WO2020195908A1 - Résine composite de cellulose fibreuse, son procédé de production, et matériau de renforcement de résine - Google Patents

Résine composite de cellulose fibreuse, son procédé de production, et matériau de renforcement de résine Download PDF

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Publication number
WO2020195908A1
WO2020195908A1 PCT/JP2020/010870 JP2020010870W WO2020195908A1 WO 2020195908 A1 WO2020195908 A1 WO 2020195908A1 JP 2020010870 W JP2020010870 W JP 2020010870W WO 2020195908 A1 WO2020195908 A1 WO 2020195908A1
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Prior art keywords
resin
fibrous cellulose
cellulose
dispersant
mixture
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PCT/JP2020/010870
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English (en)
Japanese (ja)
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一紘 松末
貴章 今井
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大王製紙株式会社
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Publication of WO2020195908A1 publication Critical patent/WO2020195908A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of 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
    • 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

Definitions

  • the present invention relates to a fibrous cellulose composite resin, a method for producing the same, and a reinforcing material for the resin.
  • Cellulose nanofibers are usually obtained in the state of a dispersion (slurry), but transportation in the state of a dispersion increases the cost. Therefore, when commercializing it, it is rational to dry the dispersion of cellulose nanofibers and transport it as a dried product. However, when the dispersion is dried, the cellulose nanofibers are strongly aggregated by hydrogen bonds. Therefore, it is difficult to disperse the cellulose nanofibers in water again, and they do not disperse as they did before drying.
  • a main problem to be solved by the present invention is to provide a fibrous cellulose composite resin having excellent strength, a method for producing the same, and a resin reinforcing material having an excellent resin reinforcing effect even when dried.
  • Patent Documents 1 and 2 are excellent in redispersibility in water but inferior in dispersibility in resin. This was one of the reasons why the strength of the resin did not improve as expected even when dried products (cellulose nanofibers, microfibrillated cellulose, etc.) were mixed with the resin. In this respect, it is possible to disperse the dried product in water once and mix it with the resin in the state of a dispersion liquid, but it is very inefficient to evaporate the water content such as cellulose nanofibers with the mixing with the resin. .. Based on this background, the means shown below have come to the fore.
  • the dispersant is at least one or more selected from melamine, urea phosphorylated starch, carbamic acid starch, lecithin, and casein.
  • the bulk specific gravity of the mixture is 0.03 or more.
  • the water content of the mixture is 50% or less.
  • the average particle size of the mixture is 1000 ⁇ m or less.
  • the fine fibers are cellulose nanofibers having an average fiber diameter of 100 nm or less.
  • the fibrous cellulose composite resin according to any one of claims 1 to 5.
  • a dispersant is mixed with a slurry of fibrous cellulose to form a mixture, and the mixture is dried and pulverized to form a powder, which is then kneaded with a resin. Fine fibers are used as part or all of the fibrous cellulose, As the dispersant, one having at least one or more functional groups selected from a hydroxyl group, a carboxy group, and an amine group is used.
  • a method for producing a fibrous cellulose composite resin is used.
  • Cellulose nanofibers having an average fiber diameter of 100 nm or less are used as the fine fibers.
  • the mixing amount of the dispersant is 1 to 40 parts by mass with respect to 100 parts by mass of the cellulose nanofibers.
  • thermoplastic resin or thermosetting resin It is a reinforcing material for thermoplastic resin or thermosetting resin.
  • a mixture of fibrous cellulose and dispersant Contains fine fibers as part or all of the fibrous cellulose
  • the dispersant has at least one or more functional groups selected from a hydroxyl group, a carboxy group, and an amine group.
  • a resin reinforcement that is characterized by this.
  • the average particle size is 1,000 ⁇ m or less.
  • the present invention is a fibrous cellulose composite resin having excellent strength, a method for producing the same, and a resin reinforcing material having an excellent resin reinforcing effect even when dried.
  • the embodiment of the present invention is an example of the present invention.
  • the scope of the present invention is not limited to the scope of the present embodiment.
  • the fibrous cellulose composite resin of this embodiment contains a mixture of fibrous cellulose and a dispersant, and a resin.
  • the fibrous cellulose is made by mixing fine fibers such as cellulose nanofibers (CNF) and microfibrillated cellulose (MFC), for example.
  • the dispersant has at least one or more functional groups selected from a hydroxyl group, a carboxy group, and an amine group.
  • This fibrous cellulose composite resin can be obtained, for example, by mixing a dispersant with a slurry of fibrous cellulose to form a mixture, drying and pulverizing the mixture to form a powder, and then kneading the mixture with the resin. The details will be described below.
