Polyurethane having a delayed relaxation behavior for compression products

Abstract

The present invention relates to medical aids, particularly compression products such as compression stockings or bandages. More specifically, the present invention relates to compression products comprising a fiber-forming polyurethane polymer that exhibits delayed, continuous relaxation behavior. The present invention also relates to N-diol-containing polyurethane polymers and corresponding quaternized polyurethane polymers, processes for producing the polyurethane polymers, blends with elastane, and uses. In one embodiment, the PU polymer contains at least one N-diol monomer component, preferably two or more, more preferably several or multiple N-diol monomer components.

Description

Technical Field

[0001] The present invention relates to medical aids, in particular compression products such as compression stockings or compression bandages. More specifically, the present invention relates to compression products containing a fiber-forming polyurethane polymer that exhibits a delayed and continuous relaxation behavior. The present invention further relates to polyurethane polymers containing N-diol and the corresponding quaternized polyurethane polymers, processes for manufacturing polyurethane polymers, blends with elastane, and uses.

Background Art

[0002] Compression stockings are special stockings designed to help prevent the occurrence of venous disorders such as edema, phlebitis, and thrombosis, and to prevent further progression. Such stockings are elastic garments worn around the leg, thereby compressing the limb. This reduces the diameter of the dilated veins and increases the blood flow velocity in the veins and the effectiveness of the valves.

[0003] In a clinical or outpatient setting, the application of compression stockings is usually performed by a physician or nurse. Alternatively, compression stockings are also applied routinely by the patient himself, for example at home.

[0004] Fitting is of crucial importance for the therapeutic effect of compression stockings. Therefore, the correct size of stockings is determined by first measuring the leg. The correct application of compression stockings can also be of crucial importance, and therefore medical personnel or patients need to be carefully trained.

[0005] In order to provide compression to the leg, the material for making compression stockings should not be too elastic or too extensible. Therefore, compression stockings can be difficult to put on. This is especially true when the patient is frail, bedridden, or sickly, or when the patient has to experience pain.

[0006] Therefore, the development of compression stockings and other medical compression products that ensure excellent compression force while being comfortable to apply remains difficult.

[0007] Typically, the elastic polymers incorporated into compression products are the subject of improvement efforts. One popular polymer often used when elasticity is desired is elastane.

[0008] Elastane (spandex, Lycra®) is a polyether - polyurethane block copolymer containing at least 85% polyurethane. Elastane was invented by DuPont in 1958 and introduced to the market in 1962. The synthetic fibers of elastane are known for their exceptional elasticity: elastane fibers, after being strongly stretched, substantially recover their original length. To that extent, elastane is an elastomer like natural rubber, but is stronger and more durable than natural rubber. Apart from medical compression products, elastane is widely used in the textile and clothing industries, for example in tights, corset goods or sportswear.

[0009] U.S. Patent Application Publication No. 2008 / 0249454 discloses compression stockings constructed from a knitted fabric containing a tensioned elastic material that provides sufficient stretch for the stocking to be easily put on the foot. Spandex is the material thought to be incorporated into this stocking.

[0010] International Publication No. 2011 / 132011 discloses a knitted - type compression article having a therapeutic and / or physiological effect, designed to facilitate its wearing with a high level of compression exceeding 20 mmHg, which includes a weft yarn with double - helix added throughout the manufactured article, with an elastomer core, particularly with elastane.

[0011] Several other elastic polymers are also used in compression products, and polyurethane is one of them. Polyurethane (PU) is a polymer produced from a number of molecular units linked by urethane (carbamate) groups. Basically, this polymer is produced by step polymerization (polyaddition), in which a monomer containing at least two isocyanate functional groups (-N=C=O) reacts with another monomer containing at least two hydroxyl (alcohol) (-OH) groups, thereby forming urethane groups (-NH-CO-O-).

[0012] U.S. Patent Application Publication No. 2007 / 0113593 discloses a functional compression sock containing polyurethane.

[0013] U.S. Patent Application Publication No. 2010 / 0191163 discloses a dynamic response anatomical bandage system containing a polyurethane foam layer.

[0014] An interesting effort in improving compression products is the use of shape memory polymers. Shape memory materials are characterized by the ability to recover from a large plastic deformation to their original shape when a specific stimulus is applied (shape memory effect). After deformation by stretching, the fibers of the shape memory polymer can cause shape recovery by various stimuli, such as light (ultraviolet and infrared light), chemical stimuli (moisture, solvents, pH changes), heat (e.g., in thermoresponsive shape memory polymers), electric or magnetic fields, or radiation. The idea behind the use of shape memory polymers is that compression products can be applied in a temporarily stored, expanded shape. When an appropriate stimulus is applied, the compression product will ultimately relax, i.e., reverse the deformation, thereby accumulating compression.

[0015] International Publication No. 2012 / 045427 discloses a medical aid for human or animal bodies, particularly body support bandages and orthotics, containing at least one element for generating or delivering support force, compression, or pressure, and containing or consisting of a shape memory material. Polyurethane is contemplated as a shape memory material. The shape memory effect is caused by body temperature.

[0016] International Publication No. 2013 / 149985 discloses a knitted fabric containing a shape memory material and an expanding agent. Polyurethane is considered to function as a shape memory material.

[0017] Chinese Patent No. 105078652 discloses an intelligent compression system based on a shape memory material.

[0018] In any case, high standards are required for elastic polymers used in medical compression products. They should provide excellent compression while having excellent application properties. Furthermore, they should exhibit excellent tensile strength, compatibility with medical uses, gentleness to the skin, compatibility with daily use, and excellent washability.

[0019] Improvements in elastic polymers for use in medical compression products are still needed.

[0020] Therefore, an object of the present invention is to provide an improved elastic polymer and thus an improved medical compression product.

Prior Art Documents

Patent Documents

[0021]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

[0022] The present invention is defined in the independent claims and achieves the object as described below in different aspects. Specific embodiments are defined in the dependent claims and are also described below.

[0023] In a first aspect, the present invention provides a compression product comprising or consisting of an elastic component or material, the elastic component or material being capable of applying a compressive force or a supporting force or a local pressure to a part of a subject's body, the elastic component or material further being capable of undergoing a first phase during which the component or material expands, a second phase during which the component or material relaxes without or not completely or only partially returning to its original shape, and a third phase during which the component or material returns to or substantially returns to or almost completely returns to its original shape, preferably continuously returns to its original shape, more preferably continuously returns to its original shape while decelerating, wherein the relaxation, preferably the second phase, more preferably the second and third phases, is self-initiated, preferably self-initiated autonomously or spontaneously in the absence of an external stimulus.

[0024] In one embodiment of the compression product, the elastic component or material is (a) a non-quaternized polyurethane (PU) polymer (PU-N) containing N-diol; and / or (b) a quaternized polyurethane (PU) polymer or ionomer (PU-N+) containing quaternized N-diol; and, optionally, (c) elastane comprising or consisting of.

[0025] In a second aspect, the present invention (a) a non-quaternized polyurethane (PU) polymer (PU-N) containing an N-diol; and / or (b) a quaternized polyurethane (PU) polymer or ionomer (PU-N+) containing a quaternized N-diol; and, optionally, (c) an elastane to provide a compression product comprising or consisting of an elastic component or material comprising or consisting of the foregoing.

[0026] In one embodiment of the first or second aspect, the compression product is a medical compression product.

[0027] In one embodiment of the first or second aspect, the compression product is selected from the group consisting of compression stockings, preferably compression stockings, socks, knee socks, tights, pantyhose, or maternity pantyhose, compression knee pads, compression arm sleeves, compression waist attachments, belts or girdles, compression bandages, body support bandages, prosthetics, liners for prosthetics, compression wound dressings, compression plasters or patches, and compression garments, preferably compression garments for medical purposes.

[0028] In one embodiment of the second aspect, the compression product, or the elastic component or material, can apply a compressive force or a support force or a local pressure to a part of the subject's body.

[0029] In one embodiment of the first or second aspect, the part of the body is selected from the group consisting of the subject's limb, leg, thigh, calf, knee, arm, upper arm, forearm, elbow, hand, finger, wrist, foot, heel, toe, ankle, Achilles tendon, shoulder, upper body, lower body, waist, neck, part of the head, cheekbone, forehead, nose, and jaw.

