WO2007088974A1 - Procede pour conferer une impermeabilite a l'eau et une resistance a l'huile a l'aide d'une nanofibre cellulosique - Google Patents

Procede pour conferer une impermeabilite a l'eau et une resistance a l'huile a l'aide d'une nanofibre cellulosique Download PDF

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Publication number
WO2007088974A1
WO2007088974A1 PCT/JP2007/051810 JP2007051810W WO2007088974A1 WO 2007088974 A1 WO2007088974 A1 WO 2007088974A1 JP 2007051810 W JP2007051810 W JP 2007051810W WO 2007088974 A1 WO2007088974 A1 WO 2007088974A1
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Prior art keywords
cellulose
paper
treatment
treatment liquid
substrate
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PCT/JP2007/051810
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English (en)
Japanese (ja)
Inventor
Tetsuo Kondo
Wakako Kasai
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Kyushu University, National University Corporation
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Priority to JP2007556933A priority Critical patent/JP5419120B2/ja
Publication of WO2007088974A1 publication Critical patent/WO2007088974A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • 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
    • D21H21/50—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 form
    • D21H21/52—Additives of definite length or shape

Definitions

  • the present invention relates to a method for imparting water repellency and oil resistance using cellulose nanofibers. More specifically, the present invention relates to the use of a non-terrier cellulose anti-collision treated product for coating the surface of paper or the like. The present invention is particularly useful for protecting the surface of a molded product for food storage paper.
  • acetic acid bacterium produces a gel-like cellulose membrane outside the cell when cultured.
  • the cellulose produced by this fungus is called bacterial cellulose.
  • Bacterial Cellulose is secreted as highly crystalline ribbon-like cellulose nanofibers with an average width of about 50 nm and a thickness of about 10 nm.
  • a gel called a nano-sized network pelicle forms a random network immediately after secretion. A film is formed.
  • Patent Document 1 discloses a coating liquid characterized by containing bacterial cellulose and a surfactant, and a recording medium using the coating liquid.
  • Patent Document 2 discloses a coating liquid characterized by containing a chitosan salt and a divalent or higher ionic substance in an aqueous cellulose dispersion, and a recording medium using the same.
  • Patent Document 3 discloses an organic fiber pulp obtained by fibrillating organic fibers, characterized in that bacterial cellulose is fixed to at least a part of the surface thereof.
  • Patent Document 4 includes a solubilized cellulose obtained from bacterial cellulose produced by stirring culture, a coating composition or composite containing a solubilized cellulose, and a solubilized cellulose. Molding composition An article or composite is disclosed.
  • the present inventors have so far cultivated cellulose-producing bacteria on a cellulose template that is molecularly oriented in a uniaxial direction, whereby bacterial cellulose nanofibers secreted by fungi have been aligned in the orientation direction.
  • a pellicle Non-patent Document 1 and Patent Document 5.
  • Patent Document 1 Japanese Patent Laid-Open No. 2004-249573
  • Patent Document 2 JP 2005-162897 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-194648
  • Patent Document 4 Japanese Patent Laid-Open No. 10-77302
  • Patent Document 5 JP 2002-142796
  • Patent Document 6 JP 2005-270891
  • Non-patent literature 1 Kondo, T., Nojiri, M., Hishikawa, Y., Togawa, E., Romanovicz, D. an d Brown, Jr., RM, Bio-directed epitaxial nanodeposition of polymers on oriented macromolecular templates, Proc. Natl. Acad. Sci. USA, 99 (22), 14008—14013 (2002) Disclosure of the Invention
  • nangu pellicle membrane
  • the present inventors considered that it is necessary to take out the nocteria cellulose as nanofibers in order to expand the use of the nocteria cellulose.
  • the crystal surface of the nocteria cellulose nanofiber has a triclinic crystal structure called cellulose I alpha (alpha), which is different from plant-derived cotton. (Unpublished). Therefore, as described above, if it can be taken out as a nanofiber, it can be expected as a fiber expressing new properties.
