CA2275898A1 - Lipophilic adhesive for secure topical attachment to the skin and comfortable removal - Google Patents
Lipophilic adhesive for secure topical attachment to the skin and comfortable removal Download PDFInfo
- Publication number
- CA2275898A1 CA2275898A1 CA002275898A CA2275898A CA2275898A1 CA 2275898 A1 CA2275898 A1 CA 2275898A1 CA 002275898 A CA002275898 A CA 002275898A CA 2275898 A CA2275898 A CA 2275898A CA 2275898 A1 CA2275898 A1 CA 2275898A1
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- styrene
- adhesive
- skin
- topical
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Classifications
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- 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
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- 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
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Heart & Thoracic Surgery (AREA)
- Birds (AREA)
- Hematology (AREA)
- Materials Engineering (AREA)
- Vascular Medicine (AREA)
- Surgery (AREA)
- Dermatology (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Materials For Medical Uses (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
Abstract
The present invention relates to lipophilic topical adhesives for attachment to the skin. In particular the present invention relates to such topical adhesives which can be preferably employed for attachment to the skin in the area were absorption of bodily liquids is desired. The lipophilic topical adhesive provides secure attachment and is pleasing to the skin upon application, yet causes no discomfort upon removal. This is achieved by selecting the chemical composition and rheological characteristics of the topical adhesives.
Description
WO 98/28015 . PCT/US97/23457 LIPOPHILIC ADHESIVE FOR SECURE TOPICAL ATTACHMENT TO THE SKIN
s AND COMFORTABLE REMOVAL
Field of the invention ~s The present invention relates to lipophilic topical adhesives for attachment to the skin. In particular the present invention relates to such topical adhesives which can be employed for attachment to the skin in the area were absorption of bodily liquids is desired) particularly for the adhesion of sanitary napkins, pantiliners) adult incontinence products or sweat pads. The lipophilic topical adhesive of the 2o present invention can also be used for attachment to the skin of other articles such as protective articles, clothing, prosthesis, heat wraps, ice wraps) hearing aids, protective face masks, ornamental articles or eye wear, or also functional articles such as cosmetic or pharmaceutical delivery articles that provide a substance to the skin. Further, the lipophilic topical adhesive of the present 2s invention can be used in functional articles that are not attached to the skin, but as a component in articles that require a high residence time on the skin such as decorative cosmetics or cleaning articles. 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 3o selecting the chemical composition and the rheological characteristics of the topical adhesives.
Back_around of the invention 3s The general prior art in the field of topical adhesives for attachment to the skin is particularly developed in the field of band-aids, plasters and bandages. These articles are, however, typically applied in an emergency situation where for example a cut into the skin of the wearer has occurred and absorption of the body liquids emanating from a wound is desired. In this context performance aspects of the absorbent article such as comfortable and easy use and application, painless removal, discreteness are subordinate to criteria such as s sterility, healing support, mechanical protection of the wound. Also such wound covering absorbent articles are mostly adhered to skin areas where prior to application of the absorbent article body hair can be removed or where Tittle or no hair grows.
The present invention relates to topical adhesives which are particularly useful to absorbent articles for absorption of body liquids which naturally emanate from a body without a wound. For example to attach sanitary napkins or pantiiiners in the genital region. Also incontinence devices which are worn e.g. in the genital region or sweat pads which are worn in the arm pit region of a person can suitably employ the adhesive of the present invention.
The present invention also relates to topical adhesives which are particularly useful to protective articles such as genital-, knee- or elbow-protectors or bandages; clothing such as bras, surgical gowns, or parts of garments during 2o fitting at a tailor; nasal plasters; prosthesis such as breast replacements or wigs;
heat wraps e.g. for relief of menstrual cramps, arthritis pain, back pain, pain from bruises during sport or work or simply to provide warmth; ice wraps e.g. to provide pain relieve from bruises and to reduce swelling; hearing aids;
protective face masks; ornamental articles such as jewelry, earrings, guises, tattoos;
2s goggles or other eye wear. Such articles are not used for absorption of body liquids. For example attachment of a wig to the skin on the skull or of elbow and knee protectors to these surfaces of the body which undergo substantial extending and wrinkling can suitably be done by the adhesive of the present invention.
3s The present invention can further relate 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 pertumes; further the lipophilic 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 s 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 that are used for absorbent articles such as sanitary napkin or pantiliners have generally been disclosed in US statutory invention registration H1602 or WO 96/33683. Some more details of the adhesive have been disclosed in PCT application WO 95/16424. In this document sanitary articles ~s 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 sate attachment to the skin but mentions also the problems of detachment of such articles after use without causing undue pain to a wearer.
zo The disclosure of WO 95/16424 includes a detailed analysis of the criteria for the topical adhesive in respect to theological criteria. However, this document has little regard to the problem of painless removal of such articles since the theological criteria taught include epilatory, i.e. hair removal, compositions which 2s are commercially available such as STREP MIELE (TM) sold in Italy by Laboratori Vaj S.p.A. The adhesives for topical attachment mentioned in WO
95/16424 include also today's pressure sensitive adhesives which are used to attach sanitary napkins to undergarments. Further, this document only identifies static theological characteristics but is silent as to the dynamic theological 3o behaviour of a topical adhesive.
. In 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 3s 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.
s AND COMFORTABLE REMOVAL
Field of the invention ~s The present invention relates to lipophilic topical adhesives for attachment to the skin. In particular the present invention relates to such topical adhesives which can be employed for attachment to the skin in the area were absorption of bodily liquids is desired) particularly for the adhesion of sanitary napkins, pantiliners) adult incontinence products or sweat pads. The lipophilic topical adhesive of the 2o present invention can also be used for attachment to the skin of other articles such as protective articles, clothing, prosthesis, heat wraps, ice wraps) hearing aids, protective face masks, ornamental articles or eye wear, or also functional articles such as cosmetic or pharmaceutical delivery articles that provide a substance to the skin. Further, the lipophilic topical adhesive of the present 2s invention can be used in functional articles that are not attached to the skin, but as a component in articles that require a high residence time on the skin such as decorative cosmetics or cleaning articles. 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 3o selecting the chemical composition and the rheological characteristics of the topical adhesives.
Back_around of the invention 3s The general prior art in the field of topical adhesives for attachment to the skin is particularly developed in the field of band-aids, plasters and bandages. These articles are, however, typically applied in an emergency situation where for example a cut into the skin of the wearer has occurred and absorption of the body liquids emanating from a wound is desired. In this context performance aspects of the absorbent article such as comfortable and easy use and application, painless removal, discreteness are subordinate to criteria such as s sterility, healing support, mechanical protection of the wound. Also such wound covering absorbent articles are mostly adhered to skin areas where prior to application of the absorbent article body hair can be removed or where Tittle or no hair grows.
The present invention relates to topical adhesives which are particularly useful to absorbent articles for absorption of body liquids which naturally emanate from a body without a wound. For example to attach sanitary napkins or pantiiiners in the genital region. Also incontinence devices which are worn e.g. in the genital region or sweat pads which are worn in the arm pit region of a person can suitably employ the adhesive of the present invention.
The present invention also relates to topical adhesives which are particularly useful to protective articles such as genital-, knee- or elbow-protectors or bandages; clothing such as bras, surgical gowns, or parts of garments during 2o fitting at a tailor; nasal plasters; prosthesis such as breast replacements or wigs;
heat wraps e.g. for relief of menstrual cramps, arthritis pain, back pain, pain from bruises during sport or work or simply to provide warmth; ice wraps e.g. to provide pain relieve from bruises and to reduce swelling; hearing aids;
protective face masks; ornamental articles such as jewelry, earrings, guises, tattoos;
2s goggles or other eye wear. Such articles are not used for absorption of body liquids. For example attachment of a wig to the skin on the skull or of elbow and knee protectors to these surfaces of the body which undergo substantial extending and wrinkling can suitably be done by the adhesive of the present invention.
3s The present invention can further relate 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 pertumes; further the lipophilic 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 s 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 that are used for absorbent articles such as sanitary napkin or pantiliners have generally been disclosed in US statutory invention registration H1602 or WO 96/33683. Some more details of the adhesive have been disclosed in PCT application WO 95/16424. In this document sanitary articles ~s 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 sate attachment to the skin but mentions also the problems of detachment of such articles after use without causing undue pain to a wearer.
zo The disclosure of WO 95/16424 includes a detailed analysis of the criteria for the topical adhesive in respect to theological criteria. However, this document has little regard to the problem of painless removal of such articles since the theological criteria taught include epilatory, i.e. hair removal, compositions which 2s are commercially available such as STREP MIELE (TM) sold in Italy by Laboratori Vaj S.p.A. The adhesives for topical attachment mentioned in WO
95/16424 include also today's pressure sensitive adhesives which are used to attach sanitary napkins to undergarments. Further, this document only identifies static theological characteristics but is silent as to the dynamic theological 3o behaviour of a topical adhesive.
. In 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 3s 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.
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 s 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.
European Patent Application EP-638 303 discloses the use of a topics! adhesive on side cuffs of sanitary napkins in order to keep the cuffs in an upright position.
Swiss publication CH-643730 discloses the use of a very long sanitary napkin ~s having chamfered outer edges with a topical adhesive at the four corners of the outer edges in order to provide a topical adhesive area well outside the region of pubic hair growth. Both applications are silent as to the adhesive composition.
Based on the above state of the art it is an objective of the present invention to 2o provide a lipophilic topical adhesive for secure attachment and painless removal from the skin. it is another objective of the present invention to ensure upon removal that no residual adhesive remains on the skin or on the hair.
It is yet a further objective of the present invention that the lipophilic adhesive for 2s 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.
