'' Medical article and method to increase the moisture transmission rate.

专利摘要:

公开号:BR112012010858B1
申请号:R112012010858
申请日:2010-11-09
公开日:2018-09-18
发明作者:R Holm David；Zhu Dong-Wei
申请人:3M Innovative Properties Co；
IPC主号:

专利说明:

(54) Title: MEDICAL ARTICLE AND METHOD FOR INCREASING THE HUMIDITY TRANSMISSION RATE.
(51) Int.CI .: A61L 15/00 (30) Unionist Priority: 2/4/2010 US 61 / 301,386, 11/9/2009 US 61 / 259,622 (73) Owner (s): 3M INNOVATIVE PROPERTIES COMPANY ( 72) Inventor (s): DAVID R. HOLM; DONG-WEI ZHU (85) National Phase Start Date: 08/05/2012
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MEDICAL ARTICLE AND METHOD FOR INCREASING THE HUMIDITY STEAM TRANSMISSION RATE
Background of the Invention [001] The description refers to medical articles and, more particularly, to wound bandages and medical tapes for use on the skin and wounds. Wound bandages and tapes may need to adhere to a variety of skin types and remain effective in the presence of varying amounts of moisture, be it a low-exuding wound, a high-exuding wound or a patient who is diaphoretic. In all these cases, the wound bandage or tape is desirably capable of responding to the dynamic levels of moisture present to ensure adequate usage time. Modifications to medical articles to optimize moisture permeability are known and include, for example, selectively or standardly coating an adhesive on a permeable film surface or creating new adhesives with greater moisture permeability. Examples of selective adhesive coating may include a continuous polymeric thin film that has a pressure sensitive adhesive (ASP) that is selectively coated on a surface of the thin polymeric film so that 40 to 75 percent of the film surface does not contain adhesive. Moisture is preferably transmitted through areas without adhesive.
[002] While the standard or selective coating may result in medical articles with higher rates of moisture transmission, the standard coated adhesive may, in certain situations, have poor edge adhesion, resulting in the lifting of the edges. The methods and equipment used for standard adhesive coating can be more expensive and elaborate than the methods and equipment used to coat the adhesive in a continuous film form. In addition, methods and equipment can be very specialized for a particular adhesive system and not interchangeable between
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2/87 different adhesive systems.
[003] Methods for creating different adhesive properties are also known and include adding additives to ASP copolymers. Plasticizers, humectants, inorganic salts, organic salts or microcolloids can be added to a pressure sensitive adhesive to enhance breathability and make the adhesive suitable for medical articles. Such compounds are mixed thoroughly and / or dispersed in the adhesive prior to the construction of a medical article. In this way, the adhesive composition as a whole is made more permeable to moisture by a uniform dispersion or mixture of hydrophilic materials. In many cases, these additives mixed or dispersed evenly can significantly change the properties of the adhesive throughout the adhesive, especially in the presence of conditions with a high moisture content.
Summary of the Invention [004] The present application provides the targeted modification of adhesive systems to optimize the moisture vapor transmission rate (MVTR) by providing a MVTR modifying material that is not uniformly dispersed in the volume of the adhesive layer. In preferred embodiments, the MVTR modifying material is only minimally dispersed, or completely not dispersed in the volume of the adhesive layer. Modalities of the present invention provide medical articles with high MVTR that can be obtained for a wide variety of ASPs instead of or in addition to the standard adhesive coating or formulation of an inherently high MVTR adhesive system that can also properly adhere to the skin under a variety of conditions.
[005] In some embodiments, the pressure sensitive adhesives of the present invention advantageously retain consistent adhesive properties prior to contact with fluid in combination with an MVTR-modifying material. Modalities of the present invention allow the
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3/87 modification of permeability and adhesion in different and controlled locations in an adhesive layer. Since an entire adhesive layer does not need to be modified, portions of the adhesive layer on the side in contact with a target site, for example, the skin, can retain consistent and desirable adhesion properties regardless of the moisture or moisture levels to which the adhesive is applied. exposed during storage or use.
[006] In one embodiment, the present invention features a medical article (for example, a wound bandage, a medical tape, a surgical dressing, etc.) that includes: an ASP layer that includes acidic functional groups or basic functional groups , with ASP including at least 0.84 mmols of acidic or basic functional groups per gram of ASP; and an MVTR modifying material that is basic when ASP includes acidic functional groups or is acidic when ASP includes basic functional groups; the modifying material of MVTR is immiscible with ASP, and reacts with the functional groups by contact to form a poly salt in the presence of fluid.
[007] In some embodiments, the adhesive contains more than 0.42 mmols of acidic or basic functional groups per gram of ASP that can be neutralized by the MVTR modifying material. Most preferably, the adhesive contains at least 0.69 mmols of these functional groups per gram of ASP. Most preferably, the adhesive contains 0.84 mmols of these functional groups. Most preferably, the adhesive contains at least 1.3 mmols of these functional groups. Most preferably, the adhesive contains at least 1.80 mmols of these functional groups. Most preferably, the adhesive contains at least 2.08 mmols of these functional groups. In most embodiments, the adhesive contains between 1.3 mmols and 2.5 mmols of these functional groups.
[008] Preferably, the sticker should contain no more than
5.6 mmols of these functional groups per gram of ASP. More preferably,
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4/87 the adhesive contains no more than 4.2 mmols of these functional groups per gram of ASP, and most preferably not more than 2.8 mmols of these functional groups per gram of ASP.
[009] In certain embodiments, ASP comprises a functional polymer, and the polymer is prepared from at least 6% by weight of acidic or basic functional monomers based on the total weight of ASP. In certain embodiments, the functional polymer is a (meth) acrylate (i.e., (meth) acrylic polymer).
[010] In certain embodiments, the medical articles of the present invention include an amount of MVTR-modifying material in relation to the functionalized groups in the ASP so that the molar ratio between the MVTR-modifying material and the acid / basic functional groups is within a range from 0.1: 1 to 100: 1 per volume of adhesive under the surface area treated with the MVTR modifying material.
[011] Various constructions of medical articles are provided. In one embodiment, the modifying material of the MVTR is arranged on a surface of the ASP layer. In some embodiments, the MVTR modifying material can be coated in a standard manner on the surface of the ASP layer.
[012] If desired, a second layer of ASP can be included, which can be the same or different from the first layer of ASP, with the modifying material of the MVTR being disposed between the two layers of ASP.
[013] In certain embodiments, the medical articles of the present invention include a framework. In certain embodiments, the modifying layer of the MVTR includes the framework. In certain preferred embodiments, the modifying material of the MVTR is incorporated within a framework that is in contact with the ASP layer. The framework can include a variety of
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5/87 suitable substrates to function as a vehicle for the MVTR modifying material. In a preferred embodiment, the framework is a non-woven fabric.
[014] In certain embodiments, the medical articles of the present invention include a support (i.e., a support layer) and the MVTR modifying material is disposed between the ASP layer and the support. In certain embodiments, the modifying material of the MVTR is in contact with the ASP layer and the support.
[015] In certain embodiments, the medical articles of the present invention include a pH modifying layer, the MVTR modifying material being disposed between the ASP layer and the pH modifying layer. In certain embodiments, the pH-modifying layer includes a pH-modifying material selected from the group consisting of polyacrylic acid, citric acid, lactic acid, or combinations thereof. In certain embodiments, the MVTR modifying material is in contact with the ASP layer and the pH modifying layer.
[016] In certain embodiments, the medical articles of the present invention include a filtration layer, the filtration layer being disposed between the MVTR modifying material and a source of fluid or target site (e.g., an injury).
[017] In certain embodiments, medical articles, particularly wound bandages, of the present invention include an absorbent layer or pad, the absorbent layer of which includes a polymeric fabric, a polymeric foam, or a combination thereof.
[018] In certain embodiments, the medical articles of the present invention include a carrier film in contact with the ASP layer; an absorbent pad arranged between the carrier film and the adhesive layer; and a support arranged between a support layer and the ASP layer.
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6/87 [019] In certain embodiments, the medical articles of the present invention include an ASP layer that includes acidic functional groups, and a MVTR modifying material that is basic. For these ASPs, the MVTR modifying material includes a base selected from a group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, silver hydroxide, zinc hydroxide, ammonium hydroxide, hydroxide magnesium, barium hydroxide, strontium hydroxide, cesium hydroxide, rubidium hydroxide, ammonium carbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, silver carbonate, lithium carbonate, lithium bicarbonate , barium bicarbonate, magnesium carbonate, cesium carbonate, hydrates thereof, and combinations thereof. Preferably, the MVTR modifying material is not a multivalent cation that can cause crosslinking of ASP polymers to the extent that this crosslinking reduces MVTR to wet.
[020] In certain embodiments, the medical articles of the present invention include an ASP layer that includes basic functional groups, and an MVTR-modifying material that is acidic. For these ASPs, the MVTR modifying material includes, for example, an acid capable of reacting with an amine group to form a poly salt.
[021] In certain embodiments, ASP includes rubber-based adhesives (for example, tachyed natural rubbers, synthetic rubbers, and styrene-butadiene block copolymers), (meth) acrylics (ie, (meth) acrylates), poly (alpha-olefins), polyurethanes, and silicones. In certain embodiments, ASP includes an amine adhesive (for example, which includes a polymer with basic amine groups in the main chain, pending on the main chain, or both). In certain embodiments, ASP includes a polymer that has carboxylic acid groups. In certain embodiments, the acid groups, or part of the acid groups in the ASP, can be incorporated by mixing
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7/87 tackiness or other additives with the polymers mentioned above.
[022] In certain embodiments, the medical articles of the present invention have a wet MVTR of at least 1200 g / ^m2 / 24 hours. In certain embodiments, the MVTR modifying material improves (i.e., increases) the wet MVTR of the medical article by at least 20% over the same article without the MVTR modifying material. In certain embodiments, the MVTR modifying material improves (i.e., increases) the dry MVTR of the medical article by at least 10% over the same article without the MVTR modifying material.
[023] In certain embodiments, the ASP layer does not include MVTR modifying material dispersed completely evenly.
[024] In one embodiment, the present invention features a wound bandage that includes: a support that has a first main surface and a second main surface; a layer of ASP arranged on at least a portion of the first main surface of the support; the ASP includes acidic functional groups or basic functional groups, with the ASP including at least 0.84 mmols of the functional groups per gram of ASP; and an MVTR modifying layer close to the ASP layer; the MVTR modifying layer includes an MVTR modifying material which is basic when ASP includes acidic functional groups, or is acidic when ASP includes basic functional groups; the modifying material of MVTR is immiscible with ASP, and reacts with the functional groups by contact to form a poly salt in the presence of fluid. In certain embodiments, the modifying layer of MVTR is in direct contact with at least a portion of the ASP layer. In certain embodiments, one or more layers are arranged between the MVTR modifying layer and the ASP layer.
[025] In one embodiment, the present invention features a wound bandage that includes: a support that has a first
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8/87 main surface and a second main surface; a layer of ASP arranged on at least a portion of the first main surface of the support; the ASP includes acidic functional groups; a support layer attached releasably to the second main surface of the support; and an MVTR modifying layer that includes MVTR modifying material in contact with the ASP layer, the ASP layer does not include MVTR modifying material dispersed completely evenly; Since the modifying material of MVTR is basic, it is immiscible with ASP, and reacts with functional groups through contact to form a poly-salt in the presence of fluid. Preferably, the ASP includes at least 0.84 mmols of the functional groups per gram of ASP.
[026] In one embodiment, the present invention features a wound bandage that includes: a support that has a first main surface and a second main surface; a layer of ASP arranged on at least a portion of the first main surface of the support; the ASP includes a (meth) acrylate polymer that has acidic functional groups, the polymer being prepared from at least 6% by weight of acidic functional monomers based on the total weight of the ASP; a support layer attached releasably to the second main surface of the support; and an MVTR-modifying layer that includes a MVTR-modifying material in contact with the ASP layer; Since the modifying material of MVTR is basic, it is immiscible with ASP, and reacts with functional groups through contact to form a poly-salt in the presence of fluid.
[027] The present invention additionally provides methods for increasing the MVTR of an adhesive layer in a medical article. In one embodiment, the method includes: providing a layer of ASP that includes acidic functional groups or basic functional groups, with ASP including at least 0.84 mmols of functional groups per gram of ASP; provide a material
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9/87 MVTR modifier which is basic when ASP includes acidic functional groups or is acidic when ASP includes basic functional groups, the MVTR modifying material being immiscible with ASP; and placing the MVTR-modifying material in the medical article in a location that allows the MVTR-modifying material to contact the ASP when the medical article comes into contact with the fluid during use (for example, when applied to the skin or wound of a an individual); the contact between the MVTR modifying material, ASP, and the fluid causes an acid-base reaction to form a poly-salt and increase the moisture permeability of at least a portion of the ASP layer.
[028] In one embodiment, the method includes: providing an ASP layer that includes a polymer that has acidic functional groups or a polymer that has basic functional groups, the polymer being prepared from at least 6% by weight of total acidic or basic functional monomers, based on the total weight of ASP; provide a MVTR modifying material that is basic when the ASP includes an acidic functional group or is acidic when the ASP includes a basic functional group, the MVTR modifying material being immiscible with the ASP; and placing the MVTR modifying material in the medical article in a location that allows the MVTR modifying material to contact the ASP when the medical article comes in contact with fluid during use; the contact between the modifying material of the MVTR, the ASP, and fluid causes an acid-base reaction to form a poly-salt and increase the moisture permeability of at least a portion of the ASP layer.
[029] In certain method modalities, placing the MVTR modifying material in the medical article in a location that allows the MVTR modifying material to contact the ASP includes coating (for example, standard coating) the MVTR modifying material on the ASP layer.
[030] In certain method modalities, the placement of the
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10/87 MVTR modifying material in the medical article in a location that allows MVTR modifying material to contact the ASP includes: providing a framework; cover the framework with the MVTR modifying material; and placing at least a portion of the ASP layer in contact with the coated framework. This could be done in addition to directly coating the modifying material of the MVTR over the ASP layer.
[031] The ability to modify the MVTR, instead of (or in addition to) the standard coating of an adhesive on a permeable film or mixture of hydrophilic additives to the adhesive in the batch, makes the present invention particularly well suited for medical articles such as, for example, medical tapes, bandages, feminine hygiene pads, diapers, surgical dressings, and various wound bandages. A professional or manufacturer can effectively control the level of moisture permeability for a given portion of an adhesive layer, allowing for a close adaptation to the nature and needs of the patient's illness. Instead of a compromise between adhesion and permeability, the present invention allows for the optimization of these two characteristics.
[032] In the present invention, fluid means water, water vapor, serum, wound secretion, sweat, and other liquid or vapor compositions.
[033] In the present invention, layer means a single layer that can be continuous or discontinuous on a surface.
[034] In the present invention, absorbent means that the material is preferably capable of absorbing fluids, particularly bodily fluids.
[035] In the present invention, poly-salt means a polymer that has at least one ionic group.
[036] In the present invention, immiscible or incompatible means that a material is unable to penetrate the core of a 0.25 cm (cm) cross section of an adhesive layer. To examine
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11/87 the immiscibility, a small portion of an adhesive polymer can be cut into a strip 0.25 cm thick X 2.5 cm wide X 10 cm long. The polymer is then placed in contact with the MVTR modifying material for 24 hours at 25 ° C and 20% to 50% relative humidity. A cross section of the adhesive strip is then analyzed for the presence of MVTR modifying material in the center of the section. An incompatible or immiscible MVTR modifying material will only penetrate the adhesive polymer slightly if it does, but not into the core (ie, center) of a 0.25 cm cross section of an adhesive layer.
[037] In the present invention, medical article means wound bandages, surgical dressings, tapes, dressings, diapers, feminine hygiene articles, and combinations thereof. Preferred medical articles include tapes, wound bandages, and bandages.
[038] In the present invention, ASP comprising an acidic functional group, polymer comprising an acidic functional group, ASP comprising acidic functional groups or polymer comprising acidic functional groups means that the ASP, or polymer included therein, has an excess of acidic groups (e.g. carboxylic acid groups) if there are acid groups and basic groups, so that the ASP, or polymer included in it, is acid.
[039] In the present invention, ASP comprising a basic functional group, polymer comprising a basic functional group, ASP comprising basic functional groups or polymer comprising basic functional groups means that the ASP, or polymer included in it, has an excess of basic groups, if there are acid groups and basic groups, so ASP, or the polymer included in it, is basic.
[040] The terms comprise and variations thereof do not have a limiting meaning, these terms appearing in the description and in the claims
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12/87 [041] The words preferential and preferably refer to the modalities of the invention that can provide certain benefits, under certain circumstances. However, other modalities may also be preferred under the same or other circumstances. In addition, the mention of one or more preferred modalities does not imply the disuse of other modalities and is not intended to exclude other modalities from the scope of the invention.
