Chemical Consumer Product Design Pukyong National University Department of Chemical Engineering Prof. Gyeongbeom Yi
Physical Form SOLID BULK SHAPED SEMI- SOLID Product form/ Delivery System Composites Cosmetic and Personal care Bar soap, Lipstick Capsules - Example Health care and pharmaceuticals Inhalant stick Whale oil Capsule Household and Office supplies Compact disk, Glue stick Microencapsulated Carbonless paper Tables - Aspirin tablet Moth balls Solid foam - - Styrofoam Powders and Granules Pastes Creams Facial powder, Baby powder, Diaper absorbent Toothpaste Cleansing cream, hair cream Powdered Herbal, Medicine Pain relief Ointment Pharmaceutical Cream Powdered Detergent, dry toner Silicone sealant, Metal adhesive Multipurpose Adhesive Liquid foams Shaving foam - - Example of chemical-based Consumer product of different forms and delivery systems. Macromolecular Solution Mouthwash, Shampoo - Dishwashing Liquid LIQUID Microemulsions Dilute emulsions And suspensions Skin cleanser, Hair conditioner Suntan lotion, Nail polish Hydrocortisone, Cyclosporine Penicillin - Correction fluid, Writing ink Solutions Perfume Eye drop, Ginseng extract Drain cleaning Solution GAS Aerosols Hair Spray Sore throat spray Aerosol paint, Antifreeze spray
Procedure for the Synthesis and Development of Consumer Products
Typical Packaging for Chemical-Based Consumer Products Type of Packaging Composite Tablet/ capsule Product Form / Delivery System Powder/ Granule Cream/ Paste iscous liquid Dilute liquid Aerosol Wrapping Carton box Paper/Plastic wrap Aluminum foil Bag(Paper/plastic) Resealable bag Scaled bag / sachet Bottle (Glass/plastic) Screw cap Flip cap Slit orifice Pump top Tube (Metal/Plastic) Collapsible Tube Squeezable tube Can (Metal) Spray can
Factors determining product performance Ingredients Active ingredients Supporting ingredients (rheological additives, Solvents, binders) Operating Conditions Speed of moving parts Temperature & pressure Humidity Process design Process flowsheet Unit operations Equipment geometry Materials of construction Material properties Physical properties Chemical properties Bioactivities Product Microstructure Particle size distribution Phase volume fraction Lamellar structure Polymorphism Product performance
Typical Market Trends to be Considered in Consumer Product Development Consumer Wants and Needs The product should last longer and / or cost less Products performing complementary functions should be combined in one product The use of a personal care product should be a pleasurable experience The product should be smaller in size, easy to carry when traveling Product Safety The product should not contain toxic solvent or allergenic materials The product should not contain dangerous chemical for little children The product should contain more natural ingredients Legal and Environmental Issues It is preferable that the product is biodegradable Refillable container should be used to reduce waste
Typical Quality Factors Expected from Chemical-Based Consumer Product Class of product Cosmetic and personal care Pharmaceutical and health care Household and office supplies Quality Factor Protection effect Cleaning power East of spread Odor Shelf life Bioactivity Dissolution or disintegration time Active ingredient release time Ease of application Cleaning power Hiding power Mechanical strength
Performance Indices for Typical Chemical-Based Consumer Product Quality Factors Product Form / Delivery System Quality Factor Composite Tablet/ capsule Powder/ Granule Cream/ Paste iscous liquid Dilute liquid Aerosol Performance Index Sensorial isual appearance: transparent opaque, pearlescent, color Smell: fragrant, odorless, stinky Taste: sweet, sour, bitter Sense upon application: smooth, oily, sticky Arbitrary indices based on panelist evaluation Physicochemical Product stability(resistance against creaming) Ability to change phase upon application Hygroscopicity Ease of dispersion in a liquid Ability to dissolve in a liquid Rate at which an active ingredient is released Shelf life Melting point, glass transition temperature Moisture absorption rate Wetting time Dissolution time Release time Mechanical Resistance to failure Resistance to indentation (hardness) Ease of failure by fracture (toughness) Elasticity Ease of flow Tensile strength Hardness numbers Fracture energy Young s modulus Flow number Rheological Ease of spreading when rubbed onto a surface, applied by brush, or shaken Ability to flow under gravity Ability applied on a surface when applied on a surface iscosity at application shear rate Yield value Minimum thickness at which even coating is observed
Examples of Typical Quality Factors for Creams and Pastes
감각적품질요인을결정하는규칙 얇게제공되는높은점성의제품은 thixotropic ( 문지르면점성이감소하다가멈추면원래대로서서히되돌아가는성질 ) 특성을가지는것이좋다. 제품이정지상태에서는두껍고, 문지르면쉽게퍼져야한다면 pseudoplastic( 문지르는속도가증가할수록점도가감소 ) 특성을가지는것이좋다. 상분리를막고제품의안정성을증가시키기위해서는고점도제품이나 semi-solid 가좋다. 제품이중력에의해흘러내리지않으려면, 적어도 20 Pa 까지견디도록한다. 로션 ( 액체같은크림 ) 은최대점도 120-500 Pa.s, 고체같은크림은최대점도 1350-3500 Pa.s 로조정하는것이인지도를높인다. 피부에적용되는제품에대해서는적용되는문지르는속도에서점도가 0.025 Pa.s 되도록조정하는것이인지도를높인다.
