US009375501 B2

(12) United States Patent (10) Patent No.: US 9,375,501 B2

Hiramoto et al. (45) Date of Patent: Jun. 28, 2016

(54) DEODORANT COMPOSITION 6,080,391 A * 6/2000 Tsuchiya et al. ................ 424,65

6,174,521 B1* 1/2001 Li et al. ........................... 424,65
(75) Inventors: Tadahiro Hiramoto, Hiratsuka (JP); 6,294,161 B1* 92001 Hiramoto et al. ... 424,76.1
Kenichiro Shiroyama, Hiratsuka (JP); 6,551,625 B1 ck 4/2003 Hilaire et al.
Hiroyasu Kumamoto, Hiratsuka (JP) 6,605,288 B1 8/2003 Okawa et al. ................. 424/401
y s 2007/0003492 A1 1/2007 Kitahata et al. ................. 424/49

(73) Assignee: TAKASAGO INTERNATIONAL FOREIGN PATENT DOCUMENTS

CORPORATION, Tokyo (JP)
CN 1732O19 A 2, 2006
(*) Notice: Subject to any disclaimer, the term of this DE 1983.1798 A1 1, 2000
patent is extended or adjusted under 35 E. g S A. 858.
U.S.C. 154(b) by 0 days. EP 1520 576 A2 4/2005
EP 1561476 * 8/2005

EP 1561476 A1 * 8, 2005
(22) PCT Filed: Mar. 22, 2007 JP 64-016713 A 1, 1989
JP 4-219136 A 8, 1992
(86). PCT No.: PCT/UP2007/056753 JP 4-346831 A 12/1992
JP 5-092.135 A 4f1993
S371 (c)(1), JP 5-269 164 A 10, 1993
(2), (4) Date: Sep. 19, 2008 JP 9-0381.83 A 2, 1997
JP 11-319051 A 11, 1999
(87) PCT Pub. No.: WO2007/111362 JP 2002-004172 A 1, 2002
JP 2003-95905 A 4/2003
PCT Pub. Date: Oct. 4, 2007 JP 2004-167218 A 6, 2004
JP 2004-242516. A 9, 2004
(65) Prior Publication Data JP 20051.43770 A 6, 2005
WO WO 2004039345 A1 * 5, 2004
US 2010/O15884.0 A1 Jun. 24, 2010 WO WO 2005O26048 A1 * 3, 2005

(30) Foreign Application Priority Data OTHER PUBLICATIONS

Mar. 22, 2006 (JP) ................................. 2006-079559 Derwent Abstract: Kosuge etal.JPO2298.345, issued Dec. 10, 1990.*
(51) Int. Cl Derwent abstract for JP 2004204085.
A. iK sM66 (2006.01) Gauillard et al.; “Oxidation of Chlorogenic Acid, Catechins, and
A6IL 9/01 2OO6. O1 4-Methylcatechol in Model Solutions by Combination of Pear (Pyrus
A6 IK 8/19 6. O communis Cv. Williams) Polyphenol Oxidase and Peroxidase: A
( .01) possible Involvement of Peroxidase in Enzymatic Browning.” 1997.
3. 2. 3.08: ACS, Journal of Agriculture and Food Chemistry, vol. 45, No. 7, pp.
2472-2476*
A6 IK 8/365 (2006.01) Harborne, Jeffery; “Phytochemical Dictionary: A Handbook of
A6 IK 8/368 (2006.01) Bioactive Compounds from Plants.” 1999, Taylor & Francis; part IV
3. 3. 3.08: Phenolics General Introduction, pp. 1-5 as provided.*
A6 IK 8/60 (2006.01) (Continued)
A 6LX8/97 (2006.01)
A6IL 9/03 (2006.01)
A61O 15/00 (2006.01) Primary Examiner — Suzanne Ziska
52) U.S.
AV e. C
we Assi
SSiStant E
Examiner — IVan Oreene
G
CPC - A61K
49%8/20 (2039): 401/19 (2039);
(2013.01); A61 K8/36 (2013.01);
(74) Attorney, Agent, or Firm Sughrue Mion, PLLC
A61K 8/365 (2013.01); A61K 8/368 (2013.01);
A61K 8/375 (2013.01); A61K 8/498 (2013.01); (57) ABSTRACT
A61K 8/602 (2013.01); A61 K8/97 (2013.01);
A61L 9/013 (2013.01); A61O 15/00 (2013.01) The present invention relates to a deodorant composition
(58) Field of Classification Search containing (a) a polyphenol compound or a plant extract
CPC ............ A61K 8/19; A61K 8/347; A61 L9/00; containing a polyphenol compound, (b) a basic Substance,
A61L 9/01: A61L 9/013: A61Q 15/00 and (c) a metal salt. The deodorant composition of the present
See application file for complete search history. invention is capable of providing a deodorizing effect in a
short period of time when it is applied to a malodor Source, is
(56) References Cited capable of providing an excellent deodorizing activity and is
U.S. PATENT DOCUMENTS also excellent in the store stability.
5,804,170 A * 9/1998 Negishi et al. ... ... 424/65
5,833,864 A * 1 1/1998 Miller et al. .................. 210,724 13 Claims, No Drawings
 US 9,375,501 B2
Page 2

