U.S. patent application number 11/982511 was filed with the patent office on 2008-05-15 for dispersible non-borate metal salt or chelate treated polygalactomannan polymers for use in personal care and household care applications.
Invention is credited to Paquita Erazo-Majewicz, Gijsbert Kroon, Thomas G. Majewicz.
Application Number | 20080112906 11/982511 |
Document ID | / |
Family ID | 39093246 |
Filed Date | 2008-05-15 |
United States Patent
Application |
20080112906 |
Kind Code |
A1 |
Erazo-Majewicz; Paquita ; et
al. |
May 15, 2008 |
Dispersible non-borate metal salt or chelate treated
polygalactomannan polymers for use in personal care and household
care applications
Abstract
The present invention relates to polygalactomannan compositions,
and more particularly guar gum compositions, which, when
crosslinked with organic chelating agents, such as non-borate metal
salt or chelates, to form discrete guar particles which are capable
of being easily dispersed in water which permits subsequent
processing of the guar, such as washing. The guar and its
derivatives are desirable for use in applications such as personal
care and household care products.
Inventors: |
Erazo-Majewicz; Paquita;
(Landenberg, PA) ; Kroon; Gijsbert; (Giessendam,
NL) ; Majewicz; Thomas G.; (Landenberg, PA) |
Correspondence
Address: |
Hercules Incorporated;Hercules Plaza
1313 N. Market Street
Wilmington
DE
19894-0001
US
|
Family ID: |
39093246 |
Appl. No.: |
11/982511 |
Filed: |
November 2, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60856486 |
Nov 3, 2006 |
|
|
|
Current U.S.
Class: |
424/59 ;
424/70.13; 536/114 |
Current CPC
Class: |
A61Q 19/10 20130101;
A61K 8/737 20130101; A61Q 5/02 20130101; C11D 3/227 20130101; A61K
2800/48 20130101; A61K 8/0241 20130101; A61Q 5/12 20130101; A61K
2800/5426 20130101; C08B 37/0096 20130101 |
Class at
Publication: |
424/059 ;
424/070.13; 536/114 |
International
Class: |
A61K 8/73 20060101
A61K008/73; C08B 37/00 20060101 C08B037/00 |
Claims
1. A composition comprising, a non-borate metal salt or chelate
treated polygalctomannan, and an active ingredient agent, wherein
the composition is a personal care or household care product.
2. The composition of claim 1, wherein the non-borate metal salt or
chelate treated polygalactomannan comprises a non-borate metal salt
or chelate treated cationic polygalctomannan.
3. The composition of claim 1, wherein the non-borate metal salt or
chelate treated cationic polygalctomannan is a non-borate metal
salt or chelate treated cationic guar.
4. The composition of claim 3, wherein non-borate metal salt or
chelate treated cationic guar has a substituent degree of
substitution (DS) lower limit of about 0.001 and an upper limit of
about 3.0.
5. The composition of claim 3, wherein non-borate metal salt or
chelate treated cationic guar has a weight average molecular weight
(Mw) with a lower limit of about 50,000 and an upper limit of about
5,000,000.
6. The composition of claim 1, wherein the non-borate metal salt or
chelate comprises a metal salt based on titanium.
7. The composition of claim 1, wherein the non-borate metal salt or
chelate comprises a metal salt based on zirconium.
8. The composition of claim 1, wherein the composition comprises a
personal care composition selected from the group consisting of
cleansing compositions, conditioners, and hair styling
products.
9. The composition of claim 8, wherein the personal care
composition further comprises one or more surfactant compounds,
selected from amphoteric surfactants, cationic surfactants, anionic
surfactants, nonionic surfactants, zwitterionic surfactants, and
combinations thereof.
10. The composition of claim 9, further comprising one or more
additional ingredients selected from the group consisting of
preservatives, thickeners, functional polymers, viscosity
modifiers, electrolytes, pH adjusting agents, perfumes, dyes, UV
screens, organosilicone materials, antidandruff agents, vitamins,
vitamin derivatives.
11. The composition of claim 8, wherein the personal care
composition is a hair care composition.
12. The composition of claim 8, wherein the personal care
composition is a skin care composition.
13. The composition of claim 1, wherein the composition comprises a
household care composition.
14. A process for producing a non-borate metal salt or chelate
treated polygalctomannan comprising the steps of: a. obtaining a
polygalactomannan; b. contacting the polygalactomannan with an
effective amount of non-borate metal salt or chelate to produce a
non-borate metal salt or chelate treated polygalactomannan; c.
dispersing the non-borate metal salt or chelate treated
polygalactomannan in water having a pH in the range of from below
about 7 to about 3; and d. washing the non-borate metal salt or
chelate treated polygalactomannan in water.
15. The process of claim 14, wherein the polygalactomannan
comprises guar.
16. The process of claim 15, wherein the polygalactomannan further
comprises cationic guar.