[0030] In one embodiment of the first or second aspect, the subject is a human, preferably a human patient or an athlete. In an alternative embodiment, the subject is an animal, preferably a companion animal or a sporting animal.

[0031] In one embodiment of the first or second aspect, the subject is a user of a medical compression product, such as a patient who applies and wears the compression product. In another embodiment, the patient wears a medical compression product, which is applied on the one hand by a third party, such as a nurse.

[0032] In one embodiment of the first or second aspect, the compression product includes or consists of at least one part or two or more parts that include or consist of an elastic component or material, and at least one different part, or two or more different parts that do not contain the elastic component or material.

[0033] In one embodiment of the first or second aspect, the part that includes or consists of the elastic component or material is located in an area that is likely to come into contact with a part of the subject's body, and that part is intended to be subjected to compression. Preferably, the part of the body is selected from the group consisting of the knee, patella, calf, elbow, wrist, heel, toe, ankle, and Achilles tendon. Optionally, the area is the ankle area or calf area of a compression stocking, the patella area of a compression knee pad, the elbow area of a compression sleeve, or the wound area of a compression wound dressing.

[0034] In one embodiment of the first or second aspect, the compression product includes two, three or more parts with different elastic components or materials. Optionally, the elastic component or material of the part located in the calf area of the compression stocking can provide a stronger compressive force compared to the elastic component or material of the part located outside the calf area. Such compartmentalization of the compression stocking can enable the activation of the calf's musco-venous pump.

[0035] In one embodiment of the first or second aspect, the compression product includes or consists of an elastic component or material according to the present invention (see the fifth aspect).

[0036] In one embodiment of the first or second aspect, the compression product comprises or consists of elastic fibers, filaments, thread yarns, or yarns according to the present invention (see the sixth aspect).

[0037] In one embodiment of the first or second aspect, any fibers, filaments, thread yarns, or yarns in the medical compression product comprise or consist of an elastic component or material according to the present invention.

[0038] In one embodiment of the first or second aspect, the amount of elastic fibers, filaments, thread yarns, or yarns according to the present invention in the medical compression product is about 1 to 100%, about 5 to 95%, about 10 to 90%, about 20 to 80%, about 30 to 50%, about 40 to 60%, or about 55 to 70% with respect to the total amount of fibers, filaments, thread yarns, or yarns.

[0039] In one embodiment of the first or second aspect, the compression product comprises or consists of a compression base fabric according to the present invention (see the seventh aspect).

[0040] In one embodiment of the first or second aspect, the compression product comprises or consists of a polyurethane (PU) polymer containing N-diol according to the present invention (see the eighth or ninth aspect).

[0041] In the third aspect, the present invention provides for the use of a compression product according to the present invention in the fields of phlebology, orthopedics, foot care, surgery, postoperative care, trauma management, wound care, or sports (see the first or second aspect).

[0042] In a fourth aspect, the present invention provides for the use of a compression product according to the present invention for the treatment, prevention or management of musco-venous pump dysfunction, venous circulatory insufficiency, venous insufficiency, preferably chronic venous insufficiency, edema, phlebitis, thrombosis, preferably deep vein thrombosis, venous embolism, lymphedema, ulcers, preferably leg ulcers, leg pain, varicose veins, reticular veins, or "economy class syndrome" (ECS) (see the first or second aspect).

[0043] In a fifth aspect, the present invention provides (a) a non-quaternized polyurethane (PU) polymer (PU-N) containing N-diol; and / or (b) a quaternized polyurethane (PU) polymer or ionomer (PU-N+) containing quaternized N-diol; and, optionally, (c) elastane to provide an elastic component or material comprising or consisting of the same.

[0044] In one embodiment, the elastic component or material comprises or consists of a blend of a non-quaternized PU polymer and / or a quaternized PU polymer or ionomer and elastane.

[0045] In one embodiment, the elastic component or material comprises or consists of a blend of a non-quaternized PU polymer and elastane. This embodiment is preferred.

[0046] In one embodiment, the elastic component or material comprises or consists of two or more different non-quaternized PU polymers and / or quaternized PU polymers or ionomers.

[0047] In one embodiment, the elastic component or material comprises or consists of fibers, filaments, thread yarns, or yarns according to the present invention (see the sixth aspect). In one embodiment, such fibers, filaments, thread yarns, or yarns are treated with a powder or an oil, such as SiO2 powder, silicone oil, or linseed oil, etc., to prevent adhesion of the fibers, filaments, etc., especially when it is being wound up.

[0048] In one embodiment, the elastic component or material is preferably processed into thread yarns or yarns according to the present invention.

[0049] In one embodiment, the elastic component or material is preferably processed into a textile or fabric, preferably a compressed base fabric, according to the present invention.

[0050] In one embodiment, the elastic component or material comprises or consists of a polyurethane (PU) polymer containing N-diol according to the present invention (see the eighth or ninth aspect).

[0051] In one embodiment, the elastic component or material can undergo a first phase during which the component or material is expanded, a second phase during which the component or material relaxes without or not completely or only partially recovering its original shape, and a third phase during which the component or material recovers its original shape, or substantially or almost completely recovers its original shape, preferably continuously recovers its original shape, more preferably continuously recovers its original shape while decelerating.

[0052] In one embodiment, the elastic component or material partially recovers during the second phase by about 15 - 80% of the total length by which the elastic component or material was expanded during the first phase, more preferably about 20 - 75%, optionally about 15 - 30% or 20 - 25%, and optionally about 65 - 80 or 70 - 75%.

[0053] In one embodiment, the elastic component or material partially recovers during the second phase by about 15 - 55%, preferably about 20 - 50%, more preferably about 25 - 45%, optionally about 15 - 30% or 20 - 25%, and optionally about 40 - 55 or 45 - 50% of the total length by which the elastic component or material was extended during the first phase.

[0054] In one embodiment of the elastic component or material, relaxation, preferably the second phase, more preferably the second and third phases, is self-initiated, preferably initiated autonomously or spontaneously in the absence of external stimuli.

[0055] In one embodiment, the elastic material or component has a delayed relaxation behavior, preferably a continuously delayed relaxation behavior.

[0056] In a sixth aspect, the present invention provides an elastic fiber, filament, thread, or yarn comprising or consisting of the elastic component or material according to the present invention (see the fifth aspect).

[0057] In one embodiment, the elastic fiber, filament, thread, or yarn comprises or consists of a polyurethane (PU) polymer containing the N-diol according to the present invention (see the eighth or ninth aspect).

[0058] In one embodiment, the elastic fiber, filament, thread, or yarn consists of the elastic component or material, or the PU polymer (from the perspective of, for example, a "naked" thread or yarn).

[0059] In one embodiment, the elastic thread or yarn comprises or consists of a core portion and / or a cover portion (such as a coating) comprising or consisting of the elastic component or material, or the PU polymer.

[0060] In one embodiment, the elastic thread or yarn comprises or consists of a core thread or yarn and a cover thread or yarn wound around the core thread and yarn respectively, and the core thread or yarn and / or the wound core thread or yarn comprises or consists of an elastic component or material, or a PU polymer.

[0061] In one embodiment, the elastic fiber, filament, thread, or yarn is processed in a textile or fabric, preferably a compression base fabric, more preferably in accordance with the present invention.

[0062] In one embodiment of the elastic fiber, filament, thread, or yarn, the textile or fabric is a knitted fabric, an interlaced fabric, a woven fabric, or a felt.

[0063] In a seventh aspect, the present invention provides a compression base fabric, preferably a compression knitted base fabric, comprising or consisting of an elastic component or material according to the present invention (see the fifth aspect).

[0064] In one embodiment, the compression base fabric comprises or consists of a polyurethane (PU) polymer containing N-diol according to the present invention (see the eighth or ninth aspect).

[0065] In one embodiment, the compression base fabric comprises or consists of a base thread and a weft thread, and the weft thread is inserted vertically through the length of the base thread.

[0066] In one embodiment of the compression base fabric, the base thread and / or the weft thread, and optionally at least one additional thread, such as a filling thread, comprises or consists of an elastic component or material, or a PU polymer.

[0067] In one embodiment, the compression base fabric is a plain knitted fabric or a circular knitted fabric.