(56) References Cited Burda, Stanislaw et al.; “Phenolic Compounds and Their Changes in
Apples during Maturation and Cold Storage.” 1990; ACS, Journal of
OTHER PUBLICATIONS Agriculture and Food Chemistry, vol. 38, No. 4, pp. 945-948.*
Oleszek, Wieslaw et al.; "Identification of Some Phenolic Com
Cho, S. W. et al.; "Halitosis inhibition against methyl mercaptain by pounds in Apples.” 1988; ACS, Journal of Agriculture and Food
polyphenol oxidase of apple extract.” Session 104B, Fruit & Veg Chemistry, vol. 36, No. 3, pp. 430-432.*
etable Products: Fruits (processed), 2003 Institute of Food Technolo Jackson, Robert J. "Metal Salts, essential oils and phenols—old or
gists Annual Meeting, retrieved from (www.internetarchive.org> as
posted online Sep. 2003, p. 1 as provided.* new'?”, 1997, Munksgaard; Peridontology 2000 (ISSN 0906-6713),
Negishi, Osamu et al.; “Enzymatic Deodorization with Raw Fruits, vol. 15, pp. 63-73.*
Vegetables and Mushrooms.” Food Science and Technology Hibino et al.; "Chemistry and Applications of Green Tea.” Chapter 11
Research, vol. 5, 1999, pp. 176-180.* of “Deodorizing Effects of Green Tea Extracts.” 1997, CRC Press;
Negishi, Osamu et al., “Deodorization with Ku-ding-cha Containing pp. 123-127.*
a Large Amount of Caffeoyl Quinic Acid Derivatives.” 2004; ACS, Chinese Office Action issued in counterpart Chinese Application No.
Journal of Agriculture and Food Chemistry, vol. 52, No. 17, pp. 2007800 100065; dated May 11, 2010.
5513-5518.*
Lewis, Richard; “Hawley's Condensed Chemical Dictionary 15" Negishi O., et al., “Effect of Polyphenol Oxidase on Deodorization'.
ed., 2007; entries for “bittern.” “bleach.” “brine.” “lye,” “metal.” and Bioscience Biotechnolgy Biochemistry, vol. 61, No. 12,
“salt”: pp. 166, 168, 180, 772, 806 and 1105.* XPO00960678, Jun. 13, 1997, pp. 2080-2084.
WebElements Periodic Table of the Elements compounds for Takezo Tanaka, et al., “Development trends of plant extracts with
Aluminim, Copper, Magnesium, Manganese and Titanium, deodorizing effects and their application to air freshener and deodor
Retrieved from <www.webelements.com on Mar. 7, 2012: pp. 1-15 izer”, Fragrance Journal, No. 12, 1995, pp. 58-59.
as provided.* Chinese Patent Office, Office Action issued in corresponding Chinese
Sigma Aldrich “Buffer Reference Center' retrieved from <www. Application No. 2007800 10006.5 on Jul. 25, 2011.
sigmaaldrich.com on Mar. 7, 2011, pp. 1-4.* Japanese Patent Office, Office Action dated Nov. 5, 2013 issued in
Cho, S. W. et al.; "Halitosis inhibition against methyl mercaptain by counterpart Japanese Patent Application No. 200950 1106.
polyphenol oxidase of apple extract.” Session 104B, Fruit & Veg Japanese Patent Office, Office Action dated Apr. 2, 2013, issued in
etable Products: Fruits (processed), 2003 Institute of Food Technolo counterpart Japanese Patent Application No. 2009-501 106.
gists Annual Meeting, retrieved from as posted online Sep. 2003, p. 1
as provided.* * cited by examiner
 US 9,375,501 B2
1. 2
DEODORANT COMPOSITION deodorizing effect in a short period of time (within 20 min
utes) when it is applied to a malodor source. In addition, the
TECHNICAL FIELD invention intends to provide a novel deodorant composition
maintaining the features described above and Scarcely under
The present invention relates to a novel deodorant compo going the restriction when it is applied as a deodorant. Fur
sition. That is, the invention relates to a novel deodorant ther, the invention intends to provide a novel deodorant com
composition comprising a polyphenol compound or a plant
extract containing a polyphenol compound, or a granulated position capable of maintaining the features described above,
Substance thereof; a basic Substance; and a metal salt. excellent in the deodorizing effect, and capable of obtaining a
More specifically, the invention relates to a deodorant com 10
deodorant composition by a simple method. Further, the
position capable of providing a deodorizing effect in a short invention also intends to provide a deodorant composition
period of time when it is applied to a malodor source, provid having an excellent deodorizing effect against malodor ingre
ing an excellent deodorizing activity and also excellent in the dient in a wide range.
storestability. Further, the invention relates to a novel deodor In the course of earnest study for Solving the Subject
ant composition used for elimination or reduction of mal 15 described above, when a metal salt is added to a mixture of a
odors felt in daily life such as bad breath, odor in refrigerator, polyphenol compound and an alkaline Substance and the
odor of raw garbage, odor of footwear cupboard, body odor obtained mixture is applied to a malodor source, the present
of human and animal, odor of feces and urine of human and
animal odors, and malodors in factories and industrial liquid inventors have unexpectedly found that it starts to provide the
Wastes. deodorizing effect rapidly and can provide the deodorizing
effect in a short period of time. They have made further
BACKGROUND OF THE INVENTION earnest studies based on the finding, and finally they have
accomplished the invention.
In recent years, with diversification of lives, improvement That is, the invention relates to the following (1) to (8).
of life level, changes and improvement of attitudes, and the (1) A deodorant composition comprising:
like, attention has been paid to various points around one's 25 (a) a polyphenol compound or a plant extract containing a
life. One of them is existence of various malodors. Main
malodorous components include nitrogen compounds Such polyphenol compound,
as ammonia, urea, indole, skatole, and amines; Sulfur com (b) a basic Substance, and
pounds Such as methyl mercaptan, hydrogen Sulfide, and (c) a metal salt.
dimethyl sulfide; and lower fatty acids such as butyric acid. 30
(2) A deodorant composition comprising:
Heretofore, there are a number of reports on deodorants that (a) a granulated Substance which contains a polyphenol
are used to eliminate or reduce the malodors. compound or a plant extract containing a polyphenol com
For example, there has been a report of using plant extracts pound,
containing various kinds of mixtures of polyphenols as deter (b) a basic Substance, and
gents (refer to Patent Document 1). While such detergents (c) a metal salt.
show a certain level of deodorizing effect, most of them 35
(3) The deodorant composition according to (1) or (2),
cannot be said to exhibit a sufficient deodorizing effect and, in which further comprises a polyphenol compound oxidase.
this regard, leave a room for improvement.
As a deodorant which improves and solves the problem, it (4) The deodorant composition according to any one of (1)
have been reported a deodorant composition comprising, as to (3), which further comprises a silicon dioxide.
an effective component, a colored compound obtained by 40 (5) The deodorant composition according to any one of (1)
reacting a polyphenol compound in an alkaline solvent under or (4), wherein the basic Substance is at least one member
the co-existence of oxygen molecules at a pH value during selected from the group consisting of brine, lye, and a bleach.
reaction of 6.5 or more has been reported (Patent Document (6) The deodorant composition according to any one of (1)
2). While the deodorant composition is an excellent deodor to (5), wherein the metal salt is bittern.
ant composition capable of maintaining the deodorizing per 45 (7) A method for deodorizing a malodor, which comprises
formance even with lapse of a long period of time when it is applying the deodorant composition according to any one of
once prepared and capable of providing an excellent deodor (1) to (6) to a malodor component.
izing effect to malodor component, particularly, to nitrogen (8) Use of the deodorant composition according to any one
containing compound or Sulfur-compound, since the effec of (1) to (6) for deodorizing a malodor.
tive ingredient is a colored Substance, a problem has been 50 In this regard, the deodorant composition changes depend
pointed out that it undergoes a certain restriction upon appli
cation as a deodorant and cannot easily provide the deodor ing on the properly of the constituent ingredient, and it is
izing effect in a short period of time when it is applied to the Sometimes colorless or white, pale gray, or gray, or some
malodor component. times has a pale color, for example, pale yellow, brown, etc.
Further, while a technique of preparing a deodorant com Further, it sometimes exhibits yellow color.
position comprising a polyphenol compound and an alkali 55 Namely, the invention provides a deodorant composition
has been reported (refer to Non-Patent Document 1), it is not comprising (a) a polyphenol compound or a plant extract
intended to provide a deodorizing effect in a short period containing a polyphenol compound, (b) a basic Substance,
upon application to a malodor source. and (c) a metal salt as effective ingredients. Further, the inven
Patent Document 1: JP-A-11-319051 tion can also be described as a deodorant composition con
Patent Document 2: JP-A-2004-167218 60 sisting essentially of (a) a polyphenol compound or a plant
Non-Patent Document 1: Fragrance Journal No. 12, pages extract containing a polyphenol compound, (b) a basic Sub
58 to 59, 1995 stance, and (c) a metal salt.
In the invention, the basic Substance and the metal salt may
DISCLOSURE OF THE INVENTION be also used in the form of a granulated substance. While the
65 ingredients described above are the essential ingredients in
In view of the above, the present invention intends to pro the inventions, other ingredients may also be present together
vide a novel deodorant composition capable of providing a So long as they do not impair the intended purpose.
 US 9,375,501 B2
3 4
The polyphenol compound oxidase may be an oxidase per dopamine, naringenin, maringin, nordihydroguairetic acid,
se of the polyphenol compound, or a plant extract containing noradrenaline, hydroquinone, Vanillin, patchouletin, her
the oxidase. bacetin, Vanillyl alcohol, Vanitrope, Vanillin propylene glycol
According to the invention, a deodorant composition acetal, Vanillic acid, bis(4-hydroxyphenyl)sulfonic acid,
capable of exhibiting a deodorizing effect in a short period of 5 bisphenol A, pyrocatechol, Vitexin, 4,4'-biphenyldiol, 4-tert
time when applied to a malodor component can be provided. butylcatechol, 2-tert-butylhydroquinone, protocatechuic
In addition, a deodorant composition exhibiting an excellent acid, phloroglucinol, phenolic resins, procyanidin, prodel
deodorizing activity and excellent in the store stability can be phinidin, phloretin, phloretin glycosides, fisetin, folin, fer
provided. Further, since the deodorant composition of the Vasetin, fraxetin, phloridzin, paeonidin, paeonidin glyco
invention is colorless or exhibits white or pale color, it 10 sides, pelargonidin, pelagugonidin glycosides, petunidin,
scarcely undergoes restriction upon application as the petunidinglycosides, hesperetin, hesperidin, gallic acid, gal
deodorant. The invention can provide a novel deodorant com lic esters (lauryl gallate, propyl gallate, butyl gallate), man
position used for elimination or reduction of malodors felt in jiferin, malvidin, malvidin glycosides, myricetin, myricetin
daily life such as bad breath, odor in refrigerators, odor of raw glycosides, 2,2'-methylenebis(4-methyl-6-tert-butylphenol),
garbage, odorin footwear cupboard, body odor of human and 15 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methyl
animal, odor of feces and urine of human and animal, and enebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-
malodor in factories or industrial liquid wastes. ethyl-6-tert-butylphenol), methylatrarate, 4-methylcatechol,
The present invention provides a deodorant composition 5-methylcatechol, 4-methoxycatechol, 5-methoxycatechol,
exhibiting an excellent deodorizing effect on various malodor methylcatechol-4-carboxylic acid, 2-methylresorcinol,
components. The deodorant composition of the invention is 5-methylresorcinol, morin, limocitrin, limocitringlycosides,
excellent in the deodorizing effect on malodor components, limocitrol, luteolin, luteolin glycosides, luteolinidin, luteo
for example, Sulfur-containing compounds such as methyl linidinglycosides, rutin, resorcin, resveratrol, resorcinol, leu
mercaptan, hydrogen Sulfide, and dimethyl sulfide and lower kocyanidin, leukodelphinidin.
fatty acids such as butyric acid and isovaleric acid among Among these polyphenol compounds, preferred are fla
malodor components, and is also excellent in the deodorizing 25 vonoids Such as quercetin, epicatechin, and epigallocatechin
effect on amine malodor components such as ammonia which and glycosides thereof; polyphenols having an o-diphenol
are alkaline. Furthermore, since the method for preparing the structure, Such as gallic acid, gallic esters, chlorogenic acid,
deodorant composition is relatively simple and it has an caffeic acid, caffeic esters, tannic acid, pyrocatechol, nordi
advantage that the deodorant performance is maintained even hydroguairetic acid, L-dopa, 4-methylcatechol. 5-methylcat
after the deodorant composition is stored for a longtime once 30 echol, 4-methoxycatechol, and 5-methoxycatechol; and hyd
the deodorant composition is prepared, the composition can roquinone.
be said to be a remarkably excellent deodorant composition. The polyphenol compounds described above may be used
each alone or as a mixture of two or more of them.
BEST MODE FOR CARRYING OUT THE The above polyphenol compounds can be prepared by
INVENTION 35 known methods but commercially available products may be
purchased. Moreover, they may be prepared by Synthesis.
The invention is to be described specifically. Furthermore, highly concentrated polyphenol fractions pre
At first, the polyphenol compound as the starting material pared from plants can be employed.
for preparing the deodorant composition of the invention is to In the invention, instead of the polyphenol compound, a
be described. The polyphenol compound used in the inven 40 plant extract containing a polyphenol compound can also be
tion means a compound in which two or more hydrogen used. As the plant extract, one prepared by a known method
atoms on one identical benzene ring are substituted with may be used or a commercially available product may be
hydroxyl groups, and glycosides thereof are also included as used.
