Dual action heat management treatment formulations for textiles

Abstract

Thermoregulating aqueous textile coating formulation or precursor thereof including at least one hydro-functional polymer as well as at least one encapsulated functional phase change material.

Description

TECHNICAL FIELD

[0001] The present invention relates to textile treatment formulations to impart heat regulation and moisture regulation, uses thereof, methods of application thereof as well as textiles, in particular bed lining, treated with corresponding formulations.PRIOR ART

[0002] Phase change materials (PCM) are compounds that have the ability to absorb, store and release thermal energy (latent heat of fusion mechanism) when changing from one physical state to another. Due to their inherent properties, PCMs are well known in textile finishing industry as a means of providing thermal comfort. When incorporated into textiles, the phase change materials respond according to the surrounding ambient temperature. For instance, when in contact with warm skin, the PCM absorbs heat and stores it. On the other hand, when the surrounding temperature decreases, the PCM releases stored heat. It was observed that the use of a mattress with PCMs showed a lower increment of the skin temperature compared to the mattress without PCMs (0.3-1.0° C.). Furthermore, the PCMs may improve the human heat dissipation between 2.7% and 25.6% compared to the conventional mattress.

[0003] EP-A-2362830 proposes an article which comprises a substrate, a first functional polymeric phase change material, and a plurality of containment structures that contain the first functional polymeric phase change material. The article may further comprise a second phase change material chemically bound to at least one of the plurality of containment structures or the substrate. In certain embodiments, the article further comprises a second phase change material and a binder that contains at least one of the first polymeric phase change material and the second phase change material. The containment structure may be a microcapsule or a particulate confinement material.

[0004] CN-A-116024821 relates to the field of textiles with phase change microcapsules and a finishing method of the textile. The finishing method of the textile with the phase-change microcapsules comprises the following steps: adding water into the phase-change microcapsules for dilution, soaking the to-be-treated textile in a phase-change microcapsule solution, taking out, padding and drying, namely attaching the phase-change microcapsules to the textile, wherein the shell material of the phase change microcapsule is self-crosslinking acrylate resin, and the core material of the phase change microcapsule is paraffin. The finishing method provided by the invention is simple in process, an adhesive does not need to be additionally added, the influence on the hand feeling, the air permeability and the washing resistance of the textile is small, and meanwhile, the wearing comfort can be effectively improved through the cool feeling effect provided by the phase change microcapsules.

[0005] CN-A-104802478 relates to an intelligent thermal-storage and temperature-adjustment composite fabric which comprises a reflecting layer, a shell fabric layer and a thin film layer, wherein the reflecting layer is formed by adhering a layer of small flower type alumite in the shell fabric layer; the thin film layer is positioned on the outer layer of the shell fabric layer; phase-change temperature-adjustment microcapsules are embedded into the thin film layer; the reflecting layer, the shell fabric layer and the thin film layer are connected through an adhesive. According to the intelligent thermal-storage and temperature-adjustment composite fabric provided by the invention, the reflecting layer is taken as the lining of the garment fabric, to resist heat radiation of a human body, reduce heat loss, provide an active heat source, and utilize the phase-change temperature-adjustment material in the thin film layer to automatically absorb excess heat. At the same time, the thin film layer has windproof, waterproof and moisture permeable functions, and in addition, automatic temperature adjustment of the fabric is realized, the thermal insulation rate is obviously increased, and effective protection is provided for temperature-adjustment microcapsules. Most of the PCMs currently in the textile market are produced from non-renewable sources with associated carbon footprint and environmental impact. Conventional PCM microcapsules used in textile industry are generally paraffins with melamine-formaldehyde based shells. However, given the environmental impact associated there is a need to move towards more sustainable solutions. Bio-based polymers with lower impact on the environment are a desirable alternative for future products.

[0006] There are different thermoregulation technologies that do not resort to the use of PCMs. Some are based on the concept of moisture management and wicking properties. Moisture management can be defined as the movement of the moisture (perspiration) from the skin to the environment through the fabric. There are cooling technologies that transport the moisture away from the skin to the outside of the fabric thus promoting evaporation.

[0007] WO-A-2019086322 discloses a textile treatment formulation is proposed containing a PPG / PEG block-copolymer. The PPG / PEG block-copolymer can be end capped with hydrocarbon systems like for example n-butyl. The PPG / PEG block-copolymer (I) is chosen to have a DSC-melting point according to DIN ISO 11357 in the range of 15-37° C. to provide for a cool touch effect and can be applied without encapsulation. Furthermore, uses of such a formulation and textiles treated with such a formulation are proposed.

[0008] US-A-2018242665 discloses microcapsules or macrocapsules which have a core composition that includes a phase changing material (PCM) encapsulated within a polymer wall with an outer shell having a siloxane tethered to an exterior surface of the polymer wall by a surfactant. The siloxane may form a crystalline or a sol-gel outer shell. Methods of making such capsules and textile fabrics and clothing incorporating such capsules include treating pre-formed capsules with a surfactant solution followed by treating with a compound containing a siloxane functional group. The surfactant connects or tethers the siloxane to the exterior surface of the polymer wall and the siloxane forms an outer shell of the capsules.

