Polymers for personal care and cosmetics based on an international symposium on polymers for cosmeti
Polymers for personal care and cosmetics based on an international symposium on Polymers for Cosmetics and Personal Care held at the 244th National ACS meeting in Philadelphia on August 22 2012 1st Edition Anjali Patil
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Sequence controlled polymers synthesis self assembly and properties as a consequence the first international symposium on sequence controlled polymers was organized at the 246th American Chemical Society national meeting in Indianapolis all the c 1st Edition Jean-Francois Lutz
In Polymers for Personal Care and Cosmetics; Patil, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
ACS SYMPOSIUM SERIES 1 148
Polymers for Personal Car e and Cosmetics
Anjali Patil , Editor
Edison, New Jersey
Michael Ferritto , Editor
Dow Corning Corporation
Michigan Sponsor
Revlon
Library Congr ess
Cataloging - - Publication Data
Polymers for personal care and cosmetics / Anjali editor , New Jersey , Michael editor , Dow Corning Michigan ; sponsored the ACS Division Polymeric Materials: Science and Engineering. pages - - (ACS symposium series ; 1 148)
Includes bibliographical references and ISBN 978 - 0 - 8412 - 2905 - 1 paper)
Cosmetics - - Materials - -
Polymers - - Industrial applications -Patil, Anjali. II. Ferritto, Michael 2013
668.9 - - dc23
2013041538
The paper used this publication meets the minimum requirements American National Standard for Information Paper for Printed Library ANSI Z39.48n1984.
Reprographic copying beyond that permitted Sections 107 108 the U.S. Copyright Act allowed for internal use only , provided that a per - chapter fee plus per page paid the Copyright Clearance Center , 222 Rosewood Republication reproduction for sale pages this book permitted only under license from ACS. Direct these and other permission requests ACS Copyright Publications 1 155 16th W
The citation trade names and / names manufacturers this publication not construed endorsement approval ACS the commercial products services referenced herein; nor should the mere reference herein any chemical process, other data regarded a license a conveyance any right permission the holder , reader , any other person reproduce, use, sell any patented invention copyrighted work that may any way related Registered used this even without specific indication are not considered unprotected law
For eword
The ACS Symposium Series was first published 1974 provide a mechanism for publishing symposia quickly book The purpose the series publish timely , comprehensive books developed from the ACS sponsored symposia based current scientific Occasionally , books are developed from symposia sponsored other ganizations when the topic keen interest the chemistry audience.
Before agreeing publish a the proposed table contents reviewed for appropriate and comprehensive coverage and for interest the audience. Some papers may excluded better focus the book; others may added provide comprehensiveness. When appropriate, overview introductory chapters are added. Drafts chapters are peer - reviewed prior final acceptance rejection, and manuscripts are prepared camera - ready
a rule, only original research papers and original review papers are included the V erbatim reproductions previous published papers are not accepted.
ACS Books Department
eface
Polymers are routinely used many personal care and cosmetic The applications take advantage the various properties these polymers impart unique benefits their The range properties varied the class polymers that have been utilized. Using polymers, cosmetic chemists can create high performance Broad spectrums polymers natural polymers, synthetic polymers, ganic polymers well silicones are used a wide range cosmetic and personal care products filmformers, emulsifiers, protective and aesthetic
Development leading edge products requires better chemical and physical properties that cannot provided traditionally used, naturally - derived raw ingredients such fats, oils, and waxes. Many valuable, new cosmetic ingredients come from broad polymer classes such polyamides, polyurethanes, polyolefins, and silicones. T oday , polymers can custom engineered produce desired end and can manufactured economically a commercial scale deliver such performance a consistent, and reproducible Molecular weights can tailored formulation
Thermal and mechanical properties can needed. Classical chemical properties such surface activity , solubility , hydrolytic stability , oxidation and other characteristics can also designed a precise and controlled manner .
This book based international symposium for Cosmetics and Personal held the 244 t h National ACS Meeting Philadelphia August The aim this book cover the many facets polymers used cosmetics and personal care products and bring together researchers from industries and academic disciplines from dif ferent
T o our knowledge, this the first compilation progress made the use polymers cosmetics and personal industry
This book comprises a collection papers presented the symposium well several review chapters. T opics this book have been divided into three sections follows: Part 1 contains reviews focused polymers described this book, polymers used colored cosmetic products, and gano functional silicones; Part 2 dedicated new synthetic methods and strategies; and Part 3 focused novel applications synthetic polymers. the synthetic portion the book (Part there are seven Some chapters discuss specific approaches controlling molecular architecture and other chapters prepare novel polymeric For example, polymer structures can controlled using free radical methods order prepare unique aqueous rheology modifiers create copolymers with unique properties.
Additionally , novel materials prepared combining poly(alphaolefins) with diphenylamine and polymers, novel cationic latex materials, and polymers with unique personal care attributes that are also biodegradable are discussed well. There are chapters structure - property relationship well non - penetrating polymerized surfactants.
The third part the book consists seven highlights novel applications materials that may not typically associated with personal care Such polymers include acetylene - based alkylacrylate crosspolymers, styrene / acrylate copolymers, and silicones. There are also some chapters that discuss other interesting applications materials utilizing the enhanced performance they impart personal care (e.g., ion permeable microcapsules and a polymer adsorption
This book will a good resource for those involved the field personal care and cosmetics who want learn recent developments. Additionally , this book will benefit the reader that would like become acquainted with the variety polymeric systems that can used personal care products and cosmetics.
The editors thank the Division Polymeric Materials: Science and Engineering for their support the symposium which this book based. W e wish thank all the authors for their cooperation and for their high quality chapters. Finally , thank T Marney , Arlene Furman and Rachel Deary from the ACS books department for their help keeping
Anjali Patil
Revlon Research Center 2121 Route Edison, New Jersey 08818
Michael Ferritto
Dow Corning Corporation 2200 W est Salzbur g Road Michigan 48686
. Anjali Patil
Anjali Patil a Senior Scientist Revlon She has been working Revlon for the last years. Her work involves synthesis and use polymers various aspects cosmetic
Anjali obtained her Ph.D. from the Indian Institute T echnology , Bombay (India) polymer chemistry and has done her post - doctoral research the University Illinois Urbana - Champaign ganic Chemistry (Dr . David Y . Curtin) and also the Institute for Polymers and ganic Solids, University Santa Barbara (Dr . Fred W She has been a member ACS for the past years. She has attended and chaired sessions the National ACS She a member the Society Cosmetic Chemists. She has published 9 scientific papers, issued U.S. patents, and published patent She has recently written a monograph Lacquer T echnology which published the Society Cosmetic Her research interests are synthesis and application
Anjali successfully ganized the symposium sponsored the PMSE division entitled for Personal Care and the fall 2012 ACS national
. Michael Ferritto
Michael Ferritto a Senior Development Specialist Dow Corning Corporation. has been working Dow Corning for years. His work involves the synthesis and application silicone polymers with emphasis ganofunctional silicones. Prior his time Dow Corning, was employed the Dow Chemical Company
Michael obtained his Ph.D. from the University Massachusetts Amherst ganic chemistry and studied polymer synthesis and application novel completed a post - doctoral fellowship the Michigan Molecular Institute where studied the synthesis novel dendrimer polymers has been a member ACS for the past a member the Polymer Chemistry and ganic Chemistry Division the ACS. has issued patents and published 7 His research interest the synthesis new polymers and the application ganic chemistry polymeric systems. Michael has - ganized (with Anjali Patil from Revlon) the symposium sponsored the PMSE division entitled for Personal Care and the fall 2012 ACS national
Chapter 1
Polymers for Personal Car e and Cosmetics: Overview
1 Revlon Resear Center , 2121 Route 27, Edison, New Jersey 08818
2 Dow Corning Corporation, 2200 W est Salzburg Road, Midland, Michigan 48686
* E - mail: Anjali.patil@r
Abstract
Polymers are routinely used many personal care and cosmetic The applications take advantage the various properties these polymers impart unique benefits their formulations. The range properties varied the class polymers that have been Using cosmetic chemists can create high performance products. Broad spectrums polymers; natural synthetic ganic polymers well silicones are used a wide range cosmetic and personal care products filmemulsifiers, thickeners, modifiers, protective barriers, and aesthetic
This book based international symposium for Cosmetics and Personal held the 244th National ACS Meeting Philadelphia August The aim this book cover the many facets polymers used cosmetics and personal care products and bring together researchers from industries and academic disciplines from dif ferent This overview chapter provides a brief description each chapter presented this book and meant provide the reader with insight the exciting developments described throughout.