the polyphenol compound. The polyphenol compound used Examples of the plant for the preparation of the plant
in the invention is not particularly restricted so long as it is a 45 extract containing a polyphenol compound include aloe,
polyphenol compound capable of attaining the intended pur anise seeds, elder, eleutherococcus, psyllium, orange flower,
pose. Among them, hydroquinone and a polyphenol com allspice, oregano, Valerian, chamomile, capsicum pepper,
pound having an o-diphenol structure are preferred. The cardamon, cassia, garlic, caraway seeds, clove, cumin seeds,
o-diphenol structure means Such a structure in which kola, coriander seeds, Rhus javanica, Saffron, Zanthoxylum,
hydroxyl groups are directly Substituted on the benzene ring 50 juniper berry, cinnamon, ginger, star anise, St. Johns wart,
and the hydroxyl groups are adjacent with each other. celery seed, savory, Sesame, pieplant, tarragon, turmeric,
Specific examples of the polyphenol compound include thistle, Anethungraveolens, nutmeg, nettle, hibiscus, hama
apigenin, apigenin glycosides, acacetin, isorhamnetin, melis, birch, basil, bitter orange, fennel, primrose, fenugreek,
isorhamnetin glycosides, isoquercitrin, epicatechin, epicat Verbena, Laurus nobilis, hop, boldo, horseradish, poppy seed,
echin gallate, epigallocatechin, epigallocatechin gallate, aes 55 gallnut, marigold, marrow, marjoram, mustard, Millefeuille,
culetin, ethyl protocatechuate salt, ellagic acid, catechol, mint leaves, melissa, mace, lindane. Gentiana scabra var.
y-acid, catechin, gardenin, gallocatechin, caffeic acid, caffeic buergeri, rosehip, rosemary, Rosmarinus officinalis, Sun
esters, chlorogenic acid, kaempferol, kaempferol glycosides, flower seeds, grape pericarp, apple, carrot leaves, banana,
quercetin, quercetin glycosides, quercetagenin, genistin, Strawberry, apricot, peach, plum, pineapple, Nashi pear, per
genistinglycoside, gossypetin, gossypetinglycosides, gossy 60 Simmon, cherry, papaya, mango, avocado, melon, loquat, fig,
pol, 4-dihydroxyanthraquinone, 1,4-dihydroxynaphthalene, kiwi, prune, blueberry, blackberry, raspberry, cranberry, cof
cyanidin, cyanidin glycosides, sinensetin, dioSmetin, dioS fee beans, cacao beans, grape seeds, grapefruits seeds, pecan
metin glycosides, 3,4'-diphenyldiol, Sinapic acid, Stearyl-3- nut, cashew nut, chestnut, coconut, peanut, walnut, green tea
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, spinacene, leaves, black tea leaves, oolong tea leaves, tobacco, perilla
tangeritin, taxifolin, tannic acid, daphnetin, tyrosine, del 65 leaves, garden thyme, sage, lavender, spearmint, peppermint,
phinidin, delphinidin glycosides, theaflavine, theaflavine spotted thistle, hyssop, Sweet basil, marigold, dandelion, arti
monogallate, theaflavine bisgallate, tricetinidin, dopa, choke, Matricaria chamomille, Agrimonia pilosa var.
 US 9,375,501 B2
5 6
japonica, licorice, anise, yarrow, eucalyptus, wormwood, the aqueous solution thereof is 6.5 or more. Particularly, the
balm, Angelica pubescens, fenugreek, Capsicum annuum var. aqueous solution preferably has pH of from 7 to 13, more
angulosum, fennel, red pepper, coriander seeds, caraway preferably, pH of from 8 to 13, and still more preferably, pH
seeds, fennel seeds, ginger, horseradish, Origanum majo offrom 9 to 11. In a case where the pH of the aqueous solution
rana, Origanum valgare, mustard, parsley, pepper, savory, is less than 6.5, a deodorant composition providing a pre
tarragon, queen lily, wasabi, dill seeds, citrus fruits, pear, ferred deodorizing effect cannot be obtained. On the other
thyme, and the like. Among them, rosemary, Sunflower seeds, hand, in a case where pH is excessively high (pH at about 14),
grape pericarp, apple, carrot leaves, banana, coffee beans, it needs caution upon handling the deodorant composition,
cacao beans, grape seeds, green tea leaves, black tea leaves, which is disadvantageous.
oolong tea leaves, perilla leaves, garden thyme, sage, spear 10 The metal salt as the essential ingredient of the invention is
mint, peppermint, pear and thyme are especially preferable. not particularly restricted so long as it can attain the intended
The plant extract can be prepared from the plants each purpose. Among various metals salts, preferred metal salts are
alone or in plurality. Further, individual plant extracts may be at least one or more metal salts selected from the group
obtained and then Such individual plant extracts may be consisting of Mg salt, Casalt, Cusalt, Mn Salt, Agsalt, Ti salt,
mixed. 15 and Zn salt. Such metal salt are known chemical Substances.
The preparation method of the plant extract is not particu Specific metal salt includes, for example, copper compounds
larly restricted. Such as copper chloride, copper fluoride, copper Sulfate, cop
Since the amount of the polyphenol compound to be used per nitrate, copper hydroxide, copper citrate, copper glucon
for obtaining the deodorant composition varies depending on ate, copper aspartate, copper glutamate, sodium copper chlo
the type of the malodor sources intended to be eliminated, the rophyllin and copper chlorophyll; zinc compounds Such as
type and the amount of coexistent basic Substance and the Zinc chloride, Zinc fluoride, Zinc sulfate, Zinc nitrate, Zinc
metal salt, etc., it cannot be defined generally, but it is about hydroxide, Zinc citrate, Zinc gluconate, Zinc aspartate, Zinc
from 1 to 90% by weight and, more preferably, from 10 to glutamate, Zinc phosphate, and Zinc lactate; calcium com
50% by weight based on the entire deodorant composition. pounds such as calcium chloride, calcium hydroxide, calcium
The basic Substance (Substance showing alkalinity) as the 25 citrate, calcium gluconate, calcium L-glutamate, calcium car
essential ingredient in the invention is a known chemical bonate, calcium lactate, calcium pantothenate, calcium dihy
Substance and not restricted particularly so long as it can drogen pyrophosphate, calcium propionate, calcium sulfate,
attain the intended purpose of the invention. Specific basic tricalcium phosphate, calcium monohydrogen phosphate,
Substance includes, for example, carbonate salts or hydrogen calcium dihydrogen phosphate, and disodium calcium ethyl
carbonate salts such as Sodium carbonate, potassium carbon 30 enediamine tetraacetate; magnesium compounds such as
ate, Sodium bicarbonate, ammonium carbonate, and guani magnesium chloride, magnesium Sulfate, magnesium
dine carbonate; borate salts such as potassium borate and hydroxide, magnesium L-glutamate, magnesium oxide, and
Sodium borate; silicate salts such as potassium silicate, magnesium carbonate; silver compounds such as silver
sodium silicate No. 1, sodium silicate No. 2, sodium silicate oxide; permanganate salts such as potassium permanganate
No. 3, Sodium orthosilicate, and sodium metasilicate; sodium 35 and manganese compounds Such as manganese sulfate, and
monohydrogen phosphate, sodium Sulfite, sodium hydroxide, the like. In addition, titanium compounds such as titanium
calcium hydroxide, potassium hydroxide, magnesium dioxide can also be used.
hydroxide, ammonium hydroxide, Sodium pyrophosphate, In the invention, bittern can be used as the metal salt.
and potassium pyrophosphate. Bittern is by produced upon preparation of table salts from sea
Further, the basic substance of the invention may also be at 40 water. It is sold and available easily.
least one member selected from brine, lye and bleaches. Since the application of bittern in foods is allowed, it is
Brine has been used for noodle preparation for a long preferably used in the deodorant composition for foods.
period of time. The main ingredient is sodium carbonate and While the amount of the metal salt used varies depending
potassium carbonate in which various other ingredients are on the polyphenol compound and the basic Substance consti
present together. It is sold and is available easily. 45 tuting the deodorant composition and the malodor Source, it is
Lye is a Supernatant obtained mainly by dissolving and preferably added such that the concentration of metal ions in
dispersing ashes of plant into water, which contains alkaline the aqueous solution of the deodorant composition is from
components such as potassium carbonate as a main ingredi 0.00005 mM to 100 mM and it is, more preferably, from
ent. It is used for laundry agent or bleach. It is sold and 0.0001 mM to 10 mMand, further preferably, from 0.01 mM
available easily. 50 to 5 mM.
The bleach means a Substance which chemically changes The deodorant composition can also be prepared by putting
colored Substances such as contaminants by oxidation or the polyphenol compound or the plant extract containing a
reduction into other Substances, for which an oxygen type polyphenol compound to a granulating treatment and using
bleach or chlorine type bleach is often used. In the invention, the granulated Substance thus obtained. The granulated Sub
oxygen type bleach is preferred. 55 stance may be a powder, granular powder, or capsule-like
Since the application of brine and lye in foods are allowed, powder. Alternatively, it includes, for example, a powder with
they are preferably used in the deodorant composition for penetration and adsorption to a porous body, a powder encap
foods. Sulated with natural gum or saccharides, a lock-in type pow
The basic Substance may be used alone, or a plurality of der sealed in a saccharide matrix, inclusion complex with
basic Substances may also be used. 60 cyclodextrin or the like, microcapsule coated with an external
Since the amount of the basic Substance used for forming wall membrane containing an excipient, or powder prepared
the deodorant composition varies depending on the type and by using a roller compactor. Further, a powder of a larger
the amount of the polyphenol compound used, the type and diameter obtained, for example, by adsorption of Such pow
the amount of the metal salt, the malodor source to be deodor der to each other is also the granulated Substance of the
ized, etc., it cannot be defined generally. A preferred result is 65 invention.
obtained, for example, a in Such a case that, when the deodor In the invention, also the basic substance or the metal salt
ant composition of the invention is dissolved in water, pH of may be put to the granulating treatment and used as the
 US 9,375,501 B2
7 8
constituent ingredient of the deodorant composition. Means rial and heated to form a molten product of the matrix mate
for granulating the basic Substance and the metal salt is not rial. Then, polyphenols are added to the obtained molten
particularly restricted and means known so far may be product and mixed and stirred while heating to obtain a highly
adopted appropriately. Viscous liquid mixture, which is Subsequently extruded by an
The powder with penetration and adsorption to a porous 5 extruder into a solvent to obtain a powder.
body is a powder obtained by penetration and adsorption of The clathrate body means a compound formed from a
the polyphenol compound or the plant extract containing a basket-like clathrate lattice prepared with host molecules and
polypyenol compound (hereinafter sometimes referred to as a intaking (including) a polyphenol compound in the space
polyphenol compound) to the porous body. thereof. While the host molecule is not particularly restricted,
The porous body is not particularly restricted so long as it 10 cyclodextrin is a typical host molecule. The cyclodextrinused
is a powder of an organic or inorganic compound capable of herein includes one or more of C-cyclodextrin, B-cyclodex
maintaining a powdery shape while carrying the polyphenol trin, and Y-cyclodextrin, as well as derivatives formed by
compound. Specifically, clay minerals such as calcium Sul C-1,6-bonding of one molecule or two molecules of saccha
fate, calcium carbonate, diatomaceous earth, silicon dioxide, rides such as glucose, maltose, and malto-triose, cyclodextrin
aluminum oxide, montmorillonite and kaolinite, inorganic 15 derivatives in which at least a portion of the glucose residue is
compounds such as Sodium chloride, low molecular weight chemically modified with a hydrophilic functional group
organic compounds such as calcium lactate and lactose, Such as hydroxyethyl, 2-hydroxypropyl. 2,3-dihydroxypro
starches such as dextrin, processed Starch, and porous starch, pyl, 2-hydroxybutyl, 2-hydroxyisobutyl, diethylaminoethyl,
cellulose derivatives such as crystalline cellulose, methyl cel and trimethyl ammoniopropyl, cyclodextrin polymers poly
lulose, and cellulose ether compounds or organic compounds 20 merized by a crosslinker Such as epichlorohydrin or polyva
Such as polyvinyl alcohol. lent glycidyl ether, and cyclodextrin derivatives selected from
When an aqueous solution or dispersion of the polyphenol branched cyclodextrins having branched side chains such as
compound is used for the porous material and a known glucose or maltose.
method is applied, a powder with penetration and adsorption While the clathrate body is obtained by stirring and mixing
to a porous body can be obtained. The grain size of the powder 25 cyclodextrins or a cyclodextrin derivative and a polyphenol
used is 0.5 mm or less and preferably, 100 um or less. compound under the presence of water, followed by filtering
The powder encapsulated with the natural gum or saccha and drying the precipitated clathrate compound, or prepared
ride means a powder in which a polyphenol compound and by using the same as an aqueous solution as it is, or further
the natural gum or saccharide are present together optionally optionally drying and powdering the clathrate compound, the
with a surfactant and the polyphenol compound is encapsu- 30 invention is not restricted at all to such methods.
lated. Among them, particularly preferred encapsulated pow The powder prepared by using the roller compactor is a
der includes a powder in which the polyphenol compound is powder prepared from a composition containing a polyphe
present together with the natural gum, optionally, a natural nol compound, and an excipient by using a roller compactor.
Surfactant is present further together, and the polyphenol As the excipient, hydrophilic Substance is preferred and
compound is encapsulated, or a powder in which the polyphe- 35 hydrophilic proteins such as gelatin, casein, Sodium casein,
nol compound is present together with the saccharide and, whey protein, defat powdered milk, whole fat powdered milk,
