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WO1996040482A1 - Procedes de fabrication de surfaces en elastomere thermoplastique a hydrophilie selective, et articles ainsi fabriques - Google Patents

Procedes de fabrication de surfaces en elastomere thermoplastique a hydrophilie selective, et articles ainsi fabriques Download PDF

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Publication number
WO1996040482A1
WO1996040482A1 PCT/US1996/008884 US9608884W WO9640482A1 WO 1996040482 A1 WO1996040482 A1 WO 1996040482A1 US 9608884 W US9608884 W US 9608884W WO 9640482 A1 WO9640482 A1 WO 9640482A1
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WO
WIPO (PCT)
Prior art keywords
hydrophilic
parts
elastomer
molding
thermoplastic elastomer
Prior art date
Application number
PCT/US1996/008884
Other languages
English (en)
Inventor
Lawrence P. Monty
Original Assignee
Monty Lawrence P
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monty Lawrence P filed Critical Monty Lawrence P
Publication of WO1996040482A1 publication Critical patent/WO1996040482A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
    • A45D2/00—Hair-curling or hair-waving appliances ; Appliances for hair dressing treatment not otherwise provided for
    • A45D2/12—Hair winders or hair curlers for use parallel to the scalp, i.e. flat-curlers
    • A45D2/24—Hair winders or hair curlers for use parallel to the scalp, i.e. flat-curlers of multi-part type, e.g. with sliding parts other than for fastening
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2021/00—Use of unspecified rubbers as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0092—Other properties hydrophilic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/718—Cosmetic equipment, e.g. hair dressing, shaving equipment
    • B29L2031/7182—Curlers

Definitions

  • This invention relates to elastomer materials whose surface is made controllably and/or selectively hydrophilic. It relates particularly to hydrophilic thermoplastic elastomer compositions, to processes for preparing hydrophilic thermoplastic elastomer molding compositions, to methods of manufacturing articles having a selectively hydrophilic elastomer surface, and to articles such as hair rollers made with a selectively hydrophilic surface having predetermined moisture capacities.
  • Controlled hydrophilicity may be used to provide elastomer surfaces with a desired coefficient of friction when in contact with wet surfaces of other materials.
  • a particular useful application is in the field of personal hair care products, such as hair curlers or rollers.
  • hydrophilicity is the property characterizing a surface with respect to its tendency to be wet by liquid water. It will be understood that any aqueous fluid may be substituted for water in the descriptions contained herein, in the uses of the invention described herein, and in those other uses of the invention that will be apparent to those skilled in the art. Hydrophilic or hydrophobic characteristics of solid surfaces are commonly characterized by a water wetting angle, such that wetting angles greater than 90° characterize a hydrophobic surface. The Greek letter ⁇ (theta) will be used herein to denote wetting angles.
  • Moisture capacity is used throughout this specification to mean the amount of water that adheres to a surface, expressed in milligrams of water per square centimeter of surface area or equivalent units. Hydrophilicity or moisture capacity may vary locally across a macroscopic surface and thus be functions of position. "Overall moisture capacity” will be used herein to denote the total amount of water that adheres to a particular defined macroscopic surface area, in the same units of milligrams per square centimeter or equivalent.
  • TPE thermoplastic elastomer
  • HTPE hydrophilic thermoplastic elastomer
  • hydrophilic polymer composite and a product containing it are described in U.S. Pat. No. 5,374,671 (Corvasce et al., 1994).
  • the hydrophilic polymer forms fibers in a resulting elastomeric matrix.
  • the elastomeric matrix interspersed with hydrophilic polymer can be used in reinforced elastomeric products such as tires.
  • U.S. Pat. No. 3,910,290 discloses a disposable hair setting roller formed of at least two layers of sheet material, including an inner paperboard layer and an outer hair-contacting layer consisting of an embossed metal foil.
  • the embossed foil provides an irregular or textured, non-absorbent outer surface.
