WO2022030391A1 - Procédé de production de cellulose fibreuse et procédé de production de composite de résine et de cellulose fibreuse - Google Patents

Procédé de production de cellulose fibreuse et procédé de production de composite de résine et de cellulose fibreuse Download PDF

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Publication number
WO2022030391A1
WO2022030391A1 PCT/JP2021/028375 JP2021028375W WO2022030391A1 WO 2022030391 A1 WO2022030391 A1 WO 2022030391A1 JP 2021028375 W JP2021028375 W JP 2021028375W WO 2022030391 A1 WO2022030391 A1 WO 2022030391A1
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cellulose
resin
fibrous cellulose
group
microfiber
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PCT/JP2021/028375
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English (en)
Japanese (ja)
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貴章 今井
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大王製紙株式会社
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    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing fibrous cellulose and a method for producing a fibrous cellulose composite resin.
  • modified cellulose nano in which the step of reacting cellulose having a hydroxyl group with a resin having an anhydrous polybasic acid structure in the molecule to obtain modified cellulose and the step of refining the obtained modified cellulose are performed in the same step.
  • a method for producing a modified cellulose nanofiber wherein the anhydrous polybasic acid structure is a cyclic anhydrous polybasic acid structure in which a carboxyl group is dehydrated and condensed in the molecule to form a cyclic structure.
  • the present proposal is "to provide a simple method for producing modified cellulose nanofibers that are easily dispersed in a solvent".
  • the problem of heat resistance that occurs when the cellulose fiber is used as a reinforcing material for the resin is not taken into consideration.
  • the cellulose fiber is heat-treated at, for example, 150 to 250 ° C. when the cellulose fiber is melt-kneaded with the resin. Therefore, the cellulose fiber is also required to have excellent heat resistance.
  • a main problem to be solved by the present invention is to provide a method for producing a fibrous cellulose having excellent heat resistance and a reinforcing effect of a resin, and a method for producing a fibrous cellulose composite resin having high strength.
  • the step of substituting the hydroxy group of the cellulose fiber with a carbamate group It has a step of defibrating cellulose fibers so that the average fiber width is 0.1 to 19 ⁇ m.
  • the replacement step has a heating step, and a drying step prior to this heating step is provided.
  • the substitution is carried out so that the temperature of 5% weight loss when the cellulose fibers are heated in an absolutely dry state (5 ° C./min, 105 ⁇ 350 ° C.) becomes 240 ° C. or higher.
  • a method for producing fibrous cellulose which is characterized by the above.
  • the substitution is performed prior to the defibration and the substitution rate is 1.0 to 2.0 mmol / g.
  • the defibration is performed so that the average fiber length of the cellulose fibers after defibration remains at 0.10 mm or more.
  • the defibration is performed so that the average fiber length ratio (average fiber length before defibration / average fiber length after defibration) is less than 30.
  • the moisture content of the cellulose fibers used in the heating step is 10% or less.
  • the heating in the heating step is performed at 200 ° C. or lower and for 15 hours or less.
  • a fibrous cellulose is obtained by the method according to any one of claims 1 to 5, and the fibrous cellulose and a resin are mixed.
  • a method for producing a fibrous cellulose composite resin is obtained by the method according to any one of claims 1 to 5, and the fibrous cellulose and a resin.
  • the present invention is a method for producing a fibrous cellulose having excellent heat resistance and a reinforcing effect of a resin, and a method for producing a fibrous cellulose composite resin having high strength.
  • 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 method for producing fibrous cellulose (cellulose fiber) of this embodiment includes a step of substituting a part or all of the hydroxy group (-OH group) of the cellulose fiber with a carbamate group, and the cellulose fiber having an average fiber width of 0.1 to. It has a step of defibrating the fiber so as to be 19 ⁇ m, that is, to be microfiber cellulose (microfibrillated cellulose).
  • the replacement step has a heating step, and a drying step prior to this heating step is provided.
  • the cellulose fibers are heated in an absolutely dry state (5 ° C./min, 105 ⁇ 350 ° C.). In this case, the temperature of the 5% weight reduction is set to 240 ° C. or higher.
  • the substitution is carried out prior to the defibration so that the substitution rate is 1.0 to 2.0 mmol / g. Further, the defibration is performed so that the average fiber length of the cellulose fibers after defibration remains at 0.10 mm or more. Further, in the method for producing the fibrous cellulose composite resin, fibrous cellulose is obtained by the above production method, and the fibrous cellulose and the resin are mixed. Hereinafter, it will be described in detail.
  • fibrous cellulose having an average fiber width (diameter) of 0.1 to 19 ⁇ m is referred to as microfiber cellulose, microfibrillated cellulose, or MFC.
  • the raw material pulp (cellulose raw material) is defibrated so as to be microfiber cellulose (microfibrillated cellulose) having an average fiber width of 0.1 to 19 ⁇ m.
  • microfiber cellulose microfibrillated cellulose
  • the reinforcing effect of the resin is remarkably improved.
  • microfiber cellulose is easier to denature (carbamate) with a carbamate group than cellulose nanofibers, which are also fine fibers.
  • carbamate the cellulose raw material before it is miniaturized, and in this case, the microfiber cellulose and the cellulose nanofiber are equivalent.
  • microfiber cellulose means a fiber having an average fiber diameter (width) larger than that of cellulose nanofiber.
  • the average fiber diameter is, for example, 0.1 to 19 ⁇ m, preferably 0.2 to 15 ⁇ m, and more preferably more than 0.5 to 10 ⁇ m.
  • the average fiber diameter of the microfiber cellulose is less than 0.1 ⁇ m (less than 0.1 ⁇ m), it is no different from that of cellulose nanofibers, and the effect of improving the strength (particularly bending elastic modulus) of the resin may not be sufficiently obtained. ..
  • the defibration time becomes long and a large amount of energy is required. Further, the dehydration property of the cellulose fiber slurry is deteriorated.
  • the cellulose fibers are thermally deteriorated and the strength may decrease.
  • the thermal decomposition temperature is remarkably lowered, so that the heat resistance may be lowered, which makes it unsuitable for kneading with a resin.
  • the average fiber diameter of the microfiber cellulose exceeds (exceeds) 19 ⁇ m, it is 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, 100 ml of an aqueous dispersion of fine fibers having a solid content concentration of 0.01 to 0.1% by mass is filtered through a membrane filter manufactured by Teflon (registered trademark), and the solvent is replaced once with 100 ml of ethanol and three times with 20 ml of t-butanol. do. Next, it is freeze-dried and coated with osmium to prepare a sample. This sample is observed with an electron microscope SEM image at a magnification of 3,000 to 30,000 times depending on the width of the constituent fibers.
  • microfiber cellulose can be obtained by defibrating (miniaturizing) the cellulose raw material.
  • the raw material pulp includes, for example, wood pulp made from broadleaf trees, coniferous trees, etc., non-wood pulp made from straw, bagasse, cotton, hemp, carrot fiber, etc., recycled paper pulp made from recovered waste paper, waste paper, etc.
  • One type or two or more types can be selected and used from (DIP) and the like.
  • DIP crushed product
  • the above-mentioned various raw materials may be, for example, in the state of a crushed product (powder) called a cellulosic powder or the like.
  • wood pulp as the raw material pulp.
  • wood pulp for example, one kind or two 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, unbleached softwood kraft pulp, or semi-bleached softwood 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
  • Cellulose fiber (raw material pulp) can 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.
  • the pretreatment by a chemical method it is preferable to carry out an enzyme treatment, and in addition, it is more preferable to carry out one or more treatments selected from an acid treatment, an alkali treatment and an oxidation treatment.
  • an enzyme treatment it is preferable to carry out one or more treatments selected from an acid treatment, an alkali treatment and an oxidation treatment.
  • the enzyme treatment will be described in detail.
  • the enzyme used for the enzyme treatment it is preferable to use at least one of the cellulase-based enzyme and the hemicellulase-based enzyme, and it is more preferable to use both in combination.
