U.S. patent application number 12/890994 was filed with the patent office on 2011-01-20 for microcapsule and method of producing same.
This patent application is currently assigned to CHEMITECH INC.. Invention is credited to Takashi Iwasaki, Radhakrishnan Janardanan Nair, An Pintens, Johan Smets, Takuya Yasuhara.
Application Number | 20110015115 12/890994 |
Document ID | / |
Family ID | 37596218 |
Filed Date | 2011-01-20 |
United States Patent
Application |
20110015115 |
Kind Code |
A1 |
Smets; Johan ; et
al. |
January 20, 2011 |
MICROCAPSULE AND METHOD OF PRODUCING SAME
Abstract
A microcapsule which is able to stably retain a benefit agent
such as a volatile substance for an extended period, and which is
also suitable for encapsulating fragrances and the like. Such
capsule encapsulates a mixture comprising a volatile substance, and
an additive that has a higher melting point than the volatile
substance and is able to undergo mutual dissolution with the
volatile substance, wherein the mixture exhibits a melting point
range, and a portion of, or all of, that melting point range falls
within a range from -20 to 60.degree. C. The present invention also
relates to consumer products including cleaning and/or treatment
compositions comprising such microcapsules, and processes of making
and using same.
Inventors: |
Smets; Johan; (Lubbeek,
BE) ; Nair; Radhakrishnan Janardanan; (Kobe, JP)
; Pintens; An; (Brasschaat, BE) ; Yasuhara;
Takuya; (Saitama City, JP) ; Iwasaki; Takashi;
(Saitama City, JP) |
Correspondence
Address: |
MOTS LAW, PLLC
1629 K STREET N.W., SUITE 602
WASHINGTON
DC
20006-1635
US
|
Assignee: |
CHEMITECH INC.,
Fuchu-shi
JP
|
Family ID: |
37596218 |
Appl. No.: |
12/890994 |
Filed: |
September 27, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11526505 |
Sep 25, 2006 |
|
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12890994 |
|
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60720861 |
Sep 27, 2005 |
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Current U.S.
Class: |
512/4 ;
264/4.7 |
Current CPC
Class: |
A61K 2800/412 20130101;
C11D 3/505 20130101; C11D 7/262 20130101; C11D 3/2006 20130101;
B01J 13/08 20130101; Y10T 428/2984 20150115; A61K 8/11 20130101;
C11D 7/24 20130101; C11D 3/18 20130101; C11D 7/265 20130101; C11D
7/261 20130101; B01J 13/18 20130101; A61Q 5/02 20130101; A61Q 5/00
20130101; Y10T 428/2982 20150115; C11D 3/2086 20130101; A61Q 13/00
20130101; C11D 17/0039 20130101; C11D 3/2079 20130101; Y10T
428/2985 20150115 |
Class at
Publication: |
512/4 ;
264/4.7 |
International
Class: |
C11D 3/50 20060101
C11D003/50; B01J 13/18 20060101 B01J013/18 |
Claims
1. A microcapsule, which encapsulates a mixture comprising a
volatile substance, and an additive that has a higher melting point
than the volatile substance and is able to undergo mutual
dissolution with the volatile substance, wherein the mixture
exhibits a melting point range, and a portion of, or all of, the
melting point range falls within a range from -20 to 60.degree.
C.
2. The microcapsule according to claim 1, wherein the additive is a
compound with a melting point within a range from 25 to 200.degree.
C.
3. The microcapsule according to claim 1, wherein the additive is
one or more compounds selected from the group consisting of
alcohols, carboxylic acids, hydroxy acids, and paraffin.
4. The microcapsule according to claim 1, wherein the mixture
comprises from 10 to 200 parts by weight of the additive per 100
parts by weight of the volatile substance.
5. The microcapsule according to claim 1, wherein the volatile
substance is a fragrance.
6. A method of producing the microcapsule according to claim 1,
comprising: preparing an emulsion of the mixture comprising the
volatile substance, and the additive that has a higher melting
point than the volatile substance and is able to undergo mutual
dissolution with the volatile substance; and adding a membrane
material to the emulsion and conducting a polymerization, thereby
forming a microcapsule which encapsulates the mixture.
7-16. (canceled)
Description
RELATED APPLICATION
[0001] The present application claims priority under 35 U.S.C.
.sctn.119 of U.S. Application Ser. No. 60/720,861 filed Sep. 27,
2005.
FIELD OF THE INVENTION
[0002] The present invention relates to a microcapsule that
encapsulates a volatile substance such as a fragrance, and a method
of producing such a microcapsule. The present invention also
relates to consumer products comprising such microcapsules, and
processes of making and using same.
BACKGROUND OF THE INVENTION
[0003] Various benefit agents, such fragrances, are expensive
and/or difficult to deliver as neat liquids as they exhibit high
volatility, and rapidly lose their aroma if left exposed to the
atmosphere. As a result, fragrances have been microcapsulated. That
is, sealed inside a capsule, to enable the aroma to be retained.
However, even if a benefit agent such as a highly volatile
fragrance is sealed within a microcapsule, the fragrance still can
escape through gaps within the microcapsules cell wall. Thus, long
term storage, particularly in the presence of other materials, is a
problem. A technique described in Japanese Laid-Open Publication
No. Hei 9-911, wherein a volatile substance is encapsulated by
incorporation within a gel-like polyurethane resin, attempts to
solve this problem. In this technique, during the capsulation
process, a polyfunctional isocyanate and a polyol are reacted
together to produce a gel-like polyurethane resin, and the volatile
substance is incorporated within this polyurethane resin. Thus,
while not being bound by theory, it is believed that release of the
volatile substance from the capsule core is suppressed.
Unfortunately such technique employs isocyanate which can produce
an irritating odor that detracts from benefit agents, particularly
the aroma of the fragrance. In addition, improvement is also
desirable in terms of the fact that the proportion of the
polyurethane resin in the encapsulated material at the core is
quite high relative to the quantity of the target volatile
substance. Such an improved microcapsule is particularly desirable
as consumers typically associate the odor of a cleaned or treated
article with the degree of cleanliness or freshness of such
article.
[0004] Accordingly, the present invention provides a microcapsule
which is able to stably retain a volatile substance for an extended
period, in the presence of other materials, such as consumer
product formulations. Such microcapsule is particularly suitable
for encapsulating fragrances and the like. In addition, consumer
products, including cleaning and/or treatment compositions that
contain the aforementioned microcapsules and processes of making
and using same are disclosed
SUMMARY OF THE INVENTION
[0005] The present invention relates to a microcapsule which
encapsulates a mixture comprising a volatile substance, and an
additive that has a higher melting point than the volatile
substance and is able to undergo mutual dissolution with the
volatile substance, wherein the mixture exhibits a melting point
range, and a portion of, or all of, the melting point range falls
within a range from -20 to 60.degree. C.
[0006] Another aspect of the present invention relates to a method
of producing the microcapsule according to the above aspect of the
present invention, comprising: preparing an emulsion of the mixture
comprising the volatile substance, and the additive that has a
higher melting point than the volatile substance and is able to
undergo mutual dissolution with the volatile substance; and adding
a membrane material to the emulsion and conducting a
polymerization, thereby forming a microcapsule which encapsulates
the mixture.
[0007] The present invention also relates to consumer products
including cleaning and/or treatment compositions comprising such
microcapsules, and processes of making and using same.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0008] As used herein consumer products include articles and
cleaning and treatment compositions.
[0009] As used herein, the term "cleaning and/or treatment
composition" includes, unless otherwise indicated, granular or
powder-form all-purpose or "heavy-duty" washing agents, especially
laundry detergents; liquid, gel or paste-form all-purpose washing
agents, especially the so-called heavy-duty liquid types; liquid
fine-fabric detergents; hand dishwashing agents or light duty
dishwashing agents, especially those of the high-foaming type;
machine dishwashing agents, including the various tablet, granular,
liquid and rinse-aid types for household and institutional use;
liquid cleaning and disinfecting agents, including antibacterial
hand-wash types, laundry bars, mouthwashes, denture cleaners, car
or carpet shampoos, bathroom cleaners; hair shampoos and
hair-rinses; shower gels and foam baths and metal cleaners; as well
as cleaning auxiliaries such as bleach additives and "stain-stick"
or pre-treat types.
[0010] As used herein, the phrase "is independently selected from
the group consisting of . . . " means that moieties or elements
that are selected from the referenced Markush group can be the
same, can be different or any mixture of elements.
[0011] As used herein, the articles "a" and "an" when used in the
specification or a claim, are understood to mean one or more of
what is claimed or described.
[0012] The test methods disclosed in the Test Methods Section of
the present application must be used to determine the respective
values of the parameters of Applicants' inventions.
[0013] Unless otherwise noted, all component or composition levels
are in reference to the active level of that component or
composition, and are exclusive of impurities, for example, residual
solvents or by-products, which may be present in commercially
available sources.
[0014] All percentages and ratios are calculated by weight unless
otherwise indicated. All percentages and ratios are calculated
based on the total composition unless otherwise indicated.
[0015] It should be understood that every maximum numerical
limitation given throughout this specification includes every lower
numerical limitation, as if such lower numerical limitations were
expressly written herein. Every minimum numerical limitation given
throughout this specification will include every higher numerical
limitation, as if such higher numerical limitations were expressly
written herein. Every numerical range given throughout this
specification will include every narrower numerical range that
falls within such broader numerical range, as if such narrower
numerical ranges were all expressly written herein.
[0016] All documents cited in the Detailed Description of the
Invention are, in relevant part, incorporated herein by reference;
the citation of any document is not to be construed as an admission
that it is prior art with respect to the present invention. To the
extent that any meaning or definition of a term in this written
document conflicts with any meaning or definition of the term in a
document incorporated by reference, the meaning or definition
assigned to the term in this written document shall govern.
Microcapsules
[0017] In a volatile substance encapsulated microcapsule according
to the present invention, a mixture is formed at the core in which
the additive that has a higher melting point than the volatile
substance is mutually dissolved with the volatile substance. By
forming a mixture of the volatile substance and the additive in
this manner, the melting point, boiling point, and volatilization
temperature of the volatile substance are adjusted, enabling the
volatility of the volatile substance to be suppressed to low
levels.
[0018] As a result, release of the volatile substance inside the
microcapsule is suppressed, enabling stable retention and sustained
release of the volatile substance over an extended period.
[0019] In addition, because the range of possible additives is
broad, an additive can be selected in accordance with the
properties of the volatile substance. For example, an odorless
additive can be selected in the case of a fragrance, meaning it is
possible to form a huge variety of encapsulated substances.
[0020] A microcapsule according to the present invention (hereafter
also referred to as simply a "capsule") encapsulates a mixture
(hereafter also referred to as the "encapsulated material" or
"encapsulation material") comprising a volatile substance, and an
additive that has a higher melting point than the volatile
substance and is able to undergo mutual dissolution with the
volatile substance.
[0021] Because the volatile substance and the additive are able to
undergo mutual dissolution, the mixture exists as a homogenous
substance of the two substances. This mixture exhibits a melting
point range (T1-T2, wherein T1<T2), and either a portion of, or
all of, this melting point range falls within a range from -20 to
60.degree. C. This includes those cases where at least one, or
perhaps both, of the lower limit temperature T1 and the upper limit
temperature T2 of this melting point range fall within the range
from -20 to 60.degree. C., and those cases where the melting point
range T1-T2 is broader than the range from -20 to 60.degree. C.,
and includes the entire range from -20 to 60.degree. C.
[0022] In other words, the possible cases include (1)
T1<-20.degree. C.<T2<60.degree. C. (wherein only T2 falls
within the specified range), (2) -20.degree.
C..ltoreq.T1<T2.ltoreq.60.degree. C. (wherein both T1 and T2
fall within the specified range), (3) -20.degree.
