Biocidal products with luminescent marking additives for textile surfaces and like

Abstract

A biocidal product for application to a surface, in particular a porous surface, such as a fabric, textile, and the like, which product incorporates an identification mark that enables the presence of the product to be confirmed and thus protected in maintenance. The biocidal composition comprises: between 0.01% and 0.05%, relative to the total weight of the product, of a vinyl ester resin acting as a carrier for the biocidal agent; the mixture is formed by combining 0.1 to 2.0 percent of dimethyl didecyl ammonium chloride and 2.0 to 10.0 percent of dimethyl octadecyl [3-(trimethoxysilyl) propyl] ammonium chloride in a medium which is formed by a mixture of 0.2 to 1.0 percent of methanol and 0.02 to 1.50 percent of ethanol; urea with a ratio of 0.2 to 1.0% and acetic acid with a ratio of 0.001 to 0.010%; and the luminescent additive is combined with the aluminosilicate metal oxide containing rare earth ions in the form of a dopant.

Description

Technical Field

[0001] The present invention discloses a biocidal product for application to any porous surface, in particular a textile surface, incorporating an additive that allows the presence of the product to be identified by a luminescent effect, such that it ensures that the surface has been previously treated with said biocidal product, which allows providing confidence to the user and ensuring the presence of the product. Background Art

[0002] Antimicrobial treatment of materials is becoming an increasingly promising mechanism for combating microbial pathogens. Microbial contamination of porous materials (such as fibers and fabrics) can be particularly difficult to prevent because the materials themselves protect microorganisms from surface sterilization methods. It is also important to develop materials with inherent antimicrobial properties that can prevent or reduce contamination over a period of time.

[0003] In the past, fibers, woven and nonwoven fabrics and similar materials such as cotton balls, sponges or wipes were combined with solvents to achieve microbial elimination, microbiocide or static growth. Antibody structures have also been used in fibers or fabrics for such purposes. Although all of these have useful physical properties, there is a substantial need to obtain biocidal compositions that exhibit significantly improved microbial capture, microbial microbiocide or static microbial growth characteristics. There is a great need in the art to eliminate harmful microbial populations from textile surfaces, but there is little or no risk of re-contamination or redeposition of wipes. In this way, it is necessary to fix microorganisms on fibers.

[0004] European patent application EP3933102 relates to a flat textile structure with a woven and / or nonwoven fabric having fibers, which are optionally at least partially provided with a coating, the coating having a dye, which is diamagnetic when activated with electromagnetic radiation, bound to the fibers or in the coating. The invention also relates to clothing made of the textile, a method for producing or functionalizing the textile, and the use of a photosensitizer bound to the textile.

[0005] U.S. Patent No. 10058099 provides methods and materials for decontaminating surfaces and fabrics such as nonwoven fabrics contaminated by infection with microorganisms such as bacteria. Biocidal oligomers having a conjugated oligo-(aryl / heteroaryl ethynyl) structure and comprising at least one cationic group can be used to decontaminate infected surfaces in the presence of oxygen and optionally lighting. Fibers incorporating biocidal oligomers having a conjugated oligo-(aryl / heteroaryl ethynyl) structure and comprising at least one cationic group can be used to form nonwoven mats, wherein the oligomers are physically associated or covalently bonded or both to the fiber-forming polymer. Unfortunately, these materials do not allow the biocidal product to remain safely adhered to the textile surface for an unlimited period of time.

[0006] There are many biocidal products in the art that allow the protection of different surfaces, however, there is a need for a biocidal product that acts indefinitely, that the user finds safe and that provides the certainty that the surface is protected by the luminous identification tag.