  • the use of these enzymes facilitates the defibration of cellulose raw materials.
  • the cellulase-based enzyme causes the decomposition of cellulose in the coexistence of water.
  • hemicellulose-based enzymes induce the decomposition of hemicellulose in the presence of water.
  • cellulase-based enzymes examples include Trichoderma (Filamentous fungus), Acremonium (Filamentous fungus), Aspergillus (Filamentous fungus), Fanerochaete (Phanerochaete), Tramethes (Tra).
  • Enzymes can be used.
  • These cellulase-based enzymes can be purchased as reagents or commercial products.
  • cellulosein T2 manufactured by HPI
  • Meicerase manufactured by Meiji Seika
  • Novozyme 188 manufactured by Novozyme
  • Multifect CX10L manufactured by Genencore
  • cellulase-based enzyme GC220 manufactured by Genecore
  • EG encodedoglucanase
  • CBH cellobiohydrolase
  • hemicellulase-based enzyme for example, xylanase, which is an enzyme that decomposes xylan, mannase, which is an enzyme that decomposes mannan, and arabanase, which is an enzyme that decomposes araban, can be used.
  • xylanase which is an enzyme that decomposes xylan
  • mannase which is an enzyme that decomposes mannan
  • arabanase which is an enzyme that decomposes araban
  • pectinase which is an enzyme that decomposes pectin
  • Hemicellulose is a polysaccharide excluding pectins between the cellulose microfibrils of the plant cell wall. Hemicellulose is diverse and varies between wood types and cell wall layers. Glucomannan is the main component in the secondary walls of conifers, and 4-O-methylglucuronoxylan is the main component in the secondary walls of hardwoods. Therefore, when fine fibers are obtained from softwood bleached kraft pulp (NBKP), it is preferable to use mannase. Further, when fine fibers are obtained from hardwood bleached kraft pulp (LBKP), it is preferable to use xylanase.
  • NNKP softwood bleached kraft pulp
  • LKP hardwood bleached kraft pulp
  • the amount of enzyme added to the cellulose fiber is determined by, for example, the type of enzyme, the type of wood used as a raw material (conifer or hardwood), the type of mechanical pulp, and the like.
  • the amount of the enzyme added to the cellulose raw material is preferably 0.1 to 3% by mass, more preferably 0.3 to 2.5% by mass, and particularly preferably 0.5 to 2% by mass. If the amount of the enzyme added is less than 0.1% by mass, the effect of the addition of the enzyme may not be sufficiently obtained. On the other hand, if the amount of the enzyme added exceeds 3% by mass, cellulose may be saccharified and the yield of cellulose fibers may decrease. In addition, there is also a problem that the improvement of the effect corresponding to the increase in the addition amount cannot be recognized.
  • the temperature during the enzyme treatment is preferably 30 to 70 ° C, more preferably 35 to 65 ° C, and particularly preferably 40 to 60 ° C, regardless of whether the cellulase-based enzyme or the hemicellulase-based enzyme is used as the enzyme. ..
  • the temperature at the time of enzyme treatment is 30 ° C. or higher, the enzyme activity is less likely to decrease, and the treatment time can be prevented from being prolonged.
  • the temperature at the time of enzyme treatment is 70 ° C. or lower, inactivation of the enzyme can be prevented.
  • the enzyme treatment time is determined by, for example, the type of enzyme, the temperature of the enzyme treatment, the pH at the time of the enzyme treatment, and the like.
  • the general enzyme treatment time is 0.5 to 24 hours.
  • a method for inactivating the enzyme for example, there are a method of adding an alkaline aqueous solution (preferably pH 10 or higher, more preferably pH 11 or higher), a method of adding hot water at 80 to 100 ° C., and the like.
  • alkali treatment When alkali treatment is performed prior to defibration, some of the hydroxyl groups of hemicellulose and cellulose in pulp are dissociated, and the molecules are anionized, weakening intramolecular and intermolecular hydrogen bonds and promoting dispersion of cellulose raw materials in defibration. Ru.
  • 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 microfiber cellulose 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 microfiber cellulose is low, dehydration is likely to occur, and the dehydration property of the cellulose fiber slurry is improved.
  • 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 cellulose fibers using. However, it is preferable to use a refiner or a jet mill.
  • the average fiber length (average length of single fibers) of cellulose is preferably 0.10 to 2.00 mm, more preferably 0.12 to 1.50 mm, and particularly preferably 0.12 to 1.50 mm. It is 0.15 to 1.00 mm. If the average fiber length is less than 0.10 mm, a three-dimensional network of fibers cannot be formed, the flexural modulus of the composite resin may decrease, and the reinforcing effect may not be improved. On the other hand, if the average fiber length exceeds 2.00 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 before defibration is preferably 0.50 to 5.00 mm, more preferably 1.00 to 3.00 mm, and particularly preferably 1.50 to 2.50 mm. If the average fiber length is less than 0.50 mm, the reinforcing effect of the resin may not be sufficiently obtained during the defibration treatment. On the other hand, if the average fiber length exceeds 5.00 mm, it may be disadvantageous in terms of manufacturing cost at the time of defibration.
  • the defibration of the cellulose fibers is preferably performed so that the average fiber length ratio is less than 30, more preferably 2 to 20, and 1.5 to 10. Especially preferable.
  • the average fiber length ratio is 30 or more, the mechanical shearing to the fiber becomes excessive and the damage to the fiber increases. Therefore, the fiber may become too short or the strength of the fiber itself may decrease, and as a result, the resin reinforcing effect when composited with the resin may not be exhibited.
  • the average fiber length ratio is a value obtained by dividing the average fiber length of the cellulose fibers before defibration by the average fiber length of the cellulose fibers after defibration (average fiber length before defibration / average after defibration). Fiber length).
  • the average fiber length of the cellulose fiber can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the average fiber length of the cellulose fiber is a value measured by a fiber analyzer "FS5" manufactured by Valmet. The same applies to the fine rate (Fine rate) described below.
  • the fine ratio of the microfiber cellulose obtained by defibration is preferably 30% or more, more preferably 35 to 99%, and particularly preferably 40 to 95%.
  • the fine ratio is 30% or more, the proportion of homogeneous fibers is large, and the destruction of the composite resin is difficult to proceed.
  • the fine ratio exceeds 99%, the flexural modulus may be insufficient.
  • the fine ratio of microfiber cellulose that is, the cellulose fiber after defibration, but it is more preferable to keep the fine ratio of the cellulose fiber before defibration within a predetermined range.
  • the fine ratio of the cellulose fibers before defibration is preferably 1% or more, more preferably 3 to 20%, and particularly preferably 5 to 18%. If the fine ratio of the cellulose fiber before defibration is within the above range, even if the fine ratio of the microfiber cellulose is defibrated to be 30% or more, the damage to the fiber is small and the reinforcing effect of the resin is considered to be improved. Be done.
  • the fine rate can be adjusted by pretreatment such as enzyme treatment.
  • pretreatment such as enzyme treatment
  • the fiber itself may become tattered and the reinforcing effect of the resin may be reduced. Therefore, the amount of the enzyme added from this point of view is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. Further, it is also one of the selection frames that the enzyme treatment is not performed (addition amount: 0% by mass).
  • the "fine ratio” refers to the mass-based ratio of pulp fibers having a fiber length of 0.2 mm or less.
  • 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, the three-dimensional network cannot be sufficiently constructed, and even if the average fiber length is 0.10 mm or more, the reinforcing effect may be insufficient. On the other hand, if the aspect ratio exceeds 15,000, the entanglement between the microfiber celluloses becomes high, and the dispersion in the resin may be insufficient.
  • 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 where catching occurs, so that the reinforcing effect increases, but on the other hand, the more catching, the lower the ductility of the resin.
  • the fibrillation rate of the microfiber 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, and dehydration may become difficult even if the fibers are defibrated within the range where the average fiber width remains 0.1 ⁇ m or more. be. On the other hand, if the fibrillation rate is lower than 1.0%, there are few hydrogen bonds between the fibrils, and there is a possibility that a strong three-dimensional network cannot be formed.