C.<T1<60.degree. C.<T2 (wherein only T1 falls within the
specified range, and (4) T1<-20.degree. C. and 60.degree.
C.<T2 (wherein T1-T2 includes the entire specified range from
-20 to 60.degree. C.).
[0023] Including the melting point (T3) of the volatile substance,
and the melting point (T4, wherein T3<T4) of the additive,
yields the relationship T3<T1<T2<T4.
[0024] Within this melting point range (T1-T2), the mixture adopts
a state in which solid and liquid coexist. In this description,
this state is referred to as a "semisolid" state. In other words,
the melting point range described above is the temperature range
over which the mixture exists as a semisolid.
[0025] At temperatures higher than T2, (a) the mixture is a
homogenous solution (liquid). When the temperature is lowered
gradually to less than T2, (b) a solid starts to gradually
precipitate out of the solution, producing a semisolid state. As
the temperature is lowered further, (c) the solid portion gradually
increases, (d) the fluidity falls, producing a sorbet-like state,
and then (e) the entire mixture develops rigidity. Finally, when
the temperature falls below T1, (f) the mixture becomes completely
solid. By gradually lowering the temperature in this manner, the
state of the mixture can be changed
(a).fwdarw.(b).fwdarw.(c).fwdarw.(d).fwdarw.(e).fwdarw.(f), and the
term "semisolid" refers to all of these states except for (a) and
(f).
[0026] T2 refers to the temperature at which solid material, no
matter how small, starts to become visible within the liquid (the
temperature at which visual inspection no longer reveals a liquid
free of solids). T1 refers to the temperature at which fluidity
disappears (or the temperature at which fluidity commences). The
existence or absence of fluidity is determined by bringing a
cylindrical glass rod with a cross-sectional diameter of 7 mm
(wherein the tip of the rod has been cut through the cross section
to generate a flat end face) into perpendicular contact with the
surface of a mixture inside a container (a 100 ml beaker), applying
a load of 700 gf, and observing whether or not the tip of the glass
rod penetrates into the mixture. Accordingly, T1 refers to the
temperature at which the glass rod is no longer able to penetrate
(or the temperature at which the rod is first able to penetrate)
the mixture.
[0027] The measurements of T2 and T1 are conducted by first
converting the mixture to a liquid, and then observing the changes
in state as the temperature is gradually lowered.
[0028] Although the solid that first begins to precipitate as the
temperature is gradually lowered comprises predominantly the higher
melting point component, namely the additive, it is thought that
the solid also incorporates a portion of the volatile substance. It
is thought that as the temperature is lowered, the proportion of
the volatile substance within the solid increases. In contrast,
although the liquid phase within the semisolid comprises mostly the
volatile substance, it is thought that the liquid also incorporates
a portion of the additive. In other words, although the proportions
of the solid component and the liquid component within the
semisolid, and the respective compositions of the two components
vary depending on the temperature, it is believed that the fact
that the solid component and the liquid component co-exist within
the melting point range enables the stability of the volatile
substance to be improve.
[0029] The melting point range for pure substances is usually quite
narrow, whereas the melting point range for mixtures is often much
broader. In the case of mixtures of substances with a large
difference in melting points, even wider melting point ranges can
be obtained.
[0030] In the present invention, the volatile substance itself is
often a mixture of organic compounds with different melting points,
and addition of the additive produces a mixture of even more
compounds, meaning a mixture with a broader melting point range is
obtained.
[0031] The broadening of the melting point range for the mixture in
this manner is advantageous in the present invention. In the
semisolid state, an equilibrium is maintained between
volatilization and retention of the volatile substance, enabling
both volatilization and retention to be achieved in a favorable
balance.
[0032] In order to suppress the volatility of the volatile
substance, either a portion of, or all of, the melting point range
for the mixture must fall within a range from -20 to 60.degree. C.,
and preferably falls within a range from -10 to 55.degree. C. In
addition, cases in which either a portion of, or all of, the
melting point range for the mixture falls within a range from 0 to
50.degree. C., which represents the temperature band in which
normal human life is conducted, is even more desirable. The reason
for this desirability is that if the upper limit temperature T2 for
the semisolid state is lower than 0.degree. C., then the
encapsulated material comprising the volatile substance will be
liquid under normal usage conditions, increasing the danger that
the volatility will be unable to be adequately suppressed, whereas
in contrast, if the lower limit temperature T1 for the semisolid
state exceeds 50.degree. C., then the encapsulated material
comprising the volatile substance will be completely solid under
normal usage conditions, increasing the danger that the volatility
will be overly suppressed, meaning the effect of the volatile
substance will not manifest adequately.
[0033] Furthermore, if the upper limit temperature T2 for the
melting point range is 60.degree. C. or lower, so that the mixture
is liquid at temperatures exceeding 60.degree. C., then a further
benefit is obtained in that when an in situ polymerization method
is selected as the microcapsulation method described below, the
capsulation can be completed easily at a temperature of 60 to
80.degree. C.
[0034] In other words, cases in which the melting point range
satisfies either (1) T1<-20.degree. C.<T2<60.degree. C.,
or (2) -20.degree. C..ltoreq.T1<T2.ltoreq.60.degree. C. are
preferred. Alternatively, T2 is preferably within a range from 40
to 60.degree. C., and even more preferably from 40 to 55.degree.
C., and most preferably from 40 to 50.degree. C.
[0035] On the other hand, the lower limit temperature T1 for the
melting point range is preferably 30.degree. C. or lower, and even
more preferably 20.degree. C. or lower, and most preferably
10.degree. C. or lower. Although there are no particular lower
limits for T1, considering normal usage conditions and the need to
achieve the required melting point range, T1 values of at least
-10.degree. C. suffice, and values of -20.degree. C. or greater are
quite satisfactory.
[0036] In addition, the difference between T1 and T2 (the melting
point range) is preferably at least approximately 10.degree. C.,
and preferably at least approximately 20.degree. C., even more
preferably at least approximately 30.degree. C., even more
preferably at least approximately 40.degree. C., and is most
preferably 50.degree. C. or greater.
[0037] In the present invention, in addition to the sustained
release effect obtained as a result of the microcapsulation, the
fact that the encapsulated material is in a semisolid state enables
the storage stability and sustained releasability of the volatile
substance to be improved dramatically.
[0038] Furthermore, because the encapsulated material is a
semisolid, the membrane strength relative to external pressure can
be increased compared with the case of a liquid material. As a
result, a capsule of adequate strength can be formed even if the
proportion of the capsule accounted for by the membrane material
(the cell material or the wall material) is reduced, and the
proportion of the encapsulated material is increased.
[0039] Generally when microcapsules are dispersed within a liquid
solvent such as a liquid ink, a liquid cosmetic, or a liquid
cleaning agent or the like, there is a danger that solvent passing
through the capsule membrane and penetrating the capsule interior
may cause a deterioration in the stability of the volatile
substance. Moreover, in those cases where the encapsulated material
is a liquid, the encapsulated material is prone to passing through
the capsule membrane and being eluted into the external phase.
[0040] In contrast, in the present invention, the volatile
substance is incorporated within a semisolid-state mixture, meaning
the properties of the volatile substance can be stably maintained,
even under this type of attack by an external solvent, and elution
of the encapsulated material into the external phase can be
prevented, thus providing improved stability relative to the
capsule external phase.
[0041] In addition, because a portion of the high-cost volatile
substance can be replaced with a comparatively low-cost additive
within the encapsulated material, the present invention is also
advantageous from a cost perspective.
[0042] Examples of suitable volatile substances include a variety
of reagents (active ingredients) that exhibit volatility, including
the various fragrances, plant-based essential oils, deodorants,
deodorizers, repellents, insect repellents, insecticides, and
agricultural chemicals, and the present invention is suited to any
of these materials when it is important to enable the effect of the
active ingredient to manifest over an extended period. Combinations
of two or more of these volatile substances may also be used.
[0043] Specific examples of suitable fragrances include animal and
plant-bawd natural fragrances such as musk, civet, castorium, rose,
jasmine, orange, lavender, sandalwood, cinnamon, rosemary, lemon,
iris, violet, lily of the valley, lily, lime, vanilla, and mint;
synthetic versions of these natural fragrances; and synthetic
fragrances such as lilac, carnation, cosmos, amaryllis, fragrant
olive, tulip, sweet briar, rugosa rose, sasanqua, thistle,
camellia, sage, hyacinth, chrysanthemum, cedar, bouquet, citron,
kabosu, coffee, curry, garlic, matsutake mushroom, banana,
chocolate, yoghurt, watermelon, beef, sauce, and steak.
[0044] Of these, oily fragrances are preferred, and fragrances such
as orange, grape, grapefruit, apple, strawberry, pineapple, peach,
melon, lime, blueberry, lemon, mint, lavender, eucalyptus, rose,
rosemary, lily of the valley, lily, freesia, cypress, and white
cedar are particularly preferred.
[0045] Examples of suitable plant-based essential oils (natural
essential oils) include eucalyptus, orange, lavender, lemon,
lemongrass, peppermint, tea tree, rosewood, citronella, rosemary,
ylang-ylang, bergamot, marjoram, myrtle, chamomile, neroli,
jasmine, cinnamon, ginger, thyme, palmarosa, fennel, lime, basil,
patchouli, black pepper, and rose absolute.
[0046] Examples of suitable repellents and insect repellents
include capsaicin, peppermint oil, eucalyptus, cypress, white
cedar, menthol oil, allyl isothiocyanate, methyl salicylate, ethyl
salicylate, and nonylic acid vanillylamide.
[0047] Examples of suitable deodorants and deodorizers include
phthalate esters, phosphate esters, plant-based oil extracts, and
terpene-based deodorizers.
[0048] Examples of suitable agricultural chemicals include
fenitrothion, methyl parathion, parathion, diazinon, warfarin,
alachlor, pyrethrin, cycloheximide, sethoxydim, and
triflumizole.
[0049] Examples of suitable insecticides include permethrin,
pyrethroid compounds, and fipronil.
[0050] There are no particular restrictions on the additive,
provided it has a melting point T4 that is higher than the melting
point T3 of the volatile substance (namely, T3<T4), is able to
undergo mutual dissolution with the encapsulated volatile
substance, and on dissolution, is able to form a mixture with a
melting point that falls within a range from -20 to 60'C.
[0051] For example, provided the additive is a compound with a
melting point T4 that falls within a range from 25 to 200.degree.
C., preparing a mixture with the volatile substance for which
either a portion of, or all of, the melting point range (T1-T2)
falls within the above range is comparatively simple, and
consequently such additives are preferred. If the additive has a
melting point higher than 200.degree. C., then dissolution with the
volatile substance may become difficult, depending on the nature of
the volatile substance.
[0052] In accordance with the usage conditions for the
microcapsules, compounds with a melting point T4 that falls within
a range from 40 to 120.degree. C., or even more preferably from 50
to 100.degree. C., are particularly desirable.
[0053] In terms of the general properties of the additive, the
additive itself preferably has either no odor or very little odor,
so that in those cases where a fragrance is encapsulated as the
volatile substance, the additive does not impair the
characteristics of the fragrance. In addition, the use of compounds
that are stable under heat and light is also preferred.
[0054] From the viewpoints of workability during microcapsulation
and solubility in the volatile substance, generally, the additive
is preferably a lipophilic compound (with low solubility in
water).
[0055] Specifically, compounds that contain a hydroxyl group and/or
a carboxyl group are preferred, and the use of alcohols, carboxylic
acids, or hydroxy acids with melting points within the range from
25 to 200.degree. C. is particularly desirable. Alternatively, the
use of paraffin (paraffin hydrocarbons) is also desirable. In
addition to these compounds, polymer compounds (such as plastics
and unvulcanized rubber) that are capable of dissolution in the
volatile substance can also be used.