In addition to the above objectives of the present invention it is also desirable for 3o topical adhesives to provide additional benefits such as delivery/dispersal of a compound or composition which is beneficial for the skin or for the body in general) or also physical protection. Further, topical adhesives which do not affect the natural skin condition e.g. by being breathable or water vapour transmitting or water vapour/sweat absorbing, are preferred.
Brief description of the invention _..._ _..__... _ ._.._..__._ _ .._T......~_____ .___.._.~ .. _~, While the present invention will be. described herein in its use on disposable absorbent articles for topical adhesive attachment to a wearer of such articles, further alternative uses of the present invention are possible.
s The present invention is also useful to attach to the skin or wear protective articles such as genital-, knee- or elbow-protectors or bandages; clothing such as bras, surgical gowns, or parts of garments during fitting at a tailor;
nasal plasters; prosthesis such as breast replacements or wigs; heat wraps e.g. for relief of menstrual cramps, arthritis pain, back pain) pain from bruises during ~o sport or work or simply to provide warmth; ice wraps e.g. to provide pain relieve from bruises and to reduce swelling; hearing aids; protective face masks;
ornamental articles such as jewelry, earrings, guises, tattoos; goggles or other eye wear. Such articles are non-absorbent for bodily liquids.
~s Further, the present invention can be 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 Zo 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, 2s stage make-up) or cleaning article (hand cleaner, face mask, hygienic cleanser especially for pores). Such articles also are non-absorbent for bodily liquids. 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 3o which is supported or improved by the topical adhesives according to the present invention. The articles typically have a wearer facing surface and an outside surface.
In its use on disposable absorbent articles the lipophilic topical adhesive of the 3s present invention is intended for topical adhesive attachment to a wearer of such articles. Disposable absorbent articles such as sanitary napkins, pantiliners, incontinence articles or underarm sweat pads, typically has a wearer facing surface and an outside surface. The article comprises an absorbent core structure between the wearer facing surface and the outside surface for absorbing liquids emanating from a wearer such as urine, feces, menses, sweat and vaginal discharge. The topical adhesive allows to attach an article to the skin s of the wearer.
Detailed analysis of the sequence of common situations occurring from the application of a such articles to the time of removal has shown that specific adhesive characteristics need to be satisfied in order to achieve the desired performance objectives, in particular secure initial attachment) secure attachment during use and painless removal at the end. The characteristics which have been considered in this context are the elastic modulus describing the elastic behaviour of the material and the viscous modulus which describes the viscous behaviour of the adhesive material.
~s 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.
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.
zo 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 on which fraction of the removal energy will be dissipated within the adhesive and which fraction is available to trigger the actual removal.
2s In order to provide topical adhesives for secure initial and prolonged attachment and easy/painless removal the relation between the elastic modulus and the viscous modulus as well as their dynamic behaviour is of key importance.
The topical adhesive has an elastic modulus at a temperature of 37°C (100°
Fahrenheit) abbreviated G'3~ and a viscous modulus at a temperature of 37°C
{100° Fahrenheit) of G"3~. The adhesive further has a dynamic elastic behaviour defined as eG'3~ which is the difference of G'3~ at a frequency of 100 rad/sec and G'3~ at a frequency, of 1 rad/sec and a dynamic viscous behaviour oG"3~ which is the difference of G"3~ at a frequency of 100 rad/sec and G"3~ at a frequency of 1 3s rad/sec.
____~____ . _._~~._...~_ _ ___._ _ The topical adhesive according to the present invention satisfies the following conditions.
~ G'3~ (1 rad/sec) is in the range 1500 Pa to 20000 Pa, s preferably 1500 Pa to 15000 Pa, most preferably 3000 Pa to 10000 Pa.
~ G"3~ (1 rad/sec) is in the range 100 Pa to 15000 Pa, preferably 100 Pa to 10000 Pa, most o preferably 300 Pa to 5000 Pa.
~ the ratio of G'3~ (1 rad/sec) / G"3~ (1 rad/sec) is in the range of 3 to 30.
~s ~ the ratio G'3~ (100 radlsec) - G"3~ (100 rad/sec) G'3~ (1 rad/sec) - G"3~ (1 rad/sec) is not less than 0.5, preferably in the range 20 0.7 to 3, most preferably in the range 1 to 1.8.
~ either the ratio of ~G'3~/G'37 (1 radlsec) is not greater than 1.5) preferably not greater than unity and most preferably is not greater than 0.8) or ~G'3~ 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'3,/G"3, at least for the frequency range from above rad/s up to 100 rad/s should preferably be 3.3 or above, more preferably 5 or above, most preferably 10 or above, white not exceeding about 30, preferably 20, anywhere in the frequency interval.
~ the rheological behaviour can also be related to the values of the Glass Transition Temperature Tg. For topical adhesives according to the present invention Tg should preferably be less than -15°C, more preferably less than -20°C and most preferably less than -25°C.
~ the rheoiogical behaviour and acceptance of a topical adhesive can also be s related to the specific heat capacity. Preferably 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 o related to the specific heat conductivity of the adhesive. Preferably 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 .
Provided the above rheological conditions are satisfied the adhesives will also ~s satisfy conditions such as sufficient cohesiveness (to prevent residue of adhesive on skin) which are critical for commercial use of such adhesives and apparent to those skilled in the art. Adhesive compositions which satisfy the above criteria can be used as topical adhesives for the above mentioned articles, or as components in the formulation of functional articles, and particularly for 2o disposable absorbent articles provided they also satisfy the common requirements of being safe for use on human or anima! skin during use and generally after disposal of the article.
Often the criteria of hygienic appearance and pleasant feel upon contact are 2s important such that adhesive composition which are transparent or white, and which prevent a cold) unpleasant feeling upon application are preferred.
The above rheological criteria and other considerations can be satisfied by the particularly preferred adhesive compositions of the present invention where the 3o composition comprises from 3% to 15%, preferably from 5% to 10%, by weight of a first copolymer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene having a triblock content higher than 70%, a styrene content higher than 25% by weight, and a molecular weight higher than 60.000; from 0% to 9%, preferably from 0% to 6%, by weight of a second copolymer polystyrene-block-3s (polyethylene-ran-butylene}-block-polystyrene having a triblock content of less than 70%, a styrene content of less than 20% by weight, and a molecular weight of less than 60.000; from 20% to 95%, preferably from 30% to 60%, by weight of __ _..__».._...T...._~ _._ .... _..___ .~.._~
WO 98/28015 PCT/LIS9?/2345?
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.
European Patent Application EP-638 303 discloses the use of a topics! adhesive on side cuffs of sanitary napkins in order to keep the cuffs in an upright position.
Swiss publication CH-643730 discloses the use of a very long sanitary napkin ~s having chamfered outer edges with a topical adhesive at the four corners of the outer edges in order to provide a topical adhesive area well outside the region of pubic hair growth. Both applications are silent as to the adhesive composition.
Based on the above state of the art it is an objective of the present invention to 2o provide a lipophilic topical adhesive for secure attachment and painless removal from the skin. it is another objective of the present invention to ensure upon removal that no residual adhesive remains on the skin or on the hair.
It is yet a further objective of the present invention that the lipophilic adhesive for 2s 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.
In addition to the above objectives of the present invention it is also desirable for 3o topical adhesives to provide additional benefits such as delivery/dispersal of a compound or composition which is beneficial for the skin or for the body in general) or also physical protection. Further, topical adhesives which do not affect the natural skin condition e.g. by being breathable or water vapour transmitting or water vapour/sweat absorbing, are preferred.
Brief description of the invention _..._ _..__... _ ._.._..__._ _ .._T......~_____ .___.._.~ .. _~, While the present invention will be. described herein in its use on disposable absorbent articles for topical adhesive attachment to a wearer of such articles, further alternative uses of the present invention are possible.
s The present invention is also useful to attach to the skin or wear protective articles such as genital-, knee- or elbow-protectors or bandages; clothing such as bras, surgical gowns, or parts of garments during fitting at a tailor;
nasal plasters; prosthesis such as breast replacements or wigs; heat wraps e.g. for relief of menstrual cramps, arthritis pain, back pain) pain from bruises during ~o sport or work or simply to provide warmth; ice wraps e.g. to provide pain relieve from bruises and to reduce swelling; hearing aids; protective face masks;
ornamental articles such as jewelry, earrings, guises, tattoos; goggles or other eye wear. Such articles are non-absorbent for bodily liquids.
~s Further, the present invention can be 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 Zo 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, 2s stage make-up) or cleaning article (hand cleaner, face mask, hygienic cleanser especially for pores). Such articles also are non-absorbent for bodily liquids. 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 3o which is supported or improved by the topical adhesives according to the present invention. The articles typically have a wearer facing surface and an outside surface.
In its use on disposable absorbent articles the lipophilic topical adhesive of the 3s present invention is intended for topical adhesive attachment to a wearer of such articles. Disposable absorbent articles such as sanitary napkins, pantiliners, incontinence articles or underarm sweat pads, typically has a wearer facing surface and an outside surface. The article comprises an absorbent core structure between the wearer facing surface and the outside surface for absorbing liquids emanating from a wearer such as urine, feces, menses, sweat and vaginal discharge. The topical adhesive allows to attach an article to the skin s of the wearer.
Detailed analysis of the sequence of common situations occurring from the application of a such articles to the time of removal has shown that specific adhesive characteristics need to be satisfied in order to achieve the desired performance objectives, in particular secure initial attachment) secure attachment during use and painless removal at the end. The characteristics which have been considered in this context are the elastic modulus describing the elastic behaviour of the material and the viscous modulus which describes the viscous behaviour of the adhesive material.
~s 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.
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.
zo 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 on which fraction of the removal energy will be dissipated within the adhesive and which fraction is available to trigger the actual removal.