[042] For use in the present invention, one, one, o, a, at least one, at least one, one or more and one or more are used interchangeably. In this way, for example, an adhesive polymer comprising an acid functional group can be interpreted as meaning that the adhesive polymer includes one or more acid functional groups. Similarly, a medical article comprising a filtration layer can be interpreted to mean that the article includes one or more layers of filtration.
[043] For use in the present invention, recitations of numeric ranges of integers include all numbers included within this range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80 , 4, 5, etc.).
[044] The previous summary of the present invention is not intended to describe each of the presented modalities or all implementations of the present invention. The following description more particularly illustrates the illustrative modalities. In several places, during application, guidance is provided through lists of examples, in which examples can be used in various ways. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list.
Brief Description of the Drawings [045] The invention will be further described with reference to the drawings, the corresponding reference characters indicating corresponding parts through all the countless views and being that:
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13/87 [046] Figure 1 is a top view of a wound bandage according to an embodiment of the present invention.
[047] Figure 2a is a side view of the injury bandage in figure 1.
[048] Figure 2b is a side view of the wound bandage according to an alternative embodiment of the wound bandage in figure 1.
[049] Figure 3a is a side view of a wound bandage according to an additional embodiment of the present invention.
[050] Figure 3b is a side view of the wound bandage according to an additional embodiment of the present invention.
[051] Figure 4 is a side view of a wound bandage in another embodiment of the present invention.
[052] Figure 5 is a side view of a wound bandage according to an additional embodiment of the present invention.
[053] Figure 6 is a side view of a medical tape according to an embodiment of the present invention.
[054] Figure 7 is a side view of a medical tape in another embodiment of the present invention.
[055] Figure 8 is a side view of a medical article in another embodiment of the present invention.
[056] Figure 9 is a side view of a medical article according to an embodiment of the present invention.
[057] Figure 10 is a top view of a wound bandage in another embodiment of the present invention.
[058] Figure 11 is a cross-sectional view of the wound bandage in Figure 10.
[059] The MVTR modifying material can be shown in the
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14/87 figures as confined to different portions of the wound bandage. This, however, is not intended to limit the location or relative concentration of the MVTR modifying material, unless specifically noted. The layers in the modalities shown are for illustrative purposes and are not intended to define the relative thickness or position of any component.
Detailed Description of the Illustrative Modalities [060] The present invention relates to a medical article that has an ASP layer and methods of preparing medical articles more permeable to moisture. Through the use of different modifying materials from MVTR and different concentrations of modifying materials from MVTR, the ASP layer can be modified to satisfy desired adhesion properties and moisture vapor transmission properties. For example, the modified wound bandages of the present invention may have a relatively low dry MVTR and a relatively high wet MVTR that vary at locations within the bandage and adhesion properties that vary within the bandage. These properties of the MVTR allow the wound under the bandage to heal in wet conditions without causing the skin surrounding the wound to become macerated and to facilitate optimal usage time and ease of removal.
[061] In some embodiments of the invention, a modifying layer of MVTR includes the modifying material of MVTR that interacts with the acidic or basic functional groups in an ASP layer. For example, if the ASP includes basic functional groups, the MVTR modifying material will be acidic. Similarly, if the ASP includes acidic functional groups, the MVTR modifying material will be basic. The modifying material of the MVTR can be placed on or near a surface of the ASP layer. Although it is not desired to stick to the theory, when the medical article is placed on a patient at a target site, the fluid can cause the material
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15/87 MVTR modifier interacts with the acid / basic groups of the polymer, resulting in an increase to the MVTR of the ASP layer.
[062] In the present invention, dry MVTR (or vertical MVTR) of the ASP layer, or of the medical article, is measured by the ASTM E-96-80 method (American Society of Testing Materials) at 40 ° C and 20% of relative humidity using a vertical cup method. The wet MVTR (or inverted MVTR) is measured by the same method, with the exception that the sample jars are inverted so that the water is in direct contact with the test sample.
[063] Factors influencing MVTR include, but are not limited to, the thickness of the ASP layer, the amount of hydrophilic ingredients in the ASP, concentration of acidic / basic functionality within the ASP layer and the amount of MVTR modifying material , the composition and structure of the backing film, the structure of the coating (i.e., continuous, fibrous, film, or pattern) of the adhesive, and the general construction of a medical article (e.g., number and arrangement of multiple layers, films, etc.).
[064] When compared to the dry MVTR of an untreated medical article of identical composition and construction with a continuous layer of adhesive, the dry MVTR of the medical article that was treated with the MVTR modifying composition according to the present invention it is preferably larger than the untreated medical article by a factor of at least 1.2 (at least 20%) more, preferably at least 3, more preferably at least 5, and most preferably, at least 10.
[065] When compared to the wet MVTR of an untreated medical article of identical composition and construction, the wet MVTR of the medical article that has been treated with a MVTR-modifying material according to the present invention is preferably greater that the medical article not treated by a factor of at least 1.2 (at least 20%) more, preferably at least 3, more preferably at least 5 and, even more preferably, at least
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16/87 least 10. The medical article that has been treated is preferably a wet MVTR of at least 1200 g / ^m2 / 24 hours, more preferably at least 3000 g / ^m2 / 24 hours, more preferably at least 7500 g / ^m2 / 24 hours, even more preferably at least 15000 g / ^m2 / 24 hours. Different regions of the medical article may include different MVTR values.
[066] The ASP layer is modified by the modifying material of MVTR due to interfacial interactions as a result of an acid-base interaction between the two materials. This acid-base interaction is a Lewis-acid-base interaction. Lewis acid-base interactions require that one chemical component be an electron acceptor (acid) and the other an electron donor (base). The electron donor provides an unshared electron pair and the electron acceptor provides an orbital system that can accommodate the additional electron unshared pair. The following general equation describes the Lewis acid-base interaction:
A (acid) +: B (base) A: B (acid-base complex).
[067] The MVTR modifying material is immiscible or incompatible with the ASP layer when the article is not in contact with the fluid, such as water or moisture. Consequently, the MVTR modifying material will not react appreciably with the adhesive until the fluid is present. When the MVTR modifier material does not interact with the adhesive layer in the presence of fluid, an Lewis acid-base reaction occurs and portions of the adhesive in contact with the MVTR modifier material are neutralized. This neutralization and the creation of ionic bonds increases the polarity of different portions of the adhesive layer, which results in an increased MVTR. In essence, this makes it possible to modify the MVTR on demand (for example, when applied dry to the target site and placed in contact with fluid). Alternatively, the fluid (for example, water) could be added to the medical article prior to packaging.
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17/87 [068] The modification of the ASP by the modifying material of the MVTR is independent of the particular functionality of the respective ASP and the modifying material of the MVTR. That is, either the ASP or the MVTR modifying material may contain acidic or basic functionality. For example, an acid functionalized polymer in the adhesive layer can be paired with a basic MVTR modifying material. Alternatively, a basic functionalized polymer of the adhesive layer can be paired with an acidic MVTR modifying material.
[069] In one embodiment of the invention, the MVTR modifying material comprises an inorganic base. Suitable examples of inorganic bases are sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, silver hydroxide, zinc hydroxide, ammonium hydroxide, magnesium hydroxide, barium hydroxide, strontium hydroxide, cesium hydroxide, rubidium hydroxide, sodium carbonate, ammonium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, silver carbonate, lithium carbonate, lithium bicarbonate, barium bicarbonate, magnesium carbonate, cesium carbonate, hydrates of these inorganic bases, or combinations thereof. In preferred embodiments, the modifying material of MVTR is sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, or hydrates thereof. Various combinations can be used, if desired. Preferably, the MVTR modifying material is not a multivalent cation that can cause crosslinking of ASP polymers to the extent that this crosslinking reduces MVTR to wet. In certain embodiments, the MVTR modifying material has a solubility in water at 25 ° C greater than 50 mg / L.
[070] In another embodiment of the invention, the modifying material of MVTR is an organic base. Suitable organic bases include, but are not limited to, poly (ethyleneimine), poly (ethyloxazoline), and other polymers
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18/87 containing amino functional groups such as, for example, poly (N, N-dimethyl amino acrylate ethyl ethyl). The appropriate organic bases must be incompatible with or immiscible in ASP.
[071] In some embodiments, the MVTR's modifying material includes an acidic functionality. The acid modifying material of MVTR can be inorganic or organic acids. Suitable examples of inorganic acids include, but are not limited to, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and mixtures thereof. Organic acids can be used, but should be limited to non-miscible / ASP-compatible compounds having basic functionality, such as formic acid. Preferably, the organic acid is monofunctional.
[072] In addition to the MVTR modifying material, a MVTR modifying layer can also include other materials incompatible / immiscible with ASP that can also help to optimize MVTR or other properties, but do not react appreciably with acidic functional groups. or basic in ASP. Suitable materials include, for example, sodium chloride and potassium chloride.
[073] The polymers suitable for ASPs in the present invention are those containing acidic or basic functionalities that generate ionic functionalities in neutralization. In addition or alternatively, the acid groups, or part of the acid groups, in the ASP can be incorporated by mixing acid-functional tackiness enhancers or other acid-functional additives with the ASP polymers. These groups, as part of the ASP polymer or as part of other additives, can be the same or different. Similarly, basic groups, or part of basic groups, in ASP can be incorporated by mixing stickiness enhancers or other additives with ASP polymers. These groups, as part of the ASP polymer or as part of other additives, can be the same or different.
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19/87 [074] For use in the present invention, an acid functional polymer is a polymer that includes acid functional groups, which can, for example, be derived from at least one acid monomer and at least one non-acid copolymerizable monomer (i.e. that is, a monomer that cannot be titrated with a base). Alternatively, the polymers can be chemically modified to include acid functional groups. The acidic polymer may optionally include other copolymerizable monomers, such as, for example, vinyl monomers and basic monomers, as long as the resulting polymer can still be titrated with a base. In this way, more acidic monomers are generally used to prepare acidic polymers than basic monomers. The acidic functional groups in any polymer can be the same or different.
[075] A basic functional polymer is a polymer that includes basic functional groups, which can, for example, be derived from at least one basic monomer and at least one non-basic copolymerizable monomer (that is, a monomer that cannot be titrated with an acid). Alternatively, the polymers can be chemically modified to include basic functional groups. Other monomers can be copolymerized with the basic monomers (for example, acid monomers, vinyl monomers, and (meth) acrylate monomers), as long as the basic copolymer retains its basicity (that is, it can still be titrated with an acid) . In addition, a basic functional polymer can be an amine-containing polymer, with the amine groups being on the main chain, pending on it, or both. The basic functional groups in any polymer can be the same or different.
[076] For a given treatment area, defined as the volume of ASP confined within the surface area of a nearby MVTR modifying layer or in contact with a pressure sensitive adhesive layer, the level of MVTR modifying material needed to increase the MVTR
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20/87 through the adhesive is based on the relative molar quantities of basic / acidic functional groups of the MVTR modifying material and the acidic / basic functional groups of the adhesive that are available for neutralization for a given treatment area. Preferably, the molar ratio between the MVTR modifying material and the total acid / basic functional groups in the adhesive by a given treated volume (ie, the volume under the treated surface area) needs to be in the range of 0.1: 1 to 100: 1. Most preferably, this ratio is 0.2: 1 to 50: 1, and most preferably 0.4: 1 to 25: 1.
[077] In some embodiments, the adhesive contains more than 0.42 mmols of acidic or basic functional groups per gram of ASP that can be neutralized by the MVTR modifying material. Most preferably, the adhesive contains at least 0.69 mmols of these functional groups per gram of ASP. Most preferably, the adhesive contains 0.84 mmols of these functional groups. Most preferably, the adhesive contains at least 1.3 mmols of these functional groups. Most preferably, the adhesive contains at least 1.80 mmols of these functional groups. Most preferably, the adhesive contains at least 2.08 mmols of these functional groups. In most embodiments, the adhesive contains between 1.3 mmols and 2.5 mmols of these functional groups.
[078] Preferably, the adhesive should contain no more than
5.6 mmols of these functional groups per gram of ASP. More preferably, the adhesive contains no more than 4.2 mmols of these functional groups per gram of ASP, and more preferably not more than 2.8 mmols of these functional groups per gram of ASP.
[079] In some embodiments of the present invention, the MVTR modifying material is in direct contact with the ASP layer. The modifying material of the MVTR can be disposed directly on the surface or can alternatively be incorporated into a framework creating, in both
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21/87 circumstances, a modifying layer of MVTR in contact with a surface of the ASP layer. The modifying layer of MVTR can extend continuously through a portion of the ASP layer or can be arranged in different locations. In additional embodiments of the present invention, a filtration layer can be arranged between the target site and the MVTR modifying layer or, alternatively, between the ASP layer and the MVTR modifying layer. In other embodiments of the invention, a pH-modifying layer is arranged between the target site and the MVTR-modifying layer to modify the pH. In some embodiments, the medical article of the present invention may include a support layer (i.e., a support). In another embodiment, the modifying layer of MVTR can be arranged between the first and second layers of ASP.
[080] The methods described here involve the use of an aqueous solution (ie, water) to lay the MVTR modifying material on a substrate (for example, the ASP layer, the framework, etc.). It is also envisaged that other solvents known to those skilled in the art can be used. As can also be understood by those skilled in the art, the methods can use a pure MVTR-modifying composition (i.e., without a solvent).
[081] Starting with reference to figures 1 and 2a, a wound bandage is shown according to a modality of the description. Figure 1 is a top view of the wound bandage, and Figure 2 is a side view of the wound bandage of Figure 1. The wound bandage 10 includes a support layer 12, an ASP layer 14 on a layer surface. support layer 12, and a modifying layer of MVTR 16 attached to a portion of the ASP layer 14. The modifying layer of MVTR 16 does not extend completely to the periphery 18 of the ASP layer 14, so that portions of the exposed surface 20 of the layer ASP 14 does not
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22/87 are in contact with the MVTR modifying layer 16. It is also contemplated that, in some modalities, the MVTR modifying layer extends to the periphery of the ASP layer, in which the MVTR modifying layer and the ASP layer are coextensive.
[082] According to the modality shown in figures 1 and 2a, the modifying layer of MVTR 16 is composed of a framework 22 and a modifying material of MVTR 24 incorporated in or deposited on the surface of said framework 22. Exemplary materials useful for the framework are described in more detail below. As shown in figure 2a, the modifying layer of MVTR 16 is a layer over a portion of the ASP 14 layer. The modifying layer of MVTR 16 can be located centrally on the surface of the ASP 14 layer, or it can be displaced anywhere direction. The location of the MVTR modifying layer 16 in relation to the center of the bandage can be guided by the nature and location of the target site and the intended application of the modified adhesive layer 14. A given treatment area can be defined by the portions of the MVTR modifying layer. 16 in contact with or attached to the surface of the ASP 14 layer. This limited contact area and the relative molar concentrations of the reactive groups can serve to prevent the entire ASP 14 layer from being modified by the MVTR 24 modifying material. The targeted modification in the treatment area it can allow portions of the ASP 14 layer to retain desirable adhesion to the skin when they come in contact with fluid.
[083] MVTR's modifying material can be impregnated or deposited on the framework using any suitable method to add the desired functionality to a substrate. Figure 2a represents the last modality, in which framework 22 is impregnated with the modifying material of MVTR 24. In one embodiment, the framework is coated by immersion in an aqueous solution containing a concentration of the material
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23/87 MVTR modifier. The framework is saturated and then extracted from the aqueous solution. The framework is then dried. It is also contemplated that the framework retains some moisture when placed in contact with the ASP layer.
[084] Figure 2b represents another modality, in which the modifying material of the MVTR 24 is deposited on a surface of the framework 22. In this modality, the modifying material of the MVTR is non-uniformly coated on the framework 22, or otherwise impregnated with it . In one embodiment, the framework is coated by immersion in an aqueous solution containing a concentration of the modifying composition of the MVTR. The framework is saturated and then extracted from the aqueous solution. An aqueous solution used in the aforementioned method can also include a concentration of C1-C4 alcohol that is easily removed during drying.
[085] MVTR's modifying material can be placed on a surface of the framework or adhesive layer in any number of patterns, including, but not limited to, distinct cavities, parallel rows or columns, and interlocking networks. The same methods could be used to directly apply the modifying material of the MVTR to the ASP layer.
[086] In additional embodiments of the invention, the incorporation of the MVTR modifying material can be achieved by coating the surfaces or by impregnating substrates with solutions, pure materials, or loading by blanket particles. These coating or impregnation methods include dip coating, spray coating, standard coating using an engraving roller, blade coating, slit matrix coating, inkjet printing, powder coating, or particle loading. blankets.
[087] Once frame 22 has been impregnated or coated with the modifying material of MVTR 24 to form the layer
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24/87 modifying MVTR 16, the modifying layer of MVTR 16 can be attached to the ASP 14 layer by methods known to those skilled in the art of conversion, lamination, coating, and / or basting.
