WO2018205003A1 - Hypoallergenic natural rubber latex, protected with polyphenols and free of ammonia, method for producing same and use thereof - Google Patents

Hypoallergenic natural rubber latex, protected with polyphenols and free of ammonia, method for producing same and use thereof Download PDF

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WO2018205003A1
WO2018205003A1 PCT/BR2018/050153 BR2018050153W WO2018205003A1 WO 2018205003 A1 WO2018205003 A1 WO 2018205003A1 BR 2018050153 W BR2018050153 W BR 2018050153W WO 2018205003 A1 WO2018205003 A1 WO 2018205003A1
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latex
natural rubber
tannin
rubber latex
ammonia
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PCT/BR2018/050153
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French (fr)
Portuguese (pt)
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Floriano PASTORE JUNIOR
Leonardo GIORDANO PATERNO
João Bosco RODRIGUES PERES JÚNIOR
Júlia ORNELAS KRAMER
Luiz Carlos PIMENTEL
Natalia Stefânia GOMES
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Fundação Universidade De Brasília
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Priority claimed from BR102017010076-6A external-priority patent/BR102017010076B1/en
Application filed by Fundação Universidade De Brasília filed Critical Fundação Universidade De Brasília
Priority to CN201880045911.2A priority Critical patent/CN110892015A/en
Publication of WO2018205003A1 publication Critical patent/WO2018205003A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00Treatment of rubber latex
    • C08C1/02Chemical or physical treatment of rubber latex before or during concentration
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00Gloves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00Recovery or working-up of waste materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/22Compounds containing nitrogen bound to another nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • C08L7/02Latex
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00Compositions of proteins; Compositions of derivatives thereof
    • C08L89/04Products derived from waste materials, e.g. horn, hoof or hair
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00Compositions of natural resins; Compositions of derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09FNATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00Treatment of rubber latex
    • C08C1/02Chemical or physical treatment of rubber latex before or during concentration
    • C08C1/04Purifying; Deproteinising
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00Chemical modification of rubber
    • C08C19/30Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00Chemical modification of rubber
    • C08C19/30Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/34Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups

Definitions

  • the present invention is in the fields of human health and the technological chain of natural rubber latex (LBN) of rubber tree Hevea brasiliensis L. and relates to the use of polyphenols to preserve LBN against biological degradation and coagulation, providing stability to stock and handling, without the need for the use of ammonia, as well as to reduce or eliminate the action of the allergenic proteins present in the LBN, allowing its industrial use in the production of many hypoallergenic or non-allergenic articles for use in general, and especially in the area of health.
  • LBN natural rubber latex
  • LBN contains several organic components such as proteins, lipids, phospholipids, carbohydrates and carotenoids, normally susceptible to microbial degradation (JACOB, JL et al., CLIN REV ALLERG IMMU, 11: 325, 1993). This makes the latex very vulnerable to deterioration, which creates even more instability in the colloidal system that constitutes the natural material, which spontaneously collapses.
  • a solid clot is not used in the industrial production of items made from latex, whose production technology requires the material to be in its liquid form, as in the case of the production of thousands of artifacts, such as contraceptive preservatives rubber (condoms), surgical and procedural gloves, probes, latex tubes, party balloons, etc.
  • artifacts such as contraceptive preservatives rubber (condoms), surgical and procedural gloves, probes, latex tubes, party balloons, etc.
  • ammonia ammonium hydroxide
  • ammonia performs two recognized functions in latex: the first, by adding negative electronic charges to proteins adjacent to the rubber particles, which, by virtue of the negative charges, repel each other, making the colloid more stable and free from clotting.
  • ammonia at concentrations in which it is added to the latex (0.5 to 0.8% w / w) acts as a very effective bactericide, especially at the higher concentrations (Blackley, D. C, Polymer Latices - Science and technology Volume 1: Fundamental principles. Netherlands: Springer, 1997).
  • ammonia is the product par excellence used for more than eighty years in the maintenance of stable liquid to be transported, concentrated by centrifugation and stabilized for use in industries.
  • Rubber in this liquid form such as 60% concentrated industrial rubber latex
  • ammonia Another disadvantage of the use of ammonia is its high volatility, which causes that the latex, in the normal handling of work, loses its protection, forcing a permanent vigilance of the latex and the replacement of the preservative as necessary, under subjective conditions, which can lead to loss of production.
  • borax also known as sodium tetraborate or sodium borate, (Na 2 B 4 07 -10H 2 O) (COOK, AS, J RUBBER RES, 16 (2) : 65-86, 1960).
  • the proteins play a key role in elastomer biosynthesis and tree protection, among others. After harvesting the LBN, these proteins cease their original biological function, but remain active and continue to react as proteins, including the reactions that trigger allergic processes.
  • the various methods of treatment may present one or more of the following disadvantages: higher cost; greater processing work; non-integral removal of proteins; lowering the quality of final rubber properties caused by the removal of proteins adjacent to the rubber particles; introduction of new proteins, in the form of enzymes, or of peptides generated in the enzymatic process, which can trigger new allergic processes.
  • the second possibility of interference of the gels in the production process stems from the formation of the gel itself as the junction of two or more particles, without the fusion of the elastomer molecules, which implies the formation of aqueous microfilms in the interior of the gel.
  • These microregions of water in the middle of the elastomer may hinder the formation of coherent films in the critical immersion production process, where the rubber deposit should have the most uniform thickness possible to avoid possible weak spots in the film, which could lead to rupture of the artifact .
  • polyphenols such as tannin, complex with collagen proteins of the animal skin nullifying their reactions, as occurs in the manufacture of leather
  • polyphenols can also be used to fulfill the same role in latex, complexing their proteins, consequently avoiding their biological degradation and reducing or canceling their allergenic action.
  • it allows to work with lower pHs, which results in less formation of gels.
  • a large amount of natural polyphenols found in plants and products extracted or derived from them are included in the category of vegetable tannins, which are of two types: hydrolyzable and condensed.
  • the tannins of the second type consisting of molecules represented in Formula i.
  • Tannin molecules contain a large number of phenolic hydroxyls, which gives them high ease of molecular interaction with other molecules through hydrogen bonds (SIEBERT, KJ, et al., J. Ag. Chem., 44 (1): 80-85, 1996). ). Economically, the most important of these reactions forms the basis of the treatment of animal skins in the production of leather in vegetable tanning (Compounding of air pollutant emission factors Volume I: Stationary point and area sources, EPA, 2016).
  • the tannin has to reach the collagen fibrils of the skin and block them so that they are no longer available for bacterial attacks, according to the model proposed by COVINGTON (COVINGTON, AD, CHEM SOC REV, 26: 111-126, 1997) presented in Formula II.
  • COVINGTON COVINGTON, AD, CHEM SOC REV, 26: 111-126, 1997) presented in Formula II.
  • COVINGTON COVINGTON, AD, CHEM SOC REV, 26: 111-126, 1997) presented in Formula II.
  • tannin reacts with all latex proteins, without distinction, generating stable and inactive products, both for bacterial attack and for acting as antigens and in this condition remain, even if they are still present in the latex, after centrifugation or even remaining after manufacture in a product made of latex, such as gloves, for example.
  • proteins complexed by the tannin molecules are also, at the similarity of the leather, not available for the bacterial degradation itself. Because proteins make up much of the digestible material by bacteria, at a higher concentration than the other non-rubber organic components (JACOB, JL et al., CLIN REV ALLERG IMMU, 11: 325, 1993), the preservation of latex will be large which is ensured by the treatment with tannin itself, thus dispensing with the addition of ammonium hydroxide.
  • the latex in natura when extracted from the tree of rubber tree, normally remains a few hours in a liquid state and it is in this condition that preservatives must be added for their conservation, in the harvest containers in the field, soon to be collected from the bowls.
  • the natural rubber latex produced today has as universal protection agent ammonia in the form of ammonium hydroxide in concentrations ranging from 0.5 to 0.8% (m / m) (BLACKLEY, D.C., Polymer Springer, 1997), which has the disadvantage of the strong smell of this substance, at any stage in which it is added to the latex, whether in the field latex harvest or in the plant centrifugation, or in the processing industry.
  • ammonia vapor released in its handling causes labor discomfort and presents a potential risk, since its sudden intense inhalation can lead to fainting, and the prolonged exposure to its vapor can cause health problems of the airways.
  • ammonium hydroxide has a dual function: alkalinize the medium to protect the colloid and serve as a bactericide, avoiding the biological degradation of the latex.
  • Alternative proposals for this treatment include the use of low or medium concentration ammonia associated with a borax or totally ammonia-free bactericide with the use of high toxicity biocides such as sodium pentachloro-phenate, known as "china powder", forbidden in Brazil and in many countries.
  • the use of tannins and coadjuvants for the treatment of latex does not present any disadvantage of this nature.
  • the results are satisfactory with regard to the reduction of free proteins determined in gloves produced with the tannin-treated latex, which would indirectly lead to the reduction of allergens of the rubber artifacts, although no specific allergenicity tests have been performed or quantification of allergenic proteins.
  • Said technology is based on the same chemical reaction of complexation between tannin and latex protein which is also the scientific basis of the present invention. However, this is the only closeness between the two.
  • the tannin in the Chinese patent application is applied to the centrifuged latex, while in the present case the tannin is added to the latex in natura, shortly after being harvested from the rubber tree.
  • tannin reacts with proteins and inactivates them, either to be the substratum of bacterial attacks or to act as allergens.
  • efficacy in lowering free proteins can not be attributed solely to tannin.
  • tannin demonstrates a lower efficacy of approach to proteins when the medium is highly alkaline (MARTIN, MM, et al., J CHEM ECOL, 11 (4): 485-494, 1985) , as is the case of the high ammonia latex used in the Chinese patent application. Therefore, the effect of these two factors, the less approximation of the tannin of the proteins with ammonia and the breakdown of the proteins by the ammonia, make believe that part of the effect achieved in the technology is not due to the reaction with tannin.
  • the tannin treatment of the present invention does not provide for the occurrence of gels in the latex normally associated with the presence of ammonia in high concentration which adversely affect the properties of the latex during storage such as viscosity increase (TARACHIWIN, L., et al., Rubber Chem Technol, 76 (5): 1177-1184, 2003), among others.
  • Japanese Patent Application JP2012207088 relates to the preparation of master batch blend, used in the manufacture of tires, which is a carbon black incorporation, vulcanization compounds and other components to the LBN, still liquid, to provide a close mixture of such ingredients with the rubber.
  • the introduction of tannin would facilitate the mixing of the charge (carbon black) in the preparation of the master batch by the dispersing characteristics of the tannin, allowing also a lower consumption of sulfuric acid in the coagulation of the master batch. Therefore, while referring to the use of tannin in LBN, this patent is in no way similar to the invention disclosed herein.
  • patent application US5741885 claims the reduction of allergenicity of LBN gloves by treating a glove face with allergy screening compounds which would result in at least reducing the allergenicity of the gloves on one side, or even part of one face of the glove, in accordance with treatment.
  • This invention may result in a costly process by the screening reagents it uses and not so safe to partially solve the problem because the untreated glove may contain allergens and end up coming in contact with mucous membranes of patients.
  • the present invention contributes decisively to the advancement of the productive techniques in the natural rubber latex production chain by enabling the production of protected latex without the use of ammonia, and therefore, free of gels, for the manufacture of hypoallergenic or non-allergenic artifacts.
  • Figure 1 shows the results of the pH measurement of: LA (low ammonia), LAB (low ammonia and borax), HA (high ammonia), TBL (tannin, borax and LESS) and TBR (tannin, borax and renex).
  • Figure 2 shows the zeta potential (mV) of the samples as a function of time.
  • the present invention has technological application in the production chain of the natural rubber latex (LBN), obtained from the rubber tree, Hevea brasiliensis, or any other source.
  • LBN natural rubber latex
  • An LBN is produced as a stable and protected material against biological degradation, free of ammonia, for use in the processing industries for the production of numerous general purpose products, including surgical and procedural gloves, condoms, catheters , surgical fields among others; in another consequence, this LBN and the products derived therefrom are of low or no allergenicity.
  • the technological solution of this patent application is the application of vegetable tannin in natural rubber latex in place of ammonia. Without the use of ammonia, today the universally used preservative, is obtained a LBN protected against biological degradation and against spontaneous coagulation, of low or null allergenicity. In addition, tannin inhibits gel formation, avoiding the production of a more viscous latex that can cause problems in films such as gloves and condoms, a phenomenon that occurs in latex today. The amendment also provides greater storage stability, avoiding losses and difficulties of industrial processing.
  • the present development achieves two main objectives: 1) to produce natural rubber latex protected against biological degradation and spontaneous or physical coagulation; and 2) preparing allergen-free or allergen-sparing LBNs and that these characteristics are passed on to products and artifacts produced from this latex.
  • the chemicals to be incorporated into the LBN dealt with in this application are:
  • Polyphenol industrially manufactured or otherwise produced, preferably tannin powder or as liquid vegetable extract in the in natura form, or processed or purified, such as degassed tannin, or tannic acid, or synthetic tannins;
  • Polyphenol as the main agent, in one of its forms, preferably tannin, and may be used in isolation, with limited application, or in association with chemicals, as secondary agents or adjuvants;
  • a bactericide which may be borax (Na 2 B 4 D D 7 OH OH 2 O), also known as sodium borate or sodium tetraborate decahydrate in one of its presentation forms, or derivatives thereof, or any other bactericide;
  • a surfactant which may be anionic, such as sodium lauryl sulfate (or sodium dodecyl sulfate), or any other, or non-anionic surfactant, such as nonyl phenol ethoxylated in one of its forms, or any other, or any other surfactant, such as cationic or amphoteric;
  • An alkalizing or basifying agent such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, or ammonia, or any other.
  • hypoallergenic natural rubber latex developed in the present invention comprises the following basic formulation:
  • the order of addition of the compounds, in the form of aqueous solutions of varying concentrations, is preferably that which is mentioned above, but may also vary according to convenience. However, one should not mix the four compounds at once and then add this mixture to the latex as it results in the production of a less biologically preserved latex.
  • Table I shows that all samples with ammonia coagulated between 2 o (48 h) and 17 th day (408 h). The two samples with tannin had a very pleasant smell until the 17th test day and thus remained for more than 6 days.
  • VFA volatile fatty acids
  • VFA As the number of VFA is a direct measure of the degree of microbiological degradation of a material, its reading can be interpreted as a corroboration of the results of the smell test and a confirmation of the protection provided by tannin.
  • the sample with high ammonia (HA) was still liquid (uncoagulated) after 54 hours because it had been kept in a refrigerator. Even so, the difference of 0.38 (treatment with tannin) to 0.93 (treatment with ammonia) after 1268 hours, or 53 days, is notorious.
  • Figure 1 is presented a graph showing the variation of pH versus time of the five samples studied for experimental basement of the present invention. It is possible to observe indications on the antimicrobial preservation provided by the tannin to the LBN:
  • the latex preserved with low ammonia (LA) has a very short life and before 24 hours was already coagulated, despite the high starting pH, close to 9.5, evidencing the high instability of the starting latex, due to seasonality and temperature on the day of collection and test installation;
  • Latex preserved in the low ammonia system with borax (LAB) and high ammonia (HA) showed similar behaviors, starting with pH of 8.7 and 9.7, respectively, and decreasing the pH constantly until they coagulate with about 320 hours and pHs in the range of 6.7 and 7.7. It is observed that this latex, very unstable, must be coagulated at pHs close to this range.