[0056] These additives can be used either alone, or in combinations
of two or more different compounds.
[0057] Specific examples of suitable alcohols include
straight-chain or branched-chain higher aliphatic alcohols with 12
or more carbon atoms, such as lauryl alcohol, myristyl alcohol,
palmityl alcohol, cetyl alcohol, stearyl alcohol, 2-octyldodecanol,
and behenyl alcohol. Mixed alcohols produced by mixing two or more
of these alcohols can also be used.
[0058] Alternatively, mixtures of one or more of these alcohols of
12 or more carbon atoms and one or more aliphatic alcohols with
less than 12 carbon atoms can also be used favorably.
[0059] In addition, the aliphatic alcohol may also be a derivative
of a sulfonic acid or phosphoric acid, or a derivative that
contains a halogen, nitrogen, sulfur, or phosphorus or the
like.
[0060] Both aliphatic carboxylic acids and aromatic carboxylic
acids can be used as the carboxylic acid, and specific examples of
suitable acids include lauric acid, myristic acid, palmitic acid,
behenic acid, stearic acid, arachidic acid, ligonceric acid,
crotonic acid, elaidic acid, erucic acid, nervonic acid, benzoic
acid, and methylbenzoic acid.
[0061] An example of a suitable hydroxy acid is salicylic acid.
[0062] Suitable paraffin compounds include mixtures containing
hydrocarbons with 20 or more carbon atoms. These mixtures may also
include hydrocarbons with less than 20 carbon atoms.
[0063] There are no particular restrictions on the ratio between
the volatile substance and the additive within the mixture, and
this ratio is preferably adjusted in accordance with the melting
points of the two materials. For example, in those cases where the
melting point of the additive is relatively high in relation to the
melting point and boiling point of the volatile substance (or those
cases where the melting point and boiling point of the volatile
substance is relatively low in relation to the melting point of the
additive; in other words, those cases where T4-T3 is large), the
blend quantity of the additive required to ensure that the melting
point of the mixture falls within the specified temperature range
is comparatively small. In contrast, in those cases where the
melting point of the additive is relatively low in relation to the
melting point and boiling point of the volatile substance (or those
cases where the melting point and boiling point of the volatile
substance is relatively high in relation to the melting point of
the additive; in other words, those cases where T4-T3 is small),
the additive must be added in a much larger quantity.
[0064] Specifically, the blend quantity of the additive is
preferably within a range from 10 to 200 parts by weight, and even
more preferably from 10 to 100 parts by weight, and most preferably
from 20 to 50 parts by weight, per 100 parts by weight of the
volatile substance. Particularly in those cases where the volatile
substance is a fragrance, in order to ensure adequate manifestation
of the aroma, the blend quantity of the additive is preferably no
more than 100 parts by weight, that is, within a range from 10 to
100 parts by weight, and is even more preferably from 20 to 50
parts by weight, per 100 parts by weight of the fragrance.
[0065] More specifically, the addition of 20 to 50 parts by weight
of an additive with a melting point from 50 to 100.degree. C. to
100 parts by weight of the volatile substance, thereby producing a
mixture with a melting point that falls within a range from 0 to
50.degree. C. is extremely desirable. This ability to increase the
relative blend quantity of the volatile substance within the
mixture of a preferred embodiment is one of the characteristic
features of the present invention. In such cases, the additive is
dissolved in the volatile substance.
[0066] The mixture that constitutes the encapsulated material of
the microcapsule may also comprise other components in addition to
the volatile substance and the additive. Examples of these other
components include organic solvents such as toluene, xylene, and
hexane, as well as lubricants, dyes, organic and inorganic
pigments, antioxidants, ultraviolet absorbers, and other organic
compounds.
[0067] There are no particular restrictions on the membrane
material of the microcapsule, and suitable examples include organic
polymer materials such as gelatin, gelatin-gum Arabic, acrylic
resins, urethane resins, melamine resins, urea-formalin resins,
nylons, polyethers, alginic acid, polyvinyl alcohol, polystyrene,
paraffin, and cellulose; and inorganic materials such as titanium
dioxide, calcium carbonate, carbon black, silica, alkali earth
metals, silicates, iron oxides, cobalt carbonate, and zinc
oxide.
Processes of Making Microcapsules
[0068] Microcapsulation of the encapsulation material can be
conducted using a variety of methods, including interfacial
polymerization, in situ polymerization, coacervation, in-liquid
drying, spray drying, in-liquid curing, and air suspension. Of
these methods, interfacial polymerization, in situ polymerization,
and coacervation are preferred, and in situ polymerization methods
are particularly desirable.
[0069] In those cases where the encapsulation material is oily (an
oil phase), the microcapsule may be prepared in an aqueous
system.
[0070] For example, in situ polymerization includes: preparing an
emulsion of a mixture comprising the volatile substance, and the
additive that has a higher melting point than the volatile
substance and is able to undergo mutual dissolution with the
volatile substance; and adding a membrane material to the emulsion
and conducting a polymerization, thereby forming a microcapsule
which encapsulates the mixture. By using this production method, a
microcapsule according to the present invention can be favorably
produced.
[0071] As follows is a description of a preferred embodiment of the
present invention.
[0072] First, a volatile substance such as an oily fragrance, and
an additive are mixed together at a temperature exceeding the
melting point T4 of the additive, thus yielding a mixture in which
the two materials are mutually dissolved. A pH regulator is
preferably used to adjust pH of the mixture. Examples of acids as
the pH regulator include formic acid, acetic acid, citric acid,
hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid,
tartaric acid, boric acid, and fumaric acid. Examples of alkalis
include alkali metal hydroxides, ammonia, and triethanolamine.
[0073] While still in a liquid state, this (lipophilic) mixture is
then mixed with water, and emulsified, thus preparing an emulsion.
During this step, an emulsion accelerator or the like is preferably
used to stabilize the oil droplets of the mixture. An anionic
water-soluble polymer is preferably used as the emulsion
accelerator for microcapsulation. Examples of anionic water-soluble
polymers include ethylene-maleic anhydride copolymer,
styrene-maleic anhydride copolymer, methylvinyl ether-maleic
anhydride copolymer, polyacrylic acid, polystyrenesulfonic acid,
acrylic acid-styrenesulfonic acid copolymer, acrylic
acid-acrylamide-acrylonitrile ternary copolymer, and acrylic
acid-acrylonitrile-acid phosphoxy polyethyleneglycol methacrylate
ternary copolymer.
[0074] Subsequently, a membrane material (such as a prepolymer) is
added to this emulsion, and this membrane material is then
polymerized around the periphery of the oil droplets, thus forming
the microcapsule walls. This yields a microcapsule slurry. If
necessary, the solvent can be removed from the slurry to produce a
microcapsule powder.
[0075] Emulsification of the mixture can be conducted using a
typical emulsification-dispersion device such as a stirrer,
homomixer, homodisper, homojetter, colloid mill, ultrasonic
dispersion device, or ultrasonic emulsifier. Specific examples of
suitable commercially available devices include general stirrers
such as the BL-series 3-1 motor stirrers (manufactured by Shinto
Scientific Co., Ltd.) and the A520 portable mixer (manufactured by
Satake Chemical Equipment Mfg., Ltd.), and general homomixers such
as the TK Homomixer Mark II 20 (manufactured by Tokushu Kika Kogyo
Co., Ltd.) and the TK Pipeline Homomixer SL (manufactured by
Tokushu Kika Kogyo Co., Ltd.).
[0076] The above microcapsulation is preferably conducted at a
temperature higher than the upper limit temperature (T2) of the
melting point range for the mixture, and for example, is preferably
conducted with the entire system maintained at a temperature within
a range from 60 to 80.degree. C.
[0077] Once the capsulation is complete, there are absolutely no
problems associated with solid-liquid or liquid-gas phase changes
caused by temperature variations within the encapsulated material
inside the capsules. This property, wherein the capsules can be
treated in the same manner regardless of whether phase changes have
occurred within the encapsulated material, is one of the
significant advantages of microcapsules.
[0078] Suitable examples of the membrane material used during the
in situ polymerization include urea resins, melamine resins,
acrylate esters, and polyisocyanates. The use of melamine resins
(melamine and formaldehyde), urea-formalin resins (urea and
formaldehyde) as the membrane material is particularly
preferred.
[0079] For example, in those cases where a melamine resin is used
as the membrane material, the production is preferably conducted in
the manner described below. First, the volatile substance and the
additive are mixed together at a temperature that exceeds the upper
limit temperature (T2) of the melting point range for the mixture
to be encapsulated, thus forming an encapsulation material (A) (oil
phase). In a separate preparation, in order to enable acceleration
and stabilization of the oil droplets of the mixture, ethylene
maleic anhydride resin as the emulsion accelerator is dissolved in
water, yielding an emulsion accelerator liquid (B). In another
preparation, an aqueous solution (C) of a melamine resin prepolymer
is also prepared. At a temperature exceeding T2, the material (A)
is then mixed with the liquid (B) and emulsified to prepare an
emulsion, and a stirring number is adjusted until the desired
average particle size is obtained. The solution (C) is then added,
and stirring is continued, thereby producing a melamine resin
membrane around the periphery of the oil droplets of the
encapsulation material, and yielding a microcapsule slurry.
[0080] The average particle size of the oil droplets within the
emulsified mixture can be set appropriately in accordance with the
desired average particle size for the final product
microcapsules.
[0081] A preferred embodiment in the case of an in situ
polymerization using a urea-formalin resin is as described below.
First, a urea resin monomer, a resorcin resin monomer, and an
ethylene maleic anhydride resin (emulsion accelerator) are
dissolved in water. This solution is heated to a temperature
exceeding the upper limit temperature (T2) of the melting point
range for the mixture to be encapsulated, an encapsulation material
(oil phase) prepared in the same manner as described above is then
added to the solution and emulsified, and stirring is continued
until the desired average particle size is obtained. Formaldehyde
is then added, and stirring is continued, thereby producing a
urea-formalin resin membrane around the periphery of the
encapsulation material, and yielding a microcapsule slurry.
[0082] Next is a description of a coacervation method. First, the
membrane material is dissolved in a water phase, and the oil phase
of the encapsulation material is then added and stirred, thereby
dispersing the encapsulation material as fine droplets. To the
water phase of the thus obtained O/W dispersion system (emulsion)
is gradually added a poor solvent relative to the membrane material
(a liquid that is unable to readily dissolve the membrane
material), thereby lowering the solubility of the membrane material
and causing the membrane material to precipitate out in a manner
that encircles the fine droplets. Alternatively, the temperature of
the O/W dispersion system may be lowered, thereby lowering the
solubility of the membrane material and causing the
precipitation.
[0083] In the above description, the W/O dispersion system could
also be formed by preparing the membrane material as the oil phase
and the encapsulation material as the water phase.
[0084] In the case of interfacial polymerization, an oil-soluble
membrane material monomer and a water-soluble monomer that react
together to form the membrane are used. First, an oil phase premix
comprising a uniform mixture of the oil-soluble membrane material
monomer and the encapsulation material, and a water phase
comprising the water-soluble monomer and an emulsion accelerator
are prepared. The oil phase premix is then dispersed within the
water phase, and the resulting O/W or W/O dispersion system is
heated, thereby effecting polymerization at the interface between
the oil phase and the water phase.
[0085] The particle size of the microcapsules can be selected in
accordance with their intended usage. Although there are no
particular restrictions, if suitability for a wide variety of
potential applications is considered, then the average particle
size is preferably within a range from 0.5 to approximately 100
.mu.m. If the particle size is too large, then the capsules
themselves become prone to rupture, making them unsuitable for a
variety of applications. In contrast, if the particle size is too
small, the capsules become overly resistant to rupture, increasing
the danger that the effects of the contents may not manifest
adequately.