  • the fibrous cellulose is also referred to as "cellulose fiber”.
  • the fibrous cellulose of this embodiment contains fine fibers in part or in whole.
  • the fine fibers include at least one of cellulose nanofibers and microfibrillated cellulose, preferably cellulose nanofibers.
  • Cellulose nanofibers have the role of significantly improving the strength of the resin.
  • Cellulose nanofibers can be obtained by defibrating (miniaturizing) the raw material pulp.
  • raw material pulp for cellulose nanofibers for example, wood pulp made from broadleaf tree, coniferous tree, etc., non-wood pulp made from straw, bagasse, cotton, linen, carrot fiber, etc., recovered waste paper, waste paper, etc. are used as raw materials.
  • One type or two or more types can be selected and used from the waste paper pulp (DIP) and the like.
  • DIP waste paper pulp
  • the above-mentioned various raw materials may be in the state of a pulverized product (powder) called, for example, a cellulosic powder.
  • wood pulp as the raw material pulp for cellulose nanofibers.
  • wood pulp for example, one or more kinds can be selected and used from chemical pulp such as hardwood kraft pulp (LKP) and softwood kraft pulp (NKP), mechanical pulp (TMP) and the like.
  • the hardwood kraft pulp may be hardwood bleached kraft pulp, hardwood unbleached kraft pulp, or hardwood semi-bleached kraft pulp.
  • the softwood kraft pulp may be softwood bleached kraft pulp, softwood unbleached kraft pulp, or softwood semi-bleached kraft pulp.
  • thermomechanical pulp examples include stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), chemi-grand pulp (CGP), thermo-grand pulp (TGP), and ground pulp (GP).
  • SGP stone ground pulp
  • PGW pressurized stone ground pulp
  • RGP refiner ground pulp
  • CGP chemi-grand pulp
  • TGP thermo-grand pulp
  • GP ground pulp
  • TMP thermomechanical pulp
  • CMP chemithermomechanical pulp
  • RMP refiner mechanical pulp
  • BTMP bleached thermomechanical pulp
  • the raw material pulp can also be pretreated by a chemical method prior to defibration.
  • Pretreatment by chemical method includes, for example, hydrolysis of polysaccharide with acid (acid treatment), hydrolysis of polysaccharide with enzyme (enzyme treatment), swelling of polysaccharide with alkali (alkali treatment), oxidation of polysaccharide with oxidizing agent (acid treatment). Oxidation treatment), reduction of polysaccharides with a reducing agent (reduction treatment), and the like can be exemplified.
  • alkali used for the alkali treatment examples include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and the like.
  • Organic alkali or the like can be used. However, from the viewpoint of manufacturing cost, it is preferable to use sodium hydroxide.
  • the water retention level of the cellulose nanofibers can be lowered, the crystallinity level can be increased, and the homogeneity can be increased. In this respect, if the water retention level of the cellulose nanofibers is low, dehydration is likely to occur, and the dehydration property of the cellulose fiber slurry is improved.
  • the raw material pulp is enzyme-treated, acid-treated, or oxidized, the hemicellulose and the amorphous region of cellulose that the pulp has are decomposed.
  • the energy of the miniaturization process can be reduced, and the uniformity and dispersibility of the cellulose fibers can be improved.
  • the pretreatment reduces the aspect ratio of the cellulose nanofibers, it is preferable to avoid excessive pretreatment in terms of using the resin as a reinforcing material.
  • beaters high-pressure homogenizers, homogenizers such as high-pressure homogenizers, stone mill type friction machines such as grinders and grinders, single-screw kneaders, multi-screw kneaders, kneader refiners, jet mills, etc. It can be done by beating the raw material pulp using it. However, it is preferable to use a refiner or a jet mill.
  • the average fiber diameter, average fiber length, water retention, crystallinity, peak value of pseudo-particle size distribution, pulp viscosity, and B-type viscosity of the dispersion liquid of the obtained cellulose nanofibers are as shown below. It is preferable to obtain a desired value or evaluation.
  • the average fiber diameter (average fiber width; average diameter of single fibers) of the cellulose nanofibers is preferably 1 to 100 nm, more preferably 10 to 80 nm, and particularly preferably 20 to 60 nm. If the average fiber diameter of the cellulose nanofibers is less than 1 nm, the dehydration property may be deteriorated. Further, in the present embodiment in which the cellulose nanofibers are mixed with the dispersant, the dispersant does not sufficiently cover the cellulose nanofibers (it does not sufficiently cling to the dispersant), and the effect of improving the redispersibility may be insufficient. .. On the other hand, if the average fiber diameter of the cellulose nanofibers exceeds 100 nm, the number of cellulose single crystals contained in each cellulose nanofiber increases, so that the reinforcing effect may be lowered.