  • a dry film coating of a water-soluble hair treating agent is distributed over the embossed outer surface, preferably being sufficiently thin that the coated surface remains rough to the touch.
  • the indentations in the foil provide reservoirs of the treating agent, which permit the rollers to be reused a number of times.
  • 3,888,266 discloses a hair curling roller comprising on its outer surface a myriad of upstanding short non-hygroscopic filaments or fibers capable of retaining moisture or lotions by capillary attraction.
  • U.S. Pat. No. 3,858,588 discloses a hair roller having a tubular body with a substantially smooth outer surface. The body is molded from a "thermoplastic material, either filled or unfilled, the plastic being etched to make it polar and hydrophilic, as is known in the art.” The mandrel surface is described as "having a pattern of small depressions thereon to increase moisture retention.”
  • 3,762,424 discloses an improvement in heatable and moistenable hair rollers.
  • the roller has an outer surface provided with means, such as a plurality of flexible resilient protrusions, for increasing the outer surface area, and thus increasing the moisture retaining capacity of the roller.
  • a groove located adjacent to the end edges prevents excess water on the rollers from overflowing the end edges and scalding the user's fingers.
  • U.S. Design Pat. No. Des 226,738 shows an ornamental design for a hair roller with a plurality of outward extending protrusions on the exterior surface and a plurality of inwardly projecting flutes on the interior surface.
  • Bagrodia et al., U.S. Pat. No. 5,346,422 (1994) disclose an article of manufacture consisting of a toy having a plurality of synthetic fibers capable of spontaneously transporting water on their surface.
  • U.S. Pat. No. 4,957,949 by Kamada et al. discloses a thermochromic color master batch for use in a thermoplastic resin comprising a wax having dispersed in it a thermochromic granular material which is coated with a hydrophilic high-molecular- weight substance.
  • U.S. Pat, No. 4,826,550 by Shimizu et al. discloses a process for preparing molded products of thermochromic polyvinyl chloride.
  • U.S. Pat. No. 4,666,949 by Shimizu et al. discloses a thermochromic polyurethane foam and a thermochromic composition comprising an electron- donating chromogenic material, an acidic substance, and a solvent.
  • Kito et al. U.S. Pat. No. 4,421,560 disclose a reversible thermochromic material which may be contained within micro-capsules and undergoes reversible metachromatism at a temperature within the range from - 50° C to + 60° C.
  • Nakasuji et al. U.S. Pat. No. 4,028,118 disclose a reversibly thermochromic material which exhibits metachromatism within a range from - 40°C to + 80°C, and which may be occluded in fine micro-capsules.
  • the basic thermochromic material or microencapsulated thermochromic material of Nakasuji et al. can be incorporated into a polymer to obtain a thermochromic polymer composition.
  • PROBLEMS SOLVED BY THE INVENTION As mentioned hereinabove under “Background of the Invention, " there are many diverse applications for a controllably and/or selectively hydrophilic elastomer surface. In these diverse application areas, it is often difficult to find a material that has a needed amount of moisture capacity per unit area. Thus available materials often hold too little or too much water on their surface (or in the case of open-cell foams, within their pores) for the particular problem at hand. These problems will be illustrated by an example from the field of hair care, specifically hair rollers.
  • a major object of the invention is a process for manufacturing a controllably and/or selectively hydrophilic elastomer surface.
  • a related object of the invention is a controllably and/or selectively hydrophilic elastomer surface.
  • a more particular object is a hydrophilic elastomer surface that has a predetermined moisture capacity.
  • Another more particular object is an elastomer surface whose moisture capacity may be varied as a function of position on its surface.
  • An even more particular object is an elastomer surface whose moisture capacity may be either a discrete function or a continuous function of position, or both in various portions of its surface.
  • a particular object is an elastomer surface which has one or more hydrophobic portions and one or more hydrophilic portions such that each hydrophilic portion has predetermined moisture capacity. Processes for manufacturing elastomer surfaces having these diverse properties are essential objects of the invention.