  • biomass resources such as cellulose and chitin are polysaccharides having a dalcoviranose skeleton.
  • This sugar skeleton molecular structure has a parent group derived from a hydroxyl group in a direction parallel to the skeleton.
  • Hydrophobic sites derived from CH groups exist in the direction perpendicular to the aqueous and skeleton (Fig. 1).
  • the cellulose natural fiber surface on which such molecules are assembled is divided into hydrophilic / hydrophobic sites having different properties.
  • a hydrophilic surface appears on the surface of the solid, it has an affinity for water, but if the hydrophobic surface is arranged on the surface, the surface will have a water repellency similar to that of Teflon TM (Fig. 2).
  • nano-sized natural fibers are capable of strong interaction at the interface with a partner substance having a large specific surface area.
  • this interfacial interaction with amphipathic properties hydrophilic and hydrophobic
  • amphipathic properties hydrophilic and hydrophobic
  • the present invention provides a method for modifying a substrate surface, which includes a step of coating cellulose nanofibers obtained by subjecting nocteria cellulose to an opposing collision treatment.
  • the present invention provides a method for producing cellulose nanofibers including a step of subjecting bacterial cellulose to opposing collision treatment, and a treatment liquid containing cellulose nanofibers obtained by subjecting bacterial cellulose to opposing collision treatment.
  • a cellulose nanofiber coating is provided that is formed by impregnating a material and / or applying the treatment liquid to a substrate surface and drying.
  • Cellulose nanofibers used for coating a substrate are not pellicles but are single nanofibers, and have an average width of 25 nm or less (preferably 20 nm or less, more preferably 15 nm or less, and even more preferably 8 to 12 nm.
  • the average thickness is 8 to 12 nm.
  • cellulose includes vegetable cellulose, bacterial cellulose, cellulose fiber, crystalline cellulose and the like, which are not limited in origin, production method, properties, etc., unless otherwise specified.
  • bacterial cellulose refers to a cellulose produced by microorganisms, except for special cases, which is a polysaccharide mainly composed of cellulose 1, 4 darcoside bonds, Except where indicated, it refers to that in the form of a gel film.
  • Nocteria cellulose can be produced by methods well known to those skilled in the art.
  • Cellulose-producing bacteria include acetic acid bacteria such as Acetobactor pasteurianum, Acetobactor pasteurianum, and Acetobactor rancens. Sarcina ventric uli, Bacteirum xvloides, Pseudomonas spp., Agrobacterium spp., Etc. Those skilled in the art can appropriately determine the above.
  • cellulose nanofiber refers to a cellulose fiber having an average width and an average thickness of 100 nm or less.
  • the average width and average thickness of the cellulose fiber can be measured by methods well known to those skilled in the art, such as a light scattering device, a laser microscope, and an electron microscope.
  • the average width is obtained by measuring several points, for example, 10 to 200 points, preferably 30 to 80 points, of the measured length, and taking the average value.
  • the average thickness is obtained by measuring several points, for example, 10 to 200 points, preferably 30 to 80 points, of the measured length, and taking the average value.
  • Preferred examples of the cellulose nanofibers used in the present invention have an average width and an average thickness equal to or less than that of nocteria cellulose (for example, an average width of 25 nm or less, preferably 20 nm or less, more preferably 15 nm or less, more preferably 8-12 nm) with an average thickness of 8-12 nm.
  • opposite collision refers to a case where a polysaccharide dispersion is injected from a pair of nozzles at a high pressure of 70 to 250 MPa, respectively, except for special cases.
  • a wet pulverization method in which cellulose fibers are pulverized by colliding with each other. Details of this method are disclosed in JP-A-2005-270891 (Patent Document 1).