  • the fibrillation rate refers to the dissociation of cellulose fibers in accordance with JIS-P-8220: 2012 "Pulp-Dissolution Method", and the obtained dissociated pulp is referred to as FiberLab. (Kajaani) means a value measured using.
  • the crystallinity of the microfiber cellulose is preferably 50% or more, more preferably 55% or more, and particularly preferably 60% or more.
  • the crystallinity is less than 50%, the mixability with other fibers such as pulp and cellulose nanofibers is improved, but the strength of the fibers themselves is lowered, so that the strength of the resin may not be improved. be.
  • the crystallinity is less than 50%, the heat resistance may be insufficient, especially in the present embodiment in which the substitution rate of the carbamate group is 1.0 mmol / g or more.
  • the crystallinity of the microfiber cellulose is preferably 95% or less, more preferably 90% or less, and particularly preferably 85% or less.
  • the crystallinity exceeds 95%, the ratio of strong hydrogen bonds in the molecule increases, the fiber itself becomes rigid, and the dispersibility becomes inferior.
  • microfiber cellulose The crystallinity of microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, and micronization treatment.
  • the crystallinity is a value measured according to JIS K 0131 (1996).
  • the pulp viscosity of the microfiber cellulose is preferably 2 cps or more, more preferably 4 cps or more. If the pulp viscosity of the microfiber cellulose is less than 2 cps, it may be difficult to suppress the aggregation of the microfiber cellulose.
  • the pulp viscosity is a value measured according to TAPPI T 230.
  • the freeness of the microfiber cellulose is preferably 500 ml or less, more preferably 300 ml or less, and particularly preferably 100 ml or less. If the freeness of the microfiber cellulose exceeds 500 ml, the effect of improving the strength of the resin may not be sufficiently obtained.
  • the freeness is a value measured in accordance with JIS P8121-2 (2012).
  • the zeta potential of the microfiber cellulose is preferably ⁇ 150 to 20 mV, more preferably -100 to 0 mV, and particularly preferably -80 to -10 mV. If the zeta potential is lower than ⁇ 150 mV, the compatibility with the resin may be significantly reduced and the reinforcing effect may be insufficient. On the other hand, if the zeta potential exceeds 20 mV, the dispersion stability may decrease.
  • the water retention of the microfiber cellulose is preferably 80 to 400%, more preferably 90 to 350%, and particularly preferably 100 to 300%. If the water retention level is less than 80%, the reinforcing effect may be insufficient because it is the same as the raw material pulp. On the other hand, when the degree of water retention exceeds 400%, the dehydration property tends to be inferior and the agglomeration tends to be easy. In this respect, the degree of water retention of the microfiber cellulose can be lowered by substituting the hydroxy group of the fiber with a carbamate group, and the dehydration property and the drying property can be improved.
  • microfiber cellulose The water retention of microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
  • the degree of water retention is JAPAN TAPPI No. It is a value measured according to 26 (2000).
  • the microfiber cellulose of this embodiment has a carbamate group. How it is supposed to have a carbamate group is not particularly limited.
  • the cellulose raw material may be carbamate to have a carbamate group, or the microfiber cellulose (finely divided cellulose raw material) may be carbamate to have a carbamate group. ..
  • having a carbamic acid group means a state in which a carbamic acid group (ester of carbamic acid) is introduced into 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 , and the like. That is, the carbamate group can be represented by the following structural formula (1).
  • R is independently a saturated linear hydrocarbon group, a saturated branched chain hydrocarbon group, a saturated cyclic hydrocarbon group, an unsaturated linear hydrocarbon group, an unsaturated branched chain hydrocarbon group, and the like.
  • saturated linear hydrocarbon group examples include a linear alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group.
  • saturated branched chain hydrocarbon group examples include a branched chain alkyl group having 3 to 10 carbon atoms such as an isopropyl group, a sec-butyl group, an isobutyl group and a tert-butyl group.
  • saturated cyclic hydrocarbon group examples include cycloalkyl groups such as cyclopentyl group, cyclohexyl group and norbornyl group.
  • Examples of the unsaturated linear hydrocarbon group include a linear alkenyl group having 2 to 10 carbon atoms such as an ethenyl group, a propene-1-yl group and a propene-3-yl group, an ethynyl group and a propyne-1.
  • Examples thereof include a linear alkynyl group having 2 to 10 carbon atoms such as an yl group and a propyne-3-yl group.
  • Examples of the unsaturated branched chain hydrocarbon group include a branched chain alkenyl group having 3 to 10 carbon atoms such as a propene-2-yl group, a butene-2-yl group and a butene-3-yl group, and butin-3.
  • a branched chain alkenyl group having 3 to 10 carbon atoms such as a propene-2-yl group, a butene-2-yl group and a butene-3-yl group, and butin-3.
  • -A branched chain alkynyl group having 4 to 10 carbon atoms such as an yl group can be mentioned.
  • aromatic group examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
  • Examples of the inducing group include the above-mentioned saturated linear hydrocarbon group, saturated branched chain hydrocarbon group, saturated cyclic hydrocarbon group, unsaturated linear hydrocarbon group, unsaturated branched chain hydrocarbon group and aromatic.
  • Examples thereof include a group in which one or more hydrogen atoms contained in the group are substituted with a substituent (for example, a hydroxy group, a carboxy group, a halogen atom, etc.).
  • microfiber cellulose having a carbamate group in which a carbamate group is introduced, a part or all of a highly polar hydroxy group is replaced with a relatively low polarity carbamate group. Therefore, the microfiber cellulose having a carbamate group has low hydrophilicity and high affinity with a resin having low polarity. As a result, the microfiber cellulose having a carbamate group is excellent in uniform dispersibility with the resin. Further, the slurry of microfiber cellulose having a carbamate group has low viscosity and good handleability.
  • the substitution rate of the carbamate group with respect to the hydroxy group of the microfiber cellulose is preferably 1.0 to 2.5 mmol / g, more preferably 1.1 to 2.0 mmol / g, and particularly preferably 1.2 to 1.8 mmol / g. g.
  • the substitution rate is 1.0 mmol / g or more, the effect of introducing the carbamate group, particularly the effect of improving the flexural modulus of the resin can be surely exhibited. This is because when the substitution rate is 1.0 mmol / g or more, the hydrogen bond between celluloses caused by the hydroxyl group of cellulose is weakened (aggregation relaxation effect), and in addition, a carbamate group having higher hydrophobicity than the hydroxyl group is introduced.
  • the affinity with the resin is enhanced (affinity improving effect), and as a result, the microfiber celluloses do not aggregate in the resin, and the role of reinforcing the resin is surely fulfilled.
  • the substitution rate of the carbamate group exceeds 2.5 mmol / g, the heat resistance of the composite resin is lowered.
  • the cellulose fiber receives heat, desorption of hydroxyl groups or the like usually occurs, and the molecular chain can be shortened starting from the place where desorption or the like occurs.
  • desorption of the hydroxyl group is more likely to occur.
  • the carbamate conversion rate is increased too much, the molecular chain becomes too short, the decomposition temperature decreases, and the heat resistance decreases.
  • the substitution rate of the carbamate group exceeds 2.5 mmol / g, the temperature of 5% weight loss when the cellulose fiber is heated in an absolutely dry state (5 ° C / min, 105 ⁇ 350 ° C) is 240. It is likely to be below ° C.
  • the substitution rate of the carbamate group exceeds 2.5 mmol / g, the average fiber length of the pulp becomes short when the cellulose fiber is carbamate, and as a result, the average fiber length of the microfiber cellulose tends to be less than 0.1 mm. , There is a risk that sufficient resin reinforcement effect cannot be obtained. If the substitution rate exceeds 5.0 mmol / g, the cellulose fibers cannot maintain the shape of the fibers.
  • the carbamate group substitution rate (mmol / g) refers to the amount of substance of the carbamate group contained in 1 g of the cellulose fiber having a carbamate group.