Anjali Patil * , 1 and Michael Ferritto 2
There denying that cosmetics and personal care products represent a very lar market for products that provide a wide range properties the consumer . Personal care products can used enhance the appearance s hair , nails Makeup generally used even out skin hide blemishes, improve s appearance, moisturize and protect from rays the same Sunscreen products protect from sun and also have anti - aging Nail polish makes nails look pretty and protects them too.
Personal care products can carry out their function a cleansing aid while often providing additional benefit that can last well after the cleansing has taken They can also provide protection the form antiperspirant / deodorant and often include perfumes that impart a nice smell. These products can also provide much more than just aesthetic sensory Cosmetics can used help build the self - esteem for individual that has a medical condition that can masked using these products. quite obvious that this class consumer products can have a very lar range Consequently , a wide range components can used ingredients within this class products.
Polymers represent one class materials that have been used ingredients ( 1 , 2 ) . The types polymers that have been used are varied the applications which include Natural and synthetic materials have been The synthetic polymers used are also quite vast ranging from ganic polymers based alpha olefins inor ganic materials based Even within a certain class polymers, the structural variations can also dictate what kinds properties are obtained. Features such the degree polymerization, the amount and the ratio the units within a copolymer can have dramatic impact the final performance attributes. the copolymers are random versus block they are ABA (AB)n can influence the The chapters within this book represent some the recent advances how the specific properties polymers have been used provide some unique benefits cosmetics and personal care products.
A lar number mostly are used the cosmetic and personal care industry . They not only fect the rheological profile the formulation but also influence application the product, water sensitivity the and delivery the active Natural and synthetic ingredients are used thickeners for a water - based system. Anhydrous systems combine one more fatty (e.g. natural synthetic lanolin, long - chain fatty alcohols, triglycerides etc.) impart structural rigidity and facilitate mold release contracting slightly upon Synthetic waxes are either mixtures long chain hydrocarbons primarily derived from petroleum synthesized from monomers like vinyl vinyl pyrrolidone ganically modified dimethicones.
Polymers play a role rheology modifier cosmetics and personal care products. Often these products are prepared using water based formulations, and are typically low viscosity . This where the polymers are added thicken and many cases gel the T o increase viscosity water - based systems sometimes natural polymers are utilized such xanthan guar
gelatin, agar etc ( 3 ) . Occasionally , natural polymers are modified for personal
care use cellulose derivatives methyl hydroxypropylcellulose). Commonly used synthetic polymers are acrylic acid based polymers, polyacrylamides, and alkylene oxide based homopolymers and Alkali soluble emulsions (ASE) are synthesized from acid functional and acrylatemonomers. When the acid group fully protonated, the polymer exists a collapsed random coil low V iscosity low acidic and when acid groups are neutralized with alkali ganic amine, viscosity increases. Polymers like acrylates copolymers thicken char induced chain chain entanglement and hydration.
Hydrophobically modified alkali soluble emulsions (HASE) are acid / acrylate copolymers with ethoxylated hydrophobes ( 4 ) . When the acid groups present the HASE polymer are neutralized with they become anionically char ged and thicken the fect char induced chain extension and through association the hydrophobic groups. Polymers like acrylates / stearethmethacrylate copolymer build viscosity quickly , and can suspend pigments particulates. Another type rheology modifiers are hydrophobically modified ethoxylated urethanes Since these urethanes are nonionic neutralization required. These polymers are stable anionic, cationic and non - ionic systems well a broad
Acrylic acid based polymers are a workhorse the industry . They can broadly classified into 2 classes: acrylic acid cross - linked with allyl ethers pentaerythritol sucrose and acrylic acid cross - linked with C 1 0 - 3 0 alkyl acrylates.
All these acrylic acid based polymers have low electrolyte tolerance. The chapter titled “ Beyond Thickening: Use Alkyl Acrylate Cross - polymer Personal Care Formulations ” describes acrylates / C 1 0 - 3 0 alkyl acrylate cross - polymers that have thickening syner when salts and / certai surfactants are used.
A class polymers have been developed that can modify rheology water based They are typically a hydrophilic polymers that are water soluble and have been modified the addition hydrophobic groups ( 5 ) . Since there obvious incompatibility between these two types has been dif ficult prepare these materials easy and cost ficient process.
W ithin the chapter titled: “ Stars and Blocks: T ailoring Polymeric Rheology with RAFT for Personal Care Applications the preparation structural variants described where such hydrophobic polymers are easily added water soluble cores one step and two step There a need further modify the polymers prepared with this technique. Structure property relationships are developed for the block and star copolymers that were prepared, and their performance thickening aqueous mixtures Additionally , the appropriate choice the architecture and structural components, thermally responsive systems are demonstrated.
A lar number natural and synthetic antioxidants are used cosmetics and personal care products. Some the commonly used antioxidants are vitamin C (ascorbic acid), butylated hydroxyanisole, butyl hydroxyl toluene, and lar number natural antioxidants such grape seed horse chestnut celery extract, cucumber extract etc. Antioxidants are used scavenge free free radicals are known contribute the aging Free radicals contain unpaired electrons the outer shell and these unpaired electrons
try snatch electron from a nearby molecule gain stability When the molecule loses its electron, becomes a free radical and this initiates a chain reaction ( 6 , 7 ) Ultraviolet rays also produce free Skin inhibits the pressure being oxidized free radicals from the environmental pollution well ultraviolet rays using natural antioxidants our bodies. Antioxidants are added cosmetic formulations neutralize free radicals and help skin stay younger for a longer periods time.
Hydrocarbons such mineral paraf fin microcrystalline wax, and ceresin wax are used cosmetic products. Poly α - olefin AO) also used the personal care industry; one example a P hydrogenated polydecene. Hydrocarbons are used the personal care industry due their thermal and light stability ( 8 ) Due non - greasy feel P they are used skin eye shadow , and lip “
Bifunctional Synthetic Fluid: Polyolefin - Diphenylamine ” describes a novel synthesis antioxidant bound polymer using ionic liquid a new way increase solubility antioxidant, use these polymers lubricants, and a pressure DSC technique evaluate oxidative stability
Antioxidants and oils are also used hair care. Hair damaged environmental factors well chemical treatments like permanent waving, straightening, coloring. Environmental factors include wind, rain, harsh weather , ultraviolet and chlorinated swimming pool water Grooming practices like shampooing, brushing, blow drying, and combing can damage hair , especially the cuticle. radiation can bleach natural melanin the hair and can cause photo - degradation proteins such and This damage fects the hair color and the cuticle, which reflected wet and dry combing forces ( 9 ) .
