WO 2021/144245
`
`PCT/EP2021/050454
`
`Native and porous starch as white pigment in toothpaste
`
`Field of the invention
`
`The present invention relates to the use of native and/or
`
`porous starch as white pigment
`
`
`
`
`
`in particular in toothpastes. The present invention also
`
`
`relates to the process of fabricating a dental health product
`
`in dental health products and
`
`
`
`
`
`composition and in particular a toothpaste composition.
`
`
`
`
`
`Background
`
`Toothpaste
`
`
`
`
`
`
`
`agent and a gelling agent
`
`humectant and various ingredients such as
`
`
`
`
`
`
`
`compositions generally contain an
`
`
`in a liquid medium consisting of
`
`flavors, colorants,
`
`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 recognized titanium dioxide particles as emerging
`oD
`
`
`
`Effects
`
`
`of
`
`Titanium
`
`Dioxide
`
`pollutants
`
`(Hazardous
`
`Nanoparticles
`
`in Ecosystem,
`
`Syed Niaz Ali
`
`Shah
`
`et al.,
`
`ID 4101735,
`
`12 pages)
`
`to human health
`
`abrasive
`
`a
`
`
`
`
`
`Bioinorganic Chemistry and Applications. Volume 2017, Article
`
`
`(Titanium dioxide in our everyday life;
`
`is it
`
`
`safe?, Matej
`
`
`and as being harmful
`
`Skocaj
`
`et
`
`al.,
`
`Radiol Oncol.
`
`2011
`
`
`Dec;
`
`A5 (A):
`
`Z227-
`
`
`247) (Titanium dioxide nanoparticles:
`
`a
`
`
`review of
`
`current
`
`toxicological data, Hongbo Shi, Particle and Fibre Toxicology
`
`
`
`volume 10, Article number: 15
`
`(2013)).
`
`n T
`
`here
`
`is
`
`thus
`
`a need to provide more environmentally
`
`
`
`
`
`
`
`
`friendly and
`
`less
`
`toxic white pigments
`
`
`for dental health
`
`products such as toothpastes.
`
`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
`
`
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`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.
`
`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.
`
`
`
`10
`
`15
`
`
`A third object of
`
`
`
`process of
`fabricating the dental health product composition
`
`invention relates to a
`
`the present
`
`
`of
`
`the
`
`present
`
`invention,
`
`in particular
`
`the
`
`toothpaste
`
`
`composition of
`
`the present
`
`20
`
`adding a native starch,
`
`as white pigment.
`
`a porous starch or a mixture thereof
`
`invention, comprising the step of
`
`
`
`
`
`
`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/EP2021/050454
`
`As used herein
`
`the expression “dental health product”
`
` refers
`
`to
`
`toothpastes.
`
`toothpastes,
`
`chewing
`
`gums,
`
`and
`
`
`preferably
`
`
`
`As used herein the expression “native starch” refers to
`
`result
`from
`
`
`starch coming from n
`
`atural
`
`sources.
`
`
`
`enzymatic
`
`or
`
`chemic
`
`al
`
`processing methods. Typical
`
`It does not
`
`
`
`
`
`
`
`native
`
`legumes
`
`SOUrCEesS
`
`for
`
`the star
`
`ches are cereal,
`
`tubers,
`
`roots,
`
`
`
`and
`
`
`fruits.
`
`In the present
`
`invention, native starch may be
`
`10
`
`recovered
`
`
`from native
`
`
`
`
`
`sources such as
`
`tapioca, waxy tapioca,
`
`waxy potato, wheat, waxy wheat, waxy
`
`pea, potato,
`
`maize,
`
`maize,
`
`potato,
`
` waxy
`
`high-amylose maize, mung bean,
`
`rice, waxy rice,
`
`sweet
`
`sweet
`
`potato, millet,
`
`sago,
`
`sorghum,
`
`quinoa,
`
`amaranth,
`
`lotus
`
`root
`
`arrowroot,
`
`processes. Native st
`
`tarch is normally extracted using either
`
`and buckwheat by extraction
`
`wet milling or dry mill
`
`ing known process.