[0009] FR-A-3112560 discloses a textile for a vehicle interior trim part comprising: a plurality of threads together forming a textile layer; at least two different phase change materials, said phase change materials being directly attached to the threads of the textile layer; and at least one humidity regulator other than phase change materials.

[0010] WO-A-2019086322 proposes a textile treatment formulation containing a PPG / PEG block-copolymer on average having PEG-blocks in the range of 37-45 terminated on both sides with on average in the range of 6-11PPG blocks. The PPG / PEG block-copolymer can be end capped with hydrocarbon systems like for example n-butyl. The PPG / PEG block-copolymer is chosen to have a DSC-melting point according to DIN ISO 11357 in the range of 15-37° C. to provide for a cool touch effect and can be applied without encapsulation. Furthermore uses of such a formulation and textiles treated with such a formulation are proposed.

[0011] The article: “New dual action textile cooling technology”, in Textiles, 14 Jan. 2022 (https: / / www.innovationintextiles.com / new-dual-action-textilecooling-technology / ) discloses a combination of a hydro-functional polymer and a biobased vegetable oil derived thermo-functional polymer.

[0012] The WEBINAR: “Dual action cooling for textiles HeiQ Cool” (URL: https: / / www.heig.com / news / webinars / heiq-cool-dual-action-cooling-2023-04-04 / ) discloses textile technology to deliver both instant contact cooling and continuous evaporative cooling.SUMMARY OF THE INVENTION

[0013] There are other thermoregulation technologies which mimic the natural ability of the body to regulate body heat. E.g. a hydro-functional polymer is capable of changing its form and affinity to moisture at different temperatures. For instance, when the body temperature rises, a hydro-functional polymer emphasizes a low moisture affinity with rapid spreading of moisture providing rapid evaporation and cooling. As the body temperature decreases the hydro-functional polymer imparts increased moisture affinity resulting in slower moisture spreading and reduced evaporation and cooling.

[0014] The present invention is an innovative technology that is a single textile treatment formulation incorporating two thermoregulation technologies with a melting energy action together with vaporising energy action, thus providing a dual action cooling effect: instantaneous and continuous cooling. The innovation is composed of a phase change thermo-polymer with a hydro-functional polymer.

[0015] The proposed technology has been designed to incorporate easily into textiles, mainly focused on bedding market. To achieve the greatest cooling impact for the user, the textile application process is preferably focused on printing application onto cotton woven fabrics for bedding articles such as sheet sets and pillowcases.

[0016] Cotton sheets are sought after by consumers for their softness and breathability. Thread count is an important parameter when it comes to the quality of woven bed sheets. Nevertheless, bed linens need characteristics such as high breathability and soft hand feel to promote sleep quality. Sleep quality is influenced also by thermal regulation parameters such as thermal conductivity and air permeability.

[0017] When incorporated into cotton sheets, PCM microcapsules provide thermal comfort by reducing the temperature of the microenvironment. The incorporation of phase change material microcapsules on cotton fabric by printing application for hospital bed sheet application leads to excess moisture absorption from the surrounding, promoting the decrease of temperature and humidity within the fabric. Moreover, the treated sample presents a greater heat conductivity than the untreated sample, and this is synergistically enhanced and supplemented by the addition of a hydro-functional polymer.

[0018] The present invention discloses in particular the printing application on cotton bed sheet sets and pillowcases with thread count higher than 250 and singles yarn count higher than 70 with the dual cooling effect and benefit to sleep quality.

[0019] Sleep plays a vital role in pursuing and maintaining good health and is a biological necessity for energy conservation and recovery. The thermal environment during sleep is one of the most important factors for sleep quality and maintaining deep restful sleep. The circadian rhythm and sleep-wake rhythm controls the thermoregulation linked to the human sleep.

[0020] The body temperature tends to decrease during nocturnal sleep, whereas body temperature tends to increase during the wake phase. The decrease of the body temperature decrease is explained by the peripheral skin temperature containing arteriovenous anastomoses capable of adjusting blood flow to the skin. When sleeping in the presence of bed covers, the sleep might be disturbed from heat exposure. Sleep efficiency may be improved when sleeping on a mattress with the adequate characteristics including the firmness, the distribution of the pressure and the ability to thermoregulate and the comfortable bed climate temperature should be within 32° C. to 34° C.

[0021] Various treatment technologies claim the ability to achieve improved thermal comfort through functional treatments such as vaporizing energy mechanism and at heat of fusion (melting) energy mechanism.

[0022] The vaporizing energy action mimics the natural mechanism of the body when producing sweat and cooling through evaporation.

[0023] The conventional melting energy action is due to the heat storage capacity of phase change materials (PCM). The effect is dependent on the mass of PCM applied and generally provides a short-time cooling effect.

