8 Cosmetics
Cosmetics have been used since prehistoric times.
Over the years, cosmetics have been developed in
many different formulations and forms whether as
powder, liquid, gel, or cream. These different formu-
lations and forms have been used for a host of topical
uses.
Conventional cosmetics contain polymers derived
from fossil fuel resources and/or minerals, which
are not biodegradable. Particular reference is made
to cosmetic powders made of nonbiodegradable
polymers such as polyethylene, polypropylene, and
polystyrene that are used for a variety of cosmetic
products such as cleansing, makeup, and sunscreen
products. The microparticles of these cosmetic prod-
ucts after use end up in the wastewater stream, and
eventually enter the aquatic environment. These
microparticles are of particular concern because the
relative density of polyethylene and polypropylene is
less than 1.0, resulting in the potential for micropar-
ticles to float, and remain suspended in the water and
travel long distances, where they can be ingested by
marine organisms and enter the food chain. Mic-
roparticles made of nonbiodegradable polymers such
as polypropylene, and particularly polyethylene, can
also absorb and concentrate organic contaminants
and transport these compounds to marine organisms
(2014, US2014026916 A, COLLEGE WILLIAM &
MARY).
Biodegradable polymers represent a viable alter-
native toward the quest of finding environmentally
friendly materials that could replace conventional
polymers in the cosmetics and health care products.
The cosmetics industry place very high demands
on the various ingredients of a cosmetics product.
Therefore, the biopolymers shall not contain toxic
substances, and shall not cause skin irritations,
including various inflammation symptoms or signs,
when applied to the skin or mucosa. Furthermore, the
new materials shall be competitive to the nonbiode-
gradable polymers in terms of cost and properties,
and shall comply to the high standards of the cosmet-
ics industry.
Biopolymers: Applications and Trends. http://dx.doi.org/10.1016/B978-0-323-35399-1.00008-9
2015 Published by Elsevier Inc. All rights reserved.
Examples of the types of cosmetic products
include:

cleansing products such as facial cleansing
cream, soap, body shampoo;
basic skin care products such as skin toners,
creams, emulsions, packs;

base makeup products such as powders,
foundations;
other facial cosmetic products such as lipstick,
blusher, eye shadow, eyeliner, mascara;
makeup products for manicures, pedicures;

hair care products such as shampoos, hair
rinses, hair conditioners, hair treatments, set-
ting lotions, blow styling lotions, hairsprays,
foam styling agents, gel styling agents, hair
liquid, hair tonic, hair cream, hair growth
tonic, hair growth stimulants, hair dyes, hair
dressings;
aromatic cosmetic products such as perfumes,
eau de colognes;
bath preparations, toothpastes; and

special cosmetic products such as sunscreen
products, depilatories, aftershave lotions, anti-
perspirants, and deodorants.
Cleansing products, skin products, makeup prod-
ucts, hair care products, and sunscreen cosmetic
products have been using biodegradable polymers in
their preparations.
Biopolymers are also used for the manufacture of
various articles and accessories for the handling of
cosmetics, as well as for the packaging of cosmetics.
There is nowadays a trend to use bio-based nonbiode-
gradable polymers as containers, bottles, casings, and
the like as replacements of corresponding polymers
derived from fossil fuel resources; for instance, bottles
made of bio-based polyolefins, especially polyethyl-
ene, are used in a series of cosmetic products.
407
408
8.1 Cleansing Preparations
Cleansing preparations are popular for their ability
to remove dirt, greasy residues, such as excess sebum,
dead skin cells, and remnants of cosmetic products
from the skin or hair of the consumer. Cleansing
preparations are available in powder, liquid, or cream
form. Examples of the types of cleansing cosmetic
products include facial and body cleansers.
8.1.1 Scrubs, Exfoliants
Many facial and body cleansing products use
suspended microparticles to mechanically scrub or
exfoliate the skin and remove oil, dirt, dead skin,
and other debris. A personal cleansing composi-
tion contains usually polyethylene microparticles
which are not biodegradable. After using a personal
cleansing product, the consumer typically washes
the skin with water. As a result, large amounts of
polyethylene microparticles are washed down the
drain, wherein they can cause problems in waste-
water treatment, find their way into water courses
and end up in the sea, where they cause irreparable
damage to marine ecosystems. Moreover, polyeth-
ylene microparticles typically have an unpleasant
odor that needs to be masked when making facial
and body cleansing products (2011, US2011275550
A1, CERVINO KIM).
Natural alternatives for polyethylene microparti-
cles are, for example, exfoliating products made from
shells, kernels, bamboo, rice, natural waxes, micro-
crystalline cellulose, poly(lactic acid) (PLA), or min-
erals. However, all these ingredients are inferior in
all their characteristics compared to polyethylene
(i.e., white color, stability, abrasiveness, suspension
capacity, etc.) [1].
JP2007197602 A (2007, ASAHI KASEI CHEMI-
CALS CORP.) discloses a skin and/or hair cleans-
ing composition comprising PLA-based fine powder
of an average particle diameter of 50300m as a
scrubbing agent.
US2011275550 A1 (2011, CERVINO KIM) dis-
closes a personal cleansing composition including a
surfactant, a thickener, an emulsifier, and at least one
particle dispersed in the thickener formed of a sub-
stantially biodegradable substance including a soy
meal-based polymer. The soy meal-based polymer is
used to replace portions of the current nonbiodegrad-
able polyethylene as a scrubbing agent, exfoliant, or
even as filler to add volume or weight to the compo-
sition. The amount of soy meal-based polymer used
Biopolymers: Applications and Trends
will depend on the type of personal care product (e.g.,
foot scrub, facial scrub, skin softener, body wash,
body scrub, scalp scrub, toothpaste, or as an exfoli-
ant in pet care products). In some embodiments, the
soy meal-based polymer forms 0.00130 wt% of the
composition. The half-life of the composition may be
modified as necessary based on the shelf life of the
product. The soy meal-based particle provides also
an improved odor profile as compared to traditional
polyethylene particle compositions. Table 8.1 shows
the composition of a facial cleansing lotion with soy
meal-based micronized biodegradable polymer.
US2011287105 A1 (2011, MICRO POWDERS
INC.) discloses a cosmetic powder composition for
topical use comprising 110wt% of a micronized
PLA and 320wt% of a carrier. The powder com-
position has an average particle size of 0.144m,
preferably, 520m. The powder composition is use-
ful for cleansing and/or removing makeup from the
skin, the eyes, the scalp and/or the hair; for use as
soap scrubs, foot scrubs, exfoliating face scrub, body
scrubs, creams, liquids, gels, and lotions. Table 8.2
shows the composition of a foaming body scrub com-
prising micronized PLA.
JP2012233057 A (2012, SUZUKI YUSHI
KOGYO KK) discloses a skin cleansing composi-
tion comprising a biodegradable scrubbing agent,
wherein the scrubbing agent is formed by cur-
ing a mixture of a melted or dissolved biodegrad-
able polymer with a natural vegetable powder.
The biodegradable polymer is selected from PLA;
poly(glycolic acid) (PGA); poly(-caprolactone)
(PCL); polyhydroxyalkanoates (PHAs) such as
poly(3-hydroxybutyrate) (P3HB), poly(3-hydroxy-
butyrate-co-3-hydroxyhexanoate) (PHBHHx);
poly(alkylene alkanoate)s such poly(butylene suc-
cinate) (PBS), poly(butylene succinate-co-adi-
pate), poly(butylene succinate-co-terephthalate),
poly(ethylene sebacate), and the like; starch fatty
acid; cellulose acetate; chitin; chitosan consisting of
coconut shell powder. The natural vegetable powder
is selected from starch flour, wood powder, bam-
boo powder, and the like. The biodegradable scrub-
bing agent is claimed to have an excellent cleaning
effect, and not to pollute the environment.
JP2007077311 A (2007, ASAHI KASEI CHEMI-
CALS CORP.) discloses in one of its embodiments an
abrasive detergent capable of safely and easily clean-
ing objects and human bodies required for the effect
of removing a tough dirt such as of a cutting oil or a
grease having a high viscosity. The abrasive detergent
comprises a porous abrasive having irregular shapes
8: Cosmetics 409