`
`
`
`
`
`
`
`first starch extraction process comprises
`An example of a
`
` following steps:
`
`
`
`
`grain kernels from foreign matters;
`
`steeping of
`
`the
`
`grain in water, alkaline solution or
`
`a
`
`15
`
`20
`
`the
`
`1)
`
`2)
`
`solution cont
`
`taining a reducing agent
`
`
`to J
`facilitate th
`
`3)
`
`25
`
`remove
`
`
`
`optionally,
`
`
`e separate of starch and protein;
`
`
`se grinding
`coar
`followed by hydrocyclone to
`
`
`the germ from the kernel;
`
` cleaning of
`
`
`
`to soften the kernels and
`
`
`
`
`
`the remaining grain kernel
`
`to release the
`
`
`
`4)
`
`
`fine
`
`
`fiber,
`
`
`grinding of
`
`protein, and starch;
`
`
`
`
`
`
`5)
`
`passi
`
`ing
`
`through
`
`screens wi
`
`th various opening sizes
`
`to
`
` tarch;
`
`separate
`
`fiber from protein and st
`
`30
`
`6)
`
`optionally,
`
`removing the excess water in slurry containing
`
`starch and protein;
`
`7)
`
`
`
`separating protein from starch by density,
`
`multiple-stage hydrocyclone;
`
`
`
`such as using
`
`
`
`
`

`

`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:
`
`i)
`
`
`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
`
`
`
`
`screens
`
`sizes;
`
`and/or
`
`filter cloths with large
`
`and
`
`
`fine opening
`
`5)
`
`concentrating starch slurry using two-
`
`or
`
`three-phase
`
`10
`
`15
`
`separator or a series of hydrocylone;
`
`6)
`
`
`dewatering the starch using centrifuge or high-pressure
`
`
`
` filtration or press filter;
`
`7)
`
`8)
`
`20
`
`
`drying the starch using flash dryer;
`
`recovering the dried starch.
`
`Advantageously,
`
`
`
`the extraction process is free of organic
`
`
`solvents and free of chemical reactants. There is no chemical
`
`Thus,
`
`the dental health products,
`
`and
`
`in
`
`
`transformation.
`
`
`
`25
`
`particular
`
`toothpastes,
`
`
`
`
`obtained from the extraction process
`
`dental health products,
`
`toothpastes.
`
`
`
`incorporating
`
`
`
`the
`
`can be
`
`native
`
`
`
`and
`
`in particular
`
`clean
`
`starch
`
`clean labeled
`
`labeled
`
`
`
`
`
`
`
`30
`
`
`
`
`
`The native starch useful
`for
`the present
`
`
`gelatinized but is under granular form.
`
`
`
`
`
`
`In a preferred embodiment of
`the present
`
`starch is a porous starch.
`
`
`
`invention is not
`
`invention,
`
`the
`
`
`
`
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`
`As used herein the expression “porous starch” refers toa
`
`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
`
`produced through an
`
`enzymatic hydrolysis
`
`
`
`
`of native
`
`starch
`
`such as a-
`
`
`
`the starch. The native starch
`
`
`
`
`
`
`
`
`
`granules with one or multiple amylolytic enzymes,
`
`10
`
`15
`
`amylase and amyloglucosidase, at a temperature inferior to the
`
`
`gelatinization temperature of
`
`granules may be based on tapioca, waxy tapioca, maize, pea,
`
`
`
`high-
`
`potato, waxy potato, wheat, waxy wheat, waxy maize,
`
`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
`
`the porous starch to
`
`weaken the granular structure prior
`
`25
`
`prior
`
`Lo
`
`
`physical modification
`
`
`
`to enzyme hydrolysis or
`
`(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/EP2021/050454
`
`on the surface with a diameter comprised between 0.01 um and 5
`
`
`
`yum, preferably between 0.05 pm and 2.5 wm, and more preferably
`
`
`
`between 0.1 pm 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
`
`diameter
`
`comprised between
`
`0.5
`
`wpm
`
`and
`
`200
`
`invention has
`
`a particle
`
`
`um, preferably
`
`
`
`
`between 1 pm and 100 pm, and more preferably between 2 um and
`
`60 ym.
`
`
`
`
`The particle diameter may be measured by laser diffraction
`
`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
`
`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
`
`
`
`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.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`Typical white pigments
`
`used
`
`in toothpaste
`
`are titanium
`
`dioxide.
`
`
`In a preferred embodiment of
`
`the presen
`
`t
`
`invention,
`
`the
`
`starch
`
`replaces
`
`up
`
` preferably up to 100%
`
`to
`
`30%, preferably up
`to 60% and more
`
`by weight of the titanium dioxide in the
`
`dental health
`
`product
`
`composition,
`
`in particular
`
`in
`
`toothpaste composition.