2s In order to provide topical adhesives for secure initial and prolonged attachment and easy/painless removal the relation between the elastic modulus and the viscous modulus as well as their dynamic behaviour is of key importance.
The topical adhesive has an elastic modulus at a temperature of 37°C (100°
Fahrenheit) abbreviated G'3~ and a viscous modulus at a temperature of 37°C
{100° Fahrenheit) of G"3~. The adhesive further has a dynamic elastic behaviour defined as eG'3~ which is the difference of G'3~ at a frequency of 100 rad/sec and G'3~ at a frequency, of 1 rad/sec and a dynamic viscous behaviour oG"3~ which is the difference of G"3~ at a frequency of 100 rad/sec and G"3~ at a frequency of 1 3s rad/sec.
____~____ . _._~~._...~_ _ ___._ _ The topical adhesive according to the present invention satisfies the following conditions.
~ G'3~ (1 rad/sec) is in the range 1500 Pa to 20000 Pa, s preferably 1500 Pa to 15000 Pa, most preferably 3000 Pa to 10000 Pa.
~ G"3~ (1 rad/sec) is in the range 100 Pa to 15000 Pa, preferably 100 Pa to 10000 Pa, most o preferably 300 Pa to 5000 Pa.
~ the ratio of G'3~ (1 rad/sec) / G"3~ (1 rad/sec) is in the range of 3 to 30.
~s ~ the ratio G'3~ (100 radlsec) - G"3~ (100 rad/sec) G'3~ (1 rad/sec) - G"3~ (1 rad/sec) is not less than 0.5, preferably in the range 20 0.7 to 3, most preferably in the range 1 to 1.8.
~ either the ratio of ~G'3~/G'37 (1 radlsec) is not greater than 1.5) preferably not greater than unity and most preferably is not greater than 0.8) or ~G'3~ 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'3,/G"3, at least for the frequency range from above rad/s up to 100 rad/s should preferably be 3.3 or above, more preferably 5 or above, most preferably 10 or above, white not exceeding about 30, preferably 20, anywhere in the frequency interval.
~ the rheological behaviour can also be related to the values of the Glass Transition Temperature Tg. For topical adhesives according to the present invention Tg should preferably be less than -15°C, more preferably less than -20°C and most preferably less than -25°C.
~ the rheoiogical behaviour and acceptance of a topical adhesive can also be s related to the specific heat capacity. Preferably 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 o related to the specific heat conductivity of the adhesive. Preferably 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 .
Provided the above rheological conditions are satisfied the adhesives will also ~s satisfy conditions such as sufficient cohesiveness (to prevent residue of adhesive on skin) which are critical for commercial use of such adhesives and apparent to those skilled in the art. Adhesive compositions which satisfy the above criteria can be used as topical adhesives for the above mentioned articles, or as components in the formulation of functional articles, and particularly for 2o disposable absorbent articles provided they also satisfy the common requirements of being safe for use on human or anima! skin during use and generally after disposal of the article.
Often the criteria of hygienic appearance and pleasant feel upon contact are 2s important such that adhesive composition which are transparent or white, and which prevent a cold) unpleasant feeling upon application are preferred.
The above rheological criteria and other considerations can be satisfied by the particularly preferred adhesive compositions of the present invention where the 3o composition comprises from 3% to 15%, preferably from 5% to 10%, by weight of a first copolymer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene having a triblock content higher than 70%, a styrene content higher than 25% by weight, and a molecular weight higher than 60.000; from 0% to 9%, preferably from 0% to 6%, by weight of a second copolymer polystyrene-block-3s (polyethylene-ran-butylene}-block-polystyrene having a triblock content of less than 70%, a styrene content of less than 20% by weight, and a molecular weight of less than 60.000; from 20% to 95%, preferably from 30% to 60%, by weight of __ _..__».._...T...._~ _._ .... _..___ .~.._~
WO 98/28015 PCT/LIS9?/2345?
an oil having a paraffinic fraction higher than 50% by weight, and an aromatic fraction less than 5% by weight, as a plasticising compound; from 0% to 50%, preferably from 30% to 50%, by weight of a hydrogenated cycloaliphatic tackifying resin; and from 0% to 10% by weight of additives such as antioxidants s or get stabilizing substances, preferably antioxidant substances are comprised in an amount of from 0.3% to 1 % by weight, and gel stabilizing substances are comprised in an amount of from 0% to 1 % by weight. The first and second copolymers polystyrene-block-(polyethylene-ran-butylene)-block-polystyrene are preferably selected from the group consisting of styrene-block-copolymers of the o type styrene-butadiene-styrene, styrene-isoprene-styrene styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene. The oil is preferably selected from the group consisting of natural or synthetic oils such as vegetable oils, mineral oils, or combinations thereof.
~s Detailed description of the invention 2o Adhesive for topical attachment The topical adhesive according to the present invention is applied directly to the skin. In a particular application the adhesive can be used on sanitary napkins which are applied in the genital region of a typically female user around the area 2s of liquid discharge. The word "skin" according to the present invention does not only relate to the specific derma of the user but includes the mucous tissue as well as the hair which is typically found in the genital region of users of sanitary napkins.
3o In order to provide fixation of an article according to the present invention to the skin it is necessary to provide a certain area on the side of the article which is facing the skin with the topical adhesive.
For sanitary napkins various designs are contemplated but preferably the topical 3s adhesive is provided along the peripheral edge of the topsheet such that a central area of the article is left without adhesive. This will most appropriately facilitate placing the napkin such that the liquid permeable topsheet region without adhesive is placed adjacent the bodily liquid emanating orifice such that emanating liquid is immediately transported into the absorbent structure of the absorbent article without the possibility of leakage or spillage.
s Physical, Rheoloaical and Adhesive Characteristics of a Topical Adhesive Even though topical adhesives are used like pressure sensitive adhesives on human skin hair and mucous tissues) 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.
In fact as the person skilled in the art of adhesives knows, the most characteristic feature that distinguishes a PSA from other substances that can temporarily stick ~s things (as e.g. water between two glass plates could) is the fact that their rheological parameters and especially the Elastic Modulus G' vary greatly with the frequency of applied stresses. More in particular, G' of PSA can increase over some orders of magnitude while the frequency of applied stresses varies from typical bonding frequency to typical debonding frequency) i.e. 1 rad/s to 2o rad/s as indicated below.
As a first consequence) it derives that it is inadmissible to def ne materials intended for use as "topical adhesives" by giving values of rheological parameters and especially of G' at a fixed value of frequency. This can be 2s misleading because in the absence of other characteristics it will include materials which have no practical value. It is hence necessary that rheological characterisation must be on the base of dynamic considerations.
This not only applies to the Elastic Modulus G' but also to the viscous modulus 3o G" and hence also for tan (8) = G" / G'. It is well known that typical PSA
have not only a high variation of G' across the considered frequencies but also there is an even higher variation of G" which can get close or become even higher than the value of G', i.e. tan (8) becomes about or even greater than 1, in particular at the frequencies that are typical of the debonding.
Without wishing to be bound by theory this can be interpreted as meaning that a high fraction of the energy applied for the debonding is dissipated within the _ ___.~~.__._.__~.._ ~_.~.~.. _._._ . _ .... . .. _..__.... . _ _ adhesive (so it is not effective in causing the debonding) while this fact causes macroscopically the recording of a very high level of adhesive force.
As indicated above materials useful as topical adhesives according to the s 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 sanitary napkin with a topical adhesive the adhesive contact is formed at a low frequency, while debonding happens at the speed of removing the article.
o 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 radls.
Therefore, the frequency range for use according to the present invention is between 1 and 100 rad/s.
~s It is believed that 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 Jlg/K) the actual temperature of the topical 2o 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, zs 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 for use in the field of sanitary napkins, and in general when using articles which are frequently removed and adhered again or replaced, while the 3o material remains soft and capable of gently adhering to skin.
The ratio of G'3~ ('t rad/sec) over G"3~ {1 rad/sec) is important to ensure that these two values are balanced upon adhesion to the skin. At the same time the absolute changes of G'3~ need to be limited within the range of frequencies 3s considered. Hence a value for the ratio of ~G'3~ (i.e. G'3~ {100 rad/sec) -G'3~ (1 rad/sec)) over G'3~ (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 OG'3~ below certain values.
Importantly, the ratio of G'3, (100 rad/sec) - G"3~ (100 rad/sec) s G'3~ ( 1 rad/sec) - G "3~ ( 1 rad/sec) needs to be large enough to ensure that the dynamic behaviour of both the elastic and the viscous module are maintained in a relationship which provides secure adhesion and painless and easy removal.
Finally the person skilled in the art will also recognise that the Glass Transition Temperature Tg of the adhesive composition, specific heat capacity, and specific ~s heat conductivity are parameters which are useful to more fully define the group of useful topical adhesives.
The following set of characteristics should be satisfied:
zo ~ G'3~ (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"3~ (1 rad/sec) is in the range 100 Pa to 15000 Pa, 2s preferably 100 Pa to 10000 Pa, most preferably 300 Pa to 5000 Pa.
~ the ratio of G'3~ (1 rad/sec) / G"3~ (1 rad/sec) is in the range of 3 to 30.
~ the ratio G'3~ (100 rad/sec) - G"3~ (100 rad/sec) G'3~ ( 1 rad/sec) - G"3~ ( 1 rad/sec) 3s is not less than 0.5, preferably in the range 0.7 to 3, most preferably in the range 1 to 1.8.
~ either the ratio of ~G'3~G'3~ (1 rad/sec) is not greater than 1.5, r __ . _._..__.. . _ r ._.._.... ...___._ preferably not greater than unity and most preferably not greater than 0.8, or ~G'3~ is not greater than 10000 Pa, preferably less s than 5000 Pa, most preferably less than 2000 Pa, or both.
