Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
  • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
  • C08B15/06—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur containing nitrogen, e.g. carbamates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
• • 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
  • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
• • 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
  • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
  • D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic 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
  • 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
  • D21C9/16—Bleaching ; Apparatus therefor with per compounds
  • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
• • 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
• • 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
  • D21H11/20—Chemically or biochemically modified 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
  • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
  • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration

Definitions

• the present invention relates to a method for producing carbamate cellulose fibers and a method for producing carbamate cellulose fine fibers.
• cellulose fibers when cellulose fibers are carbamated, they become colored (brownish brown), and even when composited with resin, the brownish brown color remains.
• bleaching the cellulose fibers may be considered to prevent coloring, but simply bleaching causes the problem that the amount of carbamate groups introduced decreases and the reinforcing effect of the resin is impaired.
• the problem to be solved by the present invention is to provide a method for producing carbamate cellulose fibers and carbamate cellulose fine fibers with high whiteness without impairing the reinforcing effect of the resin.
• Means for solving the above problem is a method for producing carbamate cellulose fibers, which comprises adding a bleaching agent to carbamate cellulose fibers and bleaching the fibers at a reaction temperature of 90 degrees or less and a pH of 7 or less. It is. It is also a method of manufacturing carbamate cellulose fine fibers by refining carbamate cellulose fibers, and the carbamate cellulose fibers are carbamate cellulose fibers having a carbamate group introduction amount of 0.5 mmol/g or more obtained by the above method. and the refinement is carried out so that the average fiber width is 0.1 to 20 ⁇ m, the average fiber length is 0.1 to 2.0 mm, and the Fine ratio A is 10 to 90%. This is a method for producing cellulose fine fibers.
• the manufacturing method of this embodiment is characterized by adding a bleaching agent to carbamate cellulose fibers and bleaching them at a reaction temperature of 90 degrees or less and a pH of 7 or less.
• the carbamate-treated cellulose fibers obtained in this manner are refined so that the average fiber width is 0.1 to 20 ⁇ m, the average fiber length is 0.1 to 2.0 mm, and the Fine ratio A is 10 to 90%.
• the method is characterized by obtaining cellulose fine fibers. At this time, the amount of carbamate groups introduced into the carbamate cellulose fiber is 0.5 mmol/g or more. This will be explained in detail below.
• cellulose fiber Cellulose fibers (fibrous cellulose) are made from pulp.
• This pulp raw material includes, for example, wood pulp made from hardwoods, softwoods, etc., non-wood pulp made from straw, bagasse, cotton, hemp, bark fibers, etc., recovered waste paper, waste paper made from waste paper, etc.
• One type or two or more types can be selected and used from pulp (DIP) and the like.
• DIP pulp
• the various raw materials mentioned above may be in the form of a pulverized material (powdered material) called, for example, cellulose powder.
• wood pulp As the raw material pulp, one or more types can be selected and used from, for example, chemical pulps such as hardwood kraft pulp (LKP) and softwood kraft pulp (NKP), mechanical pulp (TMP), and the like.
• the hardwood kraft pulp may be a bleached hardwood kraft pulp, an unbleached hardwood kraft pulp, or a semi-bleached hardwood kraft pulp.
• the softwood kraft pulp may be a bleached softwood kraft pulp, an unbleached softwood kraft pulp, or a semi-bleached softwood kraft pulp.
• Mechanical pulps include, for example, stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), chemical ground pulp (CGP), thermoground pulp (TGP), ground pulp (GP),
• SGP stone ground pulp
• PGW pressurized stone ground pulp
• RGP refiner ground pulp
• CGP chemical ground pulp
• TGP thermoground pulp
• GGP ground pulp
• TMP ground pulp
• TMP thermomechanical pulp
• CMP chemi-thermomechanical pulp
• RMP refiner mechanical pulp
• BTMP bleached thermomechanical pulp
• Cellulose fibers are made into carbamate cellulose fibers by being carbamated, that is, having carbamate groups.
• having a carbamate group means a state in which a carbamate group (carbamic acid ester) is introduced into the fibrous cellulose.
• the carbamate group is a group represented by -O-CO-NH-, for example, a group represented by -O-CO-NH 2 , -O-CONHR, -O-CO-NR 2 or the like. That is, the carbamate group can be represented by the following structural formula (1).
• R is each independently a saturated linear hydrocarbon group, a saturated branched hydrocarbon group, a saturated cyclic hydrocarbon group, an unsaturated linear hydrocarbon group, an unsaturated branched hydrocarbon group, At least one of an aromatic group and a group derived therefrom.