optionally, a natural Surfactant and/or synthesis Surfactant are and albumin, hydrophilic polysaccharides such as malto-dex
present together, and the polyphenol compound is put to the trin, processed Starch (acid-decomposed starch, oxidized
encapsulating treatment. starch, alpharized starch, grafted Starch, etherified Starch,
The natural gum includes one or more members selected 40 esterified Starch formed by reacting with acetic acid, phos
from processed starch, gum Arabic, soybean polysaccha phoric acid, etc.), hydrophilic polysaccharides such as algi
rides, etc. and the saccharides include one or more members nate salts, gum Arabic, soybean polysaccharide, guar gum,
selected from dextrin, starch, etc. Further, the natural surfac Xanthan gum, pectin, carboxymethyl cellulose, and agarose,
tant includes one or more members selected from lecithin, partially hydrolyzed proteins such as HAP. HVP, partially
saponin, quillai extract, quillai Saponin, and the synthesis 45 decomposed starch Such as oligo-saccharide, and Saccharides
Surfactant includes one or more members selected from typically represented by lactose.
Sucrose fatty acid esters, polyglycerine esters, glycerine fatty While description has been made mainly for the powder,
acid esters, Sorbitan fatty acid esters, and propylene fatty acid granules or capsules are also included in the invention. For
esterS. example, granules prepared by using the roller compactor,
After mixing and stirring each of the ingredients, they are 50 granulated substances in which powders obtained by further
put to a powdering treatment. The powdering treatment treating powders to each other are adsorbed each other are
referred to herein includes a spray drying treatment. also included in the granulated Substances referred to in the
The powder sealed in the saccharide matrix means a pow invention. Further, granulated Substances obtained by apply
der in which the polyphenol compound is sealed in the matrix ing a coating treatment with oils and the fats or cellulose to the
material. The saccharide includes, for example, monosaccha- 55 powder described above are also included in the granulated
rides, disaccharides, polysaccharides, Sugar alcohols, poly substance referred to in the invention. Further, granulated
ols, Saccharide derivatives, processed Starch, modified starch Substances obtained by a double coating treatment are also
and gums. More specifically, they include, for example, included in the granulated substance referred to in the inven
Sucrose, glucose, lactose, leVurose fluctose, maltose, glu tion.
copyranosyl mannitol, glucopyranosyl Sorbitol, ribose, dex- 60 As the constituent ingredient for the deodorant composi
trose, isomalt, Sorbitol, mannitol. Xyrol, lactitol, maltitol, tion of the invention, silicon dioxide may further be used. As
pentatol, arabinose, pentose, Xylose, gallactose, starch, a mode of using silicon dioxide, silicon dioxide may be added
hydrogenated Starch hydrolyzate, maltodeXctrin, agar, carra to a mixture of the ingredient (a), the ingredient (b), and the
geenan, polydextrose, as well as derivatives and mixtures ingredient (c), it may also be used being added to one of the
thereof. 65 ingredients described above.
The manufacturing method of the powder is as described The deodorant composition containing silicon dioxide has
below. At first, water is added optionally to the matrix mate an advantage that the handlability is improved upon applica
 US 9,375,501 B2
10
tion to the malodor Source or upon preservation. In addition, They can be blended with the deodorant composition of the
this is also effective to the improvement of the store stability invention each alone or as a combination of two or more of
of the deodorant composition. them and thus a characteristic deodorant can be prepared.
The deodorant composition of the invention can be pre Particularly, when the antibacterial agent is blended with the
pared by mixing (a) the polyphenol compound or the plant deodorant composition, the deodorizing effect is synergisti
extract containing a polyphenol compound, (b) the basic Sub cally enhanced and, accordingly it becomes possible to pre
stance, and (c) the metal salt. Each of the ingredient can be pare a more characteristic deodorant by combining the anti
stored separately and each of the ingredients may be mixed bacterial agent with other additives to develop the
when it is intended to provide the deodorizing effect. Accord performances of the additives. The mixing amount of the
ingly, the invention also includes a case of separately storing 10 additives is not particularly limited So far as the amount can
each of the ingredients constituting the deororant composi accomplish the desired purpose.
tion of the invention. For example, a mixture of the ingredient The extender includes saccharides, polysaccharides, the
(a) and the ingredient (c), and the ingredient (b) may be processed starch, casein, gelatin, carboxymethyl cellulose
considered as the deodorant composition of the invention, and (hereinafter referred to as CMC), lecithin, and the like.
a mixture of the ingredient (b) and the ingredient (c), and the 15 As the antioxidant, there are known butylhydroxy toluene,
ingredient (a) can be considered to be as the deodorant com butylhydroxyanisole, citric acid, biofavoic acid, glutathione,
position. Further, a case in which the ingredient (a) and the Selenium, licopene, Vitamin A, vitamin E, and vitamin C, as
ingredient (b) and the ingredient (c) are stored separately can well as pyrrolopyrrole derivatives, free radical scavengers
also be considered as the deodorant composition of the inven obtainable from extracts of various plants, enzymes having
tion. antioxidant properties such as Superoxide dismutases and
In the invention, each of the ingredients may be mixed with glutathione peroxidases, and the like.
the solvent into a liquid product. The solvent includes, for As the dyestuffs, dyes, lakes, organic synthetic dyestuffs
example, water, hydrous alcohol, lower alcohol (methanol, (tar dyestuffs) such as organic pigments, natural dyestuffs,
ethanol, butanol, propanol, etc.), polyol type organic solvent inorganic pigments, and the like can be employed. Specifi
(ethylene glycol, propylene glycol, etc.), benzyl alcohol, 25 cally, examples thereof include hibiscus dyestuff, huckle
glycerol, monoglyceride, diglyceride, animal and plant oils, berry dyestuff, plume dyestuff, layer dyestuff, duberry dye
essential oils, etc. stuff, grape juice dyestuff, blackberry dyestuff, blueberry
Further, each of the ingredients can be used in a state of a dyestuff, mulberry dyestuff, morello cherry dyestuff, red cur
solid product or a gelled product. While a preferred solid rant dyestuff, loganberry dyestuff, paplica powder, malt
product can include a powder, the powder has already been 30 extract, rutin, flavonoids, red cabbage dyestuff, red radish
described above. dyestuff, adzuki bean dyestuff, turmeric dyestuff, olive tea,
The microcapsule coated with an external wall membrane cowberry dyestuff, chlorella dyestuff, saffron dyestuff,
comprising the excipient means a powder obtained by coating perilla dyestuff, strawberry dyestuff, chicory dyestuff,
the polyphenol compound with the excipient. pecannut dyestuff, red rice malt dyestuff, safilower dyestuff,
As the example of the gelled Substance, gelled powder 35 purple sweet potato dyestuff, lac dyestuff, spirulina dyestuff,
obtained by causing each of the ingredients to be present onion dyestuff, tamarind dyestuff, chili pepper dyestuff, gar
together with the gelling agent is preferred. The gelling agent denia dyestuff. Gardenia jasminoides dyestuff, Sikon dye
include aqueous gelling agents such as carrageenin, carbox stuff, rosewood dyestuff, euphausiid dyestuff, orange dye
yvinyl polymers, crosslinked polyacrylic acids, hydroxyethyl stuff, carrot carotene, carmel, Sodium iron chlorophyllin,
cellulose, carboxymethyl cellulose, Sodium acrylate, agar, 40 riboflavin, norbixin potassium, norbiXin Sodium, alamance,
gelatin, pectin, furcellaran, Xanthan gum, locust bean gum, erythrocin, new coccin, phloxine B, rose bengal, acid red,
gellan gum, and collagen; oily gelling agents such as metal cutoradin, Sunset yellow, first green, brilliant blue, indigocar
soaps and dibenzylidene sorbitol. They can be used each mine, lake red C, lithol red, rhodamine, phloxine, indigo,
alone or in combination. ponceau, orange I, and Sudan blue. Further, inorganic pig
The deodorant composition of the invention can also be 45 ments include mica, talc, calcium carbonate, kaolin, silicic
Supported on carrier. As a method for Supporting the deodor anhydride, aluminum oxide, colcothar, iron oxide, ultrama
ant composition of the invention on the carrier, there can be rine, carbon black, titanium dioxide, Zinc oxide, mica, bis
mentioned a method of forming a deodorant composition in a muth oxychloride, boron nitride, photochromic pigments,
Solution state, depositing the same to the Support by means of hybrid fine powder, and synthetic mica.
coating, impregnation, spraying, or the like and Subsequently 50 The antibacterial agents include benzoic acid, Sodium ben
drying the same (e.g., air-drying at 60°C. for 12 hours), as an Zoate, isopropyl p-hydroxybenzoate, isobutyl p-hydroxyben
example. Zoate, ethyl p-hydroxybenzoate, methyl p-hydroxybenzoate,
The deodorant composition of the invention can be Sup butyl p-hydroxybeaZoate, propyl p-hydroxybenzoate,
plied on an optional carrier and, in addition, may be used after Sodium sulfite, sodium hyposulfite, potassium pyrosulfite,
capsulation by a known method using gelatin, gum arabic, 55 Sorbic acid, potassium Sorbate, sodium dehydroacetate, thu
Sodium arginate, a cellulose derivative such as ethylcellulose, japlicin, udo extract, storax extract, wild tansy extract, milt
polyvinyl alcohol, vinyl methyl ether-maleic anhydride protein extract, and Zymolytic Yokuinin extract.
copolymer, styrene-maleic anhydride copolymer, polyethyl Known deodorants include, for example, deodorants due to
ene, polystyrene, paraffin wax or the like. the desulfurizing action of iron Sulfates such as ferrous Sulfate
In the invention, commercially available various additives 60 and iron chlorides; deodorants due to the chemical reaction of
can be added to the deodorant composition obtained by the acidic agents, alkaline agents, oxidizing agents, and the like;
method described above. Examples of the additives include deodorants due to the adding or condensing action of (meth)
extenders, antioxidants, dyestuffs, known deodorizing mate acrylate esters, maleate esters, and the like as adding agents or
rials, enzymes for reducing malodor, Surfactants, fragrances glyoxal as a condensing agent; deodorants due to the ion
and flavors, stabilizers, antibacterial agents, moisture absor 65 exchanging action of amphoteric ion-exchange resins, cat
bents (calcium chloride, highly water-absorbable polymers, ionic ion-exchange resins, anionic ion-exchange resins, and
etc.), excipients (lactose, etc.), and the like. the like; deodorants due to the chemical attaching or adsorb
 US 9,375,501 B2
11 12
ing action of alkaline or acidic attaching active carbon, mix hardened palm oil fatty acids, beef-tallow fatty acids, hard
tures of active carbon and a chemical reagent; deodorants due ened beef-tallow fatty acids, and the like which are mixtures
to the adsorbing action of porous adsorbents such as neutral the Saturated and unsaturated fatty acids having 12 to 18
active carbon, fibrillated carbon deodorant, Zeolite, and active carbonatoms and, specifically, it includes N-coconut-oil fatty
white clay; deodorants due to the enzymatic action of diges acid-acyl-L-glutamic triethanolamine, lauroyl-L-glutamic
tive enzymes or enzymes produced by mouth good bacterium triethanolamine, Sodium N-coconut-oil fatty acid-acyl-L-
LS-1 lactic acid bacterium, yeasts, soil bacteria, and the like glutamate, sodium N-lauroyl-L-glutamate, Sodium N-myris
or bacteria per se, deodorants due to the antiseptic or bacte toyl-L-glutamate, sodium N-coconut-oil fatty acid-hardened
ricidal action of chloramine T. parabens, phenols, and the tallow fatty acid-acyl-L-glutamate, potassium N-coconut-oil
like; polyphenol compound deodorants such as persimmon 10
fatty acid-acyl-L-glutamate, and the like.
polyphenol, tea chatechin, rosemary extract, oolong tea For the deodorant compositions, flavors and/or fragrances
extract, tansy extract, white oak leave extract, and rice bran/ (hereinafter sometimes referred to as perfumes) may be used.
Soybean-roasted extract; and the like. In addition, they also
include cyclodextrin, champignon extract, rooibos extract, As a result, Strange odors characteristic to Substrates can be
Sodium iron chlorophyllin, active carbon, Zeolite, and the 15 masked and further pleasant aroma can be also imparted.
like. Any of the perfumes may be used with no particular restric
In the deodorant composition of the invention, a polyphe tion which may be either synthesis perfumes or natural essen
nol compound oxidase may be present together. Preferred tial oils and may be in any of liquid, paste or Solid states. For
enzymes include catechol oxidase, polyphenol oxidase, tyro example, the flavors used in the invention include synthetic
sinase, laccase, peroxydase, and the like. For the deodorant perfumes Such as esters, alcohols, aldehydes, ketones,
composition in the invention, an enzyme exhibiting an enzy acetals, phenols, ethers, lactones, furans, hydrocarbons and
matic activity in an alkaline region is used particularly pref acids, as well as natural perfumes.
erably. The fragrance used in the invention include hydrocarbons,
While the addition amount of the enzyme is not particu alcohols, phenols, aldehydes, and/or acetals, ketones and/or
larly restricted, it is preferably added in such an amount that 25 ketals, ethers, synthetic musks, acids, lactones, esters, halo
the enzymatic activity is 100 unit or more per 100 g of the gen-containing compounds, and natural perfumes.
polyphenol compound of the deodorant composition. For the Further, in addition to the flavors and fragrance described
unit of the enzymatic activity referred to herein, it is defined above, perfumes describes, for example, in “Nihon ni Okeru
as 1 unit when the absorption value at OD of 265 nm is Syokuhin Kouryou Kagoubutu no Shiyou Jittai Tyousa (In
increased by 0.001 in a case of reaction for 1 min under the 30 vestigation for the Actual Use of Food and Perfume Com