  • the average fiber diameter of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the method for measuring the average fiber diameter of cellulose nanofibers is as follows. First, 100 ml of an aqueous dispersion of cellulose nanofibers having a solid content concentration of 0.01 to 0.1% by mass is filtered through a membrane filter made of Teflon (registered trademark), and the solvent is once with 100 ml of ethanol and three times with 20 ml of t-butanol. Replace. Next, it is freeze-dried and coated with osmium to prepare a sample. This sample is observed by an electron microscope SEM image at a magnification of 3,000 to 30,000 times depending on the width of the constituent fibers.
  • the average fiber length (length of a single fiber) of the cellulose nanofibers is preferably 0.1 to 1,000 ⁇ m, more preferably 0.5 to 500 ⁇ m, and particularly preferably 1 to 100 ⁇ m. If the average fiber length of the cellulose nanofibers is less than 0.1 ⁇ m, a three-dimensional network of the cellulose nanofibers cannot be constructed, and the reinforcing effect may be reduced. On the other hand, if the average fiber length of the cellulose nanofibers exceeds 1,000 ⁇ m, the fibers are likely to be entangled with each other, and the redispersibility may not be sufficiently improved.
  • the average fiber length of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the average fiber length of cellulose nanofibers is measured by visually measuring the length of each fiber in the same manner as in the case of the average fiber diameter.
  • the average fiber length is the medium length of the measured value.
  • the water retention of the cellulose nanofibers is preferably 250 to 500%, more preferably 280 to 490%, and particularly preferably 300 to 480%. If the water retention of the cellulose nanofibers is less than 250%, the dispersibility of the cellulose nanofibers deteriorates, and there is a possibility that the cellulose nanofibers cannot be uniformly mixed with other fibers such as pulp. On the other hand, when the water retention degree of the cellulose nanofibers exceeds 500%, the water retention capacity of the cellulose nanofibers themselves becomes high, and the dehydration property of the cellulose fiber slurry may deteriorate.
  • the water retention of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the degree of water retention of cellulose nanofibers is Japan TAPPI No. It is a value measured according to 26 (2000).
  • the degree of cellulose nanofiber crystallinity is preferably 95 to 50%, more preferably 90 to 60%, and particularly preferably 85 to 70%.
  • the strength of the resin can be reliably improved.
  • the crystallinity can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the crystallinity of cellulose nanofibers is a value measured in accordance with JIS K 0131 (1996).
  • the peak value in the pseudo particle size distribution curve of cellulose nanofibers is preferably one peak.
  • the cellulose nanofibers have high uniformity of fiber length and fiber diameter, and are excellent in dehydration of the cellulose fiber slurry.
  • the peak value of cellulose nanofibers is, for example, 0.1 to 100 ⁇ m, preferably 1 to 50 ⁇ m, and more preferably 5 to 25 ⁇ m.
  • the peak value of cellulose nanofibers can be adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the peak value of cellulose nanofiber is a value measured in accordance with ISO-13320 (2009). More specifically, first, the volume-based particle size distribution of the aqueous dispersion of cellulose nanofibers is examined using a particle size distribution measuring device. Next, the medium diameter of the cellulose nanofibers is measured from this distribution. This medium diameter is taken as the peak value.
  • the pulp viscosity of the cellulose nanofibers is preferably 10.0 to 1.0 cps, more preferably 8.0 to 1.5 cps, and particularly preferably 5.0 to 2.0 cps.
  • the pulp viscosity is the viscosity of the solution after dissolving cellulose in a copper ethylenediamine solution, and the larger the pulp viscosity, the higher the degree of polymerization of cellulose.
  • the pulp viscosity is within the above range, while imparting dehydration to the slurry, decomposition of cellulose nanofibers can be suppressed when kneading with the resin, and a sufficient reinforcing effect can be obtained.
  • the pulp viscosity of cellulose nanofibers is a value measured in accordance with TAPPI T 230.
  • the cellulose nanofibers obtained by defibration can be dispersed in an aqueous medium to prepare a dispersion liquid prior to mixing with other cellulose fibers.
  • the total amount of the aqueous medium is water (aqueous solution).
  • the aqueous medium may be another liquid that is partially compatible with water.
  • the other liquid for example, lower alcohols having 3 or less carbon atoms can be used.
