# Patent

## Title
Strapless respiratory face mask

## Abstract

The present invention relates to face masks to control and improve the quality of inhaled air. Claimed and described is a respiratory face mask comprising a flange and a filter layer, the flange having an inner periphery and an outer periphery and a first and a second width measured perpendicular to the inner periphery between the inner periphery and the outer periphery, characterised in that the first width is greater than the second width. Preferably, such face masks are strapless and rely on a hydrogel adhesive for attachment and sealing. Further claimed and described is an improved cover layer for an adhesive of such a face mask.

## Background
FIELD OF THE INVENTION
The present invention relates to face masks to control and improve the quality of inhaled air. Claimed and described is a respiratory face mask comprising a flange and a filter layer, the flange having an inner periphery and an outer periphery and a first and a second width measured perpendicular to the inner periphery between the inner periphery and the outer periphery, characterised in that the first width is greater than the second width. Preferably, such face masks are strapless and rely on a hydrogel adhesive for attachment and sealing. Further claimed and described is an improved cover layer for an adhesive of such a face mask.
BACKGROUND OF THE INVENTION
A variety of face masks is known in the art and found in the market place, including re-usable and disposable masks, face masks for medical use, typically by surgeons, face masks for professional use where the inhaled air in the working environment requires so, and face masks for private use, e.g. for the prevention of spreading of infections, which are most widely used in Asian countries.
Prior art in the field of face masks includes the following documents:
U.S. Pat. No. 4,966,140, issued on Oct. 30, 1999, which discloses a face mask for the protection of the operating surgeon. The face mask comprising substantially vertical fasting tapes and a sealing strip formed along the upper marginal portion.
U.S. Pat. No. 5,735,270, issued Apr. 7, 1998, which discloses a disposable, foldable face mask comprises a single generally rectangular sheet of filter material, a foam sealing strip and a mask tieing device attached to the top corners.
U.S. Pat. No. 5,724,964, issued Mar. 10, 1998, discloses disposable face masks to be secured by a knitted head band to the head of the wearer which employs various gasket-type sealing material such as plastic film and/or hydrogels or other types of deformable material such as open cell and closed cell foams. Notably, adhesive types of hydrogels are not contemplated in this invention.
JP 10-248,948, filed Mar. 11, 1997, discloses a face mask to cover the nose and the mouth which comprises an adhesive material at the periphery of the face mask.
WO 00/07636, filed on Jul. 30, 1999, discloses novel hydrogel adhesives particularly suitable for disposable absorbent articles but also useful for respiratory face masks.
U.S. Pat. No. 4,240,420, issued on Dec. 23, 1980, and its continuation-in-part U.S. Pat. No. 4,354,4889, issued on Oct. 19, 1982, disclose filter masks which comprise separate filter elements for the nose and for the mouth of the wearer.
The prior art in the general field of adhesives for attachment to the skin is particularly developed in the field of articles such as band-aids, plasters and bandages.
In order to provide the desired level of adhesion of such bandages, the prior art typically discloses the utilisation of certain adhesives having very high cohesive strengths such as rubber based adhesives and acrylics. These adhesives are then applied as thick layers to maximise the adhesive force by which the bandage is secured to the skin of the wearer.
U.S. Pat. No. 4,699,146 discloses hydrophilic elastomeric pressure sensitive adhesives suitable for use with ostomy devices, bandages, ulcer pads, sanitary napkins, diapers, and athletic padding. The adhesive comprises at least one radiation cross linked organic polymer and an adhesive plasticiser.
GB 2 115 431 discloses adhesives for bandages, wounds or burn dressings, EKG adhesives, sanitary napkins, diapers and ulcer pads. The adhesive comprises an irradiation cross linked organic polymer such as polyvinylpyrrolodine and an adhesive plasticiser.
However, for satisfactory use with a device such as a respiratory face mask, which may be worn over extended periods of time, it is important that the adhesive has a skin compatible composition and not be harsh or aggressive towards the skin or cause skin irritation or inflammation. Also it is preferred if the adhesive is compliant with the skin of the wearer such that maximum skin surface contact between the adhesive and the skin is achieved. Moreover, it is also desirable to provide an adhesive such that the respiratory face mask can be readily removed from the wearer, without the wearer experiencing any unacceptable pain level and without leaving residues. This is particularly important under circumstances, where the device is removed and reapplication of the device once or even a number of times is required for example to allow for better communication, eating or the like, and to ensure the application of such devices on sensitive skin, e.g. of an elderly wearer. However, on the other hand the desired level of adhesion, albeit painless should of course also be maintained during such multiple applications of the device.
The problem of achieving the desired adhesion level is further exacerbated under wet skin conditions. In some cases, prior to the placement of the device the skin is cleaned and is usually as a result moist. Moreover, moisture from sweat may be developed while wearing a face mask, for example due to high ambient temperature or heavy physical work. The currently available adhesives, such as those containing hydrocolloid particles, however often do not immediately strongly adhere to the skin and may need to be held in place until sufficient minimum adhesion occurs. Moreover, the overall adhesive ability of such adhesives tends to be significantly reduced on wet skin surfaces per se, so that the device will typically not remain attached to the skin during wear if any pressure is exerted onto the device, for example by facial movements.
Another problem which is particularly prevalent for respiratory face masks usage is the ability of the adhesive to adhere on greasy or oily skin surfaces. The levels and types of grease and sebum naturally present on the skin vary from person to person. Further, the adhesive should reliably stick to hair populated skin and allow for painless removal even therefrom.
For example, WO-A-97/24149 (3M) describes a lipophilic polar pressure sensitive adhesive stated to have enhanced adhesion to greasy skin, the adhesive including a hydrophilic polymer matrix, a polar organic plasticiser and at least 9 wt % of a surfactant having an HLB (hydrophile lipophile balance) value of 10 to 17. It is stated generally that the hydrophilic polymer matrix may be selected from a range of polymers including homo- and copolymers of, for example, (meth)acrylic acid and salts thereof, acrylamide, N-vinyl pyrrolidone and acrylamidopropane sulphonic acid and salts thereof. The adhesive is prepared by polymerisation in a homogeneous aqueous mixture.
In view of the prior art mentioned above there still exists a need to provide an improved respiratory face mask, which meets the following objectives:

    
    
        The mask is comfortable and safe to wear.
        The mask is cheap to manufacture, so that it can serve as a disposable article, however, may alternatively be reusable many times.
        The mask allows for facial movement, namely to at least somewhat open the mouth, to speak, to cough and the like, while maintaining a reliable sealing to the face.
        The mask can be provided in one size to fit a large variety of consumers.
        The mask works well on wet, greasy and in particular hair populated skin.
        The mask reliably adheres to human skin over extended periods of time.
        The mask can be easily and comfortably removed.
    
    


It is another objective of the present invention to provide a cover layer for an adhesive layer, as preferably comprised by the face mask, the cover layer being easy to peel off from the adhesive and facilitating the optimal application of the mask to the face of a wearer.
It has now been surprisingly found that the above objectives can be meet by providing a respiratory face mask and a cover layer for an adhesive layer on the face mask both with the mechanical properties as defined hereinafter and preferably comprising an adhesive as defined hereinafter.
SUMMARY OF THE INVENTION
The present invention relates to face masks to control and improve the quality of inhaled air. Claimed and described is a respiratory face mask comprising a flange and a filter layer, the flange having an inner periphery and an outer periphery and a first and a second width measured perpendicular to the inner periphery between the inner periphery and the outer periphery, characterised in that the first width is greater than the second width. Preferably, such face masks are strapless and rely on a hydrogel adhesive for attachment and sealing. Further claimed and described is an improved cover layer for an adhesive of such a face mask.



BRIEF DESCRIPTION OF THE DRAWINGS
It is believed that the invention will be better understood in conjunction with the accompanying drawings in which:
FIG. 1 is a top view onto the wearer facing side of a preferred embodiment of the present invention.
FIG. 1a is a top view onto the wearer facing side of the same a preferred embodiment of the present invention, the Figure also showing the axis A defining sectors on the flange.
FIG. 2 is a side view of the same preferred embodiment of the present invention.
FIG. 3 is a top view onto the wearer facing side of a preferred embodiment of an adhesive cover layer provided by release papers.