• saturated linear hydrocarbon group examples include linear alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, and propyl group.
• saturated branched hydrocarbon group examples include branched alkyl groups having 3 to 10 carbon atoms such as isopropyl group, sec-butyl group, isobutyl group, and tert-butyl group.
• saturated cyclic hydrocarbon group examples include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a norbornyl group.
• Examples of the unsaturated linear hydrocarbon group include linear alkenyl groups having 2 to 10 carbon atoms such as ethenyl group, propen-1-yl group, propen-3-yl group, ethynyl group, propyn-1
• Examples include straight-chain alkynyl groups having 2 to 10 carbon atoms such as -yl group and propyn-3-yl group.
• Examples of the unsaturated branched hydrocarbon group include branched alkenyl groups having 3 to 10 carbon atoms such as propen-2-yl group, buten-2-yl group, buten-3-yl group, butyn-3 Examples include branched alkynyl groups having 4 to 10 carbon atoms such as -yl group.
• aromatic group examples include phenyl group, tolyl group, xylyl group, and naphthyl group.
• Examples of the derivative group include the above-mentioned saturated linear hydrocarbon group, saturated branched hydrocarbon group, saturated cyclic hydrocarbon group, unsaturated linear hydrocarbon group, unsaturated branched hydrocarbon group, and aromatic group.
• Examples include groups in which one or more hydrogen atoms are substituted with a substituent (for example, a hydroxy group, a carboxy group, a halogen atom, etc.).
• cellulose fibers that have carbamate groups have been introduced
• some or all of the highly polar hydroxy groups are substituted with carbamate groups that are considered to be relatively less polar.
• affinity with resins and the like with low polarity increases. Therefore, cellulose fibers having carbamate groups have excellent uniform dispersibility with resin.
• a slurry of cellulose fibers having carbamate groups has low viscosity and good handling properties.
• the substitution ratio of carbamate groups to hydroxy groups in the cellulose fibers is preferably 0.1 to 5.0 mmol/g, more preferably 0.6 to 3.0 mmol/g, particularly preferably 0.7 ⁇ 2.0 mmol/g.
• the substitution rate is 0.5 mmol/g or more, the effect of introducing a carbamate group, especially the effect of improving the bending elongation of the resin, can be reliably achieved.
• the substitution rate exceeds 5.0 mmol/g, the cellulose fibers may not be able to maintain their fiber shape, and the reinforcing effect of the resin may not be sufficiently obtained.
• the whiteness may decrease and even after bleaching, the whiteness may be as low as less than 70%.
• the substitution rate of carbamate groups exceeds 2.0 mmol/g, the average fiber length of the pulp raw material becomes short, resulting in the average fiber length of the fine fibers being less than 0.1 mm, making it impossible to achieve a sufficient resin reinforcing effect. There is a risk.
• the introduction of carbamate groups is preferably carried out so that the rate of decrease in the amount of carbamate groups introduced after bleaching is less than 10% relative to the amount of carbamate groups introduced before bleaching. If the reduction rate is less than 10%, the fibers with carbamate groups will not deteriorate significantly, and the fibers with carbamate groups will be dispersed in the resin, improving the adhesion between the resin and the fibers, and creating a complex in the resin. A sufficient reinforcing effect can be obtained when
• the above reduction rate is a value determined by (amount of carbamate groups introduced after bleaching - amount of carbamate groups introduced before bleaching)/amount of carbamate groups introduced after bleaching x 100 (%).
• substitution rate of carbamate groups refers to the amount of carbamate groups contained per 1 g of cellulose raw material having carbamate groups.
• the substitution rate of carbamate groups is determined by measuring the N atoms present in the carbamate-formed pulp by the Kjeldahl method, and calculating the carbamate conversion rate per unit mass.
• cellulose is a polymer having anhydroglucose as a structural unit, and has three hydroxy groups per structural unit.
• the process of carbamateing cellulose fibers can be mainly divided into, for example, mixing treatment, removal treatment, and heat treatment.
• mixing treatment and the removal treatment can also be collectively referred to as a preparation treatment for preparing a mixture to be subjected to heat treatment.
• urea etc. a derivative of urea
• urea a derivative of urea
• urea a dispersion medium
• urea or the like may be mixed into a dried cellulose fiber in the form of a sheet by impregnation, coating, or the like.
• urea and urea derivatives examples include urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, and compounds in which the hydrogen atom of urea is replaced with an alkyl group. can. These urea or urea derivatives can be used alone or in combination. However, it is preferred to use urea.