  • an object of the invention is a controllably hydrophilic thermoplastic elastomer molding composition.
  • a related object is a process for preparing a controllably hydrophilic thermoplastic molding composition.
  • Another related object is a process for manufacturing articles having at least a portion of their surface comprising an elastomer that is selectively and/or controllably hydrophilic.
  • a more particular object is a process for manufacturing articles having at least a portion of their elastomer surface hydrophilic with a predetermined moisture capacity.
  • Even more particular objects of the invention are articles having at least a portion of their surface hydrophilic with a predetermined moisture capacity.
  • This invention includes elastomer processes and materials which provide controllably and selectively hydrophilic elastomer surfaces.
  • Hydrophilic thermoplastic elastomer compositions and processes for preparing hydrophilic thermoplastic elastomer molding compositions are used in preliminary operations of a manufacturing process. The manufacturing process is completed by using further methods to manufacture articles having a controllably and or selectively hydrophilic elastomer surface.
  • a particular useful application is described to the manufacture of articles such as hair rollers made with a controllably and/or selectively hydrophilic surface having predetermined moisture capacities and optionally having predetermined variation of moisture capacity per unit area with position on the roller's surface.
  • the controlled hydrophilicity hair roller surface may also be made reversibly thermochromic. Hair rollers made by the methods disclosed have improved curl retention.
  • the invention uses molded artificial pore shapes, sizes, and density per unit area to produce a predetermined moisture retention (not simply to maximize moisture retention).
  • the artificial pore shape is adapted to fit a given wetting angle of water on a hydrophilic surface.
  • the possibility of varying pore shape, size and number per unit area with position gives the method a capability of non-uniform moisture retention — i.e. more moisture on some portions of an elastomeric surface than on others.
  • Other variations of the basic process allow production of a selectively hydrophilic surface of elastomer (i.e. some portions of the surface area being hydrophilic, while some portions of the surface area are hydrophobic).
  • Recesses are molded in a size and shape suitable to that wetting angle to make the water just fill the artificial pore or groove recesses flush and hold the predetermined desired water amount in mg/c rr of the cylindrical surface of the curler.
  • a non-re-entrant pore or groove shape is preferred.
  • a hair curler's surface is made hydrophilic, attracting a desired limited predetermined amount of moisture, as contrasted with conventional non-foam curlers (which are hydrophobic) and the common open-cell foam curler, which are hydrophilic but can retain too much water in the foam cells.
  • Each curler has a controllably hydrophilic thermoplastic elastomer surface layer (around which hair is to be curled) which covers a mandrel portion of a thermoplastic body.
  • the thermoplastic body has ends of larger diameter than the mandrel portion of the body and the mandrel may be hollow.
  • a hollow mandrel may contain a double-walled metal core, which may contain a heat-retaining material.
  • the elastomeric surface layer is preferably molded from an thermoplastic elastomer material containing particulate hydrophilic material, which preferably comprises a dye encapsulated in hydrophilic micro-capsules.
  • Fig. 1 shows a cross-section view of drops of an aqueous fluid on a surface, illustrating the definitions of wetting angle used to describe the invention.
  • Fig. 2 shows a cross section view of a portion of a surface layer, illustrating various pore shapes and a pore side wall angle used to describe the invention.
  • Figs. 3 A and 3B show perspective views of two stages in the manufacture of a preferred embodiment of a hair roller with a surface layer made in accordance with the invention.
  • Fig. 4 shows a partial cross-section of a preferred embodiment of a hair roller.
  • Fig. 5 shows a perspective view of a particular preferred embodiment of a hair roller with a surface layer made in accordance with the invention.
  • Fig. 1 shows a cross-section view of drops of an aqueous fluid on a surface, illustrating the definitions of angles used to describe the invention.
  • the Greek letter ⁇ (theta) is be used in Fig. 1 to denote the wetting angle, measured from the solid surface on which a drop rests to a tangent to the drop contour where it meets the solid surface.