  • the substitution rate of the carbamate group is measured by measuring the N atoms present in the carbamate pulp by the Kjeldahl method, and the carbamateization rate per unit weight is calculated.
  • Cellulose is a polymer having anhydrous glucose as a structural unit, and has three hydroxy groups per structural unit.
  • the cellulose fiber of this embodiment preferably has a temperature of 5% weight loss of 240 ° C. or higher when heated in an absolutely dry state (5 ° C./min, 105 ⁇ 350 ° C.), more preferably 245 ° C. or higher. It is preferably 250 ° C. or higher, and particularly preferably 250 ° C. or higher.
  • a composite resin having excellent heat resistance can be obtained.
  • the temperature of 10% weight loss when heated in an absolutely dry state is preferably 260 ° C. or higher, preferably 260 ° C. or higher. Is more preferable, and it is particularly preferable that the temperature is 270 ° C. or higher. If the temperature of 10% weight reduction is 260 ° C. or higher, damage to the fibers can be suppressed to a small extent even if heat is applied at various temperatures or multiple times during various processing such as compounding with resin. It is possible to widen the range of processing conditions without requiring an excessive restriction on the processing temperature of the resin.
  • the heating condition for measuring the above weight loss is when the temperature of the cellulose fibers is raised from 105 ° C to 350 ° C at 5 ° C / min after the cellulose fibers are in an absolutely dry state.
  • carbamate first and then defibrate. This is because the cellulose raw material before defibration has high dehydration efficiency, and the cellulose raw material is easily defibrated by heating accompanying carbamate formation.
  • the step of carbamate the cellulose fiber can be classified into, for example, a step of mixing treatment, a drying treatment (drying step), a heat treatment and the like.
  • the mixing treatment and the drying treatment can also be referred to as a preparation treatment for preparing a mixture to be subjected to the heat treatment.
  • Carbamateization also has the advantage that it can be chemically modified without the use of organic solvents.
  • cellulose fibers and urea or a derivative of urea are mixed in a dispersion medium.
  • urea or urea for example, urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, a compound in which the hydrogen atom of urea is replaced with an alkyl group or the like can be used.
  • ureas or derivatives of urea can be used alone or in combination of two or more. However, it is preferable to use urea.
  • the lower limit of the mixed mass ratio of urea or the like (urea or the like / cellulose fiber) to the cellulose fiber is preferably 10/100, more preferably 20/100.
  • the upper limit is preferably 300/100, more preferably 200/100.
  • 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 be used.
  • cellulose fibers and urea may be added to water, cellulose fibers may be added to an aqueous solution of urea or the like, or urea or the like may be added to a slurry containing cellulose fibers. Further, in order to mix uniformly, the mixture may be stirred after the addition. Further, the dispersion liquid containing the cellulose fibers and urea or the like may contain other components.
  • the drying treatment the dispersion medium is removed from the dispersion liquid containing the cellulose fibers and urea obtained in the mixing treatment. Therefore, the drying process can be said to be a removal process. By removing the dispersion medium, urea and the like can be efficiently reacted in the subsequent heat treatment.
  • dispersion medium 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, and particularly preferably 90 ° C.
  • 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 with each other and the urea may be decomposed independently.
  • the heating time in the removal treatment can be appropriately adjusted according to the solid content concentration of the dispersion liquid and the like.
  • the upper limit of the heating time (drying time) is, for example, 15 hours, preferably 13 hours, more preferably 10 hours, and particularly preferably 9 hours.
  • the lower limit is 6 hours.
  • the drying time is 6 to 9 hours, side effects such as fiber deterioration due to heating can be reliably suppressed while achieving the purpose of drying.
  • drying step prior to the heat treatment (reaction treatment).
  • the cellulose fibers subjected to the heat treatment are dried so that the moisture content is 10% or less, preferably 0 to 9%, and more preferably 0 to 8%.
  • the carbamate formation rate can be easily set to 1 mmol / g or more. In this respect, if carbamate formation is difficult, it becomes necessary to perform the heat treatment at a high temperature or for a long time, and the possibility of heat deterioration of the cellulose fibers increases. When the cellulose fiber is thermally deteriorated, the reinforcing effect of the resin is reduced.
  • reaction treatment a mixture of cellulose fibers and urea or the like is heat-treated.
  • a part or all of the hydroxy groups of the cellulose fibers react with urea or the like and are replaced with carbamate groups.
  • isocyanic acid and ammonia as shown in the following reaction formula (1).
  • Isocyanic acid is very reactive, and for example, a carbamate group is formed at the hydroxyl group of cellulose as shown in the following reaction formula (2).
  • the lower limit of the heating temperature in the heat treatment is preferably 120 ° C., more preferably 130 ° C., particularly preferably urea melting point (about 134 ° C.) or higher, still more preferably 140 ° C., and most preferably 150 ° C.
  • the upper limit of the heating temperature is preferably 200 ° C, more preferably 180 ° C, and particularly preferably 170 ° C. If the heating temperature exceeds 200 ° C., the cellulose fibers may be decomposed and the reinforcing effect may be insufficient.
  • the lower limit of the heating time in the heat treatment is preferably 1 minute, more preferably 5 minutes, and particularly preferably 30 minutes. By setting the heating time to 1 minute or more, the carbamate-forming reaction can be reliably carried out.
  • the upper limit of the heating time is preferably 15 hours, more preferably 10 hours, and particularly preferably 5 hours. If the heating time exceeds 15 hours, it is not economical and sufficient carbamate can be achieved in 15 hours.
  • the reaction temperature and the reaction time are mainly different between the drying step and the reaction step. Since the main purpose of the drying step is to remove a dispersion medium such as water, the treatment is performed at a low temperature and for a long time. On the other hand, since the main purpose of the reaction step is to promote the reaction, the treatment is carried out at a high temperature for a short time so as not to cause deterioration of the cellulose fibers. If heating is performed in the reaction step in a state where the water content is high, water or steam exposed to a high temperature state may break the acetal bond to which glucose constituting cellulose is bound. This means that the fibers will be damaged, leading to a lower thermal decomposition temperature.
  • the pH condition in the heat treatment becomes important.
  • the pH is preferably an alkaline condition of pH 9 or higher, more preferably pH 9 to 13, and particularly preferably pH 10 to 12.
  • the pH is 7 or less, preferably pH 3 to 7, and particularly preferably pH 4 to 7, which is an acidic condition or a neutral condition.
  • the average fiber length of the cellulose fibers becomes short, and the reinforcing effect of the resin may be inferior.
  • the pH is 9 or higher, the reactivity of the cellulose fibers is enhanced, the reaction with urea or the like is promoted, and the carbamate-forming reaction is carried out efficiently.
  • the average fiber length of the cellulose fibers should be sufficiently secured. Can be done.
  • the reaction of decomposing urea or the like into isocyanic acid and ammonia proceeds, the reaction with cellulose fibers is promoted, and the carbamate formation reaction is performed efficiently, so that the average fiber length of the cellulose fibers is sufficient. Can be secured.
  • 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, or the like can be used.
  • the mixture after heat treatment may be washed. This washing may be performed with water or the like. By this washing, urea, by-products and the like that remain unreacted can be removed.
  • both defibration and carbamating can be performed first, but in the case of the washing, it is preferable to defibrate after carbamating rather than carbamating after defibration. This is because when the cellulose fiber is defibrated, the water retention (degree) increases and it becomes difficult to dehydrate, and when the fiber is finely divided, it tends to irreversibly aggregate when it dries. For example, assuming that the water retention of pulp is 100%, the water retention of MFC after defibration is as high as 300%.
  • the microfiber cellulose is dispersed in an aqueous medium to form a dispersion liquid (slurry). It is particularly preferable that 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. As the other liquid, 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. If the solid content concentration is less than 0.1% by mass, excessive energy may be required for dehydration and drying. On the other hand, if the solid content concentration exceeds 10.0% by mass, the fluidity of the slurry itself is lowered, and when a dispersant is used, it may not be possible to mix uniformly.
  • the microfiber cellulose is preferably mixed with an acid-modified resin.
