. Pat. No. 4,240,450 to Grollier, et al., assigned to
`L’Oreal, Paris, France, discloses compositions compris-
`ing a combination of a cationic polymer with an anionic
`polymer. The cationic polymers are generally present in
`an amount of 0.01% to 10%‘, and preferably 0.05% to
`5%, of the total weight of the composition. The anionic
`polymers are generally present in an amount of 0.01%
`and 10%, and preferably 0.02% to 5%, of the total
`weight of the composition. The compositions are used
`in the treatment of keratin material, in particular human
`hair, skin and nails.
`
`U.S. Pat. No. 3,901,857 to Sackman, et al., assigned to
`Bayer Aktiengesellschaft, Leverkusen, Germany dis-
`closes high molecular weight cationic copolymers of
`acrylamide or methyacrylamide and dialkylaminoalk-
`ylacrylate or dialkylaminoalkylmethacrylate and a pro-
`cess for producing same. The copolymers in the form of
`aqueous solutions are used as paper auxiliaries for clean-
`ing and clarifying effluents, etc.
`U.S. Pat. No. 3,472,840 discloses cationic polymers
`which are cellulose ethers in which the anhydroglucose
`units each contain from 1 to 3 substituents containing
`quaternary ammonium groups attached to the oxygen
`atoms of hydroxyl groups. The cellulose ethers thus
`disclosed are described as useful as flocculants, pig-
`memt retention aids in paper making, antistatic agents
`for fibers and fabrics, etc.
`U.K. Pat. No. 1,136,842 to General Mills, Inc., Min-
`neapolis, Minn. discloses cationic polygalactomannan
`derivatives and their use in the production of paper.
`DESCRIPTION OF THE INVENTION
`
`Water-soluble, cationic polymers have achieved con-
`siderable
`commerical
`recognition as
`flocculating
`agents, sludge dewatering agents and paper auxiliaries
`as well as additives for cosmetic products applied to the
`skin or hair. Unfortunately, however, many solid, finely
`divided cationic polymers are disadvantaged for such
`uses since, on addition to water, the polymer particles
`form into larger aggregates during hydration. As a
`result,
`the dissolution of the polymer occurs very
`slowly. At times, dissolution can be facilitated some-
`what by the use of high efficiency mixing and stirring
`equipment. However, even using such equipment, effec-
`tive dissolution is difficult and expensive to achieve.
`It has now been found that compositions containing
`water-soluble cationic polymers can be
`rendered
`readily soluble in water, without the assistance of ex-
`pensive stirring or mixing equipment, by mixing the
`cationic polymer with a solid, finely divided, water-sol-
`uble anionic surfactant. When such mixtures are added
`to water, and stirred gently,
`the mixture dissolves
`quickly in the water without the formation of the com-
`monly encountered large gel clumps. The use of high-
`
`2
`speed stirrers or high-shear mixing units is not only
`superfluous, it is actually advisable to carry out dissolu-
`tion of the powder-form compositions of the invention
`in water without such units, i.e., with only gentle move-
`ment of the liquid.
`The composition of the invention can also be dis-
`solved in aqueous solutions already containing surfac-
`tants, for example, in cosmetic washing and cleaning
`preparations for the skin and the hair, such as shampoos,
`bathing preparations and liquid soaps, considerably
`more quickly than solid, finely divided, water-soluble
`cationic polymers alone. Another advantage is that the
`quantities of solid, finely divided, water-soluble anionic
`surfactants added from the compositions of the inven-
`tion have no deleterious effects on the above cosmetic
`preparations.
`In general, the water-solubility of any watersoluble
`cationic polymer can be enhanced by the process of this
`invention. Particularly well suited for use, however, are
`water-soluble cationic polymers, preferably having mo-
`lecular weights in the range of 1,000 to 3,000,000, which
`either contain amino or alkyl substituted amino groups
`or quaternary ammonium groups in the polymer chain
`or carry secondary or tertiary amino groups or quater-
`nary ammonium groups attached to the polymer chain
`either directly or indirectly through intermediate link-
`ages. The amino groups and quaternary ammonium
`groups referred to herein may be 5- or 6-membered ring
`systems, for example, morpholine, piperidine, pipera-
`zine or imidazole rings. Water-soluble, cationic poly-
`mers of this type are disclosed in U.S. Pat. No.
