EP0946213A1 - Adhesif pour application d'articles fonctionnels sur la peau et enlevement aise desdits articles - Google Patents

Adhesif pour application d'articles fonctionnels sur la peau et enlevement aise desdits articles

Info

Publication number
EP0946213A1
EP0946213A1 EP97952628A EP97952628A EP0946213A1 EP 0946213 A1 EP0946213 A1 EP 0946213A1 EP 97952628 A EP97952628 A EP 97952628A EP 97952628 A EP97952628 A EP 97952628A EP 0946213 A1 EP0946213 A1 EP 0946213A1
Authority
EP
European Patent Office
Prior art keywords
rad
articles
sec
skin
adhesive
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP97952628A
Other languages
German (de)
English (en)
Inventor
Peter Coles
Fabio Cinelli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Priority claimed from EP96120738A external-priority patent/EP0850619A1/fr
Priority claimed from EP97110730A external-priority patent/EP0853934A1/fr
Priority claimed from EP97120337A external-priority patent/EP0850649A1/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP97952628A priority Critical patent/EP0946213A1/fr
Publication of EP0946213A1 publication Critical patent/EP0946213A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/45—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the shape
    • A61F13/47—Sanitary towels, incontinence pads or napkins
    • A61F13/475—Sanitary towels, incontinence pads or napkins characterised by edge leakage prevention means
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/56—Supporting or fastening means
    • A61F13/66—Garments, holders or supports not integral with absorbent pads
    • A61F13/82—Garments, holders or supports not integral with absorbent pads with means for attaching to the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208—Tissues; Wipes; Patches
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/58—Adhesives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/58—Adhesives
    • A61L15/585—Mixtures of macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/005—Modified block copolymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to topical adhesives for attachment to the skin.
  • the present invention relates to such topical adhesives which can be employed for application of functional articles to the skin, particularly for the adhesion of functional articles or the improvement of the function of such articles.
  • Functional articles in this context are cosmetic or pharmaceutical delivery articles which provide a substance to the skin such as skin treatment substances, creams, lotions, hormones, vitamins, deodorants, or drugs; alternatively cosmetic or pharmaceutical delivery articles can also provide a substance to emanate away from the skin such as insecticides, inhalation drugs, or perfumes; further the adhesive of the present invention can also be used in functional articles which are not attached to the skin but as a component in articles which require a high residence time on the skin such as decorative cosmetics (lipstick, eye colors, stage make-up) or cleaning article (hand cleaner, face mask, hygienic cleanser especially for pores).
  • the topical adhesive provides secure attachment or increased residence time and is pleasing to the skin upon application, -yet causes no discomfort upon removal. This is achieved by
  • the present invention relates to topical adhesives which are particularly useful to functional articles such as cosmetic or pharmaceutical delivery articles which provide a substance to the skin such as skin treatment substances, creams, lotions, hormones, vitamins, deodorants, or drugs; alternatively cosmetic or pharmaceutical delivery articles can also provide a substance to emanate away from the skin such as insecticides, inhalation drugs, or perfumes; further the adhesive of the present invention can also be used in functional articles which are not attached to the skin but as a component in articles which require a high residence time on the skin such as decorative cosmetics (lipstick, eye colors, stage make-up) or cleaning article (hand cleaner, face mask, hygienic cleanser especially for pores). Such articles are not used for absorption of body liquids. For example attachment of a vitamin plaster to the skin or of an inhalation drug releasing article to the breast can suitably be done by the adhesive of the present invention. Inclusion of the adhesive into decorative cosmetics allows to increase their resistance to wearing off while not creating a removal problem.
  • Topical adhesives which are used for absorbent articles such as sanitary napkins or pantiliners have been disclosed in US statutory invention registration H1602 or WO 96/33683. Some more details of such adhesive have been disclosed in PCT application WO 95/16424.
  • sanitary articles having a topical adhesive which is applied on the wearer facing side of a sanitary napkin along the entire periphery are disclosed.
  • the problem underlying this document is primarily the safe attachment to the skin but mentions also the problems of detachment of such articles after use without causing undue pain to a wearer.