  • Opposite collision treatment is a wet atomization method that uses the collision energy of ultra-high pressure water to ultrafine the material. Compared to other pulverization methods, bead mill, jet mill, stirrer, high-pressure homogenizer, etc., it has various excellent advantages. For example, since no grinding media is used, there is no mixing of wear powder in the media, and a more uniform and sharp particle size distribution than the media agitation method is obtained. Furthermore, continuous treatment, large capacity is easy, and treatment with less contact time with the atmosphere For example, the oxidation of the product can be suppressed as much as possible. [0018] As a device for the counter collision treatment, a high-pressure washing device or a high-pressure homogenizer device for pulverization / dispersion / emulsification can be used.
  • cellulose is dispersed in water.
  • Cellulose may be pulverized in advance if necessary.
  • the dispersion concentration is preferably 0.1 to 10% by mass, which is preferably an appropriate concentration for passing through the pipe as a dispersion slurry.
  • the dispersion liquid is ejected from a pair of nozzles at a high pressure of 70 to 250 MPa, and the jet streams collide with each other to be pulverized, but are ejected from the pair of nozzles.
  • Adjust the angle of the high-pressure jet flow of the dispersion to adjust the number of times of pulverization by adjusting the force or the number of jets of high-pressure fluid to adjust the jet flow so that the jets collide at an appropriate angle at one point ahead of each nozzle outlet.
  • the average particle length of the cellulose fibers can be pulverized to 1Z4 or less or 10 ⁇ m, while the decrease in the degree of polymerization of cellulose can also be suppressed.
  • the collision angle ⁇ can be 95 to 178 °, for example, 100 to 170 °. If it is smaller than 95 °, for example, if it is made to collide at 90 °, structurally, the collision dispersion liquid tends to generate a portion that directly collides with the wall of the chamber, and cellulose polymerization occurs in one collision. Degradation often exceeds 10%. On the other hand, when the angle is larger than 178 °, for example, when the collision is 180 °, that is, when the collision is made in the face-to-face relationship, the degree of polymerization in one collision may be severely reduced when the collision energy is large.
  • the number of collisions may be 1 to 200 times, for example, 5 to 120 times, -60 times, -30 times, -15 times, -10 times. If the number of pulverization is large, the decrease in the degree of polymerization of cellulose may exceed 10%.
  • the collision angle and Z or the number of collisions can be appropriately designed in consideration of decomposition efficiency by cellulose and the like.
  • the average particle length of cellulose after the collision treatment can be 1Z4 or less, 1Z5 to 1Z100, 1Z6 to 1Z50, 1 Z7 to lZ20 before treatment.
  • the average particle length can be 10 m or less, 0.01-9 / ⁇ ⁇ , 0.1-8 ⁇ ⁇ , 0.1-5 ⁇ ⁇ .
  • Cellulose fibers have a particle width perpendicular to the average particle length. This width is called the average particle width, which is also less than 10 m, 0.01 to 9 / ⁇ ⁇ , and 0.1 to 8 / ⁇ ⁇ by adjusting the collision angle and ⁇ or the number of collisions. can do.
  • the processed object once subjected to the collision process is, for example, 4 to 20 ° C, or 5 as necessary. It may be cooled to ⁇ 15 ° C. Equipment for cooling can be incorporated in the opposing collision processing apparatus.
  • the average particle size is obtained by centrifuging the processed product and fractionating the supernatant as a method for taking out only the portion where the processed product has particularly strong cellulose fiber strength.
  • Cellulose fine particles with a length of less than 1 ⁇ m can be obtained.
  • the present invention also includes a method for modifying a substrate surface comprising a step of coating a cellulose nanofiber obtained by subjecting a herbaceous plant-derived cellulose fiber to opposing collision; a cellulose fiber derived from a herbaceous plant; A method for producing cellulose nanofibers, including a step of carrying out a counter-collision treatment, and a counter-collision treatment of the cellulose fibers derived from herbaceous plants to obtain a treatment liquid containing the cellulose nano-fibers, impregnating the substrate with the treatment liquid And / or providing a cellulose nanofiber coating formed by applying the treatment liquid to the surface of a substrate and drying.
  • Herbaceous plants refer to plants that have grassy or fleshy stems that do not develop much xylem, and the above-ground parts often die within a year. There are two kinds of perennials, perennials, and evergreen leaves that have been developed with strong strength. In the herbaceous plant field, gramineous plants can be suitably used, and examples of preferred gramineous plants are bamboo and bamboo.