`
`the
`
`
`
`
`
`
`
`In a preferred embodiment of
`
`
`ts from 0.5 %
`
`native starch represen
`
`the present
`
`invention,
`the
`
`
`
`to 30%, preferably from 1%
`
`to 20%
`
`and more
`
`
`preferably from 2% to 15%,
`
`and even more
`
` preferably
`
`
`from 5
`
`to
`
`weight of
`
`the dental health product
`
`10% by weight with respect
`
`
`
`tL composition,
`
`to the total
`
`in particular
`
`
`
`
`
`
`15
`
` of
`
`the toothpaste composition.
`
`
`
`In a preferred embodiment of
`
`the presen
`
`t
`
`invention,
`
`the
`
`
`
`from 0.5% to 30%, preferably from 1%
`porous starch represents
`
`
`
`preferably from 2% to 15%,
`
`and even more
`
`preferably
`
`weight of
`
`to 20%
`and more
`
`
`
`from 5
`
`to 103%
`
`by weight with respect
`
`
`
`the dental health product
`
`tL composition,
`
`to the total
`
`in particular
`
` of the toothpas
`
`te composition.
`
` lL health
`
`
`10
`
`20
`
`25
`
`30
`
`
`
`
`The
`
`dental
`
`invention and in part
`
`product
`
`
`composition of
`
`the present
`
`
`the
`ticular the toothpaste composition of
`
`present
`
`invention may
`
`further comprise abrasives,
`
`
`surfactants,
`
`thickening agents and optionally additives.
`
`
`is the main part of
`that
`Abrasive is the powder material
`
`
` function of F
`
` formula,
`
`giving the
`
`tooth cleaning.
`
`the toothpaste
`
`
`
`ts function
`is to remove the dirt on the tooth surface,
`
` luster, and,
`
`at the same time,
`
`do not wear the teeth.
`
`give
`
`
`
`humectants,
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`Examples
`
`
`of
`
`suitable
`
`abrasives
`
`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
`
`
`
`In a preferred embodiment of the present
`
`invention, water
`
`represents from 0% to 40%, preferably
`
` from 10% to 30% and even
`
`to the
`
`
`more preferably from 15% to 25% by weight with respect
`
`
`total weight of
`
`
`
`preferably of the toothpaste composition.
`
`the dental health product
`
`composition and
`
`
`
`
`
`Humectant
`
`is used to keep the toothpaste within certain
`
`level of moisture, viscosity and smoothness,
`
`paste from hardening and to render
`
`to prevent
`
`the
`
`the paste easy to extrude
`
`
`
`
`
`from the tube;
`
`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
`
`the present
`
`invention,
`
`the
`
`are
`
`
`selected from glycerin,
`
`sorbitol,
`
`propylene
`
`
`
`humectants
`
`
`
`
`
`
`
`
`
`
`
`
`glycol, butanediol, polyethylene glycol and mixtures thereof.
`
`
`
`
`mM
`The humectants represent
`from 10%
`
`
`
`to 70%, preferably from
`
`respect
`
`
`
`to the
`
`
`
`20% to 60%, and more preferably from 30% to 5
`
`
`total weight of
`the
`dental health product
`
`
`
`composition, and preferably of the toothpaste composition.
`
`0% by weight with
`
`
`
`
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
` Sur
`factants
`
`are
`
`
`ability of
`
`decontaminati
`
`used to
`
`provide
`
`
`
`
`on and of
`Foaming.
`
`a
`
`toothpaste with the
`
`
`Examples of
`
`surfactants comprise,
`
`but are not
`
`limited to,
`
` monolaurate
`
`
`sodium
`
`lauryl
`
`sodium
`
`lauryl
`
`fate,
`
`sul
`
`alcohol
`
`sodium
`
`lauroylmethylamine
`
`acetate,
`
`
`sulfonate,
`
`sodium glyceryl
`
`
`sulfonate,
`
`sodium dioctyl sult
`
`
`
`fFonated succinate.
`
`10
`
`0.1% to 7%,
`
`to 4%,
`
`
`from 0.01%
`represent
`
`
`
`and more preferably
`from 1
`
`
`The surfactants
`
`to 10%, preferably
`
`
`
`by weight with
`
`respect
`
`to
`
`the
`
`total
`
`
`weight of
`
`the
`
`dental health product
`
`
`composition and preferably of
`
`the toothpaste composition.
`
`Thickening
`
`agents
`
`aim to
`
`provide
`
`a
`
`toothpaste with
`
`15
`
`texture,
`
`
`fluidity and stability.
`
`
`In a preferred emb
`
`
`odiment of
`
`the present
`
`invention,
`
`the
`
`thickening agents
`
`are
`
`selected
`
`
`from carboxymethyl
`
`cellulose,
`
`carrageenan,
`
`
`xanthan gum and mixtures thereof.