  • the two latexes preserved with tannin, TBL and TBR have similar behavior, starting with a higher pH, between 8 and 8.5, initially decreasing to the point of 6.5, but not coagulating, and initiating a growth continued to finish at 6.8 and 7.4, respectively, when the analyzes are closed.
  • the two samples do not coagulate and present good visual and odor status, corroborating that there is effective protection using tannin and its coadjuvants.
  • Tannin a plant-derived polyphenol, protects the proteins from bacterial degradation, which explains the continuous and unambiguous increase in pH after reaching a minimum of about 6.5.
  • all other components susceptible to microbial digestion including lipids, phospholipids, carbohydrates and carotenoids, are unprotected, except for the presence of borax, which is known to be a mild bactericide.
  • borax which is known to be a mild bactericide.
  • the digestion of all these elements that also generate volatile fatty acids would be resulting in the continued decrease of the pH until, probably, its complete consummation. Thereafter, there is an increase in pH by the accommodation of ionic charges in the colloid.
  • the protection offered by polyphenols, such as tannin, to the colloid is not of an ionic nature, that is, what prevents the coagulation of particles is not the mutual repulsion of ionic charges, but rather the stereo impediment provided by the complexes of proteins and tannins that are adsorbed on the rubber particles.
  • Rubber particles have on their surface molecules of phospholipids and proteins, which are situated above their isoelectric point and, therefore, are charged with negative charges.
  • the traditional technical protection of the LBN is to accentuate the negative charges of proteins by adding ammonia in high percentages that can reach 0.8% (m / v). At these levels, the particles have a high negative charge, which prevents the fusion of the particles between them, which would result in the coagulation of the latex.
  • the zeta potential is a measure of the stability of a colloid whose particles are protected by ionic charges. If these are negative, the zeta potential lies below zero, as with the LBN, as can be seen in Figure 2, shows the evolution of the zeta potential during the analysis of the five samples LA, LAB, HA, TBL and TBR . It is observed that when samples with ammonia protection (low ammonia (LA), low ammonia with borax (LAB) or high ammonia (HA) decrease their ion protection and remain with zeta potential between -29 mV and -25 mV, The samples with tannin-based protection showed a zeta potential of less ion protection (with a lower absolute value) than samples protected with ammonia.
  • LA low ammonia
  • LAB low ammonia with borax
  • HA high ammonia
  • tannin vegetable and other polyphenols for microbiological protection of latex has as one of its innovation differentials the absence of ammonia and hence the possibility of working with lower pHs, which results in less gellation. It was already possible to observe the thickening and higher viscosity of the latex with ammonia, while the samples with tannin treatment were very fluid, even after several months of storage.
  • Another fundamental differential of the current technology is the decrease or cancellation of the allergenic effects of LBN, which are caused by the presence of thirteen proteins, as already widely proven in the specialized literature (SUBROTO, T., et al., PHYTOCHEMISTRY, 43 (1): 29-37, 1996; ARI F, SAM et al., J BIOL CHEM, 279 (23): 23933-23941, 2004; SHI, M. , et al. J BIOCHEM, 159 (2): 209-216, 2016). Therefore, the allergenic effects of latex can be monitored indirectly by the presence of proteins in general and in particular of proteins already associated with allergic processes. Two of the thirteen proteins are Hev b5 and Hev bl3, which already have immunological assay protocols and whose concentrations have an accepted upper limit on certain products.
  • Table I II shows the quantification of the Hev b5 and Hev bl3 proteins, by TARRC, where HA: high ammonia treatment; TBL: treatment with tannin, borax and LESS and TBR: treatment with tannin, borax and renex. It is possible to observe that the two main treatments analyzed were the systems with high ammonia (HA) and the best of a series of treatments, with tannin, borax and renex (TBR), according to the conclusions drawn from the previously mentioned variables such as pH, acids volatile greases, smell test and zeta potential. The main conclusions can be drawn from this table.
  • the tannin treatment requires that it be subjected to centrifugation, as this protein is found inside the feroid particles (ARI F, SAM, et al J RUBBER RES, 9 (1): 40-49, 2006 ) that, to the similarity of vacuoles in biological cells in general, are specialized in the enzymatic transformation of molecules for cellular biosynthesis.
  • the tannin does not have immediate access to the Hev bl3 proteins found in the fights, but when these particles are undone during centrifugation, part of them is eliminated with the aqueous serum of the latex and part remains in the latex, mixed with the cream with the particles of rubber.
  • the tannin has access and complexes changing the table of comparison between the two treatments: with high ammonia, the concentration (in ⁇ g / g) of this allergenic protein passes only by force of the two centrifugation steps, of 800 to 100 to 50 ⁇ g / g, while the tannin treatment goes from 1600 (when proteins are not accessible) to 120 and to 17 ⁇ g / g, reaching a lower concentration of the allergenic protein.
  • the tannin reacts and complexes with the latex proteins, biologically preserving the material, without the use of ammonia, and including in its complexation reactions the allergenic proteins, and for Hev b5, the concentration a is below the limit (0.02) of the method of analysis.
  • Latex in natura (LIN), with approximately 30% m / m of rubber content, as soon as possible after collection, 100 mL.
  • Borax in 5% w / w aqueous solution, add 20 mL to 1% (w / v) relative to the LIN.
  • EXAMPLE 1 BASIC FORMULATION REPLACING THE TANK POWDER EXTRACT BY ITS DEGOMED EXTRACT.
  • EXAMPLE 3 BASIC FORMULATION REPLACING THE EXTRACT IN TANK POWDER FROM BLACK ACACIA CASSETTE BY POWDER EXTRACTS OF MIRABOLAN AND TARA FRUIT.
  • the black acacia tannin is of the polyphenol type while the tannic extracts obtained from mirabolan and tara fruits are hydrolyzable. Preliminary tests of both also showed positive results regarding the smell, pH and Brookfield viscosity tests, comparing to the tannin of the black acacia bark. However, the color of the sample of both was clearer than the slightly tan color of the tannin of the black acacia bark, which opens up more perspectives of application for the present invention.
  • EXAMPLE 4 BASIC FORMULATION, INVERTING THE ORDER OF ENTRY OF THE INGREDIENTS: a) enter the surfactant before the tannin; b) they all enter together.

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  • Gloves (AREA)

Abstract

The present invention consists of the use of polyphenols, such as plant tannins, for protecting latex from natural rubber from the rubber tree Hevea brasiliensis L. against biological degradation, dispensing with the use of ammonia. The protection provides stability during storage and handling and blocks the allergenic proteins that exist in latex, decreasing or eliminating the incidence of allergies to products derived from the protected latex. The existing alternatives for reducing or eliminating said allergenic proteins complicate and/or encumber latex processing and do not completely solve the problem of allergenicity. With the use of polyphenols for treating latex, the present invention provides the production of a natural rubber latex raw material which allows the production of hypoallergenic products for medical use, such as surgical gloves, probes and contraceptives.

Description

LÁTEX DE BORRACHA NATURAL HIPOALERGÊNICO , PROTEGIDO COM POLIFENÓIS E ISENTO DE AMÓNIA, SEU PROCESSO DE OBTENÇÃO E USO HYPOALERGENIC NATURAL RUBBER LATEX, PROTECTED WITH POLYPHENOLS AND AMMONIUM-FREE, THEIR PROCESS OF OBTAINING AND USING
CAMPO DA INVENÇÃO A presente invenção situa-se nos campos da saúde humana e da cadeia tecnológica do látex de borracha natural (LBN) da seringueira Hevea brasiliensis L. e refere-se ao uso de polifenóis para preservar o LBN contra a degradação biológica e a coagulação, proporcionando-lhe estabilidade para estoque e manuseio, sem a necessidade do uso de amónia, bem como para reduzir ou eliminar a ação das proteínas alergênicas presentes no LBN, permitindo o seu emprego industrial na produção de muitos artigos hipoalergênicos ou não alergênicos para uso em geral, e, em especial, na área de saúde. FIELD OF THE INVENTION The present invention is in the fields of human health and the technological chain of natural rubber latex (LBN) of rubber tree Hevea brasiliensis L. and relates to the use of polyphenols to preserve LBN against biological degradation and coagulation, providing stability to stock and handling, without the need for the use of ammonia, as well as to reduce or eliminate the action of the allergenic proteins present in the LBN, allowing its industrial use in the production of many hypoallergenic or non-allergenic articles for use in general, and especially in the area of health.
ESTADO DA TÉCNICA STATE OF THE TECHNIQUE
Os primeiros registros sobre o látex e as características elásticas do material resultante da secagem do liquido exsudado da casca de árvores por nativos, foram feitos por Colombo em sua segunda viagem ao Novo Mundo em 1495 (MORAWETZ, H., RUBBER CHEM TECHNOL, 73(3) : 405-426, 2000) . Nos séculos seguintes foram feitos outros registros, ainda como curiosidade, por viajantes na Amazónia, berço genético da seringueira, depois descrita botanicamente e batizada por Hevea brasiliensis. Esta espécie, dentre as milhares que produzem látex, é a única que produz um elastômero de propriedades especiais e em quantidade de borracha, de cerca de 30% do liquido colhido, que permite a sua exploração económica (VAN BEILEN, J. B., POIRIER Y., TRENDS BIOTECHNOL, 25(11) : 522- 529, 2007) . A partir da metade do século 18, inicia-se a exploração da borracha, inicialmente para impermeabilização de tecido para fazer capas de chuva, depois para proteção de sapatos e, então, para outros inúmeros usos da borracha. The first records on latex and the elastic characteristics of the material resulting from the drying of the liquid exuded from the bark of trees by natives were made by Colombo on his second voyage to the New World in 1495 (MORAWETZ, H., RUBBER CHEM TECHNOL, 73 3): 405-426, 2000). In the following centuries other records were made, still as curiosity, by travelers in the Amazon, genetic cradle of the rubber tree, later described botanically and baptized by Hevea brasiliensis. This species, among the thousands that produce latex, is the only one that produces an elastomer of special properties and in quantity of rubber, about 30% of the liquid harvested, which allows its economic exploitation (VAN BEILEN, JB, POIRIER Y., TRENDS BIOTECHNOL, 25 (11): 522-529, 2007). From the middle of the 18th century onwards, rubber was started, initially for waterproofing fabric to make raincoats, then for shoe protection, and then for other innumerable uses of rubber.
Na metade do século 19, a descoberta da vulcanização por Charles Goodyear, processo que tornava o elastômero um material estável, no frio ou no calor, iniciou-se uma grande corrida pelo novo produto de propriedades elásticas especiais, que encontrou utilização em uma infinidade de empregos. O dominio de seu uso como pneu, por volta de 1870 viria a provocar uma nova e mais intensa corrida ao material (MORAWETZ, H., RUBBER CHEM TECHNOL, 73(3) : 405-426, 2000; HURLEY, P. E., J MACROMOL SCI A, 15(7) : 1279-1287, 1981) . Entretanto, a produção já tinha dificuldade de atender a procura, pois a borracha era produzida a partir do estoque nativo da floresta, cada vez mais longe na floresta amazônica. A domesticação ocorreu no Sudeste Asiático, a partir de 70.000 sementes levadas do Pará por Henry Wickham, por interesse do Governo Britânico. O dominio da técnica de plantio permitiu a produção de borracha em seringais de cultivo que não pararam mais de se expandir para dar conta da crescente demanda. In the middle of the 19th century, the discovery of vulcanization by Charles Goodyear, a process that made the elastomer a stable material in the cold or in the heat, started a great race for the new product with special elastic properties, which found use in a multitude of jobs. The dominance of its use as a tire, around 1870 would cause a new and more intense race to the material (MORAWETZ, H., RUBBER CHEM TECHNOL, 73 (3): 405-426, 2000; HURLEY, PE, J MACROMOL SCI A, 15 (7): 1279-1287, 1981). However, production was already difficult to meet demand, as the rubber was produced from the native stock of the forest, further and further into the Amazon forest. Domestication took place in Southeast Asia, from 70,000 seeds taken from Pará by Henry Wickham, on behalf of the British Government. The mastery of the technique of planting allowed the production of rubber in cultivated rubber plantations that did not stop to expand to meet the growing demand.
Até as últimas décadas do século 19, produtos tais como luvas e preservativos contraceptivos não existiam, o que proporcionava diversas dificuldades na época, como por exemplo, a proteção insatisfatória dos profissionais de saúde em cirurgias, em que se usava luvas de pano esterilizadas até os anos 1890. Naturalmente, tais artefatos têm elevada taxa de risco de infecção pela porosidade do material, entre outros fatores de risco (RESENDE, J. M. , À sombra do plátano: crónicas de história da medicina . São Paulo: Editora Unifesp. 408p. 2009) . Nas primeiras décadas do século 20, o látex centrifugado tornou-se disponível em larga escala para a produção de artefatos, permitindo o rápido desenvolvimento de muitos materiais de uso geral e de uso em saúde, em particular. Seguiu-se um longo periodo de várias décadas de intenso desenvolvimento de materiais feitos a partir do látex de borracha natural concentrado, de uso especialmente na área da saúde. Until the last decades of the 19th century, products such as gloves and contraceptive preservatives did not exist, which gave rise to several difficulties at the time, such as unsatisfactory protection of health professionals in surgeries, wearing cloth gloves sterilized until the 1890s. Naturally, such artifacts have a high risk of infection due to porosity of the material, among other risk factors (RESENDE, JM, In the shadow of the plane: chronicles of the history of medicine. . In the early decades of the 20th century, centrifuged latex became available on a large scale for the production of artifacts, allowing the rapid development of many materials of general use and health use in particular. There followed a long period of several decades of intense development of materials made from concentrated natural rubber latex, especially for health use.
Na Segunda Guerra Mundial, a borracha sintética SBR (Borracha de Estireno-Butadieno) foi desenvolvida e logo começou a ser utilizada substituindo a borracha natural (HURLEY, P. E., J MACROMOL SCI A, 15(7) : 1279- 1287, 1981) . Mesmo assim, o material de origem vegetal não foi substituído por completo, sendo sua utilização fundamental em pneus radiais, por exemplo, pelas propriedades especiais que o elastômero natural possui (MOOIBROEK, H., CORNISH, K., APPL MICROBIOL BIOT, 53(4) : 355-365, 2000) . In World War II, synthetic rubber SBR (Styrene-Butadiene Rubber) was developed and soon began to be used replacing natural rubber (HURLEY, P. E., MACROMOL SCI A, 15 (7): 1279-1287, 1981). Even so, the plant material has not been completely replaced, and its main use in radial tires is, for example, the special properties that the natural elastomer possesses (MOOIBROEK, H., CORNISH, K., APPL MICROBIOL BIOT, 53 4): 355-365, 2000).
Além do elastômero, o LBN contém vários componentes orgânicos como proteínas, lipídios, fosfolipidios , carboidratos e carotenoides , normalmente passíveis de degradação microbiana (JACOB, J. L., et al . CLIN REV ALLERG IMMU, 11: 325, 1993) . Isso faz com que o látex seja muito vulnerável à deterioração, o que gera ainda mais instabilidade no sistema coloidal que constitui o material natural, que acaba por colapsar espontaneamente . In addition to the elastomer, LBN contains several organic components such as proteins, lipids, phospholipids, carbohydrates and carotenoids, normally susceptible to microbial degradation (JACOB, JL et al., CLIN REV ALLERG IMMU, 11: 325, 1993). This makes the latex very vulnerable to deterioration, which creates even more instability in the colloidal system that constitutes the natural material, which spontaneously collapses.