DETAILED DESCRIPTION OF THE INVENTION
General
The present invention relates to face masks to control and improve the quality of inhaled air, which sometimes are referred to also as respiratory face masks, and herein for simplicity will also be referred to as face masks (10) or masks (10). Such masks (10) comprise at least one flange (20) and at least one air control module, such as a filter layer (30), which may be integral, or joined and which may be separable or unseparable pieces.
A respiratory face mask (10) according to the present invention may be designed to cover only the mouth of the wearer or only the nose of the wearer, but preferably is designed to cover both respiratory organs can be provided with any attachment means known in the art, such as headbands or straps which may run around the head and the neck area or which may run around the ears of wearer. Highly preferred attachment means according to the present invention are adhesive attachment means, such as a layer of adhesive provided on the wearer facing side of the flange (20).
Further, the respiratory face mask (10) may be equipped with any sealing means known in the art, for example a foam material. In most preferred embodiment of the present invention, however, the layer of adhesive is provided on the face mask (10) which serves both as an attachment means and as a sealing means.
A respiratory face mask (10), hereinafter referred to as protective face mask (10), face mask (10) or mask (10), provided in accordance with the present invention comprises as essential elements a flange (20) and a filter layer (30). Preferred embodiments are shown in FIG. 1 and FIG. 2. These embodiments are preliminary suitable as disposable masks for private users seeking infection prevention.
Flange
The flange (20) serves to seal and preferably to attach the mask (10) to the face of a wearer. The flange is not intended to cover the respiratory organs (mouth and nose) of the wearer. If the mask is designed to cover mouth and nose of a wearer, the flange will typically be in contact with the nose, the cheeks and the chin of wearer.
The flange has an inner periphery (22), surrounding the respiratory organs of the wearer, and an outer periphery (24), which typically defines the outer contours of the mask (10), confer FIGS. 1 and 2.
In one aspect, the present invention resides in the provision of the face mask (10) with a largely improved flange (20). It has been surprisingly found that providing a face mask (10) with a flange (20) of non-uniform width largely improves the sealing of the face mask (10) to the face of a wearer.
The term “width” as used herein, denotes the distance between the inner periphery (22) of the flange (20) and the outer periphery (24) of the flange (20) as measured in the direction perpendicular to the inner periphery (22).
More particularly it has been found beneficial to provide portions of a flange (20) with a high width adjacent to the nasal bone and to the centre of the chin of a wearer. It has further been found beneficial to provide portion of the flange (20) of a low width in the areas between nose and cheeks and around the corner of the mouth of the wearer. Hence, in one aspect of the present invention a plurality of first width can be measured on the flange which is greater than a plurality of second width of which can be measured on the flange. Preferably, at least one of said first width is at least 10%, more preferably at least 20%, yet more preferably at least 30%, yet even more preferably at least 40%, yet even more preferably 50%, most preferably 80% greater than at least one of said second widths.
Preferably the respiratory face mask (10) provided according to the present invention will be symmetrical about one longitudinal axis reflecting the symmetry between the left half and the right half of the human face. The “central point”, as used herein, shall be the point on the longitudinal axis which bisects the distance from the outer periphery of the nasal portion (26) to the outer periphery of the central chin portion (29), as shown in FIG. 1a. 
Referring to the angle measured in clockwise direction between the longitudinal axis and a reference axis A crossing the central point, cf. FIG. 1a, areas of lower width are preferably present in the following sectors: Firstly in a sector extending from 20° to 80°, preferable 30° to 70°, most preferably 40° to 60°, and secondly in a sector extending from 100° to 150°, preferably 105° to 140°, most preferably 110° to 130° and in the corresponding two mirror-symmetric sectors on the other side of the longitudinal axis. These areas are also referred to as cheek portions (27) and corner-of-the-mouth portions (28), cf. FIG. 1.
In another important aspect, the portions of the flange (20) having a lower width as described above, herein also referred to as “narrow portions”, provide a hinge effect allowing for facial movements. Without wishing to be bound by theory it is believed that this hinge effect can be attributed to the higher flexibility of the flange (20) at such narrower portions as less material is provided there. It is also believed that less folds are created in the narrower portions as compared to wider portions when stain, eg. due to facial movement, is exercised onto the flange (20). Such folds are believed to be a source of deficient sealing.
The face mask (10) of the present invention may have any shape, such as circular, oval, squared, rectangular or triangular. Oval shapes are preferred. Typically the shape of the face mask (10) is essentially given by the outer periphery (24) of the flange (20). If provided for an adult wearer the outer periphery (24) of the flange (20) should be shaped to have a height measure along the longitudinal axis from 5 cm to 15 cm, preferably 8 cm to 12 cm, and to have a width, measured along a transversal axis through the central point, from 8 cm to 20 cm and preferably from 10 cm to 15 cm. The height is preferably chosen so, that some facial movement and opening of the mouth is enabled. It has surprisingly be found, that the face mask (10) according to the present invention do, for example, even allow talking and coughing, which gives both a high comfort and a safety benefit.
The provision of the flange (20) in a design as described above has been surprisingly found to provide a largely improved fit and comfort of the mask (10). In particular it has been found, that in combination with the adhesives disclosed hereinafter, both improved sealing and reliable attachment can be achieved—without using an overly strong adhesive and as preferred according to the present invention without relying on further attachment means, such as straps or headbands.
Without wishing to be bound by theory it is believed that the provision of portions of a smaller width allows the flange (20), which typically prior to use has a flat or two-dimensional shape, to follow the three-dimensional contours of the human face, more accurately and without that folds occurs, with typically are harmful for the sealing of the mask (10).
In some embodiments of the present invention one air control module (30) is provided with more than one flange (20). For example, flanges (20) can be provided in a stacked arrangement, so that a used flange (20) can be peeled off and a fresh flange (20) comprising a fresh adhesive layer is provided. The stacked arrangement is hold together by the adhesive layers provided on the flanges (20) for attachment to a wearer. In such embodiment, prior to use only the outermost flange (20) should be covered by a release sheet (40).
Air Control Module
A highly preferred air control module according to the present invention is a filter layer (30). The filter layer (30) can be provided from a variety of materials and a variety of combinations of materials. Preferred materials include non-woven materials, textile materials, e.g. silk, linen or cotton, and tissue paper. Also may any material be employed which is known in the art of absorbent articles, namely sanitary napkins, panty liners and diapers, for use as a top sheet or as a back sheet of such absorbent articles. Materials known for use in a top sheet provide good liquid permeability and hence also good air permeability, while they are appropriate for skin contact. Materials known for use in a back sheet provide typically a lesser degree of air permeability, but recently developed materials provide such a high vapour and air permeability, that they may well be considered for the present use. Due to the humidity of the exhaled air, materials which provide good vapour permeability are highly preferred, as to avoid an moist feeling during wear of the face mask. On the other hand the filter layer (30) should preferably filter some moisture of the exhaled air, eg. traces of saliva or blood, to suppress the spreading of infections.
In some preferred embodiment of the present invention, the mask (10) and most preferably the filter layer (30) will also comprise an odour absorbing compound, for example activated carbon or zeolites.
The filter layer (30) comprised by the face mask (10) according to the present invention should be selected to have a certain degree of flexibility. The flexibility provides for better conformation to the individual facial contours of a wearer, low stress on the adhesive areas during facial movement and convenient packaging of the device and should be selected in view thereof.
However, the filter layer (30) comprised by the face mask (10) should also be selected to have a certain degree of rigidness. Depending on the particular embodiment of the present invention, the rigidness of the flexible sheet prevents that the sheet extends into the mouth of the wearer (if open). Contact of the tongue with this sheet may be considered as unpleasant by some wearers, for example since the taste of a non-woven material may be experienced as unpleasant.
The requirement of rigidness on one side and the requirement of flexibility on the other side can be reconciled if a somewhat rigid, or at least not flimsy material is provided with a stretching means, such as folds (32). A large variety of folding patterns can serve to provide a stretching means. Preferably the area of the filter layer (30) directly at adjacent to the mouth of a wearer is free of folds (32). Hence, preferably, folds are provided slightly above the upper lip and beneath the lower lip of a wearer, optionally folds may further be provided in the nasal are of a wearer. In highly preferred embodiments of the present invention two or four folds (32) are provided, most preferably one or two folds, respectively, above the upper lip and below the lower lip of a wearer. A preferred embodiment with four folds is shown in FIG. 2. While the folds can be arranged symmetrically, it is even more preferred to provide them asymmetrically as to provide for more stretchability in the area of the nose than in the area of the mouth.
In alternative embodiments of the present invention the air control module (30) may comprise cover more complex equipment to control the inhaled and/or exhaled air. In one preferred embodiment of the present invention the air control module (30) comprises means to control, in particular enrich the inhaled air, for example with oxygen, such as used in an apparatus for artificial respiration in medical practise. In another preferred embodiment the air control module (30) comprises means to analyse the exhaled air. Such means may be designed to analyse traces of consumed alcohol, as used by e.g. in alcohol tests by the police forces, it is also contemplated to employ means for analysing the exhaled air in respect of the metabolism of a person for broader medical purposes.
In some embodiments of the present invention the air control module (30) is releasably attached to the flange (20), hence the air control module (30) can be changed. Change of the air control module (30) can be carried out when the mask (10) is not worn, giving at least the benefit of economical reuse of the flange (20), or may in other cases be carried out while the mask is worn (eg. to adapt to different filtering requirements in a work environment) without needing to take of and reattach the flange (20).
Preferred Adhesives
According to the present invention the adhesive on the wearer facing side of the face mask (10) can be applied in any pattern, symmetrical or asymmetrically, e.g. a pattern of dots or stripes. Preferably the adhesive is only provided on the flange (20) of the face mask (10) and the filter layer (30) is free of adhesive.
The adhesive is provided in one or several areas on the wearer facing side of the respiratory face mask (10), hereinafter also referred to as a “device”, as a layer having a certain thickness or calliper C measured in millimeters (mm). Preferably the calliper C is constant for all adhesive coated areas (20), but the calliper C may also vary.
The adhesive is applied on at least portion of the wearer facing side of devices in a layer having a thickness or caliper that is preferably constant, or that alternatively can vary over the surface interested by the application of the adhesive. The adhesive can be applied to the wearer facing side of the device by any means known in the art such as slot coating, spiral or bead application or printing. Typically the adhesive is applied at a basis weight of from 20 g/m2 to 2500 g/m2, preferably from 500 g/m2 to 2000 g/m2, most preferably from 700 g/m2 to 1500 g/m2 depending in the end use envisioned.
Detailed analysis of the sequence of common situations occurring from the devices to the time of removal of such devices has shown that specific adhesive characteristics need to be preferably satisfied in order to achieve the desired performance objectives, in particular to secure initial attachment, secure attachment during use and painless removal after wear. 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.
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 to a particular surface. The elastic behaviour can be interpreted as an indication of the “hardness” behaviour of the adhesive. Its value is also important for good initial attachment. Their combination is believed to be an indicator of the required force upon removal. The relation between elastic and viscous modulus is considered to be an indication on which fraction of the removal energy will be dissipated within the adhesive and which fraction is available to trigger the actual removal.
In order to provide 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 also of importance.
The adhesive has an elastic modulus at a temperature of 37° C. (100° Fahrenheit) abbreviated G′37, a viscous modulus at a temperature of 37° C. (100° Fahrenheit) of G′′37, and a viscous modulus at a temperature of 25° C. (77° Fahrenheit) of G′′25.
The adhesive according to the present invention preferably satisfies the following conditions;













G′37 (1 rad/sec)
is in the range 500 Pa to 20000 Pa,



preferably 700 Pa to 15000 Pa, most



preferably 1000 Pa to 10000 Pa.