condition at a pH value of 6.5 and at a temperature of 25°C. pounds in Japan)' (Welfare and Science Research Report in
using (L)-DOPA (L-DOPA) as a substrate. Hei 12 (2000): published from Nippon Perfume Industry
In the invention, crude enzymes obtained from extracts of Association, March, Hei 13 (2001), “Gousei Kouryou,
the plants (hereinafter sometimes referred to as a plant-de Kagaku to Syouhin Chishiki, (Synthetic Perfumes, Chemis
rived enzyme powder) can also be used. The crude enzymes 35 try and Merchandise Knowledge)” (written by Motoichi
are not restricted particularly so long as the intended purpose Indoh, published Mar. 6, 1996, from The Chemical Daily Co.,
of the invention is not impaired. Specific plants for preparing Ltd.), and “Perfume and Flavor Chemicals (Aroma Chemi
the crude enzymes include mashrooms of agarics and boretus cals) 1.2 (Steffen Arctender (1969)) can be used.
gene, apple, banana, Nashi pear, pear, Strawberry, persim The flavors and the fragrances may be used each alone or
mon, pineapple, grape, apricot, peach, plum, papaya, quince, 40 two or more of them in admixture.
avocado, mango, cherry, apricot, melon, loquat, fig, prune, Commercial products may be used for them. Further, for
kiwi, blue berry, black berry, raspberry, cranberry, currant, the single component products, synthesis products may be
burdock, eggplant, tomato, mugwort, lotus root, lettuce, cab used or they may be introduced from natural origin Such as
bage, Sugar beat, hop, parsnip, spinach, radish, turnips, cau plants. Essential oils, resinoids, balsams, absolutes, con
liflower, chicory, onion, celery, carrot, asparagus, horse rad 45 cretes, tinctures may be prepared by known methods and
ish, ginger, aloe, green pepper, barley, wheat, corn, alfalpha, used.
malt, broad bean, soybean, azuki bean, runner bean, vigna Specific examples of the perfume ingredient include
radiate, potato, Sweet potato, Sweet corn, dasheen, tea, hydrocarbons perfumes such as limonene, pinen, Y-terepinen,
tobacco, olive, nutmeg and chrysanthemum. Among them, and caryophyllene; alcohol perfumes Such as phenyl ethyl
mashrooms of agarics and boretus gene, apple, banana, Nashi 50 alcohol, terepineol, bacdanol, geraniol, nerol, linarol, and
pear, pear, burdock, horse radish, tea and tobacco are espe cis-3-hexenol; aldehyde perfumes such as lilial, citral, alde
cially preferable. Freeze dried powder obtained by freeze hyde C-8, aldehyde C-9, aldehyde C-11, hexyl cynnamic
drying the plants, and hot blow dried powder obtained by hot aldehyde, Vanillin, and heliotropin; keton perfumes Such as
blow-drying them are also included in the enzyme of the yonon, rosephenone, woody flow, damasnin, isoe Super; other
invention, Further, acetone powder obtained from the plants 55 perfume such as musks, eugenol and coumarin, in which
are also included in the enzyme of the invention. compounds containing no Sulfur or nitrogen atom are espe
The Surfactants include nonionic type (polyoxyethylene cially preferable; essential oils such as lemon oil, orange oil,
alkyl ethers, fatty acid alkylolamides, etc.), acylglutamic acid and peppermint oil; and essences such as apple essence and
type, and the like. The surfactants are preferably used each strawberry essence. In the invention, one or more of the
alone or as a combination of two or more of them. Examples 60 perfume ingredients are contained.
of the polyoxyethylene alkyl ethers include polyoxyethylene Further, together with the perfumes, solvent (ethanol, eth
Stearyl, polyoxyethylene hardened castor oil, and the like. ylene glycol, propylene glycol, diethylene glycol, etc.), emul
Examples of the fatty acid alkylolamides include coconut-oil sifiers, Solubilizers, retainers, perfume retainers, cooling
fatty acid diethanolamide. The acylglutamic acid type agents, warming agents, enhancers, anti-oxidants and photo
includes glutamate esters of Saturated and unsaturated fatty 65 degradation inhibitors can also be used properly (refer, for
acids having 12 to 18 carbon atoms, and coconut-oil fatty example, to “Syuuchi Kanyou Giyutsusyu (Kouryou) Dai
acids, hardened coconut-oil fatty acids, palm-oil fatty acids, ichibu, Kouryou Ippan, (well-known customary technical
 US 9,375,501 B2
13 14
collection (perfume) Part 1 Perfume general)' published generation of a malodor component may be predicted, it is
from Japan Patent Office, on Jan. 29, 1999). possible to eliminate the malodor component or prevent the
While the blending amount of the perfume varies depend generation thereof. Further, the deodorant composition of the
ing on the polyphenol compound used, the object to which the invention may be applied by a spraying method.
deodorant composition is applied, method of use, etc., it is 5
EXAMPLE
usually preferred to be from 0.001 to 10% by weight based on
the deodorant composition. The present invention is to be described specifically by way
The deodorant composition of the invention is effective for of examples but the invention is no way restricted to them.
elimination or reduction of a wide range of malodors.
Specifically, it is effective for elimination or reduction of 10
Examples 1 to 5
various odors including odors felt in daily life. Such as bad
breath, odor in refrigerator, odor of feces and urine of human, Preparation of Deodorant Composition
animals, and birds, body odor, and odor of raw garbage, and 2 umol of chlorogenic acid, 100 umol of sodium hydrogen
malodors in factories and industrial liquid wastes. carbonate, and 0.5umol of a metal salt described in Table 1
Further, the deodorant composition of the invention is 15 were admixed to obtain a deodorant composition.
excellent in the deodorizing effect on Sulfur-containing com
pounds Such as methyl mercaptan, hydrogen Sulfide, and Test Example 1
dimethyl sulfide; nitrogen compounds such as ammonia,
urea, indole, skatole, and amines; and lower fatty acids Such Deodorizing effect of deodorant composition on methyl
as butyric acid. Among them, the deodorant composition of mercaptain
the invention is particularly excellent in the deodorizing Deodorant composition of Examples 1, 2 mL of water, and
effect on Sulfur-containing compounds such as methyl mer 4 LL of an aqueous 15% solution of sodium methyl mercaptain
captan, hydrogen sulfide, and dimethyl sulfide. (manufactured by Tokyo Chemical Industry Co., Ltd.) were
Further, the deodorant composition of the invention can be added to a 50 mL vial bottle, which was covered with a
incorporated into the following products or goods to exhibit 25 para-film and stirred at 25°C. In a predetermined time, 50 L
the deodorizing performance. Specifically, products or goods of a head space gas in the vial bottle was passed through a gas
include drinks such as various drinks and powdery drinks; detection tube (manufactured by GASTEC Corporation), the
foods such as jellies, tablet Sweets, munches, processed sea concentration of the contained Sulfur compound as a malodor
foods, processed meat products, seasonings, powdery foods component remained in the gas was measured and the deodor
including powdery soups and powdery desserts, baked 30
izing ratio was calculated in accordance with the following
equation. The results are shown in Table 1.
munches, retort foods, frozen foods, instant noodles, healthy Deodorization ratio (%)=100x{1-(A/B)}
foods, foods for microwave oven cooking, various confec
tionary products, and various desserts; oral care products In the formula. A represents the measured concentration of
Such as mouthwash, toothpaste, chewing gum, tablets, hard the malodor component, and B represents the concentration
candy, soft candy, capsules, and oral spray; articles for pets 35 of the malodor component measured as a control.
animals including dog, cat, rabbit, hamster, and parakeet, In the control. 2 mL of water was added to 100 umol of
Such as cat sands, cat sleeping straws, and sheets; detergents Sodium hydrogen carbonate.
Such as laundry detergents, kitchen detergents, bathroom Comparative Example 1
detergents, carpet detergents, and toilet detergents; cosmetics
Such as Soaps, body shampoos, hand soaps, lotions, face 40
2 umol of chlorogenic acid and 100 umol of sodium hydro
lotion, antiperspirants, foot deodorant sprays, and foot pow gen carbonate were mixed to obtain a deodorant composition
ders; hair care products Such as shampoos, conditioners, hair of Comparative Example 1.
rinses, hair coloring agents, permanent-wave agents, waxes,
hairsprays, and mousse; bath agents; sanitary goods such as Comparative Example 2
paper diapers, paper pads, Sanitary napkins, sheets, towels, 45
and wet tissues; household cleaning products, footwear cup After adding 50 mL of water to a mixture of 1 mmol of
board sprays, sheets in shoes, raw garbage sprays, filters for chlorogenic acid and 50 mmol of sodium hydrogen carbonate
air cleaners and air conditioners, deodorizers, air blowers and and stirring at a room temperature for three hours under the
air dischargers, deodorants for refrigerators, deodorants for condition capable of being in contact with oxygen, they were
cloths, deodorant for drawers, closets, and ambries, room or 50 freeze-dried to obtain a colored compound, and 12 mg of
car deodorants, toilet deodorants, deodorants for textile prod which was used as a deodorant composition of Comparative
ucts, cloths (underwear and socks), car sheets, deodorant Example 2.
fibers, deodorants for factories and industrial liquid wastes Comparative Example 3
and other various deodorants.
While the amount of use of the deodorant composition of 55
50 mL of water was added to a mixture of 1 mmol of
the invention varies depending on the kind and the form of the chlorogenic acid, 50 mmol of Sodium hydrogen carbonate,
products or commercial goods, it is generally within a range and 0.25 mmol of magnesium chloride and the same proce
about from 0.001 to 0.1 parts by weight and, preferably, about dures as those in Comparative Example 2 were conducted
from 0.01 to 0.05 parts by weight based on one part by weight Subsequently to obtain a colored compound, and 12 mg of
of the products or commercial goods. 60 which was used as a deodorant composition of Comparative
At deodorization of malodor using the deodorant compo Example 3.
sition of the invention, a conventional method can be applied.
For example, when a solid matter, gel matter, or liquid matter Test Example 2
of the deodorant composition of the invention is applied by a
method of directly scattering, sprinkling, wiping, immersing, 65 The deodorizing effect of the deodorant compositions of
or placing the composition to the site or place where a mal Examples 2 to 5 on methyl mercaptain was measured in accor
odor component is present or the site or place where possible dance with the same procedures as those in Test Example 1.
 US 9,375,501 B2
15 16
The results of measurement are shown in the following TABLE 2-continued
Table 1.
Metal salt +
Test Example 3 plant derived Deodorizing time
Enzyme powder 0 min 5 min 10 min 20 min 30 min
The deodorizing effect of the comparative deodorant com Example 9 +zinc O.O 70.O 95.0 1OO.O 1OOO
positions of Comparative Examples 1 to 3 on methyl mercap chloride +
tan was measured in accordance with the same procedures as banana freeze
those in Test Example 1. dried powder
The results of measurement are shown in the following
Table 1. According to Table 1 and Table 2, by mixing a predeter
mined metal salt to the system of the polyphenol compound
and basic Substance, the deodorizing effect was improved
TABLE 1.
15 remarkably more than the system of the polyphenol com
Deodorizing time pound and the basic substance. It shows more excellent effect
even when compared with the colored compound formed
Metal salt O min 5 min 10 min 20 min 30 min with an identical starting material composition.
Comp. Not added O.O O.O O.O 1S.O 2O.O It was further found that the deodorizing effect was
Example 1 improved further in a case where a polyphenol oxidase oper
Example 1 +magnesium O.O 3S.O 55.0 1OOO 1OOO ating also in an alkaline region of pH 7 or higher was present
chloride together.
Example 2 +calcium O.O 3O.O SO.O 95.0 1OOO
chloride It was further found that the deodoring effect was improved
Example 3 +copper O.O 7O.O 100.0 1OOO 1OOO further in a case where a polyphenol oxidase operating also in
chloride 25 an alkaline region of pH 7 or higher was present together.
Example 4 +Zinc O.O 40.O 70.O 1OOO 1OOO
chloride For the burdock acetone powder in the table, 400 liter of
Example 5 +manganese O.O 8OO 100.0 1OOO 1OOO acetone at -20°C. was added to 100 g of the plant, ground in
sulfate a mixer and then filtered under suction. The residue was
Comp. not added O.O O.O 2S.O 45.0 7O.O washed sufficiently with 500 ml of an aqueous 80% acetone
Example 2
Comp. magnesium O.O S.O 3O.O 6O.O 75.0 30 containing Solution at 5° C. and, after joining with filtrates
Example 3 chloride and distilling off acetone, it was freeze-dried into a powder.
contained Further, pear freeze-dried powder, apple freeze-dried pow
der, and banana freeze-dried powder were prepared by slicing
each of the plant, then freeze-drying and then pulverizing the
35 SaC.
Examples 6 to 9
Preparation of Deodorant Composition Examples 10 to 18
2 umol of chlorogenic acid, 100 umol of sodium hydrogen
carbonate, 0.5umol of metal salt described in Table 2, and 10 40
Preparation of Deodorant Composition
mg of enzyme powder derived from plants described in Table 2 umol of polyphenol compounds, 100 umol of basic Sub
2 were added and mixed to obtain a deodorant compositions. stances and 0.5umol of metal salts each described in Table 3
were added and mixed to obtain deodorant compositions.
Test Example 4
45 Test Example 5
The deodorizing effect of the deodorant compositions of
Examples 6 to 9 on methyl mercaptain was measured in accor The deodorizing effect of deodorant compositions of
dance with the same procedures as those in Test Example 1. Examples 10 to 17 on methyl mercaptain was measured in
The results of measurement are shown in the following accordance with the same procedures as in the test example 1.
Table 2. 50 Results of measurement are shown in the following Table
3.
TABLE 2
Metal salt + Comparative Examples 4 to 12
plant derived Deodorizing time
55
Enzyme powder Omin 5 min 10 min 20 min 30 min 2 umol of the polyphenol compounds and 100 umol of the
basic substances each described in Table 3 were mixed to
Example 6 +magnesium O.O 6S.O 95.0 1OOO 1OOO
chloride +
obtain comparative deodorant compositions.
burdock