  • WO 95/16424 includes a detailed analysis of the criteria for the topical adhesive in respect to rheological criteria.
  • rheological criteria include epilatory, i.e. hair removal, compositions which are commercially available such as STREP MIELE (TM) sold in Italy by Laboratori Vaj S.p.A.
  • STREP MIELE TM sold in Italy by Laboratori Vaj S.p.A.
  • this document only identifies static rheological characteristics but is silent as to the dynamic rheological behaviour of a topical adhesive.
  • WO 96/13238 a frequency dependent topical adhesive model is disclosed. However, all measurements disclosed, e.g. on page 9, were made at temperatures between -60°C and +120°C and at actual frequencies of 0.1 to 100 rad/s. In order to obtain the necessary data at application temperature (about 20°C, typical bath room, i.e. storage temperature) the Williams-Landel- Ferry (hereinafter WLF) equation was used.
  • WLF Williams-Landel- Ferry
  • This WLF equation is empirical and only valid within certain limits e.g. it cannot be used to extrapolate to temperatures below the glass transition temperature of a polymeric adhesive also the WLF cannot be used on the basis of values obtained below the glass transition temperature. Details about the WLF equation and its applicability can be found in "Principles of Polymer processing" by Z. Tadmor and C.G. Gogos, published by John Wiley & Sons or in "Viscoelastic Properties of Polymers" by J.D. Ferry also published by John Wiley & Son. Since this is already missing from WO 96/13238 the applicability of the disclosed data cannot be assessed.
  • the adhesive for topical attachment does not cause a cold or otherwise unacceptable temperature sensation upon application despite a temperature difference of the adhesive in respect to the skin temperature.
  • topical adhesives In addition to the above objectives of the present invention it is also desirable for topical adhesives to provide additional benefits such as physical protection. Further, topical adhesives which support the natural skin condition/ e.g. by being breathable or water vapour transmitting are preferred.
  • the present invention is useful to attach functional articles to the skin or improve the function of such articles when worn on the skin.
  • Functional articles are cosmetic or pharmaceutical delivery articles which provide a substance to the skin such as skin treatment substances, creams, lotions, hormones, vitamins, deodorants, or drugs; alternatively cosmetic or pharmaceutical delivery articles can also provide a substance to emanate away from the skin such as insecticides, inhalation drugs, or perfumes; further the adhesive of the present invention can also be used in functional articles which are not attached to the skin but as a component in articles which require a high residence time on the skin such as decorative cosmetics (lipstick, eye colors, stage make-up) or cleaning article (hand cleaner, face mask, hygienic cleanser especially for pores).
  • Such articles are non-absorbent for bodily liquids.
  • the article typically has a wearer facing surface and an outside surface.
  • the topical adhesive allows secure attachment of an article to the skin of the wearer and supports the functionality of the articles.
  • the term "functional" in this context means that the article after being placed on the skin fulfills an additional function which is supported or improved by the topical adhesives according to the present invention.
  • the viscous behaviour of the adhesive can be interpreted to represent an indication of the ability of the adhesive to quickly attach and securely adhere, i.e. to quickly mold to the microscopic surface pattern of skin.
  • the elastic behaviour can be interpreted as an indication of the "hardness" behaviour of the adhesive. Its value is also critical for good initial attachment. Their combination is believed to be an indicator of the required force upon removal.
  • the relation between elastic and viscous modulus is considered to be an indication which fraction of the removal energy will be dissipated within the adhesive and which fraction is available to trigger the actual removal.
  • the topical adhesive has an elastic modulus at a temperature of 37°C (100° Fahrenheit) abbreviated C37 and a viscous modulus at a temperature of 37°C (100° Fahrenheit) of C'37.
  • the adhesive further has a dynamic elastic behaviour defined as ⁇ G'37 which is the difference of G'37 at a frequency of 100 rad/sec and G'37 at a frequency of 1 rad/sec and a dynamic viscous behaviour ⁇ G"37 which is the difference of G"37 at a frequency of 100 rad/sec and G"37 at a frequency of 1 rad/sec.
  • the topical adhesive according to the present invention satisfies the following conditions.
  • G'37 (1 rad/sec) is in the range 1500 Pa to 20000 Pa, preferably 1500 Pa to 15000 Pa, most preferably 3000 Pa to 10000 Pa.
  • G"37 (1 rad/sec) is in the range 100 Pa to 15000 Pa, preferably 100 Pa to 10000 Pa, most preferably 300 Pa to 5000 Pa.