~ the value of the ratio G'3,/G"3, at least for the frequency range from above rad/s up to 100 rad/s should preferably be 3.3 or above, more preferably 5 or o above, most preferably 10 or above, while not exceeding about 30, preferably 20, anywhere in the frequency interval.
~ the rheological behaviour can also be related to the values of the Glass Transition Temperature Tg. For topical adhesives according to the present s invention 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. Preferably the specific heat capacity of the zo 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. Preferably the specific 2s heat conductivity is as low as possible (except for energy transmitting articles where high values are more desirable)) more preferable between 1 and 0.1 W/m/K, most preferably between 0.6 and 0.1 W/m/K.
Chemical and compositional characteristics of a Topical adhesive In order to provide the preferred topical adhesive compositions which satisfy the requirements of the above rheological and physical characteristics of a topical adhesive the following formulation criteria are used. It should be noted that the most of the compositions useful as topical adhesive have a substantially gel-like 3s structure and are preferably gels. This derives from the fact that:
- the prevailing component is the plasticiser which is a material liquid at room temperature - a macromolecular or polymeric component is present in minor quantities vs.
the s piasticiser. 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.
o Possible typical 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 (lipophilic) compositions in which the plasticiser is typically ~s 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).
2) Mixed phase compositions in which both hydrophobic and hydrophilic components, possibly in both plasticisers and polymers, form two or more separate phases. In such cases an emulsifier/surfactant is preferably present at zo a suitable level to form stable emulsions between the incompatible phases.
For topical adhesives according to the present invention it is preferably that the hydrophobic components are prevailing vs. the hydrophilic ones.
3) Hydrophilic compositions in which typically the plasticiser is water/glycerol/glycols and the like and/or mixtures thereof and the polymeric 2s phase is of synthetic (e.g. polyacrylics) or natural (e.g. natural gums) origin or mixtures thereof.
It is to stress that, differently from the medical field and from the cited prior art, the hydrophilic compositions are not preferred while the hydrophobic (lipophilic) 3o and mixed phases compositions 1 ) and 2) are preferred in the applications of the present invention.
This depends partially on technical reasons in the sense that many hydrophilic compositions used in the medical field show too low elastic character and 3s cohesion for being useful in the present application. The other reason to prefer hydrophobic or mixed phase compositions is that the application of the present invention in particular in the sanitary napkin field will include a probability of _._ _ _.._ ~, contacting the topical adhesive with the liquid to be absorbed. Since the liquids are all of a general aqueous kind contact with a hydrophilic topical adhesive would result in a certain absorption of the bodily liquids into the topical adhesives.
This would then have the result of changing the rheological characteristics and therefore the functionality of the topical adhesive and causing a non-hygienic appearance.
to Further hydrophilic topical adhesive also tend to be perceived as cold and wet which upon application to the skin of a human is not in line with typical expectation. Additional problems result from the fact that in particular topical adhesives comprising water as the plasticiser have a tendency to dry out unless they are sealed into an impermeable package.
Is It has been discovered that particularly preferred compositions belonging to the first family of hydrophobic compositions are those comprising:
- from 3% to 15%, preferably from 5% to 10%, by weight of a first 2o copolymer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene having a triblock content higher than 70%, a styrene content higher than 25%
by weight, and a molecular weight higher than 60.000;
- from 0% to 9%) preferably from 0% to 6%, by weight of a second 2s copolymer polystyrene-block-(polyethylene-ran-butylene)-block-polystyrene having a triblock content of less than 70%, a styrene content of less than 20%
by weight, and a molecular weight of less than 60.000.
Both the first and second copolymers polystyrene-block-(polyethylene-ran-3o butylene)-block-polystyrene are preferably selected from the group consisting of styrene-block-copolymers of the type styrene-butadiene-styrene, styrene-isoprene-styrene styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene.
3s - from 20% to 95%, preferably from 30% to 60%, by weight of an oil having a paraffinic fraction higher than 50% by weight, and an aromatic fraction less than 5% by weight, as a plasticising compound. The oil can be selected among natural or synthetic oils) such as vegetable oils, mineral oils, or combinations thereof.
- from 0% to 50%, preferably from 30% to 50%, by weight of a s hydrogenated cycloafiphatic tackifying resin. The resin has the main scope of tailoring the Tg of systems based on synthetic polymers, and must be compatible with the rubbery blocks of the styrenic copolymers.
- and from 0% to 10% by weight of additives. Such additives can be substances for facilitating and stabilising the gel and the gel forming process of the hydrophobic liquid plasticisers. These may be e.g. the fatty acids of CS
to Cue, their metallic salts and their polyoxo-derivatives; lanolin derivatives;
silica;
bentonite, montmorillonite and their derivatives; polyamides, waxes or mixtures thereof. Common additives known in the art as preservatives, antioxidants, anti ~s UV, pigments, mineral fillers, rheology modifiers etc. can also be comprised.
Preferably antioxidants substances are comprised in an amount of from 0.3% to 1 % by weight) and gel stabili2ing substances are comprised in an amount of from 0% to 1 % by weight.
2o Application of topical adhesive Absorbent articles in which the topical adhesive according to a preferred embodiment of the present invention can be used, can be made by any of the ways usual in the art. The application of the adhesive to the topsheet or, more in 2s general, to the skin facing side of such articles should not cause major problems to those skilled in the art since it can be provided by any well known techniques commonly used for other adhesives. The total area of the skin or wearer facing surface of an article that is covered by the lipophilic topical adhesive depends on its intended use. For conservation of adhesive it should be not more than 80%, 3o preferably from 30% to 60% of the wearer facing surface. In the preferred embodiment of an absorbent article the total area of the skin facing surface which is covered 'by the topical adhesive should be not more than 20 %, preferably not more than 10 %. Preferably, the adhesive is close to the periphery of the absorbent article and in the case of film topsheets (or when the backsheet 3s is folded onto the topsheet) the adhesive is preferably on a portion of the frlm which is not permeable to liquids.
_.. ..._. . ..-~.._-.__.~.r__ __ If possible, the article also provides b~eathability 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.
s The topical adhesive on an article is preferably protected prior to use. This protection can be provided by a release liner such as a siliconised or surfactant treated paper, providing easy release for the selected topical adhesive.
In a preferred embodiment this invention can be used beneficially on disposable absorbent articles which are applied directly to the skin of a user. The article usually exhibits absorbency for bodily fluids, the protection of the user's garments from soiiing, is comfortable to the user, and is easy to produce and to package. The disposable absorbent article is described below by reference to a ~s sanitary napkin or catamenial) however panty liners, adult incontinence articles or sweat pads are also included under the term disposable absorbent articles.
The term "sanitary napkin", as used herein, refers to an article which is worn by females adjacent to the pudendal region and which is intended to absorb and contain the various body fluids which are discharged from the body (e.g., vaginal 2o discharges, menses, and/or urine) and which is intended to be discarded after a single use. A disposable absorbent article is preferably thin, more preferably between 1 and 5 mm thick and either substantially flat prior to use or in a preshaped form.
2s The terms "joined" or "affixed", as used herein, encompasses configurations whereby a first member is directly connected to a second member and configurations whereby a first member is indirectly connected to a second member by connecting the first member to intermediate members which in turn are connected to the second member.
In a preferred embodiment a sanitary napkin of the present invention comprises a liquid pervious topsheet, a liquid impervious backsheet joined to the topsheet, and an absorbent core intermediate the topsheet and the backsheet. The sanitary napkin has two main surfaces, a body contacting or wearer facing 3s surface on which the topical adhesive is applied and a garment facing or contacting surface.
The topsheet is compliant, soft feeling, and non-irritating to the wearer's skin.
The topsheet also can have elastic characteristics allowing it to be stretched in one or two directions in portions of the topsheet or throughout its extension.
Further, the topsheet is fluid pervious permitting fluids (e.g., menses and/or s urine) to readily penetrate through its thickness.
Preferred topsheets for use in the present invention are typically selected from high loft nonwoven topsheets and apertured formed film topsheets. Apertured formed films are especially preferred for the topsheets because they are pervious to body exudates and yet non absorbent and have a reduced tendency to allow fluids to pass back through and rewet the wearer's skin. Thus, the surface of the formed film that is in contact with the wearer remains dry, thereby reducing body soiling and creating a more comfortable feel for the wearer.
Suitable formed films are described in U.S. Patent 3,929,135; U.S. Patent ~s 4,324,246; U.S. Patent 4,342,314; U.S. Patent 4,463,045; and U.S. Patent 5,006,394. Particularly preferred micro apertured formed film topsheets are disclosed in U.S. patent 4,609,518 and U.S. patent 4,629,643. A preferred topsheet for the present invention comprises the formed film described in one or more of the above patents and marketed on sanitary napkins by The Procter &
2o Gamble Company of Cincinnati, Ohio as "DRI-WEAVE".
Topical adhesives are most suitably used on topsheets having not a homogeneous distribution of liquid passage ways but only a portion of the topsheet comprising liquid passage ways oriented such that they result in a 2s centrally permeable and peripherally impermeable topsheet for liquids.
Another alternative are so called hybrid topsheets which incorporate fibrous and film like structures particularly useful embodiments of such hybrid topsheets are disclosed in PCT publications WO 93/09744; WO 93/11725 or WO 93111726.
When referring to the topsheet a multi layer structure or a mono layer structure is contemplated. The hybrid topsheet mentioned above is such a multi layer design but other multi layer topsheets such as primary and secondary topsheet designs are also considered.
The absorbent core also can comprise multiple layers and provides fluid storage and distribution function.
