(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`World Intellectual Property
`=
`
`>) NNN0800008
`OM ene ee
`—
`(10) International Publication Number
`International Bureau
`(43) International Publication Date —
`WO 2021/144245 Al
`22 July 2021 (22.07.2021)
`WIPOI|PCT
`
`(1) International Patent Classification:
`A6IK 8/73 (2006.01)
`A61@ 11/00 (2006.01)
`
`(21) International Application Number:
`
`PCT/EP202 1/050454
`
`(22) International Filing Date:
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`12 January 2021 (12.01.2021)
`
`English
`
`English
`
`(30) Priority Data:
`202010038301.9
`
`14 January 2020 (14.01.2020)
`
`CN
`
`(71) Applicant: ROQUETTE FRERES [FR/FR]; | rue de la
`Haute Loge, 62136 LESTREM (FR).
`
`(72) Inventors: HASJIM, Jovin; Unit 701 Building 9 Lane
`1789 North Shanxi Rd., Putuo District, SHANGHAI(CN).
`ZHANG, Guangyu; Unit 401, No.78, Lane 255, MeiChuan
`Road, Putuo District, Shanghai (CN). LI, Jia; Building 33,
`Lane 177, South Gutong Rd., New Pudong District, Shang-
`hai (CN). PORA, Bernard; Unit 1101 Building 391Lane
`1517 Huqingping Rd., QingpuDistrict, SHANGHAI (CN).
`
`(74) Agent: PLASSERAUDIP; 66 tue de la Chaussée d'Antin,
`75440 PARIS CEDEX 09 (FR).
`
`(81) Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AO,AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ,
`CA, CH,CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
`DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN,
`HR, HU, D, IL, IN, IR, IS, IT, JO, JP. KE, KG, KH, KN,
`KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD,
`ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO,
`NZ, OM,PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW,
`SA, SC, SD, SE, SG, SK, SL. ST, SV, SY, TH, TJ, TM, TN,
`TR, TT, TZ, UA, UG, US, UZ, VC, VN, WS, ZA, ZM, ZW.
`
`(84) Designated States (unless otherwise indicated, for every
`kind ofregional protection available); ARIPO (BW, GH,
`GM,KE, LR, LS, MW, MZ, NA, RW,SD, SL, ST, SZ, TZ,
`UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
`TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
`EE,ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
`MC, MK, MT. NL, NO, PL, PT, RO, RS, SE, SL SK, SM,
`TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
`KM,ML, MR, NE, SN, TD, TG).
`
`Published:
`— with international search report (Art. 21(3))
`
`(54) Title; NATIVE AND POROUS STARCH AS WHITE PIGMENT IN TOOTHPASTE
`
`(57) Abstract: The present invention relates to the use of native and/or porous starch as white pigment in dental health products and
`in particular in toothpastes. The present invention also relates to the process of fabricating a dental health product composition and in
`} particular a toothpaste composition.
`
`
`
`
`
`2021/144245A.IMTIIDIUTAMIUTATACTAA
`
`

`

`WO 2021/144245
`
`PCT/EP2021/030454
`
`Native and porous starch as white pigment in
`
`toothpaste
`
`Field
`
`of the invention
`
`invention relates to the use of native and/or
`
`in dental health products and
`
`The present
`
`porous starch as
`
`in particular in
`
`
`
`white pigment
`
`
`
`
`
`
`
`
`
`toothpastes. The present invention also
`
` Fabricating a dental health product
`relates to the process of
`
`10
`
`15
`
`composition and in particular a toothpaste composition.
`
`Background
`
`Toothpaste
`
`agent and a gelling agent
`
`in a
`
`
`
`humectant
`
`and various
`
`ingredients such as
`
`compositions generally contain an
`
`
`
`
`
`
`
`
`liquid medium consisting of a
`
`flavors, colorants,
`
`abrasive
`
`
`
`
`
`white pigments,
`
`preservatives, detergents,
`
`anti-tartar agents,
`
`antibacterial
`
`agents,
`
`and the
`
`like.
`
`Typical white pigments
`
`used in
`
`toothpastes
`
`are
`
`titanium dioxide. However,
`
`recent
`
`studies have rec
`
`pollutants
`
`(Hazardous
`
`ognized titanium dioxide particles as emerging
`
`
`
`Effects
`
`
`of
`
`Titanium
`
`Dioxide
`
`
`
`Syed Niaz Ali
`
`Shah
`
`et al.,
`
`Nanoparticles
`
`in Ecosystem,
`
`20
`
`Bioinorganic Chemistry and Applications. Volume 2017, Article
`
`
`ID 4101735,
`12 pages)
`and as being harmful
`to human health
`
`
`it safe?, Matej
`(Titanium dioxide in our everyday life;
`is
`
`
`
`
`
`
`
`Skocaj
`
`et
`
`al.,
`
`Radiol Oncol.
`
`2011
`
`Dec;
`
`45 (4):
`
`227-
`
`247) (Titanium dioxide nanoparticles:
`
`a
`
`
`review of
`
`current
`
`25
`
`toxicological da
`
`ta, Hongbo Shi,
`
`Particle and Fibre Toxicology
`
`a need to provide more environmentally
`
`
`for dental health
`
`
`
`
`friendly and
`
`less
`
`toxic white pigments
`
`products such as toothpastes.