A hair conditioner can improve hair luster shine, enhance tactile properties such dry and wet feel reduce fly - away , increase and improve manageability protecting from environmental, mechanical, and chemical Hair conditioner normally applied after shampooing the hair and then rinsed f shortly after application; this called - conditioner . also can a - conditioner: the name suggests, can applied a spray , a cream and left the hair . The chapter entitled “ Hair Care Polymers for Styling and Conditioning ” focuses polymers used styling and conditioning This chapter describes how the glass transition temperature, molecular weight and acidity the polymer fect performance the polymer and the spray , and mousse conditioning
This chapter also describes test methods used evaluate polymer performance and regulatory , and safety aspects related manufacture and use the polymers.
T ypically , cationic polymers are used hair conditioning Hair negatively char ged and therefore, cationic polymers show finity towards negatively char ged keratin. Polymer molecular weight, char density , and hydrophobicity play a role their interaction with hair . Natural polymers such polysaccharides (based cellulose and its derivatives, such starch), hydrolyzed and gums (gum gum tragacanth) and synthetic polymers (including polyvinyl pyrrolidone homo and copolymers, polyvinyl
and silicones) are often used. The chapter entitled “ Styrene / Acrylates Copolymer Film Former for Improved Hair Surface Luster ” describes the development a polymer and how can impart both hold and shine the hair . this chapter , a hairspray was developed using this polymer , and was compared conventionally used polymers for hair Dif ferent instruments such gloss meter , SEM, Diastron, and DMA are used for polymer property evaluation. Opacifiers are used personal care products such face cleanser , liquid soap, body wash, and shampoo. impart a milky white creamy appearance sometimes hide unacceptable opacifier should have a substantially dif ferent refractive index than the formulation for work.
There are two classes opacifiers used consumer products: glycol stearates Glycol stearates not only act opacifiers but also impart a pearlizing fect the formulation.
Emulsions used opacifiers are generally styrene copolymers that are anionic nature. They work well systems containing anionic surfactants. T o impart conditioning benefits hair and skin formulations cationic polymers are
Anionic opacifiers are not compatible with these formulations. The chapter titled “ A Novel Cationic Opacifier for Cleansing Formulations ” describes synthesis and evaluation a novel opacifier . Importance particle size for opacifiers depicted and a method evaluate opacity measuring backlight scattering described.
Polyurethanes are extensively used cosmetic and personal care products. solvent based and aqueous dispersions are used. Solvent based polyurethanes are used nail products secondary film - formers while aqueous dispersions are seen mascara and skin care formulations ( – ) . Film properties polyurethanes depend their structure. The chapter titled “ Modern Polyurethanes: Structure - Property Relationship ” explains how molecular phase separation, and crosslinking density fect polymer properties. Role soft and hard segments determining modulus and strength polymer and what determines stability and particle size the dispersion are explained. Many ingredients cosmetics and personal care products include those obtained from polymers prepared from ethylenically unsaturated monomers ( 1 ) . many cases, free radical polymerization methods are employed make these there are limitations the types copolymers that can prepared, and typically they will have a high polydispersity index (≥2.0) ( ) Application RAFT (Reversible Addition Fragmentation chain T ransfer) polymerization techniques have been employed make unique copolymers that can used personal care These unique materials are described the chapter titled: “ Controlled Synthesis Multifunctional Polymers with RAFT for Personal Care Applications
The RAFT process was implemented using two distinct routes. The first consists modifying a hydrophilic polymer add the required functional followed the addition a second block using the RAFT mediated polymerization. The second method simply uses typical RAFT conditions make block copolymers ABA triblock copolymer This results
materials that have potential applications hair hair styling formulations, lipsticks and mascaras.
There are several advantages using active delivery systems cosmetics and personal care One the biggest benefits the increased shelf life that typically accompanies the sequestering a bioactive component, where protected from the degrading fects other formulation components and / the environment ( ) . T ypically , the desired component has been physically entrapped within a polymeric There are several limitations using this type delivery system, such low level active loading and the release rate from within the matrix can dif ficult The materials that make the polymer matrix may also have detrimental interactions with the entrapped active, thereby decreasing its ficacy ( ) the chapter titled “ Bioactive - Based Poly(anhydride - esters) for Personal Care and Cosmetic Applications a novel active delivery system described. Instead being held within the interior a delivery the active ingredient incorporated either into the polymer chain a pendant group and can released a desired rate the hydrolytic degradation the polymer The hydrolysis releases the active perform its desired action. This results several benefits when compared previous delivery such very high active loading levels and increased active stability
The incorporation several dif ferent types actives described. Salicylic acid incorporated into the main chain a poly(anhydride - ester) and the complete release within a short time demonstrated. This active a typical component skin care products having anti - acne and other benefits for skin Antimicrobials another class active compounds that can incorporated a pendant group the poly(anhydrideester). This system can designed such that when the polymer not only the antimicrobial released but the polymer backbone can broken down another beneficial component such ethlyenediaminetetraacetic A final example bioactive components that can delivered using this method antioxidants, with ferulic acid being has been dif ficult include this potent compound due its low stability . Use this system could lead new personal care products that incorporate this
A variety dental issues result when the enamel A major component enamel hydroxyapatite which contains calcium and phosphate ions and other constituents ( ) . The loss the calcium and phosphate causes the enamel erode, which a process referred ( ) . This demineralization process can reversed with treatments that provide phosphate and fluoride ions ( ) . The chapter titled “ The fect Counterion, Concentration and T emperature the Release Bioavailable Calcium and Phosphate Ions from Ion Permeable Microcapsules for Remineralization ” studies the release calcium and phosphate from these microcapsules a function several controllable factors. These factors include the type polymer used prepare the microcapsule, the form the phosphate ion, the associated the initial ion concentration inside the microcapsule and These materials could have potential application oral decay preventative treatment a tooth whitening
Anhydride functional polymers represent a class polymers that can soluble water and such are used many personal care formulations ( ) . For example; anhydride polymers are suited for use toothpaste, mouthwash and other oral care The anhydrides will open generate acid groups and these will allow association with natural surfaces, since these are typically char ged ( ) . T o improve the use the anhydride polymers such understanding the mechanism adsorption onto the natural surfaces Once the adsorption can the impact various conditions can determined.
the chapter titled “ Adsorption / Desorption Processes - Responsive Copolymers Dental Surfaces via QCM and AFM Analysis the mechanism the adsorption a maleic anhydride methyl vinyl ether copolymer studied a function the The copolymer adsorbed onto a specially prepared substrate coated with hydroxyapatite (the main component dental surfaces) provide ultra smooth model a dental Both and concentration were varied and the mechanism and the form the adsorbed copolymer varied with these low the ionic copolymer strongly interacts with the char ged surface and results the polymer being a rigid conformation. The information obtained could lead new applications oral care
The name refers the class inor ganic polymers based a silicon oxygen There a variety structural variants and many dif ferent ganic functional groups that are included with these materials. Also, silicones have used extensively cosmetics and personal care products. One the reason silicones are used because the unique attributes these materials can impart the formulations. For example, silicone surfactants can found that stabilize both oil - - water and water - - oil emulsions ( , ) . Silicone resins add mechanical strength and long - lasting characteristics lipsticks and foundations ( ) Low molecular weight linear silicone fluids and cyclosiloxanes are volatile but also impart a unique feel once they have evaporated ( ) . The linear silicones that have two methyl groups attached each chain silicon atom are commonly referred “PDMSs”. The unique properties associated with siloxanes have been described terms the molecular attributes these materials that are very dif ferent from ganic the chapter titled “ Silicone W ettability and Its Significance Beauty Products some the unique molecular properties are investigated using contact angle measurements. The surface ener dif ferent silicones are measured and compared ganic oils and The dif ferent silicones include structural variants PDMS materials, such linear PDMS, cyclic PDMS compounds and networked including gels and Additionally , silicones that also have been modified with various ganic groups are included the discussion. Several personal care uses silicones are described throughout the chapter A variety synthetic and natural polymers have been used additives personal care applications act rheology modifiers, stabilizers, emulsifiers film A method screen the performance the polymer additive could valuable quickly identifying the appropriate material choice for the desired important function a polymer a film former for a skin application and the viscoelastic properties the polymer will determine
how the polymer performs ( ) “ Mechanical Characterization Cosmetic and V iscoelastic fects Firming Polymers a method described screen a variety synthetic and natural polymers for the firming fect
The screening the mechanical performance the polymers a given substrate and modeling indicated a correlation firmness and elasticity . When the applied polymer increased the firmness the there was also increase the elasticity . When the polymers that displayed this increase firmness and elasticity were then applied the same increase these mechanical properties was demonstrated. Although the range polymers tested was this method shows the ability quickly measure the performance a polymer for a given mechanical property .