G′′37 (1 rad/sec)
is in the range 100 Pa to 15000 Pa,



preferably 100 Pa to 10000 Pa, most



preferably 300 Pa to 5000 Pa.


and the ratio of G′37 (1 rad/sec)/
is in the range of 1 to 30.


G′′37 (1 rad/sec)









Provided the above rheological conditions are satisfied the adhesives will also satisfy conditions such as sufficient cohesiveness (to prevent residue of adhesive on the skin) which are important 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 adhesives for the device provided they also satisfy the common requirements of being safe for use on human or animal skin during use and generally after disposal of the device.
Often the criteria of hygienic appearance such that adhesive compositions which are transparent or white upon application are preferred.
It has been determined that the relation between the thickness or calliper C, measured in millimeters (mm), of the layer in which the adhesive is provided, typically onto at least a portion of the wearer facing surface of the device, and the viscous modulus G′′25 at about 100 rad/sec of the adhesive, is relevant to the scope of providing an easy and painless removal from the wearer's skin of such a adhesive applied on at least a portion of the wearer facing surface of an device for attachment of said device to the skin of a wearer.
The adhesive of the present invention is thus preferably provided as a layer having a thickness C such that the viscous modulus G′′25 (100 rad/sec) and the thickness C preferably satisfy the following empirical equation:

G′′25≦[(7.00+C)×3000]Pa

and preferably also the following empirical equation:

G′′25≦[(5.50+C)×1700]Pa

While in a preferred embodiment of the present invention the thickness C of the adhesive layer is constant, such an adhesive layer can also have different thicknesses in different portions of the wearer facing surface of the device where it is applied, provided that the above mentioned relationship between C and G′′25 is in any case satisfied in each portion.
The skin of the wearer to which the devices are typically applied will vary considerably from person to person. In particular the type and amount of grease or sebum produced can vary considerably from person to person. However, the facial area, and in particular around the chin, is generally known to produce high levels of sebum and to quickly reproduce such sebum, even if some is removed, e.g. by cleaning of the pertinent skin areas. Moreover, the wearers of such devices may apply creams to the area of skin which will contact the adhesives, e.g. moisturing creams. It is thus important to provide an adhesive which adheres to greasy skin. Accordingly the present invention provides an adhesive having a dry initial peel strength (PDI) and a greasy initial peel strength (PGI) as determined by the test method described herein, where the ratio PDI to PGI is from 1:1 to 1.0:0.2, preferably from 1:1 to 1:0.3. Typically for utilisation for devices the dry initial peel strength is (PDI) is from 0.1 N/cm to 7.0 N/cm, preferably from 0.1 N/cm to 5.0 N/cm, more preferably from 0.5 N/cm to 3 N/cm. The value of the grease initial peel strength is preferably the same as for the dry initial peel strength. However typically a lower level is achieved and is acceptable at levels from 0.1 N/cm to 5 N/cm, preferably from 0.1 N/cm to 3 N/cm, more preferably from 0.1 N/cm to 2 N/cm. It is also preferable that the adhesion to greasy skin is maintained over a period of wear time such that the ratio between the greasy initial peel strength (PGI) and the greasy final peel strength (PGF) is from 1:1 to 1:0.25 preferably from 1:1 to 1:0.5.
Due to the nature and environment in which such devices are utilised it is also preferably a feature that the adhesive has a water absorption capacity as defined in the test herein of at least 3% by weight of said adhesive (so that the adhesive adheres directly onto wet or moist skin). In particular, the ratio of the peel strength of the adhesive as determined in the test methods herein should most preferably be maintained at a constant value such that the ratio of initial peel strength (PDI) and the final peel strength (PWF) is from 2:1 to 1:4, preferably from 2:1.25 to 2:4, most preferably from 2.0:1.5 to 2.0:2.5. Typically for devices the initial peel strength for dry and more preferably also for wet skin should be from 0:1 N/cm to 7.0 N/cm, 0.1 N/cm to 5.0 N/cm, preferably from 0.5 N/cm to 3.0 N/cm.
It is further also preferable that the adhesive in addition to maintaining its peel strength over a period of time even in the presence of water also absorbs less than 15%, preferably less than 10%, more preferably less than 7% water. Whilst not intending to being bound by theory, it is believed that in order to obtain direct adhesion onto wet skin and maintain constant adhesion performance over a period of wear, even when exposed to excess liquids or high humidity the ability of the adhesive to absorb water needs to be considered. In particular, it has been identified that, not only the absolute ability of the adhesive needs to be considered, but also the rate of water absorption in order to provide an adhesive meeting the above identified performance parameters.
For example hydrocolloid particle containing adhesives which are known in the art comprising a 3-dimensional rubber matrix and colloidal absorbent particles dispersed therein are only able to absorb limited amounts of water through the colloidal particles themselves and not the matrix itself. In addition the rate at which water is absorbent is slow. Hence these prior art adhesives do not adhere to wet surfaces.
Prior art hydrogel adhesives on the other hand are able to not only absorb large quantities of water but also at a very fast rate. As a result such adhesives may be able to adhere, to wet surfaces, however due to the combination of fast rate of absorption and large absolute water uptake, these adhesives loose their adhesive strength rapidly in the presence of excess water or high humidity.
Accordingly the adhesives of the present invention exhibit both an ability to adhere directly to wet skin, by having a minimum absolute water absorption ability in combination with a rate of absorption such that the peel strength remains within defined levels over the period of wear.
The adhesive is provided with the preferred pattern, typically on the wearer facing surface of the device, as a layer having a thickness or calliper C that is preferably constant. The layer can be preferably continuous or alternatively discontinuous, e.g. in form of dots, spirals, or stripes.
Even though adhesives are used like pressure sensitive adhesives on human skin hair and mucous tissues, it is understood that the 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 adhere objects (e.g. water between two glass plates could) is the fact that their Theological 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 100 rad/s as indicated below.
As a first consequence, it is therefore inadmissible to define materials intended for use as “adhesives” by giving values of rheological parameters and especially of G′ at a fixed value of frequency. This can be misleading because in the absence of other characteristics such as surface chemistry it will include materials which have no practical value. It is hence necessary that rheological characterisation must be on the basis of dynamic considerations. This not only applies to the Elastic Modulus G′ but also to the viscous modulus G′′ and hence also for tan (d)=G′′/G′.
It is well known that typical PSAs have not only a high variation of G′ across the considered frequencies, but also that there is an even higher variation of G′′ which can get close or become even higher than the value of G′, i.e. tan (d) becomes about or even greater than 1, in particular at the frequencies that are typical of 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) and through the interface of the adhesive and the skin, while this fact causes macroscopically the recording of a very high level of adhesive force.
As indicated above materials useful as adhesives according to the present invention have rheological characteristics which are measured at a reference temperature of 37° C. (as usual body temperature of humans) and in a range of frequencies. It has been found that upon application of an device with a adhesive the adhesive contact is formed at a low frequency, while debonding happens at the speed of removing the device. This speed is expressed as a frequency of 100 rad/s, while the low frequency of forming the adhesive bond has been found to be on the order of 1 rad/s. Therefore, the frequency range for use according to the present invention is between 1 and 100 rad/s.
In order to provide good conditions of bonding, i.e. at a frequency of about 1 rad/sec, the absolute values of the elastic modulus should not be too high, otherwise the adhesive is too hard and it is not able to intimately join or mold to the surface to which it is expected to adhere. It is also important to have a low absolute value of G′′ in order to have good cohesion while the material remains soft and capable of gently adhering to skin.
The ratio of G′37 (1 rad/sec) over G′′37 (1 rad/sec) is important to ensure that these two values are balanced upon adhesion to the skin.
Importantly, the ratio of




  
    
      
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        )
      
    
  




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, the specific heat capacity, and the specific heat conductivity are parameters which are useful to more fully define the group of useful adhesives.
The following set of characteristics should preferably be satisfied for the adhesive of the present invention:
the ratio




  
    
      
        G
        ′
      
      ⁢
      37
      ⁢
      
        
      
      ⁢
      
        (
        
          100
          ⁢
          
            
          
          ⁢
          rad
          ⁢
          
            /
          
          ⁢
          sec
        
        )
      
    
    -
    
      
        G
        ′′
      
      ⁢
      37
      ⁢
      
        
      
      ⁢
      
        (
        
          100
          ⁢
          
            
          
          ⁢
          rad
          ⁢
          
            /
          
          ⁢
          sec
        
        )
      
    
  
  
    
      
        G
        ′
      
      ⁢
      37
      ⁢
      
        
      
      ⁢
      
        (
        
          1
          ⁢
          
            
          
          ⁢
          rad
          ⁢
          
            /
          
          ⁢
          sec
        
        )
      
    
    -
    
      
        G
        ′′
      
      ⁢
      37
      ⁢
      
        
      
      ⁢
      
        (
        
          1
          ⁢
          
            
          
          ⁢
          rad
          ⁢
          
            /
          
          ⁢
          sec
        
        )
      
    
  




is not less than 0.5, preferably in the range 0.7 to 3, most preferably in the range 1 to 1.8.