Typical shear rates of creams and pastes Action Shear rate ( 1 ) -------------------------------- -------------- Suspending pigment or Active ingredients 0.001-0.1 Pouring from a bottle 50-100 Extrusion from a bottle or tube 10-1000 Topical applications of lotions/creams 100-10000 Application of lipstick 2000-10000 Application of brush 5000-10000 Roller mill 1000-10000 Forcing through homogenizing valve 1000-100000 Colloid mill 100000-1000000 s
Examples of Typical Ingredients used in Creams and Pastes
성분의선택규칙 가능한한다기능성분을선택한다. 가능한한부패하지않는성분을선택한다. 품질이색갈에의해영향을받는제품에는산화나환원제를피한다. 에멀젼제품에대해서 thixotropic 특성이요구되면약한네트워크구조를가진 hydrocolloid 농축제 (gum 또는 carboxymethyl cellulose) 를추가한다. Pseudoplastic 특성이요구되면 W/O 유탁액에왁스나지방알콜같은유동학적첨가제를추가한다.
제품공급시스템의선택규칙 피부에적용될때스늘한 ( 따뜻한 ) 느낌을주기위하여 O/W (W/O) 유탁액을선택한다. 제품에느낌이없거나기름기있는맛이나지않아야하면 O/W 유탁액을사용한다. 제품이땀이나세탁에저항성을가져야하면 W/O 유탁액을사용한다. 바람직한내부상부피비가정해진유동학적성질을내지못하면이중유탁액의사용을고려한다. 약처럼주성분이장시간공급되어야하면이중유탁액의사용을고려한다. 둘다친수성 ( 소수성 ) 인서로잘적응하지못하는물질을포함하는제품에대해서는 W/O/W (O/W/O) 유탁액의사용을고려한다.
미세구조의결정규칙 연속상과분산상은 Newtonian 성질을보이고제품은 viscoelastic 성질을가지려면분산상의부피분율이매우높은에멀젼을만든다. 부드러운질감의고체같은제품을원하면연속상크리스탈이나분산상고체의입자크기를 1 μm 이하로작게만든다. 묽은 ( 농축된 ) 유탁액과현탁액의점도는연속상의점도에의해주로조절되고 ( 상관이없고 ), 입자의크기나상부피분율에는상관이없다 ( 에의해조절된다 ). 쌍봉분포를가지면크림같은경향이강한제품이된다.
유화제를선택하는기준 유화제또는유화제의조합은원하는형태의유탁액을형성해야한다. 형성된에멀젼은처리, 저장및응용중에격을여러가지조건하에서장시간동안안정적이어야한다. 유화제는혼합물에서부차적인반응이일어나지않도록다른성분들과잘어울려야한다. 유화제는고객의건강이나환경에독성을끼치지않아야한다. 유화제의비용은가능한적어야한다.