[0086] For example, in the case of capsule-containing ink or in
those cases where capsules are blended into fibers, paper, or
erasers or the like, a small particle size of approximately 1 to 20
.mu.m is preferred in terms of dispersion and processing. In
contrast, in applications where capsules are adhered to the surface
of a molded product or the like, and the application requires the
capsules to be easily ruptured, a large particle size of
approximately 20 to 100 .mu.m is preferred in terms of increasing
the frequency of contact and lowering the strength of the
capsules.
[0087] Regardless of whether in situ polymerization, interfacial
polymerization, or some other polymerization method is used, the
capsule particle size can be controlled by altering factors such as
the revolution speed and the shape of the stirring blade or rotor
blade of the stirrer or homomixer used during the emulsification
step of the microcapsulation process, or by adjusting the reaction
rate by altering the polymerization conditions (such as the
reaction temperature and time) for the membrane material.
[0088] Microcapsules can be used for a variety of applications.
Techniques for using the microcapsules include simply adding and
dispersing them in the case of liquid materials, or incorporating
the microcapsules by coating, spraying, adhesion or kneading
techniques in the case of substrates for manufacturing paper or
fabrics.
[0089] Microcapsules can be used within a wide range of products,
and potential applications in those cases where the volatile
substance is a fragrance include adding the microcapsules to inks,
coating materials (both water-based and oil-based, for pens or
spray-type applications, etc.), cosmetics, air fresheners,
deodorants, cleaning agents, and fabric softeners and the like;
spraying or bonding the microcapsules to printed matter (such as
new year greeting cards, catalogues, letter writing paper, and
seals), fabrics, textiles, textile products (such as clothing and
towels), and tissue paper; and blending or mixing the microcapsules
into molded resins, rubber, textiles, and erasers and the like or
the raw materials thereof.
[0090] The blend quantity of the microcapsules when used in these
types of products can be adjusted appropriately in accordance with
the desired product characteristics.
Consumer Products
[0091] In a first aspect of Applicants' invention, Applicants'
invention includes a consumer product such as an article and/or
cleaning and/or treatment composition comprising at least 0.00001
weight percent of a benefit agent containing microcapsule according
to, any balance of said compositions being one or more adjunct
materials.
[0092] In a second aspect of Applicants' invention, Applicants'
invention includes a consumer product such as an article and/or
cleaning and/or treatment composition comprising from about 0.00001
to about 99.9 weight percent, from about 0.00001 to about 10 weight
percent, from about 0.02 to about 5 weight percent or even from
about 0.2 to about 2 weight percent of a benefit agent containing
microcapsule according to the present invention, any balance of
said compositions being one or more adjunct materials.
[0093] When tested according to test Method 1, the aformentioned
aspects of Applicants' may comprise less than or equal to 50 ppm
formaldehyde, less than or equal to 25 ppm formaldehyde, less than
or equal to 10 ppm formaldehyde or even less than or equal to 5 ppm
formaldehyde.
[0094] When tested according to test Method 2, the aformentioned
aspects of Applicants' invention may comprise at least 5%, from
about 5 to about 99%, from about 8 to about 80% or even from about
10 to about 60% water.
[0095] If any of the aforementioned aspects of Applicants'
invention is an aqueous heavy duty liquid detergent, such detergent
may have a pH of from about 2 to about 12, from about 4 to about 10
or even from about 6 to about 9. Otherwise such consumer product
may have, when measured by Method 3, a pH of from about 8 to about
12, from about 8.5 to about 11 or even from about 9 to about
11.
[0096] Aforementioned aspects of Applicants' invention typically
contain an adjunct material that is a surfactant. Such surfactant
may be selected from anionic, nonionoic, zwitterionic, cationic and
ampholitic surfactants. Anionic surfactants are typically used in
liquid detergents in levels of from about 1 to about 80, from about
1 to about 50 or even from about 2 to about 20 percent by weight. A
representative list of surfactants can be found in the adjunct
materials section of this specification. However, when an anionic
surfactant is employed, particularly in a liquid detergent, such as
a aqueous liquid detergent, such surfactant may be selected from
the group consisting of C.sub.11-C.sub.18 alkyl benzene sulfonate
(LAS), primary, branched and random C.sub.10-C.sub.20 sulfates (AS)
and mixtures thereof.
[0097] Aforementioned aspects of Applicants' invention may contain
a microcapsule of the present invention wherein the encapsulated
benefit agent comprises a perfume, or a perfume mixture.
[0098] Aforementioned aspects of Applicants' consumer product
inventions may include other perfume systems, for example, free
perfume, pro-perfumes such as beta-ketoesters, esters, acetals,
oxazolidines, ortho-esters, beta-amino ketones and Schiff Bases,
perfume containing zeolite systems, and materials such as
cyclodextrins.
Adjunct Materials
[0099] While not essential for the purposes of the present
invention, the non-limiting list of adjuncts illustrated
hereinafter are suitable for use in the instant compositions and
may be desirably incorporated in certain embodiments of the
invention, for example to assist or enhance cleaning performance,
for treatment of the substrate to be cleaned, or to modify the
aesthetics of the cleaning composition as is the case with
perfumes, colorants, dyes or the like. The precise nature of these
additional components, and levels of incorporation thereof, will
depend on the physical form of the composition and the nature of
the cleaning operation for which it is to be used. Suitable adjunct
materials include, but are not limited to, surfactants, builders,
chelating agents, dye transfer inhibiting agents, dispersants,
enzymes, and enzyme stabilizers, catalytic materials, bleach
activators, hydrogen peroxide, sources of hydrogen peroxide,
preformed peracids, polymeric dispersing agents, clay soil
removallanti-redeposition agents, brighteners, suds suppressors,
dyes, perfumes, structure elasticizing agents, fabric softeners,
carriers, hydrotropes, processing aids, solvents and/or pigments.
In addition to the disclosure below, suitable examples of such
other adjuncts and levels of use are found in U.S. Pat. Nos.
5,576,282, 6,306,812 B1 and 6,326,348 B1 that are incorporated by
reference.
[0100] As stated, the adjunct ingredients are not essential to
Applicants' compositions. Thus, certain embodiments of Applicants'
compositions do not contain one or more of the following adjuncts
materials: surfactants, builders, chelating agents, dye transfer
inhibiting agents, dispersants, enzymes, and enzyme stabilizers,
catalytic materials, bleach activators, hydrogen peroxide, sources
of hydrogen peroxide, preformed peracids, polymeric dispersing
agents, clay soil removal/anti-redeposition agents, brighteners,
suds suppressors, dyes, perfumes, structure elasticizing agents,
fabric softeners, carriers, hydrotropes, processing aids, solvents
and/or pigments. However, when one or more adjuncts are present,
such one or more adjuncts may be present as detailed below:
[0101] Bleaching Agents--The cleaning compositions of the present
invention may comprise one or more bleaching agents. Suitable
bleaching agents other than bleaching catalysts include
photobleaches, bleach activators, hydrogen peroxide, sources of
hydrogen peroxide, pre-formed peracids and mixtures thereof. In
general, when a bleaching agent is used, the compositions of the
present invention may comprise from about 0.1% to about 50% or even
from about 0.1% to about 25% bleaching agent by weight of the
subject cleaning composition. Examples of suitable bleaching agents
include:
[0102] (1) photobleaches for example sulfonated zinc
phthalocyanine;
[0103] (2) preformed peracids: Suitable preformed peracids include,
but are not limited to, compounds selected from the group
consisting of percarboxylic acids and salts, percarbonic acids and
salts, perimidic acids and salts, peroxymonosulfuric acids and
salts, for example, Oxzone.RTM., and mixtures thereof. Suitable
percarboxylic acids include hydrophobic and hydrophilic peracids
having the formula R--(C.dbd.O)O--O-M wherein R is an alkyl group,
optionally branched, having, when the peracid is hydrophobic, from
6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when the
peracid is hydrophilic, less than 6 carbon atoms or even less than
4 carbon atoms; and M is a counterion, for example, sodium,
potassium or hydrogen;
[0104] (3) sources of hydrogen peroxide, for example, inorganic
perhydrate salts, including alkali metal salts such as sodium salts
of perborate (usually mono- or tetra-hydrate), percarbonate,
persulphate, perphosphate, persilicate salts and mixtures thereof.
In one aspect of the invention the inorganic perhydrate salts are
selected from the group consisting of sodium salts of perborate,
percarbonate and mixtures thereof. When employed, inorganic
perhydrate salts are typically present in amounts of from 0.05 to
40 wt %, or 1 to 30 wt % of the overall composition and are
typically incorporated into such compositions as a crystalline
solid that may be coated. Suitable coatings include, inorganic
salts such as alkali metal silicate, carbonate or borate salts or
mixtures thereof, or organic materials such as water-soluble or
dispersible polymers, waxes, oils or fatty soaps; and
[0105] (4) bleach activators having R--(C.dbd.O)-L wherein R is an
alkyl group, optionally branched, having, when the bleach activator
is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon
atoms and, when the bleach activator is hydrophilic, less than 6
carbon atoms or even less than 4 carbon atoms; and L is leaving
group. Examples of suitable leaving groups are benzoic acid and
derivatives thereof--especially benzene sulphonate. Suitable bleach
activators include dodecanoyl oxybenzene sulphonate, decanoyl
oxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof,
3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylene
diamine (TAED) and nonanayloxybenzene sulphonate (NOBS). Suitable
bleach activators are also disclosed in WO 98/17767. While any
suitable bleach activator may be employed, in one aspect of the
invention the subject cleaning composition may comprise NOBS, TAED
or mixtures thereof.
[0106] When present, the peracid and/or bleach activator is
generally present in the composition in an amount of from about 0.1
to about 60 wt %, from about 03 to about 40 wt % or even from about
0.6 to about 10 wt % based on the composition. One or more
hydrophobic peracids or precursors thereof may be used in
combination with one or more hydrophilic peracid or precursor
thereof.
[0107] The amounts of hydrogen peroxide source and peracid or
bleach activator may be selected such that the molar ratio of
available oxygen (from the peroxide source) to peracid is from 1:1
to 35:1, or even 2:1 to 10:1.
[0108] Surfactants--The cleaning compositions according to the
present invention may comprise a surfactant or surfactant system
wherein the surfactant can be selected from nonionic surfactants,
anionic surfactants, cationic surfactants, ampholytic surfactants,
zwitterionic surfactants, semi-polar nonionic surfactants and
mixtures thereof. When present, surfactant is typically present at
a level of from about 0.1% to about 80%, from about 1% to about 50%
or even from about 5% to about 40% by weight of the subject
composition.
[0109] Builders--The cleaning compositions of the present invention
may comprise one or more detergent builders or builder systems.
When a builder is used, the subject composition will typically
comprise at least about 1%, from about 5% to about 60% or even from
about 10% to about 40% builder by weight of the subject
composition. Builders include, but are not limited to, the alkali
metal, ammonium and alkanolammonium salts of polyphosphates, alkali
metal silicates, alkaline earth and alkali metal carbonates,
aluminosilicate builders and polycarboxylate compounds, ether
hydroxypolycarboxylates, copolymers of maleic anhydride with
ethylene or vinyl methyl ether, 1,3,5-trihydroxy
benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid,
the various alkali metal, ammonium and substituted ammonium salts
of polyacetic acids such as ethylenediamine tetraacetic acid and
nitrilotriacetic acid, as well as polycarboxylates such as mellitic
acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic
acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic
acid, and soluble salts thereof.
[0110] Chelating Agents--The cleaning compositions herein may
contain a chelating agent. Suitable chelating agents include
copper, iron and/or manganese chelating agents and mixtures
thereof. When a chelating agent is used, the subject composition
may comprise from about 0.005% to about 15% or even from about 3.0%
to about 10% chelating agent by weight of the subject
composition.