  • the B-type viscosity of the dispersion of cellulose nanofibers (concentration 1%) is preferably 2,000 to 10 cp, more preferably 1,500 to 30 cp, and particularly preferably 1,300 to 50 cp.
  • concentration 1%) is preferably 2,000 to 10 cp, more preferably 1,500 to 30 cp, and particularly preferably 1,300 to 50 cp.
  • the B-type viscosity (solid content concentration 1%) of the dispersion liquid of cellulose nanofibers is a value measured in accordance with "Method for measuring liquid viscosity" of JIS-Z8803 (2011).
  • the B-type viscosity is the resistance torque when the dispersion liquid is agitated, and the higher the viscosity, the more energy required for agitation.
  • the content of cellulose nanofibers in the cellulose fibers is preferably 10 to 95% by mass, more preferably 30 to 93% by mass, and particularly preferably 50 to 90% by mass. If the content of the cellulose nanofibers is less than 10% by mass, the strength of the resin may not be sufficiently improved. On the other hand, if the content of the cellulose nanofibers exceeds 95% by mass, the cellulose nanofibers are strongly aggregated and cannot be dispersed in the resin, and the reinforcing effect may not be sufficient.
  • microfibrillated cellulose is preferably used together with the cellulose nanofibers instead of the cellulose nanofibers.
  • Microfibrillated cellulose is larger in size than cellulose nanofibers, so it is easier to disperse in resin and build a three-dimensional network.
  • cellulose nanofibers are closer to single crystals than microfibrillated cellulose, so they are stronger. It has high physical properties and can be expected to have a reinforcing effect on the resin. In order to take advantage of both, it is desirable to mix in the above ratio.
  • Microfibrillated cellulose means fibers with an average fiber diameter larger than that of cellulose nanofibers. Specifically, for example, it is 0.1 to 15 ⁇ m, preferably 0.5 to 10 ⁇ m, and more preferably 1 to 5 ⁇ m.
  • the average fiber diameter of microfibrillated cellulose is less than 0.1 ⁇ m, it is no different from that of cellulose nanofibers, and the effect of improving the strength (particularly flexural modulus) of the resin cannot be sufficiently obtained. In addition, the defibration time becomes long and a large amount of energy is required. Further, the dehydration property of the cellulose fiber slurry is deteriorated. When dehydration deteriorates, when drying after mixing with a dispersant, a large amount of energy is required for the drying, and if a large amount of energy is applied to the drying, the microfibrillated cellulose may be thermally deteriorated and the strength may be reduced. is there. On the other hand, if the average fiber diameter of the microfibrillated cellulose exceeds 15 ⁇ m, it is no different from that of pulp, and the reinforcing effect may not be sufficient.
  • Microfibrillated cellulose can be obtained by defibrating (miniaturizing) the raw material pulp.
  • the same pulp as the cellulose nanofiber can be used, and it is preferable to use the same pulp as the cellulose nanofiber.
  • the raw material pulp for microfibrillated cellulose can be pretreated and defibrated in the same way as for cellulose nanofibers.
  • the degree of defibration is different, and for example, it is necessary to carry out in a range where the average fiber diameter remains 0.1 ⁇ m or more.
  • the differences from the case of cellulose nanofibers will be mainly described.
  • the average fiber length (average length of single fibers) of microfibrillated cellulose is preferably 0.02 to 3.0 mm, more preferably 0.05 to 2.0 mm, and particularly preferably 0.1 to 1.5 mm. Is. If the average fiber length is less than 0.02 mm, a three-dimensional network of fibers cannot be formed, and the reinforcing effect of the resin may be reduced.
  • the average fiber length can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, etc.
  • the fiber length of microfibrillated cellulose is preferably 0.2 mm or less in a proportion of 60% or more, more preferably 70% or more, and particularly preferably 75% or more. If the ratio is less than 60%, the reinforcing effect of the resin may not be sufficiently obtained. On the other hand, the fiber length of microfibrillated cellulose has no upper limit of the ratio of 0.2 mm or less, and all may be 0.2 mm or less.
  • the aspect ratio of microfibrillated cellulose is preferably 2 to 5,000, more preferably 100 to 1,000.
  • the aspect ratio is a value obtained by dividing the average fiber length by the average fiber width. It is considered that the larger the aspect ratio, the more places in the resin where the resin is caught, so that the reinforcing effect is improved, but on the other hand, the more the aspect ratio is, the lower the ductility of the resin. It should be noted that when an inorganic filler is kneaded with a resin, it is known that the larger the aspect ratio of the filler, the higher the bending strength, but the elongation is significantly reduced.