Forma-se, então, um coágulo sólido não utilizável na produção industrial de itens feitos a partir do látex, cuja tecnologia de produção exige que o material esteja em sua forma liquida, como é o caso da produção de milhares de artefatos, como preservativos contraceptivos de borracha (camisinhas), luvas cirúrgicas e de procedimento, sondas, tubos de látex, balões de festas, etc. A solid clot is not used in the industrial production of items made from latex, whose production technology requires the material to be in its liquid form, as in the case of the production of thousands of artifacts, such as contraceptive preservatives rubber (condoms), surgical and procedural gloves, probes, latex tubes, party balloons, etc.
Em decorrência dessa composição orgânica, faz-se necessário proteger biologicamente o LBN desde a sua produção no campo, passando pela usina de beneficiamento, até chegar à indústria. O látex de borracha natural, processado na forma liquida, em contraposição à borracha sólida, utilizada em pneus e tantos outros produtos, começou a ser utilizado quando se descobriu a forma de preservar o coloide natural, normalmente muito vulnerável à degradação biológica. As a result of this organic composition, it is necessary to biologically protect the LBN from its production in the field, through the processing plant, until reaching the industry. Natural rubber latex, processed in liquid form as opposed to solid rubber, used in tires and many other products, began to be used when it was discovered how to preserve the natural colloid, normally very vulnerable to biological degradation.
A melhor solução de proteção desenvolvida consiste no uso do hidróxido de amónia, referido aqui simplesmente como amónia, que constitui o preservante universal para LBN, desde as primeiras décadas de produção do látex centrifugado e suas tecnologias industriais decorrentes, na primeira metade do século 20. The best protection solution developed is the use of ammonium hydroxide, referred to here simply as ammonia, which is the universal preservative for LBN, from the first decades of the production of centrifuged latex and its resulting industrial technologies in the first half of the 20th century.
Segundo BLACKLEY, D. C. (1997), a amónia desempenha duas reconhecidas funções no látex: a primeira, por agregar cargas eletrônicas negativas às proteínas adjacentes às partículas de borracha, que, por força das cargas negativas, passam a se repelir mutuamente, fazendo com que o coloide fique mais estável e não sofra coagulação. Como segunda função, mas não menos importante, a amónia, nas concentrações em que é adicionada ao látex (entre 0,5 a 0,8% m/m) atua como bactericida muito eficaz, especialmente nas concentrações mais elevadas (BLACKLEY, D. C, Polymer Latices - Science and technology Volume 1: Fundamental principies. Netherlands : Springer, 1997) . Desta forma, a amónia é o produto por excelência utilizado, há mais de oitenta anos, na manutenção do líquido estável para ser transportado, concentrado por centrifugação e estabilizado para uso nas indústrias. A borracha nesta forma líquida, como látex industrial concentrado a 60%, de borracha, mostrou ser matéria-prima muito versátil e a inventividade humana desenvolveu milhares de usos diferentes em artefatos de espessuras delgadas ou de média espessura, empregando várias técnicas de coagulação do látex concentrado a 60% de borracha. A partir daí, uma grande quantidade destes artefatos foi desenvolvida para uso na área de saúde, sendo os mais notórios, as luvas cirúrgicas e de exame, os drenos, os cateteres, os contraceptivos masculinos e femininos e os campos cirúrgicos, dentre muitos outros. Se na utilização de borracha sólida, o uso da borracha sintética foi largamente viabilizado, no campo tecnológico do látex, esta substituição foi mais lenta e, mesmo hoje, produtos como as camisinhas, dentre outros, só podem ser fabricados com látex natural. Entretanto, esta história de inegável sucesso, de quase um século, encontra-se em ponto crucial e o uso de artefatos de látex na saúde está em cheque pela questão dos alergênicos presentes em sua composição. De fato, os primeiros registros de alergia ao látex surgiram nas décadas de 1980 e 90 (KELLET, P. B., J EMERG NURS, 23(l) :27-36, 1997), e os relatos científicos e técnicos das alergias têm crescido alarmantemente e as estatísticas para os EUA registram que a alergia ao látex atinge 6% da população em geral e 15% dos profissionais de saúde, normalmente mais expostos ao contato com materiais de látex (AMR & BOLLINGER, 2004) . Com preocupação acentuada sobre as alergias ao látex, o hospital John Hopkins, em Baltimore (EUA) , onde se iniciou o uso de luvas finas de borracha em 1890, que logo evoluíram para as luvas de látex centrifugado, suspendeu o uso das luvas de LBN, por dermatite de contato causada por resposta alérgica ao látex apresentadas por seus profissionais de saúde (JOHN HOPKINS MEDICINE, 2017) . According to BLACKLEY, DC (1997), ammonia performs two recognized functions in latex: the first, by adding negative electronic charges to proteins adjacent to the rubber particles, which, by virtue of the negative charges, repel each other, making the colloid more stable and free from clotting. As second but not least, ammonia, at concentrations in which it is added to the latex (0.5 to 0.8% w / w) acts as a very effective bactericide, especially at the higher concentrations (Blackley, D. C, Polymer Latices - Science and technology Volume 1: Fundamental principles. Netherlands: Springer, 1997). In this way, ammonia is the product par excellence used for more than eighty years in the maintenance of stable liquid to be transported, concentrated by centrifugation and stabilized for use in industries. Rubber in this liquid form, such as 60% concentrated industrial rubber latex, has proved to be a very versatile raw material and human inventiveness has developed thousands of different uses in thin or medium thickness artifacts employing various latex coagulation techniques concentrated to 60% rubber. Thereafter, a large number of these artifacts were developed for use in the health area, the most notorious being surgical and examination gloves, drains, catheters, male and female contraceptives and surgical fields, among many others. If in the use of solid rubber, the use of synthetic rubber was largely made possible, in the technological field of latex, this replacement was slower and even today, products such as condoms, among others, can only be manufactured with natural latex. However, this story of undeniable success, almost a century, is at a crucial point and the use of latex artifacts in health is in check by the question of the allergens present in its composition. In fact, early records of latex allergy emerged in the 1980s and 1990s (KELLET, PB, J EMERGER NURS, 23 (1): 27-36, 1997), and scientific and technical reports of allergies have grown alarmingly and the statistics for the USA show that latex allergy affects 6% of the general population and 15% of health professionals, usually more exposed to contact with latex materials (AMR & BOLLINGER, 2004). With a marked concern about latex allergies, the John Hopkins Hospital in Baltimore (USA), where the use of thin rubber gloves in 1890, which soon evolved into centrifuged latex gloves, discontinued the use of LBN gloves , for contact dermatitis caused by allergic response to latex presented by their health professionals (JOHN HOPKINS MEDICINE, 2017).
Assim, não obstante sua eficácia e o seu baixo custo, a substituição da amónia como preservante do LBN tem sido tema de pesquisa recorrente, pelo menos nas últimas seis décadas (MCGAVACK, J., RUBBER CHEM TECHNOL, 32(5) : 1660-1674, 1959; TARACHIWIN, L., et al., RUBBER CHEM TECHNOL, 76(5) : 1177-1184, 2003; SANTIPANUSOPON, S., RIYAJAN, S., PHYSICS PROCEDIA, 2(1) : 127-134, 2009), pela sua alta volatilidade e por ser um gás muito irritante, gerando problemas de saúde e desconforto laboral. Por estas razões, vem se pesquisando soluções que substituam a amónia, ou que permitam diminuir sua concentração, nos sistemas conhecidos como "baixo-amônia" , em concentrações de 0,2 a 0,4% m/m. No entanto, a função bactericida da amónia só é assegurada na sua alta dosagem, o que implica adicionar outro reagente que possa cumprir esta sua função bactericida (BLACKLEY, D. C, Polymer Latices - Science and technology Volume 1: Fundamental principies. Netherlands: Springer, 1997; JEWTRAGOON, P., Bottom Fraction Memhrane: Involvements in Natural Rubber Látex Allergy. Tese de Doutorado. Prince of Songkla University, 2004) . Outra desvantagem do uso da amónia é sua alta volatilidade, o que faz com que o látex, no manuseio normal de trabalho, vá perdendo a sua proteção, obrigando a uma permanente vigilia do látex e a reposição do preservante conforme necessário, em condições subjetivas, o que pode levar a perda de produção. Thus, despite its effectiveness and low cost, the substitution of ammonium as a preservative for LBN has been the subject of recurrent research, at least in the last six decades (McGavack, J., Rubber Chem Technol, 32 (5): 1660- 1674, 1959. TARACHIWIN, L., et al., RUBBER CHEM TECHNOLOG, 76 (5): 1177-1184, 2003; SANTIPANUSOPON, S., RIYAJAN, S., PHYSICS PROCEDIA, 2 (1): 127-134, 2009), because of its high volatility and because it is a very irritating gas, generating health problems and labor discomfort. For these reasons, solutions that replace ammonia, or that allow to reduce its concentration, in systems known as "low-ammonia", in concentrations of 0.2 to 0.4% m / m have been investigated. However, the bactericidal function of ammonia is only ensured at high dosage, which implies adding another reagent that can fulfill this bactericidal function (BLACKLEY, D. C, Polymer Latices - Science and technology Volume 1: Fundamental principles. Bottom Fraction Memhrane: Involvements in Natural Rubber Latex Allergy, Doctoral Thesis, Prince of Songkla University, 2004). Another disadvantage of the use of ammonia is its high volatility, which causes that the latex, in the normal handling of work, loses its protection, forcing a permanent vigilance of the latex and the replacement of the preservative as necessary, under subjective conditions, which can lead to loss of production.
Os trabalhos de investigação cientifica e tecnológica para encontrar um bactericida ideal para coadjuvar a amónia na função de proteger o LBN têm sido desafiantes. O reagente quimico que melhor desempenhou esta tarefa foi o pentaclorofenato de sódio, CIsCeONa (MURPHY, E. A., IND ENG CHEM RES, 5344(4) : 756-762, 1952) que é altamente reativo e eficaz na preservação do látex, mas, no entanto, é cancerígeno, conhecido popularmente como "pó da china" (MENON, J. A., BR MED J, 1: 1156-1158, 1958), e proibido em muitos paises, incluindo o Brasil (Ministério da Saúde, Portaria n. 11, de 08 de janeiro de 1998) . Outros bactericidas já foram investigados e encontraram uso comercial, entre eles o bórax, conhecido também como tetraborato de sódio ou borato de sódio, (Na2B407 -10H2O) (COOK, A. S., J RUBBER RES, 16(2) : 65-86, 1960) . As manifestações alérgicas decorrentes do uso de artigos de látex de borracha natural são resultantes da presença de proteínas alergênicas presentes naturalmente no látex e são bastante pesquisadas com muitas publicações e revisões na literatura especializada (TURJANMAA, K., REUNALA, T., CONTACT DERMATITIS, 20: 360-364, 1989; BUBAK, M. E., REED, C. E. MAYO CLIN PROC, 67(11) : 1075-1079, 1992; SPINA, A. M., LEVINE, H. J., OR SURG OR MED OR PA, 87(1) : 5-11, 1999; RANTA, P. M. , OWNBY, D. R. , CLIN INFECT DIS, 38 (2) : 252-256, 2004), consolidando-se como objeto de saúde pública. Portanto, a eliminação ou atenuação dessas proteínas constitui tema de pesquisa bastante difundido (KAWAHARA, S., et al . POLYM ADVAN TECHNOL, 15: 181-184, 2004; KLINKLAI, W., J APPL POLYM SCI, 93: 555- 559, 2004; GEORGE, K. M. , J APPL POLYM SCI, 114: 3319- 3324, 2009), desde que surgiram as primeiras manifestações do problema. Scientific and technological research to find an ideal bactericide to assist ammonia in protecting LBN has been challenging. The chemical reagent that best performed this task was sodium pentachlorophenate, CIsCeONa (MURPHY, EA, IND ENG CHEM RES, 5344 (4): 756-762, 1952) which is highly reactive and effective in preserving latex but, However, it is carcinogenic, popularly known as "powder of china" (MENON, JA, BR MED J, 1: 1156-1158, 1958), and banned in many countries, including Brazil (Ministry of Health, Ordinance No. 11, of January 8, 1998). Other bactericides have already been investigated and found commercial use, including borax, also known as sodium tetraborate or sodium borate, (Na 2 B 4 07 -10H 2 O) (COOK, AS, J RUBBER RES, 16 (2) : 65-86, 1960). Allergic manifestations resulting from the use of Natural rubber latex articles are the result of the presence of naturally occurring allergenic proteins in latex and are heavily researched with many publications and reviews in the specialized literature (TURJANMAA, K., REUNALA, T., CONTACT DERMATITIS, 20: 360-364, 1989 , BUBAK, ME, REED, CE MAYO CLIN PROC, 67 (11): 1075-1079, 1992; SPINA, AM, LEVINE, HJ, OR SURG OR MED OR PA, 87 (1): 5-11, 1999; , PM, OWNBY, DR, CLIN INFECT DIS, 38 (2): 252-256, 2004), consolidating itself as an object of public health. Therefore, the elimination or attenuation of these proteins is a well-publicized research topic (KAWAHARA, S., POLYM ADVAN TECHNOLOG, 15: 181-184, 2004; KLINKLAI, W., J APPL POLYM SCI, 93: 555-559 , 2004; GEORGE, KM, J APPL POLYM SCI, 114: 3319-3324, 2009), since the first manifestations of the problem appeared.
Durante a biossíntese do látex, no contexto da complexa composição biológica do citoplasma das células lactíferas da seringueira, as proteínas desempenham funções fundamentais na biossíntese do elastômero e na proteção da árvore, dentre outras. Após a colheita do LBN, estas proteínas cessam sua função biológica original, mas continuam ativas e continuam reagindo como proteínas, incluindo as reações que desencadeiam os processos alérgicos. During latex biosynthesis, in the context of the complex biological composition of the cytoplasm of rubber tree cells, the proteins play a key role in elastomer biosynthesis and tree protection, among others. After harvesting the LBN, these proteins cease their original biological function, but remain active and continue to react as proteins, including the reactions that trigger allergic processes.
O látex in natura (LIN) , após ser produzido no campo, pode ficar estocado no produtor, na usina de beneficiamento e na indústria de transformação. Na usina, ele é centrifugado para dobrar a concentração de borracha no látex. Ainda que essa operação elimine muitos componentes naturais do látex e impurezas da produção, várias proteínas permanecem no látex e continuam ativas, no sentido alergênico, mesmo após passar pelo processo produtivo industrial de artefatos como luvas cirúrgicas, preservativos, sondas hospitalares, dentre outros, desencadeando os processos alérgicos nos pacientes ou nos profissionais que os manuseiam. The latex in natura (LIN), after being produced in the field, can be stored in the producer, the processing plant and the processing industry. At the plant, it is centrifuged to double the concentration of rubber in the latex. Although this operation eliminates many natural latex components and production impurities, several proteins remain in the latex and remain active, in the allergenic sense, even after passing through the industrial production process of artifacts such as surgical gloves, condoms, hospital probes, among others, triggering allergic processes in patients or the professionals who handle them.