[0068] In an eighth aspect, the present invention provides a polyurethane (PU) polymer having a delayed continuous relaxation behavior, where the relaxation is self-initiated, preferably autonomously or spontaneously in the absence of external stimuli.

[0069] In one embodiment, the PU polymer further has a feature or a combination thereof as defined in a ninth aspect.

[0070] In a ninth aspect, the present invention provides a polyurethane (PU) polymer containing N-diol.

[0071] In one embodiment, the PU polymer includes at least one N-diol monomer component, preferably two or more, more preferably several or a large number of N-diol monomer components.

[0072] In one embodiment, the PU polymer is a non-quaternized PU polymer (PU-N). This is a preferred embodiment.

[0073] In one embodiment, the PU polymer is a quaternized PU polymer (PU-N+).

[0074] In one embodiment, the PU polymer is a quaternized PU ionomer (PU-N+).

[0075] In one embodiment, the quaternized PU polymer or ionomer is derived from a non-quaternized PU polymer.

[0076] In one embodiment, the PU polymer can be actively expanded and can relax upon release.

[0077] In one embodiment, the PU polymer can undergo a relaxation process including or consisting of an immediate relaxation phase followed by a continuous compression phase.

[0078] In one embodiment, the PU polymer can undergo a first phase during which the material expands, a second phase during which the material relaxes without or not fully or only partially returning to its original shape, and a third phase during which the PU polymer returns to or substantially returns to or almost fully returns to its original shape, preferably continuously returns to its original shape, more preferably continuously returns to its original shape while decelerating.

[0079] In one embodiment, during the second phase, the PU polymer partially returns by about 15 - 80%, more preferably about 20 - 75%, optionally about 15 - 30% or 20 - 25%, and optionally about 65 - 80 or 70 - 75% of the total length by which it expanded during the first phase.

[0080] In one embodiment, during the second phase, the PU polymer partially returns by about 15 - 55%, preferably about 20 - 50%, more preferably about 25 - 45%, optionally about 15 - 30% or 20 - 25%, and optionally about 40 - 55 or 45 - 50% of the total length by which it expanded during the first phase.

[0081] In one embodiment of the PU polymer, relaxation, preferably the second phase, more preferably the second and third phases, starts on its own, preferably autonomously or spontaneously in the absence of external stimuli.

[0082] In one embodiment of the PU polymer, relaxation starts on its own or without the impact of external stimuli.

[0083] In one embodiment of the PU polymer, relaxation starts immediately upon release.

[0084] In one embodiment of the PU polymer, relaxation starts on its own at room temperature.

[0085] In one embodiment, the PU polymer exhibits a relaxation behavior of retardation, preferably a continuous relaxation behavior of retardation, more preferably a relaxation behavior of retardation as compared to a PU polymer containing no N-diol.

[0086] In one embodiment of the PU polymer, the relaxation behavior of retardation is retarded with respect to the duration of the immediate relaxation phase and / or the continuous compression phase.

[0087] In one embodiment of the PU polymer, the relaxation behavior of retardation is retarded with respect to the relative amount of relaxation achieved during the immediate relaxation phase and / or the continuous compression phase.

[0088] In one embodiment of the PU polymer, the relaxation behavior of retardation is retarded with respect to the duration of the entire relaxation process.

[0089] In one embodiment of the PU polymer, the relaxation behavior of retardation is not retarded with respect to the start of relaxation.

[0090] In one embodiment, the PU polymer does not exhibit shape memory with respect to the effect that the shape recovery is initiated by the impact of an external stimulus.

[0091] In one embodiment, the quaternized PU polymer or ionomer contains at least one ionic group, preferably 2 or more, more preferably several or a large number of ionic groups.

[0092] In one embodiment, the quaternized PU polymer or ionomer contains ionic groups in an amount of up to about 15%, preferably between about 1, 2, or 3 to 10%, more preferably between about 4 to 10%, even more preferably between about 3 to 7%, or between about 7 to 11%, even more preferably between about 4 to 6%, or between about 8 to 10%, most preferably about 5%, or about 9% with respect to the total number of moles of the PU polymer.

[0093] In one embodiment of the quaternized PU polymer or ionomer, the ionic group is a quaternized N-containing group or a quaternary amino group, preferably a quaternized aminoalkyl group. Optionally, the quaternized aminoalkyl group is the only type of ionic group.

[0094] In one embodiment of the quaternized PU polymer or ionomer, the quaternized aminoalkyl group contains alkyl groups of different lengths. Preferably, the quaternized aminoalkyl group contains an alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. More preferably, the quaternized aminoalkyl group contains a butyl group. Most preferably, the quaternized aminoalkyl group contains one butyl group and two methyl groups (-N + -(CH3)2(CH2-CH2-CH2-CH3).

[0095] In one embodiment of the quaternized PU polymer or ionomer, the quaternized aminoalkyl group is part of the N-diol monomer component.

[0096] In one embodiment, the PU polymer comprises or consists of at least one molecular unit, preferably two or more molecular units, more preferably several or a large number of molecular units, of a diol monomer component and an isocyanate monomer component.

[0097] In one embodiment of the PU polymer, the diol monomer component and the isocyanate monomer component are bonded by a urethane bond.

[0098] In one embodiment of the PU polymer, the diol monomer (derived from the diol monomer component) is selected from the group consisting of N-diol, 1,4-butanediol (BD), and poly(tetrahydrofuran) (P(THF)).

[0099] In one embodiment, the PU polymer comprises or consists of a first molecular unit composed of an N-diol monomer component and an isocyanate monomer component, a second molecular unit composed of a 1,4-butanediol monomer component and an isocyanate monomer component, and a third molecular unit composed of a P(THF) monomer component and an isocyanate component.

[0100] In one embodiment of the PU polymer, the first, second, and third molecular units are each bonded by a urethane bond.

[0101] In one embodiment of the PU polymer, the isocyanate monomer components in the third, second, and third molecular units are the same or different. Preferably, the isocyanate monomer components are the same.

[0102] In one embodiment of the PU polymer, the isocyanate monomer (derived from the isocyanate monomer component) is methylene di(phenyl isocyanate) (MDI).

[0103] In one embodiment of the PU polymer, the N-diol is bis(2-hydroxyethyl)-3,3'-((2-(dimethylamino)ethyl)azanediyl)-dipropionate or N',N'-bis(3-(2-hydroxyethoxy)-3-oxopropyl)-N,N-dimethylethylenediamine.

[0104] In one embodiment of the PU polymer, the quaternized N-diol monomer component is produced by quaternization of a quaternizable N-diol monomer component.

[0105] In one embodiment of the PU polymer, the quaternizable N-diol monomer (derived from the quaternizable N-diol monomer component) is produced from 2-dimethylaminoethylamine (DMAE) and 2-hydroxyethyl acrylate (HEA), preferably in a ratio of 1:2 (DMAE:HEA), more preferably in the presence of tetrahydrofuran (THF) at 45 °C for 24 hours.

[0106] In one embodiment of the PU polymer, the relative amounts of the N-diol, P(THF), and BD monomer components are about 50:25:25%.

[0107] In one embodiment, the quaternized PU polymer or ionomer contains a quaternized N-containing group amount of ionic groups of up to about 15%, preferably between about 1, 2, or 3 to 10%, more preferably between about 4 to 10%, even more preferably between about 3 to 7%, or between about 7 to 11%, even more preferably between about 4 to 6%, or between about 8 to 10%, most preferably about 5%, or about 9% based on the total moles of the PU polymer.

[0108] In one embodiment, the glass transition temperature T of the PU polymer, preferably the non-quaternized PU polymer g is between about 20 and 60 °C, preferably between about 30 and 50 °C, more preferably between about 35 and 45 °C, and most preferably about 40 °C.

[0109] In one embodiment, the glass transition temperature T of the PU polymer, preferably the quaternized PU polymer, more preferably the PU polymer quaternized at about 29% g is about 40 °C and / or 70 °C.

[0110] In one embodiment, the glass transition temperature is measured by dynamic mechanical thermal analysis (DMTA).

[0111] In one embodiment, the decomposition temperature of the PU polymer, preferably the non-quaternized PU polymer, is between about 150 and 200 °C, preferably between about 170 and 195 °C, more preferably between about 180 and 190 °C, and most preferably about 185 °C.