[088] Alternatively or additionally, the MVTR modifying material can be applied directly to the ASP layer and / or the support layer. For example, ASP can be laminated directly or applied as a coating on a substrate that is coated with the MVTR modifying material. For an island-type bandage, individual blocks containing the MVTR modifying material can be cut from a blanket and placed on an adhesive-coated support using rotary conversion or other known conversion methods. For a product with multiple layers, there are a variety of methods of fixing the MVTR modifying material to the adhesive layer, such as, for example, lamination and rotary conversion, and other conversion methods known to those skilled in the art.
[089] Figures 3a and 3b show additional embodiments of the invention. A wound bandage 30 may also include a filtration layer 32 in addition to an adhesive layer 34 and an MVTR modifier layer 36. Like the MVTR modifier layer 16 of the previous embodiment, the MVTR modifier layer 36 comprises a frame 38 and a modifying material from MVTR 40. The filtration layer 32 does not initially incorporate a modifying material from MVTR, although during use, the modifying material from MVTR may migrate into and through the filtration layer 32.
[090] In the embodiment shown in figure 3a, the filtration layer 32 is disposed between the adhesive layer 34 and the modifying layer of MVTR 36. Consequently, the modifying layer of MVTR 36 and the volume of the modifying material of MVTR 40 are not in contact with adhesive layer 34 when the wound bandage is initially placed
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25/87 on the target site. As the fluid is generated and secreted by the wound or other target site, the MVTR 40's modifying material can migrate with the fluid through the filtration layer 32 to the adhesive layer 34. It is also contemplated that ambient humidity can carry small amounts of material modifier of the MVTR 40 into the filtration layer 32 before use. The filtration layer 32 can be used to selectively filter molecules that may be present in the fluid generated by the wound or other target site. The aforementioned filtration can occur physically, with a specifically designed porosity, for example.
[091] Figure 3b represents an alternative embodiment of the invention, in which a filtration layer 32 is arranged on the side facing the target site (for example, side facing the wound) of the modifying layer of MVTR 36. In this embodiment, the filtration layer 32 serves to reduce the neutralization or premature deactivation of the modifying material of the MVTR 40 before it can interact with the adhesive layer 34. The filtration layer 32 can be used to selectively filter molecules that may be present in the fluid generated by the injury or other target site. The aforementioned filtration can occur physically, with a specifically designed porosity, for example. It is also contemplated that a second filtration layer can be positioned between the adhesive layer 34 and the MVTR modifying layer 36, as shown in figure 3a. The filtration layer 32 could, alternatively or additionally, be a pH modifying layer.
[092] With reference to figure 4, another modality includes a pH 42 modifier layer disposed between the MVTR 36 modifier layer and the target site. The pH-modifying layer 42 includes a pH-46 modifying material. In some embodiments, the pH-46 modifying material has a different pKa or pKb from the pKa or pKb of the MVTR 40 modifying material. The pH-modifying material may include citric acid , polyacrylic acid, other materials
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26/87 pH modifiers known to those skilled in the art, and combinations thereof. For example, the pH 42 modifying layer could include citric acid, and the MVTR modifying material can be sodium carbonate. The inclusion of the pH 42 modifying layer with the pH 46 modifying material to the medical article can provide buffering capabilities in order to reduce the overall pH change of the fluid as it passes through the layers. Although it is not desired to stick to the theory, the pH 42 modifier layer, in this modality, can also serve to prevent the MVTR 40 modifier material from adversely modifying the pH of a target site. Although not shown in figure 4, the pH-modifying layer 42 can extend beyond the periphery of the MVTR-modifying layer and can be attached to the adhesive layer 34.
[093] The filtration layer 32 and / or the pH 42 modifier layer may include material that is the same or similar to the framework 38. The filtration layer 32 and / or the pH 42 modifier layer may also include a different material, although preferably one that is capable of absorbing moisture. The pH 46 modifying material can be incorporated within a second framework 44 or deposited on its surface by the use of various methods, as described above.
[094] Figure 5 represents a wound bandage according to an embodiment of the invention. Unlike other modalities previously shown, the wound bandage 50 includes a discontinuous MVTR modifying layer 56. As shown in Figure 5, the MVTR modifying layer 56 is composed of two or more frameworks (58 and 60) in separate portions of the adhesive layer 54. Both frames (58 and 60) can incorporate MVTR modifying material (62 and 64). The modifying material of MVTR 64 incorporated in the first framework 58 can be the same as the modifying material of MVTR 62 incorporated in the second framework 60,
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27/87 so that the MVTR of the adhesive layer 54 exposed to the MVTR modifying material (62 and 64) is essentially the same. It is also contemplated that the two MVTR modifying materials (62 and 64) may be different or may be present in different concentrations, so that portions of adhesive layer 54 may have different MVTRs.
[095] The concepts of the present invention can also be used to create surgical tapes or similar articles. Figure 6 represents one of these modalities. Surgical tape 68 includes a backing layer 70 and a pressure sensitive adhesive layer 72 on a surface of the backing layer 70. The modifying material of the MVTR 74 is incorporated into the backing layer 70 by the methods described above.
[096] In an alternative embodiment, the modifying material of the MVTR can be deposited, coated, or placed directly on a surface of the ASP layer. As shown in figure 7, medical article 80 comprises a layer of ASP 84 disposed on a support layer 82. The modifying layer of MVTR 85 includes distinct portions of MVTR 86 modifying material, but does not include a framework on the surface facing the target site. Alternatively or additionally, the ASP 84 layer may also include sections of MVTR 86 modifying material on distinct portions of the surface between the ASP 84 layer and the backing layer 82. It is contemplated, although not described, that the The embodiment further includes filtration layers attached to the surface facing the target site of adhesive layer 84.
[097] The MVTR 86 modifying material can be brought into contact with adhesive layer 84 by various methods, as described above, including, but not limited to, standard spray and powder coating. In operation, this MVTR modification method allows for selective and localized modification of moisture permeability and adhesion without
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28/87 the inclusion of a framework.
[098] Figure 8 represents another embodiment of the description, in which a modifying layer of MVTR 94 is disposed between a support layer 92 and a layer of ASP 96. The modifying layer of MVTR 94 may include a framework (not shown) and a modifying material of MVTR. The modifying layer of MVTR 94 can be extended over the entire surface of the adhesive layer 96. It is also contemplated (although not shown) that the layer of ASP 96 and the support layer 92 may extend beyond the periphery of the modifying layer of MVTR 94.
[099] The support layer 92 can be extruded directly over the MVTR modifying layer 94. The construction of the MVTR modifying layer and support layer can then be laminated directly over the ASP 96 layer. lamination can be found, for example, in European patent No. 1,255,575.
[0100] An additional embodiment of the description is shown in figure 9. A wound wick 100 can include two support layers (102 and 04) functionally attached to two ASP layers (106 and 108). The ASP 106 layer can be laminated or otherwise attached to the ASP 108 layer, so that the support and ASP layers partially confine a modifying layer of MVTR 110. The wound wick 100 has an exposed portion 112 of the modifying layer of MVTR. MVTR 110.
[0101] An additional embodiment of the description is a kit (not shown) that includes an MVTR modifying layer, an ASP layer, and a support layer. The MVTR modifying layer may comprise a framework that includes MVTR modifying material. The ASP layer can be supplied laminated or otherwise attached to the backing layer. The framework can be provided separately from ASP and support. In
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29/87 preferably, no portion of the framework contacts a surface of the ASP layer prior to use. The framework can be placed at any desired location on the surface of the ASP layer, on the surface of the support layer, or close to any of them. The shape and / or size of the framework can also be modified, if desired. It is also contemplated that the modifying material of MVTR can be supplied separately (that is, without a framework) so that it can be deposited, coated, or placed directly on a surface of the ASP layer by the professional.
[0102] Other components can also be added to the previous embodiments of the present invention without exceeding the scope of the present invention. For example, an absorbent layer can be arranged between the target site and the modifying layer of MVTR. The absorbent layer may include one or more impregnation layers, including, but not limited to, polymeric films, gels, alginates, and foams. Exemplary absorbent foams are described in U.S. Patent No. 6,548,727 (Swenson). In one embodiment, the absorbent layer comprises the foam used in the adhesive foam dressing available from 3M Company, St. Paul, MN, USA under the trade name TEGADERM.
[0103] In an embodiment in which the absorbent layer includes a pad, the absorbent pad is sometimes called an island pad because the backing layer and the ASP layer extend substantially beyond at least a portion of the periphery of the absorbent pad , and typically beyond the entire periphery of the absorbent pad. For example, the diameter of the absorbent pad can be, for example, 7.5 cm, while a support for this pad can be 12.5 cm in diameter.
[0104] The backing layer may include a transparent elastic polymeric film (eg, urethane) that has a thickness of no more than 1 mm. The construction of the support layer in this modality must be
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30/87 sufficiently rigid so that it does not bend over itself when it is not adequately supported by a support layer (as further described below) or by the absorbent pad. Portions of the backing layer can be as thin as 0.012 mm (12 microns).
[0105] Modalities of the present invention may also include, a support layer at least partially attached to the support layer, for example, by fixation by thermal adhesion or using an adhesive. The support layer allows easier placement of the wound bandage on the patient. Examples of suitable support layers can be found in US Patent No. 6,838,589 (Liedtke et al.) And 5,738,642 (Heinecke et al.), And in co-pending patent application No. 11 / 463,853 (Holm et al.).
[0106] In certain implementations of the invention, the support layer has a substantially radial configuration, as shown in figure 10, with a plurality of extensions generally departing from the center of the bandage. The support layer forms a plurality of alternate uncovered portions of the adhesive backing layer, separated by extensions along the adhesive perimeter of the wound bandage. The support layer can be a single piece of material, such as, for example, a polymeric film, or it can be two or more separate pieces.
[0107] The medical articles of the present invention can also include a cover layer. The optional covering layer includes a covering substrate and a covering adhesive layer on the surface facing the target site (for example, facing the wound) of the covering layer. The covering layer is permeable to liquids, for example, to allow the passage of liquid exudate from the wound. The cover layer may include openings formed through the cover layer to conduct exudate from the wound surface to the other layers. The openings
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31/87 can be provided as cracks, openings or other openings large enough to provide liquid to pass through the cover layer.
[0108] A cover sticker is optionally included to help secure the medical item to the patient. In one embodiment, the covering adhesive is substantially coextensive with the covering layer, that is, the covering adhesive covers substantially the entire wound-facing surface of the covering layer. In these constructions, it will be understood that the openings preferably extend through the covering substrate and the covering adhesive. It will be understood, however, that the covering adhesive may not be provided or may be provided only on a portion of the covering substrate. For example, the covering adhesive can be coated on a strip around the periphery of the covering substrate or coated in a standard manner on the covering substrate. It is further contemplated that the covering layer and the covering adhesive can be coextensive with the support layer and the ASP layer with additional components arranged between them.
[0109] The medical articles of the present invention may also include a carrier film to protect the adhesive layer until the wound bandage is ready for use. To facilitate removal, the carrier film may have a tab that protrudes from the end portion of the supporting layer. For example, the carrier film covers the surface of the medical article applied to the patient. The carrier film remains attached to the medical article until a user is ready to apply the bandage. The carrier film can be a removable single-piece or multi-piece strip and can be part of or laminated to the package (not shown) that contains the bandage or simply closed together with the bandage inside the package. The carrier film keeps the adhesive clean during the storage and transportation of the wound bandage.
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32/87 [0110] An exemplary wound bandage that incorporates the carrier film, the support layer, and an absorbent layer is shown in figures 10 and 11. The wound bandage 115 includes a support layer 118 with the first and the second second main surfaces. A layer of ASP 120 is functionally attached to the second main surface of the support layer and a support layer 116 is arranged on the first main surface. A modifying layer of MVTR 122 is functionally attached to a portion of the ASP 120 layer. An absorbent layer including absorbent tissue 124 and absorbent foam 126 is disposed on the surface of the modifying layer of MVTR 122 opposite the ASP 120 layer. As shown, the absorbent foam 126 extends beyond the periphery of the modifying layer of MVTR 122, but not to the periphery of the ASP 120 layer. It is further contemplated that the absorbent layer could be coextensive with the ASP 120 layer. The film carrier 128 is positioned on the side facing the target site of absorbent foam 126 and extends to the periphery of adhesive layer 120. Although not shown, the carrier film can be laminated to the ASP 120 layer, so that the absorbent layer and the modifying layer of MVTR 122 are closed between them.
[0111] It is further contemplated that the wound bandages of the present invention can be provided (i.e., packaged) in at least two components. In an embodiment consisting of the elements shown in figures 10 and 11, the first component can include the support layer, the support layer, the ASP layer and a carrier film. The second component can include the MVTR modifying layer and the absorbent layer. The first and second components can be packaged or supplied separately in another way, so that no portion of the MVTR modifying layer is in contact with the
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33/87
ASP, or close to it, until at least two components are functionally attached. Other elements, such as, for example, pH modifying layers and filtration layers, can be included in the above components without departing from the scope of the invention.
[0112] As one skilled in the art will understand, other implementations are suitable in order to add or remove aspects of the various types of wound bandages described here. For example, the backing layer can be multiple films or materials without deviating from the invention or the meaning of the term film as used herein. Similarly, the absorbent pad may include multiple sublayers, including films, blankets, sheets, etc. In addition, additional layers and films of other materials can be added between the materials described herein without departing from the invention.
[0113] Additional aspects of various components that can be employed in the invention will now be described in more detail.
Support Layer [0114] When a support layer is used, the material used to form the support layer is generally substantially more rigid than the support layer to prevent the support layer from improperly creasing during application to a patient. The support layer can be heat sealable to the support layer with or without a low adhesion coating, as is known in the art. In general, the support layer materials may include, but are not limited to, papers coated with polyethylene / vinyl acetate copolymer and polyester films. An example of a suitable support layer material is super calendered Kraft paper coated with polyethylene / vinyl acetate copolymer (for example, obtained from Loparex of Dixon, IL, USA).
[0115] A support layer may include perforations for
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34/87 help to separate portions of the support layer after applying the bandage to a patient. The spacing and shape of the perforations are adjusted to provide a support layer with relative ease to break when the support layer is removed from the applied bandage. Perforations can be shaped according to any of the accepted drilling patterns including linear, angular, Y-shaped, V-shaped, two-angle, sinusoidal, etc.
[0116] Exemplary modalities of support layer constructions that can be used in the present invention are further described in U.S. Patent No. 5,738,642 (Heinecke et al.), And 6,838,589 to Liedtke et al.
Support layer [0117] The support layer, also called here as support, typically includes a moisture vapor permeable and liquid impermeable polymer film, although it may include a variety of other materials, which are preferably used in combination with a moisture vapor-permeable and liquid-impermeable polymer film. The moisture-permeable and liquid-impermeable polymeric film is a conformable organic polymeric material that preferably retains its structural integrity in a humid environment. In the present invention, conformable films are those that adapt to a surface, even with movement of the surface, such as with the surface of a body part. Suitable films have a composition and thickness that allow moisture vapor to pass through them. The film helps to regulate the loss of water vapor from the wound area below the bandage. The film also acts as a barrier against bacteria and liquid water or other liquids.
[0118] Moisture-permeable polymeric films for
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35/87 use as support layers in the present invention can have a wide range of thicknesses. Preferably, they are at least 10 microns (micrometers) thick and more preferably at least 12 microns thick. Preferably, they are no more than 250 microns and, more preferably, no more than 75 microns in thickness. In addition, they can include one or more layers adapted to have the desired properties. These layers can be coextruded and / or bonded together with adhesive layers, for example, as long as the general properties of the film and the article, as described in the present invention, are satisfied.
[0119] Preferably, films suitable for use in the backing layer of the present invention have differential moisture vapor transmission properties. Preferably, a suitable film has a dry MVTR that is less than the wet MVTR of the film. Preferably, suitable films have a dry MVTR of at least 300 g / m ^2/24 hrs and a wet MVTR of at least 3000 g / ^m2 / 24 hours. Preferably, the film has a wet MVTR most 10,000 g / ^m2 / 24 hours, more preferably greater than 15,000 g / ^m2 / 24 hours. Films can be tested using the methods described above for the article.
[0120] Examples of materials suitable for moisture vapor permeable and liquid impermeable polymer films of the backing layer include synthetic organic polymers including, but not limited to: commercially available polyurethanes from BF Goodrich, Cleveland, OH, USA, under the trade name ESTANE, including ESTANE 58237 and ESTANE 58245; polyesteramide block copolymers commercially available from Elf Atochem, Philadelphia, PA, USA, under the trade name PEBAX, including PEBAX MV 1074; polyether ester block copolymers commercially available from DuPont, Wilmington, DE, USA, under the trade name HYTREL; and thermoplastic elastomers commercially available from DSM
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36/87
Engineering Plastics, Evansville, IN, USA, under the trade name ARNITEL VT. Polymeric films can be produced from one or more types of monomers (for example, copolymers) or mixtures (for example, blends) of polymers. The preferred materials are thermoplastic polymers, for example, polymers that soften when exposed to heat and return to their original condition when cooled. A particularly preferred material is a thermoplastic polyurethane.