Table 8.1 Facial Cleansing Lotion with Soy Meal-Based Micronized Biodegradable Polymer
(2011, US2011275550 A1, CERVINO KIM)
Phase Ingredient Amount (wt%)
A Water 45.55
A Carbomer 0.25
B Ammonium lauryl sulfate 4.0
B Sodium lauryl sulfate 25.00
B Cocamidopropyl betaine 10.00
C Glycol distearate 1.50
D Cocamide MEA 3.00
D Soy meal-based micronized polymer 0.30
E Caprylyl glycol+phenoxyethanol+hexylene 0.5

MEA, Monoethanolamine.

Table 8.2 Foaming Body Scrub (2011, US2011287105 A1, MICRO POWDERS INC.)
Product name INCI name % Supplier

Phase A
Deionized water Water 51.20 N/A
Carbopol Ultrez 20 Carbomer 0.60 The Lubrizol Corp.
Phase B
Propylene glycol Propylene glycol 3.50 Many
Germaben II Propylene glycol, 1.00 International Specialty
diazolidinyl urea, Products
methylparaben,
propylparaben
Phase C
Protachem ES-2 Sodium laureth sulfate 21.00 Protameen Chemicals Inc.
Proteric CAB-LC Cocamidopropyl 7.00 Protameen Chemicals Inc.
Protasorb L-20 Polysorbate 20 1.50 Protameen Chemicals Inc.
Protamide CME Cocamide MEA 3.50 Protameen Chemicals Inc.
Phase D
Deionized water Water 3.00 N/A
Disodium EDTA Disodium EDTA 0.05 Many
Phase E
Triethanolamine 99% Triethanolamine 0.65 Many
Phase F
EcoScrub 20PC PLA 7.00 Micro Powders, Inc.

EDTA, Ethylenediaminetetraacetic acid; PLA, Poly(lactic acid), polylactide.