___ _ .~__ ~_~.~ _~._._ _~_..__. _.
. WO 98/28015 PCT/US97/23457 Positioned in fluid communication with, and typically underlying the topsheet is the absorbent core. The core can comprise any usual absorbent material or combinations thereof. It preferably comprises absorbent gelling materials usually s referred to as "hydrogel", "superabsorbent", "hydrocolloid" materials in combination with suitable carriers.
Suitable absorbent gelling materials for use herein will most often comprise a substantially water-insoluble, slightly cross-linked, partially neutralised, polymeric o gelling material. This material forms a hydrogel upon contact with water.
Such polymer materials can be prepared form polymerizable, unsaturated) acid-containing monomers, such as acrylic acid, which are well known in the art.
Suitable carriers include materials which are conventionally utilised in absorbent ~s structures such as natural, modified or synthetic fibers, particularly modified or non-modified cellulose fibers, in the form of fluff and/or tissues. Suitable carriers can be used together with the absorbent gelling material, however, they can also be used alone or in combinations. Most preferred are tissue or tissue laminates in the context of sanitary napkins/panty liners.
zo The absorbent core also can comprise multiple layers and provides fluid storage and distribution function.
An embodiment of the core) particularly useful in the application of the present 2s invention, comprises a double layer tissue laminate formed by folding the tissue onto itself. These layers can be joined to each other. Absorbent gelling material or other optional material can be comprised between the layers.
The absorbent core can include optional components normally present in 3o absorbent webs such as odor control agents, in particular suitable zeolites.
The backsheet primarily prevents the exudates absorbed and contained in the absorbent core from wetting articles that contact the absorbent product such as underpants, pants) pyjamas and undergarments. The backsheet is preferably 3s impervious to liquids (e.g. menses and/or urine) and usually manufactured from a thin plastic film.
The backsheet typically extends across the whole of the absorbent core and can extend onto and form part of the topsheet by folding around the absorbent core.
Thereby a topsheet configuration as disclosed in US 4,342,314, column 16, lines 47 - 62 can be achieved without the requirement to selectively aperture the s topsheet.
Preferably, the backsheet also provides breathability to the absorbent article by being at least water vapour permeable, preferably air permeable. The backsheet can be a laminate material e.g. of a combination of microporous film and/or non-woven material, and/or apertured formed film. Breathability if desired can be limited to the periphery or the center of the backsheet or it can be across the whole backsheet.
~s An oil based composition useful on sanitary napkins according to the present invention was prepared using 10% by weight of Kraton G-1651, a Styrene/Ethylene-Butylene/Styrene block copolymer containing 33% by weight 2o styrene and available from Shell Co., and 49 % by weight of Kaydol, a paraffinic mineral oil available from Witco Co.
Moreover the composition contained 40% by weight of tackifying resin. The tackifying resin was Escorez 5300, a hydrogenated resin available from Exxon is 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.
3o Irganox 1010, an antioxidant available from Ciba-Geigy, was added at a level of 0.3 % by weight.
So finally the formulation had the following percent composition:
3s Kraton G-1651 10.0 % by weight Kaydol 49.0 % by weight Escorez 5300 40.0 % by weight _ __ ___~
Magnesium Stearate 0.7 % by weight Irganox 1010 0.3 % by weight The composition showed the following rheological properties at 37°C.
s a) Elastic Modulus at 1 rad/s, G'3~ = 7038 Pa b) Viscous Modulus at 1 radls, G"5~ = 487 Pa c) Ratio of Elastic and Viscous Modulus at 1 rad/s, G'3T I G"37 =- 14.45 G'3~ (100 rad/sec) - G"3~ (100 rad/sec) d) Ratio of ~ s G'3~ ( 1 rad/sec) - G"3~ ( 1 rad/sec) = 1.11 e) The ratio of eG'3~ over G'3~ ( 1 rad/s) was 0.291, with ~G'3~ = 2051 Pa.
The above formulation was tried in a sanitary napkin and was judged as comfortable for initial application and removal from sensitive, hairy skin.
2s COMPARATIVE EXAMPLE
A componotine 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.
Moreover the 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.
3s 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.
zz Irganox 1010, an antioxidant available, from Ciba-Geigy, was added at a level of 0.3 % by weight.
So finally the formulation had the following percent composition:
s Kraton G-1651 7.1 % by weight Kaydol 41.9 % by weight Regalrez 3102 50.0 % by weight Magnesium Stearate 0.7 % by weight Irganox 1010 0.3 % by weight The composition showed the following rheological properties at 37°C.
a) Elastic Modulus at 1 rad/s, G'z~ = 3059 Pa ~s b) Viscous Modulus at 1 rad/s, G"~, = 1208 Pa c) Ratio of Elastic and Viscous Modulus at 1 rad/s, G'3~ / G"3~ = 2.53 G'3~ (100 radlsec) - G"3~ (100 rad/sec) 2o d) Ratio of G'3~ (1 rad/sec) - G"3~ (1 rad/sec) - - 2.87 zs e) The ratio eG'3~ over G'3~ (1 rad/s) was 3.944 with OG'3~ = 12064.7 Pa.
The above formulation was judged as highly uncomfortable for deiamination from fore-arm skin. Application to sensitive hairy skin was unacceptable.
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~s Detailed description of the invention 2o Adhesive for topical attachment The topical adhesive according to the present invention is applied directly to the skin. In a particular application the adhesive can be used on sanitary napkins which are applied in the genital region of a typically female user around the area 2s of liquid discharge. The word "skin" according to the present invention does not only relate to the specific derma of the user but includes the mucous tissue as well as the hair which is typically found in the genital region of users of sanitary napkins.
3o In order to provide fixation of an article according to the present invention to the skin it is necessary to provide a certain area on the side of the article which is facing the skin with the topical adhesive.
For sanitary napkins various designs are contemplated but preferably the topical 3s adhesive is provided along the peripheral edge of the topsheet such that a central area of the article is left without adhesive. This will most appropriately facilitate placing the napkin such that the liquid permeable topsheet region without adhesive is placed adjacent the bodily liquid emanating orifice such that emanating liquid is immediately transported into the absorbent structure of the absorbent article without the possibility of leakage or spillage.
s Physical, Rheoloaical and Adhesive Characteristics of a Topical Adhesive Even though topical adhesives are used like pressure sensitive adhesives on human skin hair and mucous tissues) 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.
In fact as the person skilled in the art of adhesives knows, the most characteristic feature that distinguishes a PSA from other substances that can temporarily stick ~s things (as e.g. water between two glass plates could) is the fact that their rheological parameters and especially the Elastic Modulus G' vary greatly with the frequency of applied stresses. More in particular, G' of PSA can increase over some orders of magnitude while the frequency of applied stresses varies from typical bonding frequency to typical debonding frequency) i.e. 1 rad/s to 2o rad/s as indicated below.
As a first consequence) it derives that it is inadmissible to def ne materials intended for use as "topical adhesives" by giving values of rheological parameters and especially of G' at a fixed value of frequency. This can be 2s misleading because in the absence of other characteristics it will include materials which have no practical value. It is hence necessary that rheological characterisation must be on the base of dynamic considerations.
This not only applies to the Elastic Modulus G' but also to the viscous modulus 3o G" and hence also for tan (8) = G" / G'. It is well known that typical PSA
have not only a high variation of G' across the considered frequencies but also there is an even higher variation of G" which can get close or become even higher than the value of G', i.e. tan (8) becomes about or even greater than 1, in particular at the frequencies that are typical of the debonding.
Without wishing to be bound by theory this can be interpreted as meaning that a high fraction of the energy applied for the debonding is dissipated within the _ ___.~~.__._.__~.._ ~_.~.~.. _._._ . _ .... . .. _..__.... . _ _ adhesive (so it is not effective in causing the debonding) while this fact causes macroscopically the recording of a very high level of adhesive force.
As indicated above materials useful as topical adhesives according to the s 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 sanitary napkin with a topical adhesive the adhesive contact is formed at a low frequency, while debonding happens at the speed of removing the article.
o 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 radls.
Therefore, the frequency range for use according to the present invention is between 1 and 100 rad/s.
~s It is believed that 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 Jlg/K) the actual temperature of the topical 2o 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, zs 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 for use in the field of sanitary napkins, and in general when using articles which are frequently removed and adhered again or replaced, while the 3o material remains soft and capable of gently adhering to skin.
The ratio of G'3~ ('t rad/sec) over G"3~ {1 rad/sec) is important to ensure that these two values are balanced upon adhesion to the skin. At the same time the absolute changes of G'3~ need to be limited within the range of frequencies 3s considered. Hence a value for the ratio of ~G'3~ (i.e. G'3~ {100 rad/sec) -G'3~ (1 rad/sec)) over G'3~ (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 OG'3~ below certain values.
Importantly, the ratio of G'3, (100 rad/sec) - G"3~ (100 rad/sec) s G'3~ ( 1 rad/sec) - G "3~ ( 1 rad/sec) needs to be large enough to ensure that the dynamic behaviour of both the elastic and the viscous module are maintained in a relationship which provides secure adhesion and painless and easy removal.
Finally the person skilled in the art will also recognise that the Glass Transition Temperature Tg of the adhesive composition, specific heat capacity, and specific ~s heat conductivity are parameters which are useful to more fully define the group of useful topical adhesives.
The following set of characteristics should be satisfied:
zo ~ G'3~ (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"3~ (1 rad/sec) is in the range 100 Pa to 15000 Pa, 2s preferably 100 Pa to 10000 Pa, most preferably 300 Pa to 5000 Pa.
~ the ratio of G'3~ (1 rad/sec) / G"3~ (1 rad/sec) is in the range of 3 to 30.
~ the ratio G'3~ (100 rad/sec) - G"3~ (100 rad/sec) G'3~ ( 1 rad/sec) - G"3~ ( 1 rad/sec) 3s is not less than 0.5, preferably in the range 0.7 to 3, most preferably in the range 1 to 1.8.