  • Rag Panemites communis
  • oak, ⁇ , ⁇ , ⁇ , reed is a herbaceous plant belonging to the genus Gramineae reed and distributed in wetlands over temperate zones. Forces that can be divided into three to four species are generally considered the only species belonging to the genus Reed.
  • bamboo is a perennial herbaceous plant that belongs to the Gramineae bamboo subfamily and is distributed from the tropics to the temperate zone. Bamboo includes Horaiichita, Madatake, Mosouchita, Chishimazasa, Suzutake, and Medake.
  • the herbaceous plant-derived cellulose fiber subjected to the counter-collision treatment is obtained by using a norp (a collection of cellulose fibers taken apart) as a raw material for paper. What was obtained by the process similar to preparing may be used. In the pulp preparation process, for example, the raw material is mixed with chemicals and processed at high temperature and heat to separate the fiber and other components (such as lignin components), and the fiber is separated as necessary. Including washing.
  • FIG. 1 is a view showing hydrophilic sites and hydrophobic sites of cellulose molecules.
  • molecules such as cellulose and chitin, there are hydrophilic sites derived from hydroxyl groups in the direction parallel to the skeleton, and hydrophobic sites derived from C—H groups in the direction perpendicular to the skeleton.
  • FIG. 2 is a diagram showing the influence of the orientation angle of the glucose ring on the surface on the surface characteristics. If hydrophilic surface appears on the surface of solid, it has affinity to water. If hydrophobic surface is arranged on the surface, the surface will have the same water repellency as Teflon TM.
  • FIG. 3 includes photographs showing changes in bacterial cellulose nanofibers before and after the oncoming collision treatment. It was found that the network structure of the nanofibers in the pellicle was destroyed by the facing collision treatment and dispersed in water as a single fiber instead of the pellicle. The TEM photographic power was also found to be a fiber with a cross-sectional shape close to a square, with the width of the nanofibers reduced to about 10 and 1/4.
  • FIG. 4 is a photograph of water repellency (water contact angle) measured on the surface of a filter paper coated with bacterial cellulose subjected to counter collision.
  • water contact angle water contact angle
  • FIG. 5 is a photograph of the surface of a filter paper coated with bacterial cellulose subjected to counter collision treatment when tested for oil resistance.
  • the salad oil mixed with red and dye (Zudan IV) was dropped, and the surface at that time was observed, the untreated filter paper quickly penetrated and oozed out on the backside. Although it spread on the surface of the filter paper, it did not penetrate and the oil oozed out on the back side.
  • FIG. 6 is a photograph when the oil resistance of a filter paper surface coated with a microcrystalline cellulose fiber derived from a plant subjected to opposing collision treatment was tested. From the left, the number of applications is 1, 3, and 5. Salad oil permeated immediately, and those with a coating frequency of more than 3 times were filmed and peeled off the filter paper.
  • FIG. 7 is a photograph of the oil resistance of the filter paper surface coated with bacterial cellulose defibrated with a homogenizer. From left to right, the number of applications is 1, 3, and 5. Salad oil penetrated immediately.
  • FIG. 8 is a photograph of the bacterial cellulose treated with facing collisions when spread on a PET film. Bacterial cellulose adhered well to the PET film.
  • Fig. 9 is a photograph of the microcrystalline cellulose fiber that has been subjected to opposing collision treatment, developed on a PET film. The development was peeled off the film.
  • Fig. 10 is a photograph of the surface of the filter paper coated with bacterial cellulose subjected to the counter-impact treatment, when the water resistance was tested.
  • a 1% solution of blue stain (Coomassie brilliant blue R-250) was added dropwise and the surface at that time was observed, the untreated filter paper quickly penetrated and exuded to the back side. Although the solution spread on the surface of the filter paper, it did not permeate and did not penetrate into the back side.
