Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
  • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
  • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B29/00—Layered products comprising a layer of paper or cardboard
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C1/00—Pretreatment of the finely-divided materials before digesting
  • D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C1/00—Pretreatment of the finely-divided materials before digesting
  • D21C1/10—Physical methods for facilitating impregnation
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C3/00—Pulping cellulose-containing materials
  • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/001—Modification of pulp properties
  • D21C9/007—Modification of pulp properties by mechanical or physical means
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/1026—Other features in bleaching processes
  • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
  • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
  • D21D1/20—Methods of refining
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
  • D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
  • D21H11/14—Secondary fibres
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/32—Bleaching agents
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes

Definitions

• the present invention relates to cellulose paper composite. More particularly, the present invention relates to a reinforced cellulose paper composite having enhanced tensile strength and tensile modulus and other parameters measured to determine strength of paper.
• Nanocellulose reinforced paper could be processed in existing paper machinery, does not contain any synthetic polymer and can also provide additional advantages in smoothness and folding endurance apart from tensile strength.
• the increase in specific surface area arising from reduced fibre diameter is expected to enhance the hydrogen bonding between the fibres when water is drained out. Further colloidal interaction and mechanical interlocking is also expected to increase with increase in surface area of cellulosic fibres.
• WO2017192476A1 discloses pulp product (e.g., paper) comprising cellulose and nanocellulose, wherein the nanocellulose is derived from the cellulose in a mechanical and/or chemical step that is separate from the main pulping process.
• the pulping process may be thermomechanical pulping or hydrothermal-mechanical pulping, for example.
• the pulp product is stronger and smoother with the presence of the nanocellulose.
• the nanocellulose improves the strength properties of the corrugated medium.
• the document further discloses that the addition of nanocellulose produced onsite gives a higher- strength corrugating medium product.
• EP3228744A1 discloses a use of nano cellulose for increasing dog ear resistance of a paper product, a method of manufacturing a semi-finished paper product suitable for manufacturing a valuable document, a semi-finished paper product as well as a valuable document comprising the nano cellulose coated semi-finished paper product.
• US20170072670A1 discloses a strong, light-weight composite laminates are made by impregnating layers of paper with a cellulose nanofiber (CNF) slurry, laying the coated papers up in a plurality of layers or stack, and subjecting the stack to pressure and heat for a period of time sufficient to cause the CNF to impregnate, reinforce, and bond the paper layers into a composite.
• the composite should have good strength to weight properties, and be recyclable or compostable, wherein the composite has a flexural strength of at least about 38 MPa and a flexural modulus of at least about 3.6 Gpa and wherein the composite has a tensile strength of at least about 52 MPa and tensile modulus of at least about 8.8 GPa.
• WO2010142846A1 discloses a method for manufacturing nano structured paper or board and a novel paper or board.
• the method comprises providing a liquid suspension of nanocellulose-containing material, forming a web from the suspension, and drying the web in order to form paper or board.
• the water content of the suspension from which the web is formed is 50 % or less by weight of liquids.
• energy consumption of paper manufacturing can be significantly reduced.
• WO2010142845A1 discloses a method for manufacturing nano structured paper or board and a novel paper or board.
• the method comprises providing a liquid suspension of nanocellulose-containing material, forming a web from the suspension and drying the web in order to form paper or board.
• the water content of the suspension at the time of beginning of the drying is 50 % or less by weight of liquids so as to form a paper or board having an average pore size between 200 and 400 nm.
• WO2011113998A1 discloses a method for improving the properties of a paper product and to the corresponding paper product, wherein the paper product is formed from a fiber-based material.
• the fines fraction is separated from chemical cellulose fiber -based pulp substantially after refining, and the cellulose fiber -based pulp from which the fines fraction has been separated is formed into the paper product in a papermaking apparatus.
• the invention relates to a method for manufacturing an additive component and to the corresponding additive component.