One the components commonly added cosmetic and personal care formulations These materials provide stability these formulations since they also typically include water . When small molecule surfactants are used, they also have the ability cause irritation they penetrate into the skin ( , ) . would desirable have a compound that would provide the benefits small molecule surfactants without this detrimental side “ Next Generation Mildness for Personal Care: Nonpenetrating Polymerized Surfactants for Cleansing Applications a class materials described polymerized surfactants was discussed and tested. These materials can have a variety chemical structures and they maintain the surface activity required stabilize aqueous formulations. addition, since they are much lar ger than their small molecule counterparts, was demonstrated that they possess a dramatically lower tendency penetrate addition this the materials were also able maintain cleansing and foaming, which are critical performance and consumer These polymerized surfactants could also used with the small molecule surfactants, and this combination resulted milder compositions compared small molecule surfactants when used These materials represent a new class surfactants that provide very mild
Refer ences
Gruber , V Principles Polymer Science and T echnology Cosmetics and Personal Cosmetic Science and T echnology ; Gruber , V Eds.; Marcel Dekker Inc.: New Y ork, 1999; V ol. 22; Chapter Lochhead , Y . ACS Symp. Ser . 2007 , 961 , 3 . Clarke, T . Rheological Properties Cosmetics and T oiletries. Cosmetic Science and T echnology Series ; Marcel Dekker , New Y ork, 1993; V ol. 13, 55−152. Jones , E T oiletries 2002 , 1 , W innik , ; Y ekta , Curr . Opin. Colloid Interface Sci. 1997 , 2 , 424
In Polymers for Personal Care and Cosmetics; Patil, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
Surfactants Personal Car e oducts and Decorative Cosmetics , 3rd ed.; Rhein, Olenick, A., Schlossman, M., Somasundaran, P Surfactant Science Series; CRC Press: Boca Raton, 2007; V 341−355.
Krummel, K.; Chiron, S.; Jachowicz, The Chemistry and Manufactur e Cosmetics , 4th ed.; Allured books: Carol IL, 2009; V ol. 123−163. Nail Lacquer T echnology ; W Monograph No. Society Cosmetic Chemists: New Y ork, 1997.
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12. Collin, U.S. Patent 6,482,400, 2002. V Polymers: Chemistry and Physics Modern Materials , 3rd ed.; CRC Press:
14. Gebelein, C. G.; Cheng, T . C.; Y ang, V . Cosmetic and Pharmaceutical Applications Polymers ; Plenum Press: New Y
15. Gupta , S HAPPI 2003 January , . Mathew , ; T akagi , Structures biological minerals dental Res. Natl. Inst. Stand. T echnol. 2001 , 106 , 1035 . Dawes , What the critical and why does a tooth dissolve acid?
Can. Dent. Assoc. 2003 , , 722 . Garcia - Godoy , F ; Hicks , Maintaining the integrity the enamel surface: the role dental biofilm, saliva, and preventive agents enamel demineralization and remineralization. JADA 2008 , 139 , 25S .
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21. Hill, R. Silicone Surfactants ; Surfactant Science Series; Marcel Dekker: New Y 1999; V
22. Petrof J.; Snow , Silicone Surface Science ; Owen, J., Dvornic, P Springer: New Y ork, 2012; Chapter Inor ganic Polymers ; Jaeger , Nova Sciences Publisher: New Y ork, 2007; Chapter 16. Brand , ; Brand - Garnys , Cosmet. T oiletries 1992 , 107 , .
27. Jongh , C. ; V erberk , ; Spiekstra , W . ; Gibbs , ; Kezic , Skin T 2007 , (4) , 390
Chapter 2
Cosmetic Science and Polymer Chemistry: Perfect T ogether
Anjali Patil * and Robert W . Sandewicz
Revlon Resear Center , 2121 Rote 27, Edison, New Jersey 08818 * E - mail:
Cosmetic science has evolved significantly during the past thirty years. One the principal drivers such advancement has been the development new color cosmetic formulations that deliver a combination drastically improved functional performance and outstanding aesthetic properties. The key element enabling the creation such high performance products the increasingly widespread use a broad spectrum polymers a wide range color cosmetic
The primary reasons for this trend are rooted intrinsic attributes Polymers typically are more substantive biological substrates than are many the fatty - based raw ingredients historically used cosmetic Polymers also can customized readily meet very specific performance requirements. some formulations, polymers have supplemented fatty - based raw ingredients a means improving product performance. other formulations, advanced technology polymers have completely replaced traditional cosmetic chemicals order create products having superior skin adhesion and wear Polymer scientists should aware the safety and regulatory requirements peculiar the cosmetic industry engage cosmetic chemists a productive way .
Intr oduction
American industrialist Henry Kaiser credited with having coined the adage, “ Find a need and fill This advice typically cited within a marketing context, yet appropriately describes the ongoing relationship between cosmetic science and polymer chemistry . Classical polymer chemistry understandably might viewed part a lar ger industry”, conversely , the term cosmetic science first glance might seem How can aesthetics reconciled with ganic chemistry? What common ground could possibly exist between lipsticks and elastomers? Are the names Ziegler and Natta synonymous with beauty the names Revson and Lauder ? Despite what might appear a glaring lack similarity , both areas truly are more alike than might Both fields are highly scientific are quite adept harnessing new technologies reconcile some challenging and financially are very both cosmetic scientists and polymer chemists make high performance, high value products through skillful implementation advanced technologies , Kaiser would have finding needs and filling them.
The common ground shared cosmetic scientists and polymer chemists can summarized one word: performance . During the first three decades the t h Century , cosmetic manufacturers sought transform their businesses from small, artisanal into modern enterprises. They did not only use clever and aggressive marketing strategies, but also use increasingly sophisticated chemical The net result: products characterized outstanding aesthetics and performance - driven benefits. During that cosmetic chemists had the unenviable task attempting create such products using the relatively unsophisticated raw ingredients available them. Chemists relied almost exclusively time - naturally derived raw materials such fats, oils and waxes. Given the inherent variability biological the chemical and physical properties natural ingredients sometimes varied considerably from lot lot. Not surprisingly products intended both aesthetically pleasing and functional did not always perform consistently The fact that early cosmetic products enjoyed any commercial success pays tribute skillful formulators who were able comprehend and manage the variability a relatively small comprised mainly naturally derived raw ingredients.
During the years leading W orld W consumers demanded increasingly more sophisticated cosmetic products. Synthetic pigments became available a regular enabling formulators staple cosmetic products such nail lacquers and lipsticks broaden their shade palettes significantly . Performance attributes such ease high gloss and improved adhesion human skin and nails became more important. Fortunately , during this same timeframe, polymer chemists were busy creating synthetic ganic polymers such polyethylene and Considered rudimentary materials today , these revolutionary new polymers represented breakthrough technologies the with cosmetic dye and textile chemists had long grappled with the inherent performance shortcomings
such cotton and wool prior the advent synthetic polymers capable producing having more uniform and predictable chemical and mechanical
The fruits technical labor did not unnoticed the cosmetic industry .