[0111] Dye Transfer Inhibiting Agents--The cleaning compositions of
the present invention may also include one or more dye transfer
inhibiting agents. Suitable polymeric dye transfer inhibiting
agents include, but are not limited to, polyvinylpyrrolidone
polymers, polyamine N-oxide polymers, copolymers of
N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and
polyvinylimidazoles or mixtures thereof. When present in a subject
composition, the dye transfer inhibiting agents may be present at
levels from about 0.0001% to about 10%, from about 0.01% to about
5% or even from about 0.1% to about 3% by weight of the
composition.
[0112] Brighteners--The cleaning compositions of the present
invention can also contain additional components that may tint
articles being cleaned, such as fluorescent brighteners. Suitable
fluorescent brightener levels include lower levels of from about
0.01, from about 0.05, from about 0.1 or even from about 0.2 wt %
to upper levels of 0.5 or even 0.75 wt %.
[0113] Dispersants--The compositions of the present invention can
also contain dispersants. Suitable water-soluble organic materials
include the homo- or co-polymeric acids or their salts, in which
the polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two carbon atoms.
[0114] Enzymes--The cleaning compositions can comprise one or more
enzymes which provide cleaning performance and/or fabric care
benefits. Examples of suitable enzymes include, but are not limited
to, hemicellulases, peroxidases, proteases, cellulases, xylanases,
lipases, phospholipases, esterases, cutinases, pectinases,
mannanases, pectate lyases, keratinases, reductases, oxidases,
phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases, .beta.-glucanases, arabinosidases,
hyaluronidase, chondroitinase, laccase, and amylases, or mixtures
thereof. A typical combination is an enzyme cocktail that may
comprise, for example, a protease and lipase in conjunction with
amylase. When present in a cleaning composition, the aforementioned
enzymes may be present at levels from about 0.00001% to about 2%,
from about 0.0001% to about 1% or even from about 0.001% to about
0.5% enzyme protein by weight of the composition.
[0115] Enzyme Stabilizers--Enzymes for use in detergents can be
stabilized by various techniques. The enzymes employed herein can
be stabilized by the presence of water-soluble sources of calcium
and/or magnesium ions in the finished compositions that provide
such ions to the enzymes. In case of aqueous compositions
comprising protease, a reversible protease inhibitor, such as a
boron compound, can be added to further improve stability.
[0116] Catalytic Metal Complexes--Applicants' cleaning compositions
may include catalytic metal complexes. One type of metal-containing
bleach catalyst is a catalyst system comprising a transition metal
cation of defined bleach catalytic activity, such as copper, iron,
titanium, ruthenium, tungsten, molybdenum, or manganese cations, an
auxiliary metal cation having little or no bleach catalytic
activity, such as zinc or aluminum cations, and a sequestrate
having defined stability constants for the catalytic and auxiliary
metal cations, particularly ethylenediaminetetraacetic acid,
ethylenediaminetetra(methylenephosphonic acid) and water-soluble
salts thereof. Such catalysts are disclosed in U.S. Pat. No.
4,430,243. [0117] If desired, the compositions herein can be
catalyzed by means of a manganese compound. Such compounds and
levels of use are well known in the art and include, for example,
the manganese-based catalysts disclosed in U.S. Pat. No. 5,576,282.
[0118] Cobalt bleach catalysts useful herein are known, and are
described, for example, in U.S. Pat. No. 5,597,936; U.S. Pat. No.
5,595,967. Such cobalt catalysts are readily prepared by known
procedures, such as taught for example in U.S. Pat. No. 5,597,936,
and U.S. Pat. No. 5,595,967. [0119] Compositions herein may also
suitably include a transition metal complex of ligands such as
bispidones (WO 05/042532 A1) and/or macropolycyclic rigid
ligands--abbreviated as "MRLs". As a practical matter, and not by
way of limitation, the compositions and processes herein can be
adjusted to provide on the order of at least one part per hundred
million of the active MRL species in the aqueous washing medium,
and will typically provide from about 0.005 ppm to about 25 ppm,
from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to
about 5 ppm, of the MRL in the wash liquor. [0120] Suitable
transition-metals in the instant transition-metal bleach catalyst
include, for example, manganese, iron and chromium. Suitable MRLs
include 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.
[0121] Suitable transition metal MRLs are readily prepared by known
procedures, such as taught for example in WO 00/32601, and U.S.
Pat. No. 6,225,464.
[0122] Solvents--Suitable solvents include water and other solvents
such as lipophilic fluids. Examples of suitable lipophilic fluids
include siloxanes, other silicones, hydrocarbons, glycol ethers,
glycerine derivatives such as glycerine ethers, perfluorinated
amines, perfluorinated and hydrofluoroether solvents,
low-volatility nonfluorinated organic solvents, diol solvents,
other environmentally-friendly solvents and mixtures thereof.
[0123] Processes of Making Consumer Products The products of the
present invention can be formulated into any suitable form and
prepared by any process chosen by the formulator, non-limiting
examples of which are described in Applicants' examples and in U.S.
Pat. No. 5,879,584; U.S. Pat. No. 5,691,297; U.S. Pat. No.
5,574,005; U.S. Pat. No. 5,569,645; U.S. Pat. No. 5,565,422; U.S.
Pat. No. 5,516,448; U.S. Pat. No. 5,489,392; U.S. Pat. No.
5,486,303 all of which are incorporated herein by reference. When
benefit agent containing microcapsules are incorporated into a
consumer product, such microcapsules may need to be further
processed. Such processing typically entails homogenizing the
liquid capsule slurry by mixing or stirring, adding water to the
capsule slurry, adding a structuring agent to the capsule slurry,
adjusting the density of the capsule content, adding a dispersant
or a anti-sedimentation to the capsule slurry or a mixture thereof.
Such processing typically depends on the requirements of the
formulation and/or article that will comprise the benefit
containing microcapsule. In certain cases the microcapsules may be
embedded in a consumer product when the consumer product is
produced or formed and/or adhered to the surface of such consumer
product by physical and/or chemical means including gluing.
Method of Use
[0124] The present invention includes a method for cleaning and/or
treating a situs inter alia a surface or fabric. Such method
includes the steps of contacting an embodiment of
Applicants'consumer product, if a composition in neat form or
diluted in a wash liquor, with at least a portion of a surface or
fabric then optionally rinsing such surface or fabric. The surface
or fabric may be subjected to a washing step prior to the
aforementioned rinsing step. For purposes of the present invention,
washing includes but is not limited to, scrubbing, and mechanical
agitation. As will be appreciated by one skilled in the art, the
consumer products of the present invention are ideally suited for
use in a variety of applications including cleaning or treating a
surface for example in a laundry application. Accordingly, the
present invention includes a method for laundering a fabric. The
method comprises the steps of contacting a fabric to be laundered
with a said cleaning laundry solution comprising at least one
embodiment of Applicants' cleaning composition, cleaning additive
or mixture thereof. The fabric may comprise most any fabric capable
of being laundered in normal consumer use conditions. The solution
preferably has a pH of from about 8 to about 10.5. The compositions
may be employed at concentrations of from about 500 ppm to about
15,000 ppm in solution. The water temperatures typically range from
about 5.degree. C. to about 90.degree. C. The water to fabric ratio
is typically from about 1:1 to about 30:1.
Test Methods
[0125] Method 1: Formaldehyde is analyzed by means of a
derivatization specific to aldehydes and carbonyl compounds. This
is accomplished via room temperature derivatization with 2,4-Di
Nitro Phenyl Hydrazine (DNPH) prior to a chromatographic separation
using Reversed Phase Chromatography with UVIVis detection
(wavelength setting=365 nm). Calibration is performed through
"External Standard calibration" with reference formaldehyde
solutions made up from commercially available 36-37% Formaldehyde
solution. Activity of this material can be determined via a redox
titration. [0126] Method 2: ASTM E203-01 via Karl Fischer titration
method. [0127] Method 3: pH is determined by Health Canada's method
"Determination of the pH of Consumer Products in Aqueous Solution"
Product Safety Reference Manual, Book 5--Laboratory Policies and
Procedures Effective 2001 Oct. 28 Part B: Test Methods Section,
Method C-13 Amendment #29 [0128] Method 4. Procedure For
Determination Of % Perfume Leakage [0129] When determining the %
perfume leakage from perfume microcapsules in liquid detergent, a
fresh sample of liquid detergent with equal level of free perfume
(without Perfume Microcapsules) must also be analysed in parallel
for reference. [0130] 1. Preperation Of Internal Standard Solution
[0131] Stock solution of tonalid: Weigh 70 mg tonalid and add 20 ml
hexane p.a. [0132] Internal Standard Solution solution: Dilute 200
.mu.l of stock solution in 20 ml hexane p.a. [0133] Mix to
homogenize [0134] 2. Perfume Extraction From Liquid Detergent
Without Perfume Microcapsules (Reference) [0135] Weigh 2 g of
liquid detergent product into an extraction vessel [0136] Add 2 ml
of ethanol and 1 ml of deionised water [0137] Shake gentle to
homogenize [0138] Add 2 ml of Internal Standard Solution and close
vessel [0139] Extract perfume by gently turning the extraction
vessel upside-down for 20 times (manually) [0140] Add spoon tip of
Sodium Sulphate [0141] After separation of layers, immediately
transfer hexane-layer into Gas Chromatograph auto sampler-vial and
cap vial [0142] Inject splitless (1.5 .mu.l) into Gas Chromatograph
injection-port [0143] Run Gas Cromatographic-Mass Spectrometric
analysis: Gas Chromatographic separation on Durawax-4 (60 m, 0.32
mm ID, 0.25 .mu.m Film) 40.degree. C./4.degree. C./min/230.degree.
C./20' [0144] 3. Perfume Extraction From Liquid Detergent With
Perfume Microcapsules [0145] Weigh 20 g of liquid detergent product
into a centrifuge vessel of 50 ml [0146] Centrifuge for 5 min at
3500 rpm [0147] Take 2 g of the liquid layer (lower layer), avoid
contact with upper capsules layer [0148] Add 2 ml of ethanol and 1
ml of deionised water [0149] Shake gentle to homogenize [0150] Add
2 ml of Internal Standard Solution and close vessel [0151] Extract
perfume by gently turning the extraction vessel upside-down for 20
times (manually) [0152] Add spoon tip of Sodium Sulphate [0153]
After separation of layers, immediately transfer hexane-layer into
Gas Chromatograph auto sampler-vial and cap vial [0154] Inject
splitless (1.5 .mu.l) into Gas Chromatograph injection-port [0155]
Run Gas Chromatographic-Mass Spectrometric analysis: Gas
Chromatographic separation on Durawax-4 (60 m, 0.32 mm ID, 0.25
.mu.m Film) 40.degree. C./4.degree. C./min/230.degree. C./20'
[0156] 4. Calculation: The perfume leakage from capsules per
individual Perfume Raw Material:
[0156] Area Perfume Raw Material caps.times.Area Internal Standard
Solution ref.times.Weight ref.times.100%
% perfume leakage=Area Internal Standard Solution caps.times.Area
Perfume Raw Material ref.times.Weight caps
Examples
[0157] As follows is a more detailed description of the present
invention based on a series of examples, although the present
invention is in no way restricted to the examples presented below.
In the following description, the units "% by weight" and "parts by
weight" are abbreviated as "%" and "parts" respectively when
referring to microcapsule inventions.