• the lower limit of the mixing mass ratio of urea etc. to cellulose fibers is preferably 10 kg/pt, more preferably 20 kg/pt.
• the upper limit is preferably 300 kg/pt, more preferably 200 kg/pt.
• the dispersion medium is usually water. However, other dispersion media such as alcohol and ether, or a mixture of water and other dispersion media may also be used.
• cellulose fibers and urea may be added to water, cellulose fibers may be added to an aqueous solution of urea, or urea may be added to a slurry containing cellulose fibers. Further, in order to mix uniformly, it may be stirred after addition. Furthermore, the dispersion containing cellulose fibers, urea, etc. may contain other components. On the other hand, cellulose fibers may be made into a dry body such as a sheet, and urea or the like may be added by coating the dry body of cellulose fibers such as a sheet. At this time, the cellulose fibers in sheet form may be in the original rolled state or in the drawn state, but it is in the drawn state that urea etc. can be added uniformly. be.
• the dispersion medium is removed from the dispersion containing cellulose fibers, urea, etc. obtained in the mixing treatment.
• the dispersion medium, urea and the like can be efficiently reacted in the subsequent heat treatment.
• the removal of the dispersion medium is preferably performed by volatilizing the dispersion medium by heating. According to this method, only the dispersion medium can be efficiently removed while leaving components such as urea.
• the lower limit of the heating temperature in the removal treatment is preferably 50°C, more preferably 70°C, particularly preferably 90°C when the dispersion medium is water.
• the upper limit of the heating temperature is preferably 120°C, more preferably 100°C. If the heating temperature exceeds 120° C., the dispersion medium and urea may react, and urea may decompose alone.
• the heating time in the removal treatment can be adjusted as appropriate depending on the solid content concentration of the dispersion. Specifically, it is, for example, 6 to 24 hours.
• the mixture of cellulose fibers and urea etc. is heat treated.
• this heat treatment some or all of the hydroxyl groups of the cellulose fibers react with urea or the like and are replaced with carbamate groups. More specifically, when urea or the like is heated, it is decomposed into isocyanic acid and ammonia as shown in reaction formula (1) below.
• Isocyanic acid has very high reactivity, and forms carbamate groups on the hydroxyl groups of cellulose, for example, as shown in reaction formula (2) below.
• the lower limit of the heating temperature in the heat treatment is preferably 120°C, more preferably 130°C, particularly preferably at least the melting point of urea (about 134°C), even more preferably 150°C, and most preferably 160°C.
• the upper limit of the heating temperature is preferably 280°C, more preferably 260°C. If the heating temperature exceeds 280° C., urea and the like may be thermally decomposed and coloring may become noticeable.
• the heating time in the heat treatment varies depending on the heating temperature and method, but is preferably 1 second to 5 hours, more preferably 3 seconds to 3 hours, particularly preferably 5 seconds to 2 hours. If the heating time exceeds 5 hours, coloring may become noticeable and productivity will be poor.
• the heat treatment can also be carried out in a contact manner, such as by contacting with a heating roll.
• the heating temperature in the heat treatment can be 180-280°C, more preferably 200-270°C, particularly preferably 220-260°C, and the heating time is preferably 1-60 seconds, more preferably 1-260°C. 30 seconds, particularly preferably 1 to 20 seconds.
• the heat treatment can also be performed using a non-contact heating method such as hot air heating or far infrared heating.
• a non-contact heating method such as hot air heating or far infrared heating.
• the carbamate formation reaction can be efficiently carried out by increasing the reaction temperature.
• the pH is preferably pH 9 or higher, more preferably pH 9 to 13, particularly preferably pH 10 to 12, which is an alkaline condition.
• acidic conditions or neutral conditions with a pH of 7 or less, preferably a pH of 3 to 7, particularly preferably a pH of 4 to 7 are preferred. Under neutral pH conditions of 7 to 8, the average fiber length of cellulose fibers becomes short, and the reinforcing effect of the resin may be poor.
• the pH can be adjusted by adding an acidic compound (for example, acetic acid, citric acid, etc.) or an alkaline compound (for example, sodium hydroxide, calcium hydroxide, etc.) to the mixture.
• an acidic compound for example, acetic acid, citric acid, etc.
• an alkaline compound for example, sodium hydroxide, calcium hydroxide, etc.
• a hot air dryer for example, a paper machine, a dry pulp machine, etc. can be used.
• the mixture after heat treatment may be dehydrated and washed. This dehydration and washing may be performed using water or the like. This dehydration and washing can remove unreacted urea and the like.