[0007] It is known that certain triazine compounds are active when exposed to ultraviolet light. For example, U.S. Pat. No. 3,167,565 describes organic triazine compounds that can be used as optical brighteners, which are assumed to have an affinity for binding to fiber matrices (including cellulose, nylon, and wool). Other triazine compounds are also known to be active when exposed to UV light, but these compounds are notably characterized as UV absorbers, in other words, compounds that absorb light in the ultraviolet region of the electromagnetic spectrum but no longer emit energy absorbed as visible light. The general structure of the UV absorber molecule allows it to absorb a broad spectrum of high-energy ultraviolet rays and then release the absorbed energy as low-energy rays (usually, at non-specific wavelengths or wavelengths outside the visible band).

[0008] Finally, it is necessary to highlight the US patent application US20110268896, which describes a composition comprising an organic fluorophore or a derivative thereof; as well as an article marked with a fluorophore and a method for marking an article with a fluorophore and a method for producing fluorescent fibers. Summary of the invention

[0009] The invention discloses a transparent biocidal product which allows the protection of surfaces, in particular those which are porous, such as textiles, etc., and which, moreover, can be detected by infrared radiation. The product ensures a permanent and safe antimicrobial protection of the surfaces to which it is applied, confirming its antimicrobial protective effect. Its application therefore represents a safe alternative for the surface protection of all types of textile materials, eliminating the need for continuous disinfection, thereby achieving a very significant reduction in the consumption of chemicals, while saving the sustainability it requires.

[0010] The biocidal product of the present invention is intended to be particularly suitable for the healthcare field where textile materials are used continuously. Since medical spaces are exposed to pathogens, they are highly susceptible to becoming large reservoirs of said pathogens, which increases the possible infection between patients and medical staff in these areas. At present, due to the short-life effect of disinfectants, there is no way to know whether the treated surfaces are contaminated again, and it is impossible to guarantee when they are contaminated again until the next cleaning. The application of this product provides a guarantee of disinfection, because its presence and therefore its continuous disinfection action 24 hours a day, 7 days a week can be detected. The product is a combination of biocidal resins based on water-based vinyl esters, quaternary ammonium and ionic silver to give it antimicrobial ability. In addition, the luminescent properties of the material doped with luminescent "rare earth" ions present very significant advantages over the prior art, presenting invisibility to ambient light and activation by low-cost commercial infrared light by converting this invisible reading light into the visible emission of the product compared to standard fluorescent dyes. In addition, "rare earth" elements (lanthanides) exhibit sharp emission peaks, long fluorescence lifetimes, low long-term toxicity and high chemical photostability and easy handling, making them excellent choices for various optical safety applications. DETAILED DESCRIPTION

[0011] The present invention discloses a biocidal product for application to surfaces, particularly those hard porous surfaces such as fabrics or the like, incorporating an identifying mark which enables verification of the presence of the product and thus allows indication that it remains protective.

[0012] First, the biocidal product and the added marking additive must be stable in the mixture, keeping the additive dispersed in the biocidal composition when it is applied to the porous surface, allowing them to maintain their antimicrobial and luminescent properties and at the same time allowing them to work together.

[0013] The biocidal product is formed by mixing a biocidal composition and a luminescent additive dispersed therein, wherein the biocidal composition is formed by adding to deionized water between 0.01% and 0.05% of a vinyl ester resin relative to the total weight of the product and a mixture formed by a combination of 0.1-2.0% of dimethyldidecyl ammonium chloride and 2.0-10.0% of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, which act as biocides in a medium formed by a mixture of 0.2% to 1.0% of methanol and 0.02% to 1.50% of ethanol. In addition, urea is added in a ratio of between 0.2% and 1.0%, and acetic acid is added in a ratio of between 0.001 and 0.010 to adjust the pH of the resulting solution.

[0014] A silver ion solution, preferably formed from silver phosphate glass, is added to this resulting mixture in a proportion between 0.3% and 3.0%, thereby imparting additional antimicrobial action to the silver phosphate glass and allowing it to adhere to hard, non-porous surfaces due to its structural properties.