The value of the ratio of G′37/G′′37 at least for the frequency range above 1 rads/up to 100 rads/s should preferably be not less than 0.5, preferably from 0.7 to 10 and most preferably from 1 to 7.
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 0° C., more preferably less than −5° C. and most preferably less than −10.
In circumstances were adherence and sealing on hair populated skin is desired, as it often will be the case when the face mask is worn by male wearer, in particular those wearing a beard, the following is in addition to be considered with the regard to the optimal rheology of the adhesive:
As indicated above materials useful as adhesives according to the present invention have rheological characteristics which are measured at a reference temperature of 37° C. (as usual body temperature of humans) and in a range of frequencies. It has been found that upon application of articles with an adhesive, the adhesive contact is formed at a low frequency, while debonding happens at the speed of removing the article. This speed is expressed as a frequency of 100 rad/s, while the low frequency of forming the adhesive bond has been found to be on the order of 1 rad/s. Therefore, the frequency range for use according to the present invention is between 1 and 100 rad/s.
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 G′ should not be too high, otherwise the adhesive is too hard and it is not able to intimately join or mold to the surface to which it is expected to adhere. It is also important to have a low absolute value of G′′ in order to have good cohesion while the material remains soft and capable of gently adhering to skin.
In order to ensure the penetration of the hair through the hydrogel adhesive such that the adhesive is able to contact the skin surface and bond thereto and such that the hair is also able to readily disengage from the hydrogel adhesive upon removal without pain or leaving residues it has now been found that the elastic modulus and the viscous modulus of the adhesive need to be within certain absolute values and exhibit a minimal delta.
The following set of characteristics should be satisfied for the adhesive of the present invention:
















G′37 (1 rad/sec)
is in the range 100 Pa to 4000 Pa,




preferably 300 Pa to 2500 Pa,




most preferably 400 Pa to 1500 Pa.



G′′37 (1 rad/sec)
is in the range 100 Pa to 5000 Pa,




preferably 200 Pa to 2000 Pa,




most preferably 300 Pa to 2000 Pa.



G′37 (1 rad/sec)
is at least 50 Pa,



G′′37 (1 rad/sec)
preferably at least 150 Pa,




more preferably at least 200 Pa,




most preferably at lest 300 Pa.










In addition in order to ensure the required skin adhesion initially, and preferably over the entire period of wearer, the adhesive has a peel strength of from 0.1 N/cm to 5 N/cm, preferably from 0.2 N/cm to 3 N/cm as determined according to the test method described herein.
The values of elastic modulus, viscous modulus and peel strength can be selected from the above ranges depending on the end use envisaged.
The nature of the hair itself also affects the ability of the hair to penetrate into the hydrogel adhesive, in particular the caliper, length, density, and curliness of the hair being of importance. It has now been found that the suitability for a particular hair type for embedding within the hydrogel adhesive can be determined by the following equation based on hair from a referenced 1 sqcm area.

W×C×G′25 (1 rad/sec)<24

wherein:

    
    
        W=weight (assuming constant specific weight)
        V=volume
        C=curliness (ratio of length of stretched hair and length of unstretched hair)
    
    