`
`30
`
`The present
`
`inventors have surprisingly found that native
`
`and/or
`
`porous
`
`starch
`
`can
`
`be
`
`used
`
`as
`
`non-chemical,
`
`environmentally
`
` friendly white pigment
`
`in dental products and
`
`in particular in
`
`toothpastes.
`
`
`starches are toothfriendly,
`
`
`
`In particular, native and porous
`
`are perceived as
`
`a natural
`
`and
`
`
`
`volume 10,
`
`There
`
`is thus
`
`Article number:
`
`15
`
`(2013)).
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`healthy ingredient by the consumers,
`
`and do not have tolerance
`
`issues.
`
`Summary of the invention
`
`
`
`A first object of
`
`the present
`
`invention is directed to the
`
`
`use of
`
`starch as white pigment
`
`to replace titanium dioxide in
`
`a dental health product composition,
`
`the starch being a native
`
`starch,
`
`a porous starch or a mixture
`
`
`thereof.
`
`10
`
`
`A second object of
`
`the present
`
`invention relates to a
`
`dental
`
`health
`
`product
`
`composition
`
`and
`
`in particular
`
`a
`
`toothpaste composition comprising a white pigment containing
`
`
`or consisting of a native starch,
`
`a
`
`porous starch or a mixture
`
`
`
`
`
`thereof.
`
`A
`
`process oO
`
`third object of
`
`
`
`
`fabricating the dental health product composition
`
`the present
`
`invention relates to a
`
` of
`
`the
`
`present
`
`invention,
`
`in
`
`particular
`
`the
`
`toothpaste
`
`15
`
`20
`
`
`composition of
`
`the present
`
`invention,
`
`adding a native starch,
`
`a porous starch or a mixture
`
`as white pigment.
`
`comprising the step of
`
`
`
`
`
`thereof
`
`
`
`A fourth object of
`
`the present
`
`invention relates to a
`
`dental health product composition,
`
`in particular a toothpaste
`
`25
`
`composition
`
`obtained
`
`
`from
`
`the
`
`process
`
`
`of
`
`the
`
`present
`
`invention.
`
`Detailed description
`
`
`
`A first object of
`
`the present
`
`invention is directed to the
`
`30
`
`use of
`
`starch as white pigment
`
`to replace titanium dioxide in
`
`a dental health product composition,
`
`the starch being a native
`
`starch,
`
`a porous starch or a mixture
`
`
`thereof.
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`As used herein the expression “dental health product”
`
`
`
`toothpastes,
`
`chewing
`
`gums,
`
`and
`
`
`preferably
`
`
`refers
`
`to
`
`toothpastes.
`
`
`
`As used herein the expression
`
`
`starch coming from natural
`
`sources.
`
`“
`
`
`
`It does not
`
`
`
`“native starch” refers to
`
`result
`from
`
`enzymatic
`
`or
`
`chemical
`
`processing methods. Typical
`
`native
`
`tubers,
`
`roots,
`
`legumes
`
`
`
`and
`
`the starches are cereal,
`for
`sources
`
`
`
`In the present
`fruits.
`
`invention, native starch may be
`
`
`recovered from native sources such as
`
`tapioca, waxy tapioca,
`
`maize,
`
`pea, potato, waxy potato, wheat, waxy wheat, waxy
`
`maize, high-amylose maize, mung bean,
`
`rice, waxy rice,
`
`sweet
`
`potato, waxy
`
`sweet potato, millet,
`
`sago,
`
`sorghum,
`
`quinoa,
`
`
`
`
`
`arrowroot,
`
`amaranth,
`
`lotus root
`
`processes.
`
`
`
`Native starch is normally extracted using either
`
`wet milling or dry milling known process.
`
`and buckwheat by extraction
`
`
`
`
`An example of a first starch extraction process comprises
`
`
`the following steps:
`
`
`
`cleaning of grain kernels from foreign matters;
`
`
`
`
`
`steeping of
`
`the grain in water, alkaline solution or
`
`a
`
`1)
`
`2)
`
`solution containing a reducing agent
`
`
`to soften the kernels and
`
`
`
`
`
`
`to facilitate the separate of starch and protein;
`
`
`coarse grinding followed by hydrocyclone to
`
`
`
`10
`
`15
`
`20
`
`25
`
`30
`
`
`
`3)
`
`optionally,
`
`
`
`
`remove the germ from the kernel;
`
`4)
`
`
`
`fine grinding of the remaining grain kernel
`
` fiber, protein, and starch;
`
`to release the
`
`5)
`
`
`
`passing through
`
`
`separate fiber from protein and starch;
`
`screens with various opening sizes
`
`
`
`to
`
`
`
`6)
`
`optionally,
`
`removing the excess water in slurry containing
`
`starch and protein;
`
`7)
`
`
`separating protein from starch by density,
`
`such as using
`
`multiple-stage hydrocyclone;
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`8)
`
`drying the
`
`starch,
`
`such
`
`
`
`
`as using centrifugal
`filter,
`
`
`
`vacuum filter, belt-type dryer, and/or flash dryer;
`
`9)
`
`recovering the dried starch.