[0015] Vinyl ester resins are compatible with all fabrics, pigments and fillers, allowing the biocidal product to adhere to any porous surface to be treated, especially textile surfaces. These vinyl ester resins provide excellent chemical and physical resistance, which is even further increased if thermal post-curing is carried out at above 100°C. It is a resin that is highly resistant to weathering conditions (temperature and humidity), withstanding the most demanding and harsh conditions. The short gel curing interval reduces visible fiber markings on the surface and reduces shrinkage stresses. They allow thermal post-curing, exhibit greater elongation at break, do not shrink after hardening and do not absorb water. Therefore, it is particularly used for applications on textile surfaces, fabrics, etc.

[0016] Dimethyl didecyl ammonium chloride is an effective biocide against bacteria and is superior to benzalkonium chloride for killing already chemically resistant bacteria. In addition, it has an excellent emulsifying effect and good solubility, which allows the mixture to be stable over a wide temperature range and to be used in the medium in the product of the present invention, wherein the luminescent additive acting as a marker can be dispersed in the medium.

[0017] Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride is a disinfectant used as an antiseptic and fungicide, and can be used as a siloxane coupling agent. As a cationic quaternary ammonium salt, it will completely ionize in aqueous solution. The resulting product formed from dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride can be used as an antiseptic treatment for certain materials, such as those used in human clothing and bedding, carpets, and interior decoration.

[0018] Silver ion solutions, preferably formed from silver phosphate glasses, are soluble materials that can serve as a unique system for supplying silver ions in a controlled manner. The ions are incorporated into the glass structure and are not a separate phase; therefore, its release rate is limited by the overall degradation rate of the glass. Phosphate-based glasses have shown that the release of an optimal amount of silver ions from silver-doped phosphate-based glasses can result in a significant reduction in bacterial growth on the surface. While high concentrations of free silver ions are required for bactericidal action on surfaces, it is very important not to sacrifice any cellular / biocompatibility aspects of the material while maintaining an effective antimicrobial effect. The amount of silver released from the silver-doped glasses in the study was well below levels that were cytotoxic to human cells.

[0019] Urea is used as a cross-linking agent for washing textiles treated with the biocidal product of the invention, it also prevents the abrasion of fabrics, it is mainly applied to fibers and finishes, resistant to cotton, viscose and cloth or knitted fabric mixtures.

[0020] This biocidal composition allows continuous disinfection action 24 hours a day, 7 days a week. A coating formed from this biocidal composition (having a thickness between 10 and 30 microns) allows a reduction of viral, bacterial and fungal growth equal to or greater than 99.0% to be achieved on porous surfaces treated by a single application, with a minimum duration of 1 year.

[0021] The incorporation of metal oxides into the biocidal composition (aluminosilicate glass containing rare earth metal ions in the form of dopants) allows the coating of said composition to be detected and identified by infrared light inducing an easily detectable luminescence (green light). This luminescent additive exhibits a pattern of emitted light that allows the compounds to be unforgeably encoded, distinguishing them relative to other similar products on the market.

[0022] State-of-the-art anti-counterfeiting technologies are experiencing an increasing and continuous global demand in areas such as the fight against product counterfeiting. In this sense, high-security anti-counterfeiting labels with luminescent materials are at the forefront of the latest cryptographic technologies based on the recognition of coded luminescent patterns. Specifically, materials doped with luminescent "rare earth" ions present very significant advantages compared to standard fluorescent dyes: invisible to ambient light, activated by low-cost commercial infrared light by converting this invisible reading light into visible emission of the product. In addition, "rare earth" elements (lanthanides) exhibit sharp emission peaks, long fluorescence lifetimes, low long-term toxicity and high chemical photostability and easy handling, making them excellent choices for various optical security applications. Once the biocidal mixture is prepared, the luminescent additive is dispersed in the previously prepared biocidal composition, adding between 0.03% and 2.5% of the luminescent additive relative to the total weight of the product in deionized water, so that the proportion of deionized water in the final biocidal product is between 78.44% and 97.134%.