  • the fibrillation rate of the microfibrillated cellulose is preferably 1.0 to 30.0%, more preferably 1.5 to 20.0%, and 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 average fiber width can be defibrated within the range of 0.1 ⁇ m or more, dehydration may become difficult. There is. On the other hand, if the fibrillation rate is less than 1.0%, there are few hydrogen bonds between the fibrils, and there is a risk that a strong three-dimensional network cannot be formed.
  • the crystallinity of microfibrillated cellulose is preferably 50% or more, and more preferably 60% or more. If the crystallinity is less than 50%, the mixability with pulp and cellulose nanofibers is improved, but the strength of the fibers themselves is lowered, so that the strength may not be guaranteed.
  • the crystallinity of microfibrillated cellulose is preferably 90% or less, more preferably 88% or less, and particularly preferably 86% or less.
  • the crystallinity exceeds 90%, the ratio of strong hydrogen bonds in the molecule increases, the fiber itself becomes rigid, and the redispersibility becomes inferior.
  • microfibrillated cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, and micronization treatment.
  • the pulp viscosity of microfibrillated cellulose is preferably 2 cps or more, and more preferably 4 cps or more. If the pulp viscosity is less than 2 cps, the aggregation of microfibrillated cellulose may not be sufficiently suppressed.
  • the freeness of microfibrillated cellulose is preferably 500 cc or less, more preferably 300 cc or less, and particularly preferably 100 cc or less. If the freeness of the microfibrillated cellulose exceeds 500 cc, the average fiber diameter of the microfibrillated cellulose exceeds 10 ⁇ m, and there is a possibility that the effect on strength cannot be sufficiently obtained.
  • the degree of water retention of microfibrillated cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the content of microfibrillated cellulose in the cellulose fiber is preferably less than 50% by mass, more preferably less than 40% by mass, and particularly preferably less than 30% by mass. If the content of the microfibrillated cellulose exceeds 50% by mass, the content of the cellulose nanofibers is relatively reduced, and the effect of containing the cellulose nanofibers may not be obtained.
  • the method for measuring various physical properties of microfibrillated cellulose is the same as that for cellulose nanofibers.
  • the fibrous cellulose containing fine fibers is dispersed in an aqueous medium to form a dispersion (slurry).
  • the total amount of the aqueous medium is water, but an aqueous medium which is another liquid which is partially compatible with water can also be used.
  • the other liquid lower alcohols having 3 or less carbon atoms can be used.
  • the solid content concentration of the slurry is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass. If the solid content concentration is less than 0.5% by mass, excessive energy may be required for dehydration and drying. On the other hand, if the solid content concentration exceeds 5.0% by mass, the fluidity of the slurry itself may decrease and the dispersant may not be uniformly mixed.
  • a dispersant is mixed with the slurry of fibrous cellulose.
  • the dispersant it is preferable to use one having at least one or more functional groups selected from a hydroxyl group, a carboxy group, and an amine group. More preferably, at least one selected from melamine, urea phosphorylated starch, carbamic acid starch, lecithin, and casein is used.
  • the above dispersant inhibits hydrogen bonds between dried fine fibers.
  • the above-mentioned melamine, urea phosphorylated starch, carbamic acid starch, lecithin, and casein are easily compatible with both cellulose and resin, and the reinforcing effect of the resin can be further improved.
  • the fine fibers and the resin are kneaded, the fine fibers are surely dispersed (redispersed) in the resin.
  • the above dispersant also has a role of improving the compatibility of the fine fibers and the resin. In this respect as well, the dispersibility of the fine fibers in the resin is improved. Therefore, the dispersant of this embodiment can be said to be a compatible solvent.
  • polypropylene has a melting point of 160 ° C., so that the fibrous cellulose and the resin are kneaded at about 180 ° C.
  • a dispersant liquid
  • a masterbatch composite resin having a high concentration such as CNF
  • resins with a low melting point generally have low strength. Therefore, according to this method, the strength of the composite resin may decrease.
  • the mixing amount of the dispersant of this embodiment is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 10 to 20 parts by mass with respect to 100 parts by mass of the cellulose nanofibers.
  • the mixing amount of the dispersant of this embodiment is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 10 to 20 parts by mass with respect to 100 parts by mass of the cellulose nanofibers.
  • hydroxyic acids, glycerin or glycerin derivatives it is necessary to mix 40 parts by mass or more with 100 parts by mass of cellulose nanofibers.
  • the dispersant of this embodiment it is sufficient to mix 1 part (or more) with respect to 100 parts by mass of the cellulose nanofibers. That is, when the dispersant of the present embodiment is used, the mixing amount can be reduced.