[0121] The supports of the medical articles of the present invention may also include other breathable materials including, for example, non-woven, fabric, and mesh blankets, porous films (for example, provided by perforations or microporous structure), foams, paper , or other known supports. A preferred support includes a combination of a moisture vapor-permeable and liquid-impermeable polymer film and a moisture vapor-permeable non-woven blanket that can, among other advantages, provide optimized structural integrity and better aesthetics to the bandages. These layers of film and blanket may or may not be coextensive. Such a preferred non-woven blanket is a melt-processed polyurethane (such as, for example, available under the trade name MORTHANE PS-440 from Morton International, Seabrook, NH, USA), or hydroentangled non-woven polyester or blankets polyester rayon (such as those available under the trade name SONTARA 8010 or SONTARA 8411 from DuPont, Wilmington, DE, USA).
[0122] A low-adhesion coating (low-adhesion rear coating or LAB) can be provided on the support layer on the side that can come in contact with the support layer. The low adhesion coating reduces the need to change the bandage due to unwanted bandage removal when other tapes or devices are placed over the bandage and removed and also reduces
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37/87 superficial friction of the bandage on linen, or other fabrics, thereby offering additional protection against accidental removal of the bandage. A description of a low adhesion support material suitable for use in the present invention can be found in U.S. Patent Nos. 5,531,855 and 6,264,976.
Pressure Sensitive Adhesive [0123] Various ASPs can be used to form adhesive layer 14 on top of support layer 12 to make it adhesive. For example, ASPs can be formulated to offer good skin adhesion characteristics, excellent conformability and provide a smooth release of the skin and wound site. The ASP layer can be continuous, discontinuous, coated in a standard way, or produced by block extrusion with high speed hot air (meltblown), for example.
[0124] A well-known means of identifying ASPs is the Dahlquist criterion. This criterion defines an ASP as an adhesive having a creep compliance for 1 second greater than 1E-7 Pa (1 x 10 ^-6 cm ² / dyne), as described in Handbook of ASP Technology, Donatas Satas (Ed.), 2a Edition, page 172, Van Nostrand Reinhold, New York, NY, USA, 1989. Alternatively, as the module is, in a first approximation, the inverse of fluency complacency, ASPs can be defined as adhesives having a smaller Young modulus than 100 kPa (1 x 10 ⁶ dynes / cm ² ). Another well-known means of identifying an ASP is that it is aggressively and permanently sticky at room temperature, adhering firmly to various dissimilar surfaces on mere contact, without the need for pressure greater than that of a finger or hand, and which can be removed from smooth surfaces without leaving a residue, as described in Glossary of Terms Used in the Pressure Sensitive Tape Industry provided by the Pressure Sensitive Tape Council in 1996. Another suitable definition of a suitable ASP is that it preferably has a storage module The
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38/87 ambient temperature within the area defined by the following points, as plotted on a module graph as a function of frequency at 25 ° C: a module range of approximately 20 to 40 kPa (2 x 10 ⁵ to 4 x 10 ⁵ dynes / cm ² ) at a frequency of approximately 0.1 radians / second (0.017 Hz), and a module range of approximately 200 to 800 kPa (2 x 10 ⁶ to 8 x 10 ⁶ dynes / cm ² ) at a frequency of approximately 100 radians / second (17 Hz) (for example, see figures 8 to 16 on page 173 of the Handbook of ASP Technology (Donatas Satas, Ed.), 2nd edition, Van Nostrand Rheinhold, New York, USA, 1989). Any of these methods of identifying an ASP can be used to identify ASPs suitable for use in the methods of the present invention.
[0125] Examples of ASPs useful in the present invention include rubber-based adhesives (e.g., tachyed natural rubbers, synthetic rubbers, and styrene block copolymers), (meth) acrylics (i.e., (meth) acrylates), poly (alpha-olefins), polyurethanes and silicones. Amine-containing polymers can also be used, which have amine groups on the main chain, pending on it, or combinations thereof. A suitable example includes a poly (ethyleneimine).
[0126] Some polymers can be modified chemically to include the desired amount of acidic or basic functionality. Alternatively, polymers can be produced with acid or base-functional monomers. Alternatively or in addition, ASPs can include acid- or base-functional additives, such as, for example, stickiness enhancers, plasticizers, or other additives.
[0127] Useful natural rubber ASPs generally contain chewed natural rubber, from 25 parts to 300 parts of one or more tackiness-enhancing resins to 100 parts of natural rubber, and typically from 0.5 parts to 2.0 parts of one or more more antioxidants. Natural rubber can vary in degree from a pale pale crepe to a smoked leaf with darker ribs
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39/87 and includes examples such as CV-60, a degree of viscosity-controlled rubber and SMR-5, a degree of ribbed smoked sheet rubber. Stickiness-enhancing resins used with natural rubbers generally include, but are not limited to, wood rosin and its hydrogenated derivatives; terpene resins from various softening points, and petroleum based resins. Other materials can be added to natural rubber-based adhesives for special purposes, the additions of which may include plasticizers, pigments, and curing agents to partially vulcanize ASP. Examples of acid-modified stickiness enhancers include acid-modified polyhydric alcohol rosine ester enhancers, as described in U.S. Patent No. 5,120,781.
[0128] Another useful class of ASPs is one that includes synthetic rubber. Such adhesives are generally elastic elastomers, which are self-sticky or non-sticky, requiring stickiness enhancers. Examples of acid-modified stickiness enhancers include acid-modified polyhydric alcohol rosine ester enhancers, as described in U.S. Patent No. 5,120,781. Self-sticky synthetic rubber ASPs include, for example, butyl rubber, an isobutylene copolymer with less than 3 percent isoprene, polyisobutylene, an isoprene, polybutadiene, or styrene / butadiene rubber homopolymer.
[0129] Synthetic rubber ASPs that generally require stickiness enhancers are also generally easier to process by melting. They include polybutadiene or styrene / butadiene rubber, from 10 parts to 200 parts of a tackiness enhancer, and generally from 0.5 parts to 2.0 parts per 100 parts of an antioxidant rubber. An example of a synthetic rubber is that available from BF Goodrich under the trade name AMERIPOL 101 IA,
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40/87 a styrene / butadiene rubber. Stickiness enhancers that are useful include rosin derivatives, polyterpenes, C5 aliphatic olefin derived resins, and C9 aromatic / aliphatic olefin resins.
[0130] Styrene block copolymer ASPs generally include elastomers of type A-B or A-B-A, where A represents a thermoplastic polystyrene block and B represents an elastic block of polyisoprene, polybutadiene, or poly (ethylene / butylene), and resins. Examples of the various block copolymers useful in block copolymer ASPs include linear, radial, star and conical styrene isoprene block copolymers, such as those available under the trade names KRATON D 1107P, KRATON G1657, KRATON G 1750X, and KRATON D 1118X available from Shell Chemical Co. Polystyrene blocks tend to form domains in the shape of spheroids, cylinders, or plates that cause block copolymer ASPs to have two-phase structures. The resins associated with the rubber phase generally develop stickiness in the ASP. Examples of resins associated with the rubber phase include resins derived from aliphatic olefin, such as, for example, those available under the trade names ESCOREZ 1300 and WINGTACK from Goodyear; rosin esters, such as those available under the trade names FORAL and STAYBELITE Ester 10 from Hercules, Inc .; hydrogenated hydrocarbons, such as those available under the trade name ESCOREZ 5000 from Exxon; polyterpenes, such as those available under the trade name PICCOLYTE A; and petroleum-derived phenolic terpene resins or sources of terpentine, such as those available under the trade name PICCOFYN A100 from Hercules, Inc. Resins that are associated with the thermoplastic phase tend to harden ASP.
[0131] In the preferred ASPs of the present invention, acrylate and methacrylate monomers and polymers can be used and are collectively referred to here as (meth) acrylate monomers and polymers or
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41/87 (met) acrylics. The (meth) acrylate polymers can be copolymers, optionally, in combination with other non- (meth) acrylate monomers, for example, vinyl unsaturated. Such polymers and their monomers are well known in the polymer and adhesive techniques, as they are methods of preparing monomers and polymers. The person skilled in the art will understand and recognize that these polymers may be useful for imparting adhesive properties and will understand their use in providing an adhesive, as described in the present invention.
[0132] (meth) acrylic ASPs generally have a glass transition temperature of about -20 ° C or less, and can include from 100 to 60 weight percent of a C4-C12 alkyl ester component, such as , for example, isooctyl acrylate, 2-ethylhexyl acrylate and nbutyl acrylate and from 0 to 40 weight percent of a polar component such as acrylic acid, methacrylic acid, ethylene, vinyl acetate , N-vinyl pyrrolidone and styrene macromer.
[0133] Acid monomers suitable for preparing (meth) acrylic ASPs include those containing carboxylic acid functionality such as, for example, acrylic acid, methacrylic acid, itaconic acid, and the like; those containing sulfonic acid functionality, for example, 2-sulfoethyl methacrylate; and those containing phosphonic acid functionality. Preferred acid monomers include acrylic acid and methacrylic acid.
[0134] Additional acid monomers useful in the acid copolymer include, but are not limited to, those selected from ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof. Examples of these compounds include those selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, B-carboxyethyl acrylate, 2-sulfoethyl
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42/87 methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, vinyl phosphonic acid, and the like, and mixtures thereof.
[0135] Due to their availability, the acid monomers of the present invention are typically ethylenically unsaturated carboxylic acids. When even stronger acids are desired, acidic monomers include ethylenically unsaturated sulfonic acids and ethylenically unsaturated phosphonic acids. Suphonic and phosphonic acids generally provide a stronger interaction with a basic polymer. This stronger interaction can lead to even greater improvements in cohesive strength, as well as greater temperature resistance and solvent resistance of the adhesive.
[0136] Basic monomers suitable for preparing (meth) acrylic ASPs include those containing amine functionality such as, for example, vinyl pyridine, N, N-diethylaminoethyl methacrylate, N, N-dimethylamino-ethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, and N-tbutylaminoethyl methacrylate. Preferred basic monomers include N, Ndimethylaminoethyl methacrylate, and N, N-dimethylamino ethyl acrylate.
[0137] The (meth) acrylic ASPs can be self-sticky or tachy. Stickiness enhancers useful for (meth) acrylics are rosin esters such as those available under the trade name FORAL 85 from Hercules, Inc., aromatic resins such as those available under the trade name PICCOTEX LC -55WK from Hercules, Inc., aliphatic resins such as those available under the trade name PICCOTAC 95 from Hercules, Inc., and terpene resins such as those available under the trade names PICCOLYTE A- 115 and ZONAREZ B-100 with Arizona Chemical Co. Other materials can be added for special purposes, including hydrogenated butyl rubber, pigments, and curing agents to partially vulcanize the adhesive. Examples
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43/87 of acid-modified stickiness enhancers include acid-modified polyhydric alcohol rosin ester enhancers, as described in U.S. Patent No. 5,120,781.
[0138] Poly (alpha-olefin) ASPs, also called poly (l-alkene) ASPs, generally include a substantially non-cross-linked polymer or a non-cross-linked polymer that may have radiation-activated functional groups grafted onto it, as described in US patent No. 5,209,971 (Babu, et al.). The poly (alpha-olefin) polymer can include one or more stickiness enhancing materials, not only to improve the adhesive properties, but also to provide the basic or acidic functional groups necessary for this application. Stickiness enhancing materials are typically resins that are miscible in the poly (alpha-olefin) polymer. The total amount of tackiness-enhancing resin in the poly (alphaolefin) polymer ranges from 0 to 150 parts, by weight, per 100 parts of the poly (alphaolefin) polymer depending on the specific application. Useful tackiness-enhancing resins include resins derived by polymerization of unsaturated C5 to C9 hydrocarbon monomers, polyterpenes, synthetic polyterpenes and the like. Examples of these resins available for sale based on a C5 olefin fraction of this type include those available under the trade name WINGTACK from Goodyear Tire and Rubber Co. Other materials can be added for special purposes, including antioxidants, fillers, pigments, and radiation activated crosslinking agents.
[0139] Another useful class of ASPs can include polyurethanes. Polyurethanes can be produced by reacting a polyisocyanate with a polyalcohol (polyol). As described in the present invention, a polyisocyanate is a molecule with two or more isocyanate functional groups and a polyalcohol is a molecule with two or more hydroxyl functional groups. The reaction product is a polymer containing urethane bonds. Functional groups can
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44/87 be alkanes, esters, ethers, and other components.
[0140] Isocyanates can be classified as aromatic, such as, for example, diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI); or aliphatic, such as, for example, hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI). An example of a polymeric isocyanate is polymeric diphenylmethane diisocyanate, which is a mixture of molecules with two-, three-, and four- or more isocyanate groups, with an average functionality of 2.7. Isocyanates can be further modified by partially reacting them with a polyol to form a prepolymer. An almost prepolymer is formed when the stoichiometric ratio between the isocyanate and the hydroxyl groups is greater than 2: 1. A true prepolymer is formed when the stoichiometric ratio is 2: 1. Important characteristics of isocyanates include the main chain of the molecule,% NCO, functionality, and viscosity.
[0141] Polyols are differentiated from low molecular weight or short chain glycol extenders and crosslinkers, such as ethylene glycol (EG), 1,4-butane diol (BDO), diethylene glycol (DEG) , glycerin, and trimethylol propane (TMP). Polyols are formed by the catalyzed addition of propylene oxide (PO), ethylene oxide (EO) on an initiator containing hydroxyl or amine, or by the polyesterification of a di-acid, such as adipic acid, with glycols , such as, for example, ethylene glycol or dipropylene glycol (DPG). The choice of the initiator, extender, and the molecular weight of the polyol greatly affects its physical state and the physical properties of the polyurethane polymer. Important characteristics of polyols include the main chain of the molecule, the initiator, the molecular weight, the% of primary hydroxyl groups, the functionality and the viscosity. Examples of suitable polyurethane adhesives can include those found in U.S. Patent No. 7,160,976 (Luhmann et al.), 6,642,304 (Hansen et. Al.) And 6,518,359 (Clemens et al.).
[0142] Silicone ASPs include two main components,
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45/87 a polymer or gum, and a stickiness-enhancing resin. The polymer is typically a high molecular weight polydimethyl siloxane or polydimethyl diphenyl siloxane, which contains residual silanol (SiOH) functionality at the ends of the polymeric chain, or a block copolymer that includes soft polydiorganosiloxane segments and urea-terminated hard segments. The tackiness-enhancing resin is generally a three-dimensional silicate structure that is capped with trimethylsiloxy groups (OSiMe3) and also contains residual silanol functionality. Examples of tackiness-enhancing resins include SR 545, available from General Electric Co., Silicone Resins Division, Waterford, NY, USA, and MQD-322 available from Shin-Etsu Silicones of America, Inc., Torrance, CA, USA . The manufacture of typical silicone ASPs is described in U.S. Patent No. 2,736,721 (Dexter). The manufacture of silicone urea block copolymer ASP is described in U.S. Patent No. 5,214,119 (Leir et al.).
[0143] In some embodiments, the adhesive contains more than 0.42 mmols of acidic or basic functional groups per gram of ASP that can be neutralized by the modifying material of MVTR. Most preferably, the adhesive contains at least 0.69 mmols of these functional groups per gram of ASP. Most preferably, the adhesive contains 0.84 mmols of these functional groups. Most preferably, the adhesive contains at least 1.3 mmols of these functional groups. Most preferably, the adhesive contains at least 1.80 mmols of these functional groups. Most preferably, the adhesive contains at least 2.08 mmols of these functional groups. In most embodiments, the adhesive contains between 1.3 mmols and 2.5 mmols of these functional groups.
[0144] Preferably, the sticker should contain no more than
5.6 mmols of these functional groups per gram of ASP. Most preferably, the adhesive contains no more than 4.2 mmols of these functional groups per gram
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46/87 of ASP, and more preferably still not more than 2.8 mmols of these functional groups per gram of ASP.
[0145] In some modalities in which ASP contains a polymer formed from acidic monomers, the corresponding weight percentages can be considered. Preferably, the ASP contains more than 3 weight percent of a monomeric unit in the adhesive polymer that contains acidic / basic functional groups that can be neutralized by the MVTR modifying material. More preferably, the ASP contains at least 6 weight percent of these functionalized monomer units. Most preferably, the ASP contains at least 9 weight percent of these functionalized monomer units. Most preferably, the ASP contains at least 10 weight percent of these functionalized monomer units. Most preferably, the ASP contains at least 12 weight percent of these functionalized monomer units.