[0023] The luminescent additive acting as a marker allowing the identification of the biocidal composition is composed of 20 to 30% of silica gel combined with alumina gel in a proportion of 10 to 30% and 30 to 50% of calcium fluoride. In this mixture is added a material doped with luminescent "rare earth" ions, such as erbium (III) fluoride between 0.5% and 3%, ytterbium (III) fluoride between 5% and 15%, thulium (III) fluoride up to 5%, and europium (III) fluoride up to 1%. These percentages are relative to the total percentages of the luminescent additive.

[0024] The method for preparing the luminescent additive is carried out from the oxides and fluorides already described in detail by melting in a furnace between 1200° C. and 1500° C. for about 40 minutes. The melt is laminated by laminating rollers to facilitate cooling and subsequent grinding. The laminated melt is cut into pieces and allowed to cool to room temperature. It is then ground in a hammer mill until a particle size distribution approximately equal to D10 <1 micron; D50 <5 microns; D90 <15 microns is achieved.

[0025] Once all materials for producing the biocidal product have been added, stirring is maintained at room temperature at a speed not exceeding 2500 rpm for 30 minutes. Once stirring is complete, the mixing tank is emptied and the material ready for application is packaged.

[0026] Silica gel is used as a luminescent coating, i.e. it does not involve heat generation and is particularly useful in the main physical phenomena that allow the generation of light with characteristics such as phosphorescence and fluorescence. In addition, it is used as an insulating coating, forming a thin layer similar to a laminate on the coated surface, protecting and preserving the surface from the action of water, from scratches or other wear damage. Alumina is used as a selective adsorbent, allowing the level of fluoride in the mixture to be adjusted downward.

[0027] Calcium fluoride doped with luminescent "rare earth" ions significantly increases its fluorescence, with a broad emission that appears within the acceptable target range. Erbium fluoride increases the transmittance of infrared light and the remaining luminescent material in the marking composition. Erbium-doped silica glass fibers are active elements that amplify the luminescence effect, and in addition, their homogenization is increased due to the presence of aluminum oxide. Ytterbium fluoride also increases the amplification of the material as a luminescent marker, and thulium (III) fluoride is used to improve infrared emission and improve the upconversion of fluorescence to ultraviolet and visible light in fluoride glasses. The fluorescence of europium is used to increase the effect of marker additives.

[0028] Different tests have established that the luminescent additive of the product presents emission only under invisible infrared light (frequency of about 980 nm) with high intensity brightness, due to the absence of background noise due to zero autofluorescence of the fabric matrix or the surface to which it has been applied. Moreover, the luminescence intensity ratios between the different visible emission bands (blue, green and red) observed after the conversion of the invisible infrared reading light can be adjusted as desired (by varying the concentration level and type of doping "rare earth" ions). In other words, by designing and synthesizing on demand at the source, encoding the emitted light with an unforgeable code, a novel and disruptive proof of concept for a security mode with optical encryption is provided.

[0029] The resulting biocidal product is colorless and will be applied in the form of a spray and spread on the surface to be protected with the help of a microfiber cloth. To determine the thickness to be applied on the wet surface, a precision wet film comb is used which, thanks to its "teeth", allows to determine the extent of the applied wet film. The dry thickness will be verified using an electronic device - a coating thickness gauge Positector 6000, which returns its thickness digitally adjusted by its galvanic cell positioned on a ferrous surface.

[0030] To determine the effectiveness of this biocidal coating on different microorganisms, the following tests were performed:

[0031] - UNE-EN ISO 14476 Chemical disinfectants and antiseptics – Quantitative suspension test for the evaluation of virucidal activity in the medical field.

[0032] - UNE-EN ISO 20743 Textiles - Determination of the antimicrobial activity of textile products.

[0033] - UNE-EN ISO 18184 - Test methods for determining the antiviral activity of products against specific viruses.