[0024] The proposed combination of such functional treatments (vaporizing action and melting action) provides a synergy between two different mechanisms resulting in dual action cooling. The melting energy absorption action provides an instantaneous contact cooling effect while the vaporizing energy action provides an ongoing continuous evaporative cooling which can recharge the phase change material. The treated fabric starts cool, stays cool.

[0025] The present invention discloses in particular the printing application with the dual action cooling product on above 75% coverage area on cotton woven fabrics with thread count higher than 250 and 70 singles yarn count, imparting a durable cooling effect and providing improved sleep quality.

[0026] According to a first aspect of the present invention, it relates to a thermoregulating aqueous textile coating formulation or precursor thereof comprising at least one hydro-functional polymer as well as at least one encapsulated functional phase change material. The concentration of the at least one hydro-functional polymer is preferably in the range of 0.1-20% by weight, or 0.2-10% by weight, preferably in the range of 0.25-5% by weight or 0.3-2% by weight or in the range of 0.3-1% by weight.

[0027] The concentration of the at least one encapsulated functional phase change material is preferably in the range of 1-40% by weight, preferably in the range of 2-30% by weight or 5-25% by weight or in the range of 10-25% by weight.

[0028] The weight percent ratio between the hydro-functional polymer and the encapsulated functional phase change material is preferably in the range of 1:2-1:50, preferably in the range of 1:4-1:45 or in the range of 1:5-1:40, or in the range of 1:20-1:40. The coating formulation may consist of the following components:

[0029] (A) 0.1-20% by weight, preferably 0.25-5% by weight or 0.3-1% by weight of at least one hydro-functional polymer;

[0030] (B) 1-40% by weight, preferably 2-30% by weight or 10-25% by weight of at least one encapsulated functional phase change material;

[0031] (C) 0-30% by weight, preferably 0.1-25% by weight or 15-25% by weight of further additives different from (A), (B) and (D);

[0032] (D) 40-90% by weight, preferably 55-85% by weight or 60-80% by weight of solvent, preferably water.

[0033] The components (A)-(D) sum up to 100% by weight of the thermoregulating aqueous textile coating formulation or precursor thereof.

[0034] The above formulation and the given percentages are for the formulation of the precursor of the thermoregulating aqueous textile coating formulation, which is the product which is produced and shipped to the final user and is only adapted in formulation to the particular needs at the user's end.

[0035] Typically, for the case of a precursor coating formulation, the content in additives (C) is in the range of at most 30% by weight, for example in the range of 15-25% by weight. Also, for the case of a precursor coating formulation, the solvent proportion is typically in the range of 60-85% by weight, preferably in the range of 65-80% by weight. For the case of a precursor coating formulation, the proportion of (A) is typically in the range of 0.3-2% or 0.3-1% by weight, and / or the proportion of (B) is in the range of 5-25% or 10-22% by weight. For the precursor coating formulation, the solvent is typically water, preferably exclusively water, present in a proportion of 60-80% by weight. Such a precursor formulation typically has a viscosity in the range of 1300-2000 cP.

[0036] For the viscosity determination as defined in this application a rotational viscometer with a cylindrical spindle is used. This technique is well known in the art for liquid formulations (e.g. ISO 3219:1993 “Plastics—Polymers / resins in the liquid state or as emulsions or dispersions—Determination of viscosity using a rotational viscometer with defined shear rate). The method is generically referred to simply as a “Brookfield” viscometer. Many different spindles can be used to characterize the viscosity. The instrument used in the experiments here for aqueous formulations is a Brookfield DV-II viscometer, typically with spindle SC4-27 or SC4-29. For purposes of the experiments here the SC4-27 is applicable. For the final application, this precursor formulation can be diluted and / or supplemented as needed as a function of the specific application process, as a function of the specific substrate to be treated, as a function of the specific properties to be obtained on the final substrate and as a function of further conditions ant the user's end.

[0037] In particular for printing application, and / or if the viscosity needs to be adapted, e.g. for printing, thickener may be added as needed. Also possible is adding of water or another solvent if the viscosity is to be reduced for this or another application process.

[0038] If postprocessing steps shall be avoided, it is also possible to add postprocessing additives to the formulation before actual use. So, for example a softener can be added to the precursor formulation before the application process.

[0039] For the case of the formulation for final use derived from and based on the precursor formulation, typically, if further additives are added, the proportion of component (C) can be higher. So the proportion in additives (C) can go up to 10% or 30% by weight. If for example softener is added in a proportion of 5-20% by weight and / or thickener in a proportion of 0.5-5% by weight, the total proportion of additives (C) can end up in a range of 5-25% by weight. If a significant amount of such additional additives is added, the proportion of water or more generally speaking solvent can go down, for example to a proportion of 50-70% by weight. On the other hand, the precursor formulation may also be diluted at the user's end, leading to an increased solvent proportion, so if for example is water is added, the proportion of (D) can go up to 90% by weight for the final formulation. The further additives of component (C) are preferably selected from the group consisting of: defoamers, preferably selected as silicone-based defoamers, or a mixture thereof; softeners, preferably selected as polysiloxane based softener emulsions, or a mixture thereof; metal salts, preferably selected as NaCl, further ionic strengths modifiers (alkali or earth alkali salts), or mixtures thereof; binders, preferably as acrylate-based binders, or a mixture thereof; colourants; surfactants, rheology modifiers including thickeners; antioxidants, buffers (pH regulation), antimicrobial formulations, natural oil emulsions, probiotic formulations or mixtures thereof.