In order to provide adhesive compositions which satisfy the requirements of the above rheological and physical characteristics of an adhesive any medically suitable substantially water insoluble pressure sensitive adhesives comprising a polymer which forms a 3-dimensional matrix meeting the these characteristics may be utilised.
According to the present invention the 3-dimensional matrix also referred to herein as a gel, comprises as an essential component a polymer which can be physically or chemically cross linked. The polymer may be naturally or synthetically derived. The uncrosslinked polymer includes repeating units or monomers derived from vinyl alcohols, vinyl ethers and their copolymers, carboxy vinyl monomer, vinyl ester monomers, esters of carboxy vinyl monomers, vinyl amide monomers, hydroxy vinyl monomers, cationic vinyl monomers containing amines or quaternary groups, N-vinyl lactam monomer, polyethylene oxides, polyvinylpyrrolidone (PVP), polyurethanes, acrylics such as methyl acrylate, 2-hydroxyethyl methacrylate, methoxydiethoxyethyl methacrylate and hydroxydiethoxyethyl methacrylate, acrylamides, and sulphonated polymers such as acrylamide sulphonated polymers for example 2 acrylamido methylpropane sulphonic acid (AMPs) and acrylic (3-sulphopropyl) ester acid (SPA), and mixtures thereof. Also acrylonitrile, methacrylamide, N,N,-dimethylacrylamide (NNDMA), acrylic esters such as methyl, ethyl and butyl acrylates. Alternatively, the uncrosslinked polymer may be a homopolymer or copolymer of a polyvinyl ether, or a copolymer derived from a half ester of maleic ester. Similarly any other compatible polymer monomer units may be used as copolymers such as for example polyvinyl alcohol and polyacrylic acid or ethylene and vinyl acetate.
As another alternative, the polymers may be block copolymer thermoplastic elastomers such as ABA block copolymers such as styrene-olefin-styrene block copolymers or ethylene-propylene block copolymers. More preferably such polymers include hydrogenated grade styroVethylene-butylene/styrol (SEBS), styrene/isoprene/styrene (SIS), and styroVethylene-propylene/styrol (SEPS).
Particularly preferred polymers are acrylics, sulphonated polymers such as acrylamide sulphonated polymers, vinyl alcohols, vinyl pyrrolidone, polyethylene oxide and mixtures thereof. Most preferred are nitrogen containing polymers.
According to the present invention the 3-dimensional adhesive matrix also essentially comprises a plasticiser, which is preferably a liquid at room temperature. This material is selected such that the polymer may be solubilized or dispersed within the plasticiser. For embodiments wherein irradiation cross linking is to be carried out, the plasticiser must also be irradiation cross linking compatible such that it does not inhibit the irradiation cross linking process of the polymer. The plasticiser may be hydrophilic or hydrophobic.
Suitable plasticisers include water, alcohols, polyhydric alcohols such as glycerol and sorbitol, and glycols and ether glycols such as mono- or diethers of polyalkylene gylcol, mono- or diester polyalkylene glycols, polyethylene glycols (typically up to a molecular weight of about 600), glycolates, glycerol, sorbitan esters, esters of citric and tartaric acid, imidazoline derived amphoteric surfactants, lactams, amides, polyamides, quaternary ammonium compounds, esters such phthalates, adipates, stearates, palmitates, sebacates, or myristates, and combinations thereof. Particularly preferred are polyhydric alcohols, polyethylene glycol (with a molecular weight up to about 600), glycerol, sorbitol, water and mixtures thereof.
Typically the adhesive comprises a ratio of polymer to plasticiser by weight of from 1:100 to 100:1, more preferably from 50:1 to 1:50. However, the exact amounts and ratios of the polymer and plasticiser will depend to a large extent on the exact nature of polymer and plasticisers utilised and can be readily selected by the skilled person in the art. For example a high molecular weight polymer material will require a greater amount of plasticiser than a low molecular weight polymer.
In addition, the adhesive also further preferably comprises a lipid-micellising polymer, i.e. a so-called hypercoiling polymer. This polymer functions to micellise and remove the rolled up pockets of grease from the gel-skin interface.
This hypercoiling polymer has the capability of more effectively solvating the primary surfactant micelles that contact hydrophobic skin contaminant such as skin lipid or skin creme. The consequence of this functional role is that the work of adhesion between adhesive and skin is progressively less affected by the presence of either or both surfactant or hydrophobic skin contaminant.
The hypercoiling polymer preferably comprises any of the following, either alone or in combination: poly (maleic acid styrene), poly (maleic acid butyl vinyl ether), poly (maleic acid propyl vinyl ether), poly (maleic acid ethyl vinyl ether) and poly (acrylic acid ethyl acrylate).
A particularly preferred example is an alternating copolymer of styrene and maleic anhydride. As discussed herein after the adhesive seeks to provide a biphasic structure on polymerisation. These two phases are hydrophilic and hydrophobic. The hydrophobic phase my be provided by a hydrophobic monomer which is initially maintained as part of the homogenous reaction mixture by way of a reactive solvent bridge. Alternatively and/or additionally the hydrophobic component is provided as a polymer which separates from the aqueous phase on polymerisation.
The exact amounts and ratios of the hypercoiling polymer will depend to a large extent on the nature of the components.
In certain circumstances the reaction mixture preferably comprises from 3% to 20%, and more preferably from 8% to 18% by weight of the reaction mixture, of a stabilised polymer dispersion that is used to provide a stable phase separated system. The polymer preferably comprises any of the following either alone or in combination: vinylacetate dioctyl maleate copolymer or ethylene-vinyl acetate copolymer. Ethylene-vinylacetate copolymer is preferred, such as that marketed under the trade name DM137 by Harlow Chemicals.
The adhesive also preferably comprise surfactants such as nonionic, cationic, anionic, amphoteric and any mixtures thereof.
Suitable nonreactive nonionic surfactants include but are not limited to those selected from the group consisting of the condensation products of a higher aliphatic alcohol, such as a fatty alcohol, containing about 8 to about 20 carbon atoms, in a straight or branched chain configuration, condensed with about 3 to about 100 moles, preferably about 5 to about 40 moles and most preferably about 5 to about 20 moles of ethylene oxide. Examples of such nonionic ethoxylated fatty alcohol surfactants are the TergitolTM. 15-S series from Union. Carbide and Brij.TM. surfactants from ICI. TergitolTM. 15-S Surfactants include C.sub.11–C.sub.15 secondary alcohol polyethyleneglycol ethers. Brij.TM 58 Surfactant is Polyoxyethylene(20) cetyl ether, and Brij.TM.76 Surfactant is Polyoxyethylene(10) stearyl ether.
Other suitable nonreactive nonionic surfactants include but are not limited to those selected from the group consisting of the polyethylene oxide condensates of one mole of alkyl phenol containing from about 6 to 12 carbon atoms in a straight or branched chain configuration, with about 3 to about 100 moles of ethylene oxide. Examples of nonionic surfactants are the Igepal.TM.CO and CA series from Rhone-Poulenc. Igepal.TM.CO surfactants include nonylphenoxy poly(ethyleneoxy) ethanols. Igepal.TM. CA surfactants include octylphenoxy poly(ethyloneoxy) ethanols.
Another group of usable nonreactive nonionic surfactants include but are not limited to those selected from the group consisting of block copolymers of ethylene oxide and propylene oxide or butylene oxide.
Examples of such nonionic block copolymer surfactants are the Pluronic.TM. and Tetronic TM. Series of surfactants from BASF. Pluronic.TM. surfactants include ethylene oxide-propylene oxide block copolymers. Tetronic.TM. surfactants include ethylene oxide-propylene oxide block copolymers. Suitable examples are Pluronic L68 and Tetronic 1307. Particularly suitable examples are Pluronic L64 and Tetronic 1107.
Still other satisfactory nonreactive nonionic surfactants include but are not limited to those selected from the group consisting of sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and polyoxyethylene stearates. Examples of such fatty acid ester nonionic surfactants are the Span.TM., Tween.TM., and Myrj.TM. surfactants from ICI. Span.TM. surfactants include C.sub.12–C.sub. 18 sorbitan monoesters. Tween.TM. surfactants include poly(ethylene oxide) C.sub.12–C.sub.18 sorbitan monoesters. Myrj.TM. surfactants include poly(ethylene oxide) stearates.
Suitable anionic surfactants will normally include a hydrophobic moiety selected from the group consisting of (about C.sub.6 to about C.sub.20) alkyl, alkylaryl, and alkenyl groups and an anionic group selected from the group consisting of sulfate, sulfonate, phophate, polyoxyethylene sulfate, polyoxyethylene sulfonate, polyoxyethylene phosphate and the alkali metal salts, ammonium salts, and tertiary amino salts of such anionic groups.
Anionic surfactants which can be used in the present invention include but are not limited to those selected from the group consisting of (about C.sub.6 to about C.sub.20) alkyl or alkylaryl sulfates or sulfonates such as sodium lauryl sulfate (commercially available as Polystep.TM B-3 from Srepan Co.) and sodium dodecyl benzene sulfonate, (commercially available as Siponate.TM.DS10 from Rhone-Poulene); polyoxyethylene (about C.sub.6 to about C.sub.20) alkyl or alkylphenol ether sulfates with the ethylene oxide repeating unit in the surfactant below about 30 units, preferably below about 20 units, most preferably below about 15 units, such as Polystep.TM.B-1 commercially available from Stepan Co. and Alipal.TM.EP110 and 115 from Rhone-Poulenc; (about C.sub.6 to about C.sub.20) alkyl or alkylphenoxy poly(ethyleneoxy)ethyl mono-esters and di-esters of phosphoric acid and its salts, with the ethylene oxide repeating unit in the surfactant below about 30 units, preferably below about 20 units, most preferably below about 15 units, such as Gafac.TM.RE-510 and Gafac.TM.RE610 from GAF.
Cationic surfactants useful in the present invention include but are not limited to those selected from the group consisting of quaternary ammonium salts in which at least one higher molecular weight group and two or three lower molecular weight groups are linked to a common nitrogen atom to produce a cation, and wherein the electrically-balancing anion is selected from the group consisting of a halide (bromide, chloride, etc.), acetate, nitrite, and lower alkosulfate (methosulfate etc.). The higher molecular weight substituent(s) on the nitrogen is/are often (a) higher alkyl group(s), containing about 10 to about 20 carbon atoms, and the lower molecular weight substituents may be lower alkyl of about 1 to about 4 carbon atoms, such as methyl or ethyl, which may be substituted, as with hydroxy, in some instances. One ore more of the substituents may include an aryl moiety or may be replaced by an aryl, such as benzyl or phenyl.
In a particularly preferred embodiment of the invention the surfacant comprises at least one propylene oxide/ethylene oxide block copolymer, for 1 example such as that supplied by BASF Plc under the trade name Pluronic L64. The reaction mixture ideally comprises from 0.1% to 5%, by weight of the reaction mixture, of surfactant.
The surfactant acts to remove the grease from the skin and to form the removed grease into isolated pockets within the hydrogel without reducing the work of adhesion of the coating.
Other common additives known in the art such as preservatives, antioxidants, pigments, mineral fillers and mixtures thereof may also be comprised within the adhesive composition in quantities up to 10% by weight each respectively.
According to the present invention the polymer component of the adhesive can be physically or chemically cross linked in order to form the 3-dimensional matrix. Physical cross linking refers to polymers having cross links which are not chemical covalent bonds but are of a physical nature such that there are areas in the 3-dimensional matrix having high crystallinity or areas having a high glass transition temperature. Chemical cross linking refers to polymers which are linked by chemical bonds. Preferably the polymer is chemically cross linked by radiation techniques such as thermal-, E beam-, UV-, gamma or micro-wave radiation.
In addition when chemical crosslinks are formed in the system, a polyfunctional cross linker and/or a free radical initiator may be present in the premix to initiate the crosslinking upon irradiation. Such an initiator can be present in quantities up to 5% by weight, preferably from 0.02% to 2%, more preferably from 0.02% to 0.2%. Suitable photoinitators include type I-α-hydroxyketones and benzilidimethyl-ketals e.g. Irgacure 651 which are believed to on irradiation to form benzoyl radicals that initiate polymerization. Photoinitiators of this type that are preferred do not carry any subtitients in the para position of the aromatic ring. Particularly preferred is I-hydroxycyclohexylphenylketone (available under the trade name Irgacure 184 from Ciba Speciality Chemicals), also preferred are Darocur 1173 (2-hydroxy-2-propylphenyl ketone) and mixtures of Irgacure 184 and Darocur 1173. In addition from 0.02% to 2% of thermal initiators may also be used.
The resulting adhesive composition is mainly hydrophilic. Hydrophobic and mixed phase compositions are dependant upon the nature of the components of the adhesive. In addition a mixture of monomers whether hydrophilic or both hydrophilic and hydrophobic may result in a single phase or mixed phase of at least 2 phases. Preferably, the adhesives of the present invention are mixed phase hydrophilic hydrophobic.
A mixture of monomers which may result in 1, 2 or more phases are preferred. Mixed phase adhesives are compositions in which both hydrophobic and hydrophilic components, preferably in both plasticisers and polymers, form two or more separate phases. In such cases an emulsifier is preferably present at a suitable level to form stable emulsions between the incompatible phases.
