WO2022091581A1 - Method for producing cellulose-fiber-containing substance and method for producing cellulose-fiber composite resin - Google Patents
Method for producing cellulose-fiber-containing substance and method for producing cellulose-fiber composite resin Download PDFInfo
- Publication number
- WO2022091581A1 WO2022091581A1 PCT/JP2021/032648 JP2021032648W WO2022091581A1 WO 2022091581 A1 WO2022091581 A1 WO 2022091581A1 JP 2021032648 W JP2021032648 W JP 2021032648W WO 2022091581 A1 WO2022091581 A1 WO 2022091581A1
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- WO
- WIPO (PCT)
- Prior art keywords
- cellulose
- resin
- carbamate
- powder
- fiber
- Prior art date
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- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 110
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000000805 composite resin Substances 0.000 title claims abstract description 30
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- 229920002678 cellulose Polymers 0.000 claims abstract description 189
- 239000001913 cellulose Substances 0.000 claims abstract description 179
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- 238000000034 method Methods 0.000 claims description 31
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- 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
Definitions
- the present invention relates to a method for producing a cellulose fiber-containing material and a method for producing a cellulose fiber composite resin.
- fine fibers such as cellulose nanofibers and microfiber cellulose (microfibrillated cellulose) have been in the limelight for use as reinforcing materials for resins.
- the fine fibers are hydrophilic while the resin is hydrophobic, there is a problem in the dispersibility of the fine fibers in order to use the fine fibers as a reinforcing material for the resin. Therefore, the present inventors have proposed to replace the hydroxyl group of the fine fiber with a carbamate group (carbamate modification, carbamate formation) (see Patent Document 1). According to this proposal, the dispersibility of the fine fibers is improved, and thus the reinforcing effect of the resin is improved.
- carbamate-modified fine fibers are not completely hydrophobic, agglomerates may be formed when they are combined with the resin.
- carbamate modification rate in order to reduce agglomerates, it is conceivable to increase the carbamate formation rate (carbamate modification rate), but if the carbamate formation rate is increased, the strength of the cellulose fiber itself is impaired, and the strength of the cellulose fiber composite resin is poor. May be sufficient.
- the main problem to be solved by the present invention is to provide a method for producing a cellulose fiber-containing material capable of reducing the generation of agglomerates when compounded with a resin, and a method for producing a high-strength cellulose fiber composite resin. be.
- Microfiber cellulose and powder are mixed to form a slurry, and a cellulose fiber-containing substance is obtained from this slurry.
- Carbamate-modified microfiber cellulose having an average fiber diameter of 0.1 to 19 ⁇ m was used as the microfiber cellulose.
- Carbamate-modified microfiber cellulose concentration of the slurry is increased to 1.5% by mass or more.
- the carbamate-modified microfiber cellulose has a carbamate conversion rate of 1.0 to 2.0 mmol / g.
- the viscosity of the slurry is 1000 to 10000 cps.
- the concentration of the acid-modified resin in the slurry is set to 0.5% by mass or more.
- it is a method for producing a cellulose fiber-containing material that can reduce the generation of agglomerates when compounded with a resin, and a method for producing a high-strength cellulose fiber composite resin.
- 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 cellulose fiber-containing material of this embodiment is compounded with a resin, and the cellulose fiber (hereinafter, also referred to as “fibrous cellulose”) is a microfiber cellulose having an average fiber diameter of 0.1 to 19 ⁇ m and is hydroxylated. Carbamate-modified microfiber cellulose in which a part or all of the group (-OH group) is substituted with a carbamate group.
- the cellulose fiber inclusions include powders that do not interact with the cellulose fibers.
- the cellulose fiber-containing substance is added to the resin and the like, and the composite is obtained to obtain a cellulose composite resin.
- the cellulose fiber composite resin of the present embodiment contains a cellulose fiber-containing material containing a cellulose fiber and a powder that does not interact with the cellulose fiber, and a resin.
- the cellulose fiber which is a fine fiber in this embodiment is a microfiber cellulose (microfibrillated cellulose, MFC) having an average fiber diameter of 0.1 to 19 ⁇ m.
- MFC microfiber cellulose
- microfiber cellulose is easier to denature (carbamate) with a carbamate group than cellulose nanofibers, which are also fine fibers.
- 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 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 microfiber cellulose When the dehydration property deteriorates, a large amount of energy is required for drying, and when a large amount of energy is applied to drying, the microfiber cellulose is thermally deteriorated and the strength may decrease. On the other hand, if 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 microfiber cellulose is as follows. First, 100 ml of an aqueous dispersion of fine fibers (microfiber cellulose) 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 once with 100 ml of ethanol, 20 ml of t-butanol. Replace the solvent 3 times with. 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) a cellulose raw material (hereinafter, also referred to as "raw material pulp”).
- the raw material pulp includes, for example, wood pulp made from broadleaf tree, coniferous tree, etc., non-wood pulp made from straw, bagasse, cotton, hemp, carrot fiber, etc., recovered waste paper, waste paper pulp made from waste paper, etc.
- DIP plant-derived fiber, animal-derived fiber, microbial-derived fiber and the like can be selected and used.
- 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
- Raw 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.
- it is preferable to carry out an enzyme treatment 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.
- 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 alabang, 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 alabang
- 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 raw material is determined by, for example, the type of enzyme, the type of wood used as the 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, the cellulose may be saccharified and the yield of the fiber 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 used for the alkali treatment examples include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia solution, 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.