~ either the ratio of ~G'3~G'3~ (1 rad/sec) is not greater than 1.5, r __ . _._..__.. . _ r ._.._.... ...___._ preferably not greater than unity and most preferably not greater than 0.8, or ~G'3~ is not greater than 10000 Pa, preferably less s than 5000 Pa, most preferably less than 2000 Pa, or both.
~ the value of the ratio G'3,/G"3, at least for the frequency range from above rad/s up to 100 rad/s should preferably be 3.3 or above, more preferably 5 or o above, most preferably 10 or above, while not exceeding about 30, preferably 20, anywhere in the frequency interval.
~ the rheological behaviour can also be related to the values of the Glass Transition Temperature Tg. For topical adhesives according to the present s invention 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. Preferably the specific heat capacity of the zo 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. Preferably the specific 2s heat conductivity is as low as possible (except for energy transmitting articles where high values are more desirable)) more preferable between 1 and 0.1 W/m/K, most preferably between 0.6 and 0.1 W/m/K.
Chemical and compositional characteristics of a Topical adhesive In order to provide the preferred topical adhesive compositions which satisfy the requirements of the above rheological and physical characteristics of a topical adhesive the following formulation criteria are used. It should be noted that the most of the compositions useful as topical adhesive have a substantially gel-like 3s structure and are preferably gels. This derives from the fact that:
- the prevailing component is the plasticiser which is a material liquid at room temperature - a macromolecular or polymeric component is present in minor quantities vs.
the s piasticiser. 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.
o Possible typical 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 (lipophilic) compositions in which the plasticiser is typically ~s 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).
2) Mixed phase compositions in which both hydrophobic and hydrophilic components, possibly in both plasticisers and polymers, form two or more separate phases. In such cases an emulsifier/surfactant is preferably present at zo a suitable level to form stable emulsions between the incompatible phases.
For topical adhesives according to the present invention it is preferably that the hydrophobic components are prevailing vs. the hydrophilic ones.
3) Hydrophilic compositions in which typically the plasticiser is water/glycerol/glycols and the like and/or mixtures thereof and the polymeric 2s phase is of synthetic (e.g. polyacrylics) or natural (e.g. natural gums) origin or mixtures thereof.
It is to stress that, differently from the medical field and from the cited prior art, the hydrophilic compositions are not preferred while the hydrophobic (lipophilic) 3o and mixed phases compositions 1 ) and 2) are preferred in the applications of the present invention.
This depends partially on technical reasons in the sense that many hydrophilic compositions used in the medical field show too low elastic character and 3s cohesion for being useful in the present application. The other reason to prefer hydrophobic or mixed phase compositions is that the application of the present invention in particular in the sanitary napkin field will include a probability of _._ _ _.._ ~, contacting the topical adhesive with the liquid to be absorbed. Since the liquids are all of a general aqueous kind contact with a hydrophilic topical adhesive would result in a certain absorption of the bodily liquids into the topical adhesives.
This would then have the result of changing the rheological characteristics and therefore the functionality of the topical adhesive and causing a non-hygienic appearance.
to Further hydrophilic topical adhesive also tend to be perceived as cold and wet which upon application to the skin of a human is not in line with typical expectation. Additional problems result from the fact that in particular topical adhesives comprising water as the plasticiser have a tendency to dry out unless they are sealed into an impermeable package.
Is It has been discovered that particularly preferred compositions belonging to the first family of hydrophobic compositions are those comprising:
- from 3% to 15%, preferably from 5% to 10%, by weight of a first 2o copolymer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene having a triblock content higher than 70%, a styrene content higher than 25%
by weight, and a molecular weight higher than 60.000;
- from 0% to 9%) preferably from 0% to 6%, by weight of a second 2s copolymer polystyrene-block-(polyethylene-ran-butylene)-block-polystyrene having a triblock content of less than 70%, a styrene content of less than 20%
by weight, and a molecular weight of less than 60.000.
Both the first and second copolymers polystyrene-block-(polyethylene-ran-3o butylene)-block-polystyrene are preferably selected from the group consisting of styrene-block-copolymers of the type styrene-butadiene-styrene, styrene-isoprene-styrene styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene.
3s - from 20% to 95%, preferably from 30% to 60%, by weight of an oil having a paraffinic fraction higher than 50% by weight, and an aromatic fraction less than 5% by weight, as a plasticising compound. The oil can be selected among natural or synthetic oils) such as vegetable oils, mineral oils, or combinations thereof.
- from 0% to 50%, preferably from 30% to 50%, by weight of a s hydrogenated cycloafiphatic tackifying resin. The resin has the main scope of tailoring the Tg of systems based on synthetic polymers, and must be compatible with the rubbery blocks of the styrenic copolymers.
- and from 0% to 10% by weight of additives. Such additives can be substances for facilitating and stabilising the gel and the gel forming process of the hydrophobic liquid plasticisers. These may be e.g. the fatty acids of CS
to Cue, their metallic salts and their polyoxo-derivatives; lanolin derivatives;
silica;
bentonite, montmorillonite and their derivatives; polyamides, waxes or mixtures thereof. Common additives known in the art as preservatives, antioxidants, anti ~s UV, pigments, mineral fillers, rheology modifiers etc. can also be comprised.
Preferably antioxidants substances are comprised in an amount of from 0.3% to 1 % by weight) and gel stabili2ing substances are comprised in an amount of from 0% to 1 % by weight.
2o Application of topical adhesive Absorbent articles in which the topical adhesive according to a preferred embodiment of the present invention can be used, can be made by any of the ways usual in the art. The application of the adhesive to the topsheet or, more in 2s general, to the skin facing side of such articles should not cause major problems to those skilled in the art since it can be provided by any well known techniques commonly used for other adhesives. The total area of the skin or wearer facing surface of an article that is covered by the lipophilic topical adhesive depends on its intended use. For conservation of adhesive it should be not more than 80%, 3o preferably from 30% to 60% of the wearer facing surface. In the preferred embodiment of an absorbent article the total area of the skin facing surface which is covered 'by the topical adhesive should be not more than 20 %, preferably not more than 10 %. Preferably, the adhesive is close to the periphery of the absorbent article and in the case of film topsheets (or when the backsheet 3s is folded onto the topsheet) the adhesive is preferably on a portion of the frlm which is not permeable to liquids.
_.. ..._. . ..-~.._-.__.~.r__ __ If possible, the article also provides b~eathability 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.
s The topical adhesive on an article is preferably protected prior to use. This protection can be provided by a release liner such as a siliconised or surfactant treated paper, providing easy release for the selected topical adhesive.
In a preferred embodiment this invention can be used beneficially on disposable absorbent articles which are applied directly to the skin of a user. The article usually exhibits absorbency for bodily fluids, the protection of the user's garments from soiiing, is comfortable to the user, and is easy to produce and to package. The disposable absorbent article is described below by reference to a ~s sanitary napkin or catamenial) however panty liners, adult incontinence articles or sweat pads are also included under the term disposable absorbent articles.
The term "sanitary napkin", as used herein, refers to an article which is worn by females adjacent to the pudendal region and which is intended to absorb and contain the various body fluids which are discharged from the body (e.g., vaginal 2o discharges, menses, and/or urine) and which is intended to be discarded after a single use. A disposable absorbent article is preferably thin, more preferably between 1 and 5 mm thick and either substantially flat prior to use or in a preshaped form.
2s The terms "joined" or "affixed", as used herein, encompasses configurations whereby a first member is directly connected to a second member and configurations whereby a first member is indirectly connected to a second member by connecting the first member to intermediate members which in turn are connected to the second member.
In a preferred embodiment a sanitary napkin of the present invention comprises a liquid pervious topsheet, a liquid impervious backsheet joined to the topsheet, and an absorbent core intermediate the topsheet and the backsheet. The sanitary napkin has two main surfaces, a body contacting or wearer facing 3s surface on which the topical adhesive is applied and a garment facing or contacting surface.
The topsheet is compliant, soft feeling, and non-irritating to the wearer's skin.
The topsheet also can have elastic characteristics allowing it to be stretched in one or two directions in portions of the topsheet or throughout its extension.
Further, the topsheet is fluid pervious permitting fluids (e.g., menses and/or s urine) to readily penetrate through its thickness.
Preferred topsheets for use in the present invention are typically selected from high loft nonwoven topsheets and apertured formed film topsheets. Apertured formed films are especially preferred for the topsheets because they are pervious to body exudates and yet non absorbent and have a reduced tendency to allow fluids to pass back through and rewet the wearer's skin. Thus, the surface of the formed film that is in contact with the wearer remains dry, thereby reducing body soiling and creating a more comfortable feel for the wearer.
Suitable formed films are described in U.S. Patent 3,929,135; U.S. Patent ~s 4,324,246; U.S. Patent 4,342,314; U.S. Patent 4,463,045; and U.S. Patent 5,006,394. Particularly preferred micro apertured formed film topsheets are disclosed in U.S. patent 4,609,518 and U.S. patent 4,629,643. A preferred topsheet for the present invention comprises the formed film described in one or more of the above patents and marketed on sanitary napkins by The Procter &
2o Gamble Company of Cincinnati, Ohio as "DRI-WEAVE".
Topical adhesives are most suitably used on topsheets having not a homogeneous distribution of liquid passage ways but only a portion of the topsheet comprising liquid passage ways oriented such that they result in a 2s centrally permeable and peripherally impermeable topsheet for liquids.
Another alternative are so called hybrid topsheets which incorporate fibrous and film like structures particularly useful embodiments of such hybrid topsheets are disclosed in PCT publications WO 93/09744; WO 93/11725 or WO 93111726.