  • FIG. 11 is a photograph of the water repellency (water contact angle) of PE, PP, and PET coated with bacterial cellulose subjected to opposing collision treatment. The coating treatment made the contact angle smaller and made it hydrophilic.
  • FIG. 12 is a photograph of water and oil resistance tests on the filter paper surface coated with the cellulose nanofibers that were subjected to opposing collision treatment.
  • a 1% aqueous solution of blue stain (Coomassie brilliant blue R-250) was dropped, the solution spread on the surface of the filter paper but did not permeate, and water did not ooze out on the back side.
  • Red dye Zindan IV
  • FIG. 13 is a photograph of the surface of the filter paper coated with the bamboo-derived cellulose nanofibers subjected to the counter collision treatment when tested for water resistance and oil resistance.
  • a 1% aqueous solution of blue stain (Coomassie brilliant blue R-250) was added dropwise, a slight oozing of water into the filter paper was observed, but the rate of soaking was slow (left photo).
  • salad oil mixed with red dye (Zudan IV) was dropped, no soaking into the filter paper was observed (right photo).
  • FIG. 14 is a photograph of the coating composition when tested for water resistance and oil resistance. The oil resistance and water repellency were maintained as in Example 1.
  • the method is not particularly limited, but the liquid is usually impregnated with the substrate ( Dipping) or applying the liquid to the substrate surface and drying.
  • the impregnation and application may be performed in combination or repeatedly. There are no particular restrictions on the application means, and air spray, brush, roller, etc. can be used. Drying can be performed by heat drying, forced drying, and Z or room temperature drying.
  • an organic base material surface such as plastic, wood and paper
  • an inorganic base material surface such as concrete, stone, glass and ceramic
  • a metal surface such as iron and aluminum.
  • substrates to be coated and modified according to the present invention are paper, polyethylene terephthalate, polyethylene, polypropylene.
  • An example of a particularly suitable substrate is paper.
  • paper refers to a product made by intertwining and attaching plant fibers and other fibers, except in special cases.
  • the form can be any, such as a paperboard, a molded product, and the like, with no particular limitations on the raw material, the type of fiber constituting, and the proportion of blending. Norp mold is also included. Further, it may contain a fungicidal component other than fibers, an antibacterial component and the like.
  • the cellulose nanofibers are 0.01 to 30 g / m 2 (preferably 0.05 to 20 g / m 2 , more preferably 0.1 to 10 g / m 2 , more preferably 0.2 to 5 g / m 2. )
  • the coating method various methods used for coating the substrate, such as application by dipping or spraying, can be applied.
  • the coating of the present invention is applied to a substrate having a hydrophobic surface (water repellency) such as PET, the surface of the substrate is modified to be hydrophilic. If it is hydrophilic, it can be printed on the coated substrate with aqueous ink or pencil.
  • a part or the whole of the surface is coated with a cellulose nanofiber coating.
  • the paper product or the molded article made of paper which is formed by applying Z or the treatment liquid to the surface of the substrate and drying.
  • Examples of paper products or molded articles include food containers (for example, bento containers), tableware (paper cups, m.), Bags, cards, books, magazines, printing paper, stationery Printing paper, adhesive paper, filter, etc.
  • food containers for example, bento containers
  • tableware paper cups, m.
  • Bags cards, books, magazines, printing paper, stationery Printing paper, adhesive paper, filter, etc.
  • the present invention is also a method for imparting water repellency or hydrophilicity, or oil and fat resistance to the surface of a substrate such as paper products or paper moldings; water resistance or hydrophilicity, and oil and fat resistance.
  • a substrate such as paper products or paper moldings
  • water resistance or hydrophilicity, and oil and fat resistance Is imparted by coating part or all of the surface of a substrate such as a paper product or a paper molded product with a cellulose nanofiber coating; the cellulose nanofiber coating is formed of bacterial cellulose or gramineous Plant-derived cellulose fibers are subjected to opposing collision treatment to obtain a treatment liquid containing cellulose nanofibers, the treatment liquid is impregnated with a substrate, and Z or the treatment liquid is applied to the substrate surface and dried.