`4,240,450.
`Many other water-soluble cationic polymers are use-
`ful in the practice of this invention. They include cellu-
`lose ethers, the anhydroglucose units of which each
`contain 1 to 3 substituents containing quaternary ammo-
`nium groups attached to the oxygen atoms of the hy-
`droxyl groups. Compounds of this type are disclosed in
`U.S. Pat. No. 3,472,840.
`Other cationic polymers which are suitable for use
`herein include: graft polymers of hydroxyethyl cellu-
`lose and dimethylalkylammonium chloride. One such
`polymer is available commercially under the trade name
`Celquat L-200 (National Starch and Chemical Corp.,
`Bridgewater, N.J.). Also copolymers of acrylamide or
`methacrylamide and dialkylaminoalkylacrylate or die-
`thylaminoalkylmethacrylate,
`for
`example,
`die-
`'thylaminoethylmethacrylate as described in U.S. Pat.
`No. 3,901,857 can be used as the water-soluble cationic
`polymer.
`The present invention is particularly useful in the case
`of water-soluble cationic polymers which are in very
`finely divided solid form. Polymers of such natures
`include the cationic polygalactomannan derivatives
`disclosed in U.K. Pat. No. 1,136,842. Galactomannans
`are naturally occurring polysaccharides which are pro-
`duced commercially however from locust bean gum,
`guar gum and tara gum. They are made up of a linear
`mannan main chain consisting of mannopyranose units
`which are attached by ,8-(1,4)-glycoside bonds and to
`which individual galactopyranose residues are fixed as
`branches by a.-(1,6)-glycoside bonds. The individual
`polygalactomannans differ from one another primarily
`in the mannose-galactose ratio. The cationic derivatives
`of the polygalactomannans are prepared by the reaction
`of hydroxyl groups of the polysaccharide with reactive
`quaternary ammonium compounds. Suitable reactive
`
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`
`

`
`3
`quaternary compounds are, for example, those having
`the formula:
`
`4,746,690
`
`4
`about 8 to about 18 carbon atoms in the alkyl group and
`having from about 2 to about 6 glycoether groups in the
`molecule; acyl sarcosines, acyl taurides and acyl iseth-
`ionates containing from about 8 to about 18 carbon
`atoms in the acyl group; and alkali metal salts of a-sul-
`fofatty methylesters of Cg—C1g fatty acids.
`Although the invention is particularly practiced
`using anionic surfactants which are in solid, finely di-
`vided form, in an alternate embodiment of the inven-
`tion, one can employ anionic surfactants which, in pure
`form, cannot be produced as free-flowing powders.
`Surfactants of this nature, which are generally paste-
`like, low-melting or tacky in pure form, can be formu-
`lated into non-tacky,
`fine grained and free-flowing
`preparations using suitable adjuvants and carriers. The
`latter- are preferably finely divided solid compounds
`which are readily soluble in water. Especially well
`suited for use as the adjuvants and carriers are inorganic
`water-soluble salts such as, for example, sodium sulfate,
`sodium chloride, sodium carbonate, sodium hydrogen
`carbonate, sodium phosphate and the corresponding
`potassium and ammonium salts. Additionally, one can
`use other water-soluble carriers, which are not salts,
`such as, urea; water-soluble mono-and disaccharides,
`etc.
`
`In addition to the foregoing, the same adjuvants and
`carriers can be added to the cationic polymer -anionic
`surfactant preparations of this invention to improve the
`powder quality and/or flow properites thereof. Fur-
`thermore, small quantities of liquid or low-melting adju-
`vants can be added to the mixtures to reduce dust emis-
`
`sion. Such adjuvants include, for example, ethylene
`glycol; propylene glycol; glycerol; polyethylene gly-
`cols; polypropylene glycols; ethylene glycol - propy-
`lene glycol block polymers; liquid or low melting alkyl
`( poly) glycolethers containing from 1 to about 22 car-
`bon atoms in the alkyl groups and from 1 to about 20
`glycoether groups. These adjuvants should not com-
`prise greater than 5% by weight of the preparation of
`this invention to ensure that the freeflow powder prop-
`erties of such preparations are not adversely affected.