Várias formas de processamento do látex vêm sendo testadas, isoladamente ou combinadas, visando reduzir ou eliminar os efeitos alergênicos das proteínas do látex. As principais são: Various forms of latex processing have been tested either alone or in combination to reduce or eliminate the allergenic effects of latex proteins. The main ones are:
1) Tratamentos com enzimas proteoliticas que hidrolisam ou segmentam as proteínas em pedaços menores e, ao mudar a forma química e/ou a conformação estrutural das proteínas, as enzimas as inativam para suas reações especificas como os processos alérgicos; 1) Treatments with proteolytic enzymes that hydrolyze or segment proteins into smaller pieces, and by changing the chemical form and / or the structural conformation of the proteins, the enzymes inactivate them for their specific reactions as the allergic processes;
2) Tratamentos químicos com surfactantes ou detergentes que lavam as proteínas do sistema e com reagentes alcalinos para saponificar as proteínas e extinguir ou atenuar o seu efeito adverso; 2) Chemical treatments with surfactants or detergents that wash the proteins of the system and with alkaline reagents to saponify the proteins and extinguish or attenuate their adverse effect;
3) Processos físicos como a centrifugação, realizada por duas vezes, para retirar as proteínas por arraste no soro aquoso. 3) Physical processes such as centrifugation, performed twice, to remove the proteins by entrainment in the aqueous serum.
Entretanto, os vários métodos de tratamento podem apresentar uma ou mais das seguintes desvantagens: maior custo; maior trabalho de processamento; remoção não integral das proteínas; rebaixamento na qualidade de propriedades finais da borracha ocasionado pela retirada das proteínas adjacentes às partículas de borracha; introdução de novas proteínas, na forma de enzimas, ou de peptídeos gerados no processo enzimático, que podem desencadear novos processos alérgicos. However, the various methods of treatment may present one or more of the following disadvantages: higher cost; greater processing work; non-integral removal of proteins; lowering the quality of final rubber properties caused by the removal of proteins adjacent to the rubber particles; introduction of new proteins, in the form of enzymes, or of peptides generated in the enzymatic process, which can trigger new allergic processes.
É reconhecido também que a adição de amónia como preservante microbiano do LBN resulta na formação de géis no coloide (SANTIPANUSOPON, S., RIYAJAN, S., PHYSICS PROCEDIA, 2(1) : 127-134, 2009), os quais são entendidos como agregação de partículas do elastômero sem a sua efetiva fusão entre si, ou coagulação. Aparentemente, a formação dos géis está associada a reações cruzadas entre proteínas e fosfolipídios , adsorvidos à superfície de diferentes partículas que, então, formariam aglomerados de partículas sem coagulação (TARACHIWIN, L., et al . , RUBBER CHEM TECHNOL, 76(5) : 1177-1184, 2003) . Ainda mais, estas reações tendem a ser influenciadas pelo alto pH do meio, proporcionado pela elevada concentração de amónia, em torno de 0,8 % m/m. Os géis, pelo incremento no tamanho das partículas, acarretam progressivo aumento da viscosidade do látex durante a estocagem, o que tende a interferir na utilização industrial, em pelo menos duas situações: o espessamento do látex pelo aumento da viscosidade obriga a mudanças na formulação no sentido de diminuir a viscosidade, o que pode, por sua vez, interferir na deposição do filme nos processos de imersão {dipping) , a mais utilizada técnica de produção industrial de artefatos a partir do látex, notoriamente, luvas, camisinhas e balões. A segunda possibilidade de interferência dos géis no processo produtivo decorre da própria formação do gel como junção de duas ou mais partículas, sem a fusão das moléculas do elastômero, o que implica na formação de microfilmes aquosos no interior do gel. Estas microrregiões de água em meio ao elastômero poderão dificultar a formação de filmes coerentes no critico processo produtivo de imersão, onde o depósito de borracha deve ter a espessura mais uniforme possivel para evitar possíveis pontos fracos no filme, o que poderá levar à ruptura do artefato. It is also recognized that the addition of ammonia as a microbial preservative of LBN results in the formation of gels in the colloid (SANTIPANUSOPON, S., RIYAJAN, S., PHYSICS PROCEDIA, 2 (1): 127-134, 2009), which are understood as the aggregation of particles of the elastomer without their effective fusion between themselves, or coagulation. Apparently, the formation of gels is associated with cross-reactions between proteins and phospholipids, adsorbed to the surface of different particles which would then form clusters of particles without coagulation (TARACHIWIN, L., et al., Rubber Chem Technol, 76 (5) : 1177-1184, 2003). Further, these reactions tend to be influenced by the high pH of the medium, provided by the high concentration of ammonia, around 0.8% m / m. Gels, due to the increase in particle size, lead to a progressive increase in the viscosity of the latex during storage, which tends to interfere in the industrial use in at least two situations: thickening of the latex by increasing the viscosity causes changes in the formulation in the which can in turn interfere with film deposition in dipping processes, the most widely used technique of industrial production of latex artifacts, notably gloves, condoms and balloons. The second possibility of interference of the gels in the production process stems from the formation of the gel itself as the junction of two or more particles, without the fusion of the elastomer molecules, which implies the formation of aqueous microfilms in the interior of the gel. These microregions of water in the middle of the elastomer may hinder the formation of coherent films in the critical immersion production process, where the rubber deposit should have the most uniform thickness possible to avoid possible weak spots in the film, which could lead to rupture of the artifact .
Considerando que as proteínas estão no centro de problemas de processamento e uso do LBN, sendo sua causa principal, e que os polifenóis como o tanino, complexam com proteínas do colágeno da pele animal anulando suas reações, como ocorre na manufatura do couro (SIEBERT, K. J., et al. J AGR FOOD CHEM, 44(l) :80-85, 1996; MADHANB, B., et al. INT J BIOL MACROMOL, 37(1-2) : 47-53, 2005), os polifenóis também podem ser utilizados para cumprir o mesmo papel no látex, complexando as suas proteínas, consequentemente evitando sua degradação biológica e diminuindo ou anulando sua ação alergênica. Ademais, possibilita trabalhar com pHs mais baixos, o que resulta em menor formação de géis. Uma grande quantidade de polifenóis naturais encontrados em plantas e produtos extraídos ou derivados delas (NACZK, M. , SHAHIDI, F . , J PHARMACEUT BIOMED, 41(5) : 1523-1542, 2006) estão incluídos na categoria dos taninos vegetais, que são de dois tipos: hidrolisáveis e condensados. Os taninos do segundo tipo, constituídos por moléculas representadas na Fórmula i. (COVINGTON, A. D., CHEM SOC REV, 26: 111-126, 1997), são estáveis em meio aquoso e encontram um grande número de aplicações industriais, tais como curtimento da pele para produzir couro, (Compilation of air pollutant emission factors volume I: Stationary point and area sources, EPA, 2016), lubrificação de brocas na perfuração de poços de petróleo IBRAHIM, M. N . M., et al . JURNAL TEKNOLOGI, 38: 25-32, 2003), floculantes (BEL RAN-HEREDIA, J., DESALINATION, 249: 353-358, 2009), sedimentadores de partículas no tratamento de água (BAILEY, S. E. et al . WATER RES, 33(11) : 2469-2479, 1999) e adesivos para a indústria madeireira . Considering that proteins are at the center of problems of processing and use of LBN, being its main cause, and that polyphenols such as tannin, complex with collagen proteins of the animal skin nullifying their reactions, as occurs in the manufacture of leather (SIEBERT, KJ et al J AGR FOOD CHEM, 44 (1): 80-85, 1996; MADHANB, B., et al., INT J BIOL MACROMOL, 37 (1-2): 47-53, 2005), polyphenols can also be used to fulfill the same role in latex, complexing their proteins, consequently avoiding their biological degradation and reducing or canceling their allergenic action. In addition, it allows to work with lower pHs, which results in less formation of gels. A large amount of natural polyphenols found in plants and products extracted or derived from them (NACZK, M., SHAHIDI, F., J PHARMACEUT BIOMED, 41 (5): 1523-1542, 2006) are included in the category of vegetable tannins, which are of two types: hydrolyzable and condensed. The tannins of the second type, consisting of molecules represented in Formula i. (COVINGTON, AD, CHEM SOC REV, 26: 111-126, 1997), are stable in aqueous medium and encounter a large number of industrial applications, such as tanning to produce leather, (Compilation of air pollutant emission factors volume I: Stationary point and area sources, EPA, 2016), lubrication of drill bits in oil well drilling IBRAHIM, M. N. M., et al. JANUARY TEKNOLOGI, 38: 25-32, 2003), flocculants (BEL RAN-HEREDIA, J., DESALINATION, 249: 353-358, 2009), particulate settlers in water treatment (BAILEY, SE et al., WATER RES, 33 (11): 2469-2479, 1999) and adhesives for the timber industry.
Figure imgf000014_0001
Figure imgf000014_0001
As moléculas de tanino contêm elevado número de hidroxilas fenólicas, que lhes atribui alta facilidade de interação molecular com outras moléculas através de ligações de hidrogénio (SIEBERT, K. J., et al . J AGR FOOD CHEM, 44(1) : 80-85, 1996) . Economicamente, a mais importante dessas reações constitui a base do tratamento das peles animais na produção de couro no curtimento do tipo vegetal (Compilation of air pollutant emission factors volume I: Stationary point and area sources, EPA, 2016) . Nesse tratamento, o tanino tem que alcançar as fibrilas do colágeno da pele e bloqueá-las para que não mais estejam disponíveis para os ataques bacterianos, conforme modelo proposto por COVINGTON (COVINGTON, A. D., CHEM SOC REV, 26: 111-126, 1997) apresentado na Fórmula ii . Como neste processo ocorre a reação entre um substrato sólido, a pele animal, reagindo com um liquido, o tanino vegetal em solução, há necessidade de um longo tempo de reação, de cerca de três dias, em um reator de madeira ou aço inoxidável, num processo que depende do pH, temperatura, concentração da solução e tempo no reator (REICH, G., From collagen to leather - the theoretical background. Germany: BASF, 2007) . Tannin molecules contain a large number of phenolic hydroxyls, which gives them high ease of molecular interaction with other molecules through hydrogen bonds (SIEBERT, KJ, et al., J. Ag. Chem., 44 (1): 80-85, 1996). ). Economically, the most important of these reactions forms the basis of the treatment of animal skins in the production of leather in vegetable tanning (Compounding of air pollutant emission factors Volume I: Stationary point and area sources, EPA, 2016). In this treatment, the tannin has to reach the collagen fibrils of the skin and block them so that they are no longer available for bacterial attacks, according to the model proposed by COVINGTON (COVINGTON, AD, CHEM SOC REV, 26: 111-126, 1997) presented in Formula II. As in this process the reaction between a solid substrate, the animal skin, reacting with a liquid, the vegetable tannin in solution, there is a need for a long reaction time, about three days, in a reactor of wood or stainless steel, in a process that depends on the pH, temperature, concentration of the solution and time in the reactor (REICH, G., From collagen to leather - the theoretical background Germany: BASF, 2007).
Figure imgf000015_0001
Figure imgf000015_0001
Ao passar pelo curtimento com o tanino vegetal, as proteínas do colágeno da pele, não somente deixam de estar aptas para o ataque microbiológico, como perdem a capacidade de reagir como proteínas, pois estão ligadas ao tanino por fortes ligações de hidrogénio (SRIVASTAVA, N., MEERA, B., IJERT, 3(7) : 479-481, 2014) . Adquirem uma "capa" tanino-proteica que as impede de atuar como proteínas típicas, de uma forma irreversível e muito estável, o que se atesta pela estabilidade de couros, já curtidos, em comparação com as peles não curtidas. Not only are the collagen proteins of the skin not only unsuitable for microbiological attack but also the ability to react as proteins because they are bound to the tannin by strong hydrogen bonds (SRIVASTAVA, N ., MEERA, B., IJERT, 3 (7): 479-481, 2014). They acquire a tannin-protein "cap" that prevents them from acting as typical proteins, in an irreversible and very stable way, which is attested by the stability of already tanned leathers compared to untanned skins.
Dessa forma, as proteínas originais se encontram complexadas com o tanino e já não são passíveis de deterioração bacteriana. Se já não estão mais aptas a reagir em reações inespecificas como substrato de ataque das bactérias, estas proteínas complexadas com tanino também já não poderão participar de sensibilizações alérgicas, onde as proteínas desempenham reações muito específicas (POLEY, G . , SLATER, J., J ALLERGY CLIN IMMUNOL, 105(6-1) : 1054-1062, 2000) . Por suas características químicas, o tanino reage com todas as proteínas do látex, sem distinção, gerando produtos estáveis e inativos, tanto para o ataque bacteriano, quanto para atuarem como antígenos e nesta condição permaneçam, mesmo que ainda estejam presentes no látex, após a centrifugação ou, ainda, que permaneçam após a fabricação em um produto feito de látex, como luvas, por exemplo . In this way, the original proteins are complexed with tannin and are no longer bacterial deterioration. If they are no longer able to react in nonspecific reactions as a substrate for bacterial attack, these complexes with tannin may no longer participate in allergic sensitization, where proteins have very specific reactions (POLEY, G., SLATER, J., J ALLERGY CLIN IMMUNOL, 105 (6-1): 1054-1062, 2000). Due to its chemical characteristics, tannin reacts with all latex proteins, without distinction, generating stable and inactive products, both for bacterial attack and for acting as antigens and in this condition remain, even if they are still present in the latex, after centrifugation or even remaining after manufacture in a product made of latex, such as gloves, for example.
Ainda, as proteínas complexadas pelas moléculas de tanino estão também, à similaridade do couro, não disponíveis para a própria degradação bacteriana em si. Como as proteínas compõem grande parte do material digerível por bactérias, em concentração maior do que os outros componentes orgânicos não borracha (JACOB, J. L., et al. CLIN REV ALLERG IMMU, 11: 325, 1993), a preservação do látex estará em grande parte assegurada pelo próprio tratamento com tanino, prescindindo, assim, da adição de hidróxido de amónio. Furthermore, the proteins complexed by the tannin molecules are also, at the similarity of the leather, not available for the bacterial degradation itself. Because proteins make up much of the digestible material by bacteria, at a higher concentration than the other non-rubber organic components (JACOB, JL et al., CLIN REV ALLERG IMMU, 11: 325, 1993), the preservation of latex will be large which is ensured by the treatment with tannin itself, thus dispensing with the addition of ammonium hydroxide.
O látex in natura, ao ser extraído da árvore de seringueira, permanece normalmente algumas horas em estado líquido e é nesta condição que se devem acrescentar os produtos preservantes para sua conservação, nos vasilhames de colheita no campo, logo ao ser recolhido das tigelas. The latex in natura, when extracted from the tree of rubber tree, normally remains a few hours in a liquid state and it is in this condition that preservatives must be added for their conservation, in the harvest containers in the field, soon to be collected from the bowls.