[0146] Preferably, the ASP should contain no more than 40 weight percent of the functionalized monomer units. Most preferably, the ASP contains no more than 30 percent by weight, most preferably not more than 25 percent by weight of the functionalized monomer units and most preferably no more than 20 based on total weight of monomers used in the polymer used to make ASP. Preferably, these values apply to (meth) acrylate polymers.
[0147] In certain embodiments, ASP may include additional hydrophilic polymeric components. These hydrophilic polymeric components of ASP are different from plasticizers or other additives that can be used in the adhesive to accentuate stickiness or otherwise affect the properties of the adhesive. The hydrophilic polymer component can be reactive or non-reactive with the adhesive monomers in ASP. If the hydrophilic polymer is non-reactive (ie, not incorporated into the polymer chain) the molecular weight
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47/87 of the hydrophilic polymer component is greater than 1000. More preferably, the molecular weight is greater than 2000.
[0148] When present in the adhesive, hydrophilic polymeric components are generally present in amounts of up to 30 weight percent, based on the total weight of the ASP. In these adhesives that include a hydrophilic polymeric component, lower concentrations of acidic or basic functional groups in the ASP may be required to cause a significant increase in the MVTR when a MVTR-modifying material is incorporated into a medical article including the ASP, compared to a ASP with the same mass concentration as the acidic or basic functional groups that does not include the hydrophilic polymeric components. For example, an ASP with 10 weight percent acidic functional groups and 10 weight percent additional hydrophilic component (s) may show a greater increase in MVTR when exposed to a material MVTR modifier suitable compared to an ASP with only 10 weight percent acidic functional groups and no additional hydrophilic components. The combined weight percentage of the reactive groups (eg acid) and the hydrophilic polymeric components in the ASP is preferably at least 15%, more preferably, at least 20% and, most preferably, at least 24% by weight of the ASP. For example, if the adhesive contains 6% acidic groups, then the hydrophilic component should be at least 9% by weight, more preferably at least 14% by weight and most preferably at least 18% , by weight. If the adhesive group contains 12% by weight of acrylic acid, the hydrophilic component should be at least 3% by weight, more preferably at least 8% by weight and most preferably at least 12% by weight. ASP weight.
[0149] In certain embodiments, the ratio of the hydrophobic polymeric component (s) in the ASP to the hydrophilic polymeric component (s) in the ASP is preferably at least minus 1.5: 1. With more
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48/87 preferably at least 1.9: 1, most preferably 2.3: 1. In most modes, less than 6: 1.
[0150] In certain embodiments, an exemplary non-reactive hydrophilic polymer component includes one or more copolymers of poly (alkylene oxide). Poly (alkylene oxide) copolymers can be combined with ASP monomers (for example, (meth) acrylate monomers or other acidic monomers) or with the copolymer formed from ASP monomers. Poly (alkylene oxide) copolymers generally do not migrate to the extent of phase separation between the copolymerized acrylate monomers and the poly (alkylene oxide) copolymer. Separation of separate phases or phases means that there are no visible regions of crystallization or liquid regions in the adhesive solution or volume of adhesive.
[0151] In preferred embodiments, poly (alkylene oxide) copolymers include at least two copolymerized alkylene oxide monomers, at least one of these being hydrophilic and at least one of these being hydrophobic. A preferred copolymer is formed from ethylene oxide and propylene oxide. They can be random, alternating or block. Preferably, they are block copolymers that include hydrophobic and hydrophilic segments. Particularly useful poly (alkylene oxide) copolymers have a weight average molecular weight of about 1000 to about 15,000, preferably from about 3000 to about 12,000.
[0152] Preferred poly (alkylene oxide) copolymers have appreciable water solubility, preferably at least about 10 parts per 100 parts of water, exhibit surfactant characteristics, preferably having an HLB (hydrophilic- lipophilic) of about 3 to about 15, and more preferably, about 5 to about 12. Useful poly (alkylene oxide) copolymers have ratios between hydrophilic monomers (eg ethylene oxide) and hydrophobic monomers (eg
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49/87 (example, propylene oxide) from about 90:10 to about 10:90, more preferably, from about 80:20 to about 30:70.
[0153] Monomers that can be used to make poly (alkylene oxide) copolymers include ethylene oxide and related glycols as a hydrophilic component and propylene oxide, butylene oxide, trimethylene oxide, tetramethylene oxide and the like and related glycols as a hydrophobic component. Poly (alkylene oxide) copolymers can be terminated with lower alkyl groups, amino groups, hydroxyl groups, carboxylic acid groups, aromatic groups, or other non-reactive groups.
[0154] Examples of useful poly (alkylene oxide) copolymers include, but are not limited to, poly (alkylene oxide) copolymers available under the trade names TETRONIC (tetrafunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine with hydrophilic terminal blocks) and TETRONIC R copolymers (tetrafunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine with hydrophobic terminal blocks) available from BASF, Mt. Olive, NJ USA ; PLURONIC copolymers (triblock copolymers with poly (ethylene oxide) terminal blocks and intermediate poly (propylene oxide) blocks) and PLURONIC R (triblock copolymers with poly (propylene oxide) terminal blocks and poly ( ethylene oxide)) available from BASF; UCON Fluids (random copolymers of ethylene oxide and propylene oxide) available from Union Carbide, Danbury, Conn., USA. Various combinations of poly (alkylene oxide) copolymers can also be used. The preferred non-reactive hydrophilic polymeric components are block copolymers of polyethylene glycol and propylene glycol available from BASF, Germany under the trade name PLURONIC.
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50/87 [0155] Preferably, the poly (alkylene oxide) copolymer can be used in an amount of at least about 5 percent by weight (% w / w) based on the total weight of the adhesive composition ( for example, the copolymerized hydrophilic acid / (meth) acrylate comonomers and poly (alkylene oxide) copolymer). More preferably, the poly (alkylene oxide) copolymer is used in an amount of at least about 10% by weight and, most preferably, at least about 15% by weight. Preferably, the poly (alkylene oxide) copolymer can be used in an amount of up to about 30% by weight. The amount of poly (alkylene oxide) copolymer required depends on the type and ratios of the (meth) acrylate comonomers and hydrophilic acids used in the polymerizable mixture and the type and molecular weight of the poly (alkylene oxide) copolymer used in the adhesive composition.
[0156] In other embodiments, an exemplary reactive hydrophilic polymeric component includes a hydrophilic macromolecular monomer that has a copolymerizable vinyl group with ASP monomers. The hydrophilic macromolecular monomer contains a plurality of hydrophilic sites that impart the necessary hydrophilic capacity to the monomer. The hydrophilic macromolecular monomer can be represented by the general formula I
X — Y — Z where X is a copolymerizable vinyl group with ASP monomers, Y is a divalent bonding group, and Z is a monovalent polymer moiety, that is, containing two or more monomeric units, comprising a polyether essentially not -active under free radical initiated copolymerization conditions used to form the pressure sensitive adhesive terpolymer.
[0157] The preferred group X is the group with general formula II:
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51/87
HR ^a /
C = C /
Η where R ^a is a hydrogen atom or a methyl group.
[0158] Preferred group Y is group O
II —c— (ie, a divalent carbonyl group).
[0159] The preferred Z portion is a monovalent polyether with general formula III
where R ^ó is hydrogen, lower alkyl, phenyl, or substituted phenyl; and W is a divalent poly (lower alkylene oxide) group containing 2 to about 250 alkoxy repeat units and selected from the group consisting of a poly (ethylene oxide) radical, a poly (propylene oxide) radical , a radical of a copolymer of ethylene oxide and propylene oxide, and a poly (tetramethylene oxide) radical. In a preferred hydrophilic macromonomer, a monovalent polyether of formula III is covalently attached to the carbonyl group (i.e., in which Y is divalent carbonyl) through a terminal oxygen atom contained in the W portion.
[0160] A variety of hydrophilic macromolecular monomers are commercially available. For example, commercially available monomers that have been found to be suitable are 2- (2-ethoxyethoxy) ethyl acrylate which is available under the trade name SR-256 from Sartomer Company, West Chester, PA, USA; poly methoxy acrylate (ethylene oxide) which is available under the trade name No. 8816 from MonomerPolymer & Dajac Laboratories, Inc., Trevose, PA, USA; the 200-Dalton, 400-Dalton, and 1000-Dalton methacrylates of poly (ethylene oxide) that are
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52/87 available under the trade names No. 16664, No. 16665 and No. 16666, respectively, from Polysciences, Inc., Warrington, PA, USA; and poly hydroxy methacrylate (ethylene oxide) which is available under the trade name No. 16712 from Polysciences, Inc., Warrington, PA, USA.
[0161] Other preferred hydrophilic macromolecular monomers can be prepared using commercially available starting materials and conventional methods, for example, as described in U.S. Patent No. 4,871,812.
[0162] In general, the hydrophilic macromolecular monomer is present in an amount of about 5 to 30% of the total weight of all monomers in the terpolymer. Preferred amounts for the monomers are about 10 to 20% by weight based on the total amount of all monomers in the terpolymer.
[0163] The preferred polymers included in ASP are (meth) acrylate polymers. A particularly useful adhesive composition includes a copolymer of 2-ethyl hexyl acrylate: 65:15:20 acrylic acid mixed with a non-reactive polyalkylene oxide copolymer under the trade name PLURONIC. Other suitable examples include an isooctyl acrylate copolymer: 90:10 acrylic acid, an isooctyl acrylate terpolymer: ethylene oxide acrylate: 70:15:15 acrylic acid, and a 2-ethyl hexyl acrylate: acrylate terpolymer. butyl: 25: 69: 6 acrylic acid. Useful adhesives can be any of those that are compatible with the skin and useful for wound dressings, such as, for example, those disclosed in U.S. Patent No. Re. 24,906 (Ulrich), 5,849,325 (Heinecke, et al.), And 4,871,812 (Lucast, et. Al.) (Water-based and solvent-based adhesives); 4,833,179 (Young, et al.) (Hot-melt adhesives); 5,908,693 (Delgado, et al.) (Microsphere adhesives); 6,171,985 and 6,083,856 (both for Joseph, et al.) (Low-trauma fibrous adhesives); and, U.S. Patent No. 6,198,016 (Lucast, et al.), 6,518,343 (Lucast, et al.),
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53/87 and 6,441,082 (Gieselman) (adhesives for wet skin). The inclusion of drugs or antimicrobial agents in the adhesive is also contemplated, as described in U.S. Patents No. 4,310,509 and 4,323,557.
Framework [0164] When used, framework 22, as shown, for example, in figure 2, can include a non-woven material. Suitable non-woven materials include, but are not limited to, TENCEL / polyester, non-woven Lycocell-rayon / polyester both available from Ahlstrom Green Bay, Green Bay, WI, USA. Other suitable nonwovens include hydrowoven cotton nonwovens available from Unitika Ltd., Japan. In another embodiment, frame 22 is a TMED011 nonwoven available from National Nonwovens Co., East Hampton, MA, USA. Framework 22 may also include fabrics, knitted fabrics, foams, porous films, gels, hydrocolloids, cellulosic material, carboxy methyl cellulose, alginates, and adhesives that swell in water and absorbable in water. In preferred modalities, frame 22 is capable of absorbing moisture.
Filtration layer [0165] When used, the filtration layer 32, as shown, for example in figure 3b, can include one or more nonwoven layers. Suitable nonwoven materials include, but are not limited to, TENCEL / polyester nonwovens, and Lycocell-rayon / polyester nonwovens, both available from Ahlstrom Green Bay, Green Bay, WI, USA. Other suitable nonwovens include hydrowoven cotton nonwovens available from Unitika Ltd., Japan. In another embodiment, filtration layer 32 is a TMED011 nonwoven available from National Nonwovens Co., East Hampton, MA, USA. filtration can also be composed of fabrics, knitted fabrics, foams, porous films, gels, hydrocolloids, cellulosic material, alginates, porous adhesives (hydrophobic or hydrophilic) and
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54/87 adhesives that swell in water and absorbable in water.
[0166] Suitable examples of a filtration layer selected for filtration purposes include filtration membranes, filtration materials, nonwovens, fabrics, gels and foams.
ABSORBENT LAYER [0167] When used, the absorbent layer can be made from any of a variety of materials including, but not limited to, woven or non-woven cotton or rayon. The absorbent layer is useful because it contains numerous substances, optionally including antimicrobial agents, drugs for the transdermal application of drugs, chemical indicators for monitoring hormones or other substances in a patient, etc.
[0168] The absorbent layer may include a hydrocolloid composition, including the hydrocolloid compositions described in U.S. Patent Nos. 5,622,711 and 5,633,010. Absorbent materials can also be chosen from other synthetic and natural materials including polymer gels, foams, collagens, methyl cellulose carboxy fibers, alginates, non-woven materials or fabrics. In some embodiments, the absorbent layer may include a polymeric fabric, a polymeric foam, and combinations thereof. For example, the polymeric fabric may be a nonwoven and the polymeric foam may be the foam used in the TEGADERM foam adhesive bandage available from 3M Company, St. Paul, MN, USA. In certain embodiments, the polymeric foam is a polyurethane foam.
Cover layer [0169] When used, the cover layer is preferably soft, flexible, conformable, non-irritating and non-sensitizing. Any of a variety of polymers can be used, including polyurethane, polyethylene, polypropylene, polyamide or polyester materials. Additionally, the covering layer may be in the form of moisture vapor permeable films,
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55/87 perforated films, blankets or woven, non-woven or knitted covers.
[0170] The covering layer may also include a laminated adhesive on the surface of the filtration layer facing the wound or other target site. In this embodiment, the second adhesive can be an acrylic, silicone gel, polyurethane, or rubber-based adhesive. Exemplary modalities of suitable coating layers and adhesives can be found, for example, in U.S. Patent No. 7,612,248 to Burton et al. The cover layer can also include an additional adhesive on the surface of the cover layer opposite the target site.
Carrier films [0171] Carrier films (for example, as shown in figure 11) suitable for use with the invention can be produced from kraft paper, polyethylene, polypropylene, polyester or composites of any of these materials. The films are preferably coated with release agents such as fluorochemicals or silicones. For example, U.S. Patent No. 4,472,480 describes perfluoro-chemical liners with low surface energy. Paper liners, polyolefin films or polyester films coated with silicone release materials. Examples of commercially available silicone coated release papers are POLYSILK ™, silicone release papers available from Rexam Release (Bedford Park, Ill, USA) and silicone release papers provided by Loparex Inc. (Willowbrook, IL, USA ).
[0172] The objectives and advantages of this invention are further illustrated by the following examples, however, the materials and quantities reported in these examples, as well as other conditions and details, should not be interpreted in such a way as to unduly limit this invention. All parts and percentages are by weight, unless otherwise indicated.
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Examples
Table 1: Glossary of components
Material / Trade name description Source / Address 3M TEGADERM 9548HP Transparent film bandage 3M Company, St. Paul, MN, USA 3M TEGADERM 90612 Adhesive foam bandage 3M Company, St. Paul, MN, USA ESTANE resin 58237 Polyurethane-based resin Lubrizol, Wickliffe, OH, USA 70/30 TENCEL / non-woven fabric Grade 240 (SX-33), non-woven Ahlstrom, Green Bay, WI, USA polyester hydroentangled 40 g / m ² , network 24 with opening; 70/30 TENCEL / polyester 30/70 Grade SX-473, hydroentangled, non- Ahlstrom, Green Bay, WI, USA Lycocell-Rayon / Non-Polyesterfabric fabric without opening, 45 g / m ²Na3C6H5O7-2H20 Sodium citrate dihydrate Mallinckrodt, Phillipsburg, NJ,USA C6H8O7 Citric acid, anhydrous, USP grade Spectrum Chemical, Gardena,CA, USA or VWR International,West Chester, PA, USA. COTTOASE 100% cotton, non-wovenhydro-interlaced, 50 gsm Unitika, Japan NaOH 50% solution (w / w) diluted untildesired concentration with watersterile USP J.T. Baker Phillipsburg, NJ, USA Water USP sterile water Baxter, Deerfield, IL, USA Na2CO3-H20 Sodium carbonate monohydrate Mallinckrodt, Phillipsburg, NJ,USA or Fisher Scientific, FairLawn, NJ, USA NaHCO3 Sodium bicarbonate VWR International, West Chester,
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57/87
PA, USA. CH3N (C2H4OH) 2 Methyl diethanolamine (MDEA) Dow, Midland, MI, USA K2CO3 Potassium carbonate, anhydrous, ACS grade VWR International, WestChester, PA, USA. KHCO3 Potassium bicarbonate, USP grade Mallinckrodt, Phillipsburg, NJ, USA
Test Methods
1. Moisture vapor transmission rate - vertical MVTR (dry)
A. For samples that did not contain a foam component [0173] The vertical MVTR was measured according to the ASTM E-96-80 method using a modified Payne dome method. A 3.8 cm diameter sample was placed between the adhesive-containing surfaces of two adhesive foil rings, each having an elliptical opening of 5.1 cm ² . The holes in each ring were carefully aligned. The pressure of a finger was used to form a set of foil / sample / foil that was flat, free of creases, and that had no empty area in the exposed sample.
