CN117418416A - Bacterial cellulose sheet and preparation method and application thereof - Google Patents
Bacterial cellulose sheet and preparation method and application thereof Download PDFInfo
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- CN117418416A CN117418416A CN202210809034.XA CN202210809034A CN117418416A CN 117418416 A CN117418416 A CN 117418416A CN 202210809034 A CN202210809034 A CN 202210809034A CN 117418416 A CN117418416 A CN 117418416A
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- 229920002749 Bacterial cellulose Polymers 0.000 title claims abstract description 152
- 239000005016 bacterial cellulose Substances 0.000 title claims abstract description 152
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 58
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 229920000742 Cotton Polymers 0.000 claims description 13
- 230000035699 permeability Effects 0.000 claims description 11
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 10
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 10
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 10
- 239000011425 bamboo Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000010009 beating Methods 0.000 claims description 8
- 241000196324 Embryophyta Species 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
- 238000000855 fermentation Methods 0.000 claims description 5
- 230000004151 fermentation Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 239000012209 synthetic fiber Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000003385 bacteriostatic effect Effects 0.000 claims 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 238000003756 stirring Methods 0.000 description 9
- 241001330002 Bambuseae Species 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000209128 Bambusa Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- WQZGKKKJIJFFOK-UHFFFAOYSA-N alpha-D-glucopyranose Natural products OCC1OC(O)C(O)C(O)C1O WQZGKKKJIJFFOK-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 235000020415 coconut juice Nutrition 0.000 description 1
- 235000020197 coconut milk Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000008104 plant cellulose Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose 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
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- 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
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Paper (AREA)
Abstract
The invention provides a bacterial cellulose sheet, a preparation method and application thereof, wherein the preparation method comprises the following steps: modifying the bacterial cellulose homogenate by using a modifier to obtain modified bacterial cellulose homogenate; mixing the modified bacterial cellulose homogenate with fiber slurry to obtain net-surfing slurry, and forming by papermaking to obtain the bacterial cellulose sheet; wherein the dry weight content of the bacterial cellulose in the bacterial cellulose sheet is 30-90%. The invention overcomes the problems that the composite pulp has poor drainage property and strong adhesiveness and can not be uncovered in the papermaking process by regulating and controlling the particle size and content of the bacterial cellulose, the performance index of the composite fiber pulp and the parameters of the forming net material, so that the papermaking process is suitable for continuous production equipment such as a paper machine and the like, and continuous and industrialized production of the bacterial cellulose sheet is realized.
Description
Technical Field
The invention relates to the technical field of cellulose membrane preparation, in particular to a bacterial cellulose sheet and a preparation method and application thereof.
Background
Bacterial cellulose is a porous reticular nano-level biopolymer synthesized by microbial fermentation, is one of the most abundant natural biopolymer polymers in the world, has the characteristics of high specific surface area, biodegradability, environmental protection, excellent properties, higher purity and the like, and is widely applied to the fields of papermaking, foods, biology, medicine, sound and the like. The chemical structure of bacterial cellulose is a linear polysaccharide formed by connecting D-glucopyranose with beta-1, 4 glycosidic bond, and the chemical formula is (C 6 H 10 O 5 ) n The modified cellulose has the same chemical structure as that of plant cellulose, has rich hydroxyl structure, has natural advantage of excellent combination property, and has great use value in the paper industry.
Bacterial cellulose has a higher specific surface area, a spatial network structure and a large number of effective hydroxyl active sites, and can be compounded with other organic or inorganic molecules in various modes such as biological modification, physical modification, chemical modification and the like so as to obtain various new functions.
The existing bacterial cellulose is mainly produced by tray one-time fermentation, and has the problems of discontinuous bacterial cellulose film, strong dry film brittleness, difficult post-processing, low utilization rate, poor direct modification uniformity, low efficiency and the like, so that the existing bacterial cellulose is not suitable for direct and large-batch use, and a technical method for regenerating the bacterial cellulose film to form a continuous and industrialized sheet is required to be developed.