O látex de borracha natural produzido hoje tem como agente universal de proteção a amónia, sob a forma de hidróxido de amónio, em concentrações que variam de 0,5 a 0,8 % (m/m) (BLACKLEY, D. C, Polymer Latices - Science and technology Volume 1: Fundamental principies. Netherlands : Springer, 1997), que tem como desvantagem o forte cheiro desta substância, em qualquer estágio em que é adicionada ao látex, seja na colheita do látex ainda no campo, seja na usina de centrifugação, seja na indústria de transformação. O vapor de amónia liberado em sua manipulação provoca desconforto laboral e apresenta potencial de risco, pois sua inalação intensa súbita pode levar a desmaios, e a exposição prolongada a seu vapor pode provocar problemas de saúde das vias respiratórias . Nas concentrações referidas, o hidróxido de amónio tem dupla função: alcalinizar o meio para proteção do coloide e servir de bactericida, evitando a degradação biológica do látex. As propostas alternativas a este tratamento incluem o uso de amónia, em baixa ou média concentração, associada a um bactericida do tipo bórax, ou, então, totalmente sem amónia, com uso de biocidas de alta toxicidade, como o pentacloro fenato de sódio, também conhecido como "pó-da-china" , de uso proibido no Brasil e em muitos paises. O uso de tanino e coadjuvantes para o tratamento do látex não apresenta qualquer desvantagem dessa natureza. The natural rubber latex produced today has as universal protection agent ammonia in the form of ammonium hydroxide in concentrations ranging from 0.5 to 0.8% (m / m) (BLACKLEY, D.C., Polymer Springer, 1997), which has the disadvantage of the strong smell of this substance, at any stage in which it is added to the latex, whether in the field latex harvest or in the plant centrifugation, or in the processing industry. The ammonia vapor released in its handling causes labor discomfort and presents a potential risk, since its sudden intense inhalation can lead to fainting, and the prolonged exposure to its vapor can cause health problems of the airways. At the above concentrations, ammonium hydroxide has a dual function: alkalinize the medium to protect the colloid and serve as a bactericide, avoiding the biological degradation of the latex. Alternative proposals for this treatment include the use of low or medium concentration ammonia associated with a borax or totally ammonia-free bactericide with the use of high toxicity biocides such as sodium pentachloro-phenate, known as "china powder", forbidden in Brazil and in many countries. The use of tannins and coadjuvants for the treatment of latex does not present any disadvantage of this nature.
O problema de alergias ao LBN é relatado como de saúde pública, especialmente entre os profissionais de saúde. Essas alergias são reações da pele a proteínas existentes no LBN. Há algumas formas de reduzir a concentração dessas proteínas, tais como tratamento com ureia, com ou sem surfactante como coadjuvante, dupla centrifugação e uso de enzimas proteolíticas . Entretanto, estes tratamentos ou encarecem o processamento do látex, ou não eliminam totalmente as proteínas . The problem of allergies to LBN is reported as public health, especially among health professionals. Cheers. These allergies are skin reactions to proteins in the LBN. There are some ways to reduce the concentration of these proteins, such as urea treatment, with or without surfactant as a coadjuvant, double centrifugation and use of proteolytic enzymes. However, these treatments either make latex processing expensive, or do not completely eliminate proteins.
Outra característica destes processos que eliminam ou reduzem as proteínas é que podem diminuir as propriedades de resistência mecânica da borracha resultante. Por outro lado, o tratamento do látex com tanino e agentes coadjuvantes, que constitui a característica principal da presente tecnologia, não encarece o processamento do LBN, pois o seu custo não é elevado e pode muito bem ser absorvido pelo preço do LBN melhorado. Além disso, não há etapa adicional no processamento do látex, que poderia encarecer ou dificultar o processo. Finalmente, a borracha derivada deste LBN tratado com o tanino mantém as proteínas, que, neste caso, estarão bloqueadas com o tanino, o que não irá interferir negativamente na resistência dos artefatos derivados . Another feature of these processes that eliminate or reduce proteins is that they can decrease the mechanical strength properties of the resulting rubber. On the other hand, the treatment of latex with tannin and coadjuvant agents, which is the main characteristic of the present technology, does not increase the processing of the LBN because its cost is not high and may well be absorbed by the price of the improved LBN. In addition, there is no additional step in the processing of latex which could make the process more expensive or difficult. Finally, the rubber derived from this LBN treated with tannin maintains the proteins, which, in this case, will be blocked with the tannin, which will not negatively interfere in the resistance of the derived artifacts.
A pesquisa de anterioridade revelou o pouco uso de tanino adicionado ao látex de borracha natural com o fim de melhorar suas qualidades ou ampliar o seu escopo de uso. Assim, em comparação com algumas tecnologias existentes que possam se aproximar ao escopo da presente invenção, o pedido de patente chinês CN106279467, publicado em 04 de janeiro de 2017, é o único que também faz uso similar de tanino em LBN, neste caso, para imobilização de proteínas. Utiliza extrato de tanino vegetal, em solução de 10 a 30%, adicionado ao látex já centrifugado e também tratado de modo convencional com alta concentração de amónia para proteção do látex. Segundo a descrição, os resultados são satisfatórios quanto à redução de proteínas livres determinadas em luvas produzidas com o látex tratado com tanino, o que, indiretamente, conduziria à redução de alergênicos dos artefatos de borracha, ainda que não tenham sido feitos testes específicos de alergenicidade ou de quantificação de proteínas alergênicas . A referida tecnologia tem por base tecnológica a mesma reação química de complexação entre tanino e proteína do látex que é também o embasamento cientifico do presente invento. No entanto, esta é a única proximidade entre ambas. O tanino no pedido de patente chinês é aplicado ao látex centrifugado, enquanto no presente caso o tanino é adicionado ao látex in natura, logo após ser colhido da seringueira. Ainda mais, e esta é a principal diferença entre ambos, é que no presente desenvolvimento, faz-se uso pleno das reações entre tanino e as proteínas do látex, ainda no campo e com pH na faixa de 7 a 9. Como o tanino de fato complexa as proteínas do látex, este fica protegido contra bactérias, sem o uso de amónia. Portanto, o tanino reage com as proteínas e inativa as mesmas, seja para serem o substrato de ataques bacterianos, seja para atuarem como alergênicos. Ainda, a eficácia em diminuir as proteínas livres, conforme apontado pelos inventores da tecnologia chinesa, não pode ser atribuída somente ao tanino. É sabido que a presença de amónia em altas concentrações pode também quebrar as proteínas em pedaços menores que são arrastados juntamente com o soro aquoso durante a centrifugação (TARACHIWIN, L., et al., RUBBER CHEM TECHNOL, 76(5) : 1177-1184, 2003) . The previous research revealed the little use of tannin added to the natural rubber latex in order to improve its qualities or broaden its scope of use. Thus, in comparison with some existing technologies which may approximate the scope of the present invention, the Chinese patent application CN106279467, published January 4, 2017, is the only one which also makes similar use of tannin in LBN, in this case, for immobilization of proteins. It uses a vegetable tannin extract, in 10 to 30% solution, added to the latex already centrifuged and also treated in a conventional way with high concentration of ammonia to protect the latex. According to the disclosure, the results are satisfactory with regard to the reduction of free proteins determined in gloves produced with the tannin-treated latex, which would indirectly lead to the reduction of allergens of the rubber artifacts, although no specific allergenicity tests have been performed or quantification of allergenic proteins. Said technology is based on the same chemical reaction of complexation between tannin and latex protein which is also the scientific basis of the present invention. However, this is the only closeness between the two. The tannin in the Chinese patent application is applied to the centrifuged latex, while in the present case the tannin is added to the latex in natura, shortly after being harvested from the rubber tree. Moreover, and this is the main difference between the two, it is that in the present development, full use is made of the reactions between tannin and latex proteins, still in the field and with pH in the range of 7 to 9. As the tannin In fact, latex proteins are protected against bacteria without the use of ammonia. Therefore, tannin reacts with proteins and inactivates them, either to be the substratum of bacterial attacks or to act as allergens. Still, the efficacy in lowering free proteins, as pointed out by the inventors of Chinese technology, can not be attributed solely to tannin. It is known that the presence of ammonia in high concentrations can also break down the proteins into smaller pieces that are washed together with the aqueous serum during centrifugation (TARACHIWIN, L., et al., Rubber Chem Technol, 76 (5): 1177-1184, 2003).
Além disso, também é referido na literatura cientifica que o tanino demonstra menor eficácia de aproximação com as proteínas quando o meio está altamente alcalino (MARTIN, M. M., et al., J CHEM ECOL, 11(4) :485- 494, 1985), como é o caso do látex alto amónia utilizado no pedido de patente chinês . Portanto, o efeito desses dois fatores, a menor aproximação do tanino das proteínas com amónia e a quebra das proteínas pela amónia, fazem crer que parte do efeito conseguido na tecnologia não se deve à reação com tanino. Na medida em que o tratamento com tanino não tem amónia e o pH do meio é menor, a eficácia da ação do tanino sobre a proteína é maior (MARTIN, M. M., et al . , J CHEM ECOL, 11 ( 4 ) : 485- 494 , 1985), portanto com maior inativação das proteínas . In addition, it is also reported in the scientific literature that tannin demonstrates a lower efficacy of approach to proteins when the medium is highly alkaline (MARTIN, MM, et al., J CHEM ECOL, 11 (4): 485-494, 1985) , as is the case of the high ammonia latex used in the Chinese patent application. Therefore, the effect of these two factors, the less approximation of the tannin of the proteins with ammonia and the breakdown of the proteins by the ammonia, make believe that part of the effect achieved in the technology is not due to the reaction with tannin. As tannin treatment does not have ammonia and the pH of the medium is lower, the efficacy of the action of tannin on the protein is greater (MARTIN, MM, et al., J CHEM ECOL, 11 (4): 485- 494, 1985), therefore with greater inactivation of the proteins.
Adicionalmente, por não ter amónia, o tratamento de tanino do presente invento não proporciona a ocorrência de géis no látex, normalmente associados à presença da amónia em alta concentração, os quais alteram negativamente as propriedades do látex durante a estocagem, como o aumento da viscosidade (TARACHIWIN, L., et al., RUBBER CHEM TECHNOL, 76(5) : 1177-1184, 2003), entre outros . In addition, because of the lack of ammonia, the tannin treatment of the present invention does not provide for the occurrence of gels in the latex normally associated with the presence of ammonia in high concentration which adversely affect the properties of the latex during storage such as viscosity increase (TARACHIWIN, L., et al., Rubber Chem Technol, 76 (5): 1177-1184, 2003), among others.
Ainda referindo-se à incorporação de tanino ao LBN, o pedido de patente japonês JP2012207088 refere-se à preparação de mistura master batch, utilizada na fabricação de pneumáticos, que é uma incorporação de negro de fumo, compostos de vulcanização e outros componentes ao LBN, ainda líquido, para proporcionar uma mistura bem próxima desses ingredientes com a borracha. A introdução de tanino, conforme pleiteado na tecnologia japonesa, facilitaria a mistura da carga (negro de fumo) na preparação do máster batch pelas características dispersantes do tanino, permitindo, ainda, menor consumo de ácido sulfúrico na coagulação do master batch. Portanto, ainda que se refira ao uso de tanino em LBN, esta patente em nada é similar ao invento aqui apresentado. Still referring to the incorporation of tannin into the LBN, Japanese Patent Application JP2012207088 relates to the preparation of master batch blend, used in the manufacture of tires, which is a carbon black incorporation, vulcanization compounds and other components to the LBN, still liquid, to provide a close mixture of such ingredients with the rubber. The introduction of tannin, as claimed in Japanese technology, would facilitate the mixing of the charge (carbon black) in the preparation of the master batch by the dispersing characteristics of the tannin, allowing also a lower consumption of sulfuric acid in the coagulation of the master batch. Therefore, while referring to the use of tannin in LBN, this patent is in no way similar to the invention disclosed herein.
Outros documentos de patente podem ser aqui registrados para realce do problema dos alergênicos e da necessidade de tratamentos seja do látex, seja das luvas. No primeiro caso, encontra-se a patente estadunidense US8324312, que baseia a necessidade de tratar o LBN e reivindica o uso de hidróxido de alumínio no látex que, conforme bastante conhecido, tem a capacidade de aglomerar muitas moléculas, incluindo as proteínas, que, nesta condição, aglomeradas, têm maior facilidade de remoção do látex durante a centrifugação. Entretanto, a redução de proteínas do LBN pode levar à alteração das propriedades físico-mecânicas dos artefatos produzidos com este látex. Ademais, a possibilidade de resíduos do composto de alumínio pode comprometer, em parte, tal utilização. Outro pedido de patente estadunidense US5741885, reivindica a redução de alergenicidade de luvas de LBN, pelo tratamento de uma face da luva com compostos de detecção {screening) de alergias que resultaria que, pelo menos se teria reduzida a alergenicidade das luvas em uma face, ou mesmo, em parte de uma face da luva, conforme o tratamento. Esta invenção pode resultar em processo financeiramente dispendioso, pelos reagentes (de screening) que utiliza e não tão seguro, por resolver o problema parcialmente, pois a face não tratada da luva, pode conter alergênicos e acabar ficando em contato com mucosas de pacientes . Other patent documents can be registered here to highlight the problem of allergens and the need for treatments either latex or gloves. In the first case, U.S. Patent US8324312, which bases the need to treat LBN and claims the use of aluminum hydroxide in latex which, as is well known, has the ability to agglomerate many molecules, including proteins, which, in this agglomerated condition, have greater ease of latex removal during centrifugation. However, the reduction of LBN proteins may lead to changes in the physical-mechanical properties of the artifacts produced with this latex. Further, the possibility of residues of the aluminum compound may compromise, in part, such use. Another U.S. patent application US5741885 claims the reduction of allergenicity of LBN gloves by treating a glove face with allergy screening compounds which would result in at least reducing the allergenicity of the gloves on one side, or even part of one face of the glove, in accordance with treatment. This invention may result in a costly process by the screening reagents it uses and not so safe to partially solve the problem because the untreated glove may contain allergens and end up coming in contact with mucous membranes of patients.
Por outro lado, o pedido brasileiro PI0113709-3 trata de remover proteínas presentes em artefatos de LBN por três processos de lavagem sucessivos, um com água quente, outro com hidróxido alcalino e um final com um ou mais surfactantes . Esta tecnologia pode ser uma solução adequada na medida em que pode não alterar as propriedades mecânicas da borracha, pois o tratamento é posterior à fabricação dos artefatos e as proteínas já estarão imobilizadas na matriz de borracha. No entanto, estas mesmas proteínas, ao não serem removidas, poderão resultar reações alérgicas. On the other hand, Brazilian application PI0113709-3 attempts to remove proteins present in LBN artifacts by three successive washing processes, one with hot water, one with alkaline hydroxide, and one with one or more surfactants. This technology may be a suitable solution in that it may not alter the mechanical properties of the rubber because the treatment is subsequent to the manufacture of the artifacts and the proteins will already be immobilized in the rubber matrix. However, these same proteins, when not removed, may result in allergic reactions.
Desta forma, em comparação com algumas tecnologias existentes que possam se aproximar ao escopo da presente invenção, conclui-se que o presente invento contribui decisivamente para o avanço das técnicas produtivas na cadeia produtiva do látex de borracha natural ao viabilizar a produção de látex protegido sem o uso de amónia, e, por decorrência, isento de géis, para a fabricação de artefatos hipoalergênicos ou não alergênicos . Thus, in comparison with some existing technologies which may come close to the scope of the present invention, it is concluded that the present invention contributes decisively to the advancement of the productive techniques in the natural rubber latex production chain by enabling the production of protected latex without the use of ammonia, and therefore, free of gels, for the manufacture of hypoallergenic or non-allergenic artifacts.
DESCRIÇÃO SUCINTA DAS FIGURAS SUMMARY OF THE FIGURES
A invenção poderá ser mais bem compreendida com base nas Figuras 1 e 2, cuja descrição segue abaixo: A Figura 1 apresenta os resultados da medida de pH de: LA (baixo amónia), LAB (baixo amónia e bórax), HA (alto amónia) , TBL (tanino, bórax e LESS) e TBR (tanino, bórax e renex) . The invention may be better understood on the basis of Figures 1 and 2, the description of which is as follows: Figure 1 shows the results of the pH measurement of: LA (low ammonia), LAB (low ammonia and borax), HA (high ammonia), TBL (tannin, borax and LESS) and TBR (tannin, borax and renex).
A Figura 2 apresenta o potencial zeta (mV) das amostras em função do tempo.  Figure 2 shows the zeta potential (mV) of the samples as a function of time.