Selected Unit Operations for Mixing and Structure Formation Step in Chemical-Based Consumer Product Processing Step/Criterion Unit operation Examples of Equipment Mixing Ingredients to be Mixed Soluble liquids Mixing Agitated vessel, in-line mixer Liquid and soluble solids Dissolution Agitated vessel Liquid and insoluble solid Dispersion Agitated vessel, planetary mixer, mixer-kneader Two immiscible liquids Emulsification Agitated vessel Two solid phases Structure Formation Product delivery system Melt mixing Solids Powder coating Composite Molding Extruder Agitated vessel, high-speed mixer -shaped mixer, ribbon blender Coating machine Tablets Tableting Tableting machine Capsules Filling Encapsulation machine Powders/granules Size enlargement Size reduction Spray drying Pan granulator, roller compactor Jaw crusher, roller crusher, cutter, fluid jet mill Fluid jet mill Spray drier Creams, emulsions Homogenization Pressure homogenizer, ultrasonic homogenizer Pastes, suspensions Wet milling Ball mill, roller mill, pebble mill
혼합장치를선택하는규칙 혼합되어지는고체중의하나가상대적으로낮은용융점과유리전이온도 (Glass Transition Temperature) (50-80 C) 를가지면용융혼합을선택한다. 적절한크기를가진미립자고체를혼합하기위하여고체배합을선택한다. 큰입자의표면에아주작은입자를바르려면분말피복 (powder coating) 을선택한다. 혼합물이고농도의계면활성제를포함하면, 진공또는저교반속도의장치를선택한다.
구조형성단위조작선택규칙 만약원하는제품입자크기가혼합후입자크기보다크다면 ( 작다면 ) 크기확대 ( 크기축소 ) 를선택한다. 혼합후보다작은입자성분을가진 Tablet(Capsule) 을생산하려면크기축소후 Tableting(Capsule 삽입 ) 을한다. 만약원하는제품의형태가 ( 알갱이 ) 분말이고혼합단계의출력이액체이면분무건조다음에크기확대를한다.
Selected Equipment for Emulsification in Manufacturing Creams and Pastes Equipment Breakup Mechanism Batch/Cont. Design and Operating ariables Pre-emulsification Pipeline mixer Agitated vessel Ribbon mixer Planetary mixer Turbulent shear Turbulent shear Turbulent shear Turbulent shear B,C B C C Pumping velocity Agitation speed essel geometry Agitation speed Impeller geometry Agitation speed Impeller geometry Homogenization Colloid mill Tooth disc disperser Pressure homogenizer Ultrasonic homogenizer Laminar/turbulent shear Turbulent shear Turbulent shear/cavitation Cavitation B,C B,C B,C C Rotational speed Gap width Rotational speed Gap width Homogenizing pressure Ultrasonic wave frequency And intensity
Generic flowsheet of chemical-based consumer product manufacturing processes Ingredients Ingredients Ingredients Pretreatment Pretreatment Pretreatment Mixing Structure formation s Post treatment Filling and packaging Product
공정합성규칙 만약물이나기름에녹는성분이포함되면잘어울리는성분들을결합하기위하여사전혼합단계를거친다. 물에녹지않는성분의입자크기를원하는정도로줄이기위하여입도감소장치를이용한다. 방울크기 100 μm 이하의유탁액을만들기위해서는균질화장치를이용한다. 점도를줄여서혼합이더잘되도록하기위하여처리중에혼합물을가열한다. 상반전이문제가되면상조합이나계면활성제위치의순서변환을고려한다. 가능한방울의크기를줄이는것이바람직하지만최종제품은여전히점성을가져야한다면냉각전에균질화를실행한다. 최종제품의점성을영원히줄이고싶으면냉각후에균질화를실행한다. 만약분산상의부피분율이 30 % 보다작으면, 저에너지유화가술 ( 분산상을연속상의일부 ( C1 ) 에혼합하고유화한뒤에나머지연속상 ( C2) 을추가함 ) 사용을고려한다. 만약농축제가포함되면 C 2 상에분산되어져야한다. 결정화전의멸균장치처럼후처리장치는단지액체에만적용된다.