 410
formed of flocculated or connected approximate
spheres. The abrasive preferably has a bulk density
in the range of 0.010.35g/cm3. The materials for the
abrasive include, among other things, biodegradable
polymers such as PLA and PBS and crystalline cel-
lulose or chitosan.
US2014026916 A (2014, COLLEGE WILLIAM
& MARY) discloses in one of its embodiments the
use of PHA microbeads in exfoliating scrub formu-
lations. The PHA microbeads were obtained from
Metabolix (Mirel M2100 and Mirel M2200) and
Shenzhen Ecomann Biotechnology Co. (Ecomann
PHA). PHA microbeads can be incorporated into an
exfoliating scrub as follows:
Part A
1. Propylene glycol 30.00
2. Glycerin, 30.00
3. Methyl Gluceth-20, 33.30
4. 
Acrylates/C10-30 Alkyl acrylate polymer,
Carbopol Ultrez 20 polymer 1.00.
Part B
5. Fragrance, 0.50
6. PHA microbeads (4.19.2m), 3.80
7. Sodium magnesium aluminum silicate, liqui-
bead 10PC Red D2, 0.50
8. Euterpe oleracea pulp powder, 0.10
9. 
Phenoxyethanol and ethylhexylglycerin,
Euxyl PE 9010, 0.80 preservative.
The PHA microbeads have reduced circularity,
and are useful for cleaning body surfaces. These
abrasive PHA microbeads can have varying degrees
of hardness depending on the desired application,
and typically have hardness in the range 14 on the
Mohs hardness scale.
The PHA microbeads once rinsed and subse-
quently released into aquatic environments, sink to
the bottom of the aquatic environment. The PHA
microbeads are then sequestered by sediment-
dwelling organisms such as clamworms, or can be
buried or incorporated into structures such as tubes.
Once sequestered, the PHA microbeads are not eas-
ily resuspended, and can quickly break down into
benign monomers and oligomers.
A commercial exfoliant that is currently in the
market is Celluloscrub (Lessonia, FR) that is a
renewable and biodegradable exfoliating white scrub
Biopolymers: Applications and Trends
made of modified cellulose extracted from wood
pulp. Celluloscrub is available in three grades
(Celluloscrub 1000, Celluloscrub 500, and Cel-
luloscrub 300) and intends to replace the polyeth-
ylene beads in cosmetic products [2].
8.1.2 Blotting Sheets or Films
Sebum-absorbing/blotting sheets or films have
been widely used as disposable skin care prod-
ucts. As a sebum-absorbing raw material for the
face, linen was initially used, but recently, paper
is used from the viewpoint of the cost. However,
the sebum absorption effect of a sebum-absorbing
paper is lower than that of a sebum-absorbing linen
(2008, US2008226580 A1, RIKEN). In order to
improve the effect, JP2000139755 A (2000, MIKI
TOKUSHU PAPER MFG CO LTD.; SILK KOGEI
KK) discloses a sebum-absorbing paper in which
silk yarn manufactured from silk or waste silk
thread which occurs in a spinning is cut to lengths
of 110mm, is then subjected to alkali cooking, and
is further refined to mix raw silk yarn-fibrillated
silk fiber pulp (1060wt%), vegetable fiber pulp
(9040wt%), and a small amount of inorganic
loading material uniformly in water. Then paper is
manufactured, and the paper sheet is calendered,
densified, and glazed to obtain the sebum-absorbing
paper. The sebum-absorbing paper is claimed to
be not only superior in sebum-absorbing proper-
ties but also in sweat absorbing and stain removing
properties, simultaneously removing sebum, sweat,
and stain, resistant to breaking in use, satisfactory to
the touch, superior in properties in removing stain
from irregularities in the skin, without irritating the
skin. In spite of these claims, it is asserted that a
sufficient sebum absorption effect has not been
achieved yet (2008, US2008226580 A1, RIKEN).
Porous thermoplastic sebum-absorbing films or
sheets made of fossil fuel-based resources have also
been prepared. Although these sebum-absorbing
products have higher sebum absorption effect com-
pared to the sebum-absorbing paper, they are not
biodegradable.
JP2001078914 A (2001, COSMETICS ROO-
RANDO KK) discloses an oil absorbing film made
of a mixture of a crystalline polyolefin (5570wt%),
vinyl acetate (515wt%), a biodegradable polymer
(2030wt%), an inorganic filler (530wt%), a water-
absorbing polymer (110wt%), and a pigment (0.5
10wt%). The biodegradable polymer is preferably
8: Cosmetics
starch. The water-absorbing polymer is poly(acrylic
acid). In a preferred embodiment, the film is formed
into a bag. The oil absorbing film is used to wipe
sebum and sweat secreted on the skin of the face,
and to reduce the influence of an oil absorbing film
on the environment when it is disposed of after use.
However, not every component of the mixture is
biodegradable.
JP2004248910 A (2004, JAPAN VILENE CO
LTD.) discloses a sebum-wiping sheet for skin made
of a mixture of PLA fibers (50wt%), including non-
meltable PLA fibers and meltable PLA fibers, and
inorganic powder and/or biodegradable organic pow-
der. In another embodiment, the sebum-wiping sheet
is made of PLA fibers, a PLA binder, and inorganic
powder and/or biodegradable organic powder. The
PLA fibers are preferably made of Terramac fibers
(Unitika, Ltd.). The sebum-wiping sheet is environ-
mentally friendly. However, with respect to the raw
materials of this technique, each material alone does
not demonstrate the biodegradable effect and are not
completely biodegradable (2008, US2008226580
A1, RIKEN).
US2008226580 A1 (2008, RIKEN) discloses
in one of its embodiments a sebum-absorbing film
made of PHAs. A preferred PHA is PHBHHx. The
sebum-absorbing film has a porous structure, and
is claimed to show outstanding oil absorption abil-
ity, oil retention ability, and change in transparency
when in contact with oil. The PHA-based sebum-
absorbing film, when discarded, is decomposed at
a place where microbial activity is observed, such
as compost, a landfill of refuse, soil, an underwater
environment, a marine environment, mangroves, and
a wastewater treatment tank. The PHA-based sebum-
absorbing film can be decomposed under either aero-
bic conditions or anaerobic conditions, and can be
flushed down a toilet.
WO02100357 A1 (2002) and JP2003073233 A
(2003) of UNITIKA LTD. disclose a cosmetic prod-
uct comprising biodegradable polyester micropar-
ticles, wherein the microparticles are formed from
a PLA with a d-lactic acid content of 0.125mol%.
The density of the microparticles is 1.010.0g/cm3,
the average particle diameter is 0.011000m, the of formulations, such as powder, liquid, cream, pen-
10% deformation strength during compression is
5MPa or more, and at least 70% of the microparticles
have a major axis length/minor axis length ratio of
at least 1.5. The cosmetic product is claimed to have
high microparticle strength and be highly effective in
improving tactility (moist or smooth feel), improving
411
slip quality during application to the skin. Lactic acid
released by PLA is present in the cosmetic product,
making it easier to keep the skin mildly acidic. The
cosmetic product is preferably used as skin care prod-
uct and makeup product. Examples of the physical
states of this cosmetic product include aqueous liq-
uid, oil-based liquid, emulsion, cream, foam, semi-
solid, solid, and powder. It is also possible to use this
cosmetic product by spraying.
Example: A cosmetic cream was prepared as fol-
lows: 20pbw of PLA microparticles, 5pbw p-octyl
methoxycinnamate, 1pbw of -monoisostearyl glyc-
eryl ether, polyoxyethylene sorbitan ester, monooleic
acid ester as a fatty acid ester, 2pbw of beeswax as
a wax, 2pbw of lanolin as a wax, 20pbw of squal-
ane as a hydrocarbon, 30pbw of liquid paraffin as a
hydrocarbon, 19pbw of purified water, an adequate
amount of a preservative, and an adequate amount of
perfume were placed in a homodisperser and mixed
for 3min at 2500rpm to prepare an emulsified cos-
metic product.
The PLA microparticles were prepared as follows:
40pbw of PLA (number-average molecular weight:
Mn=60,000; content of the D-form: 1.7mol%) dried
until the moisture content reached 200ppm, and
60pbw of poly(acrylic acid) (weight-average molec-
ular weight: Mw=1,000,000) as a dispersion medium
were dry blended and fed to the feed port of a one-
way twin-screw extruder. The cylinder temperature
of the extruder was set to 180C, the materials were
melted and kneaded, and the resin composition was
extruded from the nozzle, cooled, and solidified.
The poly(acrylic acid) was then dissolved using an
amount of water 10 times the mass of the poly(acrylic
acid), and a suspension of PLA spherical particles
about 10m in diameter was obtained. This suspen-
sion was centrifuged and dried to obtain the PLA