[0112] In one embodiment, the fracture strain of the PU polymer, preferably the non-quaternized PU polymer, is between about 1,300 and 1,450 dL[%], more preferably between about 1,350 and 1,400 dL[%], more preferably between about 1,380 and 1,395 dL[%], and most preferably about 1,388 dL[%].

[0113] In one embodiment, the non-quaternized PU polymer is blended with at least one, two or more, or several quaternized PU polymers or ionomers.

[0114] In one embodiment, the quaternized PU polymer or ionomer is blended with at least one, two or more, or several non-quaternized PU polymers.

[0115] In one embodiment, the non-quaternized PU polymer and / or the quaternized PU polymer or ionomer is blended with elastane.

[0116] In one embodiment, the PU polymer is fiber or filament forming, preferably fiber forming.

[0117] In one embodiment, the PU polymer forms or is processed into thread yarn or yarn.

[0118] In one embodiment, the PU polymer is processed into a textile or fabric, preferably a compressed fabric, and optionally a compressed base fabric.

[0119] In a tenth aspect, the present invention (a) a non-quaternized polyurethane (PU) polymer (PU-N) containing N-diol; and / or (b) a quaternized polyurethane (PU) polymer or ionomer (PU-N+) containing quaternized N-diol; and (c) elastane provides a blend comprising or consisting of.

[0120] In one embodiment, the blend comprises or consists of about 5 to 40% (by weight) of the non-quaternized PU polymer or the quaternized PU polymer or ionomer and about 60 to 95% (by weight) of elastane.

[0121] In one embodiment, the blend comprises or consists of between about 10-30% (by weight) of an unquaternized PU polymer or a quaternized PU polymer or an ionomer and between about 70-90% (by weight) of elastane.

[0122] In one embodiment, the blend consists of about 30% (by weight) of an unquaternized PU polymer or a quaternized PU polymer or an ionomer and 70% (by weight) of elastane.

[0123] In one embodiment, and in a preferred embodiment, the blend consists of about 10% (by weight) of an unquaternized PU polymer or a quaternized PU polymer or an ionomer and 90% (by weight) of elastane. The advantage of this embodiment is that the large amount of elastic polymer in the blend is commercially available and relatively inexpensive elastane.

[0124] In one embodiment, in a preferred embodiment, the blend comprises or consists of an unquaternized PU polymer and elastane. The advantage of this embodiment is that the quaternization process step can be avoided.

[0125] In one embodiment, the blend comprises or consists of at least one, two or more, or several unquaternized PU polymers and elastane.

[0126] In one embodiment, the blend is fiber or filament forming, preferably fiber forming.

[0127] In one embodiment, the blend is formed into or processed into a thread or yarn.

[0128] In one embodiment, the blend is processed into a textile or fabric, preferably a compression fabric, and optionally a compression base fabric.

[0129] In one embodiment of the blend, the non-quaternized PU polymer and / or the quaternized PU ionomer is according to the present invention (see the 8th or 9th aspect).

[0130] In one embodiment, the blend can pass through a first phase during which the blend material is extended, a second phase during which the blend material relaxes without or not completely or only partially recovering its original shape, and a third phase during which the blend material recovers its original shape, or substantially or almost completely recovers its original shape, preferably continuously recovers its original shape, more preferably continuously recovers its original shape while decelerating.

[0131] In one embodiment, during the second phase, the blend material partially recovers by about 15 - 80%, more preferably about 20 - 75%, optionally about 15 - 30% or 20 - 25%, and optionally about 65 - 80 or 70 - 75% of the total length by which it was extended during the first phase.

[0132] In one embodiment, during the second phase, the blend material partially recovers by about 40 - 80%, preferably about 50 - 75%, optionally about 50 - 60% or 60 - 75% of the total length by which it was extended during the first phase.

[0133] In one embodiment of the blend, the relaxation, preferably the second phase, more preferably the second and third phases, starts by itself, preferably autonomously or spontaneously in the absence of an external stimulus.

[0134] In an eleventh aspect, the invention provides for the use of an elastic component or material according to the invention (see fifth aspect), an elastic fiber, filament, thread, or yarn (see sixth aspect), a compression substrate (see seventh aspect), a polyurethane (PU) polymer containing N-diol (see eighth or ninth aspect), or a blend (see tenth aspect) in a compression product, preferably a medical compression product, or a process for manufacturing such a product.

[0135] In a twelfth aspect, the invention provides for the use of a polyurethane (PU) polymer containing N-diol according to the invention (see eighth or ninth aspect) in a process for manufacturing a compression product, an elastic component or material, an elastic fiber, filament, thread, or yarn, or a compression substrate, preferably according to the invention.

[0136] In a thirteenth aspect, the invention provides for the use of a blend according to the invention (see tenth aspect) in a process for manufacturing a compression product, an elastic component or material, an elastic fiber, filament, thread, or yarn, or a compression substrate, preferably according to the invention.

[0137] In a fourteenth aspect, the invention (i) a step of preparing a quaternizable N-diol; (ii) a step of preparing a PU polymer containing the quaternizable N-diol produced in step (i); and, optionally, (iii) a step of quaternizing the PU polymer produced in step (ii) to provide a process for manufacturing a polyurethane (PU) polymer containing N-diol.

[0138] In one embodiment of the process, the PU polymer is a PU polymer according to the invention.

[0139] In one embodiment, in step (ii) of the process, a quaternizable N-diol monomer and 1,4-butanediol are first provided, and poly(tetrahydrofuran) is then added. This embodiment is preferred.

[0140] In one embodiment, in step (ii) of the process, a quaternizable N-diol monomer and poly(tetrahydrofuran) are first provided, and 1,4-butanediol is then added.

[0141] In a 15th aspect, the present invention provides a polyurethane (PU) polymer containing an N-diol produced according to the process of the present invention.