Example 7
acetone powder
+calcium O.O SO.O 70.O 1OOO 1OOO 60 Test Example 6
chloride +
pear freeze The deodorizing effect of deodorant compositions of Com
dried powder parative Examples 4 to 11 on methyl mercaptain was mea
Example 8 +copper OO 100.O 10O.O 1OOO 1OOO
chloride +
Sured in accordance with the same procedures as in Test
apple freeze 65 Example 1.
dried powder Results of measurement are shown in the following Table
3.
 US 9,375,501 B2
17 18
TABLE 3
Polyphenol compound Basic Substance Metals salt
Comp. Example 4 Gallic acid Bleacher
Example 10 Gallic acid Bleacher magnesium chloride
Comp. Example 5 (+)-catechin Sodium hydroxide —
Example 11 (+)-catechin Sodium hydroxide magnesium chloride
Comp. Example 6 C. Grutin Lye
Example 12 C. Grutin Lye magnesium chloride
Comp. Example 7 Caffeic acid brine
Example 13 Caffeic acid brine magnesium chloride
Comp. Example 8 green tee extract Sodium hydrogen
carbonate
Example 14 green tee extract Sodium hydrogen magnesium chloride
carbonate
Comp. Example 9 Coffee raw bean extract sodium hydroxide —
Example 15 Coffee raw bean extract sodium hydroxide magnesium chloride
Comp. Example 10 Apple extract Sodium hydroxide —
Example 16 Apple extract Sodium hydroxide magnesium chloride
Comp. Example 11 Grape pericarp extract Sodium hydrogen
carbonate
Example 17 Grape pericarp extract Sodium hydrogen bittern
carbonate
Comp. Example 12 Peppermint extract brine
Example 18 Peppermint extract brine bittern