[0174] A 120 mL glass jar was filled with approximately 50 g of tap water that contained a few drops of USP 0.02% (w / w) methylene blue aqueous solution (Basic Blue 9, CI52015), except where specifically described in an example. The jar was equipped with a screw cap having a 3.8 cm diameter hole in the center of it and a 4.45 cm diameter rubber washer having a hole of approximately 3.6 cm in its center. The rubber washer was placed over the edge of the jar and the metal foil / sample / foil set was placed face down on the rubber washer. The lid was then loosely screwed into the jar.
[0175] The set was placed in a chamber at 40 ° C and 20% relative humidity, for four hours. At the end of four hours, the lid was tightened
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58/87 inside the chamber so that the sample was level with the lid (without expansion) and the rubber washer was in the proper seating position.
[0176] The foil sample set was removed from the chamber and weighed immediately with an accuracy of 0.01 gram to an initial dry weight, W1. The set was then placed back in the chamber for at least 18 hours, the exposure time T1 in hours, after which it was removed and weighed immediately with a precision of 0.01 g to a final dry weight, W2. The MVTR in grams of water vapor transmitted per square meter of sample area for 24 hours can then be calculated using the following formula.
Vertical MVTR (dry) = (W1-W2) x (4.74 x 10 ⁴ ) / T1 B. For samples containing a foam component [0177] The vertical MVTR procedure for these samples was identical to that described above with the exception that the test sample size was a 4.45 cm diameter sample and the sample was sandwiched between two LEXAN (polycarbonate) washers (4.47 cm diameter with a 2.54 cm hole in the middle ), instead of adhesive foil rings.
2. Moisture vapor transmission rate - inverted MVTR (wet) [0178] The inverted MVTR was measured using the following test procedure. After obtaining the final dry weight, W2, as described for the vertical MVTR procedures, the set was placed back in the chamber for at least another 18 hours of exposure time, T2, with the inverted jars so that the running water was in direct contact with the test sample. The sample was then removed from the chamber and weighed with an accuracy of 0.01 gram to a final wet weight, W3. The wet MVTR inverted in grams of water vapor transmitted per square meter of sample area for 24 hours can then be calculated using the following formula.
Inverted MVTR (wet) = (W2-W3) x (4.74 x 10 ⁴ ) / T2
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59/87 [0179] Several samples from the examples below were measured for vertical (dry) and inverted (wet) MVTR. The average results are reported below, followed by the standard deviation (+/-) of the various samples.
3. Adhesion to steel [0180] The test of adhesion to steel was carried out according to the ASTM D3330M method at 30.5 cm / min and 180 degrees of detachment.
Example 1 (Comparative) [0181] A 40 g / m ² 70/30 (w / w) TENCEL / 240 grade polyester (SX-33) hydroentangled nonwoven (Ahlstrom Green Bay, Green Bay, WI, USA) manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage and left to stand for approximately 30 days before testing. Five specimens from the sample were tested for vertical and inverted moisture vapor transmission rates (MVTR). The average values of the vertical and inverted MVTR MVTR was 1150 +/- 100 g / m ^2/24 hours and 2340 +/- 190 g / m ^2/24 hours, respectively.
Example 2 (Comparative) [0182] The nonwoven of example 1 was saturated with a 2.6% (w / w) aqueous solution of dehydrated sodium citrate and dried in a laboratory scale forced air oven (Memmert Universal Oven; Wisconsin Oven Company, East Troy, WI, USA) at 80 ° C for 30 minutes. The weight of the dehydrated sodium citrate coating on the nonwoven was 15 g / m ² . This coated nonwoven was then manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. The samples were left to stand for approximately 30 days before testing. For the five specimens tested from the sample, average values of the vertical and inverted MVTR MVTR were 1000 +/- 30 g / m ^2/24 hours and 2350 +/- 90 g / m ^2/24 hours, respectively.
Example 3 (Comparative) [0183] A 100% cotton hydrowoven nonwoven
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60/87 (COTTOASE) was saturated with a 5.4% (w / w) aqueous solution of citric acid, dried in an oven at 85 ° C for approximately 30 minutes and then manually laminated to the adhesive side of a bandage 3M TEGADERM 9548HP. The samples were left to stand for 3 days before testing. The average values of the vertical and inverted MVTR MVTR for the four test specimens were 1180 +/- 60 g / m ^2/24 hours and 1720 +/- 40 g / m ^2/24 hours, respectively.
Example 4 [0184] The nonwoven of example 1 was saturated with a 0.15 M aqueous solution of sodium hydroxide, and then dried in an oven at 75 ° C for 30 minutes before laminating to the adhesive side of the bandage. The weight of the sodium hydroxide coating on the nonwoven was measured at 5 g / m ² . This coated nonwoven was then manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. Four test specimens from the sample were tested two days after the lamination step for vertical and inverted moisture vapor transmission rates (MVTR). The average values of the vertical and inverted MVTR MVTR were 1210 +/- 50 g / m ^2/24 hours and 11400 + / 1800 g / ^m2 / 24 hours, respectively.
Example 5 [0185] The nonwoven of example 1 was saturated with a 0.30 M aqueous solution of sodium hydroxide, and then dried in an oven at 75 ° C for 30 minutes before laminating to the adhesive side of the bandage. The weight of the sodium hydroxide coating on the nonwoven was measured at 7 g / m ² . This coated nonwoven was then manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. Four test specimens from the sample were tested two days after the lamination step for vertical and inverted moisture vapor transmission rates (MVTR). The average values of the vertical and inverted MVTR MVTR were 1280 +/- 60 g / m ^2/24 hours and + 16 900/870 180 058 877 Application, the 07/06/2018, p. 74/106
61/87
740 g / m ^2/24 hours, respectively.
Example 6 [0186] The nonwoven of example 1 was coated by immersion in a 4.0% (w / w) aqueous sodium carbonate monohydrate solution at a rate of 3.96 meters / min (13 feet / min ) and dried in a pilot scale forced air oven at approximately 105 ° C for about 5 minutes. The weight of the sodium carbonate coating monohydrate in the nonwoven was 16.3 g / m ² . This coated nonwoven was then manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. For the five specimens tested, the mean values of the vertical and inverted MVTR MVTR were 1070 +/- 40 g / m ^2/24 hours and 20800 +/- 980 g / m ^2/24 hours, respectively.
Example 7 [0187] A 100% cotton hydroentangled nonwoven (COTTOASE) was saturated with a 3.5% (w / w) aqueous solution of sodium bicarbonate, dried in an oven at 45 ° C until dry and then , manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. The samples were left to stand for 3 days before testing. The average values of the vertical and inverted MVTR MVTR was 1340 +/- 100 g / m ^2/24 hours and 19100 +/- 870 g / ^m2 / 24 hours, respectively.
Example 8 [0188] The nonwoven of Example 1, a 40 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven was saturated with a 5.3% (w / w) aqueous solution p) potassium carbonate and then dried at 85 ° C for 40 minutes. The weight of the potassium carbonate coating on the nonwoven was 46 g / m ² . This coated nonwoven was then manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. The samples were tested four days after the lamination step. The mean values of the vertical MVTR and inverted MVTR of four test specimens were 1390 + / Petition 870180058877, of 07/06/2018, p. 75/106
62/87 g / m ^2/24 hours and 20700 +/- 530 g / ^m2 / 24 hours, respectively.
Example 9 [0189] The 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven of example 1 was saturated with a 3.7% (w / w) aqueous solution of sodium bicarbonate potassium and then dried at 75 ° C for 30 minutes. The weight of the potassium bicarbonate coating on the nonwoven was 24 g / m ² . This coated nonwoven was then manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. The samples were tested five days after the lamination step. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1650 +/- 20 g / m ^2/24 hours and 20300 +/- 610 g / ^m2 / 24 hours, respectively.
Example 10 [0190] The 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven of example 1 was saturated with a 2.6% (w / w) aqueous solution of carbonate sodium monohydrate and then dried in a laboratory-scale forced air oven (Memmert Universal Oven; Wisconsin Oven Company, East Troy, WI, USA) at 80 ° C for 30 minutes. The weight of the sodium carbonate monohydrate coating on the nonwoven was 8.3 g / m ² . This coated nonwoven was manually laminated to the adhesive side of a 3M TEGADERM 9548HP bandage. The two layers of non-treated nonwoven were placed on top of the non-woven coated layer that was laminated to the adhesive side of the bandage. Four specimens of the samples were tested five days after the lamination step. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1190 + / 100 g / m ^2/24 hours and 16700 +/- 1700 g / ^m2 / 24 hours, respectively.
Example 11 [0191] This example was prepared as example 10 with the exception that the two layers of untreated nonwoven were placed
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63/87 between the adhesive and the non-woven layer treated with sodium carbonate monohydrate. The average MVTR values of the vertical and inverted MVTR of the test specimens were 1240 +/- 280 g / m ^2/24 hours and 9150 +/- 1280 g / ^m2 / 24 hours, respectively.
Example 12 [0192] This example was prepared as example 6 with the exception that an additional layer of nonwoven that was treated with a 2.6% (w / w) aqueous solution of citric acid and then dried at 80 ° C for 30 minutes it was placed on the non-woven layer treated with sodium carbonate monohydrate. The addition of the non-woven layer treated with citric acid occurred eight days after lamination of the sample of sodium carbonate monohydrate to the adhesive side of the bandage. The weight of the citric acid coating on the nonwoven was 18.5 g / m ² . Five test specimens of the samples were tested 24 days after adding the citric acid treated nonwoven layer to the sample. The average MVTR values of the vertical and inverted MVTR of the test specimens were 1080 +/- 30 g / m ^2/24 hours and 9880 + / 2660 g / ^m2 / 24 hours, respectively.
Example 13 [0193] This example was prepared by cutting a sample of foam approximately 7.5 cm x 7.5 cm from a 90612 3M TEGADERM foam adhesive bandage (3M Company, St. Paul, MN, USA) so that the piece of foam to separate freely from all other parts of the bandage. One side of this piece of foam was then coated with a 5.5% (w / w) aqueous sodium carbonate monohydrate solution and dried at 80 ° C for 40 minutes. The weight of the sodium carbonate coating monohydrate on the foam piece was approximately 19 g / m ² . The coated side of the foam piece was then manually laminated to the adhesive side of a 3M TEGADERM 9548HP transparent bandage. Four
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64/87 test specimens were tested 5 days after the lamination step. The average MVTR values of the vertical and inverted MVTR of the test specimens were 900 +/- 60 g / m ^2/24 hours and 7840 +/- 1600 g / ^m2 / 24 hours, respectively.
Example 14 [0194] For this example, a layer of approximately 25 microns of pressure sensitive adhesive with a 70/15/15 IOA / AA / EOA ratio was used on paper liner, as described in US Patent No. 4,737 .410, example 31 with less than 1% polyethyloxazoline. An approximately 25 micron urethane film (ESTANE 58237 resin; Lubrizol Corporation, Wickliffe, OH, USA) was extruded onto the aforementioned adhesive layer using the method described in US Patent No. 4,499,896 to form the adhesive laminate / film about the lining. The nonwoven of example 1, a 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven, was saturated with a 2.6% (w / w) aqueous solution of carbonate sodium monohydrate before drying in an oven. This saturated nonwoven was then dried at 85 ° C for approximately 30 minutes. The weight of the sodium carbonate coating monohydrate on the nonwoven was 8 g / m ² . The average MVTR values of the vertical and inverted MVTR of five test specimens were 1660 +/- 60 g / m ^2/24 hours and 18800 +/- 860 g / ^m2 / 24 hours, respectively.
Example 15 (Comparative) [0195] For this example, the adhesive of example 14 and the urethane film of example 14 were constructed as described in example 14. The nonwoven of example 1, a hydro-interwoven TENCEL / polyester nonwoven 40 g / m ² 70/30 (w / w) was manually laminated directly to the adhesive side of the laminate without the addition of MVTR modifying material. The average MVTR values of the vertical and inverted MVTR up to five test specimens were 1150 +/- 30 g / m ^2/24 hours and 2250 +/- 250 g / ^m2 / 24 hours, respectively.
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Example 16 (Comparative) [0196] The samples were prepared by laminating the example 14 adhesive to a 25 micron ESTANE 58237 film on a paper carrier using an XRL 120 cylinder laminator (Western Magnum; El Segundo, CA, USA ) adjusted to approximately 0.14 MPa (20 psig (1.4 bar)). A second layer of the adhesive was then laminated using the roller laminator to the first adhesive layer in order to double the thickness of the adhesive. A piece of untreated nonwoven used in example 1 was then manually laminated to the adhesive six days before the test. The average MVTR values of the vertical and inverted MVTR of four test specimens were 690 +/- 40 g / m ^2/24 hours and 1170 +/- 210 g / m ^2/24 hours, respectively.
Example 17 [0197] The samples were prepared as example 16 with the exception that the nonwoven was saturated with a 2.6% (w / w) aqueous sodium carbonate monohydrate solution. This saturated nonwoven was then dried at 85 ° C for approximately 30 minutes to a dry coating weight of 11 g / m ² . The average MVTR values of the vertical and inverted MVTR of four test specimens were 1235 +/- 40 g / m ^2/24 hours and 20 700 + / 500 g / m ^2/24 hours, respectively.
Example 18 [0198] The sample was prepared in a similar manner to example 14, except that: 1) the nonwoven was coated by immersion in a 3% (w / w) aqueous solution of 3.96 sodium carbonate monohydrate meters / min (13 feet / min) and dried in a pilot scale forced air oven at approximately 105 ° C for about 5 minutes; 2) a second layer of absorbent nonwoven (National Non-wovens; Easthampton, MA, USA) was placed on the nonwoven layer treated with sodium carbonate monohydrate; and 3) a third absorbent layer (polyurethane foam used in adhesive
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66/87 3M TEGADERM foam) was then placed over the second layer of absorbent nonwoven. The weight of the sodium carbonate monohydrate coating on the treated nonwoven was 12.6 g / m ^2. These samples were also irradiated with gamma rays at 35.8 to 41.4 kGy. The samples were tested 12 days after construction and 8 days after gamma irradiation. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1200 + / 60 g / m ^2/24 hours and 16000 +/- 2800 g / ^m2 / 24 hours, respectively.
Example 19 [0199] The example was prepared and conducted in the same way as Example 18 with the exception that the test solution used for the MVTR tests was a 90/10 (w / w) mixture of phosphate buffered saline and adult bovine serum instead of running water. The phosphate buffered saline was P-3813 at a pH of 7.4 (Sigma-Aldrich; St. Louis, MO, USA). Bovine serum was product B9433 (Sigma-Aldrich; St. Louis, MO, USA). The average MVTR values of the vertical and inverted MVTR of four test specimens were 1080 +/- 130 g / m ^2/24 hours and 11200 +/- 1200 g / ^m2 / 24 hours, respectively.
Example 20 (Comparative) [0200] An approximately 18 micron layer of 90/10 (w / w) thickness of IOA / AA pressure sensitive adhesive prepared as described in US Patent No. 4,737,410, example 11, was used. The adhesive was pressure laminated using the XRL 120 cylinder laminator to a ESTANE 58237 polyurethane film approximately 25 microns thick on a paper carrier. The nonwoven of example 1, a 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven, was then manually laminated to the adhesive side of the adhesive / film laminate. The samples were tested six days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 820 +/- 10 g / m ^2/24 hours and 1180 +/- 20 g / m ^2/24 hours,
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67/87 respectively.
Example 21 [0201] A pressure sensitive IOA / AA 90/10 (w / w) adhesive with a layer approximately 18 microns thick was pressure laminated using the XRL 120 cylinder laminator to a ESTANE 58237 polyurethane film of approximately 25 microns thick on a paper carrier. The nonwoven of example 1, a 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven, was treated with sodium carbonate monohydrate, dried at 85 ° C for approximately 30 minutes to a dry coating weight of 11 g / m ² . The nonwoven was then manually laminated to the adhesive side of the adhesive / film laminate. The samples were tested six days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 900 +/- 30 g / m ^2/24 hours and 1440 +/- 50 g / m ^2/24 hours, respectively.
Example 22 (Comparative) [0202] An 18 micron thick pressure sensitive adhesive on a polyester liner was made as described in US Patent No. 4,737,410, but with the following monomers and proportions: 25/69/6 2EHA / BA / AA (w / w / w). The pressure sensitive adhesive was pressure laminated using a cylinder laminator to an ESTANE 58237 polyurethane film approximately 25 microns thick on a paper carrier. The nonwoven of example 1, a 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven, was then manually laminated to the adhesive side of the adhesive / film laminate. The samples were tested six days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1500 +/- 30 g / m ^2/24 hours and 2400 +/- 160 g / ^m2 / 24 hours, respectively.