DESCRIÇÃO DETALHADA DA INVENÇÃO DETAILED DESCRIPTION OF THE INVENTION
A presente invenção tem aplicação tecnológica na cadeia produtiva do látex de borracha natural (LBN) , obtido da seringueira, Hevea brasiliensis, ou outra fonte qualquer. É produzido um LBN como matéria-prima estável e protegido contra degradação biológica, fluido, isento de amónia, para uso nas indústrias de transformação para produção de inúmeros produtos de uso geral, dentre eles, luvas cirúrgicas e de procedimento, camisinhas, sondas, cateteres, campos cirúrgicos dentre outros; em outra consequência, este LBN e os produtos dele derivados são de baixa ou nula alergenicidade . The present invention has technological application in the production chain of the natural rubber latex (LBN), obtained from the rubber tree, Hevea brasiliensis, or any other source. An LBN is produced as a stable and protected material against biological degradation, free of ammonia, for use in the processing industries for the production of numerous general purpose products, including surgical and procedural gloves, condoms, catheters , surgical fields among others; in another consequence, this LBN and the products derived therefrom are of low or no allergenicity.
A solução tecnológica deste pedido de patente consiste na aplicação de tanino vegetal em látex de borracha natural em substituição à amónia. Sem o emprego de amónia, hoje o preservante universalmente utilizado, obtém-se um LBN protegido contra degradação biológica e contra coagulação espontânea, de baixa ou nula alergenicidade. Além disso, o tanino inibe a formação de gel, evitando a produção de um látex mais viscoso que pode dar problemas em filmes como luvas e camisinhas, fenómeno que ocorre no látex atualmente. A alteração confere, também, maior estabilidade de armazenamento, evitando perdas e dificuldades de processamento industrial. The technological solution of this patent application is the application of vegetable tannin in natural rubber latex in place of ammonia. Without the use of ammonia, today the universally used preservative, is obtained a LBN protected against biological degradation and against spontaneous coagulation, of low or null allergenicity. In addition, tannin inhibits gel formation, avoiding the production of a more viscous latex that can cause problems in films such as gloves and condoms, a phenomenon that occurs in latex today. The amendment also provides greater storage stability, avoiding losses and difficulties of industrial processing.
Assim, o presente desenvolvimento alcança dois objetivos principais: 1) produzir látex de borracha natural protegido contra degradação biológica e da coagulação espontânea ou fisica; e 2) preparar LBN isento de alergias ou com alergenicidade reduzida e que estas características sejam repassadas aos produtos e artefatos produzidos a partir deste látex. Os produtos químicos a incorporar ao LBN de que trata o presente pedido são: Thus, the present development achieves two main objectives: 1) to produce natural rubber latex protected against biological degradation and spontaneous or physical coagulation; and 2) preparing allergen-free or allergen-sparing LBNs and that these characteristics are passed on to products and artifacts produced from this latex. The chemicals to be incorporated into the LBN dealt with in this application are:
Polifenol, manufaturado industrialmente ou produzido de qualquer outra forma, sendo preferencialmente tanino em pó ou como extrato vegetal liquido na forma in natura, ou processado, ou purificado, como o tanino degomado, ou o ácido tânico, ou ainda os tanantes sintéticos; Polyphenol, industrially manufactured or otherwise produced, preferably tannin powder or as liquid vegetable extract in the in natura form, or processed or purified, such as degassed tannin, or tannic acid, or synthetic tannins;
- Polifenol, como principal agente, em uma das suas formas, sendo preferencialmente o tanino, podendo ser utilizado de forma isolada, com aplicação limitada, ou em associação com produtos químicos, na condição de agentes secundários ou adjuvantes; Polyphenol, as the main agent, in one of its forms, preferably tannin, and may be used in isolation, with limited application, or in association with chemicals, as secondary agents or adjuvants;
Um bactericida, que pode ser o bórax (Na2B4<D7 · 1 OH2O) , também conhecido como borato de sódio ou tetraborato de sódio decahidratado em uma de suas formas de apresentação, ou seus derivados, ou outro bactericida qualquer; A bactericide, which may be borax (Na 2 B 4 D D 7 OH OH 2 O), also known as sodium borate or sodium tetraborate decahydrate in one of its presentation forms, or derivatives thereof, or any other bactericide;
- Um surfactante, que pode ser aniônico, como o lauril sulfato de sódio (ou dodecil sulfato de sódio) , ou outro qualquer, ou um surfactante não aniônico, como nonil fenol etoxilado em uma de suas formas, ou outro qualquer, ou ainda outro surfactante qualquer, como catiônico ou anfotérico; A surfactant, which may be anionic, such as sodium lauryl sulfate (or sodium dodecyl sulfate), or any other, or non-anionic surfactant, such as nonyl phenol ethoxylated in one of its forms, or any other, or any other surfactant, such as cationic or amphoteric;
- Um alcalinizante ou basificante, tais como o hidróxido de potássio, hidróxido de sódio, hidróxido de amónia, ou amónia, ou outro qualquer. An alkalizing or basifying agent, such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, or ammonia, or any other.
O látex de borracha natural hipoalergênico desenvolvido na presente invenção compreende a seguinte formulação básica: The hypoallergenic natural rubber latex developed in the present invention comprises the following basic formulation:
Io. Látex de campo in natura (LIN) ; I o . Field fresh latex (LIN);
2o. Bórax; 2 o . Borax;
3o. Hidróxido de potássio; 3 o . Potassium hydroxide;
4o . Polif enol , e 4 o . Polyphenol, and
5o. Surfactante. 5 o . Surfactant.
A ordem de adição dos compostos, na forma de soluções aquosas de concentrações variadas, é preferencialmente a que está supracitada, mas também pode variar conforme conveniência. Entretanto, não se deve misturar os quatro compostos de uma só vez e depois adicionar esta mistura ao látex, pois resulta na produção de um látex menos preservado biologicamente. The order of addition of the compounds, in the form of aqueous solutions of varying concentrations, is preferably that which is mentioned above, but may also vary according to convenience. However, one should not mix the four compounds at once and then add this mixture to the latex as it results in the production of a less biologically preserved latex.
A adição de compostos diretamente ao látex deve ser feita um por vez para que a mistura fique mais homogénea e as propriedades do látex se mantenham conservadas. Trata-se de uma formulação robusta, ou seja, que pode sofrer variações de uso em campo, onde normalmente falta formação técnica e os volumes adicionados podem variar em faixas de mais ou menos 10% em torno dos valores da melhor execução da invenção, sem que haja consequências graves ao látex. Pode ocorrer também em qualquer etapa da cadeia produtiva do LBN, seja no campo, na usina de centrifugação ou outra forma de processamento, ou seja, ainda, nas indústrias de transformação do LBN em artefatos e produtos derivados. The addition of compounds directly to the latex should be done one at a time so that the mixture becomes more homogeneous and the properties of the latex remain preserved. This is a robust formulation, that is, it can undergo variations of field use, where technical training is usually lacking and the added volumes may vary in ranges of plus or minus 10% around the values of the best embodiment of the invention without that there are serious consequences for latex. It can also occur at any stage of the LBN production chain, either in the field, in the centrifuge plant or other form of processing, that is, still, in the industries of transformation of the LBN in artifacts and derived products.
As particularidades do presente desenvolvimento foram avaliadas nos seguintes parâmetros no decorrer do tempo de ensaio: teste de cheiro, pH, ácidos graxos voláteis (AGV) , potencial zeta, tamanho da partícula e viscosidade Brookfield . The particularities of the present development were evaluated in the following parameters throughout the test time: smell test, pH, volatile fatty acids (VFA), zeta potential, particle size and Brookfield viscosity.
A liberação de ácidos graxos voláteis, muito característicos do processo de putrefação, pode ser monitorada como uma função do tempo para avaliar, mesmo que subjetivamente, se tal material está mais ou menos protegido contra o ataque bacteriano e assim determinar a sua degradação biológica. Na tabela I, são apresentados os tratamentos com tanino em comparação com os controles, protegidos com amónia, onde Coag indica amostra coagulada que não permite a execução do teste; Am indica amostra com forte cheiro de amónia que impede a realização do teste do cheiro (As notas variavam de 1, muito putrefato, a 10, muito agradável); LA: Tratamento baixo amónia; LAB: Tratamento baixo amónia com bórax; HA: Tratamento alto amónia; TBL: Tratamento tanino com bórax e tensoativo iônico; TBR: Tratamento tanino com bórax e tensoativo não-iônico. The release of volatile fatty acids, very characteristic of the putrefaction process, can be monitored as a function of time to evaluate, even subjectively, whether such material is more or less protected against bacterial attack and thus determine its biological degradation. In table I, the treatments with tannin are presented in comparison with the controls, protected with ammonia, where Coag indicates coagulated sample that does not allow the execution of the test; Am indicates sample with strong smell of ammonia that prevents the test of the smell (The scores ranged from 1, very rotten, to 10, very pleasant); LA: Treatment low ammonia; LAB: Low ammonia treatment with borax; HA: High ammonia treatment; TBL: Tannin treatment with borax and ionic surfactant; TBR: Tannin treatment with borax and non-ionic surfactant.
Tabela I Table I
Amostra/Tempo (horas)  Sample / Time (hours)
Trata¬ It is
Dl D2 D3 D4 D5 D6 D7 D8 mento Dl D2 D3 D4 D5 D6 D7 D8 ment
6h 30h 54h 78h 150h 222h 318h 408h  6h 30h 54h 78h 150h 222h 318h 408h
Coag Coag
LA 10 6 Coag . Coag . Coag . Coag . Coag . LA 10 6 Coag. Coag. Coag. Coag. Coag.
Coag Coag
LAB Am. Am. Am. Am. Am. Am. Am. Amostra/Tempo (horas) LAB Am. Am. Am. Am. Am. Am. Am. Sample / Time (hours)
Trata¬ It is
Dl D2 D3 D4 D5 D6 D7 D8 mento Dl D2 D3 D4 D5 D6 D7 D8 ment
6h 30h 54h 78h 150h 222h 318h 408h  6h 30h 54h 78h 150h 222h 318h 408h
Coag Coag
HA Am. Am. Am. Am. Am. Am. Am. HA Am. Am. Am. Am. Am. Am. Am.
TBL 10 10 10 9 8 7 7 5 TBL 10 10 10 9 8 7 7 5
TBR 10 10 10 9 9 8 5 8 TBR 10 10 9 9 8 5 8
A Tabela I mostra que todas as amostras com amónia coagularam entre o 2o (48h) e 17° dia (408 h) . As duas amostras com tanino estavam com cheiro muito agradável até o 17° dia de teste e assim permaneceram por mais de 6 dias . Table I shows that all samples with ammonia coagulated between 2 o (48 h) and 17 th day (408 h). The two samples with tannin had a very pleasant smell until the 17th test day and thus remained for more than 6 days.
A medida da concentração dos ácidos graxos voláteis (AGV) como função do tempo constitui uma medida objetiva da degradação bacteriana do material. A Tabela II mostra os resultados de análises de ácidos graxos voláteis do LBN com os diferentes tratamentos, e os resultados são fornecidos em números de AGV, segundo a American Society for Testing Materials (ASTM) D7610. Coa indica amostra coagulada e não há análise de AGV. Measurement of the concentration of volatile fatty acids (VFA) as a function of time is an objective measure of the bacterial degradation of the material. Table II shows the results of LBN volatile fatty acid analyzes with the different treatments, and the results are given in AGV numbers, according to the American Society for Testing Materials (ASTM) D7610. Coa indicates coagulated sample and there is no analysis of VFA.
Tabela II Table II
Figure imgf000027_0001
Figure imgf000027_0001
Como o número de AGV é uma medida direta do grau de degradação microbiológica de um material, sua leitura pode ser interpretada como uma corroboração dos resultados do teste de cheiro e uma confirmação da proteção microbiológica proporcionada pelo tanino. A amostra com alto amónia (HA) ainda se mantinha liquida (não coagulado) após 54 horas por ter sido mantida em geladeira. Mesmo assim, é notória a diferença de 0,38 (tratamento com tanino) para 0,93 (tratamento com amónia) após passadas 1268 horas, ou 53 dias. As the number of VFA is a direct measure of the degree of microbiological degradation of a material, its reading can be interpreted as a corroboration of the results of the smell test and a confirmation of the protection provided by tannin. The sample with high ammonia (HA) was still liquid (uncoagulated) after 54 hours because it had been kept in a refrigerator. Even so, the difference of 0.38 (treatment with tannin) to 0.93 (treatment with ammonia) after 1268 hours, or 53 days, is notorious.
Na Figura 1 é apresentado um gráfico que mostra a variação do pH em função do tempo das cinco amostras estudadas para embasamento experimental da presente invenção. É possivel observar indicações sobre a preservação anti-microbiana proporcionada pelo tanino ao LBN: In Figure 1 is presented a graph showing the variation of pH versus time of the five samples studied for experimental basement of the present invention. It is possible to observe indications on the antimicrobial preservation provided by the tannin to the LBN:
- O látex preservado com baixa amónia (LA) tem vida muito curta e antes de 24 horas já estava coagulado, não obstante o alto pH de partida, próximo de 9,5, evidenciando a elevada instabilidade do látex de partida, por questões de sazonalidade e temperatura no dia da coleta e instalação do ensaio; - The latex preserved with low ammonia (LA) has a very short life and before 24 hours was already coagulated, despite the high starting pH, close to 9.5, evidencing the high instability of the starting latex, due to seasonality and temperature on the day of collection and test installation;
- Os látex preservados no sistema baixo amónia com bórax (LAB) e com alto amónia (HA) , apresentam comportamentos similares, iniciando com pH de 8,7 e 9,7, respectivamente, e decrescendo o pH constantemente até coagularem com cerca de 320 horas e pHs na faixa de 6,7 e 7,7. Observa-se que este látex, muito instável, deve estar coagulado em pHs próximos desta faixa. - Latex preserved in the low ammonia system with borax (LAB) and high ammonia (HA) showed similar behaviors, starting with pH of 8.7 and 9.7, respectively, and decreasing the pH constantly until they coagulate with about 320 hours and pHs in the range of 6.7 and 7.7. It is observed that this latex, very unstable, must be coagulated at pHs close to this range.
No entanto, os dois látex preservados com tanino, TBL e TBR, têm comportamento similar, iniciando com pH mais elevado, entre 8 e 8,5, decrescem inicialmente, até o ponto de 6,5, mas não coagulam, e iniciam um crescimento continuo terminando em 6,8 e 7,4, respectivamente, quando se encerram as análises. Entretanto, as duas amostras não coagulam e apresentam bom estado visual e cheiro, corroborando que há efetiva proteção usando-se o tanino e os seus coadjuvantes. Estas amostras e outras preservadas com tanino neste mesmo plano experimental, mas não relatadas aqui, continuam por mais de seis meses, sem coagular e em bom estado. However, the two latexes preserved with tannin, TBL and TBR, have similar behavior, starting with a higher pH, between 8 and 8.5, initially decreasing to the point of 6.5, but not coagulating, and initiating a growth continued to finish at 6.8 and 7.4, respectively, when the analyzes are closed. However, the two samples do not coagulate and present good visual and odor status, corroborating that there is effective protection using tannin and its coadjuvants. These samples and others preserved with tannin in this same experimental plane, but not reported here, continue for more than six months, without coagulating and in good condition.