Whilst not intending to be bound by theory it is believed that the improved peel strength liquid stability particularly with respect to water of the adhesives is obtained from a monomer mix comprising both hydrophilic e.g. polar and/or ionic monomers preferably an ionic water soluble monomer and hydrophobic i.e water insoluble monomers. Preferably the ratio of hydrophilic monomers to hydrophobic monomers should be in the range of from 5:1 to 1:5, preferably from 3:1 to 1:3, more preferably from 2:1 to 1:2. The hydrophilicity and hydrophobicity of a monomer component is always relative to the other component. Typically prior art hydrogel adhesives comprise hydrophilic monomers only, as a consequence of which they have a high rate of water absorption and do not maintain adhesion after exposure to excess liquid. Whilst not intending to be bound by theory, it is believed that the presence of a hydrophobic component in the adhesive matrix reduces the rate of absorption of water of the adhesive. As a result the distribution of the water absorbed by the adhesive is more uniform. Consequently a water film is not generated between the surface of the skin and the adhesive, which if present, prevents the formation of bonds between skin and adhesive and thus the adhesive capacity of the adhesive itself.
Thus the invention seeks to provide a homogeneously dispersed reaction mixture comprising both hydrophobic and hydrophilic components which, on polymerisation separates into a biphasic or a multiphasic structure. The phases have in some cases been observed to have a thickness of about 100 microns +/−50 microns. The reaction mixture may contain one or more surface active agents which may assist or promote phase separation but in the course of polymersation become anistropically distributed between the result phases.
The presence of a hydrophobic monomer or polymer may be necessary in the initial homogenous dispersion in order to more effectively promote phase separation.
It is a consequence of this invention that the phase separated material contains relatively hydrophobic regions, which enable the polymer to function as a pressure sensitive adhesive, and substantially hydrophilic region, which enable the surface active agent to function in an aqueous environment at the interface between the polymer and mammalian skin. When the polymer is placed in contact with skin, the nature and quantity or surface active agent are chosen to bring about the removal of natural or synthetic hydrophobic material, such as skin lipid or skin creme, from the skin surface without adversely diminishing the work of adhesion between the hydrophobic domains and the skin surface. In as much as both the polymeric adhesive formed in this invention and the skin with which it is contacted are deformable under conditions of normal use, an equilibrium interfacial situation is reached in which some spatial exchange of hydrophobic regions and hydrophobic regions will have taken place on the skin surface.
Suitable preferred hydrophilic monomers are acrylic acid, and salts thereof, 2-acrylamido methylpropane sulphonic acid, acrylic (3-sulphopropyl) ester acid and salts thereof and combinations thereof. A particularly preferred example is 2-acrylamide.-2-methylpropane sulphonic acid sodium salt commonly known as NaAMPs available commercially from Lubrizol as either a 50% aqueous solution (reference code Lz 2405) or at a 58% solution (reference code LZ 2405 A). Suitable hydrophobic monomer components are methyl-, ethyl-, n-butyl, hexyl, iso octyl- and isodecyl acrylates and methacrylate, vinyl ethers, vinyl pyrrolidine, gylcidyl acrylate and ethoxy ethyl acrylate, tehra-hydrofurfuryl acrylate, hydroxypropyl acrylate, vinyl propionate and vinyl butyrate, and combinations thereof. Particularly preferred are ethoxy ethyl acrylate or butyl acrylate.
When the adhesive comprises a hydrophobic component, such as butyl acrylate as well as a hydrophilic monomer (i.e. the aforesaid water soluble ionic monomer), such as NaAMPS, the presence of a nonionic water soluble monomer, for example NNDMA is preferred to act as a so-called “reactive solvent bridge” to provide intimate mixing of the various seemingly incompatible components of the reaction mixture prior to polymerisation. The reaction mixture thus has a homogenous structure containing both hydrophilic and hydrophobic components that are intimately mixed, as the NNDMA acts as a solvent for both hydrophilic and hydrophobic materials, providing a clear compatible coating solution or dispersion. As the reactive solvent bridge is polymerised and thus essentially removed from the reaction mixture the stability of the system is adversely affected and the compatible coating solutions or dispersions undergo phase separation so as to provide a biphasic structure.
In a preferred embodiment of the invention the aforesaid non ionic water soluble monomer will comprise at least one of a mono- or di-N-alkylacrylamide or an analogue thereof. The term “analogue” in this context refers to non ionic water soluble monomers containing an alkyl or substituted alkyl group linked to a carbon-carbon double bond via an amido or alkylamido (—CO.NH— or CO.NR—) function. Examples of such analogues include diacetone acrylamide (N-1,1-dimethyl-3-oxobutyl-acrylamide), N-alkylated acrylamides, N,N-dialkylated acrylamides, N-vinyl pyrrolidone and acryloyl morpholine. N,N-dimethylacrylamide (NNDMA) and/or and analogue thereof is preferred. The reaction mixture preferably comprises from about 15% to about 30% and ideally from about 15% to about 25%, by weight of the reaction mixture, of the non ionic water soluble monomer.
The term “reactive solvent bridge” used herein refers to a partially lipophilic non ionic water soluble monomer which has the ability to partition between the hydrophobic and aqueous phases, whereby the hydrophobic monomer is substantially solubilised in the homogeneous reaction mixture before polymerisation begins. The solvent bridge is reactive in that it is a polymerisable monomer which takes part in the polymerisation reaction. Without wishing to be bound by theory, it is believed that the solvent bridge function of the non ionic water soluble monomer is exercised predominantly prior to, and in the relatively early stages of, the potymerisation reaction, and reduces as the polymerisation reaction proceeds.
In preparing adhesive compositions in accordance with the invention, the ingredients will usually be mixed to provide a homogeneous reaction mixture in the form of an initial pre-gel aqueous based liquid formulation, and this is then converted into a gel by a free radical polymerisation reaction. This may be achieved for example using conventional thermal initiators and/or photoinitiators or by ionizing radiation. Photoinitiation is a preferred method and will usually be applied by subjecting the pre-gel reaction mixture containing an appropriate photoinitiation agent to UV light after it has been spread or coated as a layer on siliconised release paper or other solid substrate. The incident UV intensity, at a wavelength in the range from 240 to 420 nm, is ideally substantially 40 mW/cm2. The processing will generally be carried out in a controlled manner involving a precise predetermined sequence of mixing and thermal treatment or history.
The UV irradiation time scale should ideally be less than 60 seconds, and preferably less than 10 seconds to form a gel with better than 95% conversion of the monomers and for conversion better than 99.95% exposure to UV light less than 60 seconds and preferably less than 40 seconds is preferred. Those skilled in the art will appreciate that the extent of irradiation will be dependent on the thickness of the reaction mixture, concentration of photoinitiator and nature of substrate on to which the reaction mixture is coated and the source of UV.
These timings are for medium pressure mercury arc lamps as the source of UV operating at 100 W/cm. The intensity of UV @ 254 nm and 313 nm reaching the surface of the substrate is approximately 150 μW/cm2 and 750 μW/cm2. For a given lamp UV intensity in a function of the operating power and distance of the reaction mixture from the UV source.
In order to minimize and preferably eliminate the presence of any residual monomers it is important to ensure that the reaction is complete. This is dependent upon a number of factors such as the substrate onto which the adhesive is applied, the type and intensity of the ultra violet light and the number of ultra violet light passes. Preferably the conversion of the hydrophilic monomers present such as NaAMPS should be 98%, preferably 99% most preferably 99.9% so that the amount of monomer within the adhesive is 4600 microg/g or less, preferably 2300 microg/g or less, most preferably 230 microg/g or less. Similarly, the conversion of the hydrophobic monomers present such as NNDMA should be 99%, preferably 99.9%, most preferably 99.99% so that the amount of monomer present in the adhesive is 2200 microg/g or less, preferably 220 microg/g or less, more preferably 22 microg/g or less.
The adhesive is thus typically formed by polymerising a homogeneous aqueous reaction mixture comprising from 5 to 50%, preferably from 30% to 50% by weight of the reaction mixture, of hydrophilic monomer, i.e. an ionic water soluble monomer, from 10% to 50%, preferably from 15% to 45% by weight of the reaction mixture, of a plasticiser (other than water), up to 50%, preferably from 10% to 50%, more preferably from 15% to 30% most preferably from 15% to 25% by weight of the reaction mixture, of a nonionic, water soluble monomer, from up to 40%, preferably from 0.05% to 40%, more preferably from 3 to 40%, by weight of the reaction mixture, of water. If present the reaction mixture comprises from up to 10%, preferably from 0.05% to 9%, more preferably less than 8% by weight of the reaction mixture, of a surfactant. Similarly the reaction mixture may also comprise from 0.1% to 5%, by weight of the reaction mixture, of a lipid micelling polymer, and may comprise from 1% to 30% by weight of the reaction mixture of at least one hydrophobic monomer.
The term “homogeneous aqueous reaction mixture” used herein refers to a substantially solubilised system in which substantially no phase segregation occurs prior to the polymerisation reaction. For example, an emulsion, microemulsion or phase-separated mixture in which a polymerisation reaction later occurs is not a homogeneous aqueous reaction mixture as understood for the purpose of the present invention. Where a reaction mixture includes hydrophobic components, special measures will therefore be required, to achieve homogeneity, as described in more detail herein.
Surface Characteristics of the Polymerised Materials
It is a consequence of this invention that the phase separated polymerised material contains at least at its surface relatively hydrophobic regions, which enable the polymer to function as a pressure sensitive adhesive, and substantially hydrophilic regions, which enable the surface active agent to function in an aqueous environment at the interface between the polymer and mammalian skin. When the polymer is placed in contact with skin, the nature and quantity of surface active agent are chosen to bring about the removal of natural or synthetic hydrophobic material, such as skin lipid or skin creme, from the skin surface without adversely diminishing the work of adhesion between the hydrophobic domains and the skin surface. In as much as both the polymeric adhesive formed in this invention and the skin with which it is contacted are deformable under conditions of normal use, an equilibrium interfacial situation is reached in which some spatial exchange of hydrophobic regions and hydrophobic regions will take place on the skin surface.
The phase separated polymerised surface material is found to include predominantly well defined hydrophobic phases embedded in a hydrophilic matrix in which the water is predominantly contained. The hydrophobic phases are generally of elongated form, with a transverse dimension above the wavelength of light (e.g. about 0.5 to about 100 microns). They may therefore be visualised under a light microscope on a sample stained with a dye which binds preferentially to the hydrophobic phase.
The surface morphology of the elongate hydrophobic phases can vary widely. Without wishing to the bound by theory, it is believed that variations in the surface tension at the hydrophobic/hydrophilic interface as the polymerisation reaction proceeds can cause the morphologies to vary in the final polymer. This surface tension can be affected by the nature and amount of both the reactive solvent bridge and the surfactant, and by other factors.
Thus, it is possible for the elongate hydrophobic phases at the surface of the polymerised material to congregate in a clustered, or alternatively a relatively open, arrangement. The hydrophobic phase visualised microscopically may, for example, appear as discontinuous linear and/or branched strands, or closed loops, embedded in the hydrophilic matrix.
The polymerised material is typically non-bicontinuous. At least one of the hydrophobic and hydrophilic phases exists as discrete regions within the polymerised material, and both phases do not simultaneously extend across the polymerised material (bicontinuity).
The adhesive is provided, typically on at least a portion of the wearer facing surface of the device, as a layer having a thickness or calliper C that is preferably constant, or that alternatively can vary over the surface of application of the adhesive.
When considering particularly the removal phase of an adhesive composition for attachment to the skin of a wearer, it is commonly recognised that good conditions of removal, i.e. at a frequency of about 100 rad/sec, of the adhesive applied to at least part of the wearer facing surface of the device, are achieved when the adhesive can be easily removed from the skin, and particularly from the bodily hair that may be located on this area of the skin, where the device contacts the body, without causing pain to the wearer, therefore without adhering too hard upon removal, to the skin and the hair of the wearer. Moreover, a good removal implies that the adhesive does not leave residues on the skin or on the hair.
The relationship between the thickness or calliper C measured in millimeters (mm) of the layer of the adhesive typically onto at least part of the wearer's facing surface of the device, and the viscous modulus G′′25 at 25° C. at about 100 rad/sec of the topical adhesive gives an indication of painless and easy removal of the adhesive from the skin.
Without being bound to any theory, it is believed that for higher values of G′′25 at 100 rad/sec, which overall correspond to a higher adhesiveness of the composition, a thicker calliper or thickness C of the adhesive layer is needed so that the energy applied for the removal is more evenly distributed within the mass of the adhesive, and is therefore transferred smoothly to the skin, so avoiding peaks of energy that typically cause the pain sensation to the wearer. In other words, thinner layers of the adhesive necessitate an adhesive with a lower G′′25 at 100 rad/sec to achieve a reduced pain sensation upon removal of the device.
Test Methods
Peel Adhesion Method
This is a quantitative method to determine the average peel force required to remove a sin at a specified peel angle and speed.