15. The process of claim 14, wherein the non-borate metal salt or
chelate comprises a metal salt based on titanium.
16. The process of claim 14, wherein the non-borate metal salt or
chelate comprises a metal salt based on zirconium.
17. The process of claim 15, wherein the effective amount of
titanium comprises a ratio of between about 0.001-0.025 wt
titanium/wt galactomannan polymer.
Description
RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application Ser. No. 60/856,486, filed on Nov. 3, 2006, which is
incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to polygalactomannan
compositions and more particularly guar gum compositions which,
when crosslinked with titanate organic chelating agents, form
discrete guar particles which are capable of being easily dispersed
in water which permits subsequent processing of the guar such as
washing. The guar and its derivative are desirable for use in
applications such as personal care or household care products, and
the like.
BACKGROUND OF THE INVENTION
[0003] Polygalactomannans and their derivatives are used in various
applications such as oil recovery, personal care products, textile
applications, paper applications, coating applications, food
applications, etc. Polygalactomannans and their derivatives are
difficult to disperse in aqueous solutions, as they tend to form
sticky particles which clump and agglomerate, making dissolution
difficult. To improve dissolution of the polymers, crosslinking
agents, such as borax, are used to allow for water-washing of the
polygalactomannan after reaction and for improved dispersibility of
the polygalactomannan in water.
[0004] Crosslinking agents based on borate salts, aluminum salts,
copper, iron, lead, calcium, and sodium salts have been described.
Other crosslinking agents such as metal salts based on titanium and
zirconium have been mentioned, without clear definition of the
method or procedure for their use.
[0005] There exists a concern over the hazards of boron in some
consumer products, and a need exists for alternative crosslinking
agents for use in the purification and handling of
polygalactomannan polymers and their derivatives.
[0006] In personal care applications, such as in hair care and
skincare, and in household applications, such as fabric care
applications, there is a desire to deposit a boron free coating
onto the substrate, that reduces the energy needed to move a comb
through hair in the wet or dry state or delivers a silky, soft feel
to skin or to fabric. This coating can also act to improve the
luster and moisture retention of hair and skin, as well as their
manageability and feel.
SUMMARY OF THE INVENTION
[0007] In a first aspect, the present invention relates to a
process for producing a polygalactomannan. The polygalactomannan is
produced in a process comprising the steps of obtaining a
polygalactomannan and then contacting the polygalactomannan with an
effective amount of a non-borate metal salt or chelate to produce a
crosslinked polygalactomannan particle. The preferred non-borate
metal salt or chelate comprises a metal salt based on titanium or
zirconium. The crosslinked polygalactomannan particle is then
dispersed in water having a pH in the range of from below about 12
to about 7 and washed in the water to remove impurities from the
crosslinked polygalactomannan particle.
[0008] In a second aspect, the present invention is directed to a
personal care or household care composition comprising a non-borate
metal salt or chelate crosslinked polygalactomannan polymer and
derivatives, especially titanium and zirconium crosslinked
polygalactomannan containing cationic substituents. This low
impurity content polygalactomannan is of utility in various
applications such as personal care and household care products. The
low impurity content polygalactomannan is of particular utility in
applications where the use of boron containing compounds is to be
reduced or eliminated.
DETAILED DESCRIPTION OF THE INVENTION
[0009] In the present invention, it has been found that treatment
of cationic polygalactomannan reaction mixture with titanium salts
at a ratio of between about 0.001-0.025 wt titanium/wt
galactomannan polymer leads to a water-dispersible
polygalactomannan that remains as a discrete particulate that does
not agglomerate into a gel. Other chelates, such as zirconium salts
are expected to give a similar result as the titanium salts. The
resulting crosslinked polygalactomannan particle is easily washed
in water and readily dispersible in water.
[0010] This application is of utility as a processing aid for
galactomannans Polygalactomannans are polysaccharides composed
principally of galactose and mannose units and are usually found in
the endosperm of leguminous seeds such as guar, locust bean, honey
locust, flame tree, and the like. The polygalactomannans may be
used in either their natural form or may be substituted with one or
more functional groups (e.g., carboxymethyl group). The most
commonly used polygalactomannan is guar. The guar may be
underivatized guar as well as derivatized guars such as cationic
guar, anionic guar, hydrophobic guar, and hydroxyalkyl guar.
[0011] An advantage of the use of titanate chelates over borate
salts is that borate salts disassociate in water at a higher pH
than titanate chelates. This results in the formation of swelled
gel particles or a gel mass at a higher pH. By permitting the
polygalactomannan to remain as a discrete particle at lower pH
values, washing of the polygalactomannan over a greater pH range
may be performed and thereby permitting removal of impurities that
would not be removed at the higher pH ranges, such as alkaline
species. These impurities may reduce the clarity of aqueous
solutions of the polygalactomannan or be harmful if permitted to
remain with the galactomannan in certain end use applications, such
as personal care.