microparticles.
8.2 Makeup and Other Facial
Preparations
Makeup in todays marketplace comes in a variety
cils, gels, sticks, and more. Often, it is necessary to
blend these products to produce colors and consisten-
cies during application for a desired effect.
JPH05194141 A (1993, MITSUBISHI CHEM
IND) discloses a cosmetic containing a biodegradable
polyester powder made of PHA such as P3HB having
412
an average particle diameter of 350m, preferably
535m. The cosmetic can be used as face powder,
foundation, lipstick, blusher, eyeliner, mascara, eye
shadow, foundation cream, emulsion, lotion, cream,
etc. The cosmetic is claimed to have improved in slip
characteristics, dryness feeling, moisture retention,
and excellent performance. The PHA powder causes
no problems such as skin irritation even when large
amounts of these particles are contained therein.
KR101248973 B1 (2013, BIOGENICS INC.)
discloses a makeup composition containing a sur-
face-treated carbon black (100). The carbon black
contains: 5.030.0wt% of a carbon black core (10);
1.010.0wt% of a cationic organic layer (20) on
the carbon black core; 0.15.0wt% of an organic
binder layer (30) which is coated on the surface of
the cationic organic layer; and remaining amount
of water (Figure 8.1). The cationic organic layer is
ion-adsorbed on the surface of the carbon black core.
The cationic organic layer contains a cationic surfac-
tant, a cationic polymer, fatty amines, and a mixture
thereof. The organic binder layer contains, PCL, ethyl
cellulose, PLA, PGA, and poly(lactide-co-glycolide)
(PLGA).
WO02100357 A1 (2002) and JP2003073233 A
(2003) of UNITIKA LTD. disclose a cosmetic prod-
uct comprising biodegradable polyester micropar-
ticles, wherein the microparticles are formed from
a PLA with a d-lactic acid content of 0.125mol%.
The density of the microparticles is 1.010.0g/cm3,
the average particle diameter is 0.011000m, the
10% deformation strength during compression is
5MPa or more, and at least 70% of the micropar-
ticles have a major axis length/minor axis length
Figure 8.1Surface-treated carbon black of a makeup
composition (2013, KR101248973 B1 (2013, BIO-
GENICS INC.)). 10, Carbon black core; 20, Cationic
organic layer; 30, Organic binder layer; 100, Surface-
treated carbon black.
Biopolymers: Applications and Trends
ratio of at least 1.5. The cosmetic product is claimed
to have high microparticle strength and be highly
effective in improving tactility (moist or smooth
feel), improving slip quality during application to
the skin. Lactic acid released by PLA is present in
the cosmetic product, making it easier to keep the
skin mildly acidic and to obtain a cosmetic prod-
uct that is mild on the skin. The cosmetic product
is preferably used as makeup product and skin care
product. Examples of the physical states of this
cosmetic product include aqueous liquid, oil-based
liquid, emulsion, cream, foam, semisolid, solid, and
powder. It is also possible to use this cosmetic prod-
uct by spraying. Example: A cosmetic cream was
prepared as follows: 20pbw of PLA microparticles,
5pbw p-octyl methoxycinnamate, 1pbw of alpha-
monoisostearyl glyceryl ether, polyoxyethylene sor-
bitan ester, monooleic acid ester as a fatty acid ester,
2pbw of beeswax as a wax, 2pbw of lanolin as a
wax, 20pbw of squalane as a hydrocarbon, 30pbw
of liquid paraffin as a hydrocarbon, 19pbw of puri-
fied water, an adequate amount of a preservative,
and an adequate amount of perfume were placed in
a homodisperser and mixed for 3min at 2500rpm to
prepare an emulsified cosmetic product.
The PLA microparticles were prepared as follows:
40pbw of PLA (number-average molecular weight:
Mn=60,000; content of the D-form: 1.7mol%) dried
until the moisture content reached 200ppm, and
60pbw of poly(acrylic acid) (weight-average molec-
ular weight: Mw=1,000,000) as a dispersion medium
were dry blended and fed to the feed port of a one-
way twin-screw extruder. The cylinder temperature
of the extruder was set to 180C, the materials were
melted and kneaded, and the resin composition was
extruded from the nozzle, cooled, and solidified.
The poly(acrylic acid) was then dissolved using an
amount of water 10 times the mass of the poly(acrylic
acid), and a suspension of PLA spherical particles
about 10m in diameter was obtained. This suspen-
sion was centrifuged and dried to obtain the PLA
microparticles.
8.3 Hair Care Preparations
Hair care cosmetic products include hair sham-
poos, hair rinses, hair tints and bleaches, hair condi-
tioners, hair treatments, setting lotions, blow styling
lotions, hairsprays, foam styling agents, gel styling
agents, hair liquid, hair tonic, hair cream, hair growth
8: Cosmetics
tonic, hair growth stimulants, hair dyes, hair dress-
ings, and the like.
A hair shampoo is designed to remove oils, dirt,
skin particles, dandruff, environmental pollutants,
and other contaminant particles that gradually build
up in hair, without eliminating all surface lipids as
sebum. Shampoos are usually sold in liquid format,
most commonly in bottles containing enough sham-
poo for several hair washes.
US2004202632 A1 (2004, UNILEVER HOME &
PERSONAL CARE) discloses solid cosmetic com-
positions comprising a water dissolvable solid car-
rier incorporating at least one cosmetic agent. The
solid carrier is a destructurized starch. Fragrance is
applied topically onto the solid carrier. The composi-
tions are best formed into tablets, pellets, or beads.
Particularly preferred is where the solid cosmetic
composition and carrier are foamed. Indicative uses
include shampoo solid, conditioning shampoo solid,
hair cream solid, and hair color composition. Other
uses include suntan lotion shampoo solid, foam bath
solid, soluble bath oil solid, cleansing cream solid,
skin lotions, hand lotion, facial moisturizer, baby
cleanser, and depilatory solid.
Example: A shampoo solid is prepared by warm-
ing fatty or oil-based materials to 70C to achieve
fluidity. Other liquid or solid nonmeltable materials
are then dispersed into the resultant mass with thor-
ough mixing. The product resulting therefrom is then
added with mixing to a high amylose destructurized
corn starch. This formed mass is then extruded at a
temperature of 150250C, and shaped. Fragrance is JP2006193432 A, MUKAI TAKASHI)
sprayed onto the shaped mass. The formulation of the
shampoo solid is listed in Table 8.3.
US4035267 A (1977, AMERICAN CYANA-
MID CO) discloses a dry shampoo containing
Table 8.3 Shampoo Solid Formulation
(2004, US2004202632 A1, UNILEVER HOME &
PERSONAL CARE)
Ingredients wt%
High amylose corn starch 86.39
Sodium lauryl sulfate (flakes) 10.00
Coconut diethanolamide 3.00
Germal 115 0.20
Fragrance 0.40
Colorant 0.01
413
chitin powder. The shampoo is applied to the hair
in powdered form, and then removed from the hair
by brushing, thereby removing from the hair oil or
sebum which becomes attached to the dry powder.
Powdered chitin has a large surface area and is highly
porous and therefore, readily takes up oily substances
such as sebum, either by adsorption on the surface or
by absorption into the pores.
JP2006193432 A (2006, MUKAI TAKASHI) dis-
closes a hair processing agent, such as shampoo, hair
colorant, permanent hair curling liquid, hair wax,
hair cream, hair tonic, hair spray, gel, and hair res-
toration agent, containing a biodegradable polymer
dispersion. The biodegradable polymer dispersion is
caused to adhere to the hair, and the hair is subjected
to a heat treatment by means of a hair iron after the
adherence of the biodegradable polymer dispersion
to be provided with a glossy and persistent curl set or
a straight permanent wave. Neither the glossy curl set
nor the straight permanent wave is taken away even
when the hair is shampooed using a weakly acidic
soap or the like but the biodegradable polymer is
washed away by washing using an alkali soap. A pre-
ferred biodegradable polymer is PLA. A representa-
tive shampoo formulation is shown in Table 8.4.
WO2012177617 A1 (2012, PROCTER & GAM-
BLE) discloses in one of its embodiments a hair
care preparation such as hair shampoo compris-
ing biodegradable abrasive cleaning particles. The
Table 8.4 Shampoo Formulation (2006,
Ingredients wt%
Sodium lauryl sulfate 1545
Lauramide propyl betaine 315
Cocamide diethanolamine 15
Sodium cocoampho acetate 315
Polyquaternium-10 (cationic 0.11.0
cellulose)
Paraben 0.3
Ethylenediaminetetraacetic 0.010.5
acid (EDTA-2Na)
Biodegradable polymer dispersion 110
Fragrance
Water Balance
amount
414 Biopolymers: Applications and Trends