`
`Another
`
`
`example of
`
`a
`
`second starch extraction process
`
`comprises the
`
`
`following steps:
`
`1)
`
`
`cleaning and washing of
`
`starchy root or
`
`tuber
`
`and sticks;
`
` from dirt
`
`2)
`
`removing
`
`the peel
`
`
`of
`
`the
`
`starchy root
`
`or
`
`tuber
`
`and
`
`
`chopping the flesh into chunks;
`
`3)
`
`4)
`
`pulverizing the roots into pulpy slurry;
`
`
`
`
`
`removing the coarse and fine fiber
`from starch slurry by
`
`
`
`
`and/or
`
`filter cloths with large
`
`and
`
`
`fine
`
`opening
`
`screens
`
`sizes;
`
`5)
`
`concentrating starch slurry using two-
`
`or
`
`three-phase
`
`separator or a series of
`
`hydrocylone;
`
`starch using
`
`
`centrifuge or high-pressure
`
`10
`
`15
`
`
`
`dewatering the
`6)
`
`
`filtration or press
`
`
`
`
`fil
`
`Ler;
`
`7)
`
`8)
`
`20
`
`drying the starch using
`
`recovering the dried sta
`
`rch.
`
` flash
`
`dryer;
`
`Advantageously,
`
`the extraction process is
`
`
`
`free of organic
`
`
`solvents and free of chemical reactants. There is no chemical
`
`
`transformation.
`
`Thus,
`
`the dental health products,
`
`and
`
`in
`
`
`
`particular
`
`toothpastes,
`
`
`
`incorporating
`
`the
`
`native
`
`starch
`
`can be
`
`clean labeled
`
`and
`
`in particular
`
`clean
`
`labeled
`
`
`
`
`
`
`
`
`
`
`25
`
`30
`
`
`obtained from the extraction process
`
`dental health products,
`
`toothpastes.
`
`
`
`
`
`The native starch useful
`for
`the present
`
`ar form.
`gelatinized but is under granul
`
`invention is not
`
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`starch is a porous starch.
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`As used herein the expression “porous starch” refers to a
`
`granular starch that has been hydrolyzed by one or multiple
`
`amylolytic enzymes until multiple pores are visible on
`
`
`
`the
`
`
`surface of the starch granules by microscopic technique.
`
`
`
`According to the present
`
`invention, porous starch may be
`
`
`of native
`enzymatic hydrolysis
`
`
`
`
`
`starch
`
`such as a-
`
`
`
`produced through an
`
`granules with one or multiple amylolytic enzymes,
`
`10
`
`15
`
`amylase and amyloglucosidase, at a temperature inferior to the
`
`the starch. The native starch
`
`
`
`
`gelatinization temperature of
`
`granules may be based on tapioca, waxy tapioca, maize, pea,
`
`potato, waxy potato, wheat, waxy wheat, waxy maize,
`
`high-
`
`amylose maize, mung bean,
`
`rice, waxy rice,
`
`sweet potato, waxy
`
`sweet
`
`potato, millet,
`
`sago,
`
`sorghum,
`
`quinoa,
`
`arrowroot,
`
`
`
`amaranth and buckwheat.
`
`
`The particle size of the resulting porous starch granules
`
`may
`
`be
`
`further
`
`reduced
`
`by
`
`grinding,
`
`homogenization
`
`or
`
`20
`
`micronization.
`
`Acid,
`
`
`such as hydrochloric acid and sulfuric acid, can be
`
`used to hydrolyze the native starch or
`
`weaken the granular structure prior
`
`the porous starch to
`
`
`
`to enzyme hydrolysis or
`
`25
`
`prior
`
`to
`
`physical modification
`
`(such
`
`as
`
`grinding,
`
`homogenization or micronization).
`
`The resulting starch granules may have a porous structure
`
`
`on the surface and inside the granules. Preferably,
`
`they have
`
`30
`
`
`a high number of
`
`large and small pores, which may or may not
`
`be connected to the hilum though internal channels.
`
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`porous starch used in the present
`
`invention has multiple pores
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`
`
`on the surface with a diameter comprised between 0.01 um and 5
`
`
`
`wm, preferably between 0.05 um and 2.5 wm, and more preferably
`
`
`
`between 0.1 um and 1 um.
`
`The porosity can
`
`be observed using scanning electron
`
`microscopy.
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`porous
`
`starch used in the present
`
`invention has
`
`10
`
`diameter
`
`comprised between
`
`0.5 pm and
`
`200
`
`a particle
`
`
`
`um, preferably
`
`
`between 1 um and 100 um, and more preferably between 2 pm and
`
`60 um.
`
`
`
`
`
`The particle diameter may be measured by laser diffraction
`
`15
`
`particle sizer (Beckman Coulter LS 13 320).
`
`In the present
`
`invention,
`
`
`the starch may be selected from
`
`
`the group consisting of
`
`tapioca starch, waxy tapioca starch,
`
`maize starch, pea starch, potato starch, waxy potato starch,
`
`wheat
`
`starch, waxy wheat
`
`starch, waxy maize
`
`starch,
`
`high-
`
`amylose maize starch, mung bean starch,
`
`rice starch, waxy rice
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`porous starch used in the present
`
`invention is not gelatinized
`
`
`but is under granular form.
`
`As used herein,
`
`
`the expression “white pigments” refers to
`
`
`a compound that changes the color of reflected or
`
`
`
`transmitted
`
`
`light as the result of wavelength-selective absorption.
`
`sweet potato starch, waxy sweet potato starch, millet
`
`starch,
`
`sago starch,
`
`starch,
`
`amaranth
`
`starch,
`
`lotus
`
`root
`
`starch and
`
`buckwheat
`
`starch,
`
` starch.
`
`
`sorghum starch, quinoa starch, arrowroot
`
`20
`
`25
`
`30
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`Typical white pigments used
`
`in toothpaste are titanium
`
`dioxide.