  • the mixing amount of the dispersant can be reduced.
  • the mixing of the dispersant improves the reinforcing effect of the resin by the cellulose nanofibers.
  • the dispersant must be hydrophilic (has a hydrophilic group) due to the presence of the cellulose nanofibers, and in this respect, it also has an aspect of reducing the strength of the resin.
  • the dispersant may surface on the surface over time. Therefore, it is a great advantage that the mixing amount of the dispersant can be reduced.
  • the mixture of fibrous cellulose and dispersant is preferably dried and pulverized into a powder prior to kneading with the resin. According to this form, it is not necessary to dry the fibrous cellulose when kneading with the resin, and the thermal efficiency is good. Further, since the dispersant is mixed in the mixture, there is a low possibility that the fine fibers will not be redispersed even if the mixture is dried.
  • the mixture is dehydrated to dehydrate prior to drying.
  • dehydrators such as belt presses, screw presses, filter presses, twin rolls, twin wire formers, valveless filters, center disk filters, membrane treatments, and centrifuges. Can be done using.
  • the drying of the mixture is, for example, rotary kiln drying, disc drying, air flow drying, medium flow drying, spray drying, drum drying, screw conveyor drying, paddle drying, uniaxial kneading drying, multiaxial kneading drying, vacuum drying, stirring drying. It can be carried out by selectively using one type or two or more types from the above.
  • the dried mixture (dried product) is crushed into powder.
  • the pulverization of the dried product can be carried out by selecting or using one or more of, for example, a bead mill, a kneader, a dispar, a twist mill, a cut mill, a hammer mill and the like.
  • the average particle size of the powder is preferably 1,000 ⁇ m or less, more preferably 800 ⁇ m or less, and particularly preferably 600 ⁇ m or less. If the average particle size of the powdery substance exceeds 1,000 ⁇ m, the kneadability with the resin may be inferior. However, it is not economical because a large amount of energy is required to reduce the average particle size of the powder to less than 1 ⁇ m.
  • the average particle size of the powdery substance can be controlled by classification using a classification device such as a filter or a cyclone.
  • the bulk specific gravity of the mixture (powder) is preferably 0.03 to 1.0, more preferably 0.1 to 0.8.
  • the bulk specific gravity exceeds 1.0, the hydrogen bonds between the fibrous celluloses are stronger, and it is not easy to disperse them in the resin.
  • setting the bulk specific gravity to less than 0.03 is disadvantageous in terms of transfer cost.
  • the bulk specific gravity is a value measured according to JIS K7365.
  • the water content of the mixture (powder) is preferably 50% or less, more preferably 30% or less, and particularly preferably 10% or less. If the water content exceeds 50%, the energy required for kneading with the resin becomes enormous, which is uneconomical.
  • the water content of the fiber is a value calculated by the following formula, with the mass at the time when the sample is held at 105 ° C. for 6 hours or more at 105 ° C. and no change in mass is observed using a constant temperature dryer as the mass after drying.
  • Fiber moisture content (%) [(mass before drying-mass after drying) / mass before drying] x 100
  • the powdery substance (resin reinforcing material) obtained as described above is kneaded with a resin to obtain a fibrous cellulose composite resin.
  • This kneading can be performed by, for example, a method of mixing the pellet-shaped resin and the powdery material, or a method of first melting the resin and then adding the powdery material to the melted material.
  • thermoplastic resin at least one of a thermoplastic resin and a thermosetting resin can be used.
  • thermoplastic resin examples include polyolefins such as polypropylene (PP) and polyethylene (PE), polyester resins such as aliphatic polyester resins and aromatic polyester resins, polyacrylic resins such as polystyrene, methacrylate and acrylate, and polyamide resins.
  • PP polypropylene
  • PE polyethylene
  • polyester resins such as aliphatic polyester resins and aromatic polyester resins
  • polyacrylic resins such as polystyrene, methacrylate and acrylate
  • polyamide resins One kind or two or more kinds can be selected and used from the polycarbonate resin, the polyacetal resin and the like.
  • polyester resin examples of the aliphatic polyester resin include polylactic acid and polycaprolactone, and examples of the aromatic polyester resin include polyethylene terephthalate, which are biodegradable. It is preferable to use a polyester resin having (also referred to simply as "biodegradable resin").
  • biodegradable resin for example, one or more of hydroxycarboxylic acid-based aliphatic polyester, caprolactone-based aliphatic polyester, dibasic acid polyester and the like can be selected and used.