Table 8.5 Shampoo Formulations (2012, US2012321681 A1 (2012, PROCTER & GAMBLE))
Ingredients Shampoo 1 Shampoo 2 Shampoo 3
Water q.s. q.s. q.s.
Polyquaterium 76a 0.25
Guar, hydroxylpropyl trimonium chlorideb 0.25
Polyquaterium 6c
Sodium laureth sulfate 12 10.5 10.5
Sodium lauryl sulfate 1.5 1.5
Siliconed 0.75 1.00 0.5
Cocoamidopropyl betaine 3.33 3.33 3.33
Cocoamide MEA 1.0 1.0 1.0
Ethylene glycol distearate 1.50 1.50 1.50
Biodegradable abrasive cleaning particles obtained from 1 2
PBS foam
Crosslinked PS-DVB (50% DVB 55, mean diameter D(v, 1
0.9) 75m) abrasive cleaning particles
Fragrance 0.70 0.70 0.70
Preservatives, pH, and viscosity adjusters 1% 1% 1%

aTriquatacrylamide copolymer, MW=1,000,000; CD=1.6 meq./g, Rhodia.

bJaguar C500, MW=500,000; CD=0.7meq./g, Rhodia.
cMirapol 100S, 31.5% active, Rhodia.
dDimethicone Fluid, Viscasil 330 M; particle size 30m; Momentive Silicones.

PBS, Poly(butylene succinate); PS-DVB, Polystyrene crosslinked with divinylbenzene.