Example 1
Production of Melamine Resin Membrane/Fragrance Microcapsules (In
Situ Polymerization Method)
[0158] (A) Preparation of encapsulation material (mixture): A
mixture comprising 75% of a mint fragrance (X-7028, manufactured by
Takasago International Corporation, this also applies to all
subsequent references to mint) and 25% of palmitic acid (melting
point: 63.degree. C.) is stirred at 70.degree. C., thereby
dissolving the palmitic acid in the fragrance. The melting point
range (T1-T2) for the resulting mixture is from 5 to 45.degree. C.
(confirmed visually). The mixture is held at 55.degree. C. to
prevent it solidifying prior to emulsification. [0159] (B)
Preparation of emulsion accelerator liquid: 15% of ethylene maleic
anhydride resin (Scripset-520, manufactured by Monsanto Company)
and 85% of water are mixed together at 60.degree. C., and the
mixture is adjusted to pH 4 using acetic acid. [0160] (C)
Preparation of aqueous solution of melamine resin prepolymer: 15%
of a melamine-formaldehyde resin (Sumirez Resin 615K, manufactured
by Sumitomo Chemical Co., Ltd.) is dissolved in 85% of water at
60.degree. C. [0161] (D) Capsulation: 100 parts of the above
emulsion accelerator liquid (B) is stirred at 60.degree. C. at
3,000 rpm using a TK Homomixer Mark II 20 (manufactured by Tokushu
Kika Kogyo Co., Ltd.), 100 parts of the above encapsulation
material (A) is added and emulsified, the rotational speed is then
gradually raised, and stirring is conducted at 7,000 rpm for 30
minutes, yielding an emulsion in which the average particle size of
the oil droplets of the encapsulation material is approximately 3
.mu.m (as measured by a laser diffraction particle size analyzer
SALD-3100 (manufactured by Shimadzu Corporation), this analyzer is
also used to measure all subsequent particle sizes).
[0162] To this emulsion is added 50 parts of the above melamine
resin prepolymer aqueous solution (C), and stirring is continued
for 2 hours, thus generating a melamine resin membrane around the
periphery of the encapsulation material, and forming a microcapsule
slurry with a solid fraction concentration of approximately
40%.
Example 2
Production of Melamine Resin Membrane/Fragrance Microcapsules (In
Situ Polymerization Method)
[0163] An encapsulation material (A) is prepared by mixing 75% of
the mint fragrance and 25% of behenyl alcohol (melting point:
70.degree. C.) at 75.degree. C., thereby dissolving the behenyl
alcohol in the fragrance and forming a mixture. The melting point
range for the thus obtained mixture is from 10 to 50.degree. C. The
mixture is held at 60.degree. C. to prevent it solidifying prior to
emulsification.
[0164] With the exception of using this encapsulation material (A),
a microcapsule slurry with a solid fraction concentration of
approximately 40% is prepared in the same manner as the Example
1.
Example 3
Production of Melamine Resin Membrane/Fragrance Microcapsules (In
Situ Polymerization Method)
[0165] An encapsulation material (A) is prepared by mixing 65% of
the mint fragrance and 35% of paraffin wax (EMW-0003, manufactured
by Nippon Seiro Co., Ltd., melting point: 50.degree. C.) at
60.degree. C., thereby dissolving the paraffin wax in the fragrance
and forming a mixture. The melting point range for the thus
obtained mixture is from 0 to 40.degree. C. The mixture is held at
50.degree. C. to prevent it solidifying prior to
emulsification.
[0166] With the exception of using this encapsulation material (A),
a microcapsule slurry with a solid fraction concentration of
approximately 40% is prepared in the same manner as the example
1.
Example 4
Production of Urea-Formalin Resin Membrane/Fragrance Microcapsules
(In Situ Polymerization Method)
[0167] 10% of a urea resin monomer (reagent grade, manufactured by
Nissan Chemical Industries, Ltd.), 2% of a resorcin resin monomer
(reagent grade, manufactured by Mitsui Chemicals, Inc.), and 3% of
an ethylene maleic anhydride resin (Scripset-520, manufactured by
Monsanto Company) are dissolved in 85% of water, and the solution
is adjusted to pH 3 using acetic acid.
[0168] 50 parts of the thus obtained aqueous solution is heated to
60.degree. C., 40 parts of the same encapsulation material as the
example 1 is added and emulsified, and stirring is conducted for
approximately 30 minutes, until oil droplets with an average
particle size of 3 .mu.m had been formed. To this emulsion is added
10 parts of formaldehyde, and stirring is then continued for 2
hours, thus generating a urea-formalin resin around the periphery
of the encapsulation material, and forming a microcapsule slurry
with a solid fraction concentration of approximately 40%.
Example 5
Production of Gelatin-Gum Arabic Membrane/Fragrance Microcapsules
(Coacervation Method)
[0169] Gelatin (APH, manufactured by Nitta Gelatin Inc.) is
dissolved in water to produce an aqueous solution with a gelatin
concentration of 3.6%, and the solution is adjusted to pH 6 using
acetic acid. To 30 parts of this aqueous solution is added 25 parts
of a 3.6% aqueous solution of gum Arabic (reagent grade,
manufactured by Gokyo Trading Co., Ltd.), thereby preparing an
aqueous solution for forming the microcapsule membrane. 55 parts of
this aqueous solution is heated to approximately 60.degree. C., the
pH is adjusted to 5, 40 parts of the same encapsulation material as
the example 1 is added and emulsified, and stirring is continued
until oil droplets with an average particle size of approximately 5
.mu.m had been formed.
[0170] The resulting emulsion/dispersion is cooled gradually to
10.degree. C., thus generating a gelatin-gum Arabic polymer
membrane around the periphery of the encapsulation material. 5
parts of a 25% aqueous solution of glutaraldehyde (reagent grade,
manufactured by Daicel Chemical Industries, Ltd.) is then added,
and the polymer membrane is cured, thus yielding a microcapsule
slurry with a solid fraction concentration of approximately
40%.
Comparative Example 1
[0171] With the exception of altering the encapsulation material
(A) to 100% of the mint fragrance, a microcapsule slurry with a
solid fraction concentration of approximately 40% is prepared in
the same manner as the Example 1.
Comparative Example 2
[0172] An encapsulation material (A) is prepared by mixing 75% of
the mint fragrance and 25% of phthalic acid (melting point:
234.degree. C.) at 240.degree. C., thereby dissolving the phthalic
acid in the mint fragrance and forming a mixture. The melting point
range for the thus obtained mixture is from 60 to 90.degree. C. The
mixture is held at 90.degree. C. or higher to prevent it
solidifying prior to emulsification.
[0173] An attempt is made to capsulate the encapsulation material
in the same manner as the example 1, with the temperature of the
emulsion accelerator liquid (B) held at as high a temperature as
possible (90.degree. C. or higher), but during the emulsification
step, the mixture solidified and precipitated out, meaning an
emulsion could not be obtained, and capsulation could not be
completed.
Comparative Example 3
[0174] An encapsulation material (A) is prepared by mixing 75% of
the mint fragrance and 25% of diethyl phthalate (fixative, melting
point: -40.degree. C.), thus forming a liquid mixture. This mixture
remained a liquid even at -20.degree. C. Using this liquid,
microcapsulation is conducted in the same manner as the example 1,
yielding a microcapsule slurry with a solid fraction concentration
of approximately 40%.
Comparative Example 4
[0175] The non-capsulated, neat mint fragrance liquid (100%) is
used for comparison.
[0176] Using the microcapsules obtained in the examples 1 to 5 and
the comparative examples 1 and 3, as well as the neat fragrance
liquid from the comparative example 4, the following evaluations
are conducted.
(1) Capsulation Achievability
[0177] Mixtures for which capsulation is possible are evaluated as
"A", and those for which capsulation is impossible evaluated as
"C".
(2) Strength of Aroma Immediately Following Printing
[0178] 50 parts of the obtained microcapsule slurry are added to 50
parts of a water-based binder (Vondic 1980NS, a water-dispersed
urethane resin, manufactured by Dainippon Ink and Chemicals,
Incorporated, solid fraction: 45%), thus forming a water-based
screen ink.
[0179] This ink is printed onto high quality paper using a 100-mesh
screen plate made of a PET Film (Tetlon.RTM., manufactured by
Teijin DuPont Films, print surface area: 3 cm.times.3 cm), and then
dried for 24 hours at room temperature.
[0180] The surface of each of the printed materials is scratched
lightly with fingernails using 10 back and forth movements, and the
strength of the mint aroma is evaluated. Because the comparative
example 4 is simply the neat fragrance liquid, it could not be
mixed with the water-based binder, and so the aroma of the neat
liquid is evaluated.
[0181] Evaluation is conducted by sensory assessment using a mixed
gender panel of 5 panelists. The printed material is brought
gradually closer to the nose, the maximum distance (cm) at which
the aroma could be detected is measured, and then points are
awarded based on the following criteria. 12 cm or greater: 5 points
(the aroma is detectable even when 12 cm or further from the nose),
9 cm or greater but less than 12 cm: 4 points, 6 cm or greater but
less than 9 cm: 3 points, 3 cm or greater but less than 6 cm: 2
points, 0 cm or greater but less than 3 cm: 1 point, and 0 points
if the aroma is undetectable even on contact (even at 0 cm). The
maximum possible score is 25 points.
(3) Strength of Aroma After Standing for 1 Week at 40.degree. C.
Following Printing
[0182] Each of the printed materials from (2) above is left to
stand for 1 week at 40.degree. C., and then, once again, the
surface of the printed material is scratched lightly with
fingernails using 10 back and forth movements, and the strength of
the mint aroma is evaluated in the same manner as described in (2)
above.
(4) Stability within Organic Solvent
[0183] Each of the produced microcapsule slurries is powdered using
a spray dryer, yielding a microcapsule powder.
[0184] 30 parts of this powder is added to 70 parts of toluene, and
the mixture is stored in a sealed container for 1 week at
25.degree. C. Subsequently, the toluene is evaporated off under
room temperature conditions. In the case of the comparative example
4, 30 parts of the neat fragrance liquid is added directly to 70
parts of toluene.
[0185] The microcapsules remaining after the evaporation are
ruptured by scratching lightly with fingernails using 10 back and
forth movements, and the strength of the aroma is evaluated in the
same manner as described in (2) above.
[0186] The results obtained are shown in Table 1.
TABLE-US-00001 TABLE 1 Strength of Strength of aroma aroma
Stability Capsulation immediately following 1 in organic
achievability after printing week at 40.degree. C. solvent Example
1 A 21 19 19 Example 2 A 21 20 19 Example 3 A 20 18 18 Example 4 A
21 19 18 Example 5 A 22 15 14 Comparative A 22 7 7 Example 1
Comparative C -- -- -- Example 2 Comparative A 22 9 8 Example 3
Comparative -- 25 1 0 Example 4
[0187] As is evident from Table 1, the microcapsules of the
Examples 1 to 5 enabled the aroma of the fragrance to be favorably
retained. This is because at conditions of 40.degree. C., the
encapsulated material is a semisolid, enabling the volatility of
the fragrance to be suppressed. Furthermore, the microcapsules also
exhibited no interaction with the toluene of the external phase,
and are able to be mixed in a stable manner.
[0188] In contrast, in both the Comparative Examples 1 and 3,
because the encapsulated material is a liquid, it gradually escaped
through the fine pores in the melamine resin membrane, meaning the
aroma could not be retained over an extended period. Furthermore,
in the organic solvent, it is thought that because the encapsulated
material is a liquid, a mechanism that seeks to achieve
co-solubility with the toluene draws the liquid fragrance out into
the external phase.
[0189] In the comparative Example 4, the neat fragrance liquid
volatilized at the same time as the evaporation of the toluene.
[0190] The comparative example 3 represents an example in which a
conventionally used fixative is used to suppress volatilization of
the fragrance and prolong the retention of the aroma. Examples of
typical fixatives include benzyl alcohol (melting point: 15.degree.