Equipment
















Scissors
Convenient source


Standard ruler
Convenient source


Steel Roller
5.0 kg Mass. 13 cm in diameter and 4.5 cm in width



covered with 0.5 mm thick rubber.


Polyester Film
PET 23μ available from EFFEGIDI S.p.A., 43052



Colorno, Italy.


Transfer Adhesive
3M 1524 available from 3M Italia S.p.a., 20090



Segrate Italy


Stop watch
Convenient source


Tensile Tester
Instron mod.: 6021 (or equivalent)









Test Procedure

    
    
        A) Tensile Tester Peel Settings:
    
    


















Load cell
 10 N



Test Speed
1000 mm/min



Clamp to Clamp distance
 25 mm



Pre Loading
  0.2 N



Test Path “LM”
 50 mm



Measure variable
F average (N) in “LM”










    
    
        B) Skin Condition and Preparation
         The sample is peel from the forearm. There are 3 conditions of the skin that are tested:
        
            1) Dry: The forearm is untreated and not wiped prior to test or between repetitions.
            2) Wet: To one cotton disk (Demak'up diameter 5.5 cm, weight about 0.6 g), 3 ml of distilled water is added. Next the disk is then wiped with a light pressure 3 times over the test area on the forearm. (The test area of the forearm is a rectangle approximately 2 cm wider and longer than the adhesive area).
            3) Greasy: To one cotton disk (Demak'up diameter 5.5 cm, weight about 0.6 g), 4 drops (about 0.2 g) of ‘Nivea Body’ are added. The disk is then folded in on itself to ensure the cream is absorbed. Next the disk is then wiped with a light pressure 3 times over the test area on the forearm. (The test area of the forearm is a rectangle approximately 2 cm wider and longer than the adhesive area).
        
        
        C) Sample Preparation
        
            1. Allow the samples to adjust to conditioned room (23±2° Celsius and 50±2% RH) for about 1 hr.
            2. Prepare rectangular adhesive samples 260 mm±2 length and 20 mm±2 wide.
            3. Attach on the sample surface the polyester film (using the transfer adhesive to attach the polyester to the substrate surface).
            4. Each test specimen should be prepared individually and tested immediately.
            5. Remove the release paper from the adhesive without touching it Attach one end to the skin (see section B).
            6. Roll the Steel Roller for 160 mm along the adhesive strip, once in each direction.
        
        
        D) Test Environment
         There are 2 environments the adhesive can be tested in:
        
            1) Conditioned Room as described in C1.
            2) Wet Environment. Here, after step C4, the specimen is taken and put in a humidity controlled oven for 3 hours at 85 degC. It is then taken out and steps C5, C6 are carried out.
        
        
        E) Execution
         1 minute after Step C6, take the free end of the specimen (approx. 100 mm long) and insert it in the upper end of the adhesion testing machine. Ensure the specimen is at a 90 degree angle to the forearm. Start the testing machine.
        F) Report
         Report the average of the peel strength of 5 tests. The single values are the base to calculate the standard deviation between the samples.
    
    


Residual Monomer Test Method
Test Sample
1 gram of a hydrogel sample is taken and emersed in 100 ml 0.9% saline water.
The sample is left in the saline at 40 degC. for 24 hours.
An aliquot of the liquid is diluted and analysed by electrospray LC/IMS/MS.
Calibration Sample
1 gram of reference monomers (eg NaAmps) are dissolved in 100 ml 0.9% saline water.
An aliquot of the liquid is diluted and analysed by electrospray LC/MS/MS.
Evaluation
The concentration of the test and calibration sample are determined by linear regression analysis using a software package such as VG Mass Lynx.
EXAMPLES
All formulations detailed below were coated onto polyurethane foam (EV1700X from Caligen) at a coat weight of 0.8 to 1.6 kg per square meter and cured by exposure to ultraviolet radiation emitted from a medium pressure mercury arc lamp operating at 100 W/cm power for 10 seconds.
Example 1
Mix 6.0 g of Irgacure 184 with 20 g IRR280 (PEG400 diacrylate) from UCB (Solution A). To 0.07 g of Irgacure 184 add 23.5 g of NNDMA and stir for one hour (keep container covered from light). Add 30 g of glycerol to this and stir for 5 minutes, followed by 40 g of NaAMPS (58%). Stir for another 5 minutes. Add 0.13 g of Solution A and stir the whole formulation for 1 hour before use.
Example 2
Mix 6.0 g of Irgacure 184 with 20 g IRR280 (PEG400 diacrylate) from UCB (Solution A). To 0.07 g of Irgacure 184 add 23.5 g of NNDMA and stir for one hour (keep container covered from light). Add to this 10 g of Mowilith DM137 (50% dispersion of ethylene vinyl acetate copolymer in water from Harco) and stir for 5 minutes. Add30 g of glycerol to this and stir for 5 minutes, followed by 40 g of NaAMPS (58%). Stir for another 5 minutes. Add 0.13 g of Solution A and stir the whole formulation for 1 hour before use.
Example 3
Mix 6.0 g of Irgacure 184 with 20 g IRR280 (PEG400 diacrylate) from UCB (Solution A). To 0.07 g of Irgacure 184 and 23.5 g of NNDMA and stir for one hour (keep container covered from light). Add to this 10 g of Mowilith DM137 (50% dispersion of ethylene vinyl acetate copolymer in water form Harco) and stir for 5 minutes. Add 30 g of glycerol to this and stir for 5 minutes, followed by 40 g of NaAMPS (58%). Stir for another 5 minutes. Add 0.5 g of Pluronic L64 (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) available from BASF). Add 0.13 g of Solution A and stir the whole formulation for 1 hour before use.
Example 4
Mix 6.0 g of Irgacure 184 with 20 g IRR280 (PEG400 diacrylate) from UCB (Solution A). To 0.07 g of Irgacure 184 add 23.4 g of NNDMA and stir for one hour (keep container covered from light). Add to this 2 g of Mowilith DM137 (50% dispersion of ethylene vinyl acetate copolymer in water from Harco) and stir for 5 minutes. Add 36 g of glycerol to this and stir for 5 minutes, followed by 40.36 g of NaAMPS (58%). Stir for another five minutes. Add 0.25 g of Pluronic L64 (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) available from BASF). To this add 0.8 g of a 30% aqueous solution of poly(styrene-alt-maleic acid) sodium salt available from Aldrich and stir for 10 minutes. Add 0.13 g of Solution A and stir the whole formulation for 1 hour before use.
Example 5
Mix 6.0 g of Irgacure 184 with 20 g IRR280 (PEG400 diacrylate) from UCB (Solution A). To 0.07 g of Irgacure 184 add 23.4 g of NNDMA and stir for one 30 hour (keep container covered from light). Add to this 10 g of Mowilith DM137 (50% dispersion of ethylene vinyl acetate copolymer in water from Harco) and stir for 5 minutes. Add 36 g of glycerol to this and stir for 5 minutes, followed by 40.36 g of NaAMPS (58%). Stir for another 5 minutes. Add 0.259 of Pluronic L64 (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) available from BASF). To this add 0.8 g of a 30% aqueous solution of poly(styrene-alt-maleic acid) sodium salt available form Aldrich arid stir for 10 minutes. Add 0.13 g of Solution A and stir the whole formulation for 1 hour before use.
Example 6
Mix 6.0 g of Irgacure 184 with 20 g IR280 (PEG400 diacrylate) from UCB (Solution A). To 0.07 g of Irgacure 184 add 23.49 of NNDMA and stir for one hour (keep container covered from light). Add to this 10 g of Mowilith DM137 (50% dispersion of ethylene vinyl acetate copolymer in water from Harco) and stir for 5 minutes. Add 36 g of glycerol to this and stir for 5 minutes, followed by 40.36 g of NaAMPS (58%). Stir for another 5 minutes. Add 0.5 g of Pluronic L64 (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) available from ASF). To this add 0.8 g of a 30% aqueous solution of poly(styrene-alt-maleic acid) sodium salt available from Aldrich and stir for 10 minutes. Add 0.13 g of Solution A and stir the whole formulation for 1 hour before use. Optical phase contrast microscopy showed the resultant gel to have a regularly phase segregated surface (see FIG. 1).
Example 7
Mix 6.0 g of Irgacure 184 with 20 g IRR280 (PEG400 diacrylate) from UCB (Solution A). To 0.07 g of Irgacure 184 add 23.4 g of NNDMA and stir for one hour (keep container covered from light). Add to this 209 of Mowilith DM137 (50% dispersion of ethylene vinyl acetate copolymer in water from Harco) and stir for 5 minutes. Add36 g of glycerol to this and stir for 5 minutes, followed by 40.36 g of NaAMPS (50%). Stir for another 5 minutes. Add 0.5 of Pluronic L64 (poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) available from BASF). To this add 0.8 g of a 30% aqueous solution of poly(styrene-alt-maleic acid) sodium salt available from Aldrich and stir for 10 minutes. Add 0.13 g of Solution A and stir the whole formulation for 1 our before use.
Example 8
To parts glycerol, were added 40.4 parts of a 58% solution of the sodium salt of 2-acrylamido-2-methylpropane sulphonic acid (NaAMPS) (LZ2405A) together with 0.5 parts Pluronic LF64 (BASF), and the solution stirred to ensure uniform mixing. To the solution was added 0.13 parts of solution containing 20 parts of polyethylene glycol diacrylate (PEG600) (product of UCB Chemicals marketed under the trade name designation of Ebacryl 11) in which 6 parts of 1-hydroxycyclohexyl phenyl ketone (product of Ciba and marketed under the trade name designation of Irgacure 184) had been dissolved. A promised solution of 8 parts butyl acrylate and 15.7 parts N,N-dimethylacrylamide (Kohjin) was added to that reaction mixture and this final solution cured by exposure to UV light as in example 1. Optical phase contrast microscopy showed that resultant gel to have a regularly phase-segregated surface and enhanced adhesion to skin that had previously treated with skin cream (Nivea) (see FIG. 2 below).
Example 9
To 30 parts glycerol, were added 0.5 parts of a 30% aqueous solution of poly(styrene-alt-maleic acid) sodium salt available from Aldrich and 40 parts of a 58% solution of the sodium salt of 2-acrylamido-2-methylpropane sulphonic acid (NaAMPS) (LZ2405A) together with 0.5 parts Pluronic P65 (BASF), and the solution stirred to ensure uniform mixing. To the solution was added 0.13 parts of solution containing 20 parts of polyethylene glycol diacrylate (PEG600) (product of UCB Chemicals marketed under the trade name Ebycryl 11) in which 6 parts of 1-hydrocycyclohexal phenyl ketone (product of Ciba and marketed under the trade name designation of Irgacure 184) had been dissolved. A premixed solution of 6 parts ethoxyethyl acrylate and 18 parts N,N-dimethylacrylamide (Kohjin) was added so that reaction mixture and this final solution cured by exposure to UV light as in example 5. Optical microscopy showed the resultant gel to have a regularly phase-segregated surface (see FIG. 7 and the associated discussion below).
Results