[0012] In addition, it has been found that metal chelate, or
especially titanium chelate treated cationic polygalactomannans
function well as conditioning agents and thickening agents in
personal care compositions.
[0013] In accordance with the present invention, the cationic,
anionic, hydroxalkyl, or hydrophobic polygalactomannan or
derivative thereof generally has a substituent degree of
substitution (DS) lower limit of about 0.001 and an upper limit of
about 3.0. Preferably, the lower limit of the cationic, anionic,
hydroxyalkyl, or hydrophobic DS is 0.01, and more preferably 0.05.
Preferably, the upper limit of the cationic DS is 3.0, more
preferably 1.0, and even more preferably 0.25. The cationic
polygalactomannan or derivative thereof of the present invention
generally has a weight average molecular weight (Mw) with a lower
limit of about 50,000 and an upper limit of about 5,000,000
preferably, the lower limit of the molecular weight is 300,000, and
more preferably 400,000. Preferably, the upper limit of the
molecular weight is 1,500,000, more preferably 1,000,000.
[0014] The cationic functionality of the polygalactomannan or
derivatized polygalactomannan can be added to the backbone by known
methods. For example, the polygalactomannan material can be reacted
for a sufficient time and at a sufficient temperature with tertiary
amino or quaternary ammonium alkylating reagents, such
2-dialkylaminoethyl chloride and quaternary ammonium compounds such
as 3-chloro-2-hydroxypropyltrimethylammonium chloride, and
2,3-epoxy-propyltrimethylammonium chloride. Preferred examples
include glycidyltrialkylammonium salts and
3-halo-2-hydroxypropyltrialkylammonium salts such as
glycidyltrimethylammonium chloride, glycidyltriethylammonium
chloride, gylcidyltripropylammonium chloride,
glycidylethyldimethylammonium chloride,
glycidyldiethylmethylammonium chloride, and their corresponding
bromides and iodides; 3-chloro-2-hydroxypropyltrimethylammonium
chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride,
3-chloro-2-hydroxypropyltripropylammonium chloride,
3-chloro-2-hydroxypropylethyldimethylammonium chloride, and their
corresponding bromides and iodides; and quaternary ammonium
compounds such as halides of imidazoline ring containing
compounds.
[0015] The cationic polygalactomannan may also contain other
substituent groups such as nonionic substituents, i.e.,
hydroxyalkyl wherein the alkyl represents a straight or branched
hydrocarbon moiety having 1 to 30 carbon atoms (e.g., hydroxyethyl,
hydroxypropyl, hydroxybutyl) or anionic substituents, such as
carboxymethyl groups are optional. These optional substituents are
linked to the polygalactomannan polymer by the reaction with
reagents such as (1) alkylene oxides (e.g., ethylene oxide,
propylene oxide, butylene oxide) to obtain hydroxyethyl groups,
hydroxypropyl groups, or hydroxybutyl groups, or with (2)
chloromethyl acetic acid to obtain a carboxymethyl group. The
process for preparing derivatized polygalactomannan is well known
in the art. The cationic polygalactomannan may also contain mixture
of one or more other substituent groups such as nonionic, anionic
and cationic substituents.
[0016] Cationic polygalactomannan polymers or their derivatives,
useful in the invention can be treated with several known reagents,
such as (1) caustic, (2) acids, (3) by biochemical oxidants, such
as galactose oxidase, (4) chemical oxidants, such as hydrogen
peroxide, (5) a physical method using high speed agitation and
shearing machines, (6) thermal methods, (7) enzymatic reagents, and
(8) mixtures of these reagents and methods. Reagents such as sodium
metabisulfite or inorganic salts of bisulfite may also be
optionally included.
[0017] The preferred end-use of the organic metal chelate treated
cationic polygalactomannan polymers of the invention is as a
component in personal care compositions and household care
compositions, where the personal care composition comprises a
organic titanium chelate treated cationic polygalactomannan and a
personal care ingredient. The personal care ingredient includes,
but is not limited to, active ingredients, such as for example
analgesics, anesthetics, antibiotic agents, antifungal agents,
antiseptic agents, antidandruff agents, antibacterial agents,
vitamins, hormones, antidiarrhea agents, corticosteroids,
anti-inflammatory agents, vasodilators, kerolytic agents, dry-eye
compositions, wound-healing agents, anti-infection agents, as well
as solvents, diluents, adjuvants and other ingredients such as
water, ethyl alcohol, isopropyl alcohol, propylene glycol, higher
alcohols, glycerine, sorbitol, mineral oil, preservatives,
surfactants, propellants, fragrances, essential oils, and
viscosifying agents.