O tanino, polifenol de origem vegetal, protege as proteínas da degradação bacteriana, o que explica o aumento continuo e inequívoco de pH após chegar a um minimo próximo de 6,5. No entanto, todos os outros componentes passíveis de digestão microbiana, incluindo lipídios, fosfolipidios , carboidratos e carotenoides , estão sem proteção, a não ser pela presença do bórax, reconhecidamente um bactericida brando. A digestão de todos esses elementos que também geram ácidos graxos voláteis, estaria resultando no decréscimo continuado do pH até, provavelmente, a sua consumação integral. A partir dai, há acréscimo de pH por acomodação de cargas iónicas no coloide. Tannin, a plant-derived polyphenol, protects the proteins from bacterial degradation, which explains the continuous and unambiguous increase in pH after reaching a minimum of about 6.5. However, all other components susceptible to microbial digestion, including lipids, phospholipids, carbohydrates and carotenoids, are unprotected, except for the presence of borax, which is known to be a mild bactericide. The digestion of all these elements that also generate volatile fatty acids, would be resulting in the continued decrease of the pH until, probably, its complete consummation. Thereafter, there is an increase in pH by the accommodation of ionic charges in the colloid.
Assim, a proteção oferecida pelos polifenóis, como o tanino, ao coloide, não é de natureza iônica, ou seja, o que impede a coagulação das partículas não é a mútua repulsão de cargas iónicas, mas sim, o impedimento estéreo proporcionado pelos complexos de proteínas e taninos que se situam adsorvidos nas partículas de borracha. Thus, the protection offered by polyphenols, such as tannin, to the colloid, is not of an ionic nature, that is, what prevents the coagulation of particles is not the mutual repulsion of ionic charges, but rather the stereo impediment provided by the complexes of proteins and tannins that are adsorbed on the rubber particles.
Em um sistema coloidal, duas fases imisciveis entre si por diferença de polaridade coexistem, uma minoritária, no interior de micelas em geral esféricas, que ficam flutuando na outra fase. No caso do LBN, as partículas contêm a fase elastomérica , apolar, e a outra fase é constituída por um soro aquoso polar, que contém os elementos normalmente encontrados em um citoplasma celular vegetal. No caso do látex da seringueira, há outras partículas como os lutóides, que desempenham o papel de vacúolos celulares (JACOB, J. L., et al . CLIN REV ALLERG IMMU, 11: 325, 1993), que são envoltos em densa camada de enzimas onde se desenvolvem processos de síntese de compostos fundamentais para a biossíntese do elastomero (D'AUZAC, J., et al. PHYSIOL VÉG, 20(2) : 311-331, 1982) e, ainda, as partículas de Frey-Wisling, de função ainda não totalmente conhecida (CHOW, K. S., et al. J EXP BOT, 63 (5) : 1863-1871, 2012) . In a colloidal system, two phases immiscible with each other by polarity difference coexist, a minority, inside spherical micelles, which are floating in the other phase. In the case of LBN, particles contain the apolar elastomeric phase, and the other phase consists of a polar aqueous serum containing the elements normally found in a plant cell cytoplasm. In the case of rubber latex, there are other particles such as the fights, which play the role of cellular vacuoles (JACOB, JL et al., CLIN REV ALLERG IMMU, 11: 325, 1993), which are enveloped in a dense layer of enzymes where (AUZAC, J., et al., PHYSIOL VEG, 20 (2): 311-331, 1982) and the Frey-Wisling particles of function not yet fully known (CHOW, KS, et al., J EXP BOT, 63 (5): 1863-1871, 2012).
As partículas de borracha têm em sua superfície moléculas de fosfolipídios e proteínas, as quais se situam acima de seu ponto isoelétrico e, portanto, estão carregadas com cargas negativas. A proteção técnica tradicional do LBN é acentuar as cargas negativas das proteínas por adição de amónia em altos porcentuais que podem atingir 0,8% (m/v) . Nestes níveis, as partículas estão com elevada carga negativa, que impedem a fusão das partículas entre si, o que resultaria na coagulação do látex . Rubber particles have on their surface molecules of phospholipids and proteins, which are situated above their isoelectric point and, therefore, are charged with negative charges. The traditional technical protection of the LBN is to accentuate the negative charges of proteins by adding ammonia in high percentages that can reach 0.8% (m / v). At these levels, the particles have a high negative charge, which prevents the fusion of the particles between them, which would result in the coagulation of the latex.
O potencial zeta é uma medida da estabilidade de um coloide cujas partículas estão protegidas por cargas iónicas. Se estas forem negativas, o potencial zeta se situa abaixo de zero, como acontece com o LBN, conforme pode ser visto na Figura 2, mostra a evolução do potencial zeta no decorrer da análise das cinco amostras LA, LAB, HA, TBL e TBR. Observa-se que quando as amostras com proteção de amónia (baixo amónia (LA) , baixo amónia com bórax (LAB) ou alto amónia (HA) diminuem a sua proteção iônica e ficam com potencial zeta entre -29 mV e -25 mV, o sistema já está próximo a coagular, o que pode ser atestado pelo colapso visual das amostras. As amostras com proteção à base de tanino, apresentaram potencial zeta de menor proteção iônica (com menor valor absoluto) do que as amostras protegidas com amónia e já deveriam estar coaguladas se a proteção do coloide fosse principalmente iônica. Entretanto, esta coagulação não ocorreu nem mesmo passados vários meses, o que evidencia que outra forma de proteção coloidal está atuando proporcionado pela presença do tanino e os coadjuvantes da formulação. A utilização de tanino vegetal e outros polifenóis para proteção microbiológica do látex, como descrito na presente tecnologia, tem como um de seus diferenciais de inovação a ausência de amónia e, consequentemente, a possibilidade de se trabalhar com pHs mais baixos, o que resulta em menor formação de géis. Já foi possivel observar o espessamento e a maior viscosidade do látex com amónia, enquanto as amostras com tratamento de tanino estavam bastante fluidas, mesmo após vários meses de estocagem. Outro diferencial fundamental da atual tecnologia é a diminuição ou anulação dos efeitos alergênicos do LBN, que são ocasionados pela presença de treze proteínas, conforme já amplamente comprovado na literatura especializada (SUBROTO, T., et al., PHYTOCHEMISTRY, 43(1) : 29-37, 1996; ARI F, S. A. M. et al. J BIOL CHEM, 279(23) : 23933-23941, 2004; SHI, M . , et al . J BIOCHEM, 159(2) : 209-216, 2016) . Portanto, os efeitos alergênicos do látex podem ser monitorados indiretamente pela presença das proteínas, em geral, e em particular de proteínas já associadas aos processos alérgicos. Duas das treze proteínas, são as Hev b5 e Hev bl3, que já possuem protocolos de ensaio imunológico e cujas concentrações possuem um limite máximo aceito em determinados produtos . The zeta potential is a measure of the stability of a colloid whose particles are protected by ionic charges. If these are negative, the zeta potential lies below zero, as with the LBN, as can be seen in Figure 2, shows the evolution of the zeta potential during the analysis of the five samples LA, LAB, HA, TBL and TBR . It is observed that when samples with ammonia protection (low ammonia (LA), low ammonia with borax (LAB) or high ammonia (HA) decrease their ion protection and remain with zeta potential between -29 mV and -25 mV, The samples with tannin-based protection showed a zeta potential of less ion protection (with a lower absolute value) than samples protected with ammonia. and that the presence of tannin and the coadjuvants of the formulation may be due to the use of tannin vegetable and other polyphenols for microbiological protection of latex, as described in the present technology, has as one of its innovation differentials the absence of ammonia and hence the possibility of working with lower pHs, which results in less gellation. It was already possible to observe the thickening and higher viscosity of the latex with ammonia, while the samples with tannin treatment were very fluid, even after several months of storage. Another fundamental differential of the current technology is the decrease or cancellation of the allergenic effects of LBN, which are caused by the presence of thirteen proteins, as already widely proven in the specialized literature (SUBROTO, T., et al., PHYTOCHEMISTRY, 43 (1): 29-37, 1996; ARI F, SAM et al., J BIOL CHEM, 279 (23): 23933-23941, 2004; SHI, M. , et al. J BIOCHEM, 159 (2): 209-216, 2016). Therefore, the allergenic effects of latex can be monitored indirectly by the presence of proteins in general and in particular of proteins already associated with allergic processes. Two of the thirteen proteins are Hev b5 and Hev bl3, which already have immunological assay protocols and whose concentrations have an accepted upper limit on certain products.
As quantificações de proteínas Hev b5 e Hev bl3 do atual desenvolvimento foram realizadas pelo Centro de Pesquisas Tun Abdul Razak, com sigla em inglês TARRC, sediado em Hertfordshire, próximo a Londres, na Inglaterra. Esta instituição é especializada em pesquisas e avaliação de qualidade de artefatos de borracha em geral, bem como de determinação de parâmetros normatizados e aceitos em transações comerciais internacionais. É vinculada ao Malasian Rubber Board, do Governo da Malásia, e sua existência no Reino Unido é estratégica para a realização de pesquisas e para assegurar maior confiabilidade às exportações de borracha e de seus artefatos para a Europa, no âmbito de comércio vital para aquele pais, que se manteve por várias décadas como o principal fornecedor mundial desta commodity. The quantifications of Hev b5 and Hev bl3 proteins of the current development were carried out by the Tun Abdul Razak Research Center (TARRC), based in Hertfordshire, near London, England. This institution specializes in research and evaluation of the quality of rubber artifacts in general, as well as the determination of standardized and accepted parameters in international commercial transactions. It is linked to the Malaysian Rubber Board of the Government of Malaysia and its existence in the United Kingdom is strategic for conducting research and to ensure greater reliability for exports of rubber and its artifacts to Europe within the framework of vital trade for that country , which has remained for several decades as the world's leading supplier of this commodity.
Tabela III Table III
Sem Uma Duas centrifugar centrifugação centrifugações Without A Two Centrifugation Centrifuges
Amostra Hev Sample Hev
Hev b5 Hev b5 Hev bl3 Hev b5 Hev bl3 bl3  Hev b5 Hev b5 Hev bl3 Hev b5 Hev bl3 bl3
( g/g) ( g/g) ( g/g) ( g/g) ( g/g)  (g / g) (g / g) (g / g)
( g/g)  (g / g)
HA 0, 165 800 0, 079 100 0,066 50 HA 0, 165 800 0, 079 100 0.066 50
TBL <0, 02 <0, 02 TBL <0.02 <0.02
TBR <0, 02 1600 0, 073 120 0, 078 17 A Tabela I II mostra a quantificação das proteínas Hev b5 and Hev bl3, por TARRC, onde HA : tratamento alto amónia; TBL : tratamento com tanino, bórax e LESS e TBR : tratamento com tanino, bórax e renex. É possível observar que os dois principais tratamentos analisados foram os sistemas com alto amónia (HA) e o melhor de uma série de tratamentos, com tanino, bórax e renex (TBR), conforme conclusões tiradas a partir das variáveis comentadas anteriormente como pH, ácidos graxos voláteis, teste de cheiro e potencial zeta. Seguem as principais conclusões que se podem tirar desta tabela. TBR <0.02 1600 0, 073 120 0, 078 17 Table I II shows the quantification of the Hev b5 and Hev bl3 proteins, by TARRC, where HA: high ammonia treatment; TBL: treatment with tannin, borax and LESS and TBR: treatment with tannin, borax and renex. It is possible to observe that the two main treatments analyzed were the systems with high ammonia (HA) and the best of a series of treatments, with tannin, borax and renex (TBR), according to the conclusions drawn from the previously mentioned variables such as pH, acids volatile greases, smell test and zeta potential. The main conclusions can be drawn from this table.
Para a proteína Hev b5 há a supressão por parte nos dois tratamentos com tanino, uma vez que as concentrações ficam abaixo do limite de detecção, em três determinações de um total de cinco. Para a proteína Hev bl3, o tratamento com tanino requer que seja submetido à centrifugação, pois esta proteína se encontra no interior das partículas lutóides (ARI F, S. A. M., et al. J RUBBER RES, 9(1) : 40-49, 2006) que, à similaridade dos vacúolos em células biológicas em geral, são especializadas na transformação enzimática de moléculas para a biossíntese celular. Assim, o tanino não tem acesso imediato às proteínas Hev bl3 que se encontram nos lutóides, porém quando estas partículas são desfeitas durante a centrifugação, parte delas é eliminada com o soro aquoso do látex e parte permanece no látex, misturada ao creme com as partículas de borracha. A estas moléculas de Hev bl3, o tanino tem acesso e as complexa mudando o quadro de comparação entre os dois tratamentos: com alto amónia, a concentração (em μg/g) desta proteína alergênica passa somente por força das duas etapas de centrifugação, de 800 para 100 para 50 μg/g, enquanto o tratamento com tanino passa de 1600 (quando as proteínas não estão acessíveis) para 120 e para 17 μg/g, atingindo uma concentração inferior da proteína alergênica. For the Hev b5 protein there is suppression per part in the two treatments with tannin, since the concentrations are below the limit of detection, in three determinations of a total of five. For the Hev bl3 protein, the tannin treatment requires that it be subjected to centrifugation, as this protein is found inside the feroid particles (ARI F, SAM, et al J RUBBER RES, 9 (1): 40-49, 2006 ) that, to the similarity of vacuoles in biological cells in general, are specialized in the enzymatic transformation of molecules for cellular biosynthesis. Thus, the tannin does not have immediate access to the Hev bl3 proteins found in the fights, but when these particles are undone during centrifugation, part of them is eliminated with the aqueous serum of the latex and part remains in the latex, mixed with the cream with the particles of rubber. To these molecules of Hev bl3, the tannin has access and complexes changing the table of comparison between the two treatments: with high ammonia, the concentration (in μg / g) of this allergenic protein passes only by force of the two centrifugation steps, of 800 to 100 to 50 μg / g, while the tannin treatment goes from 1600 (when proteins are not accessible) to 120 and to 17 μg / g, reaching a lower concentration of the allergenic protein.
Desta forma, o tanino reage e complexa com as proteínas do látex, preservando biologicamente o material, sem o uso de amónia, e incluindo em suas reações de complexação, as proteínas alergênicas, sendo que para Hev b5, a concentração a fica abaixo do limite de detecção (0,02) do método de análise. In this way, the tannin reacts and complexes with the latex proteins, biologically preserving the material, without the use of ammonia, and including in its complexation reactions the allergenic proteins, and for Hev b5, the concentration a is below the limit (0.02) of the method of analysis.
MELHOR EXECUÇÃO DA INVENÇÃO BEST IMPLEMENTATION OF THE INVENTION
A melhor e mais equilibrada execução da tecnologia aqui descrita, denominada aqui de formulação básica, consiste na adição dos componentes na ordem apresentada a seguir, proporcionando agitação da mistura o suficiente para o melhor contato possível entre os reagentes: The best and most balanced execution of the herein described technology, referred to herein as the basic formulation, is to add the components in the order shown below, providing sufficient mixing of the mixture to the best possible contact between the reactants:
Io. Látex in natura (LIN), com aproximadamente 30% m/m de conteúdo de borracha, o mais cedo possível após coleta, 100 mL. I o . Latex in natura (LIN), with approximately 30% m / m of rubber content, as soon as possible after collection, 100 mL.
2o. Bórax, em solução aquosa a 5% m/m, adicionar 20 mL, perfazendo 1% (m/v) em relação ao LIN. 2 o . Borax, in 5% w / w aqueous solution, add 20 mL to 1% (w / v) relative to the LIN.
3o. Hidróxido de potássio, solução 2 mols/L, colocar de 1,2 a 1,5 mL, para atingir pH entre 8 e 9. 3 o . Potassium hydroxide, solution 2 mols / L, place from 1.2 to 1.5 mL, to reach pH between 8 and 9.