Subject 2














Subject 1


Greasy
















Greasy (PGI)

Dry
(PGI)



Example
Dry (PDI)
1 min
10 min
(PDI)
1 min
10 min
















1
1.75
0.13
—
1.57
0.19
—


2
2.96
0.16
—
3.18
0.44
—


3
2.81
0.52
0.33
2.46
0.67
0.61


4
0.81
0.15
0.26
0.96
0.29
0.47


5
1.2
0.52
0.69
2.2
0.83
0.88


6
1.6
0.45
0.6
2.2
0.64
0.56


7
1.2
0.49
0.62
1.6
0.74
0.88









Microscopy
The gels of Examples 6, 8 and 9 were examined using a Leitz Dialux 20 microscope with a “Wild MPS photoautomat” camera attachment. The microscope was equipped with a 12.5× eyepiece. The image can then be magnified by a number of objectives of which the ×4, ×10 (phaco) and ×25 (phaco) were most commonly used. Both phase contrast and brightfield illumination were used.
Staining
The sample of Example 9 was stained prior to microscopy. A saturated solution of Bromopyrogallol Red in methanol was used to differentially stain the hydrophobic areas of the hydrogel surface. The solution is applied to the surface of the sample, which is then rinsed with methanol to remove any excess dye solution and dye solid. The criteria used in dye selection are outlined below.
The choice of a dye to differentially stain the more hydrophobic and more hydrophilic regions of these gels is influenced by many factors, this may be illustrated by a comparison of Bromopyrogallol Red and fluorescein sodium which are taken up or retained to different extents in different polymer types. The two major factors are charge and hydrophobicity. Bromopyrogallol Red is dominated by acidic —SO3H and —COOH groups and fluorescein sodium by a slightly acidic —COOH group. More basic regions of the polymer have most affinity for the acidic dye and the acidic regions least affinity for the acidic dye. It can also be observed that a higher water conterit material allows more rapid uptake of a dye. In conventional hydrogels this is influenced by the fact that higher water content materials will often contain the slightly basic N-vinyl pyrrolidone or N,N-dimethylacrylamide groups which attracts dyes containing acidic groups, e.g. —SO3H and COOH.
As well as acidity and basicity of the dyes and the polymers, the partition coefficients of the dyes also have a marked effect on the retention of the dyes within the materials. This property is conventionally and commonly characterised by measuring the partition coefficient of the dye between octanol and water (KOW). Bromopyrogallol Red has a 10 g KOW of −0.49 and fluorescein sodium has a log KOW of −0.98. Both of the dyes are able to partition between the aqueous and non-aqueous components of the polymers used.
However, Bromopyrogallol Red is more likely to favour the more hydrophobic than the more hydrophilic aqueous phase, in comparison to fluorescein sodium which would prefer the aqueous environment This preference is illustrated by the fact that conventional N-vinyl pyrrolidone or N,N-dimethylacrylamide based hydrogels tend to retain approximately 30% of the Brompyrogallol Red dye within the polymeric network.
The more intense colour of Brompyrogallol Red coupled with its greater affinity for hydrophobic domains and its solubility in methanol make it much more suited than sodium fluorescein for indicating by differential staining the presence of hydrophobic and hydrophilic regions in the surface of polymer gels.
Cover Layer
Prior to use an adhesive present of the wearer facing side of the face mask (10) is preferably covered by a cover layer, which may for example be provided by at least one release sheet (40) or release paper, such as siliconised paper.
According to the present invention is has been found that it is highly preferably to provide a cover layer for an article the respiratory organs of the wearer from at least two release sheets (40).
Preferably any such release sheet (40) extends from the outer periphery (24) of the flange (20) to the filter layer (30), and most preferably to the central point of the face mask (10). Such embodiment allows to peal off the release sheet (40) starting from the centre rather than from the outer periphery of the face mask (10).
In highly preferred embodiments of the present invention the release sheets (40) are provided with straight edges, which most preferably are parallel with the longitudinal axis of the face mask. Such an embodiment is shown in FIG. 3.
It is also preferred that the release sheet (40) which provides the cover layer overlap, so that at least one portion of at least one of the release sheets is not in contact with the adhesive, as to facilitate an easier pealing-off. The outer contours of the release sheets (40) may be chosen to have the same form as the outer periphery (24) of the flange (20) or may be chosen to have another form which is convenient to produce.
It has been found that face mask (10) according to the present invention provides best fit and comfort if adhesive contact of the flange (20) is first made in the nasal area and the chin area of the wearer and adhesive contact in the area of the cheeks and around the corner of the mouth is only made thereafter. This facilitates the symmetrical application of the face mask (10) so that the longitudinal axis of the face mask (10) coincides with the axis of symmetry of the face of a wearer. The provision of at least two release sheets as disclosed herein above enables a wearer to apply the face mask (10) in this preferred manner.
While a cover layer provided by at least two release sheets (40) is highly beneficial when used for a face mask (10) as disclosed herein, such a cover layer can also beneficially be used for any other article which is intended to cover the respiratory organs of a wearer. Such articles namely include anti-snoring devices, for example, as disclosed in the pending EPO patent application 00120457.7.

## Claims

1. A respiratory face mask comprising:
a flange adapted to fit on a face of a wearer and having an inner periphery and an outer periphery, said flange being symmetrical about a longitudinal axis defining left and right halves of the mask, said flange being wider at 0°, 90° and 180° relative to a central point on the axis than in sectors extending from 40° to 60° and 110° to 130°;
said flange having a wearer facing side and a garment facing side, said wearer facing side having a layer of a hydrogel adhesive having a dry initial peel strength (PDI) and a greasy initial peel strength (PGI), wherein a ratio of PDI to PGI is from 1:1 to 1.0:0.2; and
an air control module carried by said flange.

2. The mask of claim 1, wherein the ratio of PDI to PGI is from 1:1 to 1.0:0.3.

3. The mask of claim 1, wherein the PDI ranges from 0.1 N/cm to 5.0 N/cm.

4. The mask of claim 3, wherein the PGI ranges from 0.1 N/cm to 5.0 N/cm.

5. The mask of claim 1, wherein said layer has a thickness of C mm, wherein said adhesive has a viscous modulus C′′25 (100 rad/sec) at a temperature of 25° C., and wherein G′′25 (100 rad/sec)≦{(7.00+C)*3000} Pa.

6. The mask of claim 5, wherein G′′25 (100 rad/sec)≦{(5.50+C)*1700} Pa.

7. The mask of claim 1, wherein said adhesive has an elastic modulus G′37 (1 rad/sec) at a temperature of 37° C. that ranges from 500 Pa to 20,000 Pa and a viscous modulus G′′37 (1 rad/sec) at a temperature of 37° C. that ranges from 100 Pa to 15,000 Pa, and wherein a ratio of G′37 (1 rad/sec) to G′′37 (1 rad/sec) ranges from 1 to 30.

8. The mask of claim 1, wherein said adhesive is a substantially water insoluble pressure sensitive adhesive comprising a polymer that forms a 3-dimensional matrix and less than 10% by weight hydrocolloid particles.

9. The mask of claim 8, wherein said adhesive comprises less than 5% by weight hydrocolloid particles.

10. The mask of claim 1, wherein said adhesive comprises a polymer selected from the group of polymers consisting of acrylics, sulphonated polymers, vinyl alcohol, vinyl pyrrolidine, polyethylene oxide and mixtures thereof; and a plasticizer selected from the group of plasticizers consisting of polyhydric alcohol, polyethylene glycol, sorbitol, water and mixtures thereof.

11. The mask of claim 1, wherein said air control module comprises means for stretching said air control module.

12. The mask of claim 1, wherein said sectors that are less wide extend from 30° to 70° and 105° to 140°.

13. The mask of claim 12, wherein said sectors that are less wide extend from 20° to 80° and 100° to 150°.

14. The mask of claim 1, wherein said flange is at least 10% wider at 0°, 90° and 180° than in said sectors.

15. The mask of claim 14, wherein said flange is at least 40% wider at 0°, 90° and 180° than in said sectors.

16. The mask of claim 15, wherein said flange is at least 80% wider at 0°, 90° and 180° than in said sectors.