Deodorizing time
O min 5 min 10 min 20 min 30 min

Comp. Example 4 O.O O.O 1O.O 1S.O 2O.O

Example 10 O.O SO.O 7O.O 1OOO OO.O
Comp. Example 5 O.O O.O O.O 1O.O 2O.O
Example 11 O.O 3O.O 6O.O 1OOO OO.O
Comp. Example 6 O.O O.O O.O 1O.O 1S.O
Example 12 O.O 3O.O SO.O 8S.O OO.O
Comp. Example 7 O.O O.O O.O O.O 1O.O
Example 13 O.O 3S.O SO.O 95.0 OO.O
Comp. Example 8 O.O O.O 1O.O 2O.O 3S.O
Example 14 O.O 6O.O 95.0 1OOO OO.O
Comp. Example 9 O.O O.O S.O 1S.O 3O.O
Example 15 O.O SO.O 8O.O 1OOO OO.O
Comp. Example 10 O.O O.O 1.O 2O.O 3O.O
Example 16 O.O SO.O 8S.O 1OOO OO.O
Comp. Example 11 O.O O.O S.O 1O.O 3O.O
Example 17 O.O 40.O 7O.O 95.0 OO.O
Comp. Example 12 O.O O.O S.O 1S.O 3O.O
Example 18 O.O SO.O 8O.O 1OOO OO.O

