Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
  • A01N59/16—Heavy metals; Compounds thereof
  • A01N59/20—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
  • B22F3/10—Sintering only
  • B22F3/11—Making porous workpieces or articles
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/66—Salts, e.g. alums
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents

Definitions

• the present invention falls within the technical area of production of cellulose-based materials, such as paper, cardboard, or cellulose fibers, to which a biocidal agent based on copper is incorporated, particularly my mixed particles or nanoparticles mixed or laminar. coppermade.
• cellulose-based materials such as paper, cardboard, or cellulose fibers
• a biocidal agent based on copper is incorporated, particularly my mixed particles or nanoparticles mixed or laminar. coppermade.
• the products obtained according to the present invention can be used in a wide variety of applications, such as papers resistant to degradation by microorganisms, air filters, bandages or dressings, etc.
• Paper, cardboard, or other materials made from cellulose-based materials are widely used in a wide variety of products with many different applications, such as printing or writing paper, paper or cardboard used to cover drywall, paper used in different types of filters, cellulose fibers treated and used as bandages or dressings, treated paper strips used as sensors coupled to detection devices, etc.
• Each of the wide variety of applications of cellulose and more particularly of paper and cardboard, would be greatly benefited if cellulose, paper or cardboard incorporated biocidal components.
• the presence of biocidal agents in the paper would increase the shelf life of the paper, preventing its decomposition by the action of fungi or other microorganisms in humid environments.
• said agent could have catalytic properties or functions, which makes it possible to improve the use of paper air filters, and even more so, if the biocidal agent is also a conductor of electricity, it is possible to achieve a material in base to cellulose (paper) that is also conductive, and where the applications in different products is also quite wide, such as in the manufacture of special sensors, such as a material for use in touch-sensitive screens (“touchscreen”), between Many other potential applications.
• paper cellulose
• touch-sensitive screens touch-sensitive screens
• the present invention is particularly focused on the incorporation of a biocidal agent, based on copper, into a cellulose based material, preferably paper or cardboard.
• the prior art shows us some alternatives related to the manufacture of cellulosic materials to which different types of biocidal agents are added.
• US2005257908 (A1) describes cellulose treated with biocidal compounds, such as didecyldimethylammonium chloride or didecyldimethylammonium bromide, in a particular exemplified case, describe the combination of the above components with copper sulfate salts. Nowhere in the document are metallic copper microparticles mentioned, and even less dendritic or laminar microparticles, as is the case of the present invention.
• US3998944 (A) describes a paper that is treated with a composition that includes a copper compound (copper-8-quinolinolate), in addition to other components that act as binders, such as waxes, xanthan gum, among others.
• a copper compound copper-8-quinolinolate
• binders such as waxes, xanthan gum, among others.
• metallic copper microparticles let alone dendritic or laminar microparticles, as is the case of the present invention.
• GB1236855 (A) describes a paper to which compounds are added, among which copper salts stand out, where like US3998944 (A) it is mentioned as an active biocide compound to copper-8-quinolinolate.
• WO2013167098A2 describes a method for producing functionalized fibers, where the method comprises immersing the fibers in a spinning solution and then in a coagulation bath. Fibers can be used to cover wounds. In claim 10 it is indicated that the functionalization can be with copper.
• WO2008153239A1 describes a method for manufacturing materials based on cellulose (tissue paper) or cotton (cotton fabrics) which, when wetted, acquire antimicrobial and antifungal properties.
• the method consists of submerging the cellulose-based materials in a solution containing metal particles (among others) with biocidal properties.
• WO0181666A2 describes the manufacture of biodegradation resistant cellulose fibers, where the fibers can be used to be included in building materials (such products as cement or plaster boards). It is mentioned that the resistance to biodegradation is given by the incorporation of biocidal agents. Within said biocidal agents, water soluble copper salts are mentioned.
• Figure 2 SEM image x600 particles.