When referring to the topsheet a multi layer structure or a mono layer structure is contemplated. The hybrid topsheet mentioned above is such a multi layer design but other multi layer topsheets such as primary and secondary topsheet designs are also considered.
The absorbent core also can comprise multiple layers and provides fluid storage and distribution function.
___ _ .~__ ~_~.~ _~._._ _~_..__. _.
. WO 98/28015 PCT/US97/23457 Positioned in fluid communication with, and typically underlying the topsheet is the absorbent core. The core can comprise any usual absorbent material or combinations thereof. It preferably comprises absorbent gelling materials usually s referred to as "hydrogel", "superabsorbent", "hydrocolloid" materials in combination with suitable carriers.
Suitable absorbent gelling materials for use herein will most often comprise a substantially water-insoluble, slightly cross-linked, partially neutralised, polymeric o gelling material. This material forms a hydrogel upon contact with water.
Such polymer materials can be prepared form polymerizable, unsaturated) acid-containing monomers, such as acrylic acid, which are well known in the art.
Suitable carriers include materials which are conventionally utilised in absorbent ~s structures such as natural, modified or synthetic fibers, particularly modified or non-modified cellulose fibers, in the form of fluff and/or tissues. Suitable carriers can be used together with the absorbent gelling material, however, they can also be used alone or in combinations. Most preferred are tissue or tissue laminates in the context of sanitary napkins/panty liners.
zo The absorbent core also can comprise multiple layers and provides fluid storage and distribution function.
An embodiment of the core) particularly useful in the application of the present 2s invention, comprises a double layer tissue laminate formed by folding the tissue onto itself. These layers can be joined to each other. Absorbent gelling material or other optional material can be comprised between the layers.
The absorbent core can include optional components normally present in 3o absorbent webs such as odor control agents, in particular suitable zeolites.
The backsheet primarily prevents the exudates absorbed and contained in the absorbent core from wetting articles that contact the absorbent product such as underpants, pants) pyjamas and undergarments. The backsheet is preferably 3s impervious to liquids (e.g. menses and/or urine) and usually manufactured from a thin plastic film.
The backsheet typically extends across the whole of the absorbent core and can extend onto and form part of the topsheet by folding around the absorbent core.
Thereby a topsheet configuration as disclosed in US 4,342,314, column 16, lines 47 - 62 can be achieved without the requirement to selectively aperture the s topsheet.
Preferably, the backsheet also provides breathability to the absorbent article by being at least water vapour permeable, preferably air permeable. The backsheet can be a laminate material e.g. of a combination of microporous film and/or non-woven material, and/or apertured formed film. Breathability if desired can be limited to the periphery or the center of the backsheet or it can be across the whole backsheet.
~s An oil based composition useful on sanitary napkins according to the present invention was prepared using 10% by weight of Kraton G-1651, a Styrene/Ethylene-Butylene/Styrene block copolymer containing 33% by weight 2o styrene and available from Shell Co., and 49 % by weight of Kaydol, a paraffinic mineral oil available from Witco Co.
Moreover the composition contained 40% by weight of tackifying resin. The tackifying resin was Escorez 5300, a hydrogenated resin available from Exxon is 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.
3o Irganox 1010, an antioxidant available from Ciba-Geigy, was added at a level of 0.3 % by weight.
So finally the formulation had the following percent composition:
3s Kraton G-1651 10.0 % by weight Kaydol 49.0 % by weight Escorez 5300 40.0 % by weight _ __ ___~
Magnesium Stearate 0.7 % by weight Irganox 1010 0.3 % by weight The composition showed the following rheological properties at 37°C.
s a) Elastic Modulus at 1 rad/s, G'3~ = 7038 Pa b) Viscous Modulus at 1 radls, G"5~ = 487 Pa c) Ratio of Elastic and Viscous Modulus at 1 rad/s, G'3T I G"37 =- 14.45 G'3~ (100 rad/sec) - G"3~ (100 rad/sec) d) Ratio of ~ s G'3~ ( 1 rad/sec) - G"3~ ( 1 rad/sec) = 1.11 e) The ratio of eG'3~ over G'3~ ( 1 rad/s) was 0.291, with ~G'3~ = 2051 Pa.
The above formulation was tried in a sanitary napkin and was judged as comfortable for initial application and removal from sensitive, hairy skin.
2s COMPARATIVE EXAMPLE
A componotine 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.
Moreover the 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.
3s 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.
zz Irganox 1010, an antioxidant available, from Ciba-Geigy, was added at a level of 0.3 % by weight.
So finally the formulation had the following percent composition:
s Kraton G-1651 7.1 % by weight Kaydol 41.9 % by weight Regalrez 3102 50.0 % by weight Magnesium Stearate 0.7 % by weight Irganox 1010 0.3 % by weight The composition showed the following rheological properties at 37°C.
a) Elastic Modulus at 1 rad/s, G'z~ = 3059 Pa ~s b) Viscous Modulus at 1 rad/s, G"~, = 1208 Pa c) Ratio of Elastic and Viscous Modulus at 1 rad/s, G'3~ / G"3~ = 2.53 G'3~ (100 radlsec) - G"3~ (100 rad/sec) 2o d) Ratio of G'3~ (1 rad/sec) - G"3~ (1 rad/sec) - - 2.87 zs e) The ratio eG'3~ over G'3~ (1 rad/s) was 3.944 with OG'3~ = 12064.7 Pa.
The above formulation was judged as highly uncomfortable for deiamination from fore-arm skin. Application to sensitive hairy skin was unacceptable.
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Claims (5)
1. A lipophilic topical adhesive for attachment of an article to the skin, said topical adhesive comprising:
~ from 3% to 15%, preferably from 5% to 10% by weight of a first copolymer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene having a triblock content higher than 70%, a styrene content higher than 25% by weight, and a molecular weight higher than 60.000;
~ from 0% to 9%, preferably from 0% to 6%, by weight of a second copolymer polystyrene-block-(polyethylene-ran-butylene)-block-polystyrene having a triblock content of less than 70%, a styrene content of less than 20% by weight, and a molecular weight of less than 60.000;
~ from 20% to 95%, preferably from 30% to 60%, by weight of an oil having a paraffinic fraction higher than 50% by weight, and an aromatic fraction less than 5% by weight, as a plasticising compound;
~ from 0% to 50%, preferably from 305 to 50%, by weight of a hydrogenated cycloaliphatic tackifying resin;
~ from 0% to 10% by weight of additives such as antioxidants or gel stabilizing substances, preferably from 0.3% to 1 % by weight of antioxidants and from 0% to 1 % by weight of gel stabilizing substances.
~ from 3% to 15%, preferably from 5% to 10% by weight of a first copolymer polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene having a triblock content higher than 70%, a styrene content higher than 25% by weight, and a molecular weight higher than 60.000;
~ from 0% to 9%, preferably from 0% to 6%, by weight of a second copolymer polystyrene-block-(polyethylene-ran-butylene)-block-polystyrene having a triblock content of less than 70%, a styrene content of less than 20% by weight, and a molecular weight of less than 60.000;
~ from 20% to 95%, preferably from 30% to 60%, by weight of an oil having a paraffinic fraction higher than 50% by weight, and an aromatic fraction less than 5% by weight, as a plasticising compound;
~ from 0% to 50%, preferably from 305 to 50%, by weight of a hydrogenated cycloaliphatic tackifying resin;
~ from 0% to 10% by weight of additives such as antioxidants or gel stabilizing substances, preferably from 0.3% to 1 % by weight of antioxidants and from 0% to 1 % by weight of gel stabilizing substances.
2. A lipophilic topical adhesive according to claim 1, wherein ~ each of said first and second copolymers polystyrene-block-(polyethylene-ran-butylene)-block-polystyrene is selected from the following group: styrene-block-copolymers of the type styrene-butadiene-styrene, styrene-isoprene-styrene styrene-ethylene-butylene-styrene, styrene-ethylene-propylene-styrene; and ~ said oil is selected from the following group: natural or synthetic oils such as vegetable oils, mineral oils, or combinations thereof.
~ said additives are selected from the following group: fatty acids of C8 to C22, their metallic salts and their polyoxo-derivatives; lanolin derivatives; silica; bentonite, montmorillonite and their derivatives;
polyamides, waxes or mixtures thereof.
~ said additives are selected from the following group: fatty acids of C8 to C22, their metallic salts and their polyoxo-derivatives; lanolin derivatives; silica; bentonite, montmorillonite and their derivatives;
polyamides, waxes or mixtures thereof.
3. A lipophilic topical adhesive according to any of the preceding claims wherein said adhesive has a glass transition temperature of less than -15°C, preferably less than -20°C, most preferably -25°C.
4. A lipophilic topical adhesive according to any of the preceding claims wherein said article is a disposable absorbent article.