[0018] In accordance with the present invention, the personal care
ingredient must provide some benefit to the user's body. Personal
care compositions include hair care, skincare, sun care, and oral
care compositions. Examples of substances that may suitably be
included, but not limited to, in the personal care products
according to the present invention are as follows:
[0019] 1) Perfumes, which give rise to an olfactory response in the
form of a fragrance and deodorant perfumes which in addition to
providing a fragrance response can also reduce body malodor;
[0020] 2) Skin coolants, such as menthol, menthyl acetate, menthyl
pyrrolidone carboxylate N-ethyl-p-menthane-3-carboxamide and other
derivatives of menthol, which give rise to a tactile response in
the form of a cooling sensation on the skin;
[0021] 3) Emollients, such as isopropylmyristate, silicone
materials, mineral oils and vegetable oils which give rise to a
tactile response in the form of an increase in skin lubricity;
[0022] 4) Deodorants other than perfumes, whose function is to
reduce the level of or eliminate micro flora at the skin surface,
especially those responsible for the development of body malodor.
Precursors of deodorants other than perfume can also be used;
[0023] 5) Antiperspirant actives, whose function is to reduce or
eliminate the appearance of perspiration at the skin surface;
[0024] 6) Moisturizing agents, that keep the skin moist by either
adding moisture or preventing from evaporating from the skin;
[0025] 7) Cleansing agents, that remove dirt and oil from the
skin;
[0026] 8) Sunscreen active ingredients, which protect the skin and
hair from UV and other harmful light rays from the sun. In
accordance with this invention a therapeutically effective amount
will normally be from 0.01 to 10% by weight, preferable 0.1 to 5%
by weight of the composition;
[0027] 9) Hair treatment agents, that condition the hair, cleanse
the hair, detangles hair, acts as styling agent, volumizing and
gloss agents, color retention agent, anti-dandruff agent, hair
growth promoters, hair dyes and pigments, hair perfumes, hair
relaxer, hair bleaching agent, hair moisturizer, hair oil treatment
agent, and antifrizzing agent;
[0028] 10) Oral care agents, such as dentifrices and mouth washes,
that clean, whiten, deodorize and protect the teeth and gum;
[0029] 11) Denture adhesives that provide adhesion properties to
dentures;
[0030] 12) Shaving products, such as creams, gels and lotions and
razor blade lubricating strips;
[0031] 13) Tissue paper products, such as moisturizing or cleansing
tissues;
[0032] 14) Beauty aids, such as foundation powders, lipsticks, and
eye care;
[0033] 15) Textile products, such as moisturizing or cleansing
wipes; and
[0034] 16) Pigments or dyes that impart color to the hair, skin, or
textile substrate.
[0035] In accordance with the present invention, the household care
ingredient must provide some benefit to the user. Examples of
substances that may suitably be included, but not limited to,
according to the present invention are as follows:
[0036] 1) Perfumes, which give rise to an olfactory response in the
form of a fragrance and deodorant perfumes which in addition to
providing a fragrance response can also reduce odor;
[0037] 2) Insect repellent agent whose function is to keep insects
from a particular area or attacking skin;
[0038] 3) Bubble generating agent, such as surfactant that
generates foam or lather;
[0039] 4) Pet deodorizer or insecticides such as pyrethrins that
reduces pet odor;
[0040] 5) Pet shampoo agents and actives, whose function is to
remove dirt, foreign material and germs from the skin and hair
surfaces;
[0041] 6) Industrial grade bar, shower gel, and liquid soap actives
that remove germs, dirt, grease and oil from skin, sanitizes skin,
and conditions the skin;
[0042] 7) All purpose cleaning agents, that remove dirt, oil, and
grease, germs from the surface in areas such as kitchens, bathroom,
and public facilities;
[0043] 8) Disinfecting ingredients that kill or prevent growth of
germs in a house or public facility;
[0044] 9) Rug and Upholstery cleaning actives which lift and remove
dirt and foreign particles from the surfaces and also deliver
softening and perfumes;
[0045] 10) A laundry softener active, which reduces static and
makes fabric feel softer;
[0046] 11) Laundry detergent ingredients which remove dirt, oil,
grease, stains and kills germs;
[0047] 12) Laundry or detergent or fabric softener ingredients that
reduce color loss during the wash, rinse, and drying cycle of
fabric care;
[0048] 13) Dishwashing detergents which remove stains, food,
germs;
[0049] 14) Toilet bowl cleaning agents, which remove stains, kills
germs, and deodorizes;
[0050] 15) Laundry prespotter actives which helps in removing
stains from clothes;
[0051] 16) Fabric sizing agent which enhances appearance of the
fabric;
[0052] 17) Vehicle cleaning actives which removes dirt, grease,
etc. from vehicles and equipment;
[0053] 18) Lubricating agent which reduces friction between parts;
and
[0054] 19) Textile products, such as dusting or disinfecting
wipes.