• Figures 1 and 2 show SEM images at magnifications x200 and x600 (Secondary electrons), respectively. In them you can see that there are mixtures of morphologies between quasi-spherical, and cubic dendritic.
• Figure 4 and 5 shows SEM images at magnifications x200 and x500 (Secondary electrons). In them you can see that there are mixtures of morphologies between quasi-spherical, nodular and laminar.
• Figure 7 and 8 show SEM images at magnifications x200 and x500 (Secondary electrons). In them you can see that there is a predominance of laminar particles.
• Figure 10 and 11 show SEM images at magnifications x200 and x500 (Secondary electrons). In them you can see that there is a predominance of laminar particles.
• Figure 12 Fluorescence images obtained with a combination of DAPI filters with a magnification of a 4x (A), 10x (B) and 20x (C) objective. Each image shows a rectangle of 200 micro meters (200 ⁇ ) of edge.
• Figure 13 Image of the particles observed corresponds to sample 7 with a 4x magnification objective.
• Panels (B) and (C) show the identification of the particles using a series of morphological operations.
• the present invention falls within the technical area of production of cellulose-based materials, such as paper, cardboard, or cellulose fibers, to which a biocidal agent based on copper is incorporated, particularly my mixed particles or nanoparticles mixed or laminar. coppermade.
• cellulose-based materials such as paper, cardboard, or cellulose fibers
• a biocidal agent based on copper is incorporated, particularly my mixed particles or nanoparticles mixed or laminar. coppermade.
• the products obtained according to the present invention can be used in a wide variety of applications, such as papers resistant to degradation by microorganisms, air filters, bandages or dressings, fabrics, fibers used in the manufacture of fabrics, etc.
• the present invention relates to a cellulose-based product or material that incorporates a biocidal agent.
• the biocidal agent corresponds to a copper-based compound, more particularly copper microparticles or nanoparticles.
• the copper microparticles or nanoparticles are specifically mixed or laminar.
• mixed microparticles or nanoparticles refer to microparticles or nanoparticles with quasi-spherical morphologies, cubic dendritic.
• laminar microparticles or nanoparticles refer to microparticles or nanoparticles with laminar morphologies.
• the copper microparticles or nanoparticles incorporated into the cellulose-based material are copper laminar microparticles or nanoparticles, where the microparticles or nanoparticles are incorporated at a rate of between 0.5 to 5 grams per 15 grams of cellulose, obtaining between 0.01 to 0.15 grams of copper per gram of cellulose in the final product, after performing the method of the present invention.
• the cellulose-based product or material corresponds to paper, cardboard, corrugated cardboard, air filters, bandages, dressings, fabrics, fibers used in the manufacture of fabrics, based on cellulose.
• the cellulose-based product or material has gaps or spaces formed between different cellulose fibers. Said spaces, in the context of the present invention, are called vessels. In the present invention, said vessels allow to receive, receive, or house the copper microparticles or nanoparticles.
• the present invention considers a method for manufacturing a cellulose based product or material incorporating a biocidal agent.
• the method allows the manufacture of paper incorporating a biocidal agent.
• the papermaking method consists of a conventional papermaking method, such as according to ISO 5269-1: 2005, which has been modified in one or more stages, so as to incorporate the copper microparticles or nanoparticles.
• the steps described below correspond to the process for preparing paper formed from a pulp suspension on a mesh under suction.
• step viii) the sheet is subjected to pressure and dried in a dryer, preventing its contraction, under the application of specific conditions of pressure, suction and temperature.
• step i) dry pulp disintegration (*), consider the disintegration of a dry pulp mass at 30,000 revs, in demineralized water, at a rate of 30 grams of dry pulp in 2 liters of demineralized water.
• stage iii) disintegration carried out after refining the sample is disintegrated at 10,000 revs in demineralized water, maintaining the proportion used in stage i, that is, 2 liters of water per 30 grams of initial dry pulp.