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Example 23 [0203] The ASP of example 22 was pressure laminated using a cylinder laminator to a ESTANE 58237 polyurethane film approximately 25 microns thick on a paper carrier. The nonwoven of example 1, a 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven, was treated with sodium carbonate monohydrate, dried at 85 ° C for approximately 30 minutes to a dry coating weight of 11 g / m ² . The nonwoven was then manually laminated to the adhesive side of the adhesive / film laminate. The samples were tested six days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1570 +/- 80 g / m ^2/24 hours and 2540 +/- 60 g / m ^2/24 hours, respectively.
Example 24 (Comparative) [0204] The non-woven grade SX-473 (Ahlstrom, Greenbay, WI, USA) was laminated to a pressure sensitive adhesive of IOA / AA 90/10 (w / w) with a layer of approximately 38 microns thick using the XRL 120 cylinder laminator. The samples were tested eight days after laminating the nonwoven to the adhesive. The vertical average MVTR of five test specimens was 1390 +/- 420 g / m ^2/24 hours. The inverted MVTR was not measured because the specimens would have leaked during the test.
Example 25 [0205] This example was prepared as example 24 except that the non-woven grade SX-473 was saturated with a 3.4% (w / w) aqueous solution of sodium bicarbonate and dried at 50 ° C for 90 minutes and then 35 ° C overnight. The weight of the sodium bicarbonate coating was approximately 24 g / m ² . This treated nonwoven was laminated to the adhesive in example 24. The samples were tested eight days after laminating the nonwoven to the adhesive. The average vertical MVTR of five test specimens was 1860
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69/87 +/- 260 g / m ^2/24 hours.
Example 26 (Comparative) [0206] The non-woven grade SX-473 (Ahlstrom, Greenbay, WI, USA) was laminated by cylinder to a layer of approximately 38 microns thickness of the ASP of example 22, 25/69/6 (p / p / p) 2-EHA / BA / AA. The samples were tested eight days after laminating the nonwoven to the adhesive. The vertical average MVTR of five test specimens was 1390 +/- 420 g / m ^2/24 hours. The inverted MVTR was not measured because the specimens would have leaked during the test.
Example 27 [0207] This sample was prepared and tested as example 26 except that the nonwoven was saturated with a 3.4% (w / w) aqueous solution of sodium bicarbonate and dried at 50 ° C for 90 minutes and then 35 ° C overnight. The weight of the sodium bicarbonate coating was approximately 24 g / m ² . This treated nonwoven was manually laminated to the adhesive. The vertical average MVTR of five test specimens was 1680 + / 250 g / m ^2/24 hours.
Example 28 (Comparative) [0208] The adhesive in the liner in example 14 was treated with droplets of sterile water by spraying it with a spray bottle so that approximately 40% of the adhesive was covered with droplets, and then the sample was dried in a laboratory oven at 75 ° C for 35 minutes. A 25 micron thick ESTANE 58237 polyurethane film on a paper carrier was then laminated to the water-treated side of the adhesive on the liner using the XRL 120 laminator. The samples of the adhesive / film laminate were tested six days later the lamination step. The average MVTR values of the vertical and inverted MVTR of five test specimens were 940 + / 30 g / m ^2/24 hours and 1600 +/- 490 g / m ^2/24 hours, respectively. Membership
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70/87 mean steel for samples of 2.54 cm wide was measured to be 294 +/- 9 g / cm.
Example 29 [0209] This sample was prepared as example 28 with the exception that the adhesive on the liner was treated with droplets of a 1.5% (w / w) aqueous solution of sodium carbonate monohydrate using a syringe before drying. Each droplet weighed approximately 80 mg. The average MVTR values of the vertical and inverted MVTR of five test specimens were 1530 +/- 40 g / m ^2/24 hours and 9460 +/- 950 g / m ^2/24 hours, respectively. The average adhesion to steel of 2.54 cm wide samples was measured to be 166 +/- 16 g / cm.
Example 30 (Comparative) [0210] For this example, an adhesive with a layer of approximately 28 microns thick of IOA / AA 90/10 (w / w) on polyester liner was laminated to an ESTANE 58237 polyurethane film of approximately 25 microns thick on a paper carrier using the XRL 120 laminator. The example 1 nonwoven, a 40 g / m ² 70/30 (w / w) TENCEL / polyester nonwoven, was laminated directly manually to the adhesive side of the laminate without modifying material from the MVTR and the paper carrier was removed from the film side of the sample. Four specimens were tested six days after the construction of the samples. The average values of the vertical and inverted MVTR MVTR were 640 + / 15 g / m ^2/24 hours and 1090 +/- 30 g / m ^2/24 hours, respectively.
Example 31 (Comparative) [0211] The samples were prepared as example 30 except that the adhesive was only 18 microns thick. The average MVTR values of the vertical and inverted MVTR of four test specimens were 820 + / 15 g / m ^2/24 hours and 1180 +/- 20 g / m ^2/24 hours, respectively.
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Example 32 [0212] The samples were prepared as example 30 except that: (1) the nonwoven was saturated with a 2.5% (w / w) aqueous sodium carbonate monohydrate solution, dried at 85 ° C for approximately 30 minutes for a coating weight of sodium carbonate monohydrate on the dry nonwoven of 11 g / m ² ; and (2) the adhesive was only 18 microns thick. The average MVTR values of the vertical and inverted MVTR of four test specimens were 900 +/- 30 g / m ^2/24 hours and 1440 +/- 50 g / m ^2/24 hours, respectively.
Example 33 (Comparative) [0213] This sample was prepared as example 30 (no non-woven treatment with MVTR modifying material) except that the ESTANE 58237 polyurethane film on the paper carrier was laminated to an 18 micron layer thickness of the ASP of example 22, which was 25/69/6 2EHA / BA / AA (w / w / w). Four specimens were tested six days after the construction of the samples. The average values of the vertical and inverted MVTR MVTR were 1500 +/- 30 g / m ^2/24 hours and 2400 +/- 160 g / ^m2 / 24 hours, respectively.
Example 34 [0214] The samples were prepared as example 33 except that the nonwoven was saturated with an aqueous solution of 2.5% (w / w) sodium carbonate monohydrate, dried at 85 ° C for approximately 30 minutes for a coating weight of 11 g / m ² . The average MVTR values of the vertical and inverted MVTR of four test specimens were 1570 + / 80 g / m ^2/24 hours and 2540 +/- 60 g / m ^2/24 hours, respectively.
Example 35 (Comparative) [0215] A layer of approximately 22 microns thick of IOA / AA 90/10 pressure sensitive adhesive (w / w) was pressure laminated to an ESTANE 58237 polyurethane film of approximately
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72/87 microns thick on a paper carrier. The untreated nonwoven of example 1, a 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven was then manually laminated to the adhesive side of the adhesive / film laminate and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 920 +/- 10 g / m ^2/24 hours and 1460 +/- 140 g / ^m2 / 24 hours, respectively.
Example 36 [0216] The samples were prepared and tested as example 35 except that the nonwoven was saturated with a 3% (w / w) aqueous sodium carbonate monohydrate solution, dried at 75 ° C for 30 minutes, before lamination to the adhesive. The weight of the sodium carbonate coating monohydrate on the nonwoven was approximately 11 g / m ² . The average MVTR values of the vertical and inverted MVTR of four test specimens were 1040 +/- 60 g / m ^2/24 hours and 1570 +/- 100 g / ^m2 / 24 hours, respectively.
Example 37 (Comparative) [0217] A pressure sensitive adhesive approximately 22 microns thick was made as described in US Patent No. 4,737,410, but with the following monomers and proportions: ratio 46.5 / 46/7, 5 of 2EHA / BA / AA (w / w / w) was pressure laminated to a ESTANE 58237 polyurethane film approximately 25 microns thick on a paper carrier. The untreated nonwoven of example 1, a 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven was then manually laminated to the adhesive side of the adhesive / film laminate and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1560 +/- 30 g / m ^2/24 hrs
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73/87 and 2470 +/- 110 g / ^m2 / 24 hours, respectively.
Example 38 [0218] Samples were prepared and tested as example 37 except that the nonwoven was saturated with a 3% (w / w) aqueous sodium carbonate monohydrate solution, dried at 85 ° C for approximately 30 minutes for a coating weight of 11 g / m ² . The average MVTR values of the vertical and inverted MVTR of four test specimens were 1590 + / 10 g / m ^2/24 hours and 2590 +/- 130 g / m ^2/24 hours, respectively.
Example 39 (compared with amine adhesive) [0219] An amine-based adhesive was produced by polymerizing a mixture of 2-EHA (90 g), acrylamide (4 g), dimethylaminoethyl methacrylate, DMAEMA (6 g) in ethyl acetate (122 g) at 55 ° C for 16 hours followed by 65 ° C for 8 hours. The resulting adhesive in solution was coated over a removable and dry liner, resulting in an adhesive layer approximately 25 microns thick on the liner. This adhesive was then laminated by pressure to an ESTANE 58237 polyurethane film approximately 25 microns thick on a paper carrier. The nonwoven of example 1, a TENCEL / polyester 40 g / m ² 70/30 (w / w) hydroentangled nonwoven, was then manually laminated to the adhesive side of the adhesive / film laminate seven days earlier of the test. The average MVTR values of the vertical and inverted MVTR of five test specimens were 950 +/- 40 g / m ^2/24 hours and 1520 +/- 210 g / m ^2/24 hours, respectively.
Example 40 (comparative base with MVTR modifying material and basic adhesive) [0220] This sample was prepared and tested as example 39, except that the nonwoven was treated with MVTR modifying material, sodium carbonate monohydrate, dried at 85 ° C. ° C for approximately 30 minutes for a coating weight of 12 g / m ² before laminating to
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74/87 adhesive. The average MVTR values of the vertical and inverted MVTR of five test specimens were 990 +/- 30 g / m ^2/24 hours and 1590 +/- 300 g / ^m2 / 24 hours, respectively.
Example 41 (Comparative) [0221] An adhesive solution with 33% solids in ethyl acetate from the adhesive of example 14 was coated on a removable liner and dried to a thickness of 23 microns. The adhesive was pressure laminated to a ESTANE 58237 polyurethane film approximately 25 microns thick on a paper carrier. The nonwoven of example 1, a 40 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven was then manually laminated to the adhesive side of the adhesive / film construction at least seven days before of the test. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1300 +/- 30 g / m ^2/24 hours and 1950 + / 110 g / m ^2/24 hours, respectively. The average adhesion to steel of five test specimens that were 2.54 cm wide was measured to be 540 +/- 5 g / cm.
Example 42 (comparative as dispersion of material modifying the
MVTR in adhesive) [0222] Droplets of a 20% (w / w) aqueous sodium carbonate monohydrate solution were added to the adhesive solution of example 41 until approximately 20% of the acidic groups present in the adhesive were neutralized. The resulting adhesive mixture was slightly cloudy. Samples using this adhesive mixture were then prepared and tested as described in example 41. The thickness of the adhesive was approximately 26 microns. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1360 +/- 20 g / m ^2/24 hours and 2030 +/- 60 g / m ^2/24 hours, respectively. The average adhesion to steel of five test specimens that were 2.54 cm wide was measured to be 140 +/- 3 g / cm.
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Table 2: Summary of experimental results for examples 1 to 42
Example Sticker Support Compositionmodifier ofmvtr Vertical (Dry) MVTR g / ^m2 / 24 hr +/- standard deviation Inverted (Wet) MVTR g / ^m2 / 24 hr +/- standard deviation 1 65/15/20 PU film none 1150 +/- 100 2340 +/- 190 Comp. 2-EHA / AA / Pluronic (Resin 58237) 25R4 2 65/15/20 PU film Na-citrate 1000 +/- 30 2350 +/- 90 Comp. 2-EHA / AA / Pluronic (Resin 58237) 25R4 3 65/15/20 PU film Citric acid 1180 +/- 60 1720 +/- 40 Comp. 2-EHA / AA / Pluronic (Resin 58237) 25R4 4 65/15/20 PU film 0.15 M NaOH 1210 +/- 50 11400 +/- 1800 2-EHA / AA / Pluronic (Resin 58237) 25R4 5 65/15/20 PU film 0.3 M NaOH 1280 +/- 60 16900 +/- 740 2-EHA / AA / Pluronic (Resin 58237) 25R4 6 65/15/20 PU film Na carbonate 1070 +/- 40 20800 +/- 980 2-EHA / AA / Pluronic (Resin 58237) monohydrate 25R4 7 65/15/20 PU film Na bicarbonate 1340 +/- 100 19100 +/- 870 2-EHA / AA / Pluronic (Resin 58237) 25R4
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Example Sticker Support Compositionmodifier ofMVTR Vertical (Dry) MVTR g / ^m2 / 24 hr +/- Standard Deviation Inverted (Wet) MVTR g / ^m2 / 24 hr +/- Standard Deviation 8 65/15/20 PU film Carbonate 1390 +/- 40 20700 +/- 530 2-EHA / AA / Pluronic (Resin 58237) potassium 25R4 9 65/15/20 PU film Bicarbonate 1650 +/- 20 20300 +/- 610 2-EHA / AA / Pluronic (Resin 58237) potassium 25R4 10 65/15/20 PU film Na carbonate 1190 +/- 100 16700 +/- 1700 2-EHA / AA / Pluronic (Resin 58237) monohydrate - 25R4 with layers untreated added 11 65/15/20 PU film Na carbonate 1240 +/- 280 9150 +/- 1280 2-EHA / AA / Pluronic (Resin 58237) monohydrate - 25R4 with layersuntreated added between the sticker and the treated layer 12 65/15/20 PU film Layer 1 - 1080 +/- 30 9880 +/- 2660 2-EHA / AA / Pluronic (Resin 58237) Na carbonate 25R4 monohydrate Layer 2 - acid
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Example Sticker Support Composition Vertical Inverted modifier of (Dry) (Wet) MVTR MVTR g / ^m2 / 24 hr MVTR +/- Deviation g / ^m2 / 24 hr +/- Standard Standard deviation citric 13 65/15/20 PU film Na carbonate 900 +/- 60 7840 +/- 1600 2-EHA / AA / Pluronic (Resin 58237) monohydrate 25R4 over foam 14 70/15/15 (IOA / AA / EOA PU film Na carbonate 1660 +/- 60 18800 +/- 860 + less than 1% PEOX) (Resin 58237) monohydrate 15 70/15/15 (IOA / AA / EOA PU film none 1150 +/- 30 2520 +/- 250 Comp. + less than 1% PEOX) (Resin 58237) 16 50 microns PU film none 690 +/- 40 1170 +/- 210 Comp. thickness 70/15/15 (Resin 58237) (IOA / AA / EOA + less 1% PEOX) 17 50 microns PU film Na carbonate 1235 +/- 100 20700 +/- 500 thickness 70/15/15 (Resin 58237) monohydrate (IOA / AA / EOA + less 1% PEOX) 18 70/15/15 (IOA / AA / EOA PU film 3 layers - 1200 +/- 60 16000 +/- 2800 + less than 1% PEOX) (Resin 58237) Na carbonate monohydrate nonwoven treated + non-woven absorbent +
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Example Sticker Support Composition Vertical Inverted modifier of (Dry) (Wet) MVTR MVTR g / ^m2 / 24 hr MVTR +/- Deviation g / ^m2 / 24 hr +/- Standard Standard deviation foam 19 70/15/15 (IOA / AA / EOA PU film Even if the 1080 +/- 130 11200 +/- 1200 + less than 1% PEOX) (Resin 58237) example 22 except that the solution MVTR test was buffered 20 90/10 PU film none 820 +/- 10 1180 +/- 20 Comp. (IOA / AA) (Resin 58237) 21 90/10 PU film Na carbonate 900 +/- 30 1440 +/- 50 (IOA / AA) (Resin 58237) monohydrate 22 6/25/6 PU film none 1500 +/- 30 2400 +/- 160 Comp. (2-EHA / BA / AA) (Resin 58237) 23 6/25/6 PU film Na carbonate 1570 +/- 80 2540 +/- 60 (2-EHA / BA / AA) (Resin 58237) monohydrate 24 90/10 SX-473 none 1390 +/- 420 Not tested Comp. (IOA / AA) (Rayon / non- PET fabric) 25 90/10 SX-473 Na bicarbonate 1860 +/- 260 Not tested (IOA / AA) (Rayon / non- PET fabric) 26 6/25/6 SX-473 none 1380 +/- 150 Not tested Comp. (2-EHA / BA / AA) (Rayon / non-
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Example Sticker Support Composition Vertical Inverted modifier of (Dry) (Wet) MVTR MVTR g / ^m2 / 24 hr MVTR +/- Deviation g / ^m2 / 24 hr +/- Standard Standard deviation PET fabric) 27 6/25/6 SX-473 Na bicarbonate 1680 +/- 250 Not tested (2-EHA / BA / AA) (Rayon / non- PET fabric) 28 70/15/15 (IOA / AA / EOA PU film Droplets 940 +/- 30 1600 +/- 490 Comp. + less than 1% PEOX) (Resin 58237) sprinkled from Water 29 70/15/15 (IOA / AA / EOA PU film Droplets of 1530 +/- 30 9460 +/- 490 + less than 1% PEOX) (Resin 58237) Na carbonate monohydrate 30 90/10 PU film none 640 +/- 15 1090 +/- 30 Comp. (IOA / AA) (Resin 58237) 31 90/10 PU film none 820 +/- 15 1180 +/- 20 Comp. (IOA / AA) (Resin 58237) 32 90/10 PU film Na carbonate 900 +/- 30 1440 +/- 50 (IOA / AA) (Resin 58237) monohydrate 33 6/25/6 PU film none 1500 +/- 30 2400 +/- 160 Comp. (2-EHA / BA / AA) (Resin 58237) 34 6/25/6 PU film Na carbonate 1570 +/- 80 2540 +/- 60 (2-EHA / BA / AA) (Resin 58237) monohydrate 35 90/10 PU film none 920 +/- 10 1460 +/- 140 Comp. (IOA / AA) (Resin 58237)
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Example Sticker Support Compositionmodifier ofMVTR Vertical (Dry) MVTR g / ^m2 / 24 hr +/- Standard Deviation Inverted (Wet) MVTR g / ^m2 / 24 hr +/- Standard Deviation 36 90/10 PU film Na carbonate 1040 +/- 60 1570 +/- 100 (IOA / AA) (Resin 58237) monohydrate 37 46.5 / 46 / 7.5 2- PU film none 1560 +/- 30 2470 +/- 110 Comp. EHA / BA / AA (Resin 58237) 38 46.5 / 46 / 7.5 2- PU film Na carbonate 1590 +/- 10 2590 +/- 130 EHA / BA / AA (Resin 58237) monohydrate 39 Adhesive amine PU film none 950 +/- 40 1520 +/- 210 Comp. 4/9/9 (Resin 58237) (2-EHA / acrylamide / DMAEMA) 40 Adhesive amine PU film Na carbonate 990 +/- 30 1590 +/- 300 Comp. 4/9/9 (Resin 58237) monohydrate (2-EHA / acrylamide / DMAEMA) 41 33% solids in PU film none 1300 +/- 30 1950 +/- 110 Comp. ethyl acetate (Resin 58237) 70/15/15 (IOA / AA / EOA + less than 1% PEOX) 42 33% solids in PU film Na carbonate 1300 +/- 30 1950 +/- 110 Comp. ethyl acetate (Resin 58237) monohydrate for
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Example Sticker Support Compositionmodifier ofMVTR Vertical (Dry) MVTR g / ^m2 / 24 hr +/- standard deviation Inverted (Wet) MVTR g / ^m2 / 24 hr +/- standard deviation 70/15/15 (IOA / AA / EOA neutralize 20% of + less than 1% PEOX) acid groups in adhesive
2-EHA = 2-ethyl hexyl acrylate
AA = acrylic acid
BA = butyl acrylate
EOA = poly methoxy acrylate macromer (ethylene oxide)
IOA = isooctylacrylate
Na = sodium
PEOX = poly (ethyloxazoline)
Pluronic 25R4 = copolymer of poly (ethylene polypropylene) diol available from BASF, Mount Olive, NJ, USA PU = polyurethane
Example 43 (Comparative) [0223] An IOA / AA adhesive 85/15 (w / w) approximately 25 microns thick was pressure-laminated to a Estane 58237 polyurethane film approximately 25 microns thick on a paper carrier . A 70 g / m ² 70/30 (w / w) TENCEL / polyester hydroentangled nonwoven (Ahlstrom Green Bay, Green Bay, WI, USA) was then manually laminated to the adhesive side of the adhesive / film laminate. and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The mean values of the vertical MVTR and inverted MVTR of four test specimens were
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600 +/- 40 g / m ^2/24 hours and 750 +/- 30 g / m ^2/24 hours, respectively.