장치선택규칙 에너지소모가증가하는순서대로장치를선택한다. 사전유탁액을형성하기위하여분리된상을혼합하는교반용기나무동작혼합기를사용한다. 고체부피분율이높은현탁액을형성하기위하여는 Ribbon 혼합기나 Planetary 혼합기를사용한다. 유탁액이가열또는냉각에민감하면, scraper 가부착된교반용기같은불감또는정체영역이없는장치를선택한다. 분산상과연속상의점도비가 4 보다크면, colloid mill 같은전단흐름에서유화파괴가일어나는유화장치의사용을금한다. 연속상의점도가 0.02 Pa.s 이면 colloid mill 의사용을금한다.
원료주입규칙 분산상은연속상에천천히추가되어야한다. 혼합단계에서간섭을받거나처리과정중파괴되는성분은맨나중에추가된다. 만약 0.26 보다낮은분산상부피분율과작은방울크기를가진유탁액을만들려면상반전의사용을고려한다. 만약계면활성제가한상에서다른상으로이동하는것이제품점도에바람직하지못한변화를일으키면, 계면활성제를상사이에그들의용해도에따라서분배하는것을고려한다.
장치운전조건의선택규칙 유탁액의점도가높고 pseudoplastic 이면, 용기내의좀더균일한전단속도분포를위하여날개바퀴대용기지름의비율이높은프로펠러를선호한다. 제품점도의비가역적인감소를초래한다면장시간교반해선안된다. 공기가제품속에끼어드는것을최소화하기위하여날개바퀴가완전히잠기지않은채로혼합작업을하지않는다. 연속상의결정화에서크고균일한결정을얻기위하여서서히냉각한다. 처리과정에서제품이오염되지않아야한다면, 장치는미리멸균되어져야하고작업은무균상태에서수행되어야한다.
Customer Needs for Powdered Laundry Detergent Easier to carry Less space to store No agglomeration due to moisture Less water(lower forming, Stronger soil suspension) Lower temperature(40c) Containing bleach Economical
Powdered Detergent Ingredients Desired Function Ingredient Chosen Examples Removing water-insoluble grease and soils Bleaching Bleach activation ph control(10) Enhancement of washed fabric appearance Removal of unpleasant odors Removal of protein, carbohydrate carbohydrate, and fat stains Control of water hardness Providing alkalinity Preventing redeposition Preventing corrosion Improving powder flow Filling Biodegradable surfactant (Active ingredient) Inactivated bleach Bleach activator Buffer Whitening agent Fragrance Enzyme Builder Filler Sodium perborate Alkanoyloxybenzene sulfonate, N-acyl caprolactam Sodium carbonate Bistriazinyl derivatives of diaminostilbene disulfonic acid Perfumes Proteases, amylases, lipases, cellulases Zeolite A, soda ash (Na2CO3), Sodium polycarboxylate, δ-disilicate Sodium sulfate
Manufacturing powder detergent Liquid additives Surfactant Builder Other additive Binder Mixing Spray Drying High-shear mixer Screen Product Drying
Customer Needs for Shampoo and Conditioner in One Clean the hair (anti-dandruff) Desirable combing or brushing(conditioning) No buildup of any ingredient No splashing (High viscosity(500pa.s) at low shear rate) Easy spreading (Low viscosity(2pa.s) at high shear rate(10000/s)) Stable while in storage
Shampoo and Conditioner Supporting Ingredients Desired Function Ingredient Chosen Examples Aiding the deposition of conditioning agent Improving spreadability of conditioning agent Dissolving the conditioning agent Shampoo base iscosity control ph control Improving product appearance Enhance attractiveness Deposition polymer Spreading agent Organic solvent Aqueous solvent Thickening agent Acid of base Pearlescent agent Perfume, pigment Quaternary ammonium polymers Quaternary ammonium compounds Silicone oil Water Carboxyvinyl polymers, cellulose ethers, guar gum, starch Sodium hydroxide, citric acid Ethylene glycol distearate Essential oils
Manufacturing Shampoo and Conditioner Water Anionic surfactant Thickening agent ph control agent Pre- Mixing & heating Mixing Homogenization Emulsifiers Silicone oil Conditioning agent Pre- Mixing & heating Cooling Pearlescing agent Deposition polymer Spreading agent Preservatives Filling Product
Customer Needs for Toothpaste Remove stain Abrasive (Solid) Suspension Clean teeth Surfactant Prevent dental caries Fluoride component Retain moisture Humectant Taste Flavor Should not flow by itself (20Pa), squeezed easily out of tube, low viscosity when brushed Shearthinning product (Thickener) Soft and smooth texture Small particle Color, Preservatives