Chinese patent CN111118947A adsorbs rare earth luminescent element ions to bacterial cellulose to form a complex, and then the complex is compounded with plant fiber slurry to prepare fluorescent paper with high fluorescence performance and high durability, but in the paper making process, after the addition of bacterial cellulose is more than 1%, the fluorescent paper can only be formed by adopting a suction filtration method due to difficult dehydration.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a bacterial cellulose sheet, a preparation method and application thereof, and continuous and industrialized production of bacterial cellulose films is realized.
In order to achieve the above object, the present invention provides a method for preparing a bacterial cellulose sheet, comprising the steps of:
modifying the bacterial cellulose homogenate by using a modifier to obtain modified bacterial cellulose homogenate;
mixing the modified bacterial cellulose homogenate with fiber slurry to obtain net-surfing slurry, and forming by papermaking to obtain the bacterial cellulose sheet;
wherein the dry weight content of bacterial cellulose in the bacterial cellulose sheet is 30-90%;
in the bacterial cellulose homogenate, the average size of bacterial cellulose particles is 0.5-1.5mm, and the mass ratio of the bacterial cellulose particles with the size less than or equal to 0.2mm in the total amount of the particles is less than 60%;
the beating degree of the fiber slurry is 20-60 DEG SR, and the fiber length is 0.6-2mm;
the forming web used for papermaking has the following parameters: air permeability 5500-6600m 3 /m 2 h, fiber support index is 150-200fsi, support point is 1300-1500sp/cm 2 。
According to a specific embodiment of the present invention, in the above preparation method, preferably, the bacterial cellulose sheet has a dry weight content of bacterial cellulose of 50 to 70%.
According to a specific embodiment of the present invention, in the above-mentioned production method, preferably, the bacterial cellulose homogenate is obtained by granulating and then homogenizing or grinding a bacterial cellulose fermentation product. Specifically, the preparation method of the bacterial cellulose homogenate comprises the following steps: cutting the bacterial cellulose fermentation product into particles or films by a granulator, and grinding the bacterial cellulose particles by a homogenizer, colloid mill or grinder to obtain bacterial cellulose homogenate.
According to a specific embodiment of the present invention, in the above preparation method, preferably, the modifier is selected from one or more of anti-counterfeiting substance, antibacterial material, and papermaking auxiliary agent, and the papermaking auxiliary agent is selected from wet strength agent or dry strength agent.
According to a specific embodiment of the present invention, in the above-mentioned production method, preferably, the modifying agent modifies the bacterial cellulose homogenate biologically, chemically or physically.
Specifically, the modifier is added in the following three ways:
(1) Biological mode: adding a modifier into a bacterial cellulose culture solution, and grafting or adsorbing the bacterial cellulose onto the bacterial cellulose in a biological modification mode;
(2) The physical mode is as follows: slowly adding the aqueous dispersion of the modifier into the bacterial cellulose homogenate, and stirring to uniformly adsorb the aqueous dispersion on the bacterial cellulose;
(3) The chemical mode is as follows: the modifier is grafted onto the bacterial cellulose by a chemical reaction.
According to a specific embodiment of the present invention, in the above preparation method, preferably, the equipment used for papermaking is selected from cylinder machine, fourdrinier, inclined wire machine or kesai sheet machine. Therefore, the preparation method of the bacterial cellulose sheet can realize continuous and industrialized production.
According to a specific embodiment of the present invention, in the above-mentioned production method, preferably, the fiber is selected from plant fibers and/or chemical synthetic fibers; the plant fiber is selected from one or more of cotton, hemp, wood and bamboo. The addition of the fiber component makes the sheet more flexible in dry state, less prone to breakage, and convenient for diversified post-processing and application.
The invention also provides a bacterial cellulose sheet obtained by the preparation method, which is prepared from the following raw materials in percentage by weight: 30-90% of bacterial cellulose, 0.5-30% of modifier and the balance of fiber.
According to a specific embodiment of the present invention, preferably, the bacterial cellulose sheet is prepared from the following raw materials in percentage by weight: 50-70% of bacterial cellulose, 0.5-30% of modifier and the balance of fiber.