  • G'37 (1 rad/sec) - G"37 (1 rad/sec) is not less than 0.5, preferably in the range 0.7 to 3, most preferably in the range 1 to 1.8.
  • ⁇ G'37 is not greater than 10000 Pa, preferably less than 5000 Pa, most preferably less than 2000 Pa, or both.
  • the value of the ratio G'37/G"37 at least for the frequency range from above 1 rad/s up to 100 rad/s should preferably 3.3 or above, more preferably 5 or above, most preferably 10 or above while not exceeding about 50, preferably 30, anywhere in the frequency interval.
  • Tg Glass Transition Temperature
  • Tg should preferably be less than -15°C, more preferably less than - 20°C and most preferably less than -25°C.
  • the rheological behaviour and acceptance of a topical adhesive can also be related to the specific heat capacity.
  • the specific heat capacity of the topical adhesive is less than 4 J/g/K, more preferably less than 3 J/g/K and most preferably less than 2 J/g/K.
  • the rheological behaviour and acceptance of a topical adhesive can also be related to the specific heat conductivity of the adhesive.
  • the specific heat conductivity is as low as possible, preferably between 1 and 0.1 W/m/K, most preferably between 0.6 and 0.1 W/m/K .
  • Adhesive compositions which satisfy the above criteria can be used as topical adhesives for functional articles or as components in the formulation of functional articles provided they also satisfy the common requirements of being safe for use on human or animal skin during use and generally after disposal.
  • compositions where the composition comprises from 45%, preferably from 51 %, to 99.5 % of a plasticising compound or composition which is liquid at 20°C, from 0.5 to 20 %, preferably 5 % to 15 %, of a polymeric compound or composition which is soluble or swellable in the plasticising compound or composition and with a tackifying resin in an amount in the range from 0 % to 50 % by weight of the composition, preferably from 0 % to 600 % by weight of the polymeric compound.
  • the plasticising compound or composition is preferably selected from the group consisting of water, alcohols (preferably glycerol), glycols, polyglycols, liquid polybutenes, oil or combinations thereof.
  • the polymeric compound or composition is preferably selected from the group consisting of block-copolymer-thermoplastic-elastomers, styrene-block- copolymers and hydrogenated styrene-block-copolymers, polyacrylics, polyvinyl alkohol, natural gum or gelatines, polyethyleneoxide, poly vinylpyrrolidon (PVP, polyvinylethers, cellulose drivatives, or combinations thereof.
  • the topical adhesive according to the present invention is applied directly to the skin.
  • the adhesive can be used as a carrier of a function (dispensing of a compound) and for attachment while in other application improvement of the attachment and resistance to rubbing off is desirable.
  • the adhesive according to the present invention is used in the context of functional articles such as cosmetic or pharmaceutical delivery articles which provide a substance to the skin such as skin treatment, substances, creams, lotions, hormones, vitamins, deodorants, or drugs; alternatively cosmetic or pharmaceutical delivery articles can also provide a substance to emanate away from the skin such as insecticides, inhalation drugs, or perfumes; further the adhesive of the present invention can also be used in functional articles which are not attached to the skin but as a component in articles which require a high residence time on the skin such as decorative cosmetics (lipstick, eye colors, stage make-up) or cleaning article (hand cleaner, face mask, hygienic cleanser especially for pores).
  • the word "skin" according to the present invention does relate to the outer surface of the derma of humans or animals.
  • the topical adhesive is a compound to the composition of the article.
  • topical adhesives are used like pressure sensitive adhesives on human or animal skin, it is understood that the topical adhesive compositions could only with difficulty be considered typical pressure sensitive adhesives (referred to as PSA hereinafter) on the basis of the most characteristic rheological behaviours identifying such materials.
  • materials useful as topical adhesives according to the present invention have rheological characteristics which are measured at a reference temperature of 37°C (as usual body temperature of humans) and in a range of frequencies. It has been found that upon application of an article such as a vitamin plaster with a topical adhesive the adhesive contact is formed at a low frequency, while debonding happens at the speed of removing the article. This speed is expressed as a frequency of 100 rad/s while the low frequency of forming the adhesive bond has been found to be on the order of 1 rad/s. Therefore, the frequency range for use according to the present invention is between 1 and 100 rad/s.
