Cosmetics

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 formulations 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 products 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 microparticles 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. Microparticles 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 alternative 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 nonbiodegradable polymers in terms of cost and properties, and shall comply to the high standards of the cosmetics industry.

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, setting 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, antiperspirants, and deodorants. Cleansing products, skin products, makeup products, 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 nonbiodegradable 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 polyethylene, are used in a series of cosmetic products.

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.

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 composition 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 wastewater treatment, find their way into water courses and end up in the sea, where they cause irreparable damage to marine ecosystems. Moreover, polyethylene 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 microparticles are, for example, exfoliating products made from shells, kernels, bamboo, rice, natural waxes, microcrystalline cellulose, poly(lactic acid) (PLA), or minerals. 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 CHEMICALS CORP.) discloses a skin and/or hair cleansing composition comprising PLA-based fine powder of an average particle diameter of 50–300 μm as a scrubbing agent. US2011275550 A1 (2011, CERVINO KIM) discloses a personal cleansing composition including a surfactant, a thickener, an emulsifier, and at least one particle dispersed in the thickener formed of a substantially biodegradable substance including a soy meal-based polymer. The soy meal-based polymer is used to replace portions of the current nonbiodegradable polyethylene as a scrubbing agent, exfoliant, or even as filler to add volume or weight to the composition. 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 exfoliant in pet care products). In some embodiments, the soy meal-based polymer forms 0.001–30 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 1–10 wt% of a micronized PLA and 3–20 wt% of a carrier. The powder composition has an average particle size of 0.1–44 μm, preferably, 5–20 μm. The powder composition is useful 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 comprising micronized PLA. JP2012233057 A (2012, SUZUKI YUSHI KOGYO KK) discloses a skin cleansing composition comprising a biodegradable scrubbing agent, wherein the scrubbing agent is formed by curing a mixture of a melted or dissolved biodegradable polymer with a natural vegetable powder. The biodegradable polymer is selected from PLA; poly(glycolic acid) (PGA); poly(ε-caprolactone) (PCL); polyhydroxyalkanoates (PHAs) such as poly(3-hydroxybutyrate) (P3HB), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx); poly(alkylene alkanoate)s such poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate), 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, bamboo powder, and the like. The biodegradable scrubbing agent is claimed to have an excellent cleaning effect, and not to pollute the environment. JP2007077311 A (2007, ASAHI KASEI CHEMICALS CORP.) discloses in one of its embodiments an abrasive detergent capable of safely and easily cleaning 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

Deionized water

Water

51.20

N/A

Carbopol® Ultrez 20

Carbomer

0.60

The Lubrizol Corp.

Propylene glycol

Propylene glycol

3.50

Many

Germaben II

Propylene glycol, diazolidinyl urea, methylparaben, propylparaben

1.00

International Specialty Products

Phase A

Phase B

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.

Deionized water

Water

3.00

N/A

Disodium EDTA

Disodium EDTA

0.05

Many

Triethanolamine

0.65

Many

PLA

7.00

Micro Powders, Inc.