  • hydroxycarboxylic acid-based aliphatic polyester for example, a homopolymer of hydroxycarboxylic acids such as lactic acid, malic acid, glucose acid, and 3-hydroxybutyric acid, and at least one of these hydroxycarboxylic acids are used together.
  • hydroxycarboxylic acids such as lactic acid, malic acid, glucose acid, and 3-hydroxybutyric acid
  • polylactic acid a copolymer of lactic acid and the above-mentioned hydroxycarboxylic acid excluding lactic acid, polycaprolactone, or a copolymer of at least one of the above-mentioned hydroxycarboxylic acids and caprolactone, and polylactic acid is used. It is particularly preferred to use.
  • lactic acid for example, L-lactic acid, D-lactic acid, etc. can be used, and these lactic acids may be used alone or two or more kinds may be selected and used.
  • caprolactone-based aliphatic polyester for example, one or more can be selected and used from a homopolymer of polycaprolactone, a copolymer of polycaprolactone and the like and the above-mentioned hydroxycarboxylic acid, and the like. ..
  • dibasic acid polyester for example, one or more of polybutylene succinate, polyethylene succinate, polybutylene adipate and the like can be selected and used.
  • the biodegradable resin may be used alone or in combination of two or more.
  • thermosetting resin examples include phenol resin, urea resin, melamine resin, furan resin, unsaturated polyester, diallyl phthalate resin, vinyl ester resin, epoxy resin, urethane resin, silicone resin, thermosetting polyimide resin and the like. Can be used. These resins can be used alone or in combination of two or more.
  • the resin may preferably contain an inorganic filler in a proportion that does not interfere with thermal recycling.
  • Examples of the inorganic filler include simple substances and oxidation of metal elements in Groups I to VIII of the Periodic Table, such as Fe, Na, K, Cu, Mg, Ca, Zn, Ba, Al, Ti, and silicon elements. Examples thereof include substances, hydroxides, carbon salts, sulfates, silicates, sulfites, and various clay minerals composed of these compounds.
  • aluminum, magnesium hydroxide, calcium hydroxide, sodium hydroxide, magnesium carbonate, calcium silicate, clay walastonite, glass beads, glass powder, silica sand, silica stone, quartz powder, diatomaceous earth, white carbon, glass fiber, etc. be able to.
  • a plurality of these inorganic fillers may be contained. Further, it may be contained in waste paper pulp.
  • the blending ratio of the fibrous cellulose and the resin is preferably 1 part by mass or more for the fibrous cellulose and 99 parts by mass or less for the resin, and 2 parts by mass or more for the fibrous cellulose and 98 parts by mass or less for the resin. More preferably, the amount of fibrous cellulose is 3 parts by mass or more, and the amount of resin is 97 parts by mass or less.
  • the amount of fibrous cellulose is preferably 50 parts by mass or less, the amount of resin is preferably 50 parts by mass or more, the amount of fibrous cellulose is 40 parts by mass or less, the amount of resin is more preferably 60 parts by mass or more, and the amount of fibrous cellulose is 30. It is particularly preferable that the amount of the resin is 70 parts by mass or less and 70 parts by mass or less.
  • the strength of the resin composition particularly the bending strength and the tensile elastic modulus can be remarkably improved.
  • the content ratio of the fibrous cellulose and the resin contained in the finally obtained resin composition is usually the same as the above-mentioned blending ratio of the fibrous cellulose and the resin.
  • the resin composition includes kenaf, jute hemp, Manila hemp, sisal hemp, ganpi, mitsumata, ⁇ , banana, pineapple, coco palm, corn, sugar cane, bagasse, palm, papyrus, reeds, etc. It may or may not contain fibers derived from plant materials obtained from various plants such as esparto, survivorgrass, wheat, rice, bamboo, various coniferous trees (sugi and hinoki, etc.), broadleaf trees and cotton. ..
  • the resin composition for example, one or more selected from antistatic agents, flame retardants, antibacterial agents, colorants, radical scavengers, foaming agents, etc., within a range that does not impair the effects of the present invention. Can be added with. These raw materials may be added to the dispersion of fibrous cellulose, added at the time of kneading the mixture and the resin, added to these kneaded products, or added by other methods. However, from the viewpoint of production efficiency, it is preferable to add it at the time of kneading the mixture and the resin.
  • the mixture and the kneaded product of the resin can be formed into a desired shape after being kneaded again if necessary.
  • the size, thickness, shape, etc. of this molding are not particularly limited, and may be, for example, sheet-shaped, pellet-shaped, powder-shaped, fibrous-shaped, or the like.