  • the adhesive bonding characteristics are selected most appropriately at human body temperature. Since the topical adhesive according to the present invention is used directly on skin and the person skilled in the art is directed to select the adhesive composition to have a small specific heat capacity (e.g. preferably less than 4 J/g/K) the actual temperature of the topical adhesive will reach 37°C very quickly or even be warmed up by a human prior to application. In order to provide good conditions of bonding, i.e. at a frequency of about 1 rad/sec, the absolute values of the elastic modulus should not be too high, otherwise the adhesive is too hard and it is not able to intimately join or mold to the surface to which it is expected to adhere. It is also important to have a low absolute value of G" in order to have good cohesion which is particularly valuable, when using articles which are frequently removed and adhered again or replaced while the material remains soft and capable of gently adhering to skin.
  • a small specific heat capacity e.g. preferably less than 4 J/g/K
  • the ratio of G'37 (1 rad/sec) over G"37 (1 rad/sec) is important to ensure that these two values are balanced upon adhesion to the skin.
  • the absolute changes of G'37 needs to be limited within the range of frequencies considered.
  • a value for the ratio of ⁇ G'37 (i e. G'37 (100 rad/sec) - G'37 (1 rad/sec)) over G'37 (1 rad/sec) has to be kept small in order to maintain the secure attachment of the topical adhesive without causing discomfort over time or at removal/ delamination. This can also be expressed in absolute terms by keeping the ⁇ G'37 below certain values.
  • G'37 (1 rad/sec) is in the range 1500 Pa to 20000 Pa, preferably 1500 Pa to 15000 Pa, most preferably 3000 Pa to 10000 Pa.
  • G"37 (1 rad/sec) is in the range 100 Pa to 15000 Pa, preferably 100 Pa to 10000 Pa, most preferably 300 Pa to 5000 Pa.
  • G'37 (1 rad/sec) - C'37 (1 rad/sec) is not less than 0.5, preferably in the range 0.7 to 3, most preferably in the range 1 to 1.8.
  • ⁇ G'37 is not greater than 10000 Pa, preferably less than 5000 Pa, most preferably less than 2000 Pa, or both.
  • the value of the ratio G'37/G"37 at least for the frequency range from above 1 rad/s up to 100 rad/s should preferably be 3.3 or above, more preferably 5 or above, most preferably 10 or above while not exceeding about 50, preferably 30, anywhere in the frequency interval.
  • Tg Glass Transition Temperature
  • Tg should preferably be less than -15°C, more preferably less than - 20°C and most preferably less than -25°C.
  • the rheological behaviour and acceptance of a topical adhesive can also be related to the specific heat capacity.
  • the specific heat capacity of the topical adhesive is less than 4 J/g/K, more preferably less than 3 J/g/K and most preferably less than 2 J/g/K.
  • the rheological behaviour and acceptance of a topical adhesive can also be related to the specific heat conductivity of the adhesive.
  • the specific heat conductivity is as low as possible, more preferable between 1 and 0.1 W/m/K, most preferably between 0.6 and 0.1 W/m/K.
  • compositions which satisfy the requirements of the above rheological and physical characteristics of a topical adhesive the following formulation criteria can be used in addition. It should be noted that the most of the compositions useful as topical adhesive have a substantially gel-like structure and are preferably gels. This derives from the fact that:
  • the plasticiser which is a material liquid at room temperature
  • a macromolecular or polymeric component is present in minor quantities vs the plasticiser. It forms, in the preferred embodiments, a three dimensional network caused by physical or chemical links between the molecules. Particularly useful physical links are the ones present in systems containing Block Thermoplastic Elastomers.
  • compositions typically comprise:
  • macromolecular or polymeric substances can be natural and/or synthetic such as natural gums or derivatives such as natural gums and gelatines, their derivatives and alginates; polyacrilics; polyvinyl alcohol; polyethylene oxide; polyvinylpyrrolidon (PVP) or polyvinylethers, their copolymers and derivatives; cellulose derivatives; Block Copolymer Thermoplastic Elastomers and preferably Styrenic Block Copolymers and more preferably the hydrogenated grades Styrol/Ethylene-Butylene/Styrol (SEBS), Styrene/lsoprene/Styrene (SIS), and Styrol/Ethylene-Propylene/Styrol (SEPS).
  • SEBS Styrol/Ethylene-Butylene/Styrol
  • SIS Styrene/lsoprene/Styrene
  • SEPS Styrol/Ethylene-Propylene/Styrol
  • plasticising substance a plasticising substance or a mixture of plasticising substances, which are liquid at room temperature.
  • the plasticiser can be water, various alcohols (like in particular glycerol), glycols and their eithers, polyglycols, liquid polybutenes, esters such phtalates, adipates, stearates, palmitates, sebacates, or myristates, natural or synthetic oils such as vegetable oils, mineral oils, or combinations thereof.
  • composition preferably 0 % to 600 % by weight of the macromolecular polymeric substance, of a tackifying resin whose main scope is to tailor the Tg especially in systems based on synthetic polymers.