  • the above method is provided.
  • Resistance to liquids includes water repellency, oil and fat resistance (oil resistance and oil resistance), and water resistance.
  • oil resistance and oil resistance oil resistance and oil resistance
  • water resistance Each evaluation method is well known to those skilled in the art. These evaluations are usually performed not only immediately after the landing of water droplets or oil droplets on the surface, but also after the landing for several hours depending on the intended use. Good. According to the study of the present inventors, even the most wet and porous filter paper can be easily imparted with oil resistance by spraying, and this oil resistance does not change even after several hours after landing. won.
  • the present invention also provides a coating composition comprising cellulose nanofibers obtained by opposing collision treatment of cellulose fibers derived from nocteria cellulose or herbaceous plants.
  • the coating composition of the present invention can be used as a paint or as an ink.
  • the coating composition of the present invention may contain water, a pigment, and various additives as a developing agent in addition to cellulose nanofibers as a film-binding component.
  • pigments include inorganic pigments, lakes, colored pigments, extender pigments, and glitter pigments.
  • additives include dispersants, emulsifiers, suspending agents, color separation inhibitors, drying agents, Anti-sagging agents, leveling agents, plasticizers, anti-fogging agents, antifoaming agents, fireproofing agents, antiseptics, antifungal agents, disinfectants, and agents for imparting slipperiness to the coating film can be mentioned.
  • the coating composition of the present invention can be applied to the surface of various base materials and the surface of an old coating film.
  • the base material surface include organic base material surfaces such as plastic, wood, and paper; concrete, stone, glass, Surfaces of inorganic base materials such as ceramics; metal surfaces such as iron and aluminum can be listed.
  • Old coatings include acrylic resin, acrylic urethane resin, polyurethane resin, fluorine resin, silicon acrylic Examples include old coatings such as rosin, vinyl acetate, epoxy, and alkyd resins.
  • the coating composition of the present invention can also be used in combination with an undercoat material and an overcoat material.
  • the coating method of the coating composition of the present invention is not particularly limited, and can be performed by immersion, air spray, brush, roller or the like.
  • VOC volatile organic compound
  • the coating composition can be configured to be free of VOCs.
  • Such a coating composition of the present invention is mainly used for interior materials that require a texture (does not generate VOCs) or materials that are used in contact (for example, welfare materials for the elderly, used in hospitals). Particularly suitable for metal substitute materials). Specific examples include architectural interior materials, automotive interior materials, food packaging, and plastic trays.
  • the coating composition of the present invention has a coating film formed on the substrate due to the strong adsorptivity of the nanocellulose fibers to the substrate surface and the anchor effect on the material surface of the pigment component used together. It is thought that the surface can be strongly coated. Therefore, the coating composition of the present invention can be configured such that the coating film exhibits sufficient durability. [0045] With the coating composition of the present invention, painting or dyeing and oil resistance and water repellency treatment can be simultaneously performed.
  • cellulose nanofibers and cellulose nanofiber coatings are provided.
  • Cellulose cellulose has recently been reported to exhibit biocompatibility not found in cotton wool. This is because the difference in the structure of the surface reflects the difference in the effect on the cells at the contact surface. It seems to show that.
  • the surface of the nocteria cellulose takes a crystal form called I al pha (alpha) in which the aggregate state is triclinic even if it is composed of the same cellulose molecules.
  • the molecular morphology of the plant-derived surface takes the form of a monoclinic crystal called I beta, so the surface properties of nanofibers differ.
  • the conventional plant cellulose fiber and the bacterial cellulose nanofiber according to the present invention have a difference in the arrangement of the constituent molecules, and as a result, the aggregation state of the molecules on the fiber surface is different, and therefore the properties exhibited by the fiber surface are different. Conceivable. According to the study by the present inventors, the same effect as in the case of using the opposite treatment product of nocteria cellulose was not obtained with the opposite treatment product of the crystalline cellulose fiber derived from the woody plant (see Comparative Example). In addition, the same effect as that obtained when the opposite treatment product of bacterial cellulose was used was not obtained by the treatment with the high-pressure homogenizer of nocteria cellulose.