[0040] As mentioned, the formulation, in particular as precursor formulation, contains as component (D) a solvent. Preferably the solvent is a polar solvent, in particular water, which may be mixed with further in particular polar solvents such as ethanol, propanol, or other alcohol-based solvents. Also mixtures of water with more hydrophobic solvents are possible. Preferably the solvent exclusively consists of water.

[0041] If at the user's end further solvents are added, these are preferably selected as in the precursor formulation, but can also be tailored to the specific use and e.g. the viscosity and / or polarity to be achieved.

[0042] The formulation according to the present invention is preferably containing (an effective amount of) a PPG / PEG block-copolymer (I) as component (A), on average having PEG-blocks in the range of 37-45, terminated on both sides with on average in the range of 6-11 PPG blocks. The PPG / PEG block-copolymer should be end capped with hydrocarbon systems like for example n-butyl on one or both sides. The PPG / PEG block-copolymer (I) is chosen to have a DSC-melting point according to DIN ISO 11357 in the range of 15-37° C. to provide for a cool touch effect and can be applied without encapsulation.

[0043] Possible are for example systems of the type (PPG-500)-(PEG-1800)-(PPG-500), wherein the numbers stand for the molecular weight and not for the number of blocks. The corresponding backbone systems are also known as Meroxapol (International Nomenclature of Cosmetic Ingredients, INCI nomenclature). The term “Meroxapol” denotes a block copolymer consisting of polyethylene glycol terminated with polypropylene glycol. The numerical suffix designation is obtained by the following rule: The first two digits multiplied by 100 correspond to the approximate average molecular mass of the poly(oxypropylene) portion; the third digit multiplied by 10 corresponds to the percentage by weight of the poly(oxyethylene) portion. Suitable in the present context are systems like Meroxapol 86, 87, 96, 97, 106, 107, 116, 117, 126, 127 and / or Meroxapol 252, preferably endcapped at least on one side with a hydrocarbon chain with 1-18, preferably 1-6 carbon atoms.

[0044] More specifically, the textile treatment formulation may be containing (an effective amount of) the following PPG / PEG block-copolymer (I):

[0045] In this formula (I), the variables are chosen as follows:

[0046] the average value of x is in the range of 27-63, preferably 37-45;

[0047] the average value of y is in the range of y is in the range of 6-11, wherein the value of y in the left and in the right structural moiety as represented above can be different but within that range;

[0048] R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-18, preferably 1-6 carbon atoms, in which one or more carbon atoms can be replaced by a heteroatom selected from the group consisting of: nitrogen, oxygen, sulfur.

[0049] When talking about the average value of x and y, this is a mass average which is back calculated from the average mass using the molecular weight of the corresponding structural moiety. The average molecular weight of the structure without the residues R′ and R″ is typically in the range of 2600-3100 Dalton (unified atomic mass unit, Da), preferably in the range of 2700-2900 Da.

[0050] The PPG / PEG block-copolymer (I) in the formulation can be one single system with essentially the same set of parameters as defined above, it can however also be a mixture of such PPG / PEG block-copolymers (I) provided that each of the constituents is in line with the definitions as given above and that this mixture as a whole has a melting temperature in the above-mentioned range.

[0051] To provide the desired functionality of the cool-touch effect, the parameters are furthermore chosen such that the PPG / PEG block-copolymer (I) has a DSC-melting point according to DIN ISO 11357 in the range of 15-37° C.

[0052] According to a first preferred embodiment, the average value of x is in the range of 38-42, preferably in the range of 39-41. It was found that an average value of approximately 40 provides for optimum melting point conditions for optimum cool touch effects.

[0053] According to yet another preferred embodiment, wherein the average value of y is in the range of 7-10, preferably in the range of 8-9, and wherein further preferably the values of y in the left and in the right structural moiety as represented above are the same.

[0054] As a matter of fact, the balance between the PPG / PEG blocks and their length is used to adjust the melting point into the desired range and to make sure the corresponding molecule can be attached to the fibers / textiles efficiently.

[0055] Such a formulation cannot contain the PPG / PEG block-copolymer (I) without end capping, i.e. with R′═R″═H; it should be end capped at one or both ends. Correspondingly, according to yet another preferred embodiment, R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl. For the longer chain possibility R′ and R″ can be selected, independently from each other, from the group consisting of heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, wherein these can be saturated or partly unsaturated, cyclic, linear or branched, preferably they are saturated and linear with no substitution of the carbon atoms.