  • wetting angles greater than 90° conventionally characterize a hydrophobic surface.
  • Wetting angles less than 90° conventionally characterize a hydrophilic surface, such that smaller wetting angles correspond to more wetting, or higher hydrophilicity.
  • Fig. 2 shows a cross section view of a portion of an elastomer surface 10 made in accordance with the invention, illustrating various shapes of reservoir recesses and a side wall angle 0 (phi).
  • the first three recess shapes shown are non-reentrant; the recess shape at the right end of Fig. 2 is a reentrant shape.
  • Artificial reservoir recesses 20 are molded into elastomer surface 10 with predetermined shapes, sizes, and density per unit area. The shapes, sizes and density parameters of reservoir recesses 20 are not necessarily uniform over the elastomer surface, but may be varied intentionally over the useful surface area of the elastomer, depending upon the application.
  • Reservoir recesses 20 may be shaped as pores, grooves, or other cavity shapes, according to the needs of the application, but their side wall angles 0 (phi) with respect to the major elastomer surface are made to be the supplement of wetting angle ⁇ (theta) so that aqueous fluids held in reservoir recesses 20 fill the recesses flush.
  • the amount of aqueous fluid held in all of the reservoir recesses over the whole elastomer surface 10 is thus a predetermined amount.
  • the amount held in any sub-portion of the surface area is predetermined by the shapes, sizes, and areal density of the artificial reservoir recesses 20 in that sub-portion. Thus selective and optionally non-uniform moisture capacity is provided.
  • FIGs 3 A and 3B respectively show perspective views of two stages in the manufacture of a hair curler 30 in accordance with this invention.
  • Fig. 3 A illustrates the first of these two stages: a molded curler body 40, before addition of a hydrophilic thermoplastic elastomer (HTPE) layer 10 over mandrel portion 50 of curler body 40.
  • Fig. 3B illustrates the second of these two stages, having HTPE surface layer 10 in place on mandrel portion 50. While Fig. 3B shows an elastomer surface layer 10 with substantially uniform sizes and areal density of grooves, it will be understood that they need not be uniform.
  • Each curler has two integrally molded end flanges 60 having diameters larger than mandrel portions 50.
  • Fig. 4 shows a partial cross-section of hair curler 30.
  • hair curler 30 may have inserted into it a double-walled metal core element 70, having an inner wall 80 and an outer wall 90.
  • a heat-retaining substance 100 such as a wax or the like.
  • Heat-retaining substance 100 may be selected to have a phase change at the desired curler use temperature (i.e. the temperature at which the user's hair is curled).
  • Inner and outer walls 80 and 90 may be joined and sealed by a rolled edge 110 after filling, as shown in the cross-section view of Fig.
  • Inner wall 80 surrounds a cavity 120, which may be adapted to fit over heating posts of a personal hair care appliance.
  • Each curler may have a cap insert 130 shaped to snap into and be retained by curler body 30 or be retained by a portion of core element 70.
  • a substantially homogeneous HTPE composition is prepared having predetermined proportions of a TPE, plasticizer, lubricant, fillers, heat- and UV-stabilizers, and a predetermined proportion of particulate hydrophilic material.
  • the particulate hydrophilic material preferably comprises micro- capsules.
  • the TPE is preferably a saturated block copolymer having a polystyrene phase and a hydrogenated polyisoprene phase, or may be for example a block copolymer having a polystyrene phase and a butadiene phase, a block copolymer having a polystyrene phase and an ethylene propylene phase, or mixtures of these various copolymers.
  • a preferred composition has 5% to 20% by weight of the particulate hydrophilic material, and even more preferred is a mixture of 10% particulate hydrophilic material by weight.
  • the particulate hydrophilic material preferably comprises a hydrophilic concentrate material, encapsulated in micro-capsules.
  • the micro-capsules should have diameters of 3 millimeters or less (preferably 100 micrometers or less), for effective mixing, for uniform physical characteristics, and for uniform appearance of the product.