  • the acid group ionically bonds with a part or all of the carbamate group. This ionic bond improves the reinforcing effect of the resin.
  • an acid-modified polyolefin resin for example, an acid-modified polyolefin resin, an acid-modified epoxy resin, an acid-modified styrene-based elastomer resin, or the like can be used. However, it is preferable to use an acid-modified polyolefin resin.
  • the acid-modified polyolefin resin is a copolymer of an unsaturated carboxylic acid component and a polyolefin component.
  • polystyrene resin for example, one or two or more of alkene polymers such as ethylene, propylene, butadiene, and isoprene can be selected and used.
  • alkene polymers such as ethylene, propylene, butadiene, and isoprene
  • polypropylene resin which is a polymer of propylene.
  • the unsaturated carboxylic acid component for example, one or more of maleic anhydride, phthalic acid anhydride, itaconic acid anhydride, citraconic acid anhydride, citric acid anhydride and the like can be selected and used.
  • maleic anhydrides that is, it is preferable to use a maleic anhydride-modified polypropylene resin.
  • the mixing amount of the acid-modified resin is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, and particularly preferably 10 to 200 parts by mass with respect to 100 parts by mass of the microfiber cellulose.
  • the acid-modified resin is a maleic anhydride-modified polypropylene resin
  • the amount is preferably 1 to 200 parts by mass, more preferably 10 to 100 parts by mass. If the mixed amount of the acid-modified resin is less than 0.1 parts by mass, the improvement in strength is not sufficient. On the other hand, if the mixing amount exceeds 1,000 parts by mass, it becomes excessive and the strength tends to decrease.
  • the weight average molecular weight of maleic anhydride-modified polypropylene is, for example, 1,000 to 100,000, preferably 3,000 to 50,000.
  • the acid value of maleic anhydride-modified polypropylene is preferably 0.5 mgKOH / g or more and 100 mgKOH / g or less, and more preferably 1 mgKOH / g or more and 50 mgKOH / g or less.
  • the MFR (melt flow rate) of the acid-modified resin is preferably 2000 g / 10 minutes (190 ° C. / 2.16 kg) or less, more preferably 1500 g / 10 minutes or less, and 500 g / 10 minutes or less. It is particularly preferable to have it. If the MFR exceeds 2000 g / 10 minutes, the dispersibility of the cellulose fibers may decrease.
  • the acid value is measured in accordance with JIS-K2501 and titrated with potassium hydroxide.
  • the MFR measurement is based on JIS-K7210, and is determined by the weight of the sample flowing out in 10 minutes with a load of 2.16 kg at 190 ° C.
  • the microfiber cellulose of this embodiment is preferably mixed with a dispersant.
  • a dispersant a compound having an amine group and / or a hydroxyl group in an aromatic group and a compound having an amine group and / or a hydroxyl group in an aliphatic group are preferable.
  • Examples of compounds having an amine group and / or a hydroxyl group in aromatics include aniline, toluidin, trimethylaniline, anisidin, tyramine, histamine, tryptamine, phenol, dibutylhydroxytoluene, and bisphenol A. Classes, cresols, eugenols, gallic acid, guaiacol, picrinic acid, phenolphthalene, serotonin, dopamine, adrenaline, noradrenaline, timol, tyrosine, salicylic acid, methyl salicylate, anis alcohol.
  • Salicyl alcohols cinapyl alcohols, diphenidols, diphenylmethanols, cinnamyl alcohols, scopolamines, tryptofols, vanillyl alcohols, 3-phenyl-1-propanols, phenethyl alcohols, phenoxyethanols , Veratril alcohols, benzyl alcohols, benzoins, mandelic acids, manderonitriles, benzoic acids, phthalic acids, isophthalic acids, terephthalic acids, melitonic acids, silicic acids and the like.
  • Examples of compounds having an amine group and / or a hydroxyl group in aliphatics include capryl alcohols, 2-ethylhexanols, pelargone alcohols, caprin alcohols, undecyl alcohols, lauryl alcohols, and tridecyl alcohols.
  • Myristyl alcohols pentadecyl alcohols, cetanols, stearyl alcohols, erizyl alcohols, oleyl alcohols, linoleyl alcohols, methylamines, dimethylamines, trimethylamines, ethylamines, diethylamines, ethylenediamine , Triethanolamines, N, N-diisopropylethylamines, tetramethylethylenediamines, hexamethylenediamines, spermidins, spermins, amantadins, formic acids, acetic acids, propionic acids, butyric acids, valeric acids, Caproic acids, enanth acids, capricic acids, pelargonic acids, capric acids, lauric acids, myristic acids, palmitic acids, margalic acids, stearic acids, oleic acids, linoleic acids, linolenic acids, arachid
  • the above dispersants inhibit hydrogen bonds between cellulose fibers. Therefore, when the microfiber cellulose and the resin are kneaded, the microfiber cellulose is surely dispersed in the resin. Further, the above dispersant also has a role of improving the compatibility of the microfiber cellulose and the resin. In this respect, the dispersibility of the microfiber cellulose in the resin is improved.
  • the microfiber cellulose and the dispersant (drug) are mixed in advance rather than adding the chemical at this stage.
  • the fibrous cellulose-containing material is used, the chemicals are more uniformly bound to the microfiber cellulose, and the effect of improving the compatibility with the resin is enhanced.
  • polypropylene has a melting point of 160 ° C., and therefore, kneading of fibrous cellulose (microfiber cellulose) and resin is performed at about 180 ° C.
  • a dispersant liquid
  • a masterbatch composite resin having a high concentration of microfiber cellulose
  • a resin having a low melting point generally has a low strength. Therefore, according to this method, the strength of the composite resin may decrease.
  • the mixing amount of the dispersant is preferably 0.1 to 1,000 parts by mass, more preferably 1 to 500 parts by mass, and particularly preferably 10 to 200 parts by mass with respect to 100 parts by mass of the microfiber cellulose. If the mixing amount of the dispersant is less than 0.1 parts by mass, it may be considered that the improvement of the resin strength is not sufficient. On the other hand, if the mixing amount exceeds 1,000 parts by mass, the amount becomes excessive and the resin strength tends to decrease.
  • the above-mentioned acid-modified resin is intended to improve the compatibility by ionic bonding between the acid group and the carbamate group of the microfiber cellulose, thereby enhancing the reinforcing effect, and because of its large molecular weight, it is easy to be compatible with the resin. , It is considered that it contributes to the improvement of strength.
  • the above-mentioned dispersant intervenes between the hydroxyl groups of the microfiber cellulose to prevent aggregation and thus improves the dispersibility in the resin, and has a smaller molecular weight than the acid-modified resin.
  • the molecular weight of the acid-modified resin is preferably 2 to 2,000 times, preferably 5 to 1,000 times, the molecular weight of the dispersant.
  • the microfiber cellulose of this embodiment is preferably mixed with a powder that does not interact with the microfiber cellulose.
  • the microfiber cellulose can be made into a form capable of exhibiting the reinforcing property of the resin.
  • the celluloses may irreversibly aggregate with each other due to hydrogen bonds, and the reinforcing effect as a fiber may not be sufficiently exhibited. Therefore, by containing a powder that does not interact with the microfiber cellulose, hydrogen bonds between the celluloses are physically inhibited.
  • non-interacting is included in the concept that covalent bonds, ionic bonds, and strong bonds by metal bonds do not occur with cellulose (that is, hydrogen bonds and van der Waals force bonds do not interact).
  • the strong bond is a bond having a binding energy of more than 100 kJ / mol.
  • the non-interacting powder is preferably at least one of an inorganic powder and a resin powder having little action of dissociating the hydroxyl group of the cellulose fiber into hydroxide ions when coexisting in the slurry. More preferably, it is an inorganic powder.
  • an inorganic powder When having such physical properties, when microfiber cellulose or powder that does not interact with each other is mixed to form a fibrous cellulose-containing material and then compounded with a resin or the like, the cellulose fiber and the powder that does not interact with the cellulose fiber are made into a resin. It becomes possible to easily disperse to the like. Further, particularly when it is an inorganic powder, it is advantageous in terms of operation.