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`starch replaces
`
`up
`
`to 30%, preferably up
`
`to 60% and more
`
`preferably up to 100% by weight of the titanium dioxide in the
`
`
`
`composition,
`
`in particular
`
`in
`
`the
`
`
`
`
`
`dental health product
`
`toothpaste composition.
`
`
`
`In a preferred embodiment of
`
`
`native starch represents from 0.5 %
`
`the present
`
`invention,
`the
`
`
`
`to 30%, preferably from 1%
`
`
`to 20% and more preferably from 2% to 15%,
`
`
`preferably from 5
`
`
`
`
`
`weight of the dental health product composition,
`
`
`of
`the toothpaste composition.
`
`to 10% by weight with respect
`
`and even more
`
`to the total
`
`in particular
`
`
`
`
`
`10
`
`15
`
`20
`
`
`
`
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`
`
`porous starch represents from 0.5% to 30%, preferably from 1%
`
`
`
`to 20% and more preferably from 2% to 15%,
`
`and even more
`
`
`preferably from 5
`
`weight of the dental health product composition,
`
`to 10% by weight with respect
`
`
`
`to the total
`
`in particular
`
`
`of
`
`the toothpaste composition.
`
`The dental health product
`
`
`
`
`composition of
`
`the present
`
`
`the
`ticular the toothpaste composition of
`
`further comprise abrasives,
`
`
`
`humectants,
`
`
`
`invention may
`present
`
`
`thickening agents and optionally additives.
`factants,
`
`25
`
`invention and in part
`
`
`
`sur
`
`
`is the main part of
`that
`Abrasive is the powder material
`
`
`
`function of tooth cleaning.
`
`
`the toothpaste formula, giving the
`
`30
`
`Its
`
`
`
`function is to remove the dirt on the tooth surface,
`
`give
`
`luster, and, at the same time,
`
`do not wear the teeth.
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`Examples
`
`
`of
`
`suitable
`
`abras
`
`ives
`
`comprise but
`
`are
`
`not
`
`limited to,
`
`calcium carbonate,
`
`dicalcium phosphate,
`
`Silica,
`
`aluminum hydroxide,
`
`calcium pyrophosphate,
`
`dicalcium phosphate
`
`dihydrate or a mixture thereof.
`
`Typically,
`
`the abrasives represent
`
`
`from 10% to 25% (low
`
`abrasive toothpaste,
`
`
`
`preferably from 30% to 50% (high abrasive toothpaste,
`
`like silica), or
`
`
`from 25% to 50%,
`
`and
`
`like
`
`calcium carbonate/dicalcium phosphate)
`
`by weight with respect
`
`to the total weight of
`
`
`
`and preferably of the toothpaste composition.
`
`the dental health product composition
`
`
`
`
`represents from 0%
`to 40%,
`
`15% to
` from
`more preferably
`
`
`the present
`In a preferred embodiment of
`
` from ]
`ferably
`pret
`
`invention,
`
`0%
`
`to 30%
`
`and even
`
`water
`
`to the
`
`by weight with respect
`
`lth product
`
`composition and
`
`
`25% nea
`
`
`
`
` as
`
`
` from the tube;
`
`
`
`total weight of
`
`
`
`preferably of the toothp
`
`the
`
`dental
`
`Le compositi
`
`on.
`
`Humectant
`
`is used to keep ¢t
`
`he
`
`toothpaste within certain
`
`
`level of moisture,
`
`viscosity and smoothness,
`
`to prevent
`
`the
`
`paste
`
`from hardening and to render
`
`the paste easy
`
`another
`
`
`function
`
`is
`
`to reduce
`
`the
`
`
`freezing
`
`point of
`
`the
`
`toothpaste so that it can be used in cold areas.
`
`
`In a preferred embodiment of
`
`humectants
`
`are
`
`
`selected from glycerin,
`
`
`
`the present
`
`invention,
`
`the
`
`sorbitol,
`
`propylene
`
` to extrude
`
`
`
`
`
`
`
`
`glycol, butanediol, polyethylene glycol and mixtures thereof.
`
`
`
`The humectants represent
`from 10% to 70%, preferably from
`
`
`
`20% to 60%, and more preferably from 30% to 50% by weight with
`
`
`total weight of
`the dental health product
`
`respect
`
`to the
`
`
`composition, and preferably o
`
`F the toothpaste composition.
`
`
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2021/144245
`
`
`Surfactants are used to provide a
`
`
`
`
`
`ability of decontamination and of
`foaming.
`
`PCT/EP2021/050454
`
`
`toothpaste with the
`
`
`
`
`
`Examples of surfactants comprise, but are not
`
`limited to,
`
`
`
`acetate,
`
`sodium Jlauroylmethylamine
`sulfate,
`sodium lauryl
`
`
`sodium lauryl
`alcohol
`sulfonate,
`
`
`
`sodium glyceryl monolaurate
`
`
`sulfonate,
`
`sodium dioctyl sulfonated succinate.
`
` to 10%, preferably
`
`
`
`The surfactants represent
`
` from 0.01%
`
`10
`
`Q.1%6
`
`to 7%,
`
`
`and more preferably from 1
`
`to 4%,
`
`by weight with
`
`respect
`
`to the
`
`
`total weight of
`
`
`
`composition and preferably of
`F the toothpaste composition.
`
`the
`
`dental health product
`
`Thickening
`
`agents
`
`aim
`
`to
`
`provide
`
`a
`
`toothpaste with
`
`15
`
`texture,
`
`
`fluidity and stability.