[0056] Particularly beneficial properties, for example for making sure that even difficult textiles / fibers such as cotton can be treated, can be achieved if R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, n-butyl, wherein preferably R′ is selected to be n-butyl and R″ is selected to be hydrogen for example for cotton treatment.

[0057] According to another preferred embodiment, the PPG / PEG block-copolymer (I) has a DSC-melting point according to DIN ISO 11357 in the range of 20-35° C., preferably in the range of 25-33° C. This temperature window was found to be optimum for the actual cool touch effect.

[0058] The total average molecular weight of the PPG / PEG block-copolymer (I) can be in the range of 2500-3200 Da, preferably in the range of 2750-3000 Da.

[0059] In particular if R′ is selected to be n-butyl and R″ is selected to be hydrogen, the average molecular weight can be in the range of 2750-2950 Da, and if R′=R″ and selected to be n-butyl, the average molecular weight can be in the range of 2800-3000 Da.

[0060] The PPG / PEG block-copolymer (I) can be present in the formulation in unencapsulated form.

[0061] The PPG / PEG block-copolymer (I) can be present in the formulation, preferably in the form of particles / droplets in an aqueous dispersion / suspension and / or in solution, in a concentration in the range of 50-850 g / l, preferably in the range of 100-830 g / l, most preferably in a concentration in the range of 100-810 or 700-810 g / l. Below the loading is too low for reasonably applying the formulation to the fibres and above viscosity becomes an issue. The aqueous solution may contain, next to water, other liquid organic solvents if needed, for example alcohols and the like but also preservatives, and minor amounts of less than 5 weight percent. Normally, the formulation is free from curing agents so that after drying of a correspondingly coated fiber no curing step is necessary.

[0062] In addition, the formulation contains the at least one encapsulated functional phase change material as component (B), which preferably is a microencapsulated functional polymeric phase change material.

[0063] The term “phase change material” refers to a material that has the capability of absorbing or releasing heat to adjust heat transfer at or within a temperature stabilizing range. A temperature stabilizing range can include a specific transition temperature or a range of transition temperatures. In some instances, a phase change material can be capable of inhibiting heat transfer during a period of time when the phase change material is absorbing or releasing heat, typically as the phase change material undergoes a transition between two states. This action is typically transient and will occur until a latent heat of the phase change material is absorbed or released during a heating or cooling process. Heat can be stored or removed from a phase change material, and the phase change material typically can be effectively recharged by a source emitting or absorbing it. For certain implementations, a phase change material can be a mixture of two or more materials. By selecting two or more different materials and forming a mixture, a temperature stabilizing range can be adjusted for any desired application. The resulting mixture can exhibit two or more different transition temperatures or a single modified transition temperature when incorporated in the articles described herein.

[0064] The term “latent heat” refers to an amount of heat absorbed or released by a material as it undergoes a transition between two states. Thus, for example, a latent heat can refer to an amount of heat that is absorbed or released as a material undergoes a transition between a liquid state and a crystalline solid state, a liquid state and a gaseous state, a crystalline solid state and a gaseous state, two crystalline solid states or crystalline state and amorphous state.

[0065] The microcapsules preferably have an essentially spherical shape and / or an average size (D50) in the range of 2-50 μm, preferably in the range of 5-20 μm. The core is preferably formed by the mentioned phase change material, and the shell is preferably an organic shell material comprising or consisting of natural and / or synthetic polymeric materials, which process good sealing properties and good structural flexibility and resistance to the volume change associated with repetitive phase transformations of the enclosed phase change material. For the shell material, in particular melamine formaldehyde, urea formaldehyde and acrylic resins or combinations thereof can be used.

[0066] Preferably, the at least one encapsulated functional phase change material is a functional polymeric phase change material with at least one crystallizable section, preferably comprising a backbone and side chains, wherein preferably the side chains form a crystallizable section.

[0067] The at least one encapsulated functional phase change material can be a functional polymeric phase change material with a molecular weight of at least 500 Daltons, preferably at least 2000 Daltons, wherein preferably the weight of crystallizable sections makes up at least 20%, preferably at least 50%, and more preferably at least 70% of the total weight of the functional polymeric phase change material.

[0068] The at least one encapsulated functional phase change material preferably has a single-phase change temperature or multiple such temperatures, wherein preferably it has at least one phase change temperature in the range between −10° C. and 100° C., preferably in the range of 10° C. and 60° C. and / or a phase change enthalpy of at least 25 J / g.

[0069] The at least one encapsulated functional phase change material is preferably selected from the group consisting of: paraffinic, vinylic, glycolic, olefinic, acrylate, methacrylate, preferably a system based on at least one of (longchain) polyacrylate or polymethacrylate, (longchain) alkyl vinyl ester, (longchain) vinyl ether, (longchain) alkyl olefins.

[0070] According to a further aspect of the present invention, it relates to the use of such a formulation or of a treatment liquor comprising such a formulation according for the coating of fibers and / or textiles, wherein preferably the fibers and / or textiles are based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefinic, acrylic, or a mixture and / or blend thereof, in particular to impart a thermoregulating effect.