• stage iv) dilution and homogenization the product obtained in the previous step is diluted with demineralized water reaching a concentration of 0.3% w / v, where homogenization is performed for a period of between 1 to 20 minutes
• a conventional forming machine is used in step viii) of sheet forming, such as "Rapid Kóthen", allowing to dry for a period of between 2 to 20 minutes, at a temperature of between 60 ° C to 100 ° C.
• stage ix the prepared leaves are set in a heated room, considering a relative humidity of between 40% and 60%, a temperature between 15 and 30 ° C, for a period of between 1 to 5 hours . Once the setting is done, it is possible to perform tests to evaluate the characteristics of the paper formed.
• the copper microparticles or nanoparticles are added in step i) of dry pulp disintegration, and / or during step viii) of sheet formation.
• step i) of dry pulp disintegration and / or during step viii) of sheet formation.
• between 0.5 and 5 grams of copper is added for every 15 grams of cellulose.
• 0.625, 1, 25, or 3.75 grams of copper is added per 15 grams of cellulose.
• EXAMPLE 1 Structural paper analysis. By analyzing an already formed paper, it is possible to identify, at the microscopic level, holes or spaces formed between the different cellulose fibers. These spaces are called vessels. It is precisely in these vessels that there is the ability to accommodate copper microparticles of the present invention, so that their analysis allows to determine the best sizes and geometries to incorporate into the cellulose-based product. In fact, the vessels allow the incorporation of impurities (coal or others) that can be visible to the naked eye. The macroscopic representation of the existence of these vessels can be determined according to the ISO 5350 standard: "Estimation of dirt and shives", where the presence of coal or backlit pints is evaluated using a comparison template.
• the average vessel sizes were estimated, in order to determine with certainty the best sizes and geometries of the copper microparticles to be used.
• the weight is 65 gr / cm 2 ⁇ 2 and the thickness is between 80 to 100 ⁇ , it is possible to make some estimates.
• EXAMPLE 2 Selection of size and geometry of copper particles.
• Table 1 Characteristics of copper particles.
• the size distribution of each of the samples was determined through granulometry analysis by laser diffraction, whose methods and results are shown below. Morphology analyzes were also performed using scanning electron microscopy (Scanning Electron Microscope, SEM).
• Figure 1 and 2 show SEM images at magnifications x200 and x600 (Secondary electrons), respectively. In them you can see that there are mixtures of morphologies between quasi-spherical, cubic dendritic.
• Granulometry The results obtained from the laser granulometry, for the selected sample, are presented in Table 2. The distribution of particle sizes is presented in Figure 3.
• Figures 4 and 5 show SEM images at magnifications x200 and x500 (Electrons secondary). In them you can see that there are mixtures of morphologies between quasi-spherical, nodular and laminar.
• Figures 7 and 8 show SEM images at magnifications x200 and x500 (Secondary electrons). In them you can see that there is a predominance of laminar particles.
• Figures 10 and 11 show SEM images at magnifications x200 and x500 (Secondary electrons). In them you can see that there is a predominance of laminar particles.
• EXAMPLE 3 Paper manufacturing method according to ISO 5269-1: 2005.
• the steps described below correspond to the process for preparing circular sheets formed from a pulp suspension on a mesh under suction.
• the sheet is subjected to pressure and dried in a dryer, preventing its contraction, under the application of specific conditions of pressure, suction and temperature.
• Drainage measurement within 1 hour of the homogenization process of the previous step, drainage is measured.
• Pulp suspension consistency measurement The consistency of the pulp suspension in the sheet former is measured.
• Leaf formation Leaves are formed in a "Rapid Kóthen” shaper and allowed to dry for approximately 8 minutes at a drying temperature of 94 ⁇ 3 ° C.
• test sheets prepared according to this method were set in a heated room at 50 ⁇ 2% relative humidity and 23 ⁇ 1 ° C, for a period of at least 3 hours, before performing physical measurements.