`In general, the cationic polymer compositions of this
`invention will be characterized by their powder form
`and enhanced water-solubility characteristics. The
`compositions will comprise (1) from about 5% to about
`99% by weight, preferably from about 10% to about
`95% by weight, more preferably from about 40% to
`about 90% by weight and most preferably from about
`50% to about 90% by weight of a solid, finely divided,
`water-soluble cationic polymer (2) from about 1% to
`about 95% by weight, preferably from about 5% to
`about 90% by weight, more preferably from about 10%
`to about 60% by weight and most preferably from about
`10% by weight to about 50% by weight of a solid,
`finely divided, water-soluble anionic surfactant and (3)
`from 0% to about 50% by weight of inert adjuvants and
`carriers. As noted heretofore, when a liquid or low
`melting adjuvant is added to the composition for reduc-
`ing dust emissions, such material should not exceed 5%
`by weight of the composition. As a general rule, the
`adjuvants and carriers referred to herein are used only
`as needed to prevent tackiness and/or to reduce dust
`emission.
`
`In the powder-form compositions of the invention the
`finely divided water-soluble cationic polymers prefera-
`bly have a particle size such that at least about 69% by
`weight of the particles are no larger than 45 microns
`
`R2
`Rl_.Ilq(+)—R3 z(—)
`4
`
`lR
`
`in which R‘, R2 and R3 represent a lower alkyl group,
`e.g. methyl, ethyl, etc; and in which R4 is either an
`epoxyalkyl group having the formula
`
`cH2—cH—-R5-
`\ /0
`
`or a halohydrin group having the formula:
`
`X-CH2-(III-I--R5-
`on
`
`in which R5 is a lower alkylene group, e.g. a C1-C3
`alkylene group; X is a halogen atom, e.g. chlorine or
`bromine; and Z is an anion, such as for example, a chlo-
`ride, bromide, iodide group or hydrogen sulfate.
`In these cationic polymers, the degree of substitution
`should be at least 0.01 and, preferably, at least 0.05. In a
`typical compound, the degree of substitution is typically
`between 0.05 and 0.5.
`
`A quaternary ammonium derivative of a polygalacto-
`mannan is a guar hydroxypropyl trimethylammonium
`chloride which contains a cationic group having the
`formula:
`
`-ct-12——cH(oH)——cH2—N<+>(cH3)3c1<->
`
`attached to the oxygen atoms of the hydroxyl group of
`the polysaccharide. Compounds of this nature are com-
`mercially available, for example under the trade names,
`Cosmedia Guar C261 (guar hydroxypropyl
`trime-
`thylammoniumchloride degree of substitution (DS) is
`0.07—-Henkel
`Corporation);
`Jaguar
`C-13
`(DS=O.l1-0.13) and Jaguar C135 (DS=O.l3).
`As indicated heretofor, the objectives of this inven-
`tion are achieved by mixing a cationic polymer, as
`herein described, with an anionic surfactant. As the
`solid, finely divided, water-soluble anionic surfactant
`component used in the practice of this invention one
`can employ an alkali metal, eg. sodium, potassium, etc.,
`or ammonium salt of a C3-C2 alkyl sulfate. Alkali metal
`salts of sulfuric acid semiester of linear or slightly
`branched fatty alcohols containing from about 10 to
`about 16 carbon atoms, e.g. ammonium lauryl sulfate or
`sodium lauryl sulfate, are particularly suitable for use.