[0142] Finally, the present invention contemplates that the individual features or combinations thereof as described above for embodiments of a particular aspect can be equally realized in embodiments under another described aspect. Such embodiments can be directly and clearly derived from the entire content of the present application, and those skilled in the art will understand that such embodiments belong to the content of the present application at the time of filing. In certain embodiments, for example, the following are provided: (Item 1) A compression product comprising an elastic component or material, wherein the elastic component or material preferably has a delayed continuous relaxation behavior, the elastic material is capable of applying a compressive force or a support force or a local pressure to a part of a subject's body, the elastic material can further undergo a first phase during which the material is expanded, a second phase during which the component or material relaxes without recovering its original shape, and a third phase during which the component or material recovers while continuously decelerating its original shape, wherein relaxation is a compression product that starts on its own, preferably autonomously or spontaneously in the absence of external stimuli. (Item 2) Preferably the compression product according to item 1, (a) A non-quaternized polyurethane (PU) polymer (PU-N) containing N-diol; and / or (b) A quaternized polyurethane (PU) polymer or ionomer (PU-N+) containing quaternized N-diol; and, optionally, (c) Elastane A compression product comprising or consisting of an elastic component or material containing the same. (Item 3) Preferably a medical compression product, more preferably a compression stocking, preferably a compression stocking, socks, knee socks, tights, pantyhose, or maternity pantyhose, compression knee pads, compression arm sleeves, compression waist attachments, belts or girdles, compression bandages, body support bandages, prosthetics, liners for prosthetics, compression wound dressings, compression plasters or patches, and compression clothing, the compression product according to item 1 or 2 selected from the group consisting of. (Item 4) A compression product according to any one of items 1 to 3, comprising a non-quaternized PU polymer and, optionally, an elastic component or material comprising or consisting of elastane. (Item 5) Use of a compression product according to any one of items 1 to 4 for the treatment, prevention or management of venous diseases, orthopaedics, foot care, surgery, postoperative care, trauma management, wound care, or sports, or for musco-venous pump dysfunction, venous circulatory insufficiency, venous insufficiency, preferably chronic venous insufficiency, oedema, phlebitis, thrombosis, preferably deep vein thrombosis, venous embolism, lymphoedema, ulcers, preferably leg ulcers, foot pain, varicose veins, reticular veins, or "economy class syndrome" (ECS). (Item 6) A polyurethane (PU) polymer having a delayed continuous relaxation behaviour that starts spontaneously, preferably autonomously or spontaneously in the absence of external stimuli. (Item 7) A polyurethane (PU) polymer preferably containing the N-diol according to item 6, said PU polymer containing at least one N-diol monomer component, preferably 2 or more, more preferably several or many N-diol monomer components. (Item 8) The polyurethane (PU) polymer according to item 7 which is a non-quaternized PU polymer (PU-N). (Item 9) The polyurethane (PU) polymer according to item 7 which is a quaternized PU polymer (PU-N+) or a quaternized PU ionomer (PU-N+). (Item 10) The polyurethane (PU) polymer according to any one of items 7 to 9, wherein the N-diol monomer component is derived from bis(2-hydroxyethyl)-3,3'-((2-(dimethylamino)ethyl)azanediyl)-dipropionate or N',N'-bis(3-(2-hydroxyethoxy)-3-oxopropyl)-N,N-dimethylethylenediamine. (Item 11) The polyurethane (PU) polymer according to any one of items 7 to 10, comprising or consisting of a first molecular unit consisting of an N-diol monomer component and an isocyanate monomer component, a second molecular unit consisting of a 1,4-butanediol monomer component and an isocyanate monomer component, and a third molecular unit consisting of a P(THF) monomer component and an isocyanate component. (Item 12) The polyurethane (PU) polymer according to item 11, wherein the relative amounts of the N-diol, P(THF) and 1,4-butanediol monomer components are about 50:25:25%. (Item 13) The quaternized PU polymer or ionomer contains a quaternized N-containing group amount of ionic groups of up to about 15%, preferably between about 1, 2, or 3 to 10%, more preferably between about 4 to 10%, even more preferably between about 3 to 7%, or between about 7 to 11%, even more preferably between about 4 to 6%, or between about 8 to 10%, most preferably about 5%, or about 9% based on the total molar amount of the PU polymer, the polyurethane (PU) polymer according to any one of items 9 to 12. (Item 14) Glass transition temperature T g is between about 20 to 60 °C, preferably between about 30 to 50 °C, more preferably between about 35 to 45 °C, most preferably about 40 °C, the polyurethane (PU) polymer according to any one of items 8 and 10 to 12. (Item 15) (a) A non-quaternized polyurethane (PU) polymer (PU-N) containing N-diol; and / or (b) A quaternized polyurethane (PU) polymer or ionomer (PU-N+) containing quaternized N-diol; and (c) Elastane A blend comprising or consisting of. (Item 16) A blend according to item 15, comprising or consisting of a non-quaternized PU polymer between about 5 to 40% (by weight) and elastane between about 60 to 95% (by weight). (Item 17) Use of the polyurethane (PU) polymer according to any one of items 7 to 14, or use of the blend according to item 15 or 16, in a process for manufacturing a compression product, an elastic component or material, an elastic fiber, a filament, a thread yarn, or a warp knitted fabric. (Item 18) A process for manufacturing a polyurethane (PU) polymer containing N-diol, wherein the PU polymer contains at least one N-diol monomer component, preferably 2 or more, more preferably several or a large number of N-diol monomer components, (i) A step of preparing a quaternizable N-diol; (ii) A step of preparing a PU polymer containing the quaternizable N-diol produced in step (i); Optionally, (iii) A step of quaternizing the PU polymer produced in step (ii) A process comprising. (Item 19) The process according to item 18, wherein the N-diol monomer component is derived from bis(2-hydroxyethyl)-3,3'-((2-(dimethylamino)ethyl)azanediyl)-dipropionate or N',N'-bis(3-(2-hydroxyethoxy)-3-oxopropyl)-N,N-dimethylethylenediamine. (Item 20) A polyurethane (PU) polymer containing N-diol, produced according to the process described in item 18 or 19.

Brief Description of the Drawings

[0143] The present invention will be further described by the following examples in consideration of the accompanying drawings below.

[0144]

Figure 1

[0145]

Figure 2

[0146]

Figure 3

[0147]

Figure 4

[0148]

Figure 5

[0149]

Figure 6

[0150]

Figure 7

[0151]

Figure 8

[0152]

Figure 9

[0153]

Figure 10

[0154]

Figure 11

[0155]

Figure 12

[0156]

Figure 13A

Figure 13B

Figure 13C

Figure 13D

Figure 13E

[0157]

Figure 14

[0158]

Figure 15

[0159]

Figure 16

[0160]

Figure 17

[0161]

Figure 18

[0162]

Figure 19

Mode for Carrying Out the Invention

[0163] The present invention provides a compression product containing a filament-forming polyurethane (PU) polymer containing N-diol, among others. This PU polymer may exist in the form of a non-quaternized PU polymer (PU-N), or may exist in the form of a quaternized PU polymer (PU-N+) in which the N-diol groups are quaternized, also called a PU ionomer. In any state, the PU polymer exhibits a continuous relaxation behavior with retardation at room temperature.

[0164] Such a compression product can be easily expanded by hand with little physical effort on the user side (Figs. 1, 2, phase (1)). If necessary, the expansion can be assisted or achieved with the help of expansion means, such as a handbag or pocket-compatible expansion means. When the external expansion force stops ("release"), the compression product begins to relax and re-shrink to return to its original shape (Fig. 1, phase (2)).

[0165] However, the recovery of the original shape does not progress linearly over time and becomes increasingly delayed. The relaxation initially progresses more linearly (Fig. 1, phase (2)), but the relaxation rate then decelerates, for example, during the next 5 minutes (Fig. 1, phase (3)), and further decelerates during the next 10 minutes and up to several hours beyond that (Fig. 1, phase (3)).

[0166] Thus, the compression product comprising the N-diol-containing PU polymer of the present invention provides the user with a suitable time to put on or apply the product in an expanded form to a part of the body, for example, to the legs in the case of compression stockings (FIG. 2). There is no need to place the product under an external expansion force during application, as is the case with many conventional compression products. The product of the present invention then exerts a slowly increasing compression pressure on the part of the body to which the product is applied. This is more comfortable for the user than a sudden increase in pressure, and is also preferable from a medical point of view. To undress or take off, the compression product is expanded again (for example, in the case of compression stockings, stepwise from top to bottom) and taken off or removed.

[0167] Thus, the compression products of the present invention are associated with improved comfort upon application, which positively impacts user compliance.

[0168] In particular, the relaxation of the stretched PU polymer according to the invention is "self-initiated", i.e. autonomously or spontaneously or intrinsically, i.e. without being triggered by an external stimulus or activation source, begins as soon as the PU polymer is released. Thus, the compression product can be applied without the need for additional technical measures or laborious and time-consuming manipulations.

[0169] Ultimately, use of the compression products of the present invention is not only comfortable and convenient, but also cost-effective.

[0170] The remarkable relaxation behavior of the N-diol-containing PU polymers of the present invention, compared to conventional elastic polymers, is illustrated with reference to Figure 3. When a sample of elastane is stretched at a fixed rate, for example from an original length of 10 mm to a final length of 60 mm, and released (i.e., immediate termination of the stretching force), the elastane immediately recovers its original length (Figure 3A). A conventional commercial PU polymer (i.e., without N-diol) immediately recovers about 84% of the stretched length, but remains stretched about 16% for several days, i.e., does not recover its original length (Figure 3B).

[0171] In contrast, as shown in FIG. 16, the PU polymers of the present invention exhibit relaxation behavior consisting of an immediate relaxation phase (phase 2 in FIG. 1) and a relaxation phase of continuous compression (phase 3 in FIG. 1), whether non-quaternized or (to varying degrees) quaternized.

[0172] In other words, compared to elastane and conventional PU polymers, the PU polymers of the present invention exhibit a continuous but delayed relaxation behavior. Further, as demonstrated by comparison with conventional PU polymers, this delayed relaxation behavior is dependent on the presence of N-diol.

[0173] Furthermore, the delayed relaxation behavior can be controlled by modifying the composition of the PU polymers of the present invention (with respect to monomer components, e.g., the ratio of monomers), by quaternization, and by the degree of quaternization. For example, a low degree of quaternization (e.g., 9% or 5%) of the PU polymers of the present invention resulted in faster relaxation compared to the relaxation of the corresponding non-quaternized PU polymer and a PU-N+ polymer quaternized at 29%.