• WO2013076372A1 discloses a method of preparing a composite material, comprising: preparing a mixture containing water and cellulose, and at least one of graphite and graphene as an additive; and removing water to form the composite, wherein at least a portion of the cellulose comprises nanocellulose fibrils and the portion of the nanocellulose fibrils from the cellulose is between 0.1-100 %, such as 1-100%, for example 5-100 % in weight.
• US20100065236A1 discloses a method of producing cellulose based paper, the paper itself and the use thereof where the paper exhibits enhanced mechanical properties.
• the method involves providing a suspension of well dispersed modified cellulose at a low concentration.
• the properties and the chemical structure of the paper make it suitable for in vivo applications such as implant material, wherein the paper has a tensile strength of at least 250 MPa.
• WO2012098296A2 discloses a method for improving strength and retention in the manufacture of paper.
• a composition containing microfibrillated cellulose is provided in a fiber suspension, and from 0.1 to 10 w- % of microfibrillated cellulose by mass of the fiber suspension is added to improve the strength and retention of the product to be formed.
• the invention relates to a corresponding paper product.
• the present invention provides cellulose composite with enhanced tensile strength and tensile modulus.
• the main objective of the present invention is to provide cellulose composite having enhanced tensile strength and tensile modulus.
• Another objective of the present invention is to provide cellulose composite comprising 50 to 90 % of micro-cellulose and 10 to 50% of nanocellulose having enhanced tensile strength and tensile modulus.
• a cellulose paper composite comprising 80-85% of micro -cellulose and 15- 20&of nanocellulose, wherein the tear propagation resistance of the composite is increased by 50-70% is provided .
• the ratio (R) of tensile strength of sample with a existing cut or tear to the tensile strength of the sample without a cut is 75-95 %.
• an increase in tensile modulus is 15-40%, and tensile strength by 30-50 %, when compared to micro cellulose paper composite is achieved.
• the present invention provides a process for the preparation of said cellulose paper composite wherein said process comprising the steps of: a) cutting the nanocellulose source material into small pieces; b) subjecting the pieces of step (a) to alkali treatment by washing with base for 4 to 5 hours under mechanical stirring to form fibres; c) subjecting the fibres of step (b) for bleaching treatment by using bleaching solution at temperature ranging from 70°C to 80°C for the time period ranging from 3 to 4h; repeating process for 2 to 3 times to afford pulp; d) filtering and rinsing the pulp of step (c) followed by grinding the pulp in ultra-fine micro grinder and e) combining the nanocellulose pulp prepared as per above steps (a-d) with microcellulose pulp in different compositions to make a composite paper.
• the nanocellulose source material of step (a) is selected from cotton rag, sugarcane bagasse and sisal fibers.
• the alkali treatment of step (b) is carried out by washing small pieces of nanocellulose source material with 1-10% base solution at 50 to 80°C.
• the alkali treatment of step (b) is carried out by washing small pieces of nanocellulose source material with 1-10% sodium hydroxide solution at 50 to 80°C.
• the bleaching solution of step (c) comprises 1 : 1 ratio of aqueous sodium hypochlorite (NaOCl in water) and an acetate buffer (NaOH and glacial acetic acid, diluted to 1 L using distilled water).
• the fiber to liquor ratio is maintained 1:30 for both alkali and bleaching treatment.
• the present invention provides a reinforced cellulose paper composite comprising 50 to 90 % of micro-cellulose and 10 to 50% of nanocellulose having enhanced tensile strength and tensile modulus.
• the higher surface area of nanocellulose fibrils leads to more number of hydrogen bonds and more bonding area between the microcellulose and nanocellulose which linked with good mechanical interlocking provide necessary strength and stiffness to the composite paper.
• the present invention provides a reinforced cellulose paper composite comprising 50 to 90 % of micro-cellulose and 10 to 50% of nanocellulose having enhanced tensile strength and tensile modulus.
• the present invention provides a cellulose paper composite comprising 80 to 85 % of micro-cellulose and 15 to 20% of nanocellulose having enhanced tensile strength and tensile modulus.
• the tensile strength of reinforced cellulose paper composite is in the range of 20-50 MPa.
• the tensile strength of with cut and without cut sample of cotton rag nanocellulose is in the range of 20-35 MPa and 25-40 MPa respectively.