biodegradable abrasive cleaning particles are made
of PLA, and have a mean circularity of 0.10.6 and
mean solidity of 0.40.9. More preferably, the biode-
gradable abrasive particles are obtained from foamed
PLA. The composition is suitable for cleaning/
cleansing animate surfaces selected from the group
consisting of human and animal hair.
US2012321681 A1 (2012, PROCTER & GAM-
BLE) is a modification of the previous patent
application, wherein the biodegradable abrasive
particles are selected from the group consisting of
PBS, poly(butylene adipate) (PBA), poly(ethylene
succinate), poly(ethylene succinate-co-adipate), poly
(propylene succinate), poly(propylene succinate-co-
adipate), and mixtures thereof. Various shampoo for-
mulations are listed in Table 8.5.
8.4 Sunscreen Preparations
Sunscreen preparations provide protection to the
skin against the effect of ultraviolet (UV) radiation.
DE3912122 A1 (1990, WELLA AG) discloses
UV absorbing chitin and chitosan derivatives for
use in hair and skin protection agents. The UV
absorbing biopolymers are claimed to be easily
incorporated into suitable cosmetic bases such as
creams, gels, dispersions, emulsions, and aerosols,
be physiologically harmless, adhere well to the skin
and hair, and be not washed off by perspiration or
water so that they offer good protection against the
harmful effects of UV-B rays (280320nm).
JP2011201832 A (2011, SHISEIDO CO LTD.) dis-
closes a composite powder to be used preferably for
sunscreen and makeup cosmetics obtained by support-
ing biodegradable polymer such as PLA by titanium
dioxide powder particles or zinc oxide powder particles
of diameter of 0.1m. The makeup cosmetics include
lipstick, mascara, nail enamel, eye shadow, and eyebrow
pencil. The composition is claimed to have improved
UV-ray absorption property and photocatalytic activity,
and hence environmentally friendly, and can be conve-
niently used on sea, mountain, and swimming pools.
 8: Cosmetics
US2002172646 A1 (2002, ETHOX CHEMI-
CALS LLC) discloses in one of its embodiments a
waterproof sunscreen preparation comprising: a bio-
degradable polyester (298wt%) and an active UV
radiation absorber (1.030.0wt%). The biodegrad-
able polyester is selected from poly(lactic acid-co-
ricinoleic acid) and poly(glycolic acid-co-ricinoleic
acid).
The waterproof sunscreen preparation may addi-
tionally comprise:
1. a water-insoluble organic emollient compound
(020%wt) having a water solubility of less
than 1% at 25C selected from the group con-
sisting of fatty alcohols, fatty acids, esters,
ethers, alkanes, and polysiloxanes;
2. 
a surface active agent (015wt%) selected
from the group consisting of nonionic esters,
nonionic ethers, and soaps of a fatty acid
and an alkali metal, ammonium, and an
alkanolamine;
3. a volatile liquid carrier (085wt%) having a
melting temperature less than 22C, which
completely evaporates from the skin 30min
after application to the skin selected from the
group consisting of monohydric alcohols,
hydrocarbons, halogenated hydrocarbons, and
cyclic dimethylpolysiloxanes;
4. water (085 wt%);
5. suspended particulate solid matter (020wt%);
6. liquefied propellants (085wt%);
7. a thickening agent (015wt%) selected from
the group consisting of natural waxes, syn-
thetic polymers, inorganic salts, fatty acids,
fatty alcohols, esters, and organic salts; and
8. fragrance oil (03wt%).
An exemplary waterproof sunscreen gel of the
above composition is shown in Table 8.6.
WO2008101546 A1 (2008, ROVI COSMETICS
INTERNAT GMBH) discloses in one of its embodi-
ments a cosmetic preparation useful to protect or to
treat the skin and/or hair, comprising an active agent,
which can absorb UV-A and/or UV-B radiation, and
carrier material, which comprises a proportion of chi-
tosan, PLA, PGA and/or PLGA. The carrier material is
present in form of particles with an average particle size
of 101000nm. The cosmetic formulation is claimed to
have very good attachment performance on skin and/or
415
Table 8.6 Waterproof Sunscreen Gel SPFa 27
(2002, US2002172646 A1, ETHOX CHEMICALS
LLC)
Components wt%
SD alcohol 40 71.3
Poly(lactic acid-co-ricinoleic acid) 2.0
Octyl methoxycinnamate 5.0
Benzophenone-3 6.0
Octyl salicylate 5.0
PPG-15 stearyl ether 10.0
Hydroxypropyl cellulose 0.7
aSun protection factor.
hair without causing an unpleasant feeling of tackiness,
and improved transport properties and release kinetics
as compared with conventional formulations.
8.5 Manicure and Pedicure
Preparations
A typical nail lacquer formulation comprises
film-forming polymers, film modifiers, plasticizers,
organic solvents (e.g., ethyl acetate, propyl acetate,
and N-butyl acetate), colorants (e.g., pigments), sus-
pending agents, and other additives.
The primary film-former used in nail lacquers
is nitrocellulose. Acrylic polymers (acrylate and
methacrylate polymers) are also used as primary
film-formers in nail lacquers. Sometimes, secondary
film-formers are added as film modifiers; examples
of film modifiers include toluenesulfonamide/
formaldehyde resin, toluenesulfonamide/form-
aldehyde, toluenesulfonamide/epoxy resin, adipic
acid/neopentyl glycol/trimellitic anhydride copoly-
mer, and methyl methacrylate/butyl methacrylate
copolymer.
Nitrocellulose is a naturally derived polymer, but
the film-forming polymer and film modifier are non-
biodegradable synthetic resins derived from fossil
fuel resources. In nail cosmetics, there is a desire to
replace the nonbiodegradable film-forming polymer
and/or film modifier with biodegradable ones without
compromising the properties.
JP2011168552 A (2011, DAITO KASEI KOGYO
CO LTD.) discloses a biodegradable nail cosmetics
preparation comprising an amorphous PLA. The nail
416
cosmetic is claimed to have excellent applicability,
glossiness, and film strength.
JP2011126798 A (2011, TOYO BOSEKI) dis-
closes a nail manicure liquid composition compris-
ing an organic solvent and PLA. The organic solvent
contains alkyl ester of fatty acid, and aliphatic alco-
hol. The nail polish composition is claimed to have
excellent quick drying capability and solubility with
respect to nail polish remover.
KR20120123853 A (2012, KUMOH NAT INST
TECHNOLOGY IND ACAD COOP) discloses a
thermosensitive manicure composition comprising:
lacquer base (3050pbw), thermochromic pigment (0.5-
5pbw), diluents (1525pbw), nitrocellulose (918pbw), discloses a spunlaced facial mask made of PLA
sodium carboxyl methyl cellulose (510pbw), PLA
(615 pbw), isopropyl alcohol (39 pbw), hectorite spunlace technology for producing a hydroentan-
(0.52pbw), camphor (0.51.7pbw), and benzophe- gled nonwoven cloth that uses jets of high-pres-
none (0.080.15pbw). The thermochromic pigment
can have different colors, in particular yellow, orange,
magenta, rose red, red, sky blue, dark blue, fast blue,
violet, Turkish blue, green, and black. The thermosensi-
tive manicure can change color according to tempera-
ture change and to enable various expressions.
8.6 Accessories and Containers
for Handling Cosmetic Substances
8.6.1Accessories
WO02051284 (2002, AVON PROD INC.) dis-
closes an applicator brush (1) that has bristles (fil-
aments) (30) made of a biodegradable polymer,
preferably PLA. Such bristles (30) can provide
improved mechanical and aesthetic characteristics
compared to conventional bristles made from fossil
fuel-based polymers. Handle (16) of the applicator
is made preferably also of PLA. The applicator (1)
can be used as a cosmetic applicator brush to apply
a variety of cosmetics, such as eyeliner, eye shadow,
lipstick, lip gloss, mascara (Figure 8.2), nail polish
Figure 8.2 Mascara applicator brush (2002,
WO02051284, AVON PROD INC.). 1, Applicator; 12,
Core (e.g., twisted metallic wire); 14, Rod; 16, Han-
dle; 20, Bristle portion; 30, Bristles.
Biopolymers: Applications and Trends
and/or lacquer, blush and/or makeup, powder, or
rouge.
JP2007289377 A (2007, VAINQUEUR KK) dis-
closes a face washing puff formed from a soft poly-
urethane foam core wrapped with a pile knit cloth.
The pile knit cloth comprises cotton/chitin chitosan
short fibers and PLA fiber-based long fibers (e.g.,
Terramac fibers, Unitika, Ltd.). The face washing
puff is claimed to be extremely effective for remov-
ing makeup from the skin, has a water draining prop-
erty with excellent using feeling, and satisfies ideal
conditions of being gentle to the skin.
CN101491486 A (2009, UNIV JIANGNAN)
staple fibers. The mask is manufactured by the
sure water to entangle a web of loose fibers. The
PLA staple fiber mask and spunlaced nonwoven
cloth are biodegradable and characterized by soft-
ness, good air permeability, hygroscopicity, water
absorption, skin affinity, antibacterial and antifun-
gal properties.
US2012255572 A1 (2012, DAN LORRAINE
ELLEN) discloses a method for applying a facial
makeup comprising: (1) utilizing a biodegrad-
able electrostatically charged porous material that
attracts dust particles; (2) placing the cosmetic
makeup on the porous material; (3) placing an
applicator proximate to the makeup in such a way
that the cosmetic makeup particles adhere to the
applicator; and (4) using the applicator to apply
the cosmetic makeup. The porous material is in the
form of a cloth, a wipe, or a foam, and is preferably
made of PLA or vegetable fibers. This electrostati-
cally charged material is used to blot excess pow-
der from cosmetic applicators, and also serves as
a palette to mix powder cosmetics for application.
Furthermore, it is used to clean up the area at which
the cosmetics are applied.
8.6.2 Containers and Packages
The cosmetics industry creates over 120billion
units of packaging a year. Much of this is short
lived and often ends up in landfill [3]. Most cos-
metic and personal care packaging is currently made
from nonbiodegradable polymers derived from fos-
sil fuel resources or from metal. Packaging made
from nonbiodegradable polymers has the problem
of increasing waste stream. Packaging made from
8: Cosmetics
metal components often requires additional pro-
cessing steps (e.g., grinding edges, removing burrs,
cleaning, anticorrosion treatment, surface polishing
or roughening). In addition, metal parts may have
sharp edges, or splinters or shavings associated with
their production and use that could pose a hazard to
consumers. To avoid the additional processing and
safety concerns associated with metal parts, and to
reduce waste flow and negative impact on the envi-
ronment associated with nonbiodegradable poly-
mer parts, there have been developed cosmetic and
personal care packaging made from biopolymers,
and in particular biodegradable biopolymers (2014,
US2014020598 A1, ELC MAN LLC).
DE19855325 A1 (1999, FABER CASTELL A W)
discloses biodegradable outer casings for color-, lead-,
and cosmetic pencil leads made from a composition
comprising a biodegradable polymer (5080wt%),
wood- or cellulose fibers (1040wt%), inorganic filler
(210wt%), and wax and/or fatty acid derivative. The
biodegradable polymer is selected from PCL, P3HB,
polyhydroxyvalerate (P3HV), poly(3-hydroxybutyr-
ate-co-3-valerate), starch-based polymers, and syn-
thetic polymers with a decomposition accelerator. The
fiber component is selected from wood fibers, wood
particles, and cellulose fibers. The fatty acid is prefer-
ably stearic acid. The composition may also contain
other additives, lubricants, and colorants.
Example: A composition for forming the outer
casing for pencils was made comprising: a starch-
based polymer (Mater-Bi, Novamont) (55wt%),
wood sawdust (40wt%), kaolin (2wt%), and stearic
acid (3wt%). After mixing the ingredients, the com-
position could be molded or (co)extruded into pencil
casings at 140180C.
US2014020598 A1 (2014, MARTINS
AGOSTINHO; MCGUIRE ELIOT DRANGEID)
discloses a biodegradable component for a package
for storing and dispensing a cosmetic product or a
beauty care product made from compressed fibrous
biomass bound by a cosmetically compatible and
compostable binder in a mold having a sidewall draft
angle of 030. Most preferably, the mold cavity
sidewall draft angle is 0.17 to facilitate release of
the component from the cavity. The cosmetically com-
patible and compostable binder is selected from bio-
degradable polyurethane, PLA, PGA, P3HB, P3HV,
PCL, PBS, PBA, PVOH, and denatured starch. The
biomass fiber is selected from at least one of wood
pulp, cellulose, bamboo, willow, bagasse, corn, rice
straw, reed, bulrush, coconut, agave, flax, or palm.
417
Figure 8.3 illustrates an embodiment of a biodegrad-
able component (106) for a package (102) for storing
and dispensing cosmetic and beauty care products.
JP2001039426 A (2001, SHISHEIDO CO LTD.)
discloses a container for packing cosmetics made by
blending PLA and PBS in a ratio of 1/99/1. In a pre-
ferred process, the container is formed by laminating
a PLA layer and a PBS layer. The heat resistance of
the container is improved by setting the heat deflec-
tion temperature of PLA not lower than 60C. The
container is claimed to reduce the loss of moisture
content, and improve the drop strength.
JP2002167326 A (2002, OSAKA KAGAKU
GOKIN KK) discloses a bag of a biodegradable bath-
ing material formed by laminating a nonwoven fabric
made of PLA with a nonwoven fabric of vegetable
fiber (e.g., cotton), heat pressing and heat sealing the
faces of the PLA nonwoven fabric, wherein the bag has
the PLA nonwoven fabric as inner side and the cotton
nonwoven fabric as external side. A bathing prepara-
tion is packed inside the bag. The active ingredients of
the bathing preparation are eluted efficiently through
the walls of the biodegradable laminated body. The
bag can be easily disposed after use, and furthermore
easily produced due to the heat-sealing ability of PLA.
Figure 8.3 Cross-sectional side elevation view of a
biodegradable component for a package or storing
and dispensing cosmetic and beauty care products
(2014, US2014020598 A1, MARTINS AGOSTINHO;
MCGUIRE ELIOT DRANGEID). 102, Package; 103,
Solid body made of compressed fibrous biomass and
a cosmetically compatible and compostable binder;
106, Biodegradable component; 110, Cover secured
to the solid body (103); 112, Hinge for securing the
cover (110) to the body (103); 118, Reservoir cre-
ated in the body (103) for storing and dispensing a
cosmetic product (P); 120, Surface of the body (103)
adapted to contact the product; P, Cosmetic product.
418 Biopolymers: Applications and Trends