[0174] Finally, the relaxation behavior of the PU polymers of the present invention can be further modified rather than by mixing elastane. Conversely, by mixing the PU polymers of the present invention, a delayed relaxation behavior can be imparted to elastane. Such blends with elastane open up new possibilities for use, for example, in the field of compression products, depending on their relative composition.

[0175] Definition As used herein, the terms "polyurethane (PU) polymer containing N-diol" or "N-diol-containing polyurethane (PU) polymer" include the following: (1) "Non-quaternized polyurethane (PU) polymer", i.e., a PU polymer containing N-diol in which the amino group is not quaternized and is a tertiary amino group. For the sake of simplicity, "PU-N" is sometimes used. (2) "Quaternized polyurethane (PU) polymer" or "quaternized polyurethane (PU) ionomer" or "polyurethane (PU) ionomer", i.e., a PU polymer containing an N-diol in which the amino group is at least partially quaternized. For the sake of simplicity, "PU-N+" is sometimes used.

[0176] As used herein, the term "quaternization" relates to a chemical reaction in which a nitrogen atom (of a tertiary amino group) goes from three bonds to four bonds by alkylation, producing a quaternary substitution derivative (i.e., a quaternary ammonium compound). The resulting compound may be called "quaternized".

[0177] As used herein, "degree of quaternization" indicates the ratio of quaternary aminoalkyl groups to the total number of aminoalkyl groups in a given compound.

[0178] An "ionomer" is defined as an ion-containing polymer having low mol% of ionic groups along the polymer backbone chain or as pendant groups. The amount of ionic groups distinguishes ionomers from polyelectrolytes. Usually, ionomers are defined to include an ionic content of up to about 15 mol%.

[0179] Ionomers are described in the prior art, e.g., ethylene / carboxylic acid ionomer fibers for gas filters (U.S. Patent No. 5,882,519), or polyurethane ionomers for films and laminates (U.S. Patent No. 4,956,438). Further information can also be found, e.g., in Dieterich et al. (1970), Angew. Chem. internat. Edit. 9:40 - 50; Kim et al. (1998), Polymer 39:2803 - 2808; Zhu et al. (2008), Polym. Adv. Technol. 19:1745 - 1753.

[0180] The term "elastic" (or "elasticity") defines the ability of a material to resist the effects of strain or deforming forces and return to its original size and shape when those effects or forces are removed. In the case of rubber or other polymers, elasticity is brought about by the stretching of polymer chains when a force is applied.

[0181] As used herein, the term "expansion" includes stretching, enlarging, extending, elongating, straining, deforming, or other non-destructive changes in the shape of an elastic material. The term "expansion" is used more often with respect to the deformation of compression products or fabrics, and the terms "stretching" or "elongation" are used more often with respect to elastic polymers or fibers.

[0182] As used herein, the term "compression product" refers to a product that, when worn by a patient, exerts compression on the wearer. Generally, a compression product exerts such compression on the body part of the patient that comes into contact with the compression product while it is being worn. Also generally, a compression product is not a raised product and is capable of being deformed, stretched, or expanded while maintaining a tendency or property to return to its original shape. As used herein, the term "relaxation" refers to the behavior and state of a previously expanded elastic material after release.

[0183] As used herein, the term "release" refers to the termination of the expanding force or the instant at which such a force terminates or ceases.

[0184] As used herein, the "first phase" of the relaxation process refers to the "expansion phase", the "stretching phase" or the "active elongation phase". During this phase, an expanding or stretching force is gradually applied to the elastic material (or PU polymer or blend). In order to maintain the modified shape or stretched length, it is necessary to apply an additional expanding or stretching force.

[0185] "Phase 2" refers to the phase of immediate relaxation or "immediate relaxation phase". During this phase, the original shape or length of the elastic material (or PU polymer or blend) only partially recovers. Since relaxation proceeds more linearly, this phase may also be referred to as the "linear phase" or "stable phase". This Phase 2 starts on its own once the expansion force or stretching force terminates, i.e., when the external stimulus ceases.

[0186] "Phase 3" refers to the phase of continuous relaxation or "continuous relaxation phase". During this phase, the elastic material (or PU polymer or blend) continuously or gradually recovers its original shape or length. In particular, the continuous or gradual recovery is characterized by deceleration, or an increasing delay, or a progressive deceleration. In other words, Phase 3 may be divided into several sub - phases where relaxation proceeds at different rates (e.g., a first sub - phase lasting at least for example about 5 minutes and a second sub - phase lasting from for example about 10 minutes to 6 hours). Phase 3 also starts on its own and follows Phase 2. In the context of compression products in particular, this phase is also referred to as the "continuous compression phase".

[0187] In the context of Phase 3, the expressions "recover its original shape", "substantially recover its original shape", or "almost completely recover its original shape" mean that the elastic material (or PU polymer or blend) recovers at least about 85 - 100%, preferably about 90 - 100%, more preferably about 95 - 100%, even more preferably 100 ± 5%, and most preferably about 100% of the shape or total length by which the elastic material was expanded during Phase 1. Alternatively, the said expressions mean that the elastic material recovers to at least about 100 - 150%, preferably about 100 - 125%, more preferably about 100 - 110%, even more preferably 100 ± 5%, and most preferably about 100% of its original shape or original length, i.e., its shape or length before being expanded.

[0188] As used herein, the term "delayed relaxation behavior" or "delayed continuous relaxation behavior" means that the relaxation behavior is delayed in time compared to the reference relaxation behavior. As used herein, the reference material may be any elastic polymer or PU polymer that does not contain N-diol. The delay may be related to the duration of one or more phases of the relaxation process or to the duration of the entire relaxation process.

[0189] The term "continuous" associated with "delayed continuous relaxation behavior" means that the relaxation process proceeds continuously, either linearly or with a gradual delay, and in either case, for example, an intermediate shape does not persist temporarily.

[0190] As used herein, the expressions "monomer component derived from" a particular compound or "based on" a particular compound mean that the compound has been used to prepare a polymer. Thus, the monomer component corresponds to the compound, but the compound is in the state in which it is bonded within the polymer.

[0191] The term "about" as used herein with numbers or data is intended to include the deviations (±) that are normally considered in each technical field.

[0192] Abbreviations BD 1,4-butanediol DBTL Dibutyltin dilaurate DMAE 2-dimethylaminoethylamine DMTA Dynamic mechanical thermal analysis GPC Gel permeation chromatography HEA 2-hydroxyethyl acrylate MDI Methylene diisocyanate, 4,4'-diphenylmethane diisocyanate PU Polyurethane PU-N Polyurethane containing N-diol, non-quaternized PU-N+ Polyurethane containing quaternized N-diol, quaternized polyurethane P(THF) Poly(tetrahydrofuran), poly(tetramethylene ether glycol) 1000 T g Glass transition temperature TGA Thermogravimetric analysis THF Tetrahydrofuran

Example

[0193] Briefly, Examples 1 and 2 relate to the preparation of N-diol-containing PU polymers, and Example 5 relates to the preparation of the corresponding quaternized PU polymers. Generally, the described preparation process, i.e., the preparation process developed on a laboratory scale, is suitable for processing on an industrial scale.

[0194] Examples 3 and 4 describe the characterization of N-diol-containing PU polymers with respect to molecular weight and decomposition temperature; Example 6 describes the characterization of quaternized PU polymers.

[0195] Examples 7 and 8 perform a comparison of N-diol-containing PU polymers and elastane with respect to the glass transition temperature (T g ) and tensile strength (elastic modulus, elongation at break).

[0196] Example 9 relates to a blend of N-diol-containing PU polymer and elastane and describes its tensile strength.

[0197] Examples 10 and 11 respectively describe the relaxation behavior of blends of N-diol-containing PU polymers and elastane.

[0198] Table 16 summarizes the characteristics that characterize the exemplary polymer samples described and discussed in some of the following examples.

[0199] Example 1: Preparation of N-diol Chemical substance N,N-Dimethylethylenediamine (DMEA): CAS: 108-00-9, Acros, distilled before use; 2-Hydroxyethyl acrylate (HEA): CAS: 818-61-1, TCI, >95%; THF: industrial grade, dried and distilled before use; Et2O: industrial grade, dried and distilled before use.