Founded New Y ork City 1945, the Society Cosmetic Chemists (SCC) became the cornerstone professional ganization which the discipline was firmly established ( 1 ) . Then now , the scholarly journal SCC served the primary tool communicate new raw ingredient technologies, formulation techniques, manufacturing advice, and product testing Not surprisingly , new polymeric ingredients potentially useful cosmetic formulators began appearing SCC literature with increasing frequency
Creators advanced new beauty care products took note such technical advances and began experimenting with new polymeric ingredients formulations previously dominated animal - and plant - derived raw materials ( 2 ) . Due aggressive competition, new formulations were required attract increasingly savvy consumers who demanded constant innovation and ever more added value. New polymeric materials clearly would benefit formulators such complex new cosmetic with their counterparts many other industries, cosmetic chemists realized that high performance products could achieved only selecting raw ingredients truly capable sustaining such performance characteristics a predictable basis. Leading edge products required far better chemical and physical properties than could provided most naturally - derived raw
Many valuable new cosmetic ingredients came from such broad polymer classes polyamides and hydrocarbons ( 3 – 6 ) . Why this hunger for polymers cosmetics? Once again, the word performance enters the Clearly , very many non - polymeric synthetic raw ingredients are readily available cosmetic chemists today . There are many formulations having performance requirements that are met adequately without the use polymeric materials. Nevertheless, polymeric cosmetic ingredients help make higher performance attributes possible ways that their counterparts cannot Polymers have structure / activity relationships that can custom engineered produce desired end objectives, and can manufactured economically a commercial scale deliver such performance a consistent, predictable and reproducible basis. Molecular weights can tailored formulation Thermal and mechanical properties can needed. Classical chemical properties such surface activity , solubility , hydrolytic stability , oxidation resistance and other characteristics also can designed a precise and controlled manner . Clearly , cosmetic chemists have come recognize and appreciate what polymer chemists have known for many years: the potential benefits polymers beauty care products are limited mainly the imaginations those who synthesize polymers and those who determine how best use these materials end
One the many technological step - changes that have occurred cosmetic science during the past years involves the lar class polymers collectively known silicones . V ery many unique and important performance benefits highly
relevant the cosmetic industry have been made possible through the use these materials. cosmetic chemists became familiar with the solubility and compatibility profiles various silicones used combination with traditional ganic raw the very real benefits silicones became Early silicones frequently used cosmetic applications were homopolymers dimethyl Known dimethicones , these liquid polymers were employed many the same applications ganic oils, impart hydrophobicity and lubricity the skin ( 7 ) Manufacturers also began fering various ganically - modified silicones that were more readily compatible with traditional cosmetic raw and that fered a broader range visual and tactile properties. Silicone emulsifiers were developed enable formulation stable creams and Perhaps the most revolutionary silicone polymers used cosmetic applications are silicone r esins . Produced various materials such trimethylsiloxysilicate (called r esins silicone chemistry parlance) help produce cosmetic formulations having very tenacious adhesion skin, thus enabling creation entirely new classes - lip and face makeup products ( 8 – ) this point, polymers have been discussed solely within the context cosmetic formulation technology A meaningful analysis the engineering applications polymers used modern cosmetic packaging applications warrants more than a cursory and far beyond the scope this document. Manufacturers sustainable cosmetic packaging materials have struggled achieve all the protective and aesthetic properties conventional polymeric but significant advances undoubtedly will made the development biodegradable, sustainable packages exhibiting chemical and mechanical robustness equal that conventional Another important but less obvious application polymeric materials cosmetic science process Materials storage and shipping vessels used the cosmetic industry historically were constructed metal. response a wide variety contemporary factors enhanced corrosion ener conservation, sustainability initiatives, ease recycling, cost control programs, reduction tare weight mitigate shipping costs storage and transportation equipment built with polymeric materials have become more common the industrial environment. Intermediate bulk containers (sometimes called IBC’ s totes ) can constructed polypropylene instead stainless steel. with analysis polymeric packaging materials, a discussion the use engineering polymers chemical processing industries a subject worthy a separate discussion and beyond the scope this chapter . T able 1 lists the functional properties cosmetic ingredients alongside their expected consumer benefits, then provide examples polymers that have been utilized commercially meet these Examination this table reveals that appropriately selected polymers can provide nearly every functional property needed achieve meaningful consumer benefits all types cosmetic Whether the final product form solid (e.g. deodorant), liquid (e.g. nail lacquer , foundation makeup, shampoo) gaseous (e.g. aerosol hair spray) one more polymeric raw ingredients may
used combination with multiple other cosmetic chemicals deliver the level performance required meet consumer needs.
T ransfer resistance T enacious product adhesion; enhanced skin protection; improved product aesthetics; reduction number product application cycles T rimethylsiloxysilicate ( r esins silicone elastomers
T ack
Emolliency
Moisturization, chapping prevention
Surface activity
Enhanced product adhesion polybutene
Enhanced comfort & protection
Improved skin condition; more youthful skin appearance
T echnologies such dendritic polymers might fer tremendous benefits beauty care products once cosmetic chemists begin understand how best use these The concept equally the field composite polymers. recent years, numerous smaller cosmetics brands have decided market products identified ganic, mineralbased and / bio - botanical , lar gely the hope increasing market share among groups consumers with whom such terms resonate positively Conversely , lar ger cosmetic brands have chosen market products based primarily consumerperceived performance interesting observe that polymers either natural synthetic origin can provide important benefits regardless specific market Driven overarching - such sustainability , environmental sensitivity , conservation ener and natural resources, makers and users polymers across all industries will discover creative new ways exploit the great utility these with many parts.” Cosmetic chemists have come recognize and appreciate that potential benefits polymers beauty care products are limited mainly the imaginations those who synthesize polymers and those who determine how best use these materials end products. Equipped with high - tech polymers the toolbox”, successive generations cosmetic chemists and polymer scientists undoubtedly will more than able support continuous forts a need and fill it.”
Film Formation
the cosmetic industry , a - forming does not necessarily form a self - standing can a fluid film that enhances the wear the product, extends sunscreen protection, imparts water oil resistance, improves product aesthetics. A lar variety polymers are used film formers, such and
• Hydr ocarbons : Commonly used hydrocarbon polymers are polyisobutene, polycyclopentadiene, and poly(alpha olefins), frequently abbreviated P ( 6 ) They are made polymerizing α - olefins - olefin alkene with terminal double e.g. 1example a P commonly used cosmetic formulations hydrogenated Polydecenes are available a wide viscosity range, and due their non - greasy skin feel they are used skin care, eye shadow , and lip products ( 1 1 ) The most commonly used polybutenes are lower molecular weight polymers (400 - 1000 daltons) and primarily are used lip gloss formulations they are very shiny and have good adhesion lip surfaces. They are also used eye eyeliner , mascara and makeup Hydrogenated polyisobutenes are mainly used lip products along with eye shadow , eyeliner , and mascara ( ) .