  • hydrophilic or hydrophobic liquid plasticisers may be for oily systems, e.g. the fatty acids of C ⁇ to C 22 . their metallic salts and their polyoxo- derivatives; lanolin derivatives; silica; bentonite, montmorillonite and their derivatives; polyamides, waxes or mixtures thereof.
  • additives known in the art as preservatives, antioxidants, anti UV, pigments, mineral fillers, rheology modifiers etc. can also be comprised in quantities up to 10 % each.
  • a crosslinking agent can be present preferably in quantities up to 5 % by weight.
  • Chemical crosslinking can be formed also by mutual neutralisation of polymers having different functionalities as in the reaction between acid polyacrylics and polysaccharides.
  • compositions for topical adhesives can be divided into three families according to the nature of the main component, i.e. usually the liquid plasticiser(s): 1) Hydrophobic compositions in which the plasticiser is typically an oil or blend of oils of vegetable or mineral origin and the polymer is usually a synthetic polymer, preferably an elastomer, soluble or swellable in oil(s).
  • both hydrophobic and hydrophilic components possibly in both plasticisers and polymers, form two or more separate phases.
  • an emulsifier/surfactant is preferably present at a suitable level to form stable emulsions between the incompatible phases.
  • the hydrophilic components are present in an amount of 30 % to 70 % by weight while the hydrophobic components are present in an amount of 70 % to 30 % by weight.
  • Hydrophilic compositions in which typically the plasticiser is water/glycerol/glycols and the like and/or mixtures thereof and the polymeric phase is of synthetic (e.g. polyacrilics) or natural (e.g. natural gums) origin or mixtures thereof.
  • compositions are preferred while the hydrophilic and hydrophobic adhesives are less preferred in the applications of the present invention.
  • functional articles with a delivery function the compound to be delivered needs to come out of the topical adhesive composition at different speeds, e.g. perfumes can have a delivery profile which changes from high to lower values while drugs have to be delivered preferably at a constant rate to prevent overdosing.
  • Cosmetics often are lipophilic and moisturizing such that a combination of watery and oily components is most desirable.
  • Functional articles comprising the topical adhesive according to the present invention can be used, can be made by any of the ways usual in the art.
  • the functional article in this context defines whether the adhesive is provided to hold a substrate to the skin or whether the adhesive as part of a composition is directly provided to the skin.
  • the topical adhesive is preferably protected prior to use. This protection can be provided by a release liner such as a treated paper, providing easy release for the selected topical adhesive or by a closed container in which the functional articles are stored.
  • the functional article provides breathability by being at least water vapour permeable, preferably air permeable to prevent stuffiness. Breathability, if not supported by the topical adhesive as such, can be limited to the area of the article where no adhesive is applied.
  • An oil based composition according to the present invention was prepared using 9.9 % by weight of Kraton G-1651, a Styrene/Ethylene-Butylene/Styrene block copolymer containing 33% by weight styrene and available from Shell Co, and 59.3 % by weight of Kaydol, a paraffinic mineral oil available from Witco Co.
  • composition contained 301 parts of tackifying resin per 100 parts of Kraton polymer.
  • the tackifying resin was Escorez 5300, a hydrogenated resin available from Exxon Co.
  • Magnesium Stearate available from Carlo Erba S.p.A., was used a co-gelifying agent for oil at a level of 0.7 % by weight.
  • Irganox 1010 an antioxidant available from Ciba-Geigy, was added at a level of 0.3 % by weight.
  • the above formulation was tried and judged as comfortable for initial application and removal from sensitive, hairy skin. It can be mixed into hydrophobic cosmetics and increases the resistance to being rubbed off. Also use of this composition as a hand cleaner showed remarkable results.
  • a comparative oil based composition was compounded using 7.1 % by weight of Kraton G-1651 , a Styrene/Ethylene-Butylene/Styrene block copolymer containing 33% by weight styrene and available from Shell Co, and 41.9 % by weight of Kaydol, a paraffinic mineral oil available from Witco Co.
  • composition contained 704 parts of tackifying resin per 100 parts of Kraton polymer.
  • the tackifying resin was Regalrez 3102, a hydrocarbon resin available from Hercules Co.
  • Magnesium Stearate available from Carlo Erba S.p.A., was used a co-gelifying agent for oil at a level of 0.7 % by weight.
  • Irganox 1010 an antioxidant available from Ciba-Geigy, was added at a level of 0.3 % by weight.
  • the composition showed the following rheological properties at 37°C.