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`thickening agents
`
`are
`
`selec
`
`ted
`from carboxymethyl cellulose,
`
`carrageenan,
`
`
`xanthan gum and mixtures thereof.
`
`20
`
`agents
`
`represent
`
`
`from 0.
`
`01%
`
` from 1% to 2%
`
`The
`thickening
`
`
`from 0.1
`ferably
`
`6
`
`pre
`
`by
`
`
`
`weight with
`
`respect
`
`to
`
`
`
`health product composition
`
`to 5%,
`
`and more
`
`preferably
`
`
`
`
` the toothpaste
`
`the total
`weight
`
`
`and preferab]
`y of
`
`of
`
`the dental
`
`25
`
`composition.
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`additives
`
`are
`
`selected
`
` fro
`
`my,
`
`
`flavoring agents,
`
`preservatives,
`
`col
`
`orants,
`
`30
`
`
`mixtures thereof.
`
`anti-tartar
`
`agents,
`
`sweeteners,
`
`others
`
`and
`
`
`
`
`The additives represents from 0%
`
`
`
`to 10%, preferably from
`
`0.1% to 7%
`
`by weight,
`
`and
`
`
`more preferably from 1%
`
`to 4% by
`
`weight with respect
`
`to the total weight
`
`
`of
`
`the dental health
`
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`product
`
`composition
`
`and
`
`
`preferab
`
`ly
`
`
`of
`
`the
`
`toothpaste
`
`composition.
`
`
`
`
`
`ml
`
`avoring agents wel
`types of
`
`ll known in the art may be
`
`
`tal health product composition of
`
`the present
`
`
`
` All
`added to the den
`
`
`inven
`
`invention and in
`
`
`particular of
`
`the
`
`toothpaste
`
`the present
`
`tion.
`
`Flavoring agents may comprise essential
`
`oils,
`
`synthetic
`
`flavors,
`
`and mixtures
`
`
`thereo!t
`
`fF
`
`including but
`
`nowt
`
`
`
`limited to oils
`
`
`fruit essences,
`citrus oils,
`
`derived
`
`
`from plants and
`
`peppermint oil,
`
` fruits su
`
`ch as
`
`spearmint oil,
`
`
`clove oil, oil of
`
`
`flavoring agents
`
`
`
`the art will
`
`wintergreen,
`
`anise,
`
`and the like.
`
`Artificial
`
`can also be contemplated.
`
`lled in
`ski
`Those
`
`
` avoring
`ficial
`f]
`recognize that natural and arti
`
`agents may be combined in any sensorially acceptable blend.
`
`oO
`Examples of
`
`sweeteners comprise,
`
`but are
`
`not
`
`limited to,
`
`10
`
`15
`
`composition of
`
`
`
`
`from putrefying and
`health product
`
`
`
`shelf
`life
`of
`
`
`
`health
`
`
`
`deteriorating and extend
`
`products.
`
`Examples
`
`
`of
`
`
`
`dental
`
`
`
`
`
`
`
`sodium sacharin,
`
`(or steviol glycosides),
`
`
`
`neotame,
`
`sucralose,
`
`aspartame,
`
`stevia extract
`
`
`acesulfame K,
`
`sugar alcohols
`
`(such as
`
`sorbitol,
`
`xylitol, maltitol,
`
`and
`
`erythrit
`
`ol),
`
`luohanguo
`
`20
`
`
`extract, and mixtures thereof.
`
`Preservatives
`
`
`refer
`
`to substan
`
`ces
`
`that
`
`prevent dental
`
`the
`
`25
`
`30
`
`preservatives
`
`comprise, but
`
`are not
`
`limited to, methyl p-
`
`hydroxybenzoate,
`
`propyl
`
`p-hydroxybenzoate,
`
`ethyl
`
`p-
`
`
`hydroxybenzoate and mixtures thereof.
`
`
`
`
`
`
`Examples of colorants comprise, but are not
`
`limited to
`
`lutein,
`
`lycopene,
`
`zeaxanthin, brilliant blue,
`
`and mixtures
`
`thereof.
`
`10
`
`

`

`
`
`
`
`
`-
`
`10%
`
`
`by weight of
`
`the from
`
`pre
`
`10%
`
`
`by weight of
`
`
`
`
`
`10
`
`15
`
`20
`
`weight of the dental health product composition,
`
` of
`toothpaste composition,
`
`
`
`from 1%
`0.5% to 30%, preferably
`
`
`ferably from 2% to 15%,
`
`WO 2021/144245
`
`PCT/EP2021/0350454
`
`Examples
`
`
`of anti-tartar
`
`agents
`
`comprise,
`
`but
`
`are not
`
`
`
`limited to sodium monoflucrophosphate, and mixtures thereof.
`
`
`
`
`
`limited
`
`
`Examples of others additives comprise, but are not
`
`to, ethanol.