• Acrylates copolymers : Acrylates are formed free radical polymerization dif ferent acrylic monomers, either via solution emulsion They are available 100% solids form well dispersions and emulsions. They are used either alone secondary film - formers along with nitrocellulose nail enamel formulations ( 4 , ) . They also are used skin care products extend sunscreen protection wear Mascara formulations often use acrylate copolymers with acid functionalities, neutralized with alkali ( ) . the emulsion coalesces during the drying period, a relatively durable film formed eye
• Silicone acrylate copolymers : These copolymers are prepared either free radical polymerization a silicone acrylic monomer with other acrylic monomers grafting ( , ) . Some copolymers have siloxane backbones with pendant acrylic groups poly(dimethylsiloxane) - g - poly(isobutyl methacrylate) shown
Figure 1
This copolymer dissolves cosmetic solvents such isododecane and forms shiny adhesive These materials are used high - performance pigmented cosmetic such lip products and mascaras ( ) . Some copolymers have acrylic backbone with pendant silicone e.g. poly(isobutyl methacrylate) - - methyl FOSEA) - g - poly(dimethylsiloxane) used lip products ( ) . Acrylic silicone graft polymers also can prepared free radical polymerization dimethylpolysiloxane with polymerizable acrylic / methacrylic group end with acrylic / methacrylic monomers shown Figure 2 ( ) . These acrylates / dimethicone copolymers form adhesive films that have good water and oil resistance. They are used various pigmented cosmetic products well skin care products for enhanced sunscreen
• Polyester r esins : Polyesters are formed the reaction between a polyol and acids acid Polyesters used lip products are generally synthesized using aliphatic fatty acids and fatty alcohols.
These polymers confer adhesion and water Polyesters used for nail enamel applications typically are produced the reaction dicarboxylic acids adipic acid), polyols glycerin, neopentyl glycol trimethylolpropane) and acid anhydrides (e.g. maleic anhydride, phthalic anhydride trimellitic anhydride). Such polyester resins produce soft films and often are blended with nitrocellulose improve gloss, toughness and flexibility nail lacquer films ( 4 ) .
• Nitr ocellulose : The first polymer used cosmetic formulations was nitrocellulose (cellulose nitrate). produced the esterification cellulose (obtained from cotton fibers wood pulp) with nitric acid and its structure shown Figure 3 . Nitrocellulose lacquers first came into widespread use the 1920’ mainly for automobile finishes and other industrial coatings applications ( 3 ) .
Nitrocellulose a dangerous explosion and fire hazard. Nitrocellulose particularly explosive when dry , thus must wetted with ethanol isopropanol prevent detonation transit. readily degrades upon exposure many common environmental such sunlight, elemental iron and alkaline compounds. Classic evidence the degradation nitrocellulose solutions ganic solvent mixtures a yellowing browning the bulk solution. spite these formidable still the main film - former used nail lacquer formulations today ( , ) . Nitrocellulose manufactured various grades based dif ferent solvent solubility profiles and molecular Nitrocellulose used nail products has a high degree nitration for maximum durability and water resistance. Although it’ s neat films are inherently nitrocellulose forms shiny films when adequately plasticized.
• Cellulose Esters / Mixed Esters : order avoid the hazards nitrocellulose a variety industrial applications (including the manufacture early motion picture film) polymer chemists undertook development cellulose esters the 1920’ s and 1930’ esterifying the available hydroxyl groups cellulose with acetic acid alone with a mixture acetic acid and either propionic butyric several useful polymers were created: cellulose acetate (“CA”), cellulose acetate propionate (“CAP”) and cellulose acetate butyrate (“CAB”). These polymers not present the explosion hazards nitrocellulose, and they also are far more tolerant a variety environmental They are soluble a wide range commonly available ganic solvents, and are compatible with a broad range plasticizers and other Cellulose esters / mixed esters exhibit very good clarity and color stability even with prolonged exposure heat and other making them particularly valuable for use - nail topcoat formulations ( 3 ) .
• Polyur ethanes : The first polymers containing the urethane linkage ( - NCOOR were developed and prepared Otto Bayer Germany . Urethanes are esters carbamic having the structure where R ganic radical. This basic reaction still used the
production urethane today ( ) Solvent based polyurethanes are used nail products secondary film formers and also eye shadow , mascara, foundation and lipstick ( ) Aqueous polyurethane dispersions are used extensively skin care they form flexible films ( , ) .
In Polymers for Personal Care and Cosmetics; Patil, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2013.
Figur e 1 . Poly(dimethylsiloxane) - g - poly(isobutyl methacrylate).
Figur e 2 Acrylates / dimethicone copolymer 1 H alkyl R 2 alkyl oup).
Figur e 3 . Structur e nitr ocellulose.
T ransfer Resistance
When a cosmetic product does not - f”, deposit clothing glasses, when resists removal food - proof”), called - resistant”.
Transfer - resistant cosmetic products are less fected water and oil compared conventional cosmetic products and are not easily fected sebum perspiration. Early transfer - resistant lip products were prepared partially replacing the non - volatile oils with volatile solvents ( ) These products were - but they were not suf ficiently durable described - proof”. Robust food - proof products almost all have one thing common: “MQ polymers”. the alphabet”, “MQ more accurately described trimethylsiloxysilicate.or trimethylated silica. polymers are highly cross - linked structures consisting SiO 4 / 2 T rimethylsiloxysilicate dissolved / dispersed volatile solvents e.g. isododecane, volatile cyclic linear silicones also can dissolved non - volatile silicones (e.g. dif ferent viscosity dimethicones substituted dimethicones alkyl phenyl substituted
There are lar number lip, eye, and face products sold today containing trimethylsiloxysilicate ( 8 – )
T ack
Although tack usually not a pleasant feeling the skin necessary promote adhesion cosmetic products various biological substrates. Molecular weight and glass transition temperature play a role determining tack the polymer . Polyisobutylene with lower molecular weight has tack and ability flow and wet the substrate, and also imparts shine ( ) . Polyisobutylene forms occlusive barrier and locks the moisture used lip gloss. Hydrogenated polycyclopentadiene used enhance adhesion and Hydrogenated polycyclopentadiene synthesized ring opening metathesis polymerization dicyclopentadiene, then the double bond
This a low molecular weight (~500 dalton) polymer that soluble volatile and non - volatile hydrocarbons and imparts water - resistance the formulations along with adhesion. Hydrogenated polycyclopentadiene used eye liner , eye shadow , and mascara ( ) .
Emolliency
defined ingredient intended soothe and protect means the degree skin soothing and protection conferred a particular cosmetic raw ingredient ( ) . Historically , cosmetic emollients were liquid and solid fatty materials derived from plant and animal sources (e.g. castor oil and lanolin, respectively). Not surprisingly , emollients also can derived from completely synthetic feedstock octyl Polydimethyl siloxane called the dimethicone cosmetic industry , this name conforms INCI (the International Nomenclature Cosmetic Ingredient) nomenclature. Dimethicone described a MDM polymer the silicone Dimethicone has flexible silicone and oxygen (siloxane) which methyl groups are attached. Dimethicones are hydrophobic and still have high permeability water vapor Although dimethicones have very low glass transition they are not tacky sticky . Due their low surface tension (24 / m), dimethicones can spread easily and wet substrates (e.g. skin lips) easily .