`
`20
`
`25
`
`The
`thickening
`
` from 0.1% to
`preferab] y
`
`
` health product
`t with respect
`
`by weigh
`
`compositi
`
`on.
`
`to 2%
`
` 106
`
`6
`
`°6
`
` from
`QO.01
`
`
`referably from
`
` of
`
`the
`
`dental
`
`the toothpaste
`
`
`
`
`weight of
`
`and preferably
`
`agents
`
`represent
`
`5%,
`
`and more
`
`to the
`
`total
`
`Pp
`
`composit
`
`ion
`
`
`In a preferred emb
`
`additives
`
`are
`
`selected
`
`
`
`odiment of
`
`
`from,
`
`the present
`
`
`Flavoring
`
`agents,
`
`preservatives,
`
`colorants,
`
`anti-tartar
`
`30
`
`
`mixtures thereof.
`
`agents,
`
`
`
`invention,
`
`the
`
`sweeteners,
`
`others
`
`and
`
`The additives represents
`
` from 0%
`
`to 10%,
`
`preferably
`
` from
`
`
`
`ae
`
`to 7%
`
`by weight,
`
`
`and more preferably
`
`weight
`
`with respect
`
`to the total weight of
`
`
`
`from 1% to 4%
`
`by
`
`the dental health
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`product
`
`composition
`
`and
`
`pre
`
`
`ferably
`
`
`
`the
`
`toothpaste
`
`composition.
`
`
`
`
`Flavoring agents well known in the art may be
`types of
`
`
`added to the den tal health product composition of
`
` All
`
`
`
`
`
`
`
` toothpaste composition of
`
`the present
`
`invention and in
`
`pa
`
`rticular of
`
`the
`
`
`
`tion.
`
`flavors,
`
`the presen t inven
`
`oils,
`
`synthetic
`
`
`
`not
`
`
`
`oils
`limited to
`
`
`fruit
`citrus oils,
`
`Flavoring agents may comprise essential
`
`and mixtures
`
`
`thereof
`
`including but
`
`derived from plants
`
`
`and fruits such as
`
`10
`
`15
`
`essences,
`
`peppermint
`
`oil,
`
`spearmint oil,
`
`
`se, and the like. Artificial
`
`
`f wintergreen,
`
`ani
`
`
`
`clove oil, oil o
`
` flavoring agents
`
`the art will
`
`Those skilled in
`
` ficial
`recognize that natural and arti
`flavoring
`
`can also be contemplated.
`
`
`
`agents may be combined in any sensorially acceptable blend.
`
`
`Examples of sweeteners comprise, but are not
`
`limited to,
`
`sodium sacharin, neotame, sucralose, aspartame, stevia extract
`
`
`
`
`
`
`(or steviol glycosides), acesulfame K, sugar alcohols
`
`
`
`(such as
`
`sorbitol,
`
`xylitol, maltitol,
`
`and
`
`erythritol),
`
`luohanguo
`
`20
`
`
`extract, and mixtures thereof.
`
`Preservatives
`
`
`refer
`
`to substances
`
`that prevent dental
`
`
`
`health
`
`
`
`
`
`products.
`
`Examples
`
`
`of
`
`
`
`from putrefying and deteriorating and extend
`
`health product
`
`
`life
`shelf
`
`
`
`of
`
`
`
`dental
`
`
`
`comprise, but
`
`the
`
`25
`
`preservatives
`
`
`
`are not
`
`limited to, methyl p-
`
`hydroxybenzoate,
`
`hydroxybenzoa
`
`
`
`
`
`
`te and mixtures thereof.
`
`propyl
`
`p-hydroxybenzoate,
`
`ethyl
`
`p-
`
`
`Examples of
`
`colorants
`
`comprise,
`
`but are not
`
`limited to
`
`30
`
`lutein,
`
`lycopene,
`
`zeaxanthin,
`
`brilliant blue,
`
`and mixtures
`
`
`thereof.
`
`10
`
`

`

`
`
`to, ethanol.
`
`
`
`
`
`WO 2021/144245
`
`PCT/EP2021/050454
`
`Examples
`
`
`of anti-tartar
`
`agents
`
`comprise,
`
`but
`
`are not
`
`
`limited to sodium mono?
`
` Fluorophosphate, and mixtures thereof.