`
`
`
`
`
`
`In a preferred embodiment of
`the present
`
`dental health product
`
`composition
`
`and
`
`in particular
`
`the
`
`invention,
`
`the
`
`
`
`
`
`toothpaste composition comprises:
`
`
`from 0.5% to 30%, preferably from 1%
`
`
`preferably from 2% to 15%,
`
`to 20% and more
`
`
`and even more preferably from 5
`
`
`
`to
`
`native starch with respect
`
`to the total
`
`in particular
`
`to 20% and more
`
`
`and even more preferably from 5
`
`to
`
`
`
`porous starch with respect
`
`to the total
`
`weight of the dental health product composition,
`
` of the toothpaste composition,
`
`in particular
`
`and
`
`
`- optionally from 0% to 40%, preferably from 10% to 30%,
`
`
`even more preferably from 15% to 25% by weight of water with
`
`
`
`respect
`
`to the
`
`
`total weight of
`
`the dental health product
`
`composition,
`
`
`in particular of the toothpaste composition,
`
`
`
`
` from 10% to 70%, preferably from 20% to 60%,
`
`
`ferably from 30% to 50% by weight of humectant with respect
`
`
`total weight of
`the dental health product composition,
`
`and more
`
`
`
`
`
`25
`
`pre
`
`to
`
` the
`
`
`in particular of
`
`the toothpaste composition,
`
`
`
`
`- optionally from 10% to 25% (low abrasive toothpaste,
`
`
`
`and preferably from 30% to 50%
`
`Silica), or
`
`like
`
`
`from 25% to 50%,
`
`toothpaste,
`
`30
`
`(high
`
`abrasive
`
`
`
`
`
`like calcium carbonate/dicalcium
`
`to the total
`
`in particular
`
`
`phosphate) by weight of abrasives with respect
`
` of the dental health product composition,
`
`weight
`
`
`
` of
`
`the toothpaste composition,
`
`1i
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`-
`
`
`
`
`preferably 0.1% to
`from 0.01% to
`10%,
`
`
`
`preferably from 1
`to 4% by weight of surfactants with respect
`
`
`to the total weight of
`the dental health product composition,
`
`7%,
`
`and more
`
`
`
`
`
`
`in particular of
`
`the toothpaste composition,
`
`
`
`
`from 0.01% to 10%, preferably from 0.1% to 5%,
`
`
` preferably from 1% to 2% by weight of
`
`-
`
`
`
`thickening agents with
`
`and more
`
`respect
`
`to the
`
`
`total weight of
`
`the dental health product
`
`
`
`composition,
`
`10
`
`weight,
`
`
`in particular of the toothpaste composition, and
`
`
`
`- optionally from 0% to 10%, preferably from 0.1% to 7% by
`
`
`and more preferably from 1%
`
`
`
`to
`
`
`total weight of
`
`the dental
`
`4% by weight
`
`of
`
`
`
`
`additives with respect
`
`to the
`
`
`
`health product composition,
`
`in particular of
`
`the toothpaste
`
`composition.
`
`15
`
`The present
`
`
`invention also relates to a dental health
`
`
`product composition and in particular a toothpaste composition
`
`comprising a white pigment
`
`
`containing or consisting of
`
`a
`
`native
`
`starch,
`
`a porous
`
`starch or
`
`a mixture
`
`thereof
`
`as
`
`
`previously defined.
`
`20
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`25
`
`30
`
`composition
`
`does
`
`not
`
`comprise
`
`titanium dioxide
`
`as white
`
`pigment.
`
`
`Thanks to the specific dental health product composition,
`
`and
`
`in particular
`
`toothpaste
`
`composition,
`
`as
`
`previously
`
`product,
`
`and
`
`in
`
`particular
`
`toothpaste,
`
`having
`
`low
`
`
`fermentability,
`
`without
`
`and
`
`
`tolerance issues at all while having good mouthfeel
`
`being
`
`noncariogenic
`
`and
`
`nonerosive,
`
`
` defined it is possible to obtain a toothfriendly dental health
`
`
`
`and
`
`good processing properties.
`
`In particular,
`
`the dental
`
`product
`health
`
`
`toothfriendly
`
`toothfriendly
`
`
`
`
`
`
`
`and
`
`in particular
`
`the
`
`toothpaste
`
`is
`
`a
`
`dental
`
`health
`
`product,
`
`and
`
`in
`
`particular
`
`toothpaste,
`
`having
`
`
`a mouthfeel
`
`and
`
`
`flavor
`
`12
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`
`delivery characteristics similar and even improved to that of
`
`a dental health product,
`
`and in particular toothpaste, made
`
`with a
`
` native
`
`titanium dioxide
`
`as white pigment.
`
`In particular,
`
`starch
`
`and
`
`porous
`
`starch
`
`are
`
`non-chemical
`
`and
`
`
`environmentally friendly white pigments.
`
`
`In the present
`
`
`invention “a toothfriendly dental health
`
`product”
`
`
`refers
`
`to a product
`
`that has
`
`low fermentability,
`
`noncariogenic and nonerosive potential
`“Mw
`
`
`toothfriendly toothpaste”
`
`
`
`
`
`in healthy people.
`
`
`In
`
`
`refers
`
`to
`
`a
`
`same way,
`
`a
`
`the
`
` toothpaste
`
`nonerosive potential in healthy people.
`
`that
`
`has
`
`low fermentability,
`
`noncariogenic
`
`and
`
`
`
`a
`
`
`The “toothfriendly” properties of
`
`a dental health product,
`
`and in particular toothpaste,
`
`can be determined by intraoral
`
`
`pH-telemetry according to a standardized method (Toothfriendly
`
`International’s Standard Operation Procedures)
`
`described in
`
`
`
`
`
`
`
`
`
`10
`
`15
`
`20
`
`25
`
`30
`
`Imfeld,
`
`Th. N.,
`
`Identification of Law Caries Risk Dietary
`
`Components, Monographs in Oral Science, Vol. 11, 198pp., H.M.