5. Use of a lipophilic topical adhesive according to any of the preceding claims on a sanitary napkin or panty-liner.
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96120738.8 | 1996-12-23 | ||
EP96120738A EP0850619A1 (en) | 1996-12-23 | 1996-12-23 | Disposable absorbent article for topical adhesive attachment to the skin of a wearer |
EP97110730A EP0853934A1 (en) | 1996-12-23 | 1997-07-01 | Disposable absorbent article for secure topical adhesive attachment to the skin of a wearer and comfortable removal |
EP97110730.5 | 1997-07-01 | ||
EP97120338A EP0855190A1 (en) | 1996-12-23 | 1997-11-20 | Adhesive for secure topical attachment to the skin and comfortable removal, particularly of absorbent articles |
EP97120337.7 | 1997-11-20 | ||
EP97120338.5 | 1997-11-20 | ||
EP97120337A EP0850649A1 (en) | 1996-12-23 | 1997-11-20 | Adhesive for application of functional articles to the skin and comfortable removal of such articles |
PCT/US1997/023457 WO1998028015A1 (en) | 1996-12-23 | 1997-12-22 | Lipophilic adhesive for secure topical attachment to the skin and comfortable removal |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2275898A1 true CA2275898A1 (en) | 1998-07-02 |
Family
ID=54774301
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002275772A Abandoned CA2275772A1 (en) | 1996-12-23 | 1997-12-22 | Adhesive for application of functional articles to the skin and comfortable removal of such articles |
CA002275898A Abandoned CA2275898A1 (en) | 1996-12-23 | 1997-12-22 | Lipophilic adhesive for secure topical attachment to the skin and comfortable removal |
CA002275990A Abandoned CA2275990A1 (en) | 1996-12-23 | 1997-12-22 | Adhesive for application of functional articles to the skin and comfortable removal of such articles |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002275772A Abandoned CA2275772A1 (en) | 1996-12-23 | 1997-12-22 | Adhesive for application of functional articles to the skin and comfortable removal of such articles |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002275990A Abandoned CA2275990A1 (en) | 1996-12-23 | 1997-12-22 | Adhesive for application of functional articles to the skin and comfortable removal of such articles |
Country Status (7)
Country | Link |
---|---|
EP (3) | EP0948368A1 (en) |
JP (3) | JP2000505702A (en) |
KR (3) | KR20000069657A (en) |
CN (3) | CN1246067A (en) |
AU (3) | AU5801498A (en) |
CA (3) | CA2275772A1 (en) |
WO (3) | WO1998028018A1 (en) |
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US6761710B2 (en) | 1999-12-03 | 2004-07-13 | The Procter & Gamble Company | Container for the collection of menstrual flow |
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US6489534B1 (en) | 2000-04-28 | 2002-12-03 | Kimberly-Clark Worldwide, Inc. | Disposable personal articles which conform and adhere |
EP1504740B1 (en) | 2003-08-07 | 2013-03-06 | The Procter & Gamble Company | Latex bonded acquisition layer having temperature insensitive liquid handling properties |
EP1504741A1 (en) | 2003-08-07 | 2005-02-09 | The Procter & Gamble Company | Latex bonded acquisition layer having pressure insensitive liquid handling properties |
US8673282B2 (en) | 2006-05-03 | 2014-03-18 | L'oreal | Cosmetic compositions containing block copolymers, tackifiers and a selective solvent for soft blocks |
US8673283B2 (en) | 2006-05-03 | 2014-03-18 | L'oreal | Cosmetic compositions containing block copolymers, tackifiers and a solvent mixture |
US8557230B2 (en) | 2006-05-03 | 2013-10-15 | L'oreal | Cosmetic compositions containing block copolymers, tackifiers and shine enhancing agents |
US8778323B2 (en) | 2006-05-03 | 2014-07-15 | L'oréal | Cosmetic compositions containing block copolymers, tackifiers and modified silicones |
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 |
JP5546131B2 (en) * | 2006-11-30 | 2014-07-09 | ニプロパッチ株式会社 | Patch and evaluation method of patch |
US8658141B2 (en) | 2007-01-12 | 2014-02-25 | L'oreal | Cosmetic composition containing a block copolymer, a tackifier, a silsesquioxane wax and/or resin |
US8603444B2 (en) | 2007-01-12 | 2013-12-10 | L'oréal | Cosmetic compositions containing a block copolymer, a tackifier and a high viscosity ester |
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 |
US8292862B2 (en) | 2007-08-03 | 2012-10-23 | Kimberly-Clark Worldwide, Inc. | Dynamic fitting body adhering absorbent article |
US7947027B2 (en) | 2007-12-28 | 2011-05-24 | Kimberly-Clark Worldwide, Inc. | Body adhering absorbent article |
US8672911B2 (en) | 2007-08-03 | 2014-03-18 | Kimberly-Clark Worldwide, Inc. | Body adhering absorbent article |
FR2924607B1 (en) * | 2007-12-10 | 2009-12-18 | Chanel Parfums Beaute | COSMETIC COMPOSITION COMPRISING ANHYDROUS GEL AND A GLYCERYLE ESTER |
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US11147722B2 (en) | 2008-11-10 | 2021-10-19 | Kimberly-Clark Worldwide, Inc. | Absorbent article with a multifunctional acrylate skin-adhesive composition |
IT1392180B1 (en) * | 2008-12-11 | 2012-02-22 | Bouty Spa | A SELF-ADHESIVE MATRICAL SYSTEM INCLUDING A STYRENIC BLOCK COPOLYMER |
US10022468B2 (en) | 2009-02-02 | 2018-07-17 | Kimberly-Clark Worldwide, Inc. | Absorbent articles containing a multifunctional gel |
EP2485775B1 (en) * | 2009-10-08 | 2018-08-08 | Euromed Inc. | Adhesive composition |
US20120160258A1 (en) * | 2010-12-22 | 2012-06-28 | Avon Products, Inc. | Cosmetic Adhesive Composition |
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 |
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 |
US20120219516A1 (en) | 2011-02-25 | 2012-08-30 | L'oreal S.A. | Cosmetic compositions having long lasting shine |
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AU2013262833A1 (en) * | 2012-05-16 | 2014-12-04 | Archer Daniels Midland Company | Emulsifier for solubilizing polar solvents in oils and polyols |
CN103213758B (en) * | 2013-05-13 | 2016-01-20 | 孙秋玉 | Eye adornment pad pasting |
CN103756386B (en) * | 2014-01-20 | 2016-08-17 | 中山有行企业胶类制品有限公司 | Body colored drawing glue for makeup and preparation method thereof |
PT3288405T (en) * | 2015-05-01 | 2021-06-25 | Cosmo Spa Lounge & Supply Inc Dba Illumino | Chemically minimized system for time reduced application of eyelash extensions |
FR3053590B1 (en) * | 2016-07-07 | 2019-07-05 | S.A. Thalgo Tch | COMPOSITION FOR EPILATION WITHOUT BAND |
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NO134790C (en) * | 1968-07-09 | 1984-03-22 | Smith & Nephew | Kleber ,; PRESSURE SENSITIVE, WATERPUME-PERMEABLE PRODUCT FOR SKIN USE BY HUMANS. |
JPS5592306A (en) * | 1979-01-06 | 1980-07-12 | Nitto Electric Ind Co Ltd | Adherent sheet pack |
CA1218954A (en) * | 1982-02-25 | 1987-03-10 | David L. Sieverding | Hydrophilic, elastomeric, pressure-sensitive adhesive |
US4593053A (en) * | 1984-12-07 | 1986-06-03 | Medtronic, Inc. | Hydrophilic pressure sensitive biomedical adhesive composition |
JPS62209008A (en) * | 1986-03-10 | 1987-09-14 | Nikko Kemikaruzu Kk | Facial pack |
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-
1997
- 1997-12-22 JP JP10528954A patent/JP2000505702A/en active Pending
- 1997-12-22 CA CA002275772A patent/CA2275772A1/en not_active Abandoned
- 1997-12-22 CN CN97181849A patent/CN1246067A/en active Pending
- 1997-12-22 CA CA002275898A patent/CA2275898A1/en not_active Abandoned
- 1997-12-22 KR KR1019997005688A patent/KR20000069657A/en not_active Application Discontinuation
- 1997-12-22 WO PCT/US1997/023471 patent/WO1998028018A1/en not_active Application Discontinuation
- 1997-12-22 EP EP97954168A patent/EP0948368A1/en not_active Withdrawn
- 1997-12-22 CA CA002275990A patent/CA2275990A1/en not_active Abandoned
- 1997-12-22 EP EP97950989A patent/EP0948364A1/en not_active Withdrawn
- 1997-12-22 KR KR1019997005718A patent/KR20000069677A/en not_active Application Discontinuation
- 1997-12-22 WO PCT/US1997/023457 patent/WO1998028015A1/en not_active Application Discontinuation
- 1997-12-22 CN CN97181792A patent/CN1246063A/en active Pending
- 1997-12-22 AU AU58014/98A patent/AU5801498A/en not_active Abandoned
- 1997-12-22 AU AU53853/98A patent/AU5385398A/en not_active Abandoned
- 1997-12-22 WO PCT/US1997/023834 patent/WO1998028022A1/en not_active Application Discontinuation
- 1997-12-22 KR KR1019997005746A patent/KR20000069690A/en not_active Application Discontinuation
- 1997-12-22 EP EP97952628A patent/EP0946213A1/en not_active Withdrawn
- 1997-12-22 AU AU56195/98A patent/AU5619598A/en not_active Abandoned
- 1997-12-22 JP JP52896398A patent/JP2001507962A/en active Pending
- 1997-12-22 JP JP52905998A patent/JP2001507591A/en active Pending
- 1997-12-22 CN CN97181848A patent/CN1246066A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0948368A1 (en) | 1999-10-13 |
AU5619598A (en) | 1998-07-17 |
EP0948364A1 (en) | 1999-10-13 |
JP2001507591A (en) | 2001-06-12 |
AU5801498A (en) | 1998-07-17 |
WO1998028018A1 (en) | 1998-07-02 |
WO1998028015A1 (en) | 1998-07-02 |
CN1246063A (en) | 2000-03-01 |
WO1998028022A1 (en) | 1998-07-02 |
CA2275772A1 (en) | 1998-07-02 |
KR20000069677A (en) | 2000-11-25 |
AU5385398A (en) | 1998-07-17 |
CN1246066A (en) | 2000-03-01 |
CN1246067A (en) | 2000-03-01 |
KR20000069657A (en) | 2000-11-25 |
CA2275990A1 (en) | 1998-07-02 |
KR20000069690A (en) | 2000-11-25 |
EP0946213A1 (en) | 1999-10-06 |
JP2001507962A (en) | 2001-06-19 |
JP2000505702A (en) | 2000-05-16 |
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