Input Information for Toothpaste Composition Solid phase Silica (abrasive) Carboxymethyl cellulose (thickener) Silica aerogel (thickener) Polyethylene glycol (thickener) Liquid/aqueous phase Sodium monofluorophosphate (active agent) Sorbitol (humectant) Glycerin (humectant) Sodium benzoate (preservative) Dye solution (color) Water (solvent) Others Flavors Surfactant Aqueous Phase iscosity,μ c Density, ρ c Solid Particles Hamaker constant, A Dielectric constant, ε r Density, ρ d 14 % 0.3% 8.0% 5.0% 0.8% 32.7% 20.1% 0.1% 0.5% 14.8 % 2.2% 1.5% 0.14 Pa s 1,100 kg/m 3 8.55X10-20 J 48.65 1,600 kg/m 3
Toothpaste Manufacture Thickeners Water-soluble ingredients Premixing Size reduction Silica Flavor & Other minor ingredients Mixing Surfactant Deaeration Filling Product
Customer Needs for Hand Lotion Maintain the skin in a fully moisturized condition Emollient Easily applicable and has to rub in quickly Low viscosity when applied to the skin Flow when poured from the bottle but should not appear runny High viscosity at low shear Shearthinning product (Thickener) Smooth and does not feel oily or greasy O/W emulsion Maintain the humidity of the lotion Humectant Attractive Perfume, Preservatives
Input Information for Hand Lotion Continuous Phase Composition Purified water (solvent) Glycerol (humectant) Water-soluble polymers (thickener) iscosity K n Ea Density, Dispersed Phase Composition Mineral oil (Solvent) Stearic acid (Solvent) Cetyl alcohol (emollient) Isopropyl palmitate (emollient) Petrolatum (emollient) iscosity, K at 25 n E a Density, ρ d Emulsion Surfactants Glyceryl monostearate PEG-40 stearate Interfacial tension, σ Excess surface concentraition, Γ Surfactants critical micelle concentrantion (CMC) 80-90% 4-8% 1.1%(variable) 0.025 Pa.s 9.83xt 1.91 Pa s 0.0598x -0.97 15,800J/mol 1,019 kg/m 3 30% 12% 12% 23% 23% 6.54*10-2 Pa s 1.0 17,200J/mol 985kg/m 3 80% 20% 2*10-2 Pa s 1.0*10-6 kg/m 2 30kg/m 3 Equipment Colloid mill rotor radius 5cm
Process Design for Hand Lotion Mineral oil Stearic acid Cetyl alcohol I.Palmitate Petrolatum Pre-mixing & heating Mixing Homogenization Emulsifiers Cooling Water Glycerol Carbomer Pre-mixing & heating Filling Product (a) Standard
Mineral oil Stearic acid Cetyl alcohol I.Palmitate Petrolatum Pre-mixing & heating Mixing (Stage1) Homogenization Emulsifiers Heating Water Glycerol Carbomer Premixing Mixing (Stage) Filling (b) Low Energy Product
Design Factors for Preservative Free Lotion Pump-top bottle with hydrophobic filter to sterilize entering air Low viscosity (0.1~0.5Pa.s) during pumping (10/s) Good feeling when applied to the skin 0.025 Pa.s at high shear rate 500/s Reduce water activity < 0.8 by humectant Acidic condition (ph < 4.5) Natural anti-bacterial ingredients Chelating agent to bind metal ions High surfactant concentration
Preservative-Free Lotion Ingredients Desired Function Ingredient Chosen Examples Moisturize skin Control of lotion humidity Emulsion stabilization Increasing viscosity and obtaining shear-thinning behavior Providing additional attractiveness Reducing water activity ph control Preventing deterioration of fragrance and color Emollient (Active) Humectant Surfactant Thickener Aroma chemicals Salts Organic acid Chelating agent Stearic acid, cetul alcohol, petrolatum Glycerol Glyceryl monostearate, quaternary ammonium salts Carbomer, propylene glycol Essential oils Aluminum chlorohydrate, cationic surfactants Citric acid EDTA, citric acid