`
`
`Examples of others additives comprise, but are not limited
`
`
`
`In a pret
`
`
`
`ferred embodiment of
`the present
`
`
`
`invention,
`
`dental
`
`health
`
`product
`
`composition
`
`and
`
`in particular
`
`the
`
`the
`
`
`
`10
`
`15
`
` from
`0.5% to 30%,
`
` ferabl
`
`y from 2%
`pret
`
`toothpaste composition comprises:
`
` preferably from 1%
`
`to 20% and more
`
`10%
`
`b
`
`y
`
`weight of
`
`
`weight of
`
`the dental
`
`to 15%,
`
` | hea
` nat
`
`
`and even more preferably from 5
`
`to
`
`ive starch with respect
`
`to the total
`
`lth product composition,
`
`in particular
`
`
`
`oO
`
`
`f the toothpaste composition,
`
`
`
`preferably from 1%
`
` from
`0.5% to 30%,
`
`
`
`Ferabl
`y from 2%
`pref
`
`to 15%,
`
`
`and even more preferably from 5
`
`to
`
`to 20% and more
`
`10%
`
`b
`
`
`weight of
`
`por
`
`ous starch with respect
`
`to the total
`
`y
`
`
`
`| hea
`
`the dental
`
`lth product composition,
`
`in particular
`
`weight of
`oO
`
`
`f the toothpaste composition,
`
`
`
`
`40%, preferably from 10% to 30%,
`
`and
`
`from 0% to
`
`from 15% to 25% by weight of water with
`ferably
`even more pret
`
`optionally
`
`
`
`
`
`
`
`the dental health product
`
`respect
`
`to the
`
`total
`
`
`weight of
`
`
`
`
`
`
`in particular of the toothpaste composition,
`
`
`
`
`from 10% to 70%, preferably from 20% to 60%,
`
`
`preferably from 30% to 50% by weight of humectant with respect
`
`
`to the total weight of
`the dental health product composition,
`
`
`in particular of
`the toothpaste composition,
`
`composition,
`
`-
`
`
`
`
`
`like calcium carbonate/dicalcium
`
`and more
`
`
`
`
`like
`
`
`
`to the total
`
`in particular
`
`
`
`
`
`
`
`50%,
`
`
` by weigh
`
`
`or
`
`f a
`
`silica)
`
`(high
`
`brasive
`
`
`from 25% to
`
`too
`te,
`thpas
`
`phosphat
`
`Le)
`
`weight
`
` of
`
`
`t of
`
`che dental heal
`
`oO
`
`
`f the
`
`toothpaste composition,
`
`11
`
`
`
` th product composition,
`
`
`abrasives with respect
`
`
`- optionally from 10% to 25% (low abrasive toothpaste,
`
`
`
`and preferably from 30% to 50%
`
`20
`
`25
`
`30
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`to
`
`10%,
`
`26
`
`from OQ.
`
`O1
`
` preferably 0.1% to
`
`
`surfactants
`to 4% by weight of
`
`
`the total weight of
`the dental health product composition,
`
`
`
`7%,
`
`and more
`
`with respect
`
`
`
`
`particular oft
`
`
`
`F
`
`the too
`
`thpaste composition,
`
`
`
`from 0.1%
`preferably
`
`to 5%
`
`,
`
`and more
`
`preferably
`
` from
`
`-
`
`to
`
`in
`
`-
`
`
`from 0.01%
`
` preferably
` from
`
`to
`
`103,
`
`1% to 2%
`
`
`by weight of
`
`thickening
`
`agents with
`
`total
`
`weight
`
` of
`
`the
`
`dental
`
`health product
`
`respect
`
`to
`
`composition,
`
`- op
`
`tionally
`
`the
`
`
`in particular of
`
`from 0%
`
`10
`
`weight,
`
`and
`
`more
`
`CO
`
`1%
`
`the toothpaste composition,
`
`
` from
`preferably
`103%,
`
` from
`preferably
`
`and
`
`0.1%
`
`to 7% by
`
`to 4% by
`
`weight
`
`
`of
`
`addit
`
`tives with
`
`respect
`
`to
`
`the
`
`total
`
`weight
`
`
`of
`
`the dental
`
`healt
`
`th product
`
`composition,
`
`in particular
`
` of
`
`the
`
`toothpaste
`
`composition.
`
`15
`
`The presen
`
`t
`
`invention
`
`also
`
`relates
`
`to a den
`
`product composition and in particular a toothpaste composition
`
`tal health
`
`
`
`20
`
`25
`
`30
`
`comprising a white pigment
`
`
`containing or consisting of
`
`native
`
`starch,
`
`a porous
`
`starch or
`
`a mixture
`
`
`thereof
`
`a
`
`as
`
`
`previously defined.