Example 44 [0224] The nonwoven of example 43 was saturated with a 4.0% (w / w) aqueous sodium carbonate monohydrate solution at a rate of 3.96 meters / min (13 feet / min) and dried in a pilot scale forced air oven at approximately 105 ° C for about 5 minutes. The weight of the sodium carbonate coating monohydrate in the nonwoven was 16.3 g / m ² . This coated nonwoven was then manually laminated to the adhesive side of the 43C adhesive / film laminate. The specimens were tested seven days after lamination. The average MVTR values of the vertical and inverted MVTR of four test specimens were 720 +/- 100 g / m ^2/24 hours and 1090 +/- 230 g / m ^2/24 hours, respectively.
Example 45 (Comparative) [0225] An IOA / AA 87.5 / 12.5 (w / w) adhesive approximately 25 microns thick was pressure-laminated to a Estane 58237 polyurethane film approximately 25 microns thick on a paper carrier. The untreated nonwoven of example 44 was then manually laminated to the adhesive side of the adhesive / film laminate and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 600 +/- 10 g / m ^2/24 hours and 800 +/- 20 g / m ^2/24 hours, respectively.
Example 46 [0226] This example was prepared and tested as example 45 except that the soda-coated nonwoven of example 44 was manually laminated to the adhesive side of IOA / AA 87.5 / 12.5 (w / w ) of the adhesive / film laminate, rather than an untreated nonwoven. The mean values of the vertical MVTR and inverted MVTR of four test specimens were 600 + / Petition 870180058877, of 07/06/2018, p. 96/106
83/87 g / ^m2 / 24 hours and 910 +/- 100 g / ^m2 / 24 hours, respectively.
Example 47 (Comparative) [0227] An IOA / AA / EOA 80/10/10 (w / w / w) adhesive approximately 25 microns thick was pressure-laminated to a Estane 58237 polyurethane film approximately 25 microns thick. thickness on a paper carrier. The untreated nonwoven of example 44 was then manually laminated to the adhesive side of the adhesive / film laminate and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1580 +/- 40 g / m ^2/24 hours and 3070 +/- 130 g / m ^2/24 hours, respectively.
Example 48 [0228] This example was prepared and tested as example 47 except that the soda-coated nonwoven of example 44 was manually laminated to the adhesive side of IOA / AA / EOA 80/10/10 (w / w / p) the adhesive / film laminate, instead of an untreated nonwoven. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1440 +/- 110 g / m ^2/24 hours and 3350 +/- 190 g / m ^2/24 hours, respectively.
Example 49 (Comparative) [0229] An IOA / AA / EOA75 / 12.5 / 12.5 (w / w / w) adhesive of approximately 25 microns in thickness was pressure laminated to a Estane 58237 polyurethane film of approximately 25 microns thick on a paper carrier. The untreated nonwoven of example 44 was then manually laminated to the adhesive side of the adhesive / film laminate and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1500 +/- 100 g / m ^2/24 hours and 2870 +/- 240 g / m ^2/24 hours, respectively.
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Example 50 [0230] This example was prepared and tested as example 49 except that the soda-coated nonwoven of example 44 was manually laminated to the adhesive side of IOA / AA / EOA 75 / 12.5 / 12.5 (w / w / w) of the adhesive / film laminate, instead of an untreated nonwoven. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1450 +/- 80 g / m ^2/24 hours and 11400 +/- 600 g / ^m2 / 24 hours, respectively.
Example 51 (Comparative) [0231] An IOA / AA / EOA 84/6/10 (w / w / w) adhesive approximately 25 microns thick was pressure-laminated to a Estane 58237 polyurethane film approximately 25 microns thick. thickness on a paper carrier. The untreated nonwoven of example 44 was then manually laminated to the adhesive side of the adhesive / film laminate and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1880 +/- 90 g / m ^2/24 hours and 4250 +/- 260 g / ^m2 / 24 hours, respectively.
Example 52 [0232] This example was prepared and tested as example 51 except that the soda-coated nonwoven of example 44 was manually laminated to the adhesive side of IOA / AA / EOA 84/6/10 (w / w / p) the adhesive / film laminate, instead of an untreated nonwoven. The average MVTR values of the vertical and inverted MVTR of four test specimens were 1740 +/- 40 g / m ^2/24 hours and 5400 +/- 1400 g / ^m2 / 24 hours, respectively.
Example 53 (Comparative) [0233] An IOA / AA / EOA adhesive 74/6/20 (w / w / w) approximately 25 microns thick was pressure-laminated to a Estane 58237 polyurethane film approximately 25 microns thick. thickness
Petition 870180058877, of 07/06/2018, p. 98/106
85/87 on a paper carrier. The untreated nonwoven of example 44 was then manually laminated to the adhesive side of the adhesive / film laminate and the paper carrier was removed from the film side of the sample. The samples were tested seven days after laminating the nonwoven to the adhesive. The average MVTR values of the vertical and inverted MVTR of four test specimens were 2410 +/- 80 g / m ^2/24 hours and 8350 +/- 510 g / ^m2 / 24 hours, respectively.
Example 54 [0234] This example was prepared and tested as example 53 except that the soda-coated nonwoven of example 44 was manually laminated to the adhesive side of IOA / AA / EOA 74/6/20 (w / w / p) the adhesive / film laminate, instead of an untreated nonwoven. The average MVTR values of the vertical and inverted MVTR of four test specimens were 2190 +/- 50 g / m ^2/24 hours and 10500 +/- 1780 g / ^m2 / 24 hours, respectively.
Table 3: Summary of experimental results for examples 43 to 54
Example Sticker Support Compositionmodifier ofmvtr Vertical (Dry) MVTR g / ^m2 / 24 hr +/- standard deviation Inverted (Wet) MVTR g / ^m2 / 24 hr +/- standard deviation 43 Comp. 85/15 PU Film (Resin none 600 +/- 40 750 +/- 30 IOA / AA 58237) 44 85/15 PU Film (Resin Na carbonate 720 +/- 100 1090 +/- 230 IOA / AA 58237) monohydrate 45 Comp. 87.5 / 12.5 PU Film (Resin none 600 +/- 10 800 +/- 20 IOA / AA 58237) 46 87.5 / 12.5 PU Film (Resin Na carbonate 600 +/- 20 910 +/- 100 IOA / AA 58237) monohydrate
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47 Comp. 10/10/10IOA / AA / EOA PU Film (Resin58237) none 1580 +/- 40 3070 +/- 130 48 10/10/10 PU Film (Resin Na carbonate 1440 +/- 110 3350 +/- 190 IOA / AA / EOA 58237) monohydrate 49 Comp. 75 / 12.5 / 12.5 PU Film (Resin none 1500 +/- 100 2870 +/- 240 IOA / AA / EOA 58237) 50 75 / 12.5 / 12.5 PU Film (Resin Na carbonate 1450 +/- 80 11400 +/- 600 IOA / AA / EOA 58237) monohydrate 51 Comp. 6/6/10 PU Film (Resin none 1880 +/- 90 4250 +/- 260 IOA / AA / EOA 58237) 52 6/6/10 PU Film (Resin Na carbonate 1740 +/- 40 5400 +/- 1400 IOA / AA / EOA 58237) monohydrate 53 Comp. 6/6/20 PU Film (Resin none 2410 +/- 80 8350 +/- 510 IOA / AA / EOA 58237) 54 6/6/20 PU Film (Resin Na carbonate 2190 +/- 50 10500 +/- 1780 IOA / AA / EOA 58237) monohydrate
AA = acrylic acid
IOA = isooctylacrylate
EOA = poly (polyethylene oxide) ethylene macromer [0235] The complete descriptions of the patents, patent documents and publications cited in the present invention are hereby incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this invention will become apparent to those skilled in these techniques without departing from the scope and spirit of the invention. It should be understood that this invention is not intended to be unduly limited by the modalities and illustrative examples presented here and that these examples and modalities are
Petition 870180058877, of 07/06/2018, p. 100/106
87/87 presented by way of example only, the scope of the invention being intended to be limited only by the claims presented here as follows.
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1/4

权利要求:
Claims (15)
[1]
Claims
1. MEDICAL ARTICLE, characterized by understanding:
a pressure sensitive adhesive layer (ASP) comprising acidic functional groups or basic functional groups, the ASP including at least 0.84 mmols of acidic or basic functional groups per gram of ASP; and a moisture vapor transmission rate modifier (MVTR) material that is basic when the ASP comprises acidic functional groups or is acidic when the ASP comprises basic functional groups;
wherein the MVTR modifying material is present in an MVTR modifying layer that includes a framework or where the MVTR modifying material is disposed on the surface of the ASP layer;
the modifying material of the MVTR is immiscible with the ASP, and reacts with the functional groups of the ASP through contact to form a poly-salt in the presence of fluid.
[2]
2. ARTICLE, according to claim 1, characterized in that the ASP comprises a functional polymer, said polymer being prepared from at least 6% by weight of acidic or basic functional monomers, based on the total weight of the ASP.
[3]
3. ARTICLE according to claim 1, characterized in that the ASP includes at least 1.8 mmols of acidic or basic functional groups per gram of ASP.
[4]
4. ARTICLE according to any one of claims 1 to 3, characterized in that the modifying material of the MVTR is arranged on a surface of the ASP layer.
[5]
5. ARTICLE according to claim 1, characterized in that it additionally comprises a second layer of ASP, in which the MVTR modifying material is disposed between the two layers of ASP.
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2/4
[6]
6. ARTICLE, according to any one of claims 1 to 4, characterized by the modifying material of the MVTR being incorporated within a framework that is in contact with the ASP layer.
[7]
7. ARTICLE, according to claim 1, characterized in that it comprises a support and the MVTR modifying material is disposed between the ASP layer and the support.
[8]
8. ARTICLE, according to claim 1, characterized in that it additionally comprises a pH modifying layer, in which the MVTR modifying material is disposed between the ASP layer and the pH modifying layer, with the modifying layer of pH being pH comprises a pH modifying material selected from the group consisting of polyacrylic acid, citric acid, and combinations thereof.
[9]
9. ARTICLE, according to claim 1, characterized by additionally comprising:
a carrier film in contact with the ASP layer; an absorbent pad disposed between the carrier film and the adhesive layer; and a support arranged between a support layer and the ASP layer.
[10]
10. ARTICLE according to claim 1, characterized in that the ASP layer comprises a polymer that has acidic functional groups, and the MVTR modifying material is basic.
[11]
11. ARTICLE according to claim 10, characterized in that the MVTR modifying material comprises a base selected from a group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, silver hydroxide, hydroxide zinc, ammonium hydroxide, magnesium hydroxide, barium hydroxide, strontium hydroxide, cesium hydroxide, rubidium hydroxide, ammonium carbonate, carbonate
Petition 870180058877, of 07/06/2018, p. 103/106
3/4 sodium, sodium bicarbonate, potassium carbonate, potassium bicarbonate, silver carbonate, lithium carbonate, lithium bicarbonate, barium bicarbonate, magnesium carbonate, cesium carbonate, hydrates thereof, and combinations thereof.
[12]
12. ARTICLE according to any one of claims 10 to 11, characterized in that the ASP comprises adhesives based on rubber, (meth) acrylics, poly (alpha-olefins), polyurethane, silicones, and combinations thereof.
[13]
13. ARTICLE, according to claim 1, characterized in that the ASP comprises basic functional groups, and the MVTR modifying material is acidic.
[14]
14. An article according to any one of claims 1 to 13, characterized by a wet MVTR of at least 1200 g / ^m2 / 24 hours.
[15]
15. METHOD FOR INCREASING THE HUMIDITY STEAM TRANSMISSION RATE, from an adhesive layer on a medical article, as defined in any one of claims 1 to 14, characterized by comprising:
providing a layer of ASP comprising acidic functional groups or basic functional groups, the ASP including at least 0.84 mmols of acidic or basic functional groups per gram of ASP;
providing a MVTR modifying material that is basic when the ASP comprises acidic functional groups or is acidic when the ASP comprises basic functional groups, the MVTR modifying material being immiscible with the ASP; and placing the MVTR-modifying material in the medical article in a location that allows the MVTR-modifying material to contact the ASP when the medical article comes in contact with fluid during use;
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4/4 the contact between the modifying material of the MVTR, the ASP, and the fluid causes an acid-base reaction to form a poly-salt and increase the moisture permeability of at least a portion of the ASP layer.
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1/4
2/4
3/4
4/4

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法律状态:
2018-04-10| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2018-08-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2018-09-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |

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2018-10-02| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/11/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) REF. RPI 2489 DE 18/09/2018 QUANTO AO ITEM (54) TITULO. |

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2021-08-31| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |

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2021-12-21| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2643 DE 31-08-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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US25962209P| true| 2009-11-09|2009-11-09|

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US30138610P| true| 2010-02-04|2010-02-04|

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PCT/US2010/055958|WO2011057240A1|2009-11-09|2010-11-09|Medical articles and methods of making using immiscible material|

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