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  • Life Sciences & Earth Sciences (AREA)
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  • Animal Behavior & Ethology (AREA)
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  • Heart & Thoracic Surgery (AREA)
  • Birds (AREA)
  • Materials Engineering (AREA)
  • Surgery (AREA)
  • Dermatology (AREA)
  • Medicinal Preparation (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Cosmetics (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Materials For Medical Uses (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)

Abstract

L'invention concerne des adhésifs topiques destinés à la fixation sur la peau, notamment des adhésifs topiques qui peuvent être utilisés pour l'application sur la peau d'articles fonctionnels, en particulier pour coller des articles fonctionnels ou pour améliorer la fonction desdits articles. Dans ce contexte, les articles fonctionnels sont des articles d'apport cosmétique ou pharmaceutique, qui amènent une substance à la peau, tels que produits de traitement de la peau, crèmes, lotions, hormones, vitamines, déodorants ou médicaments; ou d'autres articles d'apport pharmaceutique, qui peuvent également amener une substance afin qu'elle se répande à distance de la peau, tels qu'insecticides, médicaments à inhaler ou parfums. L'adhésif de l'invention peut également être utilisé dans des articles fonctionnels qui ne sont pas fixés sur la peau, mais comme composant d'articles qui nécessitent un long temps de séjour sur la peau, tels que cosmétiques (rouge à lèvres, fard à paupières, maquillage de théâtre) ou articles nettoyants (produit de nettoyage pour les mains, masque facial, démaquillant, notamment pour les pores). Cet adhésif topique assure une bonne fixation ou un temps de séjour accru, et il est agréable à la peau après application, mais ne provoque pas de sensation désagréable une fois enlevé. Sa composition chimique et ses caractéristiques rhéologiques ont été choisies dans ce but.
EP97952628A 1996-12-23 1997-12-22 Adhesif pour application d'articles fonctionnels sur la peau et enlevement aise desdits articles Withdrawn EP0946213A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97952628A EP0946213A1 (fr) 1996-12-23 1997-12-22 Adhesif pour application d'articles fonctionnels sur la peau et enlevement aise desdits articles

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
EP96120738 1996-12-23
EP96120738A EP0850619A1 (fr) 1996-12-23 1996-12-23 Article absorbant jetable pourvu d'un adhésive pour la fixation d'article sur la peau
EP97110730A EP0853934A1 (fr) 1996-12-23 1997-07-01 Article absorbant jetable pourvu d'un adhesif pour la fixation d'article sur la peau
EP97110730 1997-07-01
EP97120337A EP0850649A1 (fr) 1996-12-23 1997-11-20 Adhésif pour coller des articles fonctionnels à la peau et enlèvement confortable de ces articles
EP97120337 1997-11-20
EP97952628A EP0946213A1 (fr) 1996-12-23 1997-12-22 Adhesif pour application d'articles fonctionnels sur la peau et enlevement aise desdits articles
PCT/US1997/023834 WO1998028022A1 (fr) 1996-12-23 1997-12-22 Adhesif pour application d'articles fonctionnels sur la peau et enlevement aise desdits articles

Publications (1)

Publication Number Publication Date
EP0946213A1 true EP0946213A1 (fr) 1999-10-06

Family

ID=54774301

Family Applications (3)

Application Number Title Priority Date Filing Date
EP97954168A Withdrawn EP0948368A1 (fr) 1996-12-23 1997-12-22 Adhesif pour l'application sur la peau d'articles fonctionnels et leur retrait agreable
EP97952628A Withdrawn EP0946213A1 (fr) 1996-12-23 1997-12-22 Adhesif pour application d'articles fonctionnels sur la peau et enlevement aise desdits articles
EP97950989A Withdrawn EP0948364A1 (fr) 1996-12-23 1997-12-22 Adhesif lipophile con u pour etre fixe localement a la peau de maniere sure et enleve de maniere agreable

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP97954168A Withdrawn EP0948368A1 (fr) 1996-12-23 1997-12-22 Adhesif pour l'application sur la peau d'articles fonctionnels et leur retrait agreable

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP97950989A Withdrawn EP0948364A1 (fr) 1996-12-23 1997-12-22 Adhesif lipophile con u pour etre fixe localement a la peau de maniere sure et enleve de maniere agreable

Country Status (7)