In Table 3, bleach, lye, brine, and bittern are commercial After adding ethanol togrape pericarp (variety: Campbell),
products. it was stirred and extracted at 70° C. for 2 hours. The extract
Extracts Referred in Table 3: 45 which was concentrated and dried to Solid was used as a grape
Green Tea Extract: pericarp extract.
1 Kg of boiled tea was extracted under stirring with 10 L of From the results shown in Table 3, it was found that by
hot water at 90° C. for one hour and tea leaves were removed mixing a predetermined metal salt to the system of the
by filtration to obtain 8.3 L of extract. The solution was polyphenol compound and the basic Substance, the deodor
concentrated to 1 L, to which 1 L of acetone was added and 50 izing effect was remarkably improved more than that in the
stirred, and resultant insoluble matters were removed by cen system of the polyphenol compound and the basic Substance.
trifugation. 1 L of ethyl acetate was added to the Supernatant
and stirred and stood still for 30 min. The obtained ethyl Example 19
acetate layer was concentrated under a reduced pressure,
transformed into an aqueous layer, and then freeze-dried to 55 Preparation of Deodorant Composition
obtain 97 g of green tea extract at 60% purity. The following polyphenol compound-containing granu
Coffee Raw Bean Extract: lated Substance was prepared, the granulated Substance was
After pulverizing coffee raw bean by a pulverizer (5 mm weighed by Such an amount that the polyphenol compound
mesh), water was added to extract at 85 to 95°C. for 2 hours. content was 2 Limol, and then 100 umol of Sodium hydrogen
After filtration of extracts, filtrate was adsorbed to an XAD-2
60 carbonate and 0.5 Limol of magnesium chloride were added
column (manufactured by Organo Corp.). Afterwashing with and mixed to obtain a deodorant composition.
Preparation of Polyphenol Compound-Containing Granu
water and leached with ethanol, it was concentrated and dried lated Substance
to solid to form coffee raw bean extract.
While stirring together with 10 parts by weight of catechin
Apple Extract: 65 (polyphenol powder GTP90: manufactured by Aiya Co.) dis
Manufactured by Nikka Whisky Co. persed in 27 mL of ion exchanged water, 66.79 parts by
Grape Pericarp Extract: weight of isomalt (palatinit), 0.95 parts by weight of pro
 US 9,375,501 B2
19 20
cessed starch (purity gum 59: manufactured by National time when applied to a malodor component can be provided.
Starch and Chemicals Co.), and 22.26 parts by weight of In addition, a deodorant composition exhibiting an excellent
dextrin (Pinedex #1: manufactured by Matsuo Chemical deodorizing activity and excellent in the store stability can be
Industries Co.) were heated to obtain uniform molten prod provided. Further, since the deodorant composition of the
uct. Then, the molten product was extruded to a filament invention is colorless or exhibits white or pale color, it
shape into isopropyl alcohol cooled to -10° C. by using an scarcely undergoes restriction upon application as the
extruder, rapidly quenched and then stirred and pulverized.
Then, the pulverization product was removed with isopropyl deodorant. The invention can provide a novel deodorant com
alcohol by a centrifugal treatment, to obtain a granulated position used for elimination or reduction of malodors felt in
Substance containing the polyphenol compound. 10
daily life such as bad breath, odor in refrigerators, odor of raw
garbage, odorin footwear cupboard, body odor of human and
Example 20 animal, odor of feces and urine of human and animal, and
malodor in factories or industrial liquid wastes.
Preparation of Deodorant Composition The present invention provides a deodorant composition
The following polyphenol compound-containing granu exhibiting an excellent deodorizing effect on various malodor
lated Substance was prepared, the granulated Substance was 15
components. The deodorant composition of the invention is
weighed by Such an amount that the polyphenol compound
content was 2 Limol, and then 100 umol of Sodium hydrogen excellent in the deodorizing effect on malodor components,
carbonate and 0.5 Limol of magnesium chloride were added for example, Sulfur-containing compounds such as methyl
and mixed to obtain a deodorant composition. mercaptan, hydrogen Sulfide, and dimethyl sulfide and lower
Preparation of Polyphenol Compound-Containing Granu fatty acids such as butyric acid and isovaleric acid among
lated Substance malodor components, and is also excellent in the deodorizing
A mixture of 10 kg of sorbitol and 0.2 kg of catechin effect on amine malodor components such as ammonia which
(polyphenol powder GTP90: manufactured by Aiya Co.) was are alkaline. Furthermore, since the method for preparing the
spontaneously dropped in a hopper, then moved horizontally deodorant composition is relatively simple and it has an
by utilizing a horizontal screw at a number of rotation of the 25 advantage that the deodorant performance is maintained even
screw of 15 rpm and supplied between compression rollers. after the deodorant composition is stored for a longtime once
The catechin was compressed under the conditions at a roller the deodorant composition is prepared, the composition can
compression pressure of 25 N/cm, with a roller distance of 0.5
mm, and at the number of rotation of roller of 15 rpm, to be said to be a remarkably excellent deodorant composition.
obtain a plate-like product. The plate-like product was cooled 30
by a cold blow. The invention claimed is:
The cooling product was pulverized by a rotational pulver 1. A deodorant composition consisting essentially of
izer, and aligned for the size, to obtain a polyphenol com (a) a polyphenol compound,
pound-containing granulated Substance. (b) a basic Substance, and
Example 21 35 (c) a metal salt,
wherein the components (a), (b), and (c) are present as an
Preparation of Deodorant Composition admixture thereof;
The following polyphenol compound-containing granu wherein the polyphenol compound is at least one member
lated Substance was prepared, the granulated Substance was Selected from the group consisting of chlorogenic acid,
weighed by Such an amount that the polyphenol compound 40 gallic acid, catechin, rutin, and caffeic acid;
content was 2 Limol, and then 100 umol of Sodium hydrogen wherein the basic substance is at least one member selected
carbonate and 0.5 Limol of magnesium chloride were added from the group consisting of sodium carbonate, Sodium
and mixed, to obtain a deodorant composition. hydroxide, sodium hydrogen carbonate, brine, lye, and a
Preparation of Polyphenol Compound-Containing Granu bleach;
lated Substance 45 wherein the metal salt is at least one member selected from
After dissolving 15 kg of water, 8.9 kg of dextrin as an the group consisting of magnesium chloride, calcium
excipient (manufactured by Matsuya Chemical Industry Co., chloride, copper chloride, Zinc chloride, and manganese
Ltd.), and 0.1 kg of an emulsifier (polyglycerin fatty acid Sulfate,
ester), 1 kg of catechin (polyphenol powder GTP90: manu wherein a polyphenol compound oxidase is not included in
factured by Aiya Co.) were added and stirred and mixed by 50 the deodorant composition,
using a TK mixer, to obtain an emulsion. Then, the emulsion
was spray-dried by a spray drier set to an inlet temperature of wherein the amount of the polyphenol compound is from 1
180° C. and an exhaust temperature of 90° C., to obtain a to 50% by weight based on the deodorant composition,
polyphenol compound-containing granulated Substance. and
While the invention has been described in detail and with wherein the amount of the basic Substance is such that,
reference to specific embodiments thereof, it will be apparent 55 when the deodorant composition is dissolved in water to
to one skilled in the art that various changes and modifications make an aqueous solution thereof, the aqueous Solution
can be made therein without departing from the scope thereof. has a pH of 7.0 or more.
This application is based on Japanese patent application 2. A deodorant composition consisting essentially of
No. 2006-079559 filed Mar. 22, 2006, the entire contents (a) a granulated Substance which contains a polyphenol
thereof being hereby incorporated by reference. 60 compound,
Further, all references cited herein are incorporated in their (b) a basic Substance, and
entireties. (c) a metal salt,
wherein the components (a), (b), and (c) are present as an
INDUSTRIAL APPLICABILITY admixture thereof;
65 wherein the polyphenol compound is at least one member
According to the invention, a deodorant composition Selected from the group consisting of chlorogenic acid,
capable of exhibiting a deodorizing effect in a short period of gallic acid, catechin, rutin, and caffeic acid;
 US 9,375,501 B2
21 22
wherein the basic substance is at least one member selected wherein the amount of the basic Substance is such that,
from the group consisting of sodium carbonate, sodium when the deodorant composition is dissolved in water to
hydroxide, sodium hydrogen carbonate, brine, lye, and a make an aqueous solution thereof, the aqueous Solution
bleach; has a pH of 7.0 or more.
wherein the metal salt is at least one member selected from 7. A deodorant composition consisting essentially of
the group consisting of magnesium chloride, calcium (a) a granulated Substance which contains a plant extract
containing a polyphenol compound,
chloride, copper chloride, Zinc chloride, and manganese (b) a basic Substance, and
Sulfate, (c) a metal salt,
wherein a polyphenol compound oxidase is not included in 10 wherein the components (a), (b), and (c) are present as an
the deodorant composition, admixture thereof;
wherein the amount of the polyphenol compound is from 1 wherein the plant extract containing a polyphenol com
to 50% by weight based on the deodorant composition, pound is at least one member selected from the group
and consisting of green tea extract, coffee raw bean extract,
wherein the amount of the basic Substance is such that, 15
apple extract, and grape pericarp extract;
wherein the basic substance is at least one member selected
when the deodorant composition is dissolved in water to from the group consisting of sodium carbonate, Sodium
make an aqueous solution thereof, the aqueous Solution hydroxide, sodium hydrogen carbonate, brine, lye, and a
has a pH of 7.0 or more. bleach;
3. The deodorant composition according to claim 2, wherein the metal salt is at least one member selected from
wherein the basic substance is at least one member selected the group consisting of magnesium chloride, calcium
from the group consisting of brine, lye, and a bleach. chloride, copper chloride, Zinc chloride, and manganese
4. A method for deodorizing a malodor, which comprises Sulfate,
applying the deodorant composition according to claim 1 or 2 wherein a polyphenol compound oxidase is not included in
to a malodor component. the deodorant composition,
5. The method according to claim 4, wherein the malodor 25 wherein the amount of the polyphenol compound is from 1
component comprises a Sulfur-containing compound, a lower to 50% by weight based on the deodorant composition,
and
fatty acid, and/or an amine. wherein the amount of the basic Substance is such that,
6. A deodorant composition consisting essentially of
(a) a plant extract containing a polyphenol compound, when the deodorant composition is dissolved in water to
(b) a basic Substance, and 30 make an aqueous solution thereof, the aqueous Solution
(c) a metal salt, has a pH of 7.0 or more.
wherein the components (a), (b), and (c) are present as an 8. A method for deodorizing a malodor, which comprises
admixture thereof applying the deodorant composition according to claim 6 or 7
wherein the plant extract containing a polyphenol com to a malodor component.
pound is at least one member selected from the group 35 9. The method according to claim 8, wherein the malodor
consisting of green tea extract, coffee raw bean extract, component comprises a Sulfur-containing compound, a lower
apple extract, and grape pericarp extract; fatty acid, and/or an amine.
wherein the basic substance is at least one member selected 10. The deodorant composition according to claim 1,
from the group consisting of sodium carbonate, sodium wherein each of the components (a), (b) and (c) is in a state of
hydroxide, sodium hydrogen carbonate, brine, lye, and a 40 a solid product.
bleach; 11. The deodorant composition according to claim 2,
wherein the metal salt is at least one member selected from wherein each of the components (a), (b) and (c) is in a state of
the group consisting of magnesium chloride, calcium a solid product.
chloride, copper chloride, Zinc chloride, and manganese 12. The deodorant composition according to claim 6.
Sulfate, 45 wherein each of the components (a), (b) and (c) is in a state of
wherein a polyphenol compound oxidase is not included in a solid product.
the deodorant composition, 13. The deodorant composition according to claim 7.
wherein the amount of the polyphenol compound is from 1 wherein each of the components (a), (b) and (c) is in a state of
to 50% by weight based on the deodorant composition, a solid product.
and