[0055] The above list of personal care and household care active
ingredients are only examples and are not a complete list of active
ingredients that can be used. Other ingredients that are used in
these types of products are well known in the industry. In addition
to the above ingredients conventionally used, the composition
according to the present invention can optionally also include, but
is not limited to, ingredients such as a colorant, preservative,
antioxidant, nutritional supplements, alpha or beta hydroxy acid,
activity enhancer, emulsifiers, functional polymers, viscosifying
agents (such as salts, i.e., NaCl, NH.sub.4Cl & KCl,
water-soluble polymers, i.e., hydroxyethylcellulose,
hydroxypropylmethylcellulose, and fatty alcohols, i.e., cetyl
alcohol), alcohols having 1-6 carbons, fats or fatty compounds,
antimicrobial compound, zinc pyrithione, silicone material,
hydrocarbon polymer, emollients, oils, surfactants, medicaments,
flavors, fragrances, suspending agents, and mixtures thereof.
[0056] In accordance with the present invention, examples of
functional polymers that can be used in blends with the metal
organic chelate treated polygalactomannan or derivatives thereof of
this invention include water-soluble polymers such as acrylic acid
homopolymers such as Carbopol.RTM. product and anionic and
amphoteric acrylic acid copolymers, vinylpyrrolidone homopolymers
and cationic vinylpyrrolidone copolymers; nonionic, cationic,
anionic, and amphoteric cellulosic polymers such as
hydroxyethylcellulose, hydroxypropylcellulose,
carboxymethylcellulose, hydroxypropylmethylcellulose, cationic
hydroxyethylcellulose, cationic carboxymethylhydroxyethylcellulose,
and cationic hydroxypropylcellulose; acrylamide homopolymers and
cationic, amphoteric, and hydrophobic acrylamide copolymers,
polyethylene glycol polymers and copolymers, hydrophobic
polyethers, hydrophobic polyetheracetals, hydrophobically-modified
polyetherurethanes and other polymers referred to as associative
polymers, hydrophobic cellulosic polymers,
polyethyleneoxide-propylene oxide copolymers, and nonionic,
anionic, hydrophobic, amphoteric, and cationic polysaccharides such
as xanthan, chitosan, alginates and gum arabic.
[0057] In accordance with the invention, the silicone materials
which can be used are polyorganosiloxanes that can be in the form
of polymers, oligomers, oils, waxes, resins, or gums or
polyorganosiloxane polyether copolyols, amodimethicones, cationic
polydimethylsiloxane materials and any other silicone material that
is used in personal care or household care compositions.
[0058] In one embodiment, the hair care or skin care composition of
the present invention is an aqueous system comprising water and the
polymer of the invention. In one embodiment, the hair care or skin
care composition of the present invention contains one or more
surfactant compounds, including amphoteric surfactants, cationic
surfactants, anionic surfactants, nonionic surfactants,
zwitterionic surfactants, and combinations thereof.
[0059] It has been found that titanium organic chelate treated
cationic polygalactomannans can deposit with high efficacy on
hair/skin and can impart great conditioning benefits to the
discussed keratin substrates.
[0060] Such polymers impart other benefits in hair styling, body
lotions and sunscreens due to hydrophobic film formation on keratin
substrates that would act as barrier between the these surfaces and
the surrounding atmosphere.
[0061] The polymers of this invention can be useful as conditioning
agents in 2-in-1 shampoos, body lotions, sunscreens, antifrizz and
hair styling. The polymers of this invention can also be used to
improve hair volume, manageability, hair repair, or color
retention, skin moisturization and moisture retention, fragrance
retention, sunscreen longevity on hair, skin, and fabrics, flavor
enhancement and antimicrobial performance in oral care
applications, and improve fabric abrasion resistance and
colorfastness in household care applications.
[0062] Wet and dry hair combability measurements are typical test
methods used to measure conditioning performance in shampoo and
conditioner applications. In skincare applications, skin lubricity
or reduced friction or softer feel of the skin, reduced water vapor
transmission and improved skin elasticity are test methods used to
measure skin conditioning. In surfactant-based household cleansing
product formulations where conditioning performance is desired,
such as dish detergents, fabric softeners, and antistatic products,
conditioning refers to imparting a softer feel to fabric and
eliminating static effects, eliminating fabric fiber breakage or
deformation known as pilling. Imparting color retention properties
to fabrics is also important and can be measured.
[0063] The following examples demonstrate the crosslinking of
cationic guar with organic titanium chelates (Tyzor.RTM.LA organic
titanates, supplied by E.I. du Pont de Nemours and Company) and
their use in personal care compositions. In addition, it has been
found that titanium organic chelate treated cationic
polygalactomannans function well as conditioning agents and
thickening agents in personal care compositions.
[0064] The examples are merely set forth for illustrative purposes
all parts and percentages being by weight, unless otherwise
indicated. It is to be understood that other modifications of the
present invention can be made by skilled artisans in the related
industry without departing from the spirit and scope of the
invention.