Phase D

Phase E Triethanolamine 99% Phase F EcoScrub® 20PC

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 0.01–0.35 g/cm3. The materials for the abrasive include, among other things, biodegradable polymers such as PLA and PBS and crystalline cellulose or chitosan. US2014026916 A (2014, COLLEGE WILLIAM & MARY) discloses in one of its embodiments the use of PHA microbeads in exfoliating scrub formulations. 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 (4.1–9.2 μm), 3.80 7. Sodium magnesium aluminum silicate, liquibead 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 1–4 on the Mohs hardness scale. The PHA microbeads once rinsed and subsequently released into aquatic environments, sink to the bottom of the aquatic environment. The PHA microbeads are then sequestered by sedimentdwelling organisms such as clamworms, or can be buried or incorporated into structures such as tubes. Once sequestered, the PHA microbeads are not easily 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 Celluloscrub™ 300) and intends to replace the polyethylene 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 products. 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 1–10 mm, is then subjected to alkali cooking, and is further refined to mix raw silk yarn-fibrillated silk fiber pulp (10–60 wt%), vegetable fiber pulp (90–40 wt%), 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 properties 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 compared to the sebum-absorbing paper, they are not biodegradable. JP2001078914 A (2001, COSMETICS ROORANDO KK) discloses an oil absorbing film made of a mixture of a crystalline polyolefin (55–70 wt%), vinyl acetate (5–15 wt%), a biodegradable polymer (20–30 wt%), an inorganic filler (5–30 wt%), a waterabsorbing polymer (1–10 wt%), and a pigment (0.5– 10 wt%). 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 (50 wt%), including nonmeltable PLA fibers and meltable PLA fibers, and inorganic powder and/or biodegradable organic powder. 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 environmentally 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 ability, oil retention ability, and change in transparency when in contact with oil. The PHA-based sebumabsorbing 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 sebumabsorbing film can be decomposed under either aerobic conditions or anaerobic conditions, and can be flushed down a toilet. WO02100357 A1 (2002) and JP2003073233 A (2003) of UNITIKA LTD. disclose a cosmetic product comprising biodegradable polyester microparticles, wherein the microparticles are formed from a PLA with a d-lactic acid content of 0.1–25 mol%. The density of the microparticles is 1.0–10.0 g/cm3, the average particle diameter is 0.01–1000 μm, the 10% deformation strength during compression is 5 MPa 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 product and makeup 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 product by spraying. Example: A cosmetic cream was prepared as follows: 20 pbw of PLA microparticles, 5 pbw p-octyl methoxycinnamate, 1 pbw of α-monoisostearyl glyceryl ether, polyoxyethylene sorbitan ester, monooleic acid ester as a fatty acid ester, 2 pbw of beeswax as a wax, 2 pbw of lanolin as a wax, 20 pbw of squalane as a hydrocarbon, 30 pbw of liquid paraffin as a hydrocarbon, 19 pbw of purified water, an adequate amount of a preservative, and an adequate amount of perfume were placed in a homodisperser and mixed for 3 min at 2500 rpm to prepare an emulsified cosmetic product. The PLA microparticles were prepared as follows: 40 pbw of PLA (number-average molecular weight: Mn = 60,000; content of the D-form: 1.7 mol%) dried until the moisture content reached 200 ppm, and 60 pbw of poly(acrylic acid) (weight-average molecular weight: Mw = 1,000,000) as a dispersion medium were dry blended and fed to the feed port of a oneway twin-screw extruder. The cylinder temperature of the extruder was set to 180 °C, 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 10 μm in diameter was obtained. This suspension was centrifuged and dried to obtain the PLA microparticles.

8.2  Makeup and Other Facial Preparations Makeup in today’s marketplace comes in a variety of formulations, such as powder, liquid, cream, pencils, gels, sticks, and more. Often, it is necessary to blend these products to produce colors and consistencies 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 3–50 μm, preferably 5–35 μm. 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 surface-treated carbon black (100). The carbon black contains: 5.0–30.0 wt% of a carbon black core (10); 1.0–10.0 wt% of a cationic organic layer (20) on the carbon black core; 0.1–5.0 wt% 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 surfactant, 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 product comprising biodegradable polyester microparticles, wherein the microparticles are formed from a PLA with a d-lactic acid content of 0.1–25 mol%. The density of the microparticles is 1.0–10.0 g/cm3, the average particle diameter is 0.01–1000 μm, the 10% deformation strength during compression is 5 MPa or more, and at least 70% of the microparticles have a major axis length/minor axis length

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 product 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 product by spraying. Example: A cosmetic cream was prepared as follows: 20 pbw of PLA microparticles, 5 pbw p-octyl methoxycinnamate, 1 pbw of alphamonoisostearyl glyceryl ether, polyoxyethylene sorbitan ester, monooleic acid ester as a fatty acid ester, 2 pbw of beeswax as a wax, 2 pbw of lanolin as a wax, 20 pbw of squalane as a hydrocarbon, 30 pbw of liquid paraffin as a hydrocarbon, 19 pbw of purified water, an adequate amount of a preservative, and an adequate amount of perfume were placed in a homodisperser and mixed for 3 min at 2500 rpm to prepare an emulsified cosmetic product. The PLA microparticles were prepared as follows: 40 pbw of PLA (number-average molecular weight: Mn = 60,000; content of the D-form: 1.7 mol%) dried until the moisture content reached 200 ppm, and 60 pbw of poly(acrylic acid) (weight-average molecular weight: Mw = 1,000,000) as a dispersion medium were dry blended and fed to the feed port of a oneway twin-screw extruder. The cylinder temperature of the extruder was set to 180 °C, 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 10 μm in diameter was obtained. This suspension was centrifuged and dried to obtain the PLA microparticles.

8.3  Hair Care Preparations Figure 8.1 Surface-treated carbon black of a makeup composition (2013, KR101248973 B1 (2013, BIOGENICS INC.)). 10, Carbon black core; 20, Cationic organic layer; 30, Organic binder layer; 100, Surfacetreated carbon black.