C.), benzyl benzoate (melting point: 21.degree. C.), triethylene
citrate (melting point: -55.degree. C.), and dipropylene glycol
(melting point: -40.degree. C.), and all of these have a melting
point lower than 25.degree. C., meaning they are unable to form a
semisolid in the range from -20 to 60.degree. C.
[0191] In the comparative example 2, although the encapsulation
material needed to remain a liquid during the emulsification step
of the microcapsulation, it is thought that microcapsulation could
not be achieved because it proved impossible to maintain the
temperature of both the emulsion accelerator liquid and the
emulsion at a temperature exceeding the upper limit temperature
(T2=90.degree. C.) for the mixture melting point range.
[0192] The evaluation score for the example 5 is lower than those
for the examples 1 to 4, and it is thought that this reflects the
fact that the airtightness of the gelatin-gum Arabic of the capsule
membrane is lower than that of both the melamine resin and the
urea-formalin resin. However, the results for the example 5 are
still vastly superior to those of the comparative examples.
Consumer Product Examples
[0193] The following definitions are used in the consumer product
examples that are given below. Any of the consumer product examples
given below may comprises one or more of the microcapsules that is
claimed or disclosed in this specification. [0194] LAS Sodium
linear C.sub.11-13 alkylbenzene sulphonate. [0195] CxyAS Sodium
C.sub.1x-C.sub.1y alkyl sulfate. [0196] CxyEzS C.sub.1x-C.sub.1y
sodium alkyl sulfate condensed with an average of z moles of
ethylene oxide. [0197] CxEOy Cx alcohol with an average of
ethoxylation of y [0198] QAS
R.sub.2.N+(CH.sub.3).sub.2(C.sub.2H.sub.4OH) with
R.sub.2.dbd.C.sub.10-C.sub.12 [0199] Soap Sodium linear alkyl
carboxylate derived from a 80/20 mixture of tallow and coconut
fatty acids. [0200] Silicate Amorphous Sodium Silicate
(SiO.sub.2:Na.sub.2O ratio=1.6-3.2:1). [0201] Zeolite A Hydrated
Sodium Aluminosilicate of formula
Na.sub.12(AlO.sub.2SiO.sub.2).sub.12.27H.sub.2O having a primary
particle size in the range from 0.1 to 10 micrometers (Weight
expressed on an anhydrous basis). [0202] (Na-)SKS-6 Crystalline
layered silicate of formula .delta.-Na.sub.2Si.sub.2O.sub.5. [0203]
Citrate Tri-sodium citrate dihydrate. [0204] Citric Anhydrous
citric acid. [0205] Carbonate Anhydrous sodium carbonate. [0206]
Sulphate Anhydrous sodium sulphate. [0207] MA/AA Random copolymer
of 4:1 acrylate/maleate, average molecular weight about
70,000-80,000. [0208] AA polymer Sodium polyacrylate polymer of
average molecular weight 4,500. [0209] PB1/PB4 Anhydrous sodium
perborate monohydrate/tetrahydrate. [0210] PC3 Anhydrous sodium
percarbonate [2.74 Na.sub.2CO.sub.3.3H.sub.2O.sub.2] [0211] TAED
Tetraacetyl ethylene diamine. [0212] NOBS Nonanoyloxybenzene
sulfonate in the form of the sodium salt. [0213] DTPA Diethylene
triamine pentaacetic acid. [0214] HEDP Hydroxyethane di phosphonate
[0215] HEDMP Hydroxyethane di(methylene)phosphonate [0216] DETPMP
Diethyltriamine penta(methylene)phosphonate [0217] EDDS Na salt of
Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer [0218] Protease
Proteolytic enzyme sold under the tradename Savinase.RTM.,
Alcalase.RTM., Everlase.RTM., by Novozymes A/S, Properase.RTM.,
Purafect.RTM., Purafect MA.RTM. and Purafect Ox.RTM. sold by
Genencor and proteases described in patents WO 91/06637 and/or WO
95/10591 and/or EP 0 251 446. [0219] Amylase Amylolytic enzyme sold
under the tradename Purastar.RTM., Purafect Oxam.RTM. sold by
Genencor; Termamyl.RTM., Fungamyl.RTM. Duramyl.RTM., Stainzyme.RTM.
and Natalase.RTM. sold by Novozymes A/S [0220] Lipase Lipolytic
enzyme sold under the tradename Lipolase.RTM. Lipolase Ultra.RTM.
by Novozymes A/S. [0221] Cellulase Cellulytic enzyme sold under the
tradename Carezyme.RTM., Celluzyme.RTM. and/or Endolase.RTM. by
Novozymes A/S or a Glucanase enzyme [0222] Pectate Lyase
Pectawash.RTM., Pectaway.RTM. sold by Novozymes [0223] Mannanase
Mannaway.RTM. sold by Novozymes [0224] CMC or HEC Carboxymethyl or
Hydroxyethyl or ester modified cellulose. or EMC [0225] SS Agglom.
12% Silicone/silica, 18% stearyl alcohol, 70% starch in granular
form [suds suppressor agglomerate]. [0226] TEPAE
Tetreaethylenepentaamine ethoxylate. [0227] Photobleach Sulfonated
zinc phtalocyanine [0228] Microcapsule Aqueous slurry containing
perfume loaded capsules [0229] pH Measured as a 1% solution in
distilled water at 20.degree. C. [0230] MEA borate Monoethanolamine
borate [0231] HCl Hydrogen Chloride [0232] SRP Soil Removal Polymer
[0233] PVNO polyvinylpyridine N-oxide
Example #6
[0234] Bleaching high duty laundry detergent compositions are
prepared:
TABLE-US-00002 I II III IV V VI VII VIII Blown Powder Zeolite A
13.65 13.65 -- -- -- -- -- -- Na Sulfate 22.67 22.67 24.43 30.13 --
-- -- -- LAS 6.21 6.21 5.65 -- -- -- -- -- QAS -- -- -- 2.95 -- --
-- -- MA/AA 1.42 1.42 3.50 4.25 -- -- -- -- EDDS 0.19 0.19 0.19
0.23 -- -- -- -- Brightener 0.07 0.07 0.06 0.08 -- -- -- -- Mg
Sulfate 0.65 0.65 0.39 0.48 -- -- -- -- HEDMP 0.17 0.17 0.17 0.21
-- -- -- -- Agglomerate 1 QAS -- -- 0.9 -- -- -- -- -- Carbonate --
-- 2.45 -- -- -- -- -- Na Sulfate -- -- 2.45 -- -- -- -- --
Agglomerate 2 C.sub.14-15EO.sub.7 -- -- 2.79 2.21 -- -- -- -- Na
Sulfate -- -- 6.65 6.84 -- -- -- -- Agglomerate 3 LAS -- -- -- --
13.63 14.96 -- 13.63 Zeolite A -- -- -- -- 21.42 23.51 -- 21.42
Agglomerate 4 LAS -- -- -- -- -- -- 8.12 -- Na Sulfate -- -- -- --
-- -- 23.54 -- Na Carbonate -- -- -- -- -- -- 8.12 -- Dry additives
LAS -- -- 6.40 -- -- -- -- -- MA/AA -- -- 0.89 0.89 0.95 0.95 0.99
0.95 (particle) TAED 3.58 3.58 3.80 2.70 5.89 5.89 6.14 -- NOBS --
-- -- -- -- -- -- 5.50 LAS (flakes) -- -- -- 27.0 -- -- -- --
Silicate R 2.0 3.85 3.85 3.85 2.80 -- -- -- -- Citric/Citrate 3.58
3.58 3.58 3.58 3.80 3.80 3.96 3.80 Na Carbonate 7.72 7.72 13.84 --
12.35 -- 12.87 12.35 HEDP -- -- -- -- 0.48 0.48 0.50 0.48 PC3 or
PB1 11.01 11.01 11.01 8.00 8.55 8.55 8.91 8.55 Protease 0.009 0.009
0.009 0.009 0.039 0.039 0.039 0.039 Amylase 0.005 0.005 0.005 0.005
0.013 0.013 0.013 0.013 Lipase -- -- -- -- 0.002 0.002 0.002 0.002
Pectate lyase -- -- -- -- 0.003 0.003 0.003 0.003 Cellulase 0.003
-- 0.001 -- 0.0005 -- -- -- SS agglom. 0.36 0.36 0.36 0.55 0.62
0.62 0.64 0.62 Soap 0.40 0.40 0.40 0.40 0.48 0.48 0.50 0.48
Brightener -- -- -- -- 0.10 0.10 0.10 0.10 Na Sulfate 4.48 4.48 --
-- 14.30 22.85 14.90 14.30 Spray-on C.sub.12-14EO.sub.7 4.00 4.00
-- -- 3.00 3.00 1.00 3.00 Microcapsule 1 0.8 2.0 1.5 0.7 1.2 0.3
0.2 0.1 Microcapsule 2 -- -- -- -- 0.5 1.0 -- -- Density (g/L) 600
600 600 600 800 800 800 800
Example #7
[0235] The following laundry compositions, which can be in the form
of granules or tablet, are prepared according to the present
invention.