• first stage means the first time that the pulp slurry before dehydration (after disintegration) was subjected to the dehydration process.
• second stage and subsequent stages means that the first stage described above is completely completed and the same dehydration step is performed again after addition of dilution water and stirring.
• Dn-1 Displacement cleaning rate in the first stage
• Amount of water contained in it Amount of pulp aqueous dispersion after dehydration - Pulp concentration after dehydration x
• Amount of pulp aqueous dispersion after dehydration An: Amount of filtrate after dehydration
• the replacement cleaning rate is preferably 80% or more. If it is difficult to achieve a cleaning rate of 80% or more with one dehydration cleaning, it is preferable to repeat the dehydration cleaning several times until the cleaning rate reaches 80% or more, and then perform diluted dehydration cleaning.
• Carbamate cellulose fibers are bleached by adding a bleaching agent.
• bleaching agents include sodium hypochlorite, sodium dichloroisocyanurate, hydrogen peroxide, sodium percarbonate, sodium perborate, ozone, chlorine dioxide, monopersulfuric acid, potassium permanganate, ammonium peroxodipersulfate, and persulfate.
• Persulfates such as sodium sulfate and potassium monopersulfate (potassium monopersulfate), hydrosulfite, thiourea dioxide, and the like can be used. However, it is preferred to use potassium monopersulfate. Note that the above bleaching agents may be used in combination.
• potassium monopersulfate is preferable from an environmental point of view, since sodium hypochlorite may react with compounds with aromatic rings such as residual lignin to produce chlorinated dioxins.
• hydrogen peroxide has a lower oxidizing power than potassium monopersulfate, so it is necessary to increase the amount added, lengthen the reaction time, and raise the reaction temperature, so potassium monopersulfate is better. preferable.
• metal salts when metal salts are present in the system, hydrogen peroxide may be disproportionated to generate hydroxyl radicals, which may attack cellulose and affect pulp viscosity. Cellulose is denatured by heating, producing conjugated double bonds, and changes color when it absorbs visible light.
• cellulose undergoes a Maillard reaction with amino acids and reducing sugars through a carbamate reaction, producing a brown substance.
• Chlorine bleaches such as sodium hypochlorite may remove not only double bonds that cause coloration but also carbamate groups, which may reduce the amount introduced.
• hydrogen peroxide it is necessary to use strong alkaline conditions with a pH of 10 or more, so there is a risk that the carbamate group will be eliminated as well.
• ozone, chlorine dioxide, monopersulfate, sodium persulfate, potassium permanganate, and ammonium peroxodipersulfate which can be used in a neutral to acidic region, are preferable. Potassium monopersulfate is preferred.
• the reaction temperature is preferably 90 degrees or less and the pH is 7 or less, more preferably the reaction temperature is 10 to 90 degrees and the pH is 2 to 7, and the reaction temperature is 30 to 90 degrees. It is particularly preferable to set the conditions to a high temperature and a pH of 4 to 7.
• the reaction temperature exceeds 90° C., the bleaching agent decomposes, the bleaching effect decreases, and the reaction efficiency may reach a plateau.
• the reaction takes place under high pressure, which requires a large amount of energy.
• the reaction temperature is less than 10 degrees Celsius, the bleach may not dissolve and remain in the solvent.
• the reaction rate is significantly reduced, there is a possibility that a large amount of reaction time will be required.
• the pH exceeds 7 the carbamate groups may be eliminated and the amount of carbamate groups introduced may decrease.
• the amount of potassium monopersulfate added is preferably 1 to 100 kg/pt, more preferably 3 to 80 kg/pt, and 5 to 50 kg/pt. It is particularly preferable that If the amount of potassium monopersulfate added is less than 1 kg/pt, the bleaching effect may be insufficient. On the other hand, if the amount of potassium monopersulfate added exceeds 100 kg/pt, not only the effect commensurate with the addition may not be obtained, but also the fiber length may become short and the reinforcing effect of the resin may be reduced.
• Bleached carbamate cellulose fibers can be pretreated by chemical methods prior to micronization (fibrillation).
• pretreatments using chemical methods include hydrolysis of polysaccharides with acids (acid treatment), hydrolysis of polysaccharides with enzymes (enzyme treatment), swelling of polysaccharides with alkalis (alkali treatment), and oxidation of polysaccharides with oxidizing agents ( Examples include oxidation treatment), reduction of polysaccharide with a reducing agent (reduction treatment), and the like.
• it is preferable to perform enzyme treatment it is preferable to perform enzyme treatment, and in addition, it is more preferable to perform one or more treatments selected from acid treatment, alkali treatment, and oxidation treatment.