`
`Myers
`
`(ed.), S. Karger AG, Basel, 1983.
`
`In this standardized
`
`method,
`
`
`the pH of
`
`interdental plaque is measured during and
`
`for
`
`30 minutes after
`
`health product
`
`the consumption or use of
`
`the dental
`
`
`
`
`and in particular of
`
`the
`
`toothpaste
`
`to be
`
`
`
` tested with
`
`a
`
`plaque-covered
`
`electrode.
`
`A dental health
`
`product,
`
`and in particular toothpaste,
`
`
`
`low fermentability, noncariogenic and nonerosive potential
`
`is considered to have
`
`
`if
`
`
`it does not depress the pH of the interdental plaque below 5.7
`
`by bacterial
`
`
`fermentation, neither during consumption/use nor
`
`
`
`
`
`during a period of 30 minutes following consumption/use.
`
`In particular,
`
`the present
`
`inventors have
`
`
`
`
`
`found that
`
`
`native and porous starch were not easily fermented by bacteria
`
`
`in the mouth thus the pH of
`
`the interdental plaque after the
`
`consumption or
`
`
`the use of dental health product
`
`in particular
`
`13
`
`
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`the toothpaste does not drop to critical
`
`levels
`
`(pH 5.7).
`
` of
`
`In
`
`a preferred embodiment
`
`
`of
`
`the present
`
`
`interdental plaque after
`
`the consumption or
`
`
`
`invention,
`
`the
`
`
`the use of
`the
`
`dental health product
`
`composition
`
`and
`
`in particular
`
`the
`
`composition does not
`
`to a
`
`pH below 5.7,
`
`drop
`
`
`preferably the interdental plaque after the consumption or the
`
`
`
`
`toothpaste
`
`
`
`use
`
`
`of
`
`the
`
`
`
`dental health product
`
`
`
`composition
`
`has
`
`ae
`
`pH
`
`
`
`
`
`
`comprised between 5.7 and 7, and more preferably between 6 and
`
`7.
`
`
`The abrasion of
`
`the dental health product may
`
`tested
`
`according to the protocol described in Tawakoli et al., 2015,
`
`Swiss Dent J, 125, 1210-9.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`
`
`
`
`
`
`
`Another aspect of
`
`
`
`coothfriendly dental health product composition and preferably
`
`toothpaste composition with native starch, porous
`
`
`
`
`
`the present
`
`invention is
`
`to make
`
`a
`
`
`
`starch or
`
`
`
`mixture thereof as white pigment, while keeping mouthfeel and
`
`flavor delivery characteristics similar and even improved to
`
`
`that of a dental health product composition, and in particular
`
`
`
`toothpaste composition, made with a titanium dioxide as white
`
`pigment.
`
`In particular, native starch and porous starch are
`
`non-chemical
`
`
`and environmentally friendly white pigments and
`
`do not have tolerance issues.
`
`
`
`
`Thus, another object of the present invention relates to a
`
`
`
`
`process of
`fabricating the dental health product composition
`
`
`
`as
`
`previously
`
`defined,
`
`in
`
`particular
`
`the
`
`toothpaste
`
`
`composition as previously defined,
`
`comprising the
`
`
`step of
`
`adding native
`
`starch,
`
`porous
`
`starch or mixture
`
`
`thereof
`
`as
`
`white pigment.
`
`14
`
`

`

`WO 2021/144245
`
`PCT/EP2021/0350454
`
`
`invention does not comprise a step of adding titanium dioxide
`
`
`In a preferred embodiment,
`
`
`as white pigment.
`
`the process of
`
`the present
`
`
`
`
`composition of
`
`the present
`
`toothpaste composition may be
`
`The dental health product
`
`invention and in particular the
`
`
`
`10
`
`15
`
`20
`
`
`manufactured by sequentially adding the various dental health
`
`product
`
`ingredients to a commercially available mixer known in
`
`
`
`the art.
`
`The present
`
`invention also relates to the dental health
`
`product composition,
`
`and in particular toothpaste composition,
`
`
`
`obtained from the process of the
`
`present invention.
`
`invention will
`The
`
`
`
`following figures and examples,
`
`now be
`
`
`illustrated by means of
`
`the
`
`it being understood that
`
`these
`
`are intended to explain the invention,
`
`and in no way to limit
`
`
`
`its scope.
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`15
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`WO 2021/144245
`
`PCT/EP2021/0350454
`
`Brief description of the drawings:
`
`Figure
`
`1:
`
`scanning electron
`
`
`micrograph of porous waxy
`
`maize starch
`
`Figure
`
`2: pH-telemetry
`
`
` of
`results
`the toothpaste made with
`
`native waxy
`
`
`maize starch of
`
`example
`
`Figure
`
`3: pH-telemetry
`
`results
`
` of the toothpaste made with
`
`porous waxy
`
`
`maize starch of
`
`example
`
`10
`
`16
`
`

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`WO 2021/144245
`
`EXAMPLES
`
`PCT/EP2021/0350454
`
`In
`
`the
`
`
`following
`
`examples,
`
`the
`
`
`following
`
`commercial
`
`products are used:
`
`- Neosorb 70/70B (liquid sorbitol) commercialized by Roquette
`
`- Sodium lauryl sulfate commercialized by Sinopharm
`
`- Carboxymethyl cellulose commercialized by Ashland
`
`
`- Ethanol commercialized by Sinopharm
`
`- Flavor commercialized by IFF
`
`
`
`
`
`10
`
`15
`
`- Sodium saccharin commercialized by Sinopharm
`
`
`
`- Methyl p-hydroxy benzoate commercialized by Sinopharm
`
`- Propyl p-hydroxybenzoate commercialized by Sinopharm
`
`
`- Sodium monofluorophosphate commercialized by Sinopharm
`
`The native waxy maize starch used in example 1 was produced
`
`
`
`according to the protocol mentioned in the first example of
`
`starch extraction process described in the description.