[0071] The textiles preferably are cotton or cotton-based textiles, preferably with thread count higher than 250 and 70 singles yarn count, preferably bed textiles, and preferably the formulation is applied by printing, wherein before treatment with the formulation the textiles can be treated with a softener formulation and / or cationic fixer formulation, preferably based on quaternary polyamine systems.

[0072] For printing, the viscosity of the formulation as to be used for application preferably has a viscosity between 12,000 and 20,000 centipoises (cPs), this can also be further adapted at the user's end by adding further thickener to the precursor formulation.

[0073] Preferably, the formulation is applied by patterned printing, in particular (roll) screen printing Preferably the coverage area of the printing is in the range of 70-80% of the full area.

[0074] Further preferably, the dry add on (DAO) of the formulation is in the range of 5-30 g / m2, preferably 10-20 g / m2.

[0075] According to yet another aspect of the present invention, it relates to a method for treatment of cotton or cotton-based textiles with such a formulation in particular to impart a thermoregulating effect.

[0076] Subsequent to the treatment with the formulation the textiles can be subjected to at least one of the following post-treatments after drying: padding, sanforization, compacting, calendaring, decatizing, raising, emerizing, condensation of crosslinkers or self-crosslinking polymers.

[0077] Last but not least the present invention relates to cotton or cotton based, preferably woven textile treated with such a formulation or resulting from such a method, in particular woven bed textile with at least 50% preferably at least 75% coverage area of saif formulation on cotton woven fabrics preferably with thread count higher than 250 and 70 singles yarn count. Further embodiments of the invention are laid down in the dependent claims.BRIEF DESCRIPTION OF THE DRAWINGS

[0078] Preferred embodiments of the invention are described in the following with reference to the drawings, which are for the purpose of illustrating the present preferred embodiments of the invention and not for the purpose of limiting the same. In the drawings,

[0079] FIG. 1 shows the measured surface temperature (° F.) of treated test sample compared to the untreated control sample through time (seconds);

[0080] FIG. 2 shows the surface temperature difference (° F.) between treated test sample vs the untreated control samples. A positive (+) temperature difference indicates the surface of the Control Sample was warmer than the surface of the Test sample. A negative (−) temperature difference indicates that the surface of the Control Sample was colder than the surface of the Test Sample;

[0081] FIG. 3 shows IR thermal images of the triplicate Treated test sample immediately following water contact with the surface (upper images) and also following absorption of the water (lower images);

[0082] FIG. 4 shows IR thermal images of the triplicate untreated Control sample immediately following water contact with the surface (upper images) and also following absorption of the water (lower images).DESCRIPTION OF PREFERRED EMBODIMENTS

[0083] The dual action cooling effect treatment formulation was applied by printing application onto cotton woven fabrics and characterized through Surface Temperature Measurement of Filled Textile Finished Products after wetting to perceive the effectiveness of the dual cooling effect.EXAMPLE

[0084] The fabric used in the working examples was a 400TC Cotton Woven Satin.

[0085] In order to ensure a successful implementation of a printing application of the proposed formulation, it is beneficial to adhere to a set of defined parameters. One important parameter is the viscosity of the printing paste, which should achieve a viscosity between 12,000 and 20,000 centipoise (cPs). It should however be noted that not all products exhibit such high viscosities. In such instances, the use of a thickener can be required.

[0086] The formulation as used for printing was as follows:

[0087] 99% by weight Dual Action Cooling Product (precursor)

[0088] 1% by weight Thickener (e.g. in the form of the commercially available product HeiQ Operator CTT)

[0089] The Dual Action Cooling Precursor Product is composed as given in the Table below:Components% w / wAHydro-functional polymer 0.4%BEncapsulated functional phase change material13.6%CPrecursor auxiliary components19.7%DWater66.3%Total 100%

[0090] The preparation of the printing paste:

[0091] 1. Properly stir the Dual Action Cooling Product in a vessel with a mechanical mixer. The product should be mixed at mild agitation. Too high speed is not recommended.

[0092] 2. Slowly add the required amount of Thickener and mix very well.

[0093] 3. Check viscosity (target 12,000 and 20,000 centipoises (cPs)).

[0094] The prepared printing paste is then placed on a rotary screen printing roll that comes into contact with the cotton fabric. This roll has a specific artwork pattern, a specific mesh and consequently a specific printed coverage area.

[0095] Mesh count refers to the number of polyester threads crossing each other per square inch on a screen; with higher counts providing finer detail and lower counts accommodating thicker inks or rougher surfaces. The mesh will contribute to the amount of product that will pass onto the fabric surface.

[0096] Coverage Area is the area covered with the printing. Briefly, it is the area treated with the Dual Action Cooling Product.

[0097] Furthermore, inside the roller there is a rod, whose weight influences the pressure applied to the roller against the fabric, facilitating the passage of product onto the fabric.