• the enzyme treatment will be explained in detail below.
• the above-mentioned bleaching process oxidizes or reduces the substances that cause coloration (mainly molecules with conjugated double bonds (lignin, caramel reactants, etc.)) to a state that dissolves in water, and then removes them from the system together with the filtrate. It turns white when discharged.
• the enzymatic treatment described below is a treatment for facilitating micronization and simply decomposes cellulose into glucose.
• the enzyme used for the enzyme treatment it is preferable to use at least one of a cellulase enzyme and a hemicellulase enzyme, and it is more preferable to use both in combination.
• the use of these enzymes makes it easier to defibrate cellulose fibers.
• cellulase enzymes cause the decomposition of cellulose in the presence of water.
• hemicellulase enzymes cause the decomposition of hemicellulose in the presence of water.
• cellulase enzymes include Trichoderma, Acremonium, Aspergillus, Phanerochaete, and Trametes. It is produced by the genus Humicola, the genus Bacillus, the genus Schizophyllum, the genus Streptomyces, and the genus Pseudomonas. Enzymes can be used. These cellulase enzymes can be purchased as reagents or commercial products.
• EG encodedoglucanase
• CBH cellobiohydrolase
• hemicellulase enzymes examples include xylanase, an enzyme that decomposes xylan, mannase, an enzyme that decomposes mannan, and arabanase, an enzyme that decomposes alaban. can.
• Pectinase which is an enzyme that degrades pectin, can also be used.
• Hemicellulose is a polysaccharide excluding pectin, which is present between cellulose microfibrils in plant cell walls. Hemicellulose is diverse and varies depending on the type of wood and the wall layers of the cell wall. In the secondary wall of softwood, glucomannan is the main component, and in the secondary wall of hardwood, 4-O-methylglucuronoxylan is the main component. Therefore, when obtaining fine fibers from softwood bleached kraft pulp (NBKP), it is preferable to use mannase. Moreover, when obtaining fine fibers from hardwood bleached kraft pulp (LBKP), it is preferable to use xylanase.
• NNKP softwood bleached kraft pulp
• LLKP hardwood bleached kraft pulp
• the amount of enzyme added to cellulose fibers is determined by, for example, the type of enzyme, the type of wood used as a raw material (softwood or hardwood), the type of mechanical pulp, etc.
• the amount of enzyme added to the cellulose fibers is preferably 0.1 to 3% by mass, more preferably 0.3 to 2.5% by mass, particularly preferably 0.5 to 2% by mass. If the amount of the enzyme added is less than 0.1% by mass, there is a risk that the effect of the addition of the enzyme may not be sufficiently obtained. On the other hand, if the amount of enzyme added exceeds 3% by mass, cellulose may be saccharified and the yield of fine fibers may decrease. Another problem is that it is not possible to recognize an improvement in the effect commensurate with the increase in the amount added.
• the temperature during the enzyme treatment is preferably 30 to 70°C, more preferably 35 to 65°C, particularly preferably 40 to 60°C, regardless of whether a cellulase enzyme or a hemicellulase enzyme is used as the enzyme. . If the temperature during the enzyme treatment is 30° C. or higher, the enzyme activity will be less likely to decrease, and the treatment time can be prevented from becoming longer. On the other hand, if the temperature during enzyme treatment is 70° C. or lower, deactivation of the enzyme can be prevented.
• the time for enzyme treatment is determined by, for example, the type of enzyme, the temperature of enzyme treatment, the pH at the time of enzyme treatment, etc.
• the general enzyme treatment time is 0.5 to 24 hours.
• Examples of methods for inactivating enzymes include adding an alkaline aqueous solution (preferably pH 10 or higher, more preferably pH 11 or higher), adding hot water at 80 to 100°C, and the like.
• alkali used in the alkali treatment examples include sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia aqueous solution, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc.
• Organic alkalis and the like can be used. However, from the viewpoint of manufacturing cost, it is preferable to use sodium hydroxide.
• the degree of water retention of cellulose fibers can be lowered, the degree of crystallinity can be increased, and the homogeneity can be increased.
• the water retention of cellulose fibers is low, it becomes easier to dehydrate, and the dehydration properties of the cellulose fiber slurry improve.
• Cellulose fibers that have been bleached, pretreated, etc. are made finer (defibrated).
• This refinement can be achieved by using, for example, a beater, a high-pressure homogenizer, a homogenizer such as a high-pressure homogenizer, a grinder, a stone mill friction machine such as an attritor, a single-shaft kneader, a multi-shaft kneader, a kneader refiner, a jet mill, etc.