`
`
`
`
`
`The porous waxy maize starch used in example 2 was produced
`
`from the
`
`native waxy maize
`
`according
`
`to
`
`the
`
`
`following
`
`20
`
`protocol.
`
`1. Suspending native waxy maize starch in decarbonated water
`
`to 26% solid content.
`
`2. Adjusting pH of
`
`starch slurry to 7.0 using 3.3% NaOH
`
`solution.
`
`25
`
`3. Adding
`
`thermosable
`
`a-amylase
`
`Novozymes, 2.67 mg enzyme/g dry starch)
`
`and reacting at
`
`
`55°c for 4 hours.
`
`
`
`4, Stopping the reaction by adjusting the pH to 3-3.5 using
`
`
`5% hydrochloric solution and holding for one hour.
`
`(Liquozyme
`
`Supra
`
`
`from
`
`
`
`30
`
`5. Adjusting back
`
`the
`
`hydroxide solution.
`
`pH to 4.5-5.5 using
`
`3.3% sodium
`
`
`
`
`
`6. Cooling the starch slurry to about 25°C.
`
`7. Press filtering the slurry to obtain porous starch cake.
`
`8. Washing the cake with decarbonated water.
`
`17
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`WO 2021/144245
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`PCT/EP2021/0350454
`
`9. Drying the cake using a
`
`
`flash dryer
`
`into powder with
`
`moisture content below 12%.
`
`
`The scanning electron micrograph of porous waxy maize starch
`
`is shown on Figure 1.
`
`Example
`
`1: Analysis
`
`fermentability of
`toothpaste made using native waxy maize starch
`
`
`of
`
`abrasivity and
`
`
`
`10
`
`
`The recipe of
`
`the toothpaste sample to be tested is presented
`
`in table 1.
`
`Ingredients
`
`Percentage by
`
`Neosorb 70/70B
`
`Waxy maize starch (white
`
`pigment/potential abrasive)
`
`
`Sodium lauryl sult
`
`
`(surfactant)
`
`Carboxymethyl cellulose
`
`
`
`
`
`(anti-tartar agent)
`
`(thickening agent)
`
` Ethanol
`
`Flavor
`
`
`
`(flavoring agent)
`
`Sodium saccharin (sweet
`
`methyl p-hydroxy benzoate
`
`(preservative)
`
`
`
`propyl p-hydroxybenzoate
`
`(preservative)
`
`
`Sodium monofluorophosphate
`
`Table 1
`
`18
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`

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`WO 2021/144245
`
`PCT/EP2021/0350454
`
`
`The toothpaste sample was prepared according to the following
`
`
`
`protocol:
`
`1.
`
`Preparing a first solution by dissolving sodium saccharin
`
`
`and sodium monofluocrophosphate in water at 50°C.
`
`2.
`
`Preparing a second solution by adding the preservatives to
`
`
`
`the NEOSORB
`
`
`70/70B sorbitol
`
`solution at
`
`80°C. This
`
`second
`
`
`
`solution
`
`is
`
`
`
`then
`
`cooled
`
`to
`
`50°C
`
`and
`
`the
`
`carboxymethyl
`
`
`cellulose is dispersed under conditions of vigorous agitation.
`
`10
`
`3.
`
`Adding the first solution to the second solution. Allowing
`
`
`the resulting mixture to stand for 30 minutes.
`
`4.
`
`5.
`
`
`Vacuum-mixing for 5 minutes.
`
`
`
`Adding half of
`
`
`the waxy maize starch and mixing for
`
`10
`
`
`
`
`
`minutes.
`
`15
`
`6.
`
`
`
`
`
`Adding the second half of
`the waxy maize starch and mixing
`
`for another 10 minutes.
`
`
`
`7. and=ethanol,Adding sodium lauryl sulfate solution
`
`
`
`
`
`
`
`
`
`
`
`
`followed by 3 minutes of mixing.
`
`8.
`
`Finally,
`
`
`adding flavoring agent
`
`and mix
`
`
`for
`
`5 minutes
`
`20
`
`under vacuum.
`
`
`The “toothfriendly quality” of
`
`the resulting toothpaste was
`
`tested
`
`by
`
`using
`
`the
`
`pH-telemetric
`
`standardized method
`
`
`(Toothfriendly International’s Standard Operation Procedures
`
`Identification of Law Caries Risk
`
`described in Imfeld, Th. N.,
`
`25
`
`Dietary Components, Monographs
`
`in Oral Science, Vol.
`
`ii,
`
`198pp., H.M. Myers
`
`(ed.),
`
`S. Karger AG, Basel,
`
`1983). The
`
`sample has been tested in a volunteer having a 5-day old
`
`plaque.
`
`30
`
`
`Results are shown on figure 2.
`
`
`the obtained plaque
`2,
`on
`shown
`As
`figure
`
`demonstrated that
`the
`toothpaste sample was not associated
`
`pH-curve
`
`19
`
`

`

`WO 2021/14424