`However, other anionic surfactants, in powder form,
`can be used. These include alkali metal salts of linear
`and branched-chain alkylbenzene sulfonates containing
`from 6 to 16 carbon atoms in the alkyl groups; alkene
`and hydroxyalkane sulfonates of the type obtained by
`the sulfonation of a-olefins containing 10 to 18 carbon
`atoms; alkali metal salts of sulfosuccinic acid monoalky-
`lesters containing from about 8 to about 18 carbon
`atoms in the alkyl groups; alkali metal salts of sulfosuc-
`cinic acid dialkylesters containing from about 6 to about
`10 carbon atoms in the alkyl groups; mono- and dialkyl-
`naphthalene sulfonate alkali metal salts containing from
`about
`1 to about 8 carbon atoms in the alkyl group;
`alkylpolyglycol ether carboxylates containing from
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`

`
`5
`and at least 98% by weight of the particles are no larger
`than about 105 microns. The particle size of the anionic
`surfactant should not exceed a size which is five times
`larger than that of the cationic polymers.
`The compositions of this invention are readily pre-
`pared by mixing the cationic polymer and the anionic
`surfactant at room temperature. Where the particle size,
`or the particle quality of one of the components differs
`from the size or quality of the other, it is preferable to
`reduce, by grinding, the coarser component to the size
`and/or quality of the finer component. In the most
`preferred embodiment of the invention, the components
`are first mixed and subsequently the mixture is made
`homogeneous by grinding. When carried out in this
`manner, the possibility is minimized that the compo-
`nents of the mixture will separate during transport,
`handling or storage. Where the water-soluble cationic
`polymer component is produced in powder form by the
`spray drying of an aqueous solution thereof, it is pre-
`ferred to dissolve the anionic surfactant in the aqueous
`cationic polymer solution and spray drying the compo-
`nents of the solution together.
`For a fuller understanding of the invention, reference
`can be made to the following examples which are in-
`tended as further illustration of the invention and are
`not to be construed in a limiting sense.
`EXAMPLES
`
`EXAMPLE 1
`
`(a) In this example, 4.0 grams of guar hydroxapropyl~
`trimethylammonium chloride and 2.0 grams of sodium
`dodecyl sulfate were added to, mixed together and
`lightly hand ground at room temperature in a mortar. A
`homogeneous, finely divided powder was obtained.
`Dissolution Test: 0.5 grams of the powdery composi-
`tion of this example was poured onto the surface of 100
`ml of water, in a 250 ml glass beaker, at a temperature of
`20° C. After about, thirty seconds,
`the powder was
`gently stirred into solution. Additional 0.5 gram por-
`tions of the composition of this example were separately
`added to and dissolved in the solution until 3.0 grams
`total was used. It was observed that the preparations of
`the invention, when added to the water, dispersed im-
`mediately over the surface of the water and some rela-
`tively large clumps of powder spontaneously disinte-
`grated. Upon gentle stirring, the composition of the
`invention was uniformly dispersed in the water and
`dissolved, without forming relatively large gel clumps,
`in a few seconds to form a homogeneous slightly cloudy
`solution.
`
`(b) For comparative purposes, 3.0 grams of powdery
`pure guar hydroxyptoplytrimethylammonium chloride
`was added in 0.5 gram portions, to 100 ml of water in a
`250 ml glass beaker. The powder remained on the sur-
`face of the water and gel clumps, some with inclusions
`of powder, formed when stirring commenced. It was
`noted that, even after stirring for five minutes, the gel
`clumps still had not dissolved.
`
`EXAMPLE 2
`
`The procedure of Example 1 was repeated, except
`that 1.0 gram of Texapon L100 (Henkel Corporation
`trademark for a sodium alkyl
`(C1z—C1g)-sulfate) re-
`placed the 2.0 grams of sodium dodecyl sulfate used in
`Example 1.
`The powdery composition, thus obtained, was evalu-
`ated for its water-solubility by the Dissolution Test
`described in Example 1. It was found that the composi-
`
`4,746,690
`
`6
`tion of this Example uniformly dispersed in water and
`with gentle stirring dissolved in a few seconds to form
`a homogeneous slightly cloudy solution.
`EXAMPLE 3
`
`l0
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`The procedure of Example 1 was repeated once
`again, except that the 2.0 grams of sodium dodecyl
`sulfate employed in Example 1 was replaced by 2.0
`grams of ammonium dodecyl sulfate.