• This can be done by beating the cellulose fibers.
• the fibrous cellulose (cellulose fiber) that is the fine fiber is preferably microfiber cellulose (microfibrillated cellulose) with an average fiber diameter of 0.1 ⁇ m or more. Microfiber cellulose significantly improves the reinforcing effect of the resin.
• microfiber cellulose refers to fibers that have a thicker average fiber width than cellulose nanofibers.
• the average fiber diameter is, for example, 0.1 to 20 ⁇ m, preferably 0.2 to 15 ⁇ m, and more preferably more than 0.5 to 10 ⁇ m. If the average fiber diameter of microfiber cellulose is less than (below) 0.1 ⁇ m, it will not be different from cellulose nanofibers, and there is a possibility that the effect of improving the strength (especially flexural modulus) of the resin will not be sufficiently obtained. . Furthermore, the defibration time becomes longer and a large amount of energy is required. Furthermore, the dehydration properties of the cellulose fiber slurry deteriorate.
• the microfiber cellulose may be thermally degraded and its strength may be reduced.
• the average fiber diameter of the microfiber cellulose exceeds (exceeds) 20 ⁇ m, it becomes no different from pulp, and the reinforcing effect may not be sufficient.
• the method for measuring the average fiber diameter of fine fibers is as follows. First, 100ml of an aqueous dispersion of fine fibers with a solid content concentration of 0.01 to 0.1% by mass was filtered through a Teflon (registered trademark) membrane filter, and the solvent was replaced once with 100ml of ethanol and three times with 20ml of t-butanol. do. Next, it is freeze-dried, coated with osmium, and used as a sample. This sample is observed using an electron microscope SEM image at a magnification of 3,000 times to 30,000 times depending on the width of the constituent fibers.
• the average fiber length (average length of single fibers) of the microfiber cellulose is preferably 0.1 to 2.0 mm, more preferably 0.2 to 1.5 mm, particularly preferably 0.3 to 1.2. be. If the average fiber length is less than 0.1 mm, a three-dimensional network of fibers cannot be formed, and the reinforcing effect (particularly the flexural modulus) of the composite resin may be reduced. On the other hand, if the average fiber length exceeds 2.0 mm, the reinforcing effect may be insufficient because the length is the same as that of the raw material pulp.
• the average fiber length of the cellulose fibers that are the raw material for microfiber cellulose is preferably 0.50 to 5.00 mm, more preferably 1.00 to 3.00 mm, particularly preferably 1.50 to 2.50. If the average fiber length of the cellulose raw material is less than 0.50 mm, there is a possibility that the reinforcing effect of the resin will not be sufficiently obtained during defibration treatment. On the other hand, if the average fiber length exceeds 5.00 mm, it may be disadvantageous in terms of manufacturing cost during defibration.
• the reduction rate in fiber length is 50% or less before and after bleaching.
• the average fiber length of microfiber cellulose can be arbitrarily adjusted, for example, by selecting the raw material pulp, pretreatment, fibrillation, etc.
• the fine ratio A of the microfiber cellulose is preferably 10 to 90%, more preferably 20 to 60%, and particularly preferably 25 to 50%.
• the fine ratio A is 10% or more, the proportion of homogeneous fibers is large, making it difficult for the composite resin to break down.
• the Fine ratio A exceeds 90%, the bending elastic modulus may become insufficient.
• the fine ratio A of the microfiber cellulose is the fine ratio A of the microfiber cellulose, but it is more preferable to keep the fine ratio A of the cellulose fiber that is the raw material for the microfiber cellulose within a predetermined range.
• the Fine ratio A of the cellulose fibers that are the raw material for microfiber cellulose is preferably 1% or more, more preferably 3 to 25%, and particularly preferably 5 to 20%. . If the fine ratio A of the cellulose raw material before defibration is within the above range, even if the fine ratio A of the microfiber cellulose is defibrated to 10% or more, there will be little damage to the fibers and the reinforcing effect of the resin will improve. It is thought that then.
• the fine ratio B of the microfiber cellulose is preferably 1 to 75%, more preferably 10 to 75%, and particularly preferably 35 to 75%. If the Fine ratio B is less than 1%, there are many fibers with a short fiber length or many fibers with a large fiber width, so the reinforcing effect may not be sufficient. On the other hand, if the Fine ratio B exceeds 75%, there will be many thin and long fibers, and the fibers will become entangled with each other, and when an external impact is applied, the entangled portion of the fibers will act as a trigger like a foreign object. It may break and the bending properties and impact resistance of the composite resin may deteriorate.