[0034] Biocidal surface protection of between 12 and 18 months has been determined, allowing hard non-porous surfaces to remain protected for a long time with a single application. The product is effective for biocidal protection of different porous surfaces (especially textiles) against different microorganisms, such as Escherichia coli, Staphylococcus aureus, Enterococcus hilarii, Pseudomonas aeruginosa, Candida albicans, and certain types of viruses with and without an outer envelope.

[0035] As an added value, the luminescent feature of the invention clearly distinguishes the invention with respect to the prior art, as it allows the user to visualize where the product has been applied, as well as to identify the coded light pattern to indicate that the product is authentic. Using a simple and compact portable handheld device (pocket spectrometer), it will allow the end user to illuminate with a low-cost commercial infrared laser pointer to detect the custom-coded, unforgeable luminescent pattern, thus verifying that the applied product is protected by the biocidal composition. This luminescent technology using infrared light and color coding using "rare earth" ions are at the forefront of anti-counterfeiting light technology in terms of the technological line used for document authentication (passports, security inks) and for secure encryption of legal tender banknotes. Therefore, its application in the original identification of biocidal products undoubtedly constitutes an absolute novelty, which defines a clear and significant difference from other products with similar characteristics on the market. The biocidal product is formulated in an aqueous base, thus obtaining a good drying time ranging from 2 to 3 minutes. The product is easy to apply. Using an atomizer, it allows effective application on the surface with the help of a cloth.

Claims

1. A biocidal product with a luminescent marking additive for use on textile surfaces, etc., characterized in that: The biocidal product is formed by mixing a biocidal composition and a luminescent additive dispersed therein, wherein the biocidal composition is formed by adding to deionized water: between 0.01% and 0.05% of a vinyl ester resin, relative to the total weight of the product, as a carrier for the biocide; a mixture formed by a combination of 0.1% to 2.0% of dimethyldidecyl ammonium chloride and 2.0% to 10.0% of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, which acts as a biocide in a medium formed by 0.2% to 1.0% of methanol and 0.02% and 1.50% of ethanol; urea in a proportion of between 0.2% and 1.0% and between 0.001% and 0.010% of acetic acid, and the luminescent additive in deionized water is in a proportion of between 0.03% and 2.5% relative to the total weight of the biocidal product, the luminescent additive includes between 20% and 30% silica gel combined with 10% and 30% alumina gel; between 30% and 50% calcium fluoride by weight; and a mixture of materials doped with luminescent "rare earth" ions, wherein the mixture of materials doped with luminescent "rare earth" ions includes between 0.5% and 3% erbium (III) fluoride, between 5% and 15% ytterbium (III) fluoride, a maximum of 5% thulium (III) fluoride and a maximum of 1% europium (III) fluoride, wherein the proportion of deionized water in the final biocidal product is between 78.44% and 97.134%.

2. The biocidal product with luminescent marking additive for textile surfaces etc. according to claim 1, characterized in that: The method of preparing the luminescent additive is performed from oxides and fluorides by melting in a furnace between 1200° C. and 1500° C. for about 40 minutes.

3. Biocidal product with luminescent marking additive for textile surfaces etc. according to claims 1 and 2, characterized in that The molten luminescent additive is laminated, cut into sheets and cooled to room temperature.

4. Biocidal product with luminescent marking additive for textile surfaces etc. according to the preceding claims, characterized in that The luminescent additive is ground until a particle size distribution approximately equal to D10 < 1 micron is achieved.

5. The biocidal product with luminescent marking additive for textile surfaces etc. according to claims 1-3, characterized in that: The luminescent additive is ground until a particle size distribution approximately equal to D50 < 5 microns is achieved.

6. The biocidal product with luminescent marking additive for textile surfaces etc. according to claims 1-3, characterized in that: The luminescent additive is ground until a particle size distribution approximately equal to D90 < 15 microns is achieved.