Hair care cosmetic products include hair shampoos, hair rinses, hair tints and bleaches, hair conditioners, hair treatments, setting lotions, blow styling lotions, hairsprays, foam styling agents, gel styling agents, hair liquid, hair tonic, hair cream, hair growth

8: Cosmetics

413

tonic, hair growth stimulants, hair dyes, hair dressings, 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 shampoo for several hair washes. US2004202632 A1 (2004, UNILEVER HOME & PERSONAL CARE) discloses solid cosmetic compositions comprising a water dissolvable solid carrier incorporating at least one cosmetic agent. The solid carrier is a destructurized starch. Fragrance is applied topically onto the solid carrier. The compositions 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 warming fatty or oil-based materials to 70 °C to achieve fluidity. Other liquid or solid nonmeltable materials are then dispersed into the resultant mass with thorough 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 150–250 °C, and shaped. Fragrance is sprayed onto the shaped mass. The formulation of the shampoo solid is listed in Table 8.3. US4035267 A (1977, AMERICAN CYANAMID 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

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) discloses a hair processing agent, such as shampoo, hair colorant, permanent hair curling liquid, hair wax, hair cream, hair tonic, hair spray, gel, and hair restoration 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 preferred biodegradable polymer is PLA. A representative shampoo formulation is shown in Table 8.4. WO2012177617 A1 (2012, PROCTER & GAMBLE) discloses in one of its embodiments a hair care preparation such as hair shampoo comprising biodegradable abrasive cleaning particles. The Table 8.4  Shampoo Formulation (2006, JP2006193432 A, MUKAI TAKASHI) Ingredients

wt%

Sodium lauryl sulfate

15–45

Lauramide propyl betaine

3–15

Cocamide diethanolamine

1–5

Sodium cocoampho acetate

3–15

Polyquaternium-10 (cationic cellulose)

0.1–1.0

Paraben

0.3

Ethylenediaminetetraacetic acid (EDTA-2Na)

0.01–0.5

Biodegradable polymer dispersion

1–10

Fragrance

–

Water

Balance amount

414

Biopolymers: Applications and Trends

Table 8.5  Shampoo Formulations (2012, US2012321681 A1 (2012, PROCTER & GAMBLE)) Ingredients Water Polyquaterium

76a

Guar, hydroxylpropyl trimonium chlorideb

Shampoo 1

Shampoo 2

Shampoo 3

q.s.

q.s.

q.s.

0.25

–

–

–

0.25

–

12

10.5

10.5

1.5

1.5

Polyquaterium 6c Sodium laureth sulfate Sodium lauryl sulfate 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 PBS foam

1

2 1

Crosslinked PS-DVB (50% DVB 55, mean diameter D(v, 0.9) 75 μm) abrasive cleaning particles Fragrance

0.70

0.70

0.70

Preservatives, pH, and viscosity adjusters

≤1%

≤1%

≤1%

aTriquat

acrylamide copolymer, MW = 1,000,000; CD = 1.6  meq./g, Rhodia. C500, MW = 500,000; CD = 0.7 meq./g, Rhodia. cMirapol 100S, 31.5% active, Rhodia. dDimethicone Fluid, Viscasil 330 M; particle size 30 μm; Momentive Silicones. PBS, Poly(butylene succinate); PS-DVB, Polystyrene crosslinked with divinylbenzene. bJaguar

biodegradable abrasive cleaning particles are made of PLA, and have a mean circularity of 0.1–0.6 and mean solidity of 0.4–0.9. More preferably, the biodegradable 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 & GAMBLE) 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-coadipate), and mixtures thereof. Various shampoo formulations 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 (280–320 nm). JP2011201832 A (2011, SHISEIDO CO LTD.) discloses a composite powder to be used preferably for sunscreen and makeup cosmetics obtained by supporting biodegradable polymer such as PLA by titanium dioxide powder particles or zinc oxide powder particles of diameter of 0.1 μm. 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 conveniently used on sea, mountain, and swimming pools.