According to a specific embodiment of the present invention, the bacterial cellulose flakes preferably have a basis weight of 10 to 40g/m 2 The thickness is 15-60 μm.
The invention also provides application of the bacterial cellulose sheet in preparation of anti-counterfeiting objects and/or antibacterial paper.
According to a specific embodiment of the present invention, in the above application, preferably, the security object is security paper, security fiber or security label.
The technical scheme provided by the invention has the following beneficial effects:
(1) The invention overcomes the problems that bacterial cellulose has poor drainage property and strong adhesiveness and can not be uncovered in the papermaking process by regulating and controlling the particle size and content of the bacterial cellulose, the performance index of the compound fiber slurry and the parameters of the forming net material, so that the papermaking process is suitable for continuous production equipment such as a paper machine and the like, and continuous and industrialized production of bacterial cellulose sheets is realized;
(2) The bacterial cellulose sheet has the bacterial cellulose content of 30% -90%, can fully exert the characteristics of higher specific surface area and spatial network structure of the bacterial cellulose, strengthens the bearing effect of the bacterial cellulose sheet on the modifier, and can better exert the additional function of the sheet;
(3) The bacterial cellulose sheet has ultrahigh bacterial cellulose content, is easy to wet, has strong toughness in a wet state and multiple free hydroxyl groups, is convenient to process into a marker, and has good binding fastness when being added into anti-counterfeiting paper; in addition, the bacterial cellulose sheet has higher wet strength, and can adapt to the papermaking process after proper cutting processing to manufacture anti-counterfeiting paper;
(4) The bacterial cellulose sheet has low morphological requirements on bacterial cellulose wet films and particles, can be produced by utilizing leftover materials, optimizes an industrial structure and reduces production cost.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The bacterial cellulose wet film adopted in the embodiment of the invention is prepared by the method disclosed in the embodiment 1 of the Chinese invention patent CN96100534.3, and specifically comprises the following steps: 1000g of coconut water is filtered, then 100 ℃ is heated, 100g of sugar and 4.5g of ammonium sulfate are added, the mixture is melted and stirred uniformly, the mixture is cooled to normal temperature, 3g of saccharomycetes, 10g of glue film acetic acid bacteria and 5g of lactic acid bacteria are inoculated, and the mixture is fermented for 5 days to become white semitransparent solid, cut into blocks and sterilized to obtain the coconut milk.
The invention is described below in connection with specific embodiments.
Example 1
The embodiment provides a preparation method of a bacterial cellulose sheet, which specifically comprises the following steps:
(1) Cutting the bacterial cellulose wet film into particles with the size of 5mm by a granulator, grinding the particles into bacterial cellulose homogenate with the average particle size of 0.93mm and the mass ratio (based on the total weight of the particles) of 45% of the particles with the size of less than 0.2mm by a colloid mill;
(2) Adding 3.2% of wet strength agent and 1.8% of dry strength agent into bacterial cellulose homogenate based on dry weight of bacterial cellulose for modification, and uniformly stirring to obtain modified bacterial cellulose homogenate;
(3) Mixing the obtained modified bacterial cellulose homogenate with a fiber slurry at a dry weight ratio (bacterial cellulose to fiber dry weight ratio) of 6:4 to form a netty slurry; wherein the fiber length of the fiber slurry is 1.72mm, the beating degree is 35 DEG SR, and the fibers in the fiber slurry consist of cotton and PA66 fibers with the mass ratio of 3:1;
(4) The sheet is manufactured by using a Kaiser sheet machine, and the forming wire is a polyester wire (air permeability 6600 m) 3 /m 2 h. Fiber support index 197fsi, support point 1365sp/cm 2 ) The quantitative ratio is 30.63g/m 2 Is a bacterial cellulose sheet of (a).
The bacterial cellulose flakes prepared in this example comprise the following components in weight percent: 57% of bacterial cellulose, 1.92% of wet strength agent, 1.08% of dry strength agent, 30% of cotton and 10% of PA66 fiber.