WO0027611 A1 (2000, FRAUNHOFER GES plug (13) are formed from the same biodegradable
FORSCHUNG) discloses a rod-shaped composite thermoplastic polymer. The shaft is claimed to have
body consisting of a core surrounded by at least excellent physical characteristics, such as rigidity,
one polymer. The polymer is a natural polymer cutting ability, and oil proof flat permeability, have
based on lignin, which is mixed with native oils light weight, provide comfortable feel to the user,
and/or waxes. Due to its wood-like character and and be easily decomposed after disposal. The shaft
its thermoplastic processability, the lignin can be also does not generate toxic substances when inciner-
further mixed with natural fibers, such as cellulose ated (Figure 8.4).
fibers to render the material very similar to natu- Biodegradable containers and packages used in
rally grown wood with regard to its composition commercial cosmetics products are listed in Table 8.7.
and surface properties. The composite body can be
coated, for example, painted, in a known fashion,
and is especially used as a writing or drawing pen-
cil, crayon, or cosmetic pencil.
JP2001192502 A (2001, OKIWA CORP.; NIP-
PON KOONSUTAAC KK) discloses a tubular syn-
thetic shaft (11), as a substitute for a wood shaft,
for pencil cosmetics such as eyebrow and lip liner,
formed from a biodegradable thermoplastic polymer
composition comprising a starch ester (5095wt%),
filler (550wt%), and a biodegradable thermoplastic
polymer other than starch ester (<40wt%) such as
cellulose. The hollow portion of biodegradable shaft Figure 8.4 Tubular synthetic shaft for pencil-shaped
is filled with cosmetic core (12). An end plug (13) is cosmetic (2001, JP2001192502 A, OKIWA CORP.;
detachably attached to rear end of the synthetic shaft, NIPPON KOONSUTAAC KK). 11, Synthetic shaft;
which acts as stopper. Both the cap (14) and the end 12, Cosmetic core; 13, End plug; 14, Cap.