`
`
`
`In a preferred embodiment of
`
`the present
`
`invention,
`
`the
`
`composition
`
`does
`
`not
`
`comprise
`
`titanium dioxide
`
`as white
`
`pigment.
`
`
`
`Thanks to the speci
`fic dental health product composition,
`
`and
`
`in
`
`particular
`
`de
`fined it is possible
`
`toothpaste
`
` Lo
`
`composition,
`
`obtain a too
`
` th
`
`
`friendly dental health
`
`as
`
`previously
`
`having
`
`low
`
`
`
`product,
`
`and
`
`in
`
`particular
`
`toothpaste,
`
`
`fermentability,
`
`being
`
`noncariogenic
`
`and
`
`nonerosive,
`
`and
`
`
`all while having good mouthfeel
`
`
`
`without
`
`toleran
`
`ce
`
`issues
`
`at
`
`and
`
`good processing properties.
`
`In
`
`particular,
`
`the dental
`
`health
`product
`
`
` -ooth Friendly
`
`
`
`
`tooth friend]
`
`y
`
`and
`
`dental
`
`
`
`in
`
`particular
`
`the
`
`toothpaste
`
`1s
`
`a
`
`health
`
`product,
`
`and
`
`in
`
`particular
`
`
`
`flavor
`
`toothpaste,
`
`having
`
`a
`
`
`mouthfeel
`
`and
`
`12
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`
`delivery characteristics similar and even improved to that of
`
`a dental health product,
`
`with a
`
` native
`
`titanium dioxide
`
`porous
`and
`starch
`
`
`environmentally friendly white pigments.
`
`and in particular toothpaste, made
`
`as white pigment.
`
`In particular,
`
`starch
`
`are
`
`non-chemical
`
`and
`
`
`
`In the present
`
`
`invention “a toothfriendly dental health
`
`product”
`
`
`refers
`
`to a product
`
`that has
`
`
`
`low fermentability,
`
`
`
`
`
`in healthy people.
`
`
`refers
`
`to
`
`In
`
`a
`
`10
`
`15
`
`noncariogenic and nonerosive potential
`Mw
`
`
`toothfriendly toothpaste”
`
`same way,
`
`a
`
`the
`
` toothpaste
`
`
`
`nonerosive potential in healthy people.
`
`that
`
`has
`
`low fermentability,
`
`noncariogenic
`
`and
`
`
`
`
`
`
`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
`
`
`
`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
`
`
`
`a
`
`plaque-covered
`
`electrode.
`
`A dental health
`
`
`
` tested with
`
`
`
`
`
`
`product,
`
`low fermentability, noncariogenic and nonerosive potential
`
`and in particular toothpaste,
`
`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
`
`
`
`
`
`
`in the mouth thus the pH of
`
`
`
`
`native and porous starch were not easily fermented by bacteria
`
`consumption or
`
`
`the use of dental health product
`
`in particular
`
`13
`
`
`the interdental plague after the
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`the toothpaste does not drop to critical
`
`levels
`
`(PH 5.7).
`
`a preferred embodiment
`
` of
`
`the present
`
`invention,
`
` of
`
`In
`
`
`interdental plaque after
`
`the consumption or
`
`the
`
`the
`
`
`use of
`the
`
`
`
`
`
`
`
`dental health product
`
`composition
`
`and
`
`in particular
`
`the
`
`toothpaste
`
`composition
`
`does
`
`not
`
`to a
`
`pH
`
`below
`
`5.7,
`
`drop
`
`
` preferably the interdental plaque after the consumpt
`
`use
`
`
`of
`
`the dental health
`
`
`
`
`
`product
`
`tion or the
`
`
`
`composition
`
`has
`
`a
`
`pH
`
`comprised between 5.7 a
`
`7.
`
`10
`
`
`nd 7, and more preferably bet
`
`tween 6 and
`
`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.
`
`15
`
`
`Another aspect of
`
`the present
`
`invention is
`
`to make
`
`a
`
`
`
`
`toothfriendly dental health product composition and pret
`
`
`
`
`
`toothpaste composition
`
` toothpaste composition,
`
`
`mixture thereof as white pigment,
`
`flavor delivery charact
`
`
`that of a dental health
`
`
`
`with native starch, porous
`
`starch or
`
`
`while keeping mouthfeel
`
`and
`
`fFerably
`
`20
`
`25
`
`teristics
`
`Similar and even
`
`improved to
`
`product composition,
`
`made with a
`
`titanium dioxide as white
`
`and in particular
` starch and porous starch
`
`pigment.
`
`In particular
`
`f
`
`native
`
`are
`
`non-chemical
`
`and environmentally
`
` friendly white
`
`pigments
`
`and
`
`do not have tolerance issues.