The sheet was tested to have a thickness of 41 μm, a gas permeability of 11mL/min, a fracture length of 6098m, an elongation of 2.28% and a wet strength of 38.7%. The sheet was cut into 4X 4mm squares, and was put into a high-frequency fluffer (frequency: 3000 rpm), immersed for 24 hours, and fluffed for 360000 rpm, and remained intact.
Example 2
The embodiment provides a preparation method of a bacterial cellulose sheet, which specifically comprises the following steps:
(1) Cutting the bacterial cellulose wet film into particles with the size of 5mm by a granulator, grinding the particles into bacterial cellulose homogenate with the mass ratio (based on the total weight of the particles) of 51% of the particles with the average size of 0.97mm and the size of less than 0.2mm by a colloid mill;
(2) Based on the dry weight of bacterial cellulose, adding 3% of wet strength agent and 2% of dry strength agent into bacterial cellulose homogenate for modification, and uniformly stirring to obtain modified bacterial cellulose homogenate;
(3) Mixing the obtained modified bacterial cellulose homogenate with bamboo fiber slurry at a dry weight ratio of 6:5 (dry weight ratio of bacterial cellulose to bamboo fiber) to form a net-surfing slurry; wherein the fiber length of the bamboo fiber slurry is 1.52mm, and the beating degree is 42 DEG SR;
(4) Paper making is carried out by using a fourdrinier machine, and a forming wire is a polyester wire (air permeability 6600m 3 /m 2 h. Fiber support index 197fsi, support point 1365sp/cm 2 ) The quantitative yield was 27.64g/m 2 Is a bacterial cellulose sheet of (a).
The bacterial cellulose flakes prepared in this example comprise the following components in weight percent: 51.82% of bacterial cellulose, 1.64% of wet strength agent, 1.09% of dry strength agent and 45.45% of bamboos.
The sheet was tested to have a thickness of 38 μm, a permeability of 1.8mL/min, a fracture length of 6128m, an elongation of 1.98% and a wet strength of 36.6%. The sheet was cut into 4X 4mm squares, and was put into a high-frequency fluffer (frequency: 3000 rpm), immersed for 24 hours, and fluffed for 360000 rpm, and remained intact.
Example 3
The embodiment provides a preparation method of a bacterial cellulose sheet, which specifically comprises the following steps:
(1) Cutting the bacterial cellulose wet film into particles with the size of 5mm by a granulator, grinding the particles into bacterial cellulose homogenates with the average size of 0.93mm and the mass ratio (based on the total weight of the particles) of 45% of the particles with the size of less than 0.2mm by a colloid mill;
(2) Adding 5% of near infrared up-conversion fluorescent anti-counterfeiting powder (average particle diameter 713 nm) into bacterial cellulose homogenate by taking dry weight of bacterial cellulose as a reference, stirring for 30min, adding 3% of wet strength agent and 2% of dry strength agent, and stirring uniformly to obtain modified bacterial cellulose homogenate;
(3) Mixing the obtained modified bacterial cellulose homogenate with cotton fiber slurry at a dry weight ratio of 7:3 (dry weight ratio of bacterial cellulose to cotton fiber) to form a net-feeding slurry; wherein, the fiber length of the cotton fiber slurry is 1.45mm, and the beating degree is 48 DEG SR;
(4) Paper making is carried out by using a fourdrinier machine, and a forming wire is a polyester wire (air permeability 6600m 3 /m 2 h. Fiber support index 197fsi, support point 1365sp/cm 2 ) The quantitative ratio was 29.32g/m 2 Is a bacterial cellulose sheet of (a).
The bacterial cellulose flakes prepared in this example comprise the following components in weight percent: 63% of bacterial cellulose, 3.5% of near infrared up-conversion fluorescent anti-counterfeiting substance, 2.1% of wet strength agent, 1.4% of dry strength agent and 30% of cotton.