  • the treatment with a high-pressure homogenizer may be useful from the viewpoint of water-solubilization of cellulose, but naturally it involves physical molecular cleavage, so that cellulose is reduced in molecular weight and the degree of polymerization is reduced.
  • oncoming collisions act to tear off the molecules and the degree of polymerization does not decrease much.
  • the aggregation state of the molecules on the fiber surface is expected to differ depending on the treatment method. Therefore, nano-sized considerations produce fibers with different surface properties depending on the treatment method, even if the starting material is the same.
  • Opposing collision treatment technology is important in that it is a non-destructive operation of molecular structure without lowering the degree of polymerization.
  • the present application provides the property that only bacterial cellulose that has been subjected to facing collision treatment can be expressed at the present time.
  • the present invention makes use of the surface properties of nanofibers.
  • the surface structure and size of a bacterial cell mouth that has been subjected to an appropriate number of counter-collision treatments are the same as the parents of cellulose molecules and their aggregates. It ’s medium! The potential characteristics will be expressed more clearly! /!
  • the present invention also provides a property resulting from the molecular aggregation state (crystallinity and packing state) of the fiber surface of the cellulose fiber derived from the herbaceous plant subjected to the counter collision treatment. It is the same in terms of plant origin, and it is the same crystalline structure of cell mouth fiber derived from bamboo and bamboo, and cellulose fiber of wood (wood). It is thought that the properties exhibited by the fiber surface are different. Therefore, the surface activity effect of nanofibers due to underwater collision will also be different. Cellulose fibers derived from herbs that are softer and less crystalline than wood and cotton fibers have a lot of fluffing of nanofibers on the surface when facing each other, resulting in an extremely large specific surface area. It is thought that it becomes easy to adsorb to the material. As a result, in the surface modification of the base material, the same excellent effect as that of the bacterial cellulose nanofiber is exhibited.
  • Acetobactor xylinum (3 ⁇ Gluconacetobactor xvnnus) (producing strain: ATCC 53582) was cultured (the preparation method of the medium for bacterial cellulose culture is Hestrin, S. & Schramm, M. ( 1954) According to Biochem. T. 58, 345—352.)
  • the obtained cellulose pellicle was cut into lcm square size as it was, suspended in water, Manufactured), pressure 200mPa, number of collisions
  • a suspension of cellulose nanofibers was obtained by applying the suspension 34 times to a solid concentration of about 0.4%.
  • the filter paper surface was coated with nanofibers by using filter paper as a base material, dipping in a suspension of cellulose nanofibers and drying at 105 ° C.
  • the coating amount is 2-3g / m 7 hot.
  • FIG. 3 shows a TEM photograph. It was found that the nanofiber network structure in the pellicle was destroyed and dispersed in water as a single fiber rather than a pellicle. Furthermore, bacterial cellulose nanofibers usually have a width of 40-60 nm and a thickness of 10 nm. After the impact treatment, the nanofiber width is reduced to about 10 ⁇ m, about 1/4, and the cross-section is nearly square. It became clear that TEM photography power became.
  • the fiber adsorption on the filter paper surface by purely the interaction between the nanofiber surface and the filter paper surface forms a pellicle, which is significantly better than the case of bacterial nanofibers. it was thought. That is, since the filter paper is hydrophilic, the hydrophilic side of the nanofibers is adsorbed on the surface, and the hydrophobic side is directed to the air side, so that the surface is considered to be hydrophobic.
  • the contact angle of the surface of the filter paper immersed in the suspension was measured (Fig. 4).
  • the suction of water into the filter paper was so strong that the contact angle could not be measured.
  • the suction of water was significantly slowed, the contact angle could be measured, and a numerical value of 51 ° could be obtained with a single soaking treatment, giving hydrophobicity. it was thought.