TABLE-US-00003 Base Product I II III IV V C.sub.14-C.sub.15
AS/Tallow AS 8.0 5.0 3.0 3.0 3.0 LAS 8.0 -- 8.0 -- 7.0
C.sub.12C.sub.15AE.sub.3S 0.5 2.0 1.0 -- --
C.sub.12C.sub.15AE.sub.5/AE.sub.3 2.0 -- 5.0 2.0 2.0 QAS -- -- --
1.0 1.0 Zeolite A 20.0 18.0 11.0 -- 10.0 (Na--)SKS-6 (I) -- -- 9.0
-- -- (dry add) MA/AA 2.0 2.0 2.0 -- -- AA polymer -- -- -- -- 4.0
Citrate -- 2.0 -- -- -- Citric 2.0 -- 1.5 2.0 -- DTPA 0.2 0.2 -- --
-- EDDS -- -- 0.5 0.1 -- HEDP -- -- 0.2 0.1 -- PB1 3.0 5.0 10.0 --
4.0 Percarbonate -- -- -- 18.0 -- NOBS 3.0 4.0 -- -- 4.0 TAED -- --
2.0 5.0 -- Carbonate 15.0 18.0 8.0 15.0 15.0 Sulphate 5.0 12.0 2.0
17.0 3.0 Silicate -- 1.0 -- -- 8.0 Microcapsule 0.5 0.2 1.3 0.7 2.0
Protease 0.033 0.033 0.033 0.046 0.033 Lipase 0.008 0.008 0.008
0.008 0.006 Amylase 0.001 0.001 0.001 0.0014 0.001 Cellulase 0.0014
0.0014 0.0014 0.01 --
Example #8
[0236] The following granular detergents are prepared:
TABLE-US-00004 I II III IV V VI VII LAS 7.23 8.46 6.50 7.09 11.13
16.0 16.0 QAS 0.75 -- 0.60 0.60 1.00 -- -- C.sub.14-15EO.sub.7 3.50
5.17 3.50 3.70 3.50 -- -- C.sub.12-14AE.sub.3S 0.25 -- -- -- --
0.70 1.0 C.sub.12-14--N.sup.+(CH.sub.3).sub.2(C2H.sub.4OH) -- -- --
-- -- 0.50 0.50 Na tripolyphosphate 18.62 25.00 18.62 24.00 45.00
15.0 18.0 Zeolite A -- -- 0.79 -- -- 0.18 0.3 Citric acid 1.29 --
1.29 -- -- -- -- Sodium Silicate 3.10 8.00 4.26 3.87 10.00 8.0 6.0
Sodium Carbonate 18.04 11.00 18.04 18.98 0.42 14.5 16.0 Sulfate
17.58 3.98 19.93 15.48 10.13 30.0 30.0 CMC -- -- -- -- -- 0.20 0.20
AA/MA 2.15 1.50 1.85 1.60 1.94 0.1 0.05 AA polymer -- -- -- -- --
-- 1.20 Amine ethoxylate polymer 0.60 -- 0.49 -- -- -- 1.25 Cyclic
polyamine polymer 0.07 -- 0.07 -- -- -- -- Percarbonate 13.15 --
10.77 -- -- -- -- PB1/PB4 -- 9.0/9.0 -- 10.45/0 2.37/0 -- -- TAED
2.50 5.00 1.58 1.52 0.66 -- -- DTPA 0.34 0.34 0.37 0.39 0.24 0.30
0.30 Mg Sulfate 1.37 1.43 1.37 1.41 0.58 -- -- Protease 0.005 0.011
0.006 -- -- 0.006 0.003 Amylase 0.001 0.003 0.001 0.001 -- -- 0.001
Cellulase 0.0003 0.0002 0.0003 0.0003 -- -- -- Brightener 0.10 0.17
0.08 0.08 0.08 0.23 0.15 Microcapsule 1 0.6 1.2 1.5 0.2 0.1 1.9 0.7
Microcapsule 2 -- -- -- 0.5 1.8 -- --
Example #9
[0237] The following granular fabric detergent compositions which
provide "softening through the wash" are Prepared:
TABLE-US-00005 I II III IV C.sub.12-15AS 0.3 3.43 2.52 1.05 LAS
11.0 5.3 6.55 7.81 C.sub.12-14AE.sub.3S -- 0.74 0.33 -- LAS (mid
branched) -- -- 1.71 1.37 C.sub.14-15EO.sub.7 -- 2.00 2.00 2.00 QAS
-- 1.57 1.20 1.35 Citric acid 2.5 1.28 1.28 1.28 (Na--)SKS-6 4.0
4.71 4.96 4.71 Zeolite A 12.0 13.51 11.31 15.6 Percarbonate 6.5
9.03 9.03 10.3 TAED 1.5 2.48 2.48 3.22 EDDS 0.1 0.1 0.1 0.1 HEDP
1.2 0.20 0.20 0.20 Smectite clay 10.0 -- 13.84 -- Polyethylene
oxide 0.2 0.22 0.22 -- (MW approx. 300,000) Microcapsule 1 0.5 0.4
0.3 1.7 Microcapsule 2 -- 0.3 -- -- Protease 0.011 0.009 0.009
0.009 Amylase 0.002 0.001 0.001 0.001 Cellulase -- 0.0006 0.0006
0.0006 Na Carbonate 25.0 29.68 30.52 28.30 Magnesium Sulfate 0.1
0.03 0.03 0.03 Suds suppressor 1.0 1.0 1.0 1.0 EMC -- 1.10 1.10
1.10 HEC 0.8 -- -- -- Sodium sulfate 18.0 balance balance
Balance
Example #10
[0238] The following liquid detergent formulations are
prepared:
TABLE-US-00006 I II III IV V VI LAS 7.8 12.2 4.4 12.2 5.7 1.3
Sodium alkyl -- -- 14.4 -- 9.2 5.4 ether sulfate Alkyl ethoxylate
5.7 8.8 2.2 8.8 8.1 3.4 Amineoxide 1.0 1.5 0.7 1.5 -- -- Fatty acid
5.3 8.3 3.0 8.3 -- -- Citric acid (50%) 1.1 6.8 2.0 3.4 1.9 1.0 Ca
and Na formate -- -- 0.2 -- -- -- Na cumene 0.8 2 -- 2.0 -- --
sulphonate Borate -- -- 1.5 2.4 2.9 -- MEA borate 1.5 2.4 -- -- --
-- Na hydroxide 3.2 3.2 3.0 4.9 1.9 1.0 Ethanol 1.4 1.4 2.5 1.4 1.5
-- 1,2 Propanediol 4.9 5.0 6.6 4.9 4.0 -- Sorbitol -- -- -- -- 4.0
-- Ethanolamine 0.5 0.8 1.5 0.8 0.1 -- TEPAE 0.4 0.4 Protease 0.02
0.028 0.04 0.028 0.04 -- Lipase -- -- -- -- 0.002 -- Amylase 0.001
0.002 0.0002 0.01 -- -- PVNO -- -- Brightener 0.1 0.14 0.15 0.2
0.12 0.12 Silicone antifoam -- -- -- 0.05 -- -- Mannanase 0.0004
0.0006 -- -- -- -- Cellulase 0.0003 0.0002 0.0003 -- -- -- Amine
ethoxylate 0.8 1.3 1.8 2.1 -- -- polymer AA or MA/AA -- -- -- --
0.6 0.2 DTPMP, DTPA, 0.3 0.3 0.1 -- -- 0.1 EDTA mixture
Microcapsule 1 0.5 1.9 0.3 1.2 0.7 0.5 Microcapsule 2 -- -- 0.5 --
0.2 --
Example #11
[0239] The following liquid detergent compositions which provide
"softening through the wash" are prepared:
TABLE-US-00007 I II III IV V VI LAS 16.0 16.0 16.0 16.0 16.0 16.0
C.sub.24EO.sub.7 2.0 2.0 2.0 1.2 1.2 1.2 Citric acid 2.5 2.5 2.5
1.5 1.5 1.5 Fatty acid 11.4 11.4 11.4 6.84 6.84 6.84 Protease 0.48
0.48 0.48 0.35 0.35 0.35 Amylase 0.13 0.13 0.13 0.08 0.08 0.08 NA
Metaborate 1.3 1.3 1.3 0.79 0.79 0.79 Chelant 1.5 1.5 1.5 0.9 0.9
0.9 Amine -- 0.08 0.08 0.05 -- 0.05 Brightener 0.14 0.14 0.14 0.09
0.09 0.09 Structurant 0.18 0.18 0.18 0.26 0.26 0.26 Ethanol 0.76
0.76 0.76 2.38 2.38 2.38 1,2 Propanediol 8.0 8.0 8.0 4.82 4.82 4.82
Na Hydroxide 6.2 6.2 6.2 3.8 3.8 3.8 Solvent 2.0 2.0 2.0 1.2 1.2
1.2 Silicone 0.2 0.2 0.2 0.12 0.12 0.12 Dispersant 0.06 0.06 0.06
0.04 0.04 0.04 Perfume 0.81 -- 0.6 0.48 0.65 0.40 Dye 0.004 0.003
0.005 0.003 0.003 -- Bentonite clay 3.36 3.36 3.36 3.36 3.36 3.36
Microcapsule 1 -- 2.0 0.5 0.7 0.3 -- Microcapsule 2 -- -- -- 0.3
1.2 0.7
Example #12
[0240] The following concentrated liquid detergent formulations are
prepared:
TABLE-US-00008 I II III IV V VI VII VIII MEA 8.6 8.0 8.0 8.0 8.0
8.0 8.0 8.0 Propanediol 19.5 22.0 21.9 21.8 21.0 21.0 22.0 21.9
Sulfite solution 0.15 0.15 0.15 0.15 0.15 0.15 -- --
C.sub.24EO.sub.7 19.6 19.5 19.6 19.4 19.8 19.8 19.8 19.8 Brightener
0.28 0.38 -- 0.28 0.28 0.28 0.28 0.28 LAS 23.7 23.0 23.1 22.9 23.3
23.3 23.3 23.3 Dispersant 3.2 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Fatty
acid 17.3 17.3 17.4 17.3 17.6 17.6 17.6 17.6 Perfume 1.5 -- 1.5 1.6
0.9 -- 1.5 1.6 Protease 1.16 1.16 1.16 1.16 -- -- -- -- Amylase --
0.14 0.14 0.14 -- -- -- -- Mannanase -- 0.12 0.12 0.12 -- -- -- --
Dye 0.002 0.001 0.005 0.005 0.004 0.004 0.001 0.001 Antimicrobial
Agent 0.0006 -- -- -- -- -- -- -- Preservative: 0.001 -- -- -- --
-- -- -- Glutaraldehyde Bentonite clay 0.2 -- -- -- -- -- -- --
Structurant 0.2 -- -- -- -- -- -- -- Microcapsule 1 2.5 3.5 -- 1.1
-- 2.0 1.7 -- Microcapsule 2 -- -- 2.0 1.2 4.0 2.0 -- 3.5
Example #13
[0241] The following concentrated/dilute liquid fabric softening
compositions are prepared.
TABLE-US-00009 Ingredients 1 2 Softener Active: Rewoquat V3682
17.61 5.2 from Goldschmidt Silicone: Antifoaming agent: 0.01 0.004
MP10 from Dow Corning HEDP (Sodium salt) 0.17 -- HCl 0.005 0.013
SRP: Texcare 3639 from Clariant 0.05 -- CaCl.sub.2 0.035 --
Stabilizer: PEG-4K Pluriol E4050E 0.50 -- Preservative:
gluteraldehyde -- 0.025 50% - from BASF Perfume -- 0.32 Dye 0.003
0.0006 Microcapsule 4.0 2.0 Demineralized water Bal. Bal.
Example #14
[0242] The following hair conditioners are prepared.
TABLE-US-00010 Ingredient 1 2 3 Stearamidopropyldimethyl amine 2.0
1.0 Behenyltrimethyl Ammonium Chloride 3.4 Quaternium 18 .75 PEG-2M
.5 Emulsifying Wax .5 L-glutamic acid .64 Cetyl Alcohol 2.5 .96 2.0
Stearyl Alcohol 4.5 .64 3.6 Dimethicone/Cyclomethicone 4.2 (15/85
blend) Dimethicone 4.2 4.2 Hydroxyethyl Cellulose .25 Glyceryl
Monostearate .25 Additional Perfume .3 .2 .2 Chemitech
microcapsules .4 .6 Chemitech microcapsules .4 Citric Acid .13 NaOH
.014 Benzyl Alcohol .4 .4 .4 EDTA .1 .1 Kathon .0005 .0005 .0005
Disodium EDTA .127
Example #15
[0243] The following shampoos are prepared:
TABLE-US-00011 Example No. Component 1 2 3 4 Water-USP Purified
& Q.S. Q.S. Q.S. Q.S. Minors to 100 to 100 to 100 to 100
Ammonium Laureth 10 11.67 10 6 Sulfate Ammonium Lauryl 6 2.33 4 10
Sulfate Cocamidopropyl -- 2 -- -- betaine Cocamide MEA -- 0.8 0.8
0.8 Citric Acid 0.04 0.04 0.04 0.04 Sodium Citrate 0.45 0.45 0.45
0.45 Dihydrate Disodium EDTA 0.1 0.1 0.1 0.1 Kathon 0.0005 0.0005
0.0005 0.0005 Sodium Benzoate 0.25 0.25 0.25 0.25 Disodium EDTA
0.1274 0.1274 0.1274 Cetyl Alcohol -- 0.6 0.9 0.6 Ethylene Glycol
1.5 1.5 1.5 Distearate Polyox PEG7M -- -- .1 -- Trihydroxystearin
.25 (Thixin R, Rheox) Polyquaternium-10 0.5 0.15 (KG30M)
Polyquaternium-10 -- -- -- .25 (LR30M) Guar 0.5 -- -- Hydroxy-
propyltrimonium Chloride1 Dimethicone -- 1.4 4.0 (Viscasil 330M)
Dimethicone 5.0 microemulsion (Dow 1664) Zinc Pyridinethione 1
Chemitech 1 1.5 .5 microcapsules (1) Chemitech .5 .8 microcapsules
(2) Additional Perfume 0.3 0.7 0.2 0.7 Sodium Chloride 0-3 0-3 0-3
0-3 Ammonium Xylene 0-3 0-3 0-3 0-3 Sulfonate
[0244] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modifications that are within the scope of
this invention.
* * * * *