  • preferred micro-capsules contain a liquid or low-melting hydrophilic concentrate, encapsulated with a hydrophilic high-molecular-weight polymer compound.
  • micro-capsule material is XantrixTM ADS 7000 Series (manufactured by Himont U.S.A. Inc. of Wilmington, DE). Any dye materials used are preferably used in a micro-capsule form in the preferred size range, with the encapsulant being a high-molecular- weight hydrophilic polymer substantially inert to the TPE composition.
  • suitable high-molecular- weight hydrophilic polymer encapsulants are polypropylene, polyvinyl alcohol, polyacrylic acid, gelatin, methyl cellulose or alginic acid.
  • a preferred amount of moisture capacity for hair curlers is between 50 and 70 mg ⁇ O/in. and more preferably about 58 mg ⁇ O/in. (equivalent to about 9.0 mg ⁇ O/cm ⁇ ).
  • a suitable plasticizer oil is a paraffinic or naphthalenic plasticizer oil, such as "Shellflex 371N,” available from the Shell Chemical Company. Many suitable inert particulate fillers are well-known in the art.
  • the anti-oxidants and UV-stabilizers may be "Irganox 1010" and “Tinuvin 328" available from the Ciba Geigy Corporation, for example.
  • suitable lubricants are calcium stearate, stearic acid, palmitic acid, saturated fatty acids or their esters, or waxes.
  • the hydrophilic particulate material may be, for example, "XantrixTM ADS 7015H” available from Himont U.S.A. Inc. of Wilmington, DE.
  • a metal core element 70 is prepared, containing a heat-retaining material 100.
  • a curler body 40 with integral end flanges 60 is molded from a thermoplastic resin, such as polypropylene or polycarbonate. Core element 70 is inserted into curler body 40.
  • the above-mentioned HTPE composition is insert-molded around mandrel portion 50 of the molded thermoplastic curler body 40 to a preferred thickness of between 0.5 mm and 3 mm, with a predetermined number of artificial pores, cavities, or grooves 20 per unit area, completing manufacture of curler 30.
  • the artificial cavities, pores, or grooves are used as reservoir recesses for aqueous fluids on the elastomer surface layer 10.
  • the HTPE may be insert-molded or otherwise applied to one end of curler body 40.
  • An alternative manufacturing method would use a mandrel portion subassembly and would extrusion-mold the HTPE layer onto the mandrel portion subassembly, and then fasten flange portions to the mandrel portion, for example.
  • a tailored hydrophilic surface as described above is insert molded in a predetermined pattern with a similar elastomer not treated to be hydrophilic and not having reservoir recesses, i.e. an elastomer surface is made selectively hydrophilic with the predetermined H2O capacity.
  • the basic method also has the capability of effectively varying hydrophilicity locally (in other words, creating a patterned elastomer surface having some portions of the surface holding more moisture per unit surface area than other portions).
  • One type of use for such a patterned elastomer surface is that a water-based material like ink or paint can be transferred from an ink source using that patterned elastomer, to print the pattern on another surface, such as paper or fabric.
  • the methods and materials of the invention may be used to manufacture articles having a controllably and/or selectively hydrophilic elastomer surface.
  • a particular useful application is the manufacture of articles such as hair rollers made with a mandrel portion having a controllably and/or selectively hydrophilic surface, which has a predetermined moisture capacity and which optionally has predetermined variation of moisture capacity per unit area with position on the roller's mandrel surface. Hair rollers made by the methods have improved curl retention.