EXAMPLES 1-6
Cationic Guar Preparation
[0065] Cationic guar was prepared by known procedures, without the
use of a crosslinking agent.
[0066] Guar splits (750 g), and water (450 g) were mixed in a
stirred reactor under nitrogen. The reactor was pressurized with
nitrogen and vented to remove oxygen. The reaction was conducted at
a temperature between 30-50.degree. C., after addition of
3-chloro-2hydroxypropyltrimethylammonium chloride (288 g), followed
by 250 grams 25% sodium hydroxide. The reaction was cooled to room
temperature. The reaction product is shown in Example 1, and it
used for crosslinking experiments in Examples 3-7 in Table 1.
[0067] A similar reaction was conducted with addition of sodium
borate tetrahydrate to crosslink the cationic guar. This reaction
product is shown in Example 2.
Titanium Crosslinking
[0068] The unpurified cationic guar reaction product was placed in
a container and the specified quantity of Tyzor.RTM. LA organic
titanates, diluted with water in Examples 3, 4, 5, 6 is added to
the splits while mixing with a hand held mixer over two minutes.
The reaction was conducted at ambient temperature. For Examples 4
and 6, a diluted solution of glacial acetic acid was added to the
splits using the same mixing procedure, prior to addition of the
Tyzor.RTM. LA organic titanates, solution.
[0069] For example 7, the cationic guar reaction product was placed
in an ABBE blender, with the rotational speed set at 2 (85 rpm).
The system was evacuated to 10 in HG and pressurized with nitrogen
to 10 psi, followed by a 2 minute hold. This procedure was repeated
5 times. After venting, 31.9 grams Tyzor LA (50% active, E.I Du
Pont de Nemours, Wilmington, Del.) in 369 grams water was added to
the cationic guar solids (pH11.5) over 30 minutes, evacuating and
pressurizing with nitrogen after each 50 ml addition. The
temperature was maintained at 18-22 C. After the final Tyzor
addition, the mixture was held at 22.degree. C. and mixed for 30
minutes, under 10 psi nitrogen pressure. The stirring was stopped
and the product recovered.
Wash Procedure
[0070] A measured weight of the crosslinked or non-crosslinked
polymer was placed in an 8 ounce jar and distilled water was added
as specified for wash 1 in Table 1. After 30-40 minutes, the top
water layer was decanted from the splits and measured. A second
wash was performed using the specified quantity of water in Table
1, and the slurry remained at room temperature for 24 hrs.
[0071] If a top layer of water was present, it was decanted and
measured as Wash 3 recovered. Note that there was a significant
amount of water decanted from the second wash of Examples 2 (borate
crosslink control), Example 5 and 6 (titanate crosslinking). The
form of the polymer in Examples 2, 5, and 6 was as discrete
particulates after Wash 2, indicating sufficient crosslinking had
occurred to prevent polymer swelling during the wash step. The
polymer in Example 1 (no crosslinker control) formed a continuous
gel plug after Wash 2, as no crosslinker was present, and the
polymer was dissolving in the wash water. In Examples 3 and 4, the
polymer was present as swollen, but discrete gel particles after
wash 2, indicating some crosslinking had occurred, but an
insufficient amount to prevent polymer swelling during the wash
step.
[0072] Resuspension of the polymer phases in Examples 1-6 in a
third wash step demonstrates that crosslinking occurred in Examples
2-6, with recovery of a decanted water phase and isolation of
particulate polymer phase. Example 1 (no crosslinker control)
yielded a swollen gel which continued to swell with further
addition of water.
[0073] For Example 7, the product (660 parts by weight) was mixed
with 3300 pbw water for 30-40 minutes using a mechanical stirrer.
The product then settled to the bottom of the beaker, and the
liquid phase was decanted. The solid product was dried 72 hrs in a
hood, with air draft, to a solids content of 87%. The product was
chilled with dry ice, then ground through a 0.5 mm then a 0.2 mm
screen in a fluidized bed drier. This product was then used to
prepare the conditioning shampoo of Example 8 and bodywash of
Example 10, in Tables 2 and 3, respectively.
[0074] These examples demonstrate the preparation of a
water-dispersible polygalactomannan on treatment with sufficient
amounts of titanium crosslinkers. TABLE-US-00001 TABLE 1
Crosslinking of Cationic Guar EXAMPLE 1 No 2 crosslinker Borate
control Control 3 4 5 6 7 Cat guar(DS0.13; XA1232-62) 47.08 25 25
25 399.08 Cationic guar(DS0.13; 56% water) 107 56.8181818
56.81818182 56.81818182 907 Tyzor LA(50%) active 0.4708 0.25 3.75
3.75 15.9632 wt boron/guar 0 0.003 wt Titanium/wt guar 0 0
0.001598639 0.00159864 0.023979592 0.023979592 0.006394558 grams
50% Tyzor solution 0.9416 0.5 7.5 7.5 31.9264 grams water to dilute
Tyzor 50 27 400 grams glacial acetic acid 0.87 0.87 31.9264 grams
water to dilute acid 23 23 368.0736 rxn temp/C. 34 C. 20 C. 20 C.