  • a method for adjusting the water content of the fibrous cellulose-containing material for example, a method of directly applying an aqueous dispersion (a mixture of fibrous cellulose and non-interacting powder) to a metal drum as a heat source is used for drying (a mixture of fibrous cellulose and non-interacting powder).
  • a method of drying with a Yankee dryer or a cylinder dryer, etc. and a method of heating without directly contacting the water dispersion with a heat source, that is, a method of drying in air (for example, drying with a constant temperature dryer, etc.).
  • a method of drying in air for example, drying with a constant temperature dryer, etc.
  • the average particle size of the non-interacting powder is preferably 1 to 10,000 ⁇ m, more preferably 10 to 5,000 ⁇ m, and particularly preferably 100 to 1,000 ⁇ m. If the average particle size exceeds 10,000 ⁇ m, when the aqueous medium is removed from the fibrous cellulose slurry, the effect of entering the gaps between the cellulose fibers and inhibiting aggregation may not be exhibited. On the other hand, if the average particle size is less than 1 ⁇ m, hydrogen bonds between microfiber celluloses may not be inhibited due to the fineness.
  • the powder that does not interact with each other is a resin powder
  • the effect of inhibiting aggregation by entering the gaps between the cellulose fibers is effectively exhibited when the average particle size is in the above range.
  • it is economical because it has excellent kneadability with a resin and does not require a large amount of energy. Since the resin powder melts when kneaded with the resin and does not affect the appearance as particles, a powder having a large particle size can be effectively used.
  • the resin powder is an inorganic powder
  • the average particle size of the inorganic powder is in the above range, the effect of entering the gaps between the cellulose fibers and inhibiting aggregation is exhibited, but the inorganic powder is kneaded.
  • the size does not change significantly, so if the particle size is too large, it may affect the appearance as grains.
  • the resin powder physically intervenes between the microfiber celluloses to inhibit hydrogen bonds, thereby improving the dispersibility of the microfiber celluloses.
  • the acid-modified resin described above improves compatibility by ionic bonding an acid group and a carbamate group of microfiber cellulose, thereby enhancing a reinforcing effect.
  • the dispersant inhibits hydrogen bonds between microfiber celluloses in the same manner, but since the resin powder is micro-order, it physically intervenes and suppresses hydrogen bonds. Therefore, although the dispersibility is lower than that of the dispersant, the resin powder itself melts into a matrix, which does not contribute to deterioration of physical properties.
  • the dispersant since the dispersant is at the molecular level and is extremely small, it has a high effect of covering the microfiber cellulose to inhibit hydrogen bonds and improving the dispersibility of the microfiber cellulose. However, it may remain in the resin and work to reduce the physical properties.
  • the average particle size of the non-interacting powder is determined by using a particle size distribution measuring device (for example, a laser diffraction / scattering type particle size distribution measuring device manufactured by Horiba Seisakusho Co., Ltd.) with the powder as it is or in the state of an aqueous dispersion. It is a medium diameter calculated from the measured volume-based particle size distribution.
  • a particle size distribution measuring device for example, a laser diffraction / scattering type particle size distribution measuring device manufactured by Horiba Seisakusho Co., Ltd.
  • Examples of the inorganic powder include simple substances and oxides of metal elements in Groups I to VIII of the Periodic Table of the Periodic Table, such as Fe, Na, K, Cu, Mg, Ca, Zn, Ba, Al, Ti, and silicon elements. , Hydroxides, carbon salts, sulfates, silicates, sulfites, various clay minerals composed of these compounds, and the like can be exemplified. Specifically, for example, barium sulfate, calcium sulfate, magnesium sulfate, sodium sulfate, calcium sulfite, zinc oxide, heavy calcium carbonate, light calcium carbonate, aluminum borate, alumina, iron oxide, calcium titanate, aluminum hydroxide, etc.
  • Magnesium hydroxide, calcium hydroxide, sodium hydroxide, magnesium carbonate, calcium silicate, clay, wallastnite, glass beads, glass powder, silica gel, dry silica, colloidal silica, silica sand, silica stone, quartz powder, diatomaceous earth, white carbon , Glass fiber and the like can be exemplified.
  • a plurality of these inorganic fillers may be contained. Further, it may be contained in recycled paper pulp, or may be a so-called recycled filler obtained by regenerating an inorganic substance in paper sludge.
  • At least one inorganic powder selected from calcium carbonate, talc, white carbon, clay, calcined clay, titanium dioxide, aluminum hydroxide, recycled filler, etc. which are suitably used as fillers and pigments for papermaking. It is preferable to use at least one selected from calcium carbonate, talc, and clay, and it is more preferable to use at least one of light calcium carbonate and heavy calcium carbonate. Especially preferable.
  • calcium carbonate, talc, or clay it is easy to combine with a matrix such as a resin. Further, since it is a general-purpose inorganic material, there is an advantage that there are few restrictions on its use. Further, calcium carbonate is particularly preferable for the following reasons.
  • the same resin as that used when obtaining the composite resin can be used.
  • they may be different, but they are preferably the same.
  • the blending amount of the non-interacting powder is preferably 1 to 9900% by mass, more preferably 5 to 1900% by mass, and particularly preferably 10 to 900% by mass with respect to the fibrous cellulose (microfiber cellulose). If the blending amount is less than 1% by mass, it may enter into the gaps between the cellulose fibers and the action of suppressing aggregation may be insufficient. On the other hand, if the blending amount exceeds 9900% by mass, the function as a cellulose fiber may not be exhibited. When the powder that does not interact with the powder is an inorganic powder, it is preferable to mix the powder in a ratio that does not interfere with thermal recycling.
  • Inorganic powder and resin powder can be used in combination as the non-interacting powder.
  • the inorganic powder and the resin powder exert an effect of preventing each other from aggregating even when the inorganic powder and the resin powder are mixed under the condition of agglomeration.
  • powder with a small particle size has a large surface area and is more susceptible to the influence of intermolecular force than the influence of gravity, and as a result, it is more likely to aggregate. Therefore, when mixing the powder and the microfiber cellulose slurry, the powder is used.
  • the powders may not be loosened well in the slurry, or the powders may aggregate with each other when the water content is adjusted, so that the effect of preventing the aggregation of the microfiber cellulose may not be sufficiently exhibited.
  • the combined use of the inorganic powder and the resin powder can alleviate the agglutination of the powder itself.
  • the ratio of the average particle size of the inorganic powder to the average particle size of the resin powder is preferably 1: 0.1 to 1: 10000, more preferably 1: 1 to 1: 1000.
  • problems arise from the strength of its own cohesive force for example, when mixing powder and microfiber cellulose slurry, the powder does not loosen well in the slurry, or when adjusting the water content, the powder It is considered that the effect of preventing the aggregation of microfiber cellulose can be sufficiently exerted without causing the problem that the bodies aggregate with each other.).
  • the ratio of the mass% of the inorganic powder to the mass% of the resin powder is preferably 1: 0.01 to 1: 100, more preferably 1: 0.1 to 1:10.
  • the ratio of the mass% of the inorganic powder to the mass% of the resin powder is preferably 1: 0.01 to 1: 100, more preferably 1: 0.1 to 1:10.
  • the mixture is dehydrated if necessary 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.
  • Drying of the mixture or dehydrated product is, for example, rotary kiln drying, disk drying, air flow drying, medium flow drying, spray drying, drum drying, screw conveyor drying, paddle drying, uniaxial kneading drying, multiaxial kneading drying, vacuum. It can be carried out by selectively using one kind or two or more kinds from drying, stirring drying and the like.
  • the dried mixture (dried product) is preferably crushed into a 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 disper, a twist mill, a cut mill, a hammer mill and the like.