  • the patterned selectively hydrophilic thermoplastic elastomer surface described above is its use to transfer ink or paint from a source, to print the pattern on another surface, such as paper or fabric.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Hair Curling (AREA)

Abstract

Compositions à mouler en élastomère thermoplastique hydrophile, et leurs procédés de préparation. Ces compositions sont destinées aux opérations préliminaires d'un processus de fabrication de surfaces en élastomère à hydrophilie modulable et sélective. Lesdits procédés consistent à utiliser une matière particulaire hydrophile dans une composition d'élastomère thermoplastique. Au processus de fabrication s'ajoutent d'autres procédés de fabrication d'articles présentant une surface en élastomère (10) à hydrophilie modulable et/ou sélective. Lesdites compositions trouvent application notamment dans la fabrication d'articles tels que des bigoudis (30) équipés d'une partie mandrin (50) présentant une surface (10) à hydrophilie modulable et/ou sélective, cette surface ayant des capacités de rétention d'eau déterminées, et présentant éventuellement une variation prédéterminée (210, 220, 230) de la capacité de rétention par unité de surface, en fonction de la position à la surface (10) du bigoudi. La surface en élastomère (10) présente une texture artificielle composée de pores ou de rainures (20) de forme déterminée, afin que la surface retienne une quantité d'eau spécifique par unité de surface. Les bigoudis obtenus selon lesdits procédés permettent de former des boucles plus durables.
PCT/US1996/008884 1995-06-07 1996-06-05 Procedes de fabrication de surfaces en elastomere thermoplastique a hydrophilie selective, et articles ainsi fabriques WO1996040482A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47471695A 1995-06-07 1995-06-07
US08/474,716 1995-06-07

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WO1996040482A1 true WO1996040482A1 (fr) 1996-12-19

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3858588A (en) * 1973-01-02 1975-01-07 Clairol Inc Hair roller
US4164951A (en) * 1976-11-08 1979-08-21 Shaler Amos J Hair curler system
US4240451A (en) * 1979-02-26 1980-12-23 Helen Of Troy Corporation Differential hair engagement retainer
US4361159A (en) * 1980-09-15 1982-11-30 Helene Curtis Industries, Inc. Hair roller
US4371485A (en) * 1977-12-12 1983-02-01 Akzona Incorporated Process for making hydrophilic polyester fiber
US4598722A (en) * 1984-09-17 1986-07-08 Conair Corporation Elastomer hair roller
US4823458A (en) * 1983-12-21 1989-04-25 Henkel Kommanditgesellschaft Auf Aktien Foam bodied hair curler
US5002075A (en) * 1987-08-06 1991-03-26 Creative Product Resource Associates, Ltd. Hydrophilic foam pad for hair styling, conditioning and coloring
US5261426A (en) * 1991-05-30 1993-11-16 Creative Products Resource Associates, Ltd. Hydrophilic foam pad for hair styling
US5366805A (en) * 1992-12-10 1994-11-22 Shin-Etsu Chemical Company, Ltd. Polycarbonate resin/silicone rubber integrally molded article and method for making

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3858588A (en) * 1973-01-02 1975-01-07 Clairol Inc Hair roller
US4164951A (en) * 1976-11-08 1979-08-21 Shaler Amos J Hair curler system
US4371485A (en) * 1977-12-12 1983-02-01 Akzona Incorporated Process for making hydrophilic polyester fiber
US4240451A (en) * 1979-02-26 1980-12-23 Helen Of Troy Corporation Differential hair engagement retainer
US4361159A (en) * 1980-09-15 1982-11-30 Helene Curtis Industries, Inc. Hair roller
US4823458A (en) * 1983-12-21 1989-04-25 Henkel Kommanditgesellschaft Auf Aktien Foam bodied hair curler
US4598722A (en) * 1984-09-17 1986-07-08 Conair Corporation Elastomer hair roller
US5002075A (en) * 1987-08-06 1991-03-26 Creative Product Resource Associates, Ltd. Hydrophilic foam pad for hair styling, conditioning and coloring
US5261426A (en) * 1991-05-30 1993-11-16 Creative Products Resource Associates, Ltd. Hydrophilic foam pad for hair styling
US5366805A (en) * 1992-12-10 1994-11-22 Shin-Etsu Chemical Company, Ltd. Polycarbonate resin/silicone rubber integrally molded article and method for making

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