20 C. 20 C. 20 C. pH 11.9 10.1 11.9 9.5 11.5 moles Tyzor/moles guar
pH after rxn 11.2 9.57 Wash Step grams polymer 17.2 9.3 12.3 9 13.4
14.4 wash 1 100 ml 100 ml 100 ml 100 ml 100 ml 100 ml recovered
wash 1(30 minutes) 50 ml 50 ml 50 ml 50 ml 50 ml 50 ml wash 2(24
hr) 70 70 60 70 90 ml 90 ml recovered wash 2(24 hr) 0 (swollen 70
ml 0 (swollen 1 (swollen 70 ml(compact 70 ml(compact gel) (compact
particulates) particulates) particulates) particulates)
particulates) wash 3(1 hr) 70 ml 70 ml 70 ml 70 ml 70 ml 70 ml
recovered wash 3(1 hr) 0 70 ml 50 ml 50 ml 70 ml 70 ml pH wash 2
11.9 12 11.9 9.6
EXAMPLE 8 AND COMPARATIVE EXAMPLES 9-10
Demonstration of Conditioning Performance of Products of the
Invention
[0075] The use of the cationic polygalactomannan materials of the
invention of Example 7 in a conditioning shampoo formulation is
demonstrated in Example 8, Table 2, and contrasted with a
comparative control shampoo containing a borate crosslinked
cationic guar of (Example 9) and a shampoo containing no cationic
guar (Example 10).
Shampoo Preparation
[0076] The conditioning shampoo formulations in Table 2 were
prepared by combining 77 parts by weight (pbw) of the surfactant
premix composition shown in Table 3 with 19 pbw deionized water,
and 0.3 pbw of the polymer of the invention using a Caframo
overhead mechanical stirrer with a dispersion blade, stirring at
600 rpm, and allowing the composition to mix for 45 minutes at
ambient temperature. At this time, 3 pbw of a silicone emulsion
(Dow Corning 1784) was added to the formulation, and mixing was
continued for an additional 15 minutes. The shampoo compositions
were maintained at ambient temperature overnight, and the viscosity
of each shampoo was measured using a Brookfield LVT viscometer with
a small sample adapter, spindle 31, at the specified rotation
speed.
Shampoo Viscosity Measurements
[0077] Comparison of the shampoo viscosity for Example 8, which
contains the glyoxal crosslinked cationic guar of the invention,
with comparative Example 10, which contains no polymer,
demonstrates the viscosifying performance of the products of the
invention. The viscosity of the shampoo in Examples 8 is similar to
the viscosity of the shampoo containing borate crosslinked cationic
guar in Example 9.
[0078] Cationic polysaccharides and other polymers have been used
widely in personal care, household care, industrial, and
institutional products to perform a function in the final product,
ranging from the use of the polymer as gellants, binders,
thickeners, stabilizers, emulsifiers, spreading and deposition aids
and carriers for enhancing the rheology, efficacy, deposition,
aesthetic and delivery of chemically and physiologically active
ingredients in personal care, household care, institutional and
industrial compositions. Depending on the application, the
substrate to which the product is applied can be skin, hair, or
textile substrates.
[0079] Cationic polysaccharides are used in hair care products to
provide conditioning to the hair. In skin care products, these same
polymers can provide conditioning effects to the skin. When
incorporated into detergent and fabric softening formulations,
these same polymers can provide conditioning, softening,
anti-abrasion and antistatic characteristics to fabrics.
[0080] Wet and dry combability measurements are typical test
methods used to measure conditioning performance in shampoo and
conditioner applications. The combing performance of each shampoo
formulation was measured within 24 hours of shampoo preparation, on
two medium brown virgin European hair tresses (National Hair
Importers, New Jersey) that had been previously treated with a
solution of sodium lauryl sulfate (SLS), rinsed, and dried
overnight at 23.degree. C. and 50% relative humidity.
Combing Performance Measurements
[0081] Combing performance was measured by applying the shampoo
formulation to a tress wet with water, at a ratio of 0.5 pbw
shampoo/1 pbw hair tress. The tress was kneaded for 60 seconds,
then rinsed with 40.degree. C. water for 30 seconds. This process
was repeated, then the tress was rinsed with deionized water and
excess water squeezed from the tress. The tress was placed on the
double comb apparatus and wet combing force measured 8 times on an
Instron 5542 at a cross head speed of 12.5 cm/min using the double
comb method, with Ace hard rubber fine pocket combs, at 23.degree.