Country Link
EP (3) EP0948368A1 (fr)
JP (3) JP2000505702A (fr)
KR (3) KR20000069657A (fr)
CN (3) CN1246067A (fr)
AU (3) AU5619598A (fr)
CA (3) CA2275772A1 (fr)
WO (3) WO1998028022A1 (fr)

Families Citing this family (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6620143B1 (en) 1994-10-28 2003-09-16 Kimberly-Clark Worldwide, Inc. Sanitary napkin article having body-facing adhesive
EP1104666A1 (fr) 1999-12-03 2001-06-06 The Procter & Gamble Company Receptacle collecteur du flux menstruel
US6761710B2 (en) 1999-12-03 2004-07-13 The Procter & Gamble Company Container for the collection of menstrual flow
FR2805275B1 (fr) * 2000-02-21 2004-12-10 Plasto Sa Procede de fixation de protheses externes
US6489534B1 (en) 2000-04-28 2002-12-03 Kimberly-Clark Worldwide, Inc. Disposable personal articles which conform and adhere
EP1504740B1 (fr) 2003-08-07 2013-03-06 The Procter & Gamble Company Couche de collecte liée par une colle de latex avec des caractéristiques de manipulation de liquides insensible à la température
EP1504741A1 (fr) 2003-08-07 2005-02-09 The Procter & Gamble Company Couche de collecte liée par une colle de latex avec des caractéristiques de manipulation de liquides insensible à la pression
US8673282B2 (en) 2006-05-03 2014-03-18 L'oreal Cosmetic compositions containing block copolymers, tackifiers and a selective solvent for soft blocks
US8778323B2 (en) 2006-05-03 2014-07-15 L'oréal Cosmetic compositions containing block copolymers, tackifiers and modified silicones
US8557230B2 (en) 2006-05-03 2013-10-15 L'oreal Cosmetic compositions containing block copolymers, tackifiers and shine enhancing agents
US8758739B2 (en) 2006-05-03 2014-06-24 L'oreal Cosmetic compositions containing block copolymers, tackifiers and gelling agents
US8673284B2 (en) 2006-05-03 2014-03-18 L'oreal Cosmetic compositions containing block copolymers, tackifiers and a selective solvent for hard blocks
US8673283B2 (en) 2006-05-03 2014-03-18 L'oreal Cosmetic compositions containing block copolymers, tackifiers and a solvent mixture
CN102252962B (zh) * 2006-11-30 2014-02-19 尼普洛外用药品株式会社 贴剂及贴剂的评价方法
US8603444B2 (en) * 2007-01-12 2013-12-10 L'oréal Cosmetic compositions containing a block copolymer, a tackifier and a high viscosity ester
US8658141B2 (en) 2007-01-12 2014-02-25 L'oreal Cosmetic composition containing a block copolymer, a tackifier, a silsesquioxane wax and/or resin
US7947027B2 (en) 2007-12-28 2011-05-24 Kimberly-Clark Worldwide, Inc. Body adhering absorbent article
US8292862B2 (en) 2007-08-03 2012-10-23 Kimberly-Clark Worldwide, Inc. Dynamic fitting body adhering absorbent article
US8672911B2 (en) 2007-08-03 2014-03-18 Kimberly-Clark Worldwide, Inc. Body adhering absorbent article
US8734413B2 (en) 2007-08-03 2014-05-27 Kimberly-Clark Worldwide, Inc. Packaged body adhering absorbent article
US8251969B2 (en) 2007-08-03 2012-08-28 Kimberly-Clark Worldwide, Inc. Body adhering absorbent article
FR2924607B1 (fr) * 2007-12-10 2009-12-18 Chanel Parfums Beaute Composition cosmetique renfermant un gel anhydre et un ester de glyceryle
WO2010039374A1 (fr) * 2008-10-01 2010-04-08 Action Bandage, L.L.C Dispositif cicatrisant
US11147722B2 (en) 2008-11-10 2021-10-19 Kimberly-Clark Worldwide, Inc. Absorbent article with a multifunctional acrylate skin-adhesive composition
IT1392180B1 (it) * 2008-12-11 2012-02-22 Bouty Spa Un sistema matriciale auto-adesivo comprendente un copolimero a blocchi stirenico
US10022468B2 (en) 2009-02-02 2018-07-17 Kimberly-Clark Worldwide, Inc. Absorbent articles containing a multifunctional gel
EP2485775B1 (fr) * 2009-10-08 2018-08-08 Euromed Inc. Composition adhésive
EP2654474B1 (fr) * 2010-12-22 2016-02-03 Avon Products, Inc. Composition adhésive cosmétique
US8758547B2 (en) 2011-02-08 2014-06-24 Kimberly-Clark Worldwide, Inc. Method of manufacturing a body adhering absorbent article orientated in the cross-machine direction with reduced curl
US8764922B2 (en) 2011-02-08 2014-07-01 Kimberly-Clark Worldwide, Inc. Method of manufacturing a body adhering absorbent article orientated in the machine direction with reduced curl
US20120219516A1 (en) 2011-02-25 2012-08-30 L'oreal S.A. Cosmetic compositions having long lasting shine
CN102600042A (zh) * 2012-04-16 2012-07-25 苏州卫生职业技术学院 一种粘贴式眼影
MX2014013881A (es) * 2012-05-16 2015-08-14 Archer Daniels Midland Co Emulsificante para solubilizar solventes polares en aceites y polioles.
CN103213758B (zh) * 2013-05-13 2016-01-20 孙秋玉 眼妆贴膜
CN103756386B (zh) * 2014-01-20 2016-08-17 中山有行企业胶类制品有限公司 一种化妆用身体彩绘胶及其制备方法
DK3288405T3 (da) * 2015-05-01 2021-07-26 Cosmo Spa Lounge & Supply Inc Dba Illumino Kemisk minimeret system til tidsreduceret påsætning af øjenvippeforlængelser
FR3053590B1 (fr) * 2016-07-07 2019-07-05 S.A. Thalgo Tch Composition pour epilation sans bande