• EXAMPLE 4 Method 1: Preparation of paper with copper particles, incorporated in the sheet formation stage.
• the cellulose mixture was deposited with water and copper, thus achieving high homogenization that is evident in the paper samples that finally formed.
• the paper formation process continues once the sheet is formed by placing it between Ederoles that fulfill the function of extracting the excess water from the sheet and then placing them in a press for a period of 5 minutes at 410kPa +/- 10, The sheet is then inverted, and placed in a second press for a period of 2 minutes at 410 kPa +/- 10, to finally take to the pre-drying and drying chamber for 3 hours of setting in a room heated to 50 % relative humidity + 1-2 and 23 ° C +/- 1.
• EXAMPLE 5 Method 2: Preparation of paper with copper particles, incorporated in the disintegration stage.
• the sample was homogenized in 5 liters of demineralized water at 0.3% for 5 minutes, and then the process was continued as indicated in the previous example, until the sheets of paper were obtained .
• EXAMPLE 6 Obtaining and evaluating sheets of paper obtained according to Examples 4 and 5.
• Example 4 By process described in Example 4: In this process, as mentioned above, the copper particles were added directly into the sheet former. Because the mixing process at this stage was only 5 seconds to then decant the water, the copper particles cannot mix homogeneously with the cellulose, preferably staying on the surface of the water, probably because the particles are not capable of break the surface tension of the water, and in many cases agglomerating for electrostatic reasons or by vortex accumulation. This produced that when draining the water in the former, papers with distributions of non-homogeneous copper particles were obtained. The type of copper deposition by means of this methodology resulted in the majority of the particles being on the sheet.
• EXAMPLE 7 Evaluation of sheets of paper with copper particles.
• the samples to be analyzed correspond to sheets of paper which contain, to a lesser or greater degree, particles in their volume and visible on their surface.
• the images of the samples were obtained in an Olympus microscope (1X81) under the technique of wide field fluorescence. This technique was chosen because it has taken advantage of the auto fluorescence that the sample possesses, composed of vegetable fibers with high cellulose content, as shown in gray tones of high luminosity in Figure 12, obtained from the sample labeled as White.
• the particles are listed and discriminated by size. At this point any particle with an area less than 10 ⁇ 2 (which is equivalent to an average radius of 1, 94 ⁇ ) is discarded, since the morphological filtrate generates non-existent particles due to variations in image intensity.
• Table 4 Characteristics of the particles for each sample.
• the mode of particle size is between 4 and 6 microns in radius, in addition to the size distribution and the total area they occupy in a defined area.
• Figures 14, 15, 16 correspond to photographs obtained for sample 4 at different magnifications. From the images we can see that this type of particles is a mixture of spherical particles, agglomerations and dendritic particles (laminar). It is interesting to note that the copper particles are at the surface level and inside the matrix, as was determined in analysis by optical microscopy and fluorescence.
• Figures 17 and 18 correspond to photographs obtained for sample 7 at different magnifications. In this case the particles are at higher levels and trapped by the matrix but the copper is nodular type.
• Figures 19 and 20 correspond to photographs obtained for sample 10 at different magnifications. In these figures a high density of particles is observed in addition to being predominantly laminar.
• Figures 21, 22, and 23 correspond to photographs obtained for sample 13 at different magnifications. These figures show the existence of high particle agglomeration of copper in the cellulose matrix and mostly of the laminar type as shown in detail in the x3000 image of Figure 23.
• EXAMPLE 8 Evaluation of bactericidal or biocidal activity of copper paper.
• the test method is based on the test according to ISO 20645: 2004. This method is applicable to the determination of the antibacterial effect of treatments applied to flat woven textiles. The method states that other materials can be tested using this method, provided it is properly adapted.