C. and 50% relative humidity. Hair tresses were then allowed to dry
overnight at 23.degree. C. and 50% relative humidity, and the dry
comb performance was measured using the same double comb method.
The normalized comb energies in Table 2 represent the total comb
energy/weight of tress.
[0082] The conditioning performance of the products of the
invention is demonstrated by the significantly reduced wet and dry
combing energy results for Example 8 compared to the higher combing
energies for the no polymer control shampoo in Example 10. The
combing energies for Examples 8 compare well with the comb energy
for the shampoo containing borate crosslinked cationic guar in
Example 9. TABLE-US-00002 TABLE 2 Titanium Lactate Crosslinked
Cationic Galactomannan Polymers Performance in Conditioning Shampoo
Example 7 Treatment Titanium Lactate Cationic DS 0.14 % Moisture
7.8 Aqueous Viscosity @ 1% as received 2650 Silicone Shampoo
Examples with Comb Energy on Virgin Medium Brown European Hair
Example 10(Comparative 9(comparative Example- 8 example).sup.1 No
Polymer) Conditioning Shampoo 3285 6010 1421(12 rpm) viscosity
(Brookfield (3 rpm; pH 5.8) LVT sp. #31, small sample adapter, 6
rpm, pH 5.1) Normalized Wet Comb 1273 963 2340 Energy (gf-mm/g)
Normalized Dry Comb 329 242 670 Energy (gf-mm/g) .sup.1N-Hance
.RTM. 3196 cationic guar, borate crosslinked (Aqualon Division of
Hercules Incorporated)
[0083] TABLE-US-00003 TABLE 3 Shampoo Premix Composition Parts by
Ingredient manufacturer weight(pbw) Deionized water 896 Stepanol AM
Stepan Company, 1027 Northfield, IL Steol CA-330 Stepan Company 310
Amphosol CA Stepan Company 186 Glydant Lonza Group LTD, 16.25 Basel
Switzerland 25 wt % Ammonium 65 Chloride(aq)
EXAMPLES 11 AND COMPARATIVE EXAMPLE 12
Demonstration of Use in Skin Care Application, Bodywash
[0084] The thickening performance of the products of the invention
in a bodywash formulation are demonstrated in Table 4. Bodywash
formulations were prepared by addition of 0.3 pbw of the polymers
of the invention in Example 7 to 76 pbw of the bodywash premix
formulation in Table 5, and water (added to bring the volume to
100). Mixing was performed using an overhead mechanical stirrer
with a dispersion blade, for 1 hr. The pH of the bodywash was
5.6.
[0085] The bodywash example 11 contains the polymer of the
invention of Example 7. Addition of the polymer of the invention to
the bodywash formulation leads to increased viscosity of the
bodywash relative to the comparative control bodywash, containing
no cationic guar, in Example 12. TABLE-US-00004 TABLE 4 Performance
of Products of the Invention in Bodywash Formulation Example 11 12
Polymer Ex. 7 None Viscosity/cps.sup.1 3080(6 rpm) 1864
.sup.1Brookfield LVT, spindle3, 12 rpm
[0086] TABLE-US-00005 TABLE 5 Bodywash Premix Formulation Parts by
Ingredient Manufacturer weight Stepanol AM Stepan Company,
Northfield, IL 697 Steol CA 330 Stepan Company 2500 Amphosol CA
Stepan Company 500 Deionized Water 279 Glydant Lonza Group LTD,
Basel Switzerland 24.5
[0087] In addition to the use of non-borate metal salts as
crosslinking agents for polygalactomannan polymers and their
derivatives, other agents which form a water-swellable or
water-dispersible complex with the polygalactomannan polymers, can
also act to improve the water-dispersibility of the
polygalactomannan. These agents include oligomers or polymers
containing phosphate, sulfate, sulfonate, carboxylate, or carbonate
groups, including sodium hexametaphosphate polystyrene sulfonate,
and proteins such as casein or whey which can form a
water-dispersible complex with cationic polygalactomannan polymers.
These agents also include anionic, cationic, and amphoteric
surface-active agents such as ammonium lauryl sulfate, sodium
lauryl sulfate, cetyltrimethylammonium chloride or bromide, and
cocamidopropyl betaine.
[0088] In addition, other crosslinkers, such as chloroformate,
siloxane based crosslinking reagents, such as triethoxysilane,
glyoxal and other dialdehyde materials can be used to crosslink the
polygalactomannan, rendering it water-dispersible.
[0089] The water-dispersible crosslinked products described above
can then be used in applications such as personal care or household
care products, where they can be dispersed and dissolved in aqueous
phases by appropriate adjustment of the solution pH or by addition
of salts.
[0090] Although the invention has been described with referenced to
preferred embodiments, it is to be understood that variations and
modifications in form and detail thereof may be made without
departing from the spirit and scope of the claimed invention. Such
variations and modifications are to be considered within the
purview and scope of the claims appended hereto.
* * * * *