[0098] In this case, the Mesh was 60 and the Coverage Area 80-85%.

[0099] The amount applied to the fabric is calculated using the Wet Add-On (WAO) or the Dry Add-On (DAO). The Wet Add-On is the subtraction between the weight of the wet treated fabric in a given area and the weight of the wet untreated fabric in that given area. The same applies to the DAO but with fabrics dried.

[0100] The DAO obtained was between 10-20 gsm.

[0101] After the printing application, the fabric was subjected to a padding bath with a softener to improve the handfeel. Finally, to ensure its dimensional stability, fabric was submitted to Sanforization.

[0102] The recipe for the printing application can be adjusted to suit different requirements. For instance, instead of submitting the fabric to a second step to a padding bath with softener to improve the handfeel, a softener can be introduced into the printing recipe.

[0103] An example:

[0104] 79% Dual Action Cooling Product

[0105] 20% Softener

[0106] 1% Thickener

[0107] The test involved a comparison of the surface temperature of two samples measured with an infra-red thermometer (FLIR). A volume of warm water was applied the test sample and to the control sample respectively while the temperature was measured at the locations where the water was delivered. Testing was stopped after the temperature of both the samples reached a stable level. Water was applied to 3 different locations on each sample and the surface temperature data recorded as an average of the 3 locations on each sample (FIG. 1). The ambient laboratory conditions during both sample conditioning (24 hours prior to testing) and testing were air temperature 20±5° C. Relative humidity 65±5% R.H. The first peak in FIG. 2 indicates the instantaneous cooling effect provided by the PCM thermo-polymer incorporated on cotton fabric. The second, more prolonged peak, indicates the evaporative cooling effect of the hydro-functional polymer that provides an ongoing cooling effect.

[0108] Additionally, IR thermal images of both samples were taken at the moment of initial water contact on the surface and also following water drop absorption.

[0109] It can be observed from comparing FIG. 3 and FIG. 4 that after water drop absorption, the temperature of the treated fabric sample is lower than the Control fabric sample.

[0110] The dual action cooling effect treatment formulation was applied by printing application onto cotton woven bed-sheet fabrics and were characterized in a sleep study in comparison to untreated control samples. The study showed that, compared to the untreated control fabrics, the data for treated fabrics indicated improved sleep quality; improved mood and wellbeing; and improved symptoms of sweating during sleep.

Claims

1. Thermoregulating aqueous textile coating formulation or precursor thereof comprising at least one hydro-functional polymer as well as at least one encapsulated functional phase change material.

2. Coating formulation according to claim 1, wherein the concentration of the at least one hydro-functional polymer is in the range of 0.1-20% by weight, or 0.2-10% by weight, or in the range of 0.25-5% by weight or 0.3-2% by weight;and / or wherein the concentration of the at least one encapsulated functional phase change material is in the range of 1-40% by weight, or in the range of 2-30% by weight or 5-25% by weight;and / or wherein the weight percent ratio between the hydro-functional polymer and the encapsulated functional phase change material is in the range of 1:2-1:50, or in the range of 1:4-1:45 or in the range of 1:5-1:40.

3. Coating formulation according to claim 1, wherein it consists of the following components:(A) 0.1-20% by weight, or 0.25-5% by weight of at least one hydro-functional polymer;(B) 1-40% by weight, or 2-30% by weight of at least one encapsulated functional phase change material;(C) 0-30% by weight, or 0.1-25% by weight of further additives different from (A), (B) and (D);(D) 40-90% by weight, or 55-85% by weight of solvent, including waterwherein the components (A)-(D) sum up to 100% by weight of the coating formulation or precursor thereof.

4. Coating formulation according to claim 1, wherein component (C) is present in the formulation in a proportion in the range of 0.1-30% by weight, or in the range of 0.1-25% by weight or 0.1-20% by weight, in particular in case of a precursor coating formulation;and / or wherein the further additives of component (C) are selected from the group consisting of: defoamers, including those selected as silicone-based defoamers, or a mixture thereof; softeners, including those selected as polysiloxane based softener emulsions, or a mixture thereof; metal salts, including those selected as NaCl, further ionic strengths modifiers (alkali or earth alkali salts), or mixtures thereof; binders, including acrylate-based binders, or a mixture thereof; colourants; surfactants, rheology modifiers including thickeners; antioxidants, buffers (pH regulation), antimicrobial formulations, natural oil emulsions, probiotic formulations or mixtures thereof.

5. Coating formulation according to claim 1, wherein the at least one hydro-functional polymer is a PPG / PEG block-copolymer (I) or a mixture thereof:whereinthe average value of x is in the range of 27-63, or in the range of 37-45;the average value of y is in the range of y is in the range of 6-11, wherein the value of y in the left and in the right structural moiety as represented above can be different but within that range;R′ and R″ are selected, independently from each other, from the group consisting of:hydrogen, saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-18 carbon atoms, in which one or more carbon atoms can be replaced by a heteroatom selected from the group consisting of: nitrogen, oxygen, sulfur;andwherein the PPG / PEG block-copolymer (I) has a DSC-melting point (peak value) according to DIN ISO 11357 in the range of 15-37° C.,wherein the average value of x can be in the range of 38-42, or in the range of 39-41.