  • the contact angle of water is 20 ° for glass and 45 for stainless steel. And 70 for aluminum. (Refer to DuPont HP HYPERLINK "http://www.dupont.co.jp/tc/seinou/” http://www.duDont.co.iD/tc/seinou/). Compared with these values, the 51 ° value of the filter paper that had been soaked was considered to have the same water repellency as stainless steel.
  • Plant-derived cellulose microcrystalline fibers (Funacel II: average particle size 80 micrometers: Funakoshi Co., Ltd.) are subjected to opposing collision treatment (30 collisions, suspension solid concentration about 0.5%), The suspension obtained by subjecting to the same conditions as in Example 1 was applied to the filter paper by spraying, dried at 105 ° C., and the oil resistance of the filter paper was tested (FIG. 6).
  • the suspension obtained by treating bacterial cellulose with a homogenizer (product name: Hiscotron, manufactured by Microtec •-Thion) at 20,000 rpm for 5 minutes was applied by spraying, and the other conditions were as in Examples.
  • the oil resistance of the filter paper was tested in the same way as in Fig. 1 (Fig. 7).
  • the bacterial cellulose suspension obtained in Example 1 was developed on a PET film (FIG. 8).
  • the bacterial cellulose subjected to the counter collision treatment was in good contact with the PET film.
  • Other than paper, PET, PP, PE, and other substrates could be coated with bacterial cellulose.
  • Filter paper obtained by spraying the bacterial cellulose suspension that had been subjected to the counter-treatment 34 times in the same manner as in Example 1 and air-drying it 15 times, and finally drying at 40 ° C for about 1 hour. The water resistance of was evaluated.
  • nanocellulose was sprayed onto a synthetic polymer (PE, PP, PET) film, then air-dried, and then dried at 40 degrees for 30 minutes to 1 hour.
  • PE polymer
  • PET synthetic polymer
  • nanocellulose was dropped onto the film and applied to the entire film surface using a wire bar (a product in which a stainless steel wire was precisely wound around a precision shaft). It was air dried and then dried at 40 degrees for 30 minutes to 1 hour.
  • a wire bar a product in which a stainless steel wire was precisely wound around a precision shaft. It was air dried and then dried at 40 degrees for 30 minutes to 1 hour.
  • Pear pulp was loosened by stirring in water to prepare a suspension of pear.
  • Example 2 This was subjected to an oncoming collision.
  • the conditions were the same as in Example 1, using an optimizer (manufactured by Suginomashin), pressure 200 raPa, number of collisions 34 times, and solid concentration of suspension about 0.4 ° /. It was.
  • a blue dyeing agent (Coomassie brilliant blue R-250) was added to the cellulose nanofiber suspension with 34 collisions obtained in Example 1 to a concentration of 0.1% to obtain a coating composition.
  • Example 1 The results are shown in FIG. The oil resistance and water repellency were maintained as in Example 1. From this, it was considered that by using the cellulose nanofiber suspension, coating or dyeing and oil-resistant / water-repellent treatment can be performed simultaneously.

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  • Nanotechnology (AREA)
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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Paper (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Wrappers (AREA)
  • Cartons (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un procédé de reformage consistant à obtenir un liquide de traitement contenant une nanofibre cellulosique par traitement de collision opposée d'une fibre cellulosique dérivée d'une plante herbacée ou d'une cellulose bactérienne, à imprégner un matériau de base du liquide de traitement et/ou à appliquer le liquide sur la surface du matériau de base, puis à sécher le support pour ainsi former une couche de nanofibre cellulosique sur la surface du matériau de base. Le papier constitue un bon exemple du matériau de base. Cette invention concerne également une composition de revêtement contenant une nanofibre cellulosique produite par traitement de collision opposée d'une fibre cellulosique dérivée d'une plante herbacée ou d'une cellulose bactérienne.
PCT/JP2007/051810 2006-02-02 2007-02-02 Procede pour conferer une impermeabilite a l'eau et une resistance a l'huile a l'aide d'une nanofibre cellulosique WO2007088974A1 (fr)

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