`
`
`
`as
`
`previously
`
`defined,
`
`
`
`
`Thus, another object of the present invention
`
`
`
`
`process of
`fabricating
`
`the dental health product composition
`
`
`
`relates
`
`Lo a
`
`
`
`
`
`in
`
`particular
`
`the
`
`toothpaste
`
`
`composition as previously deft
`Fined,
`
`comprising
`
`the
`
`
`step of
`
`30
`
`adding native starch,
`
`porous
`
`starch or mixture
`
`
`thereo?
`
`fF
`
`as
`
`white pigment.
`
`14
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`
`In a preferred embodiment,
`
`
`invention does not comprise a step of adding titanium dioxide
`
`the process of
`
`the present
`
`
`
`
`composition of
`
`the present
`
`
`as white pigment.
`
`
`The dental health product
`
`
`
`
`
`invention and in particular the toothpaste composition may be
`
` 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.
`
`10
`
`15
`
`20
`
`15
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`Brief description of the drawings:
`
`Figure
`
`1:
`
`
`scanning electron micrograph of porous waxy
`
`maize starch
`
`
`
`Figure 2: pH-telemetry results of the toothpaste made with
`
`
`native waxy maize starch of example 1.
`
`
`
`Figure 3: pH-telemetry results of the toothpaste made with
`
`
`porous waxy maize starch of example
`
`5
`
`10
`
`16
`
`

`

`WO 2021/144245
`
`EXAMPLES
`
`PCT/EP2021/050454
`
`In
`
`the
`
`
`following
`
`examples,
`
`the
`
`
`following
`
`commercial
`
`products are
`
`used:
`
`- Neosorb 70
`/70B (liquid sorbitol) commercialized by Roquette
`
`- Sodium lau
`ryl sulfate commercialized by Sinopharm
`
`
`- Carboxymet
`
` hyl cellulose commercialized by Ashland
`
`
`
`- Ethanol commercialized by Sinopharm
`
`
`
`- Flavor commercialized by IFF
`
`- Sodium sac
`
`charin commercialized by Sinopharm
`
`- Methyl p-h
`
`- Propyl p-h
`
`
`
`ydroxy benzoate commercialized by Sinopharm
`
`ydroxybenzoate commercialized by Sinopharm
`
`- Sodium mon
`
` ofluorophosphate 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 extra
`
`ction process described in the description.
`
`
`
`10
`
`15
`
`25
`
`30
`
`
`
`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.
`
`3. Adding
`
`thermosable
`
`a-amylase
`
`(Liquozyme
`
`Supra
`
`
`from
`
`Novozymes, 2.67 mg enzyme/g dry starch)
`
`and reacting at
`
`r 4 hours.
`
`55°C fo
`
`4. Stopping the reaction by adjusting the pH to 3-3.5 using
`
`5% hydr ochloric solution and holding for one hour.
`
`
`
`3.3% sodium
`
`5. Adjusting back
`
`the
`
`pH to 4.5-5.5 using
`
`hydroxide solution.
`
`the starch slurry to about 25°C.
`
`6. Cooling
`
`
` the cake with decarbonated water.
`
`7. Press
`
`filtering the slurry to obtain porous starch cake.
`
`38. Washing
`
`17
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`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
`
`
`of
`
`abrasivity and
`
`
`
`fermentability of
`
`toothpaste made using native waxy maize starch
`
` f the toothpaste sample to be tested is presented
`
`10
`
`The recipe o
`
`in table 1.
`
`Ingredients
`
`Percentage by
`
`Neosorb 70/70B
`
`Waxy maize starch (white
`
`pigment/potential abrasive)
`
`Sodium lauryl
`
`
`(sur factant)
`
`
`
`
`
`
`
`
`
`(anti-tartar agent)
`
`
`Carboxymethyl cellulose
`
`(thickening agent)
`
` Ft
`
`Flavor
`
`
`(flavoring agent
`
`Sodium saccharin (sweet
`
`
`
`
`
`1 p-hydroxy benzoate
`
`(preservative)
`
`
`
`
`
`propyl p-hydroxybenzoate
`
`(preservative)
`
`
`Sodium monofluorophosphate
`
`Table 1
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`
`The toothpaste sample was prepared according to the following
`
`
`
`protocol:
`
`1.
`
`
`Preparing a first solution by dissolving sodium saccharin
`
`
`and sodium monofluorophosphate in water at 50°C.
`
`
`
`2.