  • the average particle size of the powder is preferably 1 to 10,000 ⁇ m, more preferably 10 to 5,000 ⁇ m, and particularly preferably 100 to 1,000 ⁇ m. If the average particle size of the powdery substance exceeds 10,000 ⁇ m, the kneadability with the resin may be inferior. On the other hand, it is not economical because a large amount of energy is required to make the average particle size of the powdery substance less than 1 ⁇ m.
  • the average particle size of the powder can be controlled not only by controlling the degree of crushing, but also by classifying using a classifying 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 0.04 to 0.9, and particularly preferably 0.05 to 0.8.
  • the bulk specific density exceeds 1.0, it means that the hydrogen bonds between the fibrous celluloses are stronger and it is not easy to disperse them in the resin.
  • making the bulk specific density less than 0.03 is disadvantageous in terms of transfer cost.
  • the bulk specific density is a value measured according to JIS K7365.
  • the water content of the mixture is preferably less than 18%, more preferably 0 to 17%, and particularly preferably 0 to 16%.
  • the water content is 18% or more, it may not be possible to reduce the coloring of the fibrous cellulose composite resin due to the components derived from the cellulose fibers.
  • the substitution rate of the carbamate group is 1 mmol / g or more, it may not be possible to reduce the coloring.
  • the water content is 18% or more, the microfiber cellulose and the high temperature water come into contact with each other when exposed to a high temperature of, for example, 180 ° C.
  • the originally existing coloring-causing substance hemicellulose, etc.
  • the coloring-causing substance has a low molecular weight
  • the coloring-causing substance remains in the microfiber cellulose, the above-mentioned high-temperature water and the coloring-causing substance come into contact with each other, and the coloring becomes remarkable.
  • the water content content is a value calculated by the following formula, where the mass at the time when the sample is held at 105 ° C. for 6 hours or more using a constant temperature dryer and no change in mass is observed is taken as the mass after drying.
  • Moisture content (%) [(mass before drying-mass after drying) ⁇ mass before drying] x 100
  • the dehydrated and dried microfiber cellulose may contain a resin other than the resin powder as a powder that does not interact with each other.
  • the resin is contained, the hydrogen bonds between the dehydrated and dried microfiber celluloses are inhibited, and the dispersibility in the resin at the time of kneading can be improved.
  • Examples of the form of the resin contained in the dehydrated / dried microfiber cellulose include powder, pellet, and sheet. However, powder (powder resin) is preferable.
  • the average particle size of the powdered resin contained in the dehydrated and dried microfiber cellulose is preferably 1 to 10,000 ⁇ m, more preferably 10 to 5,000 ⁇ m, and particularly preferably 100 to 1,000 ⁇ m. If the average particle size exceeds 10,000 ⁇ m, it may not enter the kneading device due to the large particle size. On the other hand, if the average particle size is less than 1 ⁇ m, hydrogen bonds between microfiber celluloses may not be inhibited due to the fineness.
  • the resin such as the powder resin used here may be the same type as or different from the resin to be kneaded with the microfiber cellulose (resin as a main raw material), but it is preferable that the resin is the same type.
  • the powder resin having an average particle diameter of 1 to 10,000 ⁇ m is preferably mixed in an aqueous dispersed state before dehydration and drying.
  • the powder resin can be uniformly dispersed among the microfiber celluloses, and the microfiber celluloses can be uniformly dispersed in the composite resin after kneading, further improving the strength and physical characteristics. Can be done.
  • the fibrous cellulose-containing material (resin reinforcing material) obtained as described above is kneaded with a resin to obtain a fibrous cellulose composite resin.
  • This kneading can be performed, for example, by a method of mixing the pellet-shaped resin and the reinforcing material, or by a method of first melting the resin and adding the reinforcing material to the melt.
  • the acid-modified resin, dispersant and the like can also be added at this stage.
  • kneading process for example, one or two or more types are selected and used from a single-screw or two-screw multi-screw kneader, a mixing roll, a kneader, a roll mill, a Banbury mixer, a screw press, a disperser, and the like. be able to.
  • a multi-screw kneader having two or more shafts. Two or more multi-axis kneaders with two or more axes may be used in parallel or in series.
  • the temperature of the kneading treatment is equal to or higher than the glass transition point of the resin and varies depending on the type of resin, but is preferably 80 to 280 ° C, more preferably 90 to 260 ° C, and 100 to 240 ° C. Is particularly preferable.
  • thermoplastic resin it is preferable to use at least one of a thermoplastic resin and a thermosetting resin.
  • 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 a above (simply also referred to as “biodegradable resin”).
  • biodegradable resin for example, one or more can be selected and used from among hydroxycarboxylic acid-based aliphatic polyesters, caprolactone-based aliphatic polyesters, dibasic acid polyesters and the like.
  • hydroxycarboxylic acid-based aliphatic polyester for example, a homopolymer of a hydroxycarboxylic acid such as lactic acid, malic acid, glucose acid, or 3-hydroxybutyric acid, or at least one of these hydroxycarboxylic acids is used.
  • a hydroxycarboxylic acid such as lactic acid, malic acid, glucose acid, or 3-hydroxybutyric acid
  • One type or two or more types can be selected and used from the polymers and the like.
  • polylactic acid a polymer of the above hydroxycarboxylic acid excluding lactic acid and lactic acid, polycaprolactone, and a polymer of at least one of the above hydroxycarboxylic acids and caprolactone, and polylactic acid is preferably used.
  • polylactic acid is preferably used. Especially preferred to use.
  • lactic acid for example, L-lactic acid, D-lactic acid and the like 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 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 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, and oxidation. 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, claywa lastnite, glass beads, glass powder, silica sand, silica stone, quartz powder, diatomaceous earth, white carbon, glass fiber and the like are exemplified. be able to.
  • a plurality of these inorganic fillers may be contained. Further, it may be contained in recycled paper pulp.
  • the blending ratio of the fibrous cellulose (microfiber cellulose) and the resin is preferably 1 to 80% by mass for the fibrous cellulose and 20 to 90% by mass for the resin, 5 to 60% by mass for the fibrous cellulose, and 5 to 60% by mass for the resin. It is more preferably 30 to 80% by mass, and particularly preferably 10 to 50% by mass of fibrous cellulose and 40 to 70% by mass of resin. It is considered that if the blending ratio of the fibrous cellulose is relatively low, the interaction between the reinforcing fibers disappears, and the reinforcing effect cannot be sufficiently exerted by reinforcing the resin by the fiber alone.
  • the reinforcing fibers interact with each other, and in addition to the reinforcing property of the fiber alone, the reinforcing property is complemented by the fibers, thereby enhancing the reinforcing effect of the resin. I think that it will be fully demonstrated.
  • 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 compounding ratio of the fibrous cellulose and the resin.
  • the difference in SP value is preferably 10 to 0.1, more preferably 8 to 0.5, and particularly preferably 5-1. If the difference in SP value exceeds 10, the microfiber cellulose may not be dispersed in the resin and the reinforcing effect may not be obtained. On the other hand, if the difference in SP value is less than 0.1, the microfiber cellulose dissolves in the resin and does not function as a filler, so that the reinforcing effect cannot be obtained. In this respect, the smaller the difference between the SP POL value of the resin (solvent) and the SP MFC value of the microfiber cellulose (solute), the greater the reinforcing effect.
  • the solubility parameter (cal / cm 3 ) 1/2 (SP value) is a measure of the intramolecular force acting between the solvent and the solute, and the closer the SP value is to the solvent and solute, the higher the solubility. ..
  • the fibrous cellulose-containing substance and the kneaded resin can be kneaded again if necessary, and then formed into a desired shape.
  • 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. Further, the kneaded product may be spun into a fibrous form and mixed with the above-mentioned plant material or the like to form a mat shape or a board shape.
  • the mixed fiber can be, for example, a method of simultaneous deposition by an air ray or the like.
  • an apparatus for forming a kneaded product for example, one or two from injection molding machines, blow molding machines, hollow molding machines, blow molding machines, compression molding machines, extrusion molding machines, vacuum forming machines, pneumatic molding machines and the like. You can select and use more than one species.
  • 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 fibrous cellulose may contain cellulose nanofibers together with microfiber cellulose.