8: Cosmetics

US2002172646 A1 (2002, ETHOX CHEMICALS LLC) discloses in one of its embodiments a waterproof sunscreen preparation comprising: a biodegradable polyester (2–98 wt%) and an active UV radiation absorber (1.0–30.0 wt%). The biodegradable polyester is selected from poly(lactic acid-coricinoleic acid) and poly(glycolic acid-co-ricinoleic acid). The waterproof sunscreen preparation may additionally comprise: 1. a water-insoluble organic emollient compound (0–20% wt) having a water solubility of less than 1% at 25 °C selected from the group consisting of fatty alcohols, fatty acids, esters, ethers, alkanes, and polysiloxanes; 2.  a surface active agent (0–15 wt%) 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 (0–85 wt%) having a melting temperature less than 22 °C, which completely evaporates from the skin 30 min after application to the skin selected from the group consisting of monohydric alcohols, hydrocarbons, halogenated hydrocarbons, and cyclic dimethylpolysiloxanes;

4. water (0–85  wt%); 5. suspended particulate solid matter (0–20 wt%); 6. liquefied propellants (0–85 wt%); 7. a thickening agent (0–15 wt%) selected from the group consisting of natural waxes, synthetic polymers, inorganic salts, fatty acids, fatty alcohols, esters, and organic salts; and 8. fragrance oil (0–3 wt%).

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 embodiments 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 chitosan, PLA, PGA and/or PLGA. The carrier material is present in form of particles with an average particle size of 10–1000 nm. 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 Hydroxypropyl cellulose aSun

10.0 0.7

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), suspending 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/formaldehyde, toluenesulfonamide/epoxy resin, adipic acid/neopentyl glycol/trimellitic anhydride copolymer, and methyl methacrylate/butyl methacrylate copolymer. Nitrocellulose is a naturally derived polymer, but the film-forming polymer and film modifier are nonbiodegradable 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) discloses a nail manicure liquid composition comprising an organic solvent and PLA. The organic solvent contains alkyl ester of fatty acid, and aliphatic alcohol. 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 (30–50 pbw), thermochromic pigment (0.55 pbw), diluents (15–25 pbw), nitrocellulose (9–18 pbw), sodium carboxyl methyl cellulose (5–10 pbw), PLA (6–15  pbw), isopropyl alcohol (3–9  pbw), hectorite (0.5–2 pbw), camphor (0.5–1.7 pbw), and benzophenone (0.08–0.15 pbw). 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 thermosensitive manicure can change color according to temperature change and to enable various expressions.

8.6  Accessories and Containers for Handling Cosmetic Substances 8.6.1 Accessories WO02051284 (2002, AVON PROD INC.) discloses an applicator brush (1) that has bristles (filaments) (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

Biopolymers: Applications and Trends

and/or lacquer, blush and/or makeup, powder, or rouge. JP2007289377 A (2007, VAINQUEUR KK) discloses a face washing puff formed from a soft polyurethane 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 removing makeup from the skin, has a water draining property with excellent using feeling, and satisfies ideal conditions of being gentle to the skin. CN101491486 A (2009, UNIV JIANGNAN) discloses a spunlaced facial mask made of PLA staple fibers. The mask is manufactured by the spunlace technology for producing a hydroentangled nonwoven cloth that uses jets of high-pressure water to entangle a web of loose fibers. The PLA staple fiber mask and spunlaced nonwoven cloth are biodegradable and characterized by softness, good air permeability, hygroscopicity, water absorption, skin affinity, antibacterial and antifungal properties. US2012255572 A1 (2012, DAN LORRAINE ELLEN) discloses a method for applying a facial makeup comprising: (1) utilizing a biodegradable 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 electrostatically charged material is used to blot excess powder 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

Figure 8.2  Mascara applicator brush (2002, WO02051284, AVON PROD INC.). 1, Applicator; 12, Core (e.g., twisted metallic wire); 14, Rod; 16, Handle; 20, Bristle portion; 30, Bristles.

The cosmetics industry creates over 120 billion units of packaging a year. Much of this is short lived and often ends up in landfill [3]. Most cosmetic and personal care packaging is currently made from nonbiodegradable polymers derived from fossil 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 processing 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 environment associated with nonbiodegradable polymer 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 (50–80 wt%), wood- or cellulose fibers (10–40 wt%), inorganic filler (2–10 wt%), and wax and/or fatty acid derivative. The biodegradable polymer is selected from PCL, P3HB, polyhydroxyvalerate (P3HV), poly(3-hydroxybutyrate-co-3-valerate), starch-based polymers, and synthetic polymers with a decomposition accelerator. The fiber component is selected from wood fibers, wood particles, and cellulose fibers. The fatty acid is preferably 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 starchbased polymer (Mater-Bi®, Novamont) (55 wt%), wood sawdust (40 wt%), kaolin (2 wt%), and stearic acid (3 wt%). After mixing the ingredients, the composition could be molded or (co)extruded into pencil casings at 140–180 °C. 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 0°–30°. Most preferably, the mold cavity sidewall draft angle is 0.1°–7° to facilitate release of the component from the cavity. The cosmetically compatible and compostable binder is selected from biodegradable 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 biodegradable 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 1/9–9/1. In a preferred 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 deflection temperature of PLA not lower than 60 °C. 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 bathing 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 preparation 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 created 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 FORSCHUNG) discloses a rod-shaped composite body consisting of a core surrounded by at least one polymer. The polymer is a natural polymer based on lignin, which is mixed with native oils and/or waxes. Due to its wood-like character and its thermoplastic processability, the lignin can be further mixed with natural fibers, such as cellulose fibers to render the material very similar to naturally grown wood with regard to its composition 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 pencil, crayon, or cosmetic pencil. JP2001192502 A (2001, OKIWA CORP.; NIPPON KOONSUTAAC KK) discloses a tubular synthetic 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 (50–95 wt%), filler (5–50 wt%), and a biodegradable thermoplastic polymer other than starch ester (<40 wt%) such as cellulose. The hollow portion of biodegradable shaft is filled with cosmetic core (12). An end plug (13) is detachably attached to rear end of the synthetic shaft, which acts as stopper. Both the cap (14) and the end