• the method is applicable to antimicrobial terminations of hydrophilic and air permeable materials, or to products incorporated in the fiber. Qualitatively determines the activity of antimicrobial treatment when different products are compared. Semi-quantitative information can be obtained when different concentrations are compared in the same product.
• Samples of the material to be tested were placed on two-layer agar plates.
• the lower layer consists of culture medium with agar without bacteria and the upper one is a layer of culture medium with agar that is inoculated, before gelling, with a strain of bacteria selected.
• the level of antibacterial activity is evaluated according to the extent of bacterial growth in the area of contact between the agar and the specimen specimen. The zone of bacterial growth inhibition around the sample is also measured, if present.
• Sample pretreatment The samples were not sterilized by any method.
• Sample size, number and preparation 12 paper samples of 16 cm diameter and 1.2 g weight were used, corresponding to four types of paper with three quantities of copper (4 x 3), in addition to a sample control.
• Sample storage prior to the test The samples were delivered in a folder containing individual bags where the paper samples were contained. The samples were manipulated since their manufacture with gloves and the pairs of specimens cut for this test were handled as little as possible with nitrile gloves and tweezers, and stored individually in transparent polyethylene bags. Both the original samples and the cut specimens were kept at room temperature and without extensive exposure to light. The specimens were not sterilized by any method.
• Staphylococcus aureus subsp. aureus ATCC 29213 Gram positive bacteria. Standard strain of CLSI2 for antibiotic sensitivity tests.
• Klebsiella pneumoniae subsp. Pneumoniae ATCC 700603 Gram negative bacteria.
• Samples should be tested on both sides, but it was assumed that the front and back of the sheets of paper were the same. When positioning the specimens of the samples, it was noted that there is one face that appears to be brighter and smoother than the other. The face of the specimens that were positioned on the agar was random.
• Table 6 shows the results of bacterial growth inhibition achieved by each of the analyzed samples.
• the papers derived from the samples with copper content of 0.05 g did not show an effect on bacterial growth in the area of contact with the paper.
• the papers derived from the samples with a copper content of 0.05 and 0.1 g were not shown to generate an inhibition halo in either of the two bacterial strains. It should be noted that although the halo of bacterial growth inhibition is visually more striking at the macroscopic level, this standard considers it only secondarily. This is because to generate a halo of inhibition the substance that has the antibacterial effect must diffuse in the agar, which could imply a lower fixation of this active principle to the substrate, in this case the paper.
• Table 7 shows some halo inhibition values in mm with copper present in sheets analyzed by atomic absorption spectroscopy and contact area defined by optical Fluorescence microscopy analysis.
• the deposition of the copper particles preferably on the surface may present better properties of antibacterial action by diffusion to those achieved in the process where copper is added in stage i) of dry pulp disintegration in the manufacture of paper in the cellulose matrix.
• the analyzes showed that the mixtures with the highest amount of retained copper, as well as those with the greatest area of contact exposure have notable effects on the halo of bacterial inhibition for all types of particles, always being the least effective that of characteristics with multiple morphologies or so-called mixed particles in the context of the present invention (samples 2 to 4).
• the particles that demonstrated the best effect were samples 8 to 13 corresponding to laminar particles. This effect is undoubtedly due to the shape of these particles since for the same mass of copper there is a greater contact surface.
• the present invention has a wide industrial application, as for example in the generation of papers resistant to degradation by microorganisms, air filters, bandages or dressings, fabrics, fibers used in the manufacture of fabrics, etc. wherever a cellulose-based material or product with biocidal properties is required.

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• Life Sciences & Earth Sciences (AREA)
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• 2015
  • 2015-04-10 CL CL2015000921A patent/CL2015000921A1/es unknown
• 2016
  • 2016-04-05 BR BR112017021449-0A patent/BR112017021449B1/pt active IP Right Grant
  • 2016-04-05 WO PCT/CL2016/050014 patent/WO2016161533A1/es active Application Filing

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