• the tensile modulus of reinforced cellulose paper composite is in the range of 3150 to 5050 MPa.
• the present invention provides a process for the preparation of said Reinforced Cellulose Paper composite comprising the steps of: a) cutting the nanocellulose source material into small pieces; b) subjecting the pieces of step (a) to alkali treatment by washing with base for 4 to 5 hours under mechanical stirring to form fibres; c) subjecting the fibres of step (b) for bleaching treatment by using bleaching solution at temperature ranging from 70°C to 80°C for the time period ranging from 3 to 4h; repeating process for 2 to 3 times to afford pulp; d) filtering and rinsing the pulp of step (c) followed by grinding the pulp in ultra-fine micro grinder and e) combining the nanocellulose pulp prepared as per above steps (a-d) with microcellulose pulp in different compositions to make a composite paper.
• the nanocellulose source material of step (a) is selected from cotton rag, sugarcane bagasse or sisal fibers.
• the alkali treatment of step (b) is carried out by washing small pieces of nanocellulose source material with 1-10% base solution at 50 to 80°C.
• the alkali treatment of step (b) is carried out by washing small pieces of nanocellulose source material with 1-10% sodium hydroxide solution at 50 to 80°C.
• the bleaching solution of step (c) comprises 1 : 1 ratio of aqueous sodium hypochlorite (NaOCl in water) and an acetate buffer (NaOH and glacial acetic acid, diluted to 1 L using distilled water).
• the fiber to liquor ratio are maintained 1:30 for both alkali and bleaching treatment.
• the nanocellulose pulp of step (d) is combined with microcellulose pulp to afford composite paper.
• the present invention provides a paper making process comprising the steps of: a) preparing A4 printing paper pulp with the consistency of 1.2 to 1.57 wt%; b) beating the pulp in valley beater to get required Schopper-Riegler (SR) value, e.g. 40, 50, or 60 as per requirement and c) adding said A4 recycled pulp of step (b) to sheet former machine to form paper.
• SR Schopper-Riegler
• different source of nanocellulose/ A4 recycled composites paper are made by varying nanocellulose content from 10 to 50 %.
• the process is carried out at ambient temperature.
• the present invention provides effect of with cut and without cut sample of nanocellulose source material on tensile strength and tensile modulus of A4 recycled paper.
• Table 1 represent the effect of cotton rag (CR) nano cellulose on the mechanical properties of the composite paper. Values in bracket represent the standard deviation.
• the tensile strength of with cut and without cut sample of cotton rag nanocellulose is in the range of 25-35 MPa and 35-40 MPa respectively.
• the tensile modulus of with cut and without cut sample of cotton rag nanocellulose is in the range of 3250-4330 MPa and 3600-4400 MPa respectively.
• Table 2 represent the effect of sugarcane (SC) nanocellulose on the mechanical properties of the composite paper. Values in bracket represent the standard deviation.
• the tensile strength of with cut and without cut sample of sugarcane nanocellulose is in the range of 25-40 MPa and 30-50 MPa respectively.
• the tensile modulus of with cut and without cut sample of sugarcane nanocellulose is in the range of 3500-5100 MPa and 3400-4200 MPa.
• Table 3 represent the effect of sugarcane nano cellulose from sisal on the mechanical properties of the composite paper. Bracket value represents the standard deviation. Table 3:
• the tensile strength of with cut and without cut sample of sisal nanocellulose is in the range of 25-35 MPa and 30-40 MPa.
• the tensile modulus of with cut sample of sisal nanocellulose is in the range of 3500-4800 MPa and 3700-4300 MPa respectively.
• the ratio of tensile strength and tensile modulus for Cotton rag, sugarcane and sisal nano cellulose paper composites is listed in Table 4
• R ratio of tensile strength with cut to tensile strength without cut
• R is a measure of tear propagation resistance to total tear resistance
• Total tear resistance consists of tear initiation and tear propagation resistance
• the tensile strength and tensile modulus in table 4 is expressed as a ratio of tensile strength or modulus of paper measured for each concentration of nano cellulose (with or without cut) to tensile strength or modulus of A4 paper(with or without cut respectively).