• Fine ratios A and B can be adjusted simultaneously with bleaching in the addition of potassium monopersulfate as described above.
• the amount of potassium monopersulfate added is preferably 1 to 100 kg/pt, more preferably 3 to 80 kg/pt, particularly preferably 5 to 50 kg/pt.
• Fine ratio A refers to the mass-based ratio of cellulose fibers having a fiber length of 0.2 mm or less and a fiber width of 75 ⁇ m or less.
• Fine ratio B refers to the mass-based ratio of cellulose fibers whose fiber length exceeds 0.2 mm and whose fiber width is 10 ⁇ m or less.
• the fiber length etc. of cellulose fibers are measured using a fiber analyzer "FS5" manufactured by Valmet.
• the aspect ratio of the microfiber cellulose is preferably 2 to 15,000, more preferably 10 to 10,000. If the aspect ratio is less than 2, a three-dimensional network cannot be constructed, so even if the average fiber length exceeds 0.02 mm, the reinforcing effect may be insufficient. On the other hand, when the aspect ratio exceeds 15,000, the microfiber cellulose becomes highly entangled with each other, and there is a possibility that the dispersion in the resin becomes insufficient.
• Aspect ratio is the value obtained by dividing the average fiber length by the average fiber width. As the aspect ratio increases, the number of places where snags occur increases, so the reinforcing effect increases, but on the other hand, it is thought that the more snags occur, the more the ductility of the resin decreases.
• the fibrillation rate of microfiber cellulose is preferably 1.0 to 30.0%, more preferably 1.5 to 20.0%, particularly preferably 2.0 to 15.0%. If the fibrillation rate exceeds 30.0%, the contact area with water becomes too large, so even if the fibers are defibrated within a range where the average fiber width remains at 0.1 ⁇ m or more, dehydration may become difficult. be. On the other hand, if the fibrillation rate is less than 1.0%, there are few hydrogen bonds between fibrils, and a strong three-dimensional network may not be formed.
• Fibrillation rate is defined as cellulose fibers being disintegrated in accordance with JIS-P-8220:2012 "Pulp - Disintegration Method", and the resulting disintegrated pulp being processed by FiberLab. (Kajaani).
• the crystallinity of the microfiber cellulose is preferably 50% or more, more preferably 55% or more, particularly preferably 60% or more.
• the degree of crystallinity is less than 50%, although the mixability with pulp and cellulose nanofibers is improved, the strength of the fibers themselves decreases, so there is a possibility that the strength of the resin cannot be improved.
• the crystallinity of the microfiber cellulose is preferably 95% or less, more preferably 90% or less, particularly preferably 85% or less.
• the degree of crystallinity exceeds 95%, the proportion of strong intramolecular hydrogen bonds increases, the fiber itself becomes rigid, and its dispersibility becomes poor.
• the degree of crystallinity of microfiber cellulose can be arbitrarily adjusted, for example, by selecting the raw material pulp, pretreatment, and refining treatment.
• the crystallinity is a value measured in accordance with JIS K 0131 (1996).
• the pulp viscosity of the microfiber cellulose is preferably 2 cps or more, more preferably 4 cps or more. When the pulp viscosity of the microfiber cellulose is less than 2 cps, it may be difficult to suppress aggregation of the microfiber cellulose.
• the pulp viscosity is a value measured according to TAPPI T230.
• the freeness of the microfiber cellulose is preferably 500 ml or less, more preferably 300 ml or less, particularly preferably 100 ml or less. If the freeness of the microfiber cellulose exceeds 500 ml, the average fiber diameter of the microfiber cellulose will exceed 10 ⁇ m, and there is a possibility that the effect of improving the strength of the resin will not be sufficiently obtained.
• Freeness is a value measured in accordance with JIS P8121-2 (2012).
• the zeta potential of microfiber cellulose is preferably -150 to 20 mV, more preferably -100 to 0 mV, particularly preferably -80 to -10 mV. If the zeta potential is less than -150 mV, the compatibility with the resin may decrease significantly and the reinforcing effect may become insufficient. On the other hand, if the zeta potential exceeds 20 mV, there is a risk that the dispersion stability will decrease.
• the microfiber cellulose is dispersed in an aqueous medium to form a dispersion (slurry).
• aqueous medium consists entirely of water, but an aqueous medium that is partially composed of other liquids that are compatible with water can also be used.
• other liquids lower alcohols having 3 or less carbon atoms can be used.
• the solid content concentration of the slurry is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass.
• the solid content concentration is less than 0.1% by mass, excessive energy may be required during dehydration and drying.