`The powdery composition, thus obtained, was evalu-
`ated for its solubility by the Dissolution Test described
`in Example 1. The composition of this Example uni-
`formly dispersed in water with gentle stirring and dis-
`solved in a few seconds to form a homogeneous slightly
`cloudy solution.
`
`EXAMPLE 4
`
`In this Example 3.0 grams of a water-soluble, cationic
`polymer (a graft polymer of the hydroxyethyl cellulose
`and dimethyldialkylammonium chloride - trade name
`“Celquat L-200” National Starch and Chemical Corp.,
`Bridgewater, N.J.) and 2.0 grams of sodium dodecyl
`sulfate were added to and mixed together in a mortar at
`room temperature. They were gently ground into a
`homogeneous, finely divided powder.
`The powdery composition, thus obtained, was evalu-
`ated for its solubility by the Dissolution Test described
`in Example 1. The composition of this Example uni-
`formly dispersed in water with gentle stirring and dis-
`solved in a few seconds to form a homogeneous slightly
`cloudy solution.
`For comparative purposes, 3.0 grams of Celquat
`L-200 was added, in 0.5 gram portions, to 100 ml of
`water in a 250 ml glass beaker. The powder remained on
`the surface of the water and gel clumps, some coated
`with powder, when stirring commenced. The gel
`clumps had not dissolved even after five minutes stir-
`ring.
`What is claimed is:
`
`1. A polymer composition in powdered form which is
`readily soluble in water which comprises (1) from about
`5% to about 99% by weight of at least one solid, finely
`divided, water-soluble cationic polymer and (2) from
`about 1% to about 95% by weight of at least one solid,
`finely divided, water-soluble anionic surfactant wherein
`the finely divided, water-soluble cationic polymer has a
`particle size such that at least about 69% by weight of
`the particles are no larger than 45 microns and at least
`about 98% by weight of the particles are no larger than
`about 105 microns, and the particle size of the finely
`divided, water-soluble amonic surfactant does not ex-
`ceed a size which is five times larger than that of the
`cationic polymer.
`2. The composition of claim 1 wherein there is pres-
`ent up to about 50% by weight of an inert carrier.
`3. The composition of claim 1 wherein there is pres-
`ent from about 10% to about 95% by weight of compo-
`nent (I) and from about 5% to about 90% by weight of
`component (2).
`4. The composition of claim 1 wherein there is pres-
`ent from about 40% to about 90% by weight of compo-
`nent (1) and from about 10% to about 60% by weight of
`component (2).
`,
`5. The composition of claim 1 wherein there is pres-
`ent from about 50% to about 90% by weight of compo-
`nent (1) and from about 10% to about 50% by weight of
`component (2).
`
`4
`
`

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`7
`
`4,746,690
`
`6. The composition of claim 1 wherein the cationic
`
`polymer is a cationic polygalactomannan derivative. ._
`7. The composition of claim 6 wherein the cationic
`polygalactomannan derivative is guar hydroxypropy1—
`trimethylammonium chloride.
`
`8. The composition of claim 1 wherein component (2)
`is an alkali metal or ammonium salt of a C3-C22 alkyl
`sulfate.
`
`9. The composition of claim 8 wherein component (2)
`is sodium dodecyl sulfate.
`
`10. The composition of claim 8 wherein component
`(2) is ammonium dodecyl sulfate.
`
`5
`
`10
`
`8
`11. A process for producing cationic polymer-con-
`taining compositions which are in powder form and
`readily soluble in water which comprises the steps of
`A. mixing (1) from about 5% to about 99% by weight
`of a solid, finely divided, water-soluble cationic
`polymer and (2) from about 1% to about 95% by
`weight of a solid, finely divided, water-soluble
`anionic surfactant, and
`B. grinding the resulting mixture to obtain a product
`at least 69% by weight of the particles of which are
`no larger than 45 microns and at least 98% by
`weight of which are no larger than 105 microns.
`12. The polymer composition of claim 1 wherein the
`particle size of the amonic surfactant is approximately
`15 the same as that of the cationic polymer.
`*
`*
`*
`Ill
`=8
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