[0200]

Table 18

[0201] Procedure 115.3 ml (1.099 mol) of HEA and 100 ml of THF were placed in a 500 ml three-necked round-bottom flask under an inert gas (argon) at room temperature (20 ± 2 °C). 60 ml (0.594 mol) of DMEA was added dropwise to this solution. The mixture was stirred in an oil bath at 45 °C for 24 hours. Thereafter, the solvent was removed, and the residue (a yellowish liquid) was extracted with Et2O (4 × 100 ml of Et2O, the product is insoluble in Et2O). The product was dried in vacuo at 50 °C. Yield: 132 g, 75%.

[0202] The product was characterized by 1H-NMR spectroscopy.

[0203] The reaction scheme is shown in Figure 4.

[0204] Example 2: Preparation of a polyurethane (PU) polymer (PU-N) containing N-diol Chemicals 1,4-Butanediol (BD): CAS: 110-63-4, distilled before use; Poly(THF)1000: CAS: 25190-60-1, M n (number average molar mass) = 1,000 g / mol, Merck; 4,4'-Diphenylmethane diisocyanate (MDI): CAS: 101-68-8, >97%, TCI; Dibutyltin dilaurate (DBTL): CAS: 77-58-7, Sigma-Aldrich; THF: industrial grade, dried and distilled before use.

[0205] Reaction 1:

Table 19

[0206] Reaction 2:

Table 20

[0207] Reaction 3:

Table 21

[0208] Procedure MDI and DBTL were mixed with 20 ml of dry THF in a 100 ml nitrogen flask under argon. The solution was cooled in an ice bath. N-diol and BD were added dropwise to this cooled solution within 10 minutes. After the addition was complete, the mixture was stirred at room temperature for 30 minutes. Thereafter, poly(THF) was added dropwise and stirring was continued for 1 hour. Then, the reaction content was heated at 50 °C (oil bath temperature) for 2 hours. Thereafter, the resulting polymer was precipitated in MeOH and dried under vacuum at 50 °C. Yield: 89%.

[0209] The reaction scheme is shown in Figure 5.

[0210] Example 3: Comparison of Monomers with Different Ratios The synthesis of PU-N described in Example 2 was carried out based on the monomer ratios described in Table 1 below.

[0211]

Table 1

[0212] Samples containing the PU-N product were analyzed by GPC (Figure 7) and TGA (Figure 8).

[0213] Gel permeation chromatography (GPC) was used for molar mass determination (instrument: Agilent Technologies 1200 Series / 1260 Infinity; column 1: PSS SDV 5μm 100000; column 2: PSS SDV 5μm 10000; column 3: PSS SDV 5μm 1000; column 4: PSS SDV 5μm 100; detector 1: Waters 486 UV; detector 2: Techlab Shodex RI; eluent: THF; flow rate: 1.0 ml / min; column temperature: 40 °C; calibration standard: polystyrene).

[0214] Thermogravimetric analysis (TGA) was used to determine the thermal stability. Netzsch TG 209 F1 Libra was used. The sample was heated from 25 to 800 °C in an Al2O3 pan. Approximately 5 - 10 mg of the polymer was weighed and placed in the sample pan. The overall measurement was carried out in air at a heating rate of 10 °C / min. The temperature at which weight loss began is referred to as the decomposition temperature.

[0215] As shown in Figure 7, it was found that the molecular weights of the PUs contained in the comparative samples PH18N-6 (100% N-diol) and PH21N-6 (50% N-diol, 50% BD) were too low. The maximum molecular weight was shown by the comparative sample PH15D-6 (50% P(THF), 50% BD).

[0216] Among the PU-N samples, PH24N-6 (50% N-diol, 25% P(THF), 25% BD), PH23N-6 (25% N-diol, 50% P(THF), 25% BD), and PH18J-7 (25% N-diol, 25% P(THF), 50% BD), the molecular weight increased with the amounts of P(THF) and BD.

[0217] The results shown in Figure 7 are summarized in Table 2 below.

[0218]

Table 2

[0219] As shown in Fig. 8, when the amount of P(THF) or BD increases, the decomposition temperature becomes higher.

[0220] The results obtained from Fig. 8 are summarized in Table 3 below.

[0221]

Table 3

[0222] Example 4: Comparison of monomers with different addition orders The synthesis of PU-N described in Example 2 was carried out by adding N-diol + P(THF) first and then BD (Option 1), or adding N-diol + BD first and then P(THF) (Option 2).

[0223] Option 1: PH23N-6, PH24N-6, PH18J-7 (i) MDI + DBTL in anhydrous THF, cooled on ice (ii) Add (dropwise) N-diol + P(THF), stir at room temperature for 30 minutes (iii) Add (dropwise) BD Option 2: PH12D-6, PH16J-7, PH17J-7 (i) MDI + DBTL in anhydrous THF, cooled on ice (ii) Add (dropwise) N-diol + BD, stir at room temperature for 30 minutes (iii) Add (dropwise) P(THF)

[0224] The ratio of the monomers was as described in Table 4 below.

[0225]

Table 4

[0226] Samples containing the PU-N product were analyzed by GPC (Figure 9) and TGA (Figure 10).

[0227] As shown in Figure 9, the molar mass increased by adding P(THF) after BD (Option 2).

[0228] The results obtained from Figure 9 are summarized in Table 5 below.

[0229]

Table 5

[0230] As can be seen from Figure 10, the monomer addition order had virtually no effect on the decomposition temperature.

[0231] The results obtained from Figure 10 are summarized in Table 6 below.

[0232]

Table 6

[0233] Example 5: Quaternization of N-diol-containing PU polymers Chemical substances PU-N (produced in Example 2); 1-bromobutane: CAS. 105-65-9, Merck, >98%; THF: industrial grade, distilled before use.

[0234] Reaction

Table 22

[0235] Procedure 10 g of PU-N was dissolved in 30 ml of THF at 60 °C. 5 ml of 1-bromobutane was added. The reaction mixture was stirred at 60 °C for different time intervals to vary the degree of quaternization. The quaternized polymer was precipitated in hexane and dried under vacuum at 50 °C. Yield: 96%.

[0236] The product PU-N+ was characterized by 1H-NMR spectroscopy.

[0237] The reaction scheme is shown in Figure 6, and Figure 11 further illustrates the principle of quaternization.

[0238] The degree of quaternization is exemplified and summarized in Table 7 below.

[0239]

Table 7

[0240] Example 6: Characterization of the Quaternized PU Polymer (PU-N+) Samples containing non-quaternized or quaternized PU polymers (i.e., PU-N or PU-N+) were analyzed by TGA (Figure 12). As shown, quaternization did not affect the decomposition temperature.

[0241] The results obtained from Figure 12 are summarized in Table 8 below.

[0242]

Table 8

[0243] Example 7: Dynamic Mechanical Thermal Analysis (DMTA) Samples containing non-quaternized or quaternized PU polymers (i.e., PU-N or PU-N+) were analyzed by DMTA; elastane was used for comparison (Figure 13).

[0244] For DMTA, a Rheometric Scientific DMTA instrument was used.

[0245] In contrast to elastane (Figure 13A), the PU polymer samples showed a glass transition temperature (T g ) above 0 °C, regardless of whether they were quaternized.

[0246] Furthermore, as shown, an increase in the amount of BD led to an increase in the glass transition temperature (Fig. 13B: T g = 40 °C; Fig. 13D: T g = 55 °C).

[0247] Finally, the quaternization of PU-N (resulting in PU-N+) induced an increase in the glass transition temperature observed for non-quaternized PU-N (Fig. 13C: T g1 = 70 °C, i.e., > 40 °C; Fig. 13E: T g1 = 70 °C, i.e., > 55 °C).

[0248] Example 8: Stress-Strain Test The mechanical properties of the generated PU polymers were tested. For that purpose, samples of non-quaternized PU or quaternized PU polymers (i.e., PU-N or PU-N+) were analyzed by a strain stress test (tensile test); elastane was used for comparison.

[0249] For the test, a Zwick / Noell BT1-FR 0.5TN.D14 machine was used (preload: 0.01 N / mm, test speed: 50 mm / min). Sample preparation: 1 g of PU (PU-N or PU-N+) was dissolved in 10 ml of HFIP (hexafluoroisopropanol), dropped onto a glass plate to form a film. After drying the film at room temperature for 24 hours, it was vacuum dried at 45 °C for 24 hours. The film was cut to dimensions for mechanical testing (W: 5 mm, L: ≥ 40 mm).