`
`Preparing a second solution by adding the preservatives to
`
`
`
`
`
`the NEOSORB
`
`70/70B sorbitol
`
`solution
`
`is
`
`then
`
`cooled
`
`to
`
`solution at
`
`80°C. This
`
`second
`
`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.
`
`Adding
`
`sodium lauryl
`
`
`sulfate
`
`solution
`
`and
`
`ethanol,
`
`
`
`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
`
`described in Imfeid, 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).
`
`The
`
`sample has been tested in a volunteer having a 5-day old
`
`plaque.
`
`25
`
`30
`
`
`Results are shown on figure 2.
`
`
`
`
`
`on
`shown
`As
`figure
`
`demonstrated that
`the
`toothpaste sample was not associated
`
`2,
`
`the obtained plaque
`
`pH-curve
`
`19
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`
`with a depression of
`
`interdental plaque pH below 5.7,
`
`neither
`
`during nor
`
`
`ait
`
`Fter 30 min of
`
`swirling the toothpaste slurry in
`
`the mouth.
`
`The
`
`water rising
`
`(W)
`
`
`increase of
`
`
`and paraffin chewing (PC) as well as the drop
`
`the interdental plaque pH during
`
`
`
`
`
`
`
`
` of
`
`the
`
`control
`
`proper
`
`treat
`
`tment
`
`
`
`
`functioning
`
`interdental
`
`plaque
`
`pH below 5
`
`following positive
`
`(with 10% sucrose solution) demonstrated the
`
`obtained
`curve with
`pH
`
`demonstrated that
`the
`tested product also lacked of
`
`of
`
`
`
`the
`
`plaque-covered
`
`electrodes.
`
`The
`
`the
`
`plaque-covered
`
`electrode
`
`an erosive
`
`
`
`
`
`10
`
`potential.
`
`Thus,
`
`the toothpaste sample made using waxy maize
`
`starch has
`
`low
`
`
`fermentability
`
`(pH25.7).
`
`15
`
`The abrasion
`
`(RDA) of
`
`the toothpaste
`
`Sa
`
`mple made using waxy
`
`maize starch was tested according to the
`
`following protocol.
`
`Six bovine tooth roots were radioactivel
`
`the irradiation,
`
`irradiated. Due
`
`to LO
`
` y
`
`20
`
`25
`
`30
`
`
`the phosphorus of
`
`the apatite was changed
`
`radioactive #3#4P and gamma
`an acrylic re
`
`
`
`sin and later brushed using an automatized 8
`
`radiation. The roots were embedded in
`
`placebrushing
`
`machine
`
`
`for
`
`25 min with
`
`a
`
`total
`
`
`of
`
`1,500
`
`horizontal brushing strokes
`
`(60 strokes per min).
`
`The brushing
`
`load was amounted to 2.5 N.
`
`As a ret
`
`
`ference toothbrush,
`
`manual
`
`toothbrushes with a plane bristle layout
`
`
`
`Esro AG) were used. The brushing medium was either a slurry
`
`
`prepared from the toothpaste sample or a slurry prepared from
`
`(Paro M43 medium,
`
`
`
`abrasive.
`
`
`40 mL artificial
`
`For
`
`the
`
`slurry preparation,
`
`25
`
`og
`
`
`
`
`
`saliva and 50 wh silicon anti
`
`
`
`a
`
`standard
`
`
`
`toothpaste,
`
`anti-frothing agent
`
`
`
`
`
`g
`
`
`
`
`(Fluka Chemie) were dispersed for
`
`The standard slurry was prepared by mixing 10 g ISO Sident,
`
`
`solution from carboxymethyl
`
`
`
`(10%) und artificial saliva. The brushing runs were performed
`
`cellulose
`
`(0.5%),
`
`glycerine
`
`technique.
`
`The
`
`first
`
`run was
`
`20
`
`in
`
`a
`
`so-called “sandwich”
`
`
`
`5 min.
`
`50
`
`
`
`

`

`WO 2021/144245
`
`PCT/EP2021/050454
`
`
`formed with the standard abrasive slurry,
`per
`
`with
`the
`toothpaste
`
`and
`
` finally
`
`slurry
`
` followed by a
`
`run
`
`with
`
`the
`
`stan
`
`dard
`
`abrasive slurry.
`
`A
`fter each run,
`
`
`0.5 g of
`
`the used slur
`
`ries
`
`were pipetted and the
`
`32P-irradiation
`
`in
`
`“decays per minute”
`
`(dpm)
`
`were measured
`
`with
`
`a
`
`Phosphorimagers®
`
`(Molec
`
`Dynamics).
`
`