The sheet was tested to have a thickness of 35 μm, a permeability of 7.8mL/min, a fracture length of 5850m, an elongation of 1.71%, a wet strength of 35.3% and a strong fluorescence response at 980nm wavelength excitation light.
The sheet is cut into squares with the length of 4 multiplied by 4mm, added with a high-frequency fluffer (the frequency is 3000 r/min), soaked for 24 hours, and after fluffing for 360000 r, the sheet is still intact and the fluorescence effect still meets the requirement, so that the sheet can be suitable for a papermaking system. The sheet is cut into a specific shape and then added into the paper making process, so that the anti-counterfeiting paper is obtained.
Example 4
The embodiment provides a preparation method of a bacterial cellulose sheet, which specifically comprises the following steps:
(1) Cutting the bacterial cellulose wet film into particles with the size of 5mm by a granulator, grinding the particles into bacterial cellulose homogenates with the average size of 0.93mm and the mass ratio (based on the total weight of the particles) of 45% of the particles with the size of less than 0.2mm by a colloid mill;
(2) Adding 0.5% of nano silver (average particle size of 5-7 nm) into bacterial cellulose homogenate by taking dry weight of bacterial cellulose as a reference, stirring for 10min, adding 3% of wet strength agent and 2% of dry strength agent, and stirring uniformly to obtain modified bacterial cellulose homogenate;
(3) Mixing the obtained modified bacterial cellulose homogenate with cotton fiber slurry at a dry weight ratio of 6:4 (dry weight ratio of bacterial cellulose to cotton fiber) to form a net-feeding slurry; wherein, the fiber length of the cotton fiber slurry is 1.45mm, and the beating degree is 48 DEG SR;
(4) Paper making is carried out by using a fourdrinier machine, and a forming wire is a polyester wire (air permeability 6600m 3 /m 2 h. Fiber support index 197fsi, support point 1365sp/cm 2 ) The quantitative amount of the catalyst was 35g/m 2 Bacterial cellulose flakes having a thickness of 32 μm.
The bacterial cellulose flakes prepared in this example comprise the following components in weight percent: 56.7% of bacterial cellulose, 0.3% of nano silver, 1.8% of wet strength agent, 1.2% of dry strength agent and 40% of cotton
Through testing, the sheet meets the requirements of ISO22196 antibacterial test standard.
Comparative example 1
This comparative example provides a method of preparing a bacterial cellulose sheet, which is identical to example 1, except that the dry weight ratio of the modified bacterial cellulose homogenate to the bamboo fiber slurry (the ratio of bacterial cellulose to the dry weight of the fibers) of this comparative example is 95:5. The method specifically comprises the following steps:
(1) Cutting the bacterial cellulose wet film into particles with the size of 5mm by a granulator, grinding the particles into bacterial cellulose homogenate with the average particle size of 0.93mm and the mass ratio (based on the total weight of the particles) of 45% of the particles with the size of less than 0.2mm by a colloid mill;
(2) Adding 3.2% of wet strength agent and 1.8% of dry strength agent into bacterial cellulose homogenate based on dry weight of bacterial cellulose for modification, and uniformly stirring to obtain modified bacterial cellulose homogenate;
(3) Mixing the obtained modified bacterial cellulose homogenate with a fiber slurry at a dry weight ratio of 95:5 (dry weight ratio of bacterial cellulose to fiber) to form a netty slurry; wherein the fiber length of the fiber slurry is 1.72mm, the beating degree is 35 DEG SR, and the fibers in the fiber slurry consist of cotton and PA66 fibers with the mass ratio of 3:1;
(4) The sheet is manufactured by using a Kaiser sheet machine, and the forming wire is a polyester wire (air permeability 6600 m) 3 /m 2 h. Fiber support index 197fsi, support point 1365sp/cm 2 ) The result is: because the bacterial cellulose content is higher and the plant fiber content is less in the papermaking process, the adhesion of the net-surfing slurry is too strong, and the paper can not be torn off normally.