  • the temperature during the molding process is equal to or higher than the glass transition point of the resin and varies depending on the type of resin, but is, for example, 90 to 260 ° C, preferably 100 to 240 ° C.
  • Molding of the kneaded product can be performed by, for example, mold molding, injection molding, extrusion molding, hollow molding, foam molding, or the like. It is also possible to spin the kneaded product into a fibrous form and mix it with the above-mentioned plant material or the like to form a mat shape or a board shape.
  • the mixed fiber can be produced by, for example, a method of simultaneously depositing with an air ray.
  • an apparatus for molding a kneaded product for example, one or two of injection molding machines, blow molding machines, hollow molding machines, blow molding machines, compression molding machines, extrusion molding machines, vacuum molding machines, pressure molding machines, and the like. More than a species can be selected and used.
  • the above molding can be performed after kneading, or the kneaded product is once cooled and made into chips by using a crusher or the like, and then the chips are put into a molding machine such as an extrusion molding machine or an injection molding machine. You can also do it.
  • a molding machine such as an extrusion molding machine or an injection molding machine. You can also do it.
  • molding is not an essential requirement of the present invention.
  • the raw material pulp (LBKP: 98% by mass of water) was pre-beaten with a Niagara beater for 2 hours and 30 minutes.
  • the defibration treatment was performed twice with a stone mill type disperser (“Super Mascoroider” manufactured by Masuyuki Sangyo Co., Ltd.) to obtain an aqueous dispersion (concentration 2% by mass) of cellulose nanofibers (fibers).
  • the cellulose nanofibers contained in this aqueous dispersion had one peak in the pseudo particle size distribution of the particle size distribution measurement using laser diffraction, and the water retention degree was 350% or more.
  • aqueous dispersion and the aqueous solution of melamine (drug) were stirred with a magnetic stirrer for 60 minutes at 1200 rpm to obtain a mixed solution.
  • the mixing ratio (mass basis) of cellulose nanofibers and melamine was 10: 1.
  • the mixed solution was dried at 105 ° C. for 6 hours to obtain a film-shaped cellulose nanofiber-containing dried product.
  • the moisture content of this dried product was 9.8% by mass.
  • the obtained dried product was pulverized so that the average particle size was 1 mm or less.
  • cellulose nanofiber composite resin 11 g of pulverized product (powder), 5 g of polypropylene maleic anhydride, and 85 g of polypropylene (resin) were kneaded with a kneader at 180 ° C. for 1 hour to obtain a cellulose nanofiber composite resin (Test Example 1).
  • cellulose nanofiber composite resins were obtained by variously changing the chemicals (Test Examples 2 to 5; Test Example 6 did not use chemicals).
  • the rate of increase in flexural modulus was investigated for each cellulose nanofiber composite resin. The results are shown in Table 1.
  • the flexural modulus and the increase rate, and the details of each drug are as follows.
  • the bulk specific gravity and water content are as described above.
  • the present invention can be used as a fibrous cellulose composite resin, a method for producing the same, and a reinforcing material for the resin.

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Abstract

Le problème décrit par la présente invention est de fournir : une résine composite de cellulose fibreuse ayant une excellente résistance ; son procédé de production ; et un matériau de renforcement de résine ayant un excellent effet de renforcement de résine même lorsqu'il est créé en un produit séché. À cet effet, la présente invention concerne une résine composite de cellulose fibreuse comprenant une résine et un mélange (matériau de renforcement) d'une cellulose fibreuse et d'un dispersant, une partie ou la totalité de la cellulose fibreuse étant une fibre fine, et le dispersant ayant au moins un groupe fonctionnel sélectionné parmi un groupe hydroxyle, un groupe carboxyle et un groupe amine. De plus, la résine composite est produite par : le mélange d'un dispersant dans une suspension de cellulose fibreuse pour former un mélange ; sécher et pulvériser le mélange pour former une poudre ; puis malaxer la poudre avec une résine, une partie ou la totalité de la cellulose fibreuse étant une fibre fine, et le dispersant ayant au moins un groupe fonctionnel sélectionné parmi un groupe hydroxyle, un groupe carboxyle et un groupe amine.
PCT/JP2020/010870 2019-03-27 2020-03-12 Résine composite de cellulose fibreuse, son procédé de production, et matériau de renforcement de résine WO2020195908A1 (fr)

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EP4365227A1 (fr) * 2021-07-01 2024-05-08 National University Corporation Kanazawa University Procédé de production d'une composition de polysaccharide mélangé à des nanofibres de polysaccharide

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