  • Cellulose nanofibers are fine fibers like microfiber cellulose, and have a role of complementing microfiber cellulose for improving the strength of the resin.
  • 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 fibrous cellulose may contain pulp. Pulp has a role of significantly improving the dehydration property of the cellulose fiber slurry. However, as in the case of cellulose nanofibers, it is most preferable that pulp is not blended, that is, the content is 0% by mass.
  • fibrous cellulose composite resin includes kenaf, jute hemp, Manila hemp, sisal hemp, ganpi, sansho, ⁇ , 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 fibrous cellulose composite resin for example, one or more of antistatic agents, flame retardants, antibacterial agents, colorants, radical scavengers, foaming agents, etc. are selected to inhibit the effect of the present invention. It can be added to the extent that it does not. These raw materials may be added to the dispersion liquid of fibrous cellulose, added at the time of kneading the fibrous cellulose and the resin, added to these kneaded products, or added by other methods. good. However, from the viewpoint of production efficiency, it is preferable to add it at the time of kneading the fibrous cellulose and the resin.
  • the fibrous cellulose composite resin may contain an ethylene- ⁇ -olefin copolymer elastomer or a styrene-butadiene block copolymer as a rubber component.
  • ⁇ -olefins include butene, isobutene, pentene, hexene, methyl-pentene, octene, decene, dodecene and the like.
  • the manufacturing method of the present embodiment may be performed continuously using various devices or may be performed in a batch system regardless of whether or not various devices are used.
  • the carbamate formation is performed by immersing a sheet-shaped fibrous cellulose-containing material in a reaction solution containing urea or the like and drying it in a dryer (for example, it is dried for 4 hours). It can be realized by reacting after making it react.
  • a paper machine-like device actual machine
  • the sheet-shaped fibrous cellulose-containing material has a thickness of about 5 mm, it takes a long time to dry, and it is not suitable for a continuous type, and is suitable for a batch type. In this case, it is conceivable to shorten the drying time by exposing the sheet-shaped fibrous cellulose-containing material to, for example, 3 to 5 days at room temperature (air drying). On the other hand, if the thickness is about 100 ⁇ m, drying can be continuously performed by using a device such as a dryer, which is suitable for a continuous type. In the case of the continuous type, instead of impregnating the reaction liquid in the batch type, it is advisable to apply the reaction liquid using an apparatus such as a size press.
  • Coniferous kraft pulp with a water content of 10% or less, an aqueous urea solution having a concentration of 10%, and a pH adjusting solution were mixed so as to have the composition shown in Table 1 in terms of mass ratio in terms of solid content.
  • This mixture was dried at 105 ° C. except for Test Example 3 to bring the water content of the mixture to 10% or less. On the other hand, in Test Example 3, the mixture was not dried and the water content of the mixture was not set to 10% or less.
  • Test Example 6 the unmodified pulp was diluted with distilled water and stirred, and dehydration washing was repeated twice. The washed unmodified pulp was beaten with Niagara beater for 4 hours to obtain microfiber cellulose.
  • the reference example is a numerical value for the TEMPO-catalyzed oxidized cellulose fiber, and the low heat resistance can be read.
  • the mixture was then heat-treated at the reaction temperature shown in the table for a reaction time of 3 hours to obtain carbamate-modified pulp.
  • the obtained carbamate-modified pulp was diluted with distilled water and stirred, and dehydration washing was repeated twice.
  • the washed carbamate-modified pulp was beaten with a Niagara beater for 4 hours to obtain carbamate-modified microfiber cellulose.
  • the above-mentioned various microfiber celluloses are prepared as an aqueous dispersion having a solid content concentration of 2% by weight.
  • aqueous dispersion having a solid content concentration of 2% by weight.
  • maleic anhydride-modified polypropylene and 85 g of polypropylene powder are added, and the mixture is heated and dried at 105 ° C. to carry carbamate-modified microfibers.
  • a cellulose-containing material was obtained.
  • the water content of this carbamate-modified microfiber cellulose-containing material was less than 10%.
  • This carbamate-modified microfiber cellulose-containing material was kneaded with a twin-screw kneader under the conditions of 180 ° C.
  • the flexural modulus of the resin itself is 1, the case where the flexural modulus of the composite resin is 1.60 times or more is ⁇ , and the case where the flexural modulus is 1.40 times or more and less than 1.60 times is ⁇ .
  • the case of less than 1.40 times is described as x.
  • the bending strength of the resin itself is 1, the case where the bending strength of the composite resin is 1.30 times or more is ⁇ , the case where the bending strength is 1.20 times or more and less than 1.30 times is ⁇ , 1.18 times or more, and The case of less than 1.20 times is described as ⁇ , and the case of less than 1.18 times is described as ⁇ .
  • the measurement of the average fiber length and the 5% weight loss temperature is as described above.
  • the present invention can be used as a method for producing fibrous cellulose and a method for producing a fibrous cellulose composite resin.

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Abstract

La présente invention a pour objet une cellulose fibreuse qui présente une excellente résistance à la chaleur et un excellent effet de renforcement de résine et un procédé de production d'un composite de résine et de cellulose fibreuse à haute résistance. À cet effet, l'invention porte sur un procédé de production de cellulose fibreuse comprenant une étape de remplacement de groupes hydroxy présents dans des fibres de cellulose par des groupes carbamate et une étape de défibrage des fibres de cellulose de façon telle que la largeur moyenne de fibre devient de 0,1 à 19 µm ; l'étape de remplacement comportant une étape de chauffage ; une étape de séchage étant prévue avant cette étape de chauffage ; et le remplacement étant réalisé de façon telle que la température correspondant à une perte de poids de 5 % lorsque les fibres de cellulose sont chauffées dans un état absolument sec (à 5 °C/min, 105 → 350 °C) devient supérieure ou égale à 240 °C. De plus, l'invention porte sur un procédé de production d'un composite de résine et de cellulose fibreuse dans lequel de la cellulose fibreuse obtenue par le procédé ci-dessus est mélangée avec de la résine.
PCT/JP2021/028375 2020-08-04 2021-07-30 Procédé de production de cellulose fibreuse et procédé de production de composite de résine et de cellulose fibreuse WO2022030391A1 (fr)

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JP2024051836A (ja) * 2022-09-30 2024-04-11 大王製紙株式会社 カルバメート化セルロース繊維の製造方法

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WO2017094812A1 (fr) * 2015-12-03 2017-06-08 国立大学法人京都大学 Composition de résine et son procédé de fabrication
WO2018159473A1 (fr) * 2017-02-28 2018-09-07 大王製紙株式会社 Microfibre de cellulose et son procédé de fabrication
WO2018230600A1 (fr) * 2017-06-14 2018-12-20 国立大学法人京都大学 Fines fibres de cellulose, leur procédé de production, bouillie et composite
WO2019221256A1 (fr) * 2018-05-18 2019-11-21 大王製紙株式会社 Microfibres de cellulose et leur procédé de fabrication
WO2020203147A1 (fr) * 2019-03-29 2020-10-08 大王製紙株式会社 Résine composite de cellulose fibreuse et procédé de production associé, et matériau de renforcement de résine

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WO2017094812A1 (fr) * 2015-12-03 2017-06-08 国立大学法人京都大学 Composition de résine et son procédé de fabrication
WO2018159473A1 (fr) * 2017-02-28 2018-09-07 大王製紙株式会社 Microfibre de cellulose et son procédé de fabrication
WO2018230600A1 (fr) * 2017-06-14 2018-12-20 国立大学法人京都大学 Fines fibres de cellulose, leur procédé de production, bouillie et composite
WO2019221256A1 (fr) * 2018-05-18 2019-11-21 大王製紙株式会社 Microfibres de cellulose et leur procédé de fabrication
WO2020203147A1 (fr) * 2019-03-29 2020-10-08 大王製紙株式会社 Résine composite de cellulose fibreuse et procédé de production associé, et matériau de renforcement de résine

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Publication number Priority date Publication date Assignee Title
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