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO134790C (no) * 1968-07-09 1984-03-22 Smith & Nephew Klebende,; trykkfoelsomt, vanndamp-permeabelt produkt for bruk paa hud hos mennesker.
JPS5592306A (en) * 1979-01-06 1980-07-12 Nitto Electric Ind Co Ltd Adherent sheet pack
CA1218954A (fr) * 1982-02-25 1987-03-10 David L. Sieverding Colle de contact elastomere hydrophile
US4593053A (en) * 1984-12-07 1986-06-03 Medtronic, Inc. Hydrophilic pressure sensitive biomedical adhesive composition
JPS62209008A (ja) * 1986-03-10 1987-09-14 Nikko Kemikaruzu Kk パツク剤
US5071704A (en) * 1990-06-13 1991-12-10 Fischel Ghodsian Fariba Device for controlled release of vapors and scents
US5276079A (en) * 1991-11-15 1994-01-04 Minnesota Mining And Manufacturing Company Pressure-sensitive poly(n-vinyl lactam) adhesive composition and method for producing and using same
CA2122660A1 (fr) * 1993-12-14 1995-06-15 John Philip Vukos Article absorbant a bande adhesive
EP0788338B2 (fr) * 1994-10-28 2006-06-28 Kimberly-Clark Worldwide, Inc. Article absorbant auto-adhesif
WO1996014822A1 (fr) * 1994-11-15 1996-05-23 Osmotics Corporation Procedes et compositions de soins pour la peau
ZA96225B (en) * 1995-01-24 1997-07-11 Bristol Myers Squibb Co Method and closure tape for improved wound or incision healing
FR2734574A1 (fr) * 1995-05-24 1996-11-29 Pacific Corp Feuilles de masque adhesives a usage cosmetique et medical
US5559165A (en) * 1995-08-08 1996-09-24 National Starch And Chemical Investment Holding Corporation Hot melt adhesives for bonding to sensitive areas of the human body

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9828022A1 *

Also Published As

Publication number Publication date
CA2275772A1 (fr) 1998-07-02
AU5801498A (en) 1998-07-17
WO1998028018A1 (fr) 1998-07-02
AU5385398A (en) 1998-07-17
KR20000069690A (ko) 2000-11-25
CN1246063A (zh) 2000-03-01
JP2001507591A (ja) 2001-06-12
AU5619598A (en) 1998-07-17
CN1246066A (zh) 2000-03-01
CA2275898A1 (fr) 1998-07-02
JP2001507962A (ja) 2001-06-19
JP2000505702A (ja) 2000-05-16
WO1998028022A1 (fr) 1998-07-02
EP0948368A1 (fr) 1999-10-13
WO1998028015A1 (fr) 1998-07-02
KR20000069657A (ko) 2000-11-25
CN1246067A (zh) 2000-03-01
EP0948364A1 (fr) 1999-10-13
CA2275990A1 (fr) 1998-07-02
KR20000069677A (ko) 2000-11-25

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