6. Coating formulation according to claim 5, wherein the average value of y is in the range of 7-10, or in the range of 8-9, and wherein the values of y in the left and in the right structural moiety as represented above can be the same, or x is 41 and y is 9and / or wherein R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, saturated or at least partly unsaturated linear, cyclic or branched hydrocarbon chain with 1-6 carbon atoms, including those selected from the group: methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, 3-methylbut-2-yl, 2-methylbut-2-yl, 2,2-dimethylpropyl, at least one of R′ and R″ can be selected not to be hydrogenand / or wherein R′ and R″ are selected, independently from each other, from the group consisting of: hydrogen, n-butyl, wherein R′ can be selected to be n-butyl and R″ can be selected to be hydrogenand / or wherein the PPG / PEG block-copolymer (I) has a DSC-melting point according to DIN ISO 11357 in the range of 20-35° C., or in the range of 25-33° C.,and / or wherein the onset in of the peak in the DSC is below 0° C.and / or wherein the end of the peak in the DSC is below 50° C., or below 45° C.;and / or wherein the full width at half height of the peak is smaller than 20° C., or smaller than 15° C.;and / or wherein the peak in the DSC is bimodal or monomodal.

7. Formulation according to claim 5, wherein the total average molecular weight of the PPG / PEG block-copolymer (I) is in the range of 2500-3200 Da, or in the range of 2750-3000 Da, and if R′ is selected to be n-butyl and R″ is selected to be hydrogen, the average molecular weight can be in the range of 2750-2950 Da, and if R′═R″ and selected to be n-butyl the average molecular weight can be in the range of 2800-3000 Da,and / or wherein PPG / PEG block-copolymer (I) is present in the formulation in unencapsulated form,and / or wherein the viscosity of the formulation as to be used for printing application has a viscosity between 12,000 and 20,000 centipoises (cPs).

8. Coating formulation according to claim 1, wherein the at least one encapsulated functional phase change material is a microencapsulated functional polymeric phase change material,and / or wherein the at least one encapsulated functional phase change material is a functional polymeric phase change material with at least one crystallizable section, including those comprising a backbone and side chains, wherein the side chains can form a crystallizable section,and / or wherein the at least one encapsulated functional phase change material is a functional polymeric phase change material with a molecular weight of at least 500 Daltons, or at least 2000 Daltons, wherein the weight of crystallizable sections can make up at least 20%, or at least 50%, or at least 70% of the total weight of the functional polymeric phase change material.

9. Coating formulation according to claim 1, wherein the at least one encapsulated functional phase change material has a single-phase change temperature or multiple such temperatures, wherein it can have at least one phase change temperature in the range between −10° C. and 100° C., or in the range of 10° C. and 60° C. and / or a phase change enthalpy of at least 25 J / g.

10. Coating formulation according to claim 1, wherein the at least one encapsulated functional phase change material is selected from the group consisting of: paraffinic, vinylic, glycolic, olefinic, acrylate, methacrylate, including systems based on at least one of (longchain) polyacrylate or polymethacrylate, (longchain) alkyl vinyl ester, (longchain) vinyl ether, (longchain) alkyl olefins.

11. Method of using a formulation according to claim 1 for the coating of fibers and / or textiles, wherein the fibers and / or textiles can be based on cotton, hemp, flax, lyocell, rayon, jute, wool, polyester, polyamide, modacrylic, olefinic, acrylic, or a mixture and / or blend thereof, to impart a thermoregulating effect.

12. Method according to claim 11, wherein the textiles are cotton or cotton-based textiles, including those with thread count higher than 250 and 70 singles yarn count, and wherein the formulation can be applied by (patterned) printing, including (roll) screen printing, wherein the viscosity of the formulation as to be used for printing application can have a viscosity between 12,000 and 20,000 centipoises (cPs), wherein the coverage area of the printing can be in the range of 70-80% of the full area, wherein the dry add on (DAO) of the formulation can be in the range of 5-30 g / m2, or 10-20 g / m2, wherein before treatment with the formulation the textiles can be treated with a softener formulation and / or cationic fixer formulation, including those based on quaternary polyamine systems.

13. Method for treatment of cotton or cotton-based textiles with a formulation according to claim 1, including impart a thermoregulating effect.

14. Method according to claim 12, wherein subsequent to the treatment with the formulation the textiles are subjected to at least one of the following post-treatments after drying: padding, sanforization, compacting, calendaring, decatizing, raising, emerizing, condensation of crosslinkers or self-crosslinking polymers.

15. Cotton or cotton based, including woven textile treated with a formulation according to claim 1, including woven bed textile with at least 50% or at least 75% coverage area of saif formulation on cotton woven fabrics including those with thread count higher than 250 and 70 singles yarn count.

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