Table 8.7 Biodegradable Containers and Packages in Commercial Cosmetics Products

Commercial product Company Biopolymer
Cosmetic pen Weckerle Cosmetics (DE) Cellulose ester compound
(Biograde C 7500 CL,
FKuR Kunststoff GmbH)
PlantLove lipstick case Cargo Cosmetics (CA) PLA (Ingeo, NatureWorks)
4-part lipstick case Leoplast Srl. (IT); products PLA (Ingeo, NatureWorks)
used by pLaboratoires Phyts;
Laboratoires Cosmediet;
Laboratoires Science
et Nature; Intercos [4]
Bottles for Urara range of Shiseido Co Ltd. (JP) PLA (Ingeo, NatureWorks)
products (shampoo,
conditioner, body soap, etc.)
Impact Zeroface and body Eudermic Srl (IT) PLA (Ingeo, NatureWorks)
lotion bottle
Mascara packaging Oekametall (DE) PTT (Biomax PTT1100, Du
Pont)
Shampoo (Pantene V) and condi- Procter & Gamble (USA) Bio-PE (Braskem)
tioner bottles
8: Cosmetics 419

Table 8.7 Biodegradable Containers and Packages in Commercial Cosmetics Productscontd

Commercial product Company Biopolymer

Sapien Women line (bottles for Surya (BR) Bio-PE (Braskem)

shampoo, conditioner, leave-in
combing cream and split end
repair cream)
Sapien Men line (bottles for
shampoo, conditioner, shave
cream, aftershave, shower gel,
and hair styling gel)
Sundown sun care bottles Johnson & Johnson (USA) Bio-PE (Braskem) (60wt%)
and recycled PE (40wt%)
Body care packaging film Sidaplax (USA) PLA, EarthFirst (Ingeo,
NatureWorks)
Hair care packaging film Sidaplax (USA) EarthFirst (Ingeo
NatureWorks)
Cosmetic bag FKuR Kunststoff GmbH (DE) PLA/copolyester blend
(Bio-flex, FKuR Kunststoff
GmbH; PLA used was
Ingeo, NatureWorks)
Laundry olive oil soap Ecolive Umbria Olii Int. (IT) PLA/copolyester blend
multilayer wrapping film (Bio-flex 2110 and
Bio-flex 4100 C FKuR
Kunststoff GmbH)

bio-PE, bio-based polyethylene; PLA, poly(lactic acid), polylactide; PTT, poly(trimethylene terephthalate).
Patents
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UV-radiation absorbing
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composition
Continued
contd

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US2012255572 A1 20121011 US201113080150 20110405 DAN LORRAINE ELLEN DAN LORRAINE Disposable cosmetic
ELLEN makeup palette
US2011275550 A1 20111110 US2013065808 A1 20130314; US201113104149 20110510; CERVINO KIM CERVINO KIM Biodegradable personal
US8637440 B2 20140128; US20100333147P 20100510 cleansing composi-
US8329628 B2 20121211 tions and methods
relating to same
WO2012177617 A1 20121227 WO2012177615 A1 20121227; US201161498776P 20110620 GONZALES DENIS PROCTER & Liquid cleaning and/
US2012317735 A1 20121220; ALFRED; GAMBLE or cleansing
US8440603 B2 20130514; DKIDAK AICH; composition
US2012321680 A1 20121220; JAMES MARTIN IAN
US8703685 B2 20140422;
MX2013014785 A 20140120;
JP2014522888 A 20140908;
EP2721134 A1 2014423;
EP2721133 A1 20140423;
CN103608445 A 20140226;
CA2839953 A1 20121227
US2012321681 A1 20121220 US8852643 B2 20141007 US201213526605 20120619; GONZALES DENIS PROCTER & Liquid cleaning and/
US201161498741P 20110620 ALFRED; GAMBLE or cleansing
DKIDAK AICHA; composition
JAMES MARTIN IAN
Continued
contd

Patent number Publication date Family members Priority numbers Inventors Applicants Title

US2014020598 A1 20140123 WO2014015218 A1 20140123 US201213554083 20120720 MARTINS AGOSTINHO; ELC MAN LLC Biodegradable and
MCGUIRE ELIOT compostable com-
DRANGEID ponent for cosmetic
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US2014026916 A 20140130 US201313950493 20130725; HAVENS KIRK J; COLLEGE Method for reducing
US201261675410P 20120725 BILKOVIC DONNA WILLIAM & marine pollution
MARIE; MARY using polyhydroxyal-
STANHOPE DAVID M; kanoate microbeads
ANGSTADT KORY T
WO2008101546 A1 20080828 EP2120845 A1 20091125; WO2007EP51694 BLUME GABRIELE; ROVI COSMET- Nanopartikel zur
EP2120845 B1 20121024; 20070221 TEICHMUELLER DIRK ICS INTERNAT Verwendung in
ES2397538 T3 20130307 GMBH kosmetischen und
dermatologischen
Zubereitungen.
Nanoparticles for
use in cosmetic
and dermatological
formulations
8: Cosmetics
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