• an increase in tensile modulus by 15-40%, preferably 20-40%, is achieved by the addition of 15-20% nano cellulose for uncut paper.
• an increase in tensile strength by 30-50 % is achieved by the addition of 15-20% nano cellulose for uncut paper.
• the ratio (R) of tensile strength of sample with a existing cut or tear (which is a measure of only tear propagation resistance) to the tensile strength of the sample without a cut ( a measure of both tear initiation and propagation resistance) is measured. Referring to table 4, a 75-95% enhancement is seen for an addition of 15-20 nano cellulose. In a preferred embodiment, the ratio R is enhanced by 80-90% for an addition of 15-20 nano cellulose.
• Tear propagation resistance is studied. Tear propagation resistance is the ratio of ratio of tensile strength of paper with cut measured for each concentration of nano cellulose to tensile strength or modulus of A4 paper with cut. The tear propagation resistance of cut paper is increased by 50-70% for an addition of 15-20% nano cellulose to micro cellulose. The tear propagation resistance is preferably enhanced by 50-65% by the addition of 15-20% nano cellulose to micro cellulose.
• the figure 1 is pictorial representation of nanocellulose preparation form the raw source material.
• Al, B l, CI represent the raw material sugarcane bagasse, cotton rag and sisal respectively.
• A2, B2, C2 represent the bleached pulp of sugarcane bagasse, cotton rag and sisal respectively.
• A3, B3, C3 represent the final nanocellulose product of sugarcane bagasse, cotton rag and sisal respectively.
• the figure 2 shows with cut and without cut samples. Without cut samples data gives information about tensile strength and modulus for the specimen which is not having any deformation in it. It is similar to Edge-tearing strength (TAPPI standard T-470) and is a measure of the force needed to initiate a tear. With cut samples data gives information about tensile strength and modulus of a specimen where a tear is already initiated. This is similar to commonly used tearing test (TAPPI T-414), also often called the Elmendorf tear test, which measures the internal tearing resistance of paper rather than the edge-tear strength of paper.
• TAPPI T-414 also often called the Elmendorf tear test
• the paper composite prepared by the composition of the invention comprising 80-85% micro cellulose and 15-20% nano cellulose is useful in preparing security documents.
• the paper composition of the invention has enhanced folding resistance and is smooth and is versatile to be used for preparing paper for security applications.
• Security documents are documents made of paper that need to identified or authenticated as genuine using security features and are selected from, but not limited to currency notes, passports, bonds, certificates, agreements, stamp or stamp paper, share certificates and such like. Examples Following examples are given by way of illustration therefore should not be construed to limit the scope of the invention.
• the nanocellulose source material was cut into small pieces. Alkali treatment was carried out by washing the pieces with base for 4 to 5 hours under mechanical stirring to form fibres. Bleaching treatment was carried out on fibres by bleaching solution at the temperature ranging from 70°C-80°C for the time period ranging from 3 to 4h; repeating process for 2 to 3 times to afford pulp. Then it was filtered and rinsed followed by grinding said pulp in ultra- fine micro grinder. Then the nano cellulose pulp was combined with micro cellulose pulp to form composite paper in ratios listed in the tables. After drying the paper are tested by tensile testing machine (INSTRON UTM) at rate lmm/min. The 13 mmX40 mm rectangular shape specimen are used. At least 6 specimens were tested for each composition listed below in the tables 1-3. Two types of mode were tested with cut and without cut.
• INHTRON UTM tensile testing machine

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• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Mechanical Engineering (AREA)
• Paper (AREA)

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• 2018
  • 2018-10-05 EP EP18864422.3A patent/EP3692206A4/de not_active Withdrawn
  • 2018-10-05 WO PCT/IN2018/050632 patent/WO2019069325A1/en not_active Ceased
  • 2018-10-05 JP JP2020519313A patent/JP2021508007A/ja active Pending
  • 2018-10-05 US US16/753,888 patent/US20200340182A1/en not_active Abandoned

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