[0250] As shown in Fig. 14, PU-N+ (Fig. 14B) showed a different strain behavior from elastane (Fig. 14A).

[0251] Furthermore, as shown in Table 9 below, quaternization induced a decrease in the fracture strain.

[0252]

Table 9

[0253] Example 9: PU Polymer / Elastane Blend The generated PU polymer was blended with elastane (commercially available). The mechanical properties were tested using the stress-strain test described in Example 8.

[0254] As shown in Figure 15, a blend of 70% PU-N+ and 30% elastane (Figure 15B) showed different strain behaviors from elastane (Figure 15A).

[0255] Furthermore, the fracture strains and elastic moduli measured for different PU-N+ / elastane blends are listed in Table 10 below.

[0256]

Table 10

[0257] For comparison, the fracture strains and elastic moduli measured for different PU-N (i.e., non-quaternized) / elastane blends are listed in Table 11 below.

[0258]

Table 11

[0259] Example 10: Relaxation Behavior Samples of non-quaternized PU (PU-N) or corresponding quaternized PU (PU-N+) (29% quaternized) were stretched from 10 mm (original length of the sample) to 40 mm (Figures 16A, 16B). Upon release, both samples recovered to their original length in about 6 hours. At that time, a recovery of about 180% was achieved in about 5 minutes, and then the remaining 120% recovered much more slowly than that. In this regard, the relaxation behavior of PU-N and PU-N+ was almost the same.

[0260] Similarly, samples of PU-N+ with different degrees of quaternization, namely 9% or 5%, were stretched from 10 mm to 50 mm (Figures 16C, 16D). Upon release, 300% and 280% of the original length of the sample recovered immediately, and an additional 140% and 160% recovered after 5 minutes, respectively. Thus, a total recovery rate of about 90% was achieved within about 5 minutes.

[0261] Therefore, the relaxation behavior depends, at least in part, on the degree of quaternization.

[0262] The results shown in Figure 16 are summarized in Table 12 below.

[0263]

Table 12

[0264] Example 11: Relaxation Behavior of PU Polymer / Elastane Blend

[0265] Non-quaternized PU (PU-N) or corresponding quaternized PU (PU-N+) with different degrees of quaternization (29%, 9% or 5%) was blended with elastane (commercially available), respectively. The samples were stretched and released in the same manner as described in Example 10 (stretching of the sample from 10 mm to 50 mm).

[0266] The results are summarized in Tables 13 - 15 below.

[0267]

Table 13

[0268] First, the relaxation behavior of individual PU-N and elastane changed due to the mixing of elastane and PU-N.

[0269] As can be seen from Table 13, the blend showed a total recovery rate of about 80 - 90% immediately after release, depending on the relative amounts of PU-N and elastane. The remaining 10 - 20% recovery took about 15 minutes to 6 hours, also depending on the relative amounts of PU-N and elastane. More generally, as the relative amount of PU-N increased, the total relaxation time increased.

[0270] [Table 14]

[0271] As can be seen from Table 14, as the relative amount of PU-N increased, the total relaxation time increased. Furthermore, compared to non-quaternized PU-N (Table 13), PU-N+ was associated with an increase in the total relaxation time. Separately, when used in blends with elastane, PU-N+ with a high degree of quaternization (29%) did not offer specific advantages over non-quaternized PU-N.

[0272] [Table 15]

[0273] As can be seen from Table 15, blends with low-degree quaternized (here: 9%) PU-N+ showed a relaxation time of about 30 minutes to 1 hour for all tested compositions. Separately, the relaxation behavior was very similar to that of blends with non-quaternized PU-N (i.e., an immediate total recovery rate of about 80% was achieved).

[0274] [Table 16]

[0275] As can be seen from Table 16, the relaxation behavior of the blend with a low degree of quaternization (here: 5%) of PU-N+ is very similar to the relaxation behavior of the blends with PU-N+ (9% quaternization) (Table 15) and non-quaternized PU-N (Table 13).

[0276]

Table 17-1

Table 17-2

Table 17-3

Table 17-4

[0277] Example 12: Polymer Fiber / Filament A sample of the quaternized PU polymer (PU-N+) (PH07F-8_PU-N + = 50% N-diol, 25% P(THF) 25% BD, 5% quaternized (5% N + )) was ground into powder using a ZM200 ultra-centrifugal mill. The mill was equipped with a sieve with a pore size of 1 mm. A machine with any other pore size could also be used, and the diameter of the sieve is not important. The aim was to convert the polymer mass into a powder that could be easily fed to an extruder for filament production. Subsequently, it was spun into monofilaments using a twin-screw extruder (Process 11 from Thermo Scientific). To prevent the residual stickiness / tackiness of the filaments and enable their storage (so that they do not stick to each other when wound on a roll), the extruded filaments were continuously passed through a trough with SiO2 powder. Using this configuration, the melt spinning of the PU ionomer into monofilaments is facilitated and large-scale production is possible.

[0278] A microscopic image of such a filament is shown in Fig. 17 (magnification 500x). The filament is not transparent and has an opaque surface.

[0279] The mechanical properties of the spun filaments were tested. For that purpose, one or more filaments produced were analyzed by a strain stress test (tensile test). For the test, a Zwick / Noell BT1FR0.5TN.D14 machine was used. (Preload: 0.1 kPa, test speed: 50 mm / min). The diameter of the filament was 280+ / -30 μm and the filament was subjected to a tensile test.

[0280] The following results were obtained:

Table 23

[0281] E mod = Elastic modulus; dL = Delta length; % = Weight percent; Filament diameter = 208+-30 μm

[0282] The results of the strain stress test are shown in Fig. 18.

[0283] The relaxation behavior of such filaments is shown in Fig. 19. Due to such relaxation behavior, filaments of the quaternized polyurethane polymer were stretched from 10 mm (original length of the filament) to 50 mm. When released, the filament recovered its original length of the sample in about 35 - 65 minutes.

[0284] In summary, in this example, the inventors have shown that the polyurethane ionomer can be reproducibly spun into filaments and its adhesiveness can be prevented by spraying SiO2 powder or similar powder or a suitable oil. This powder does not interfere with the relaxation behavior.

Claims

1. A compression product comprising an elastic component or material, wherein the elastic component or material has a delayed continuous relaxation behavior, the elastic component or material is capable of applying a compressive force or a supporting force or a local pressure to a part of the subject's body, the elastic component or material can further undergo a first phase during which the elastic component or material is expanded, a second phase during which the elastic component or material relaxes without recovering its original shape, and a third phase during which the elastic component or material recovers while continuously decelerating its original shape, wherein relaxation is self-initiated, initiated autonomously or spontaneously in the absence of external stimuli if necessary, the compression product is, (a) a non-quaternized polyurethane (PU) polymer (PU-N) containing N-diol obtained by polymerizing a monomer containing an N-diol monomer; and / or (b) a quaternized polyurethane (PU) polymer (PU-N+) containing a quaternized N-diol obtained by polymerizing a monomer containing an N-diol monomer; and, if necessary, (c) elastane comprising or consisting of an elastic component or material, wherein the N-diol is produced from 2-dimethylaminoethylamine and 2-hydroxyethyl acrylate, a compression product.

2. The compression product according to claim 1, wherein the compression product is a medical compression product.

3. The compression product according to any one of claims 1 to 2, wherein the compression product is selected from the group consisting of compression stockings, compression socks, knee pads, arm sleeves, waist attachments, belts, girdles, compression bandages, body support bandages, prostheses, liners for artificial appliances, compression wound dressings, compression plasters, patches, and compression clothing.

4. The compression product according to any one of claims 1 to 3, comprising a non-quaternized PU polymer and, if necessary, an elastic component or material comprising or consisting of elastane. **Claim 5**: The compression product according to any one of claims 1 to 4, for use in the fields of phlebology, orthopaedics, foot care, surgery, postoperative care, trauma management, wound care, or sports, or for use in the treatment, prevention, or management of musco-venous pump dysfunction, venous circulatory insufficiency, venous insufficiency, oedema, phlebitis, thrombosis, venous embolism, lymphoedema, ulcers, foot pain, varicose veins, reticular veins, or "economy class syndrome" (ECS).

Images