4o. Tanino comercial como extrato em pó da casca da acácia negra, em solução a 25%, preparada com um dia de antecedência, adicionar 2 mL, finalizando a 0,5%4 o . Commercial tannin and powdered extract of the black acacia bark in 25% solution, prepared one day in advance, add 2 mL, ending at 0.5%
(m/v) em relação ao LIN. (m / v) relative to the LIN.
5o. Lauril éter sulfato de sódio (LESS) como solução comercial a 23% = 4 mL, perfazendo cerca de 1% (m/v) em relação ao LIN. EXEMPLOS 5 o . Sodium lauryl ether sulfate (LESS) as a 23% commercial solution = 4 ml, making up to about 1% (w / v) in relation to LIN. EXAMPLES
No desenvolvimento da presente inovação tecnológica na cadeia produtiva do látex de borracha natural (LBN) , foram realizados vários conjuntos de experimentos, cada um contendo variáveis que envolviam os componentes da formulação, a concentração dos reagentes, o pH do meio e a forma de adição dos ingredientes. Seguem seis exemplos mais ilustrativos e representativos da invenção com os respectivos e necessários comentários de esclarecimento. É importante destacar que a presente invenção não se limita aos exemplos citados, podendo ser utilizada em todas as aplicações descritas ou em quaisquer outras variações equivalentes . In the development of the present technological innovation in the production chain of the natural rubber latex (LBN), several sets of experiments were carried out, each containing variables that involved the components of the formulation, the concentration of the reagents, the pH of the medium and the form of addition two ingredients. Here are six more illustrative and representative examples of the invention with the respective necessary clarification comments. It is important to note that the present invention is not limited to the cited examples and may be used in all described applications or in any other equivalent variations.
EXEMPLO 1: FORMULAÇÃO BÁSICA SUBSTITUINDO O EXTRATO EM PÓ DE TANINO PELO SEU EXTRATO DEGOMADO . EXAMPLE 1: BASIC FORMULATION REPLACING THE TANK POWDER EXTRACT BY ITS DEGOMED EXTRACT.
Esta solução foi proposta com a perspectiva de melhoria em ralação ao uso do tanino tradicional, porque este tem gomas e açucares na ordem de 25%, que poderiam influir negativamente na aplicação do tanino no LBN. No entanto, este uso do tanino degomado não apresentou melhora substancial em relação à formulação básica, fazendo com que seja descartada esta solução que poderia acarretar custo adicional desnecessário à invenção pleiteada. A explicação pode ser que as gomas e açucares inseridos no látex com o tanino normal, provavelmente não interferem na reação de tanino com as proteínas do látex e, acabam por sair no processo de centrifugação juntamente com outras impurezas. EXEMPLO 2: FORMULAÇÃO BÁSICA SUBSTITUINDO O SURFACTANTE IÔNICO (LESS) POR UM NÃO IÔNICO (Renex) . This solution was proposed with the prospect of improvement in relation to the use of traditional tannin, because it has gums and sugars in the order of 25%, which could negatively influence the application of tannin in the LBN. However, this use of degassed tannin did not show substantial improvement over the basic formulation, causing this solution to be discarded, which could lead to unnecessary additional cost to the claimed invention. The explanation may be that the gums and sugars inserted into the latex with the normal tannin probably do not interfere with the reaction of tannin with the proteins of the latex and they end up leaving the process of centrifugation together with other impurities. EXAMPLE 2: BASIC FORMULATION REPLACING THE IONIC SURFACTANT (LESS) FOR A NON-IONIC (Renex).
Este exemplo de tratamento proporcionou resultados muito positivos e no que concerne à proteção do látex e a retirada dos alergênicos, talvez até melhores e mais estáveis do que a formulação básica. No entanto, uma experimentação posterior, em que a amostra foi misturada intensamente por oito horas de agitação mecânica, apontou que o látex, apesar de ter um bom resultado com teste de cheiro e pH, apresentou uma visivel cremagem do látex, fenómeno caracterizado pela progressiva separação de fases quando o sistema é deixado em repouso, formando-se um creme superior, contendo o elastômero, e um inferior, o soro aquoso. Este é um processo muito pouco utilizado para concentrar o látex in natura de cerca de 30 % de borracha para 60 %, em comparação com o processo de centrifugação, que abrange a grande maioria do LBN concentrado internacionalmente. Esta cremagem será melhor estudada em para verificar a possibilidade de uso no processo de tratamento do látex com tanino. Entretanto, a melhor forma de execução da presente invenção é a aplicação da fórmula básica, ainda que não se exclua o uso imediato da fórmula apresentada neste exemplo, sem, no entanto, proceder o tratamento a longo processo de agitação. This example of treatment provided very positive results as regards the protection of latex and the withdrawal of allergens, perhaps even better and more stable than the basic formulation. However, a later experiment, in which the sample was mixed intensely by eight hours of mechanical agitation, pointed out that latex, despite having a good result with smell and pH test, presented a visible latex cremation, a phenomenon characterized by progressive separation of phases when the system is allowed to stand, forming a superior cream containing the elastomer, and a lower one, the aqueous serum. This is a very little used process for concentrating the latex in natura from about 30% rubber to 60% as compared to the centrifugation process, which covers the vast majority of the LBN concentrated internationally. This cremation will be better studied in order to verify the possibility of use in the treatment process of latex with tannin. However, the best embodiment of the present invention is the application of the basic formula, although immediate use of the formula given in this example is not excluded without, however, carrying out the long-term stirring treatment.
EXEMPLO 3: FORMULAÇÃO BÁSICA SUBSTITUINDO O EXTRATO EM PÓ DE TANINO DA CASCA DA ACÁCIA NEGRA PELO EXTRATOS EM PÓ DOS FRUTO DE MIRABOLANO E DE TARA. EXAMPLE 3: BASIC FORMULATION REPLACING THE EXTRACT IN TANK POWDER FROM BLACK ACACIA CASSETTE BY POWDER EXTRACTS OF MIRABOLAN AND TARA FRUIT.
O tanino de acácia negra é do tipo de polifenol condensado, enquanto os extratos tânicos obtidos dos frutos de mirabolano e tara são do tipo hidrolisável . Os testes preliminares de ambos também apontaram resultados positivos quanto aos testes de cheiro, pH e viscosidade Brookfield, comparando-se ao tanino da casca da acácia negra. No entanto, a cor da amostra de ambos se mostrou mais clara que a cor levemente amarronzada do tanino da casca da acácia negra, o que abre mais perspectivas de aplicação para a presente invenção. EXEMPLO 4 : FORMULAÇÃO BÁSICA, INVERTENDO A ORDEM DE ENTRADA DOS INGREDIENTES : a) entra o surfactante antes do tanino; b) entram todos juntos. The black acacia tannin is of the polyphenol type while the tannic extracts obtained from mirabolan and tara fruits are hydrolyzable. Preliminary tests of both also showed positive results regarding the smell, pH and Brookfield viscosity tests, comparing to the tannin of the black acacia bark. However, the color of the sample of both was clearer than the slightly tan color of the tannin of the black acacia bark, which opens up more perspectives of application for the present invention. EXAMPLE 4: BASIC FORMULATION, INVERTING THE ORDER OF ENTRY OF THE INGREDIENTS: a) enter the surfactant before the tannin; b) they all enter together.
A alteração da ordem de adição dos reagentes, mostrou-se importante para elucidar se há diferença de resultados com tais mudanças. O que se concluiu é que a alteração, colocando-se o surfactante antes do que o tanino, resultou em tratamentos praticamente iguais entre si, o que permite mais liberdade de tratamento em campo. No entanto, a sugestão é de que se mantenha a ordem de adição: bórax, KOH, tanino e surfactante. Por outro lado, a mistura de todos os ingredientes previamente à sua adição ao látex de campo resultou, de forma inequívoca, em um tratamento de pior proteção do látex. Portanto, recomenda-se que este procedimento não seja utilizado. Altering the order of addition of the reactants has proved important to elucidate whether there are differences in results with such changes. What was concluded is that the change, placing the surfactant before the tannin, resulted in almost equal treatments between each other, which allows more freedom of treatment in the field. However, the suggestion is to maintain the order of addition: borax, KOH, tannin and surfactant. On the other hand, the mixing of all the ingredients prior to their addition to the field latex resulted, unequivocally, in a poorer latex treatment treatment. Therefore, it is recommended that this procedure is not used.

Claims

REIVINDICAÇÕES
1. LÁTEX DE BORRACHA NATURAL, caracterizado por ser hipoalergênico, fluido, protegido contra degradação biológica, coagulação espontânea e isento de amónia. NATURAL RUBBER LATEX, characterized by being hypoallergenic, fluid, protected against biological degradation, spontaneous and ammonia-free coagulation.
2. LÁTEX DE BORRACHA NATURAL de acordo com a reivindicação 1, caracterizado pela inativação das proteínas alergênicas He h5 e Hev hl3. NATURAL RUBBER LATEX according to claim 1, characterized by the inactivation of the allergenic proteins He h5 and Hev hl3.
3. LÁTEX DE BORRACHA NATURAL de acordo com uma das reivindicações 1 ou 2 , caracterizado pela interação de suas proteínas alergênicas Hev h5 e Hev hl3 com polifenóis, preferencialmente o tanino.  NATURAL RUBBER LATEX according to one of claims 1 or 2, characterized by the interaction of its allergenic proteins Hev h5 and Hev hl3 with polyphenols, preferably tannin.
4. LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 1 a 3, caracterizado por ser associado a um surfactante tensoativo iônico e da interação com polifenóis, preferencialmente o tanino, em pH entre 7 e 9.  NATURAL RUBBER LATEX according to one of Claims 1 to 3, characterized in that it is associated with an ionic surface-active surfactant and the interaction with polyphenols, preferably tannin, at pH between 7 and 9.
5. LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 1 a 4, caracterizado por o surfactante tensoativo ser aniônico, como o lauril sulfato de sódio (ou dodecil sulfato de sódio) , ou outro, ou um surfactante não aniônico, como nonil fenol etoxilado em uma de suas formas, ou outro, ou ainda outro surfactante catiônico ou anfotérico .  NATURAL RUBBER LATEX according to one of Claims 1 to 4, characterized in that the surfactant surfactant is anionic, such as sodium lauryl sulfate (or sodium dodecyl sulfate), or other, or non-anionic surfactant, as nonyl phenol ethoxylated in one of its forms, or another, or other cationic or amphoteric surfactant.
6. LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 1 a 5, caracterizado por ser associado a um bactericida como borato de sódio ou tetraborato de sódio decahidratado (bórax) em uma de suas formas de apresentação, ou seus derivados e similares. NATURAL RUBBER LATEX according to one of Claims 1 to 5, characterized in that it is associated with a bactericide such as sodium borate or sodium tetraborate decahydrate (borax) in one of its presentation forms or derivatives and the like .
7. LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 1 a 6, caracterizado por ser associado a um alcalinizante ou basificante, tais como o hidróxido de potássio, hidróxido de sódio, hidróxido de amónia, ou amónia, ou outro qualquer de efeito similar. NATURAL RUBBER LATEX according to one of Claims 1 to 6, characterized in that it is associated with an alkalizing or basifying agent, such as potassium hydroxide, sodium hydroxide, ammonium hydroxide, or ammonia, or any of similar effect.
8. LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 1 a 7 , caracterizado por ser de origem vegetal, preferencialmente da seringueira de espécie Hevea brasiliensis . NATURAL RUBBER LATEX according to one of Claims 1 to 7, characterized in that it is of vegetable origin, preferably of the rubber tree of the Hevea brasiliensis species.
9. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL, conforme definido em uma das reivindicações de 1 a 8, caracterizado por consistir na adição direta ao látex in natura dos compostos: a. Bórax; b. Hidróxido de potássio; c. Polifenol; d. Surfactante. A process for the preparation of natural rubber latex as defined in one of claims 1 to 8, characterized in that it comprises direct addition to the in natura latex of the compounds: a. Borax; B. Potassium hydroxide; W. Polyphenol; d. Surfactant.
10. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL de acordo com a reivindicação 9, caracterizado por o bórax ser preferencialmente 20 mL em solução aquosa a 5%, perfazendo 1% (m/v) em relação a 100 mL de látex in natura. A process for the preparation of natural rubber latex according to claim 9, characterized in that the borax is preferably 20 ml in 5% aqueous solution, making up to 1% (w / v) relative to 100 ml of latex in natura.
11. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL de acordo com a reivindicação 9 ou 10, caracterizado por o hidróxido de potássio ser preferencialmente 1,2 a 1,5 mL de solução 2 mol/L. A process for the preparation of natural rubber selva according to claim 9 or 10, characterized in that the potassium hydroxide is preferably 1.2 to 1.5 ml of 2 mol / l solution.
12. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL de acordo com uma das reivindicações de 9 a 11, caracterizado por o polifenol ser preferencialmente 2 mL de tanino em solução a 25%, perfazendo 0,5% (m/v) em relação a 100 mL de látex in natura. A process for the preparation of natural rubber selva according to one of claims 9 to 11, characterized in that the polyphenol is preferably 2 ml of tannin in solution at 25% to 0.5% (w / v) relative to 100 mL of fresh latex.
13. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL de acordo com uma das reivindicações de 9 a 12, caracterizado por o surfactante ser preferencialmente um tensoativo iônico, compreendendo 4 mL de lauril éter sulfato de sódio (LESS) como solução comercial a 23%, perfazendo cerca de 1% (m/v) em relação a 100 mL de látex in natura. A process for the preparation of natural rubber lactone according to one of claims 9 to 12, characterized in that the surfactant is preferably an ionic surfactant comprising 4 ml of sodium lauryl ether sulfate (LESS) as a 23% commercial solution, to about 1% (w / v) relative to 100 mL of fresh latex.
14. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 9 a 13, caracterizado por o polifenol, preferencialmente o tanino, ser utilizado como preservante. A process for the preparation of natural rubber latex according to one of claims 9 to 13, characterized in that the polyphenol, preferably the tannin, is used as a preservative.
15. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 9 a 14, caracterizado por ocorrer em pH entre 7 e 9, preferencialmente 9. A method of obtaining natural rubber selva, according to one of claims 9 to 14, characterized in that the pH is between 7 and 9, preferably 9.
16. PROCESSO DE OBTENÇÃO DE LÁTEX DE BORRACHA NATURAL, de acordo com uma das reivindicações de 9 a 15, caracterizado por ser na complexação do látex in natura com polifenóis, preferencialmente o tanino. A process for the preparation of natural rubber latex according to one of claims 9 to 15, characterized in that in the complexing of the latex in natura with polyphenols, preferably the tannin, is used.
17. USO DE LÁTEX DE BORRACHA NATURAL, conforme definição em uma das reivindicações de 1 a 16, caracterizado por ser na fabricação de produtos de média ou delgada espessura, como luvas cirúrgicas ou de procedimento, campos cirúrgicos, drenos, cateteres, sondas, preservativos masculinos e femininos, tubos de látex, balões, entre outros produtos. Use of natural rubber latex as defined in one of claims 1 to 16, characterized in that it is for the manufacture of products of medium or thin thickness, such as surgical or procedural gloves, surgical fields, drains, catheters, probes, condoms men and women, latex tubes, balloons, among other products.
PCT/BR2018/050153 2017-05-12 2018-05-10 Hypoallergenic natural rubber latex, protected with polyphenols and free of ammonia, method for producing same and use thereof WO2018205003A1 (en)

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