plug (13) are formed from the same biodegradable thermoplastic polymer. The shaft is claimed to have excellent physical characteristics, such as rigidity, cutting ability, and oil proof flat permeability, have light weight, provide comfortable feel to the user, and be easily decomposed after disposal. The shaft also does not generate toxic substances when incinerated (Figure 8.4). Biodegradable containers and packages used in commercial cosmetics products are listed in Table 8.7.

Figure 8.4  Tubular synthetic shaft for pencil-shaped cosmetic (2001, JP2001192502 A, OKIWA CORP.; NIPPON KOONSUTAAC KK). 11, Synthetic shaft; 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 used by pLaboratoires Phyt’s; Laboratoires Cosmediet; Laboratoires Science et Nature; Intercos [4]

PLA (Ingeo™, NatureWorks)

Bottles for Urara range of products (shampoo, conditioner, body soap, etc.)

Shiseido Co Ltd. (JP)

PLA (Ingeo™, NatureWorks)

Impact Zero—face and body lotion bottle

Eudermic Srl (IT)

PLA (Ingeo™, NatureWorks)

Mascara packaging

Oekametall (DE)

PTT (Biomax® PTT1100, Du Pont)

Shampoo (Pantene V) and conditioner bottles

Procter & Gamble (USA)

Bio-PE (Braskem)

8: Cosmetics

419

Table 8.7  Biodegradable Containers and Packages in Commercial Cosmetics Products—cont’d Commercial product

Company

Biopolymer

Sapien Women line (bottles for 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)

Surya (BR)

Bio-PE (Braskem)

Sundown® sun care bottles

Johnson & Johnson (USA)

Bio-PE (Braskem) (60 wt%) and recycled PE (40 wt%)

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” multilayer wrapping film

Umbria Olii Int. (IT)

PLA/copolyester blend (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 Patent number

Publication date

CN101491486 A

Family members

Priority numbers

Inventors

Applicants

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DONGXIAO SHENG; YIJIANG MA; HAIJIN CAO; KUN QIAN; HONGFU WANG

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ECKL WILHELM; NAEGELE HELMUT; PFITZER JUERGEN; EISENREICH NORBERT; EYERER PETER; ELSNER PETER

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JPH05194141 A

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NOGUCHI HIROSHI; MIZUNO SUMIKO; NOZAWA SEIICHI

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MIKI TERUHISA; NINAGAWA TAKASHI

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OKUYAMA YOSHIKAZU; HOSOE ISAO; SHIMA KIYOO; SAEGUSA MASASHI; TANAKA HIDEYUKI; MIYAJI NOBUO

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JP2007077311 A

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JP2007197602 A

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JP5093834 B2 20121212

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FUJIMOTO KATSUHIRO; KOBAYASHI AKIO

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JP2007289377 A

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SAKAMOTO KANRYU

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US2008226580 A1

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JP2008222876 A 20080925; EP1980235 A1 20081015

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MAEDA MIZUO; SUDESH KUMAR K; IWATA TADAHISA

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JP2011126798 A

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TOYO BOSEKI

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Publication date

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Family members

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Applicants

Title

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TANAKA TAKUMI

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Manicure preparation

JP2011201832 A

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MARTINS AGOSTINHO; MCGUIRE ELIOT DRANGEID

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Biodegradable and compostable component for cosmetic packaging

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Method for reducing marine pollution using polyhydroxyalkanoate microbeads

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20080828

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BLUME GABRIELE; TEICHMUELLER DIRK

ROVI COSMETICS INTERNAT GMBH

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8: Cosmetics

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