Dimethicones come a broad viscosity range from 0.65 cSt thousands cSt dimethicone volatile and used a solvent a diluent, while higher viscosity dimethicones are used protective agents. Due its hydrophobicity , low surface tension and ability spread easily , dimethicone recognized the Food and Drug Administration a protecting agent topical skin care products ( ) The skin protectant monograph allows dimethicone claimed active ingredient when incorporated into OTC (over the counter) products concentrations 1 30%. anti - chapping claim can made for a lip product contains least
Moisturization
The term defined a process which skin made smooth and supple keeping relatively For most biological moisture provided mainly water . Maintenance the proper amount water the skin can accomplished depositing a hydrophobic barrier layer over skin surfaces prevent retard trans - epidermal water loss (known “TEWL”) ( ) This tactic sometimes called “occlusion”. has direct parallels the plant world: cacti and other plants living arid regions have waxy surface layers that fectively prevent loss precious water . Following this hydrophobic liquid polymers such hydrogenated polydecene are used natural moisture, thus making the skin feel and look more moist and These polymers are more substantive than their mono - molecular counterparts, and recent years have replaced older moisturizers such mineral oil A second method moisturization involves attracting water skin surfaces. This type activity called “humectancy”. Most humectants contain one more functionalities capable forming hydrogen bonds with water . While the archetypal mono - molecular humectant glycerol 3 - carbon tri - hydroxy alcohol) polymers having similar architecture also can provide humectant
Surface Activity
Some examples surface active polymers are poly(ethylene poly(propylene and poly(ethylene oxide - propylene oxide) They are prepared homo - - polymerization the corresponding ether . INCI nomenclature classifies homopolymers ethylene oxide into two categories. Ethylene oxide polymers with molecular weights below 20,000 are designated PEG - where N represents the number ethylene oxide monomer units the polymer ( ) . When alcohol (e.g. methanol) used initiate the polymerization a lower molecular weight methyl - terminated polyether , the INCI designation PEG - N methyl ether . Polymers with molecular weights greater than are referred poly(ethylene oxides) and the INCI designation PEG#M, where # a whole number and the M indicates 1000, and together they represent the approximate number moles ethylene oxide the polymer PEG - comprised 3000 moles ethylene oxide. These high molecular weight poly(ethylene oxide)s are solid materials. The dif ference between poly(ethylene oxide) and poly(propylene oxide) a single methyl group, but that dif ference has significant implications. Poly(ethylene oxide) homopolymers are water soluble all molecular weights and all proportions. contrast, presence the additional methyl group propylene oxide imparts hydrophobicity poly(propylene oxide) making them waterinsoluble. Random / copolymers are water soluble when they contain least 50% ethylene Not surprisingly , block - polymerization and produces amphiphilic polymers that legitimately can described - ionic surfactants”. entire class surfactants created adjusting the - - ratio various block - polymers across the full spectrum HLB / lipophilic values. Hydrogen bonding responsible for the finity between water and the moiety / Because this situation, random / copolymers exhibit a phenomenon known “ inverse cloud point”, defined the temperature which such polymers collapse upon themselves and precipitate from aqueous solution. the solution cools, hydrogen bonds - the polymer - disperses and then - These polymers have a slippery feel. Due their surface activity , they are very good for dispersing pigments sparingly water - soluble raw ingredients into water .
Structur e Development
Cosmetic products are marketed a variety convenient forms.(e.g. lipsticks and anhydrous blush formulations) are very popular products ( ) . They are manufactured melting and mixing solid, semi - solid and liquid fatty raw ingredients then casting the hot molten liquid either into molds directly into final containers. This procedure has parallels other industrial such steel casting a foundry injection molding a plastics factory . T raditionally , hot pour formulations must incorporate one more fatty waxes, lanolin, long - chain fatty alcohols, triglycerides etc.) impart structural rigidity and facilitate mold release contracting
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A CHRISTMAS CAROL
HE Christ-child lay on Mary’s lap, His hair was like a light. (O weary, weary were the world, But here is all aright.)
The Christ-child lay on Mary’s breast, His hair was like a star (O stern and cunning are the Kings, But here the true hearts are.)
The Christ-child lay on Mary’s heart, His hair was like a fire. (O weary, weary is the world, But here the world’s desire.)
The Christ-child stood at Mary’s knee, His hair was like a crown, And all the flowers looked up at Him And all the stars looked down. G. K. C
EX ORE INFANTIUM
ITTLE Jesus, wast Thou shy Once, and just so small as I? And what did it feel like to be Out of Heaven, and just like me?
Didst Thou sometimes think of there. And ask where all the angels were? I should think that I would cry For my house all made of sky; I would look about the air, And wonder where my angels were; And at waking ’twould distress me— Not an angel there to dress me!
Hadst Thou ever any toys, Like us little girls and boys? And didst Thou play in Heaven with all The angels, that were not too tall, With stars for marbles? Did the things Play Can you see me? through their wings? And did Thy Mother let Thee spoil Thy robes, with playing on our soil? How nice to have them always new In Heaven, because ’twas quite clean blue.
Didst Thou kneel at night to pray, And didst Thou join Thy hands, this way? And did they tire sometimes, being young, And make the prayer seem very long? And dost Thou like it best, that we Should join our hands to pray to Thee? I used to think, before I knew, The prayer not said unless we do. And did Thy Mother at the night
Kiss Thee, and fold the clothes in right? And didst Thou feel quite good in bed, Kiss’d, and sweet, and Thy prayers said?
Thou canst not have forgotten all That it feels like to be small: And Thou know’st I cannot pray To Thee in my father’s way— When Thou wast so little, say, Couldst Thou talk Thy Father’s way?— So, a little Child, come down And hear a child’s tongue like Thy own; Take me by the hand and walk, And listen to my baby-talk.
To Thy Father show my prayer (He will look, Thou art so fair), And say: “O Father, I, thy Son, Bring the prayer of a little one.”
And He will smile, that children’s tongue Has not changed since Thou wast young!
A SONG OF CHRISTMAS
HE Christmas moon shines clear and bright; There were poor travellers such a night Had neither fire nor candle-light.
One plucked them stars out of the sky To show the road to travel by; So that the Ass go warily
She had all Heaven safe in her hold, Hidden within her mantle’s fold— All Heaven, and It was one hour old.
Her hair under, over Him spread His spun-gold coverlet and His bed, Twined with His little golden head.
She sang and rocked Him to-and-fro Such songs as little babies know, With Lullaby Sweet, and Lullalo.
He had no need of moons and suns, Nor the gold-crested bird-legions, Singing their lauds and orisons.
The Christmas moon shows a cold beam; He hath His Mother, she hath Him: Together they sleep, together dream.
K T
THE HOLLY AND THE IVY
HE holly and the ivy, Now are both well grown. Of all the trees that are in the wood
The holly bears the crown.
The holly bears a blossom As white as the lily flower, And Mary bore sweet Jesus Christ To be our sweet Saviour.
The holly bears a berry As red as any blood, And Mary bore sweet Jesus Christ To do poor sinners good.
The holly bears a prickle As sharp as any thorn, And Mary bore sweet Jesus Christ On Christmas Day in the morn.
The holly bears a bark As bitter as any gall, And Mary bore sweet Jesus Christ For to redeem us all.
The holly and the ivy Now are both well grown, Of all the trees that are in the wood The holly bears the crown.
A CRADLE HYMN
USH! my dear, lie still and slumber, Holy angels guard thy bed! Heavenly blessings without number Gently falling on thy head.
How much better thou’rt attended Than the Son of God could be, When from heaven He descended And became a child like thee!
Soft and easy is thy cradle: Coarse and hard thy Saviour lay, When His birthplace was a stable And His softest bed was hay.
See the kinder shepherds round Him, Telling wonders from the sky! Where they sought Him, there they found Him, With His Virgin Mother by.
See the lovely babe adressing; Lovely infant, how He smiled! When He wept, the Mother’s blessing Soothed and hush’d the holy child.
Lo, He slumbers in His manger, Where the hornèd oxen fed:
Peace, my darling; here’s no danger, Here’s no ox anear thy bed.
I W
BEFORE DAWN
IM-BERRIED is the mistletoe
With globes of sheenless grey, The holly mid ten thousand thorns
Smolders its fires away; And in the manger Jesu sleeps
This Christmas Day.
Bull unto bull with hollow throat
Makes echo every hill, Cold sheep in pastures thick with snow
The air with bleatings fill; While of His Mother’s heart this Babe Takes His sweet will.