Comparative example 2
This comparative example provides a method for producing a bacterial cellulose sheet, which is the same as example 2, except that in the bacterial cellulose homogenate of this comparative example, the average particle size is 0.3mm, and the mass ratio of particles having a size of less than 0.2mm (based on the total weight of the particles) is 77%. The method specifically comprises the following steps:
(1) Cutting the bacterial cellulose wet film into particles with the size of 5mm by a granulator, grinding the particles into bacterial cellulose homogenate with the average size of 0.3mm and the mass ratio (based on the total weight of the particles) of 77% of the particles with the size of less than 0.2mm by a colloid mill;
(2) Based on the dry weight of bacterial cellulose, adding 3% of wet strength agent and 2% of dry strength agent into bacterial cellulose homogenate for modification, and uniformly stirring to obtain modified bacterial cellulose homogenate;
(3) Mixing the obtained modified bacterial cellulose homogenate with bamboo fiber slurry at a dry weight ratio of 6:5 (dry weight ratio of bacterial cellulose to bamboo fiber) to form a net-surfing slurry; wherein the fiber length of the bamboo fiber slurry is 1.52mm, and the beating degree is 42 DEG SR;
(4) Using fourdrinier to make paper, the forming wire is polyester wire (air permeability 6600m 3 /m 2 h. Fiber support index 197fsi, support point 1365sp/cm 2 ) The result is: because bacterial cellulose homogenates are difficult to filter due to improper paper machine size, paper is still difficult to uncover after quantitative adjustment.
Claims (10)
1. A method for preparing bacterial cellulose flakes comprising the steps of:
modifying the bacterial cellulose homogenate by using a modifier to obtain modified bacterial cellulose homogenate;
mixing the modified bacterial cellulose homogenate with fiber slurry to obtain net-surfing slurry, and forming by papermaking to obtain the bacterial cellulose sheet;
wherein the dry weight content of bacterial cellulose in the bacterial cellulose sheet is 30-90%;
in the bacterial cellulose homogenate, the average size of bacterial cellulose particles is 0.5-1.5mm, and the mass ratio of the bacterial cellulose particles with the size less than or equal to 0.2mm in the total amount of the particles is less than 60%;
the beating degree of the fiber slurry is 20-60 DEG SR, and the fiber length is 0.6-2mm;
the forming web used for papermaking has the following parameters: air permeability 5500-6600m 3 /m 2 h, fiber support index is 150-200fsi, support point is 1300-1500sp/cm 2 。
2. The method of claim 1, wherein the bacterial cellulose flakes have a dry weight content of bacterial cellulose of 50-70%.
3. The preparation method according to claim 2, wherein the bacterial cellulose homogenate is obtained by granulating and homogenizing or grinding a bacterial cellulose fermentation product.
4. The preparation method of claim 2, wherein the modifier is one or more selected from anti-counterfeiting substances, antibacterial and bacteriostatic materials and papermaking aids, and the papermaking aids are selected from wet strength agents or dry strength agents.
5. The method of claim 1, wherein the modifying agent modifies the bacterial cellulose homogenate biologically, chemically, or physically.
6. The method according to claim 1, wherein the equipment used for making paper is selected from cylinder machine, fourdrinier, inclined wire machine or kesai sheet machine.
7. The method of manufacturing according to claim 1, wherein the fibers are selected from plant fibers and/or chemical synthetic fibers; the plant fiber is selected from one or more of cotton, hemp, wood and bamboo.
8. A bacterial cellulose sheet obtainable by the process of any one of claims 1 to 7, prepared from the following raw materials in weight percent: 30-90% of bacterial cellulose, 0.5-30% of modifier and the balance of fiber.
9. The bacterial cellulose sheet according to claim 8, wherein its basis weight is 10-40g/m 2 The thickness is 15-60 μm.
10. Use of the bacterial cellulose sheet according to claim 8 or 9 for the preparation of anti-counterfeit and/or antibacterial bacteriostatic paper; preferably, the anti-counterfeiting object is anti-counterfeiting paper, anti-counterfeiting fiber or anti-counterfeiting label.
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