• the solid content concentration exceeds 10.0% by mass, the fluidity of the slurry itself decreases, and there is a possibility that uniform mixing may not be possible when a dispersant is used.
• Cellulose fibers may include cellulose nanofibers as well as cellulose microfibers.
• Cellulose nanofibers are fine fibers similar to microfiber cellulose, and have a complementary role to microfiber cellulose in improving the strength of resin. However, if possible, it is preferable to use only microfiber cellulose without including cellulose nanofibers as fine fibers.
• the average fiber diameter (average fiber width; average diameter of single fibers) of the cellulose nanofibers is preferably 4 to 100 nm, more preferably 10 to 80 nm.
• the cellulose fibers may contain pulp. Pulp has the role of greatly improving the dewaterability of cellulose fiber slurry. However, as in the case of cellulose nanofibers, it is most preferable that the pulp is not blended, that is, that the content is 0% by mass.
• carbamate-modified cellulose was obtained by the following procedure. First, a sizing agent was added to the pulp slurry to produce a pulp sheet having a predetermined Cobb sizing degree and basis weight. Next, using a urea aqueous solution with a solid content concentration of 40% in coating equipment, the pulp is coated with a predetermined ratio of pulp to urea in terms of solid content. Obtained paper. The obtained urea-coated paper was reacted in a roll-to-roll reactor at a predetermined temperature and time to obtain carbamate-modified cellulose.
• carbamate-modified cellulose was obtained by the following procedure. First, softwood kraft pulp with a moisture content of 10% or less and a urea aqueous solution with a concentration of 30% are impregnated in a predetermined ratio to form a mixture. The mixture is dried at 105°C, and the reaction temperature is 160°C and the reaction time is 1 hour. Heat treatment was performed to obtain carbamate-modified cellulose. Note that the above details are also shown in Table 2.
• carbamate-modified cellulose After obtaining carbamate-modified cellulose as described above, bleached carbamate-modified cellulose was produced in the following procedure. First, carbamate-modified cellulose was diluted with water to a solid content concentration of 5% and disintegrated using a disintegrator. The aqueous dispersion of carbamate-modified cellulose obtained by disintegration was repeatedly dehydrated and washed twice.
• Each carbamate-modified cellulose obtained by the above method was bleached by the following method.
• the washed carbamate-modified cellulose is adjusted to a predetermined pulp concentration, bleach is added to the predetermined amount, and the mixture is left standing in water at a predetermined temperature using a water bath for a predetermined period of time.
• a bleached carbamate-modified cellulose was obtained.
• the pH during this bleaching was adjusted using an aqueous sodium hydroxide solution.
• the obtained bleached carbamate-modified cellulose was diluted with distilled water and stirred, and dehydration and washing were repeated twice to obtain a washed bleached carbamate-modified cellulose.
• Table 1 shows the whiteness recovery rate and the rate of decrease in the amount of introduced carbamate groups for each bleached carbamate cellulose fiber obtained.
• the whiteness recovery rate is a value calculated from "whiteness after bleaching/whiteness before denaturation”. Whiteness was measured in accordance with JIS P8148.
• the introduction amount reduction rate is a value calculated by "(introduction amount before bleaching - introduction amount after bleaching)/introduction amount before bleaching x 100".
• Oxone manufactured as manufactured as potassium monopersulfate.
• the reason why the introduction amount reduction rate is positive is considered to be due to a measurement error.
• the upper limit of the reaction temperature is 90°C. This is for the following reasons. That is, the reaction temperature is controlled such that when the temperature drops too much, heating is performed, and when the temperature rises too much, heating is stopped. In other words, when the temperature exceeds 90°C, the temperature is not actively lowered, but is lowered passively. Therefore, if the upper limit of the reaction temperature is set to exceed 90°C, the reaction temperature may reach 100°C instantaneously, and the pressure within the system will increase, causing undesirable reactions such as decomposition of fibers other than the desired bleaching reaction. No reaction may occur. However, although a reaction temperature as high as possible is preferred in order to increase reaction efficiency, a reaction temperature of 100° C.
• reaction temperature in a range that does not reach 100°C, and the upper limit of the reaction temperature is considered to be 90°C.
• the reaction temperature is 100° C. or higher, the amount of carbamate groups introduced will decrease, and there will also be disadvantages such as the need for a pressure vessel. It is clear from the above test results that a reaction temperature of 100° C. or higher is not preferable.
• the present invention can be used as a method for producing carbamate cellulose fibers and a method for producing carbamate cellulose fine fibers.

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