All flowers and butterflies lie hid, The blackbird and the thrush Pipe but a little as they flit Restless from bush to bush; Even to the robin Gabriel hath
Cried softly, “Hush!”
Now night is astir with burning stars In darkness of the snow; Burdened with frankincense and myrrh
And gold the Strangers go Into a dusk where one dim lamp Burns faintly, Lo!
No snowdrop yet its small head nods, In winds of winter drear; No lark at casement in the sky
Sings matins shrill and clear; Yet in this frozen mirk the Dawn
Breathes, Spring is here!
W M
THE WAITS
HERE were sparkles on the window-pane and sparkles in the sky, The moon it sparkled like a star above the world so high, There was star-shine on the ceiling, there was star-shine on the bed, There was star-shine in my eyes, I think, and star-shine in my head.
I clambered from my sleep, I did; I flung the window wide, I wanted all that waited in the Christmas Eve outside, I wanted for myself to hear the Christmas people sing, I wanted for myself to hear the Christmas joy-bells ring.
And there outside were waiting three grey Shepherds in the snow, (I knew that they were Shepherds, for they all had crooks, you know,)
And when they saw me waiting too they sang to me a song— The stars, they caught and whispered it the whole wide sky along.
And then the Shepherds went their way and three black camels came,
They stayed beneath the window there and waited just the same, And each black camel on his back had brought an Eastern King, And though each King was very great each had a song to sing.
They sang it as the Shepherds sang, a little low sweet song,— The white stars caught and whispered it the whole wide sky along; And then the camels went their way, I watched them down the street, The snow lay white and soft and still beneath their silent feet.
There was singing in the tree-tops, there was singing in the sky, The moon was singing to the clouds above the world so high, And all the stars were singing too and when I looked below,
I saw a little, tiny Child was waiting in the snow
And first I watched him wait there—watched and only waved my hand,
For though the song was in my heart I did not understand, Until at last it burst in words, because at last I knew, And then he looked at me and laughed and sang the star-song too.
And right across the misty fields I heard the church bells ring, The star-song echoed far and wide for all the world to sing, But still the tiny Child stood there—the Child that once was born— We sang His birthday song—we did—upon His Christmas morn.
M. N
IN PRÆSEPIO
N stable straw the Infant lay, Turned from the hostelry away, There was no room its doors within, For Him Who is the whole world’s Inn.
Creation sang, no longer dumb, Because her great Desire was come; The sad earth in His joy had part, Who bore her sorrow in His Heart.
The Angels danced, the Shepherds piped, Because earth’s tears away were wiped; The Ox and Ass adoring saw The Infant lying in the straw.
R. L. G
WHEN CHRIST WAS BORN
HEN Christ was born of Mary free, In Bethlehem in that fair citie, Angels sang there with mirth and glee, In Excelsis Gloria!
Herdsmen beheld these angels bright, To them appearing with great light, Who said, “God’s Son is born this night,” In Excelsis Gloria!
This King is come to save mankind, As in Scripture truths we find, Therefore this song have we in mind, In Excelsis Gloria!
Then, dear Lord, for Thy great grace, Grant us the bliss to see Thy face, That we may sing to Thy solace, In Excelsis Gloria!
THE CAROL OF THE POOR CHILDREN
E are the poor children, come out to see the sights On this day of all days, on this night of nights, The stars in merry parties are dancing in the sky, A fine star, a new star, is shining on high!
We are the poor children, our lips are frosty blue, We cannot sing our carol as well as rich folk do, Our bellies are so empty we have no singing voice, But this night of all nights good children must rejoice.
We do rejoice, we do rejoice, as hard as we can try, A fine star, a new star is shining in the sky! And while we sing our carol, we think of the delight The happy kings and shepherds make in Bethlehem to-night.
Are we naked, mother, and are we starving poor— Oh, see what gifts the kings have brought outside the stable door, Are we cold, mother, the ass will give his hay To make the manger warm and keep the cruel winds away.
We are the poor children, but not so poor who sing Our carol with our voiceless hearts to greet the new-born king, On this night of all nights, when in the frosty sky A new star, a kind star, is shining on high!
R M
STAR OF THE EAST
TAR of the East, that long ago Brought wise men on their way Where, angels singing to and fro, The Child of Bethlehem lay—
Above that Syrian hill afar Thou shinest out to-night, O Star!
Star of the East, the night were drear
But for the tender grace That with thy glory comes to cheer Earth’s loneliest, darkest place; For by that charity we see Where there is hope for all and me.
Star of the East! show us the way In wisdom undefiled
To seek that manger out and lay Our gifts before the Child—
To bring our hearts and offer them
Unto our King in Bethlehem!
E F
A CHRISTMAS CAROL
EFORE the paling of the stars, Before the winter morn, Before the earliest cock-crow, Jesus Christ was born: Born in a stable, Cradled in a manger, In the world His Hands had made Born a stranger.
Priest and King lay fast asleep In Jerusalem, Young and old lay fast asleep In crowded Bethlehem: Saint and angel, ox and ass, Kept a watch together Before the Christmas daybreak In the winter weather.
Jesus on His mother’s breast
In the stable cold, Spotless Lamb of God was He, Shepherd of the Fold: Let us kneel with Mary Maid, With Joseph bent and hoary, With saint and angel, ox and ass, To hail the King of Glory
C R
YULE-TIDE FIRES
LEANSE with the burning log of oak
The canker of thy care, Deck with the scarlet-berried bough
The temple of the fair; Spread pure-white linen for a feast, Perchance some guest may share.
Give forth thy gold and silver coins, For they were lent to thee; Put out to usury thy dross, One talent gaineth three. Perchance the hungered and the poor May pray to God for thee.
Once a pale star rose in the East For watching herds to see, And weakness came to Bethlehem, And strength to Galilee. Perchance! if thou dost keep thy tryst A star may rise for thee.
A
SIX GREEN SINGERS
HE frost of the moon fell over my floor And six green singers stood at my door.
“What do ye here that music make?”
“Let us come in for Christ’s sweet Sake.”
“Long have ye journeyed in coming here?”
“Our Pilgrimage was the length of the year.”
“Where do ye make for?” I asked of them.
“Our Shrine is a Stable in Bethlehem.”
“What will ye do as ye go along?”
“Sing to the world an ever-green song.”
“What will ye sing for the listening earth?”
“One will sing of a brave-souled Mirth,
“One of the Holiest Mystery, The Glory of glories shall one song be,
“One of the Memory of things, One of the Child’s imaginings,
“One of our songs is the fadeless Faith, And all are the Life more mighty than death.”
“Ere ye be gone that music make, Give me an alms for Christ’s sweet Sake.”
“Six green branches we leave with you; See they be scattered your house-place through.
“The staunch blithe Holly your board shall grace,
Mistletoe bless your chimney place,
“Laurel to crown your lighted hall, Over your bed let the Yew-bough fall,
“Close by the cradle the Christmas Fir, For elfin dreams in its branches stir,
“Last and loveliest, high and low, From ceil to floor let the Ivy go.”
From each glad guest I received my gift And then the latch of my door did lift—
“Green singers, God prosper the song ye make As ye sing to the world for Christ’s sweet Sake.”
E F
THAT HOLY KING
HEY all were looking for a king
To slay their foes and lift them high: Thou cam’st, a little baby thing That made a woman cry.
O Son of Man, to right my lot Naught but Thy presence can avail; Yet on the road Thy wheels are not, Nor on the sea Thy sail!
My how or when Thou wilt not heed, But come down thine own secret stair, That Thou mayst answer all my need— Yea, every bygone prayer. G M