- the raw material pulp is subjected to enzyme treatment, acid treatment, or oxidation treatment, the hemicellulose and the amorphous region of cellulose that the pulp has are decomposed. As a result, the energy of defibration can be reduced, and the uniformity and dispersibility of the cellulose fibers can be improved.
- the pretreatment lowers the aspect ratio of the microfiber cellulose, it is preferable to avoid excessive pretreatment when it is used as a reinforcing material for the resin.
- beaters For defibration (miniaturization) of raw pulp, for example, beaters, high-pressure homogenizers, homogenizers such as high-pressure homogenizers, millstone friction machines such as grinders and grinders, single-screw kneaders, multi-screw kneaders, kneader refiners, etc.
- homogenizers such as high-pressure homogenizers
- millstone friction machines such as grinders and grinders
- single-screw kneaders single-screw kneaders, multi-screw kneaders, kneader refiners, etc.
- refiner or a jet mill it is preferable to use a refiner or a jet mill.
- the average fiber length (average length of single fibers) of the microfiber cellulose is preferably 0.10 to 2.00 mm, more preferably 0.12 to 1.50 mm, and particularly preferably 0.15 to 1.00 mm. be. If the average fiber length is 0.10 mm or less, a three-dimensional network of fibers cannot be formed, and the reinforcing effect (particularly, flexural modulus) of the composite resin may decrease. 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 raw material as a raw material for microfiber cellulose 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 of the cellulose raw material is less than 0.50 mm, the effect of reinforcing the resin during the defibration treatment may not be sufficiently obtained. 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 average fiber length of microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
- the length of each fiber is visually measured 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 fiber length of the microfiber cellulose is preferably 20% or more, more preferably 40% or more, and particularly preferably 60% or more in a ratio of more than 0.02 mm. If the ratio is less than 20%, the reinforcing effect of the resin may not be sufficiently obtained. On the other hand, the fiber length of the microfiber cellulose has no upper limit of the ratio of more than 0.02 mm, and all of them may be more than 0.02 mm.
- the aspect ratio of the microfiber cellulose is preferably 2 to 15,000, more preferably 10 to 10,000. If the aspect ratio is less than 2, a three-dimensional network cannot be constructed, and even if the average fiber length exceeds 0.01 mm, 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 the 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 was determined by dissociating fine fibers in accordance with JIS-P-8220: 2012 "Pulp-Dissolution Method", and dissociating the obtained dissociated pulp in FaberLab. (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. When the crystallinity is less than 50%, the mixing property with 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.
- the crystallinity of the microfiber cellulose is preferably 95% or less, more preferably 90% or less, and particularly preferably 85% or less. When 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 by the X-ray diffraction method in accordance with the "general rule of X-ray diffraction analysis" of JIS-K0131 (1996).
- the fine fiber has an amorphous portion and a crystalline portion, and the crystallinity means the ratio of the crystalline portion to the entire fine fiber.
- 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 average fiber diameter of the microfiber cellulose exceeds 19 ⁇ m, and the effect of improving the strength of the resin may not be sufficiently obtained.
- 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%, dehydration tends to be inferior, and aggregation tends to occur. In this respect, the degree of water retention of the microfiber cellulose can be lowered by substituting the hydroxy group of the cellulose fiber with a carbamate group, and the dehydration property and the drying property can be improved.
- the water retention level of the 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 carbamate group means a state in which carbamate (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 group.
- Examples thereof include a group in which one or more hydrogen atoms having one or more hydrogen atoms 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 polar 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 good handleability.
- the substitution rate of the carbamate group with respect to the hydroxy group of the microfiber cellulose is preferably 1.0 to 2.0 mmol / g, more preferably 1.1 to 1.9 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, particularly the effect of improving the bending elongation of the resin can be surely exhibited.
- the substitution rate exceeds 2.0 mmol / g, the cellulose fibers may not be able to maintain the shape of the fibers, and the reinforcing effect of the resin may not be sufficiently obtained. It does not disperse sufficiently and may cause aggregation when mixed with resin powder or the like.
- the carbamate group substitution rate refers to the amount of substance of the carbamate group contained in 1 g of the cellulose raw material having a carbamate group.
- Cellulose is a polymer having anhydrous glucose as a structural unit, and has three hydroxy groups per structural unit.
- the step of carbamate microfiber cellulose or the like can be mainly classified into, for example, a mixing treatment, a removal treatment, and a heat treatment.
- the mixing treatment and the removing treatment can also be referred to as an adjustment treatment for preparing a mixture to be subjected to the heat treatment.
- microfiber cellulose or the like which may be a cellulose raw material as described above; the same applies hereinafter
- urea and / or a derivative of urea hereinafter, also simply referred to as “urea or the like” are used as a dispersion medium. Mix in.
- 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 and urea derivatives 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 / microfiber cellulose or the like) to the microfiber cellulose or the like 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.
- microfiber cellulose or the like and urea or the like are added to water, or microfiber cellulose or the like is added to an aqueous solution of urea or the like, urea or the like is added to a slurry containing microfiber cellulose or the like. You may. Further, in order to mix uniformly, the mixture may be stirred after the addition. Further, the dispersion liquid containing microfiber cellulose or the like and urea or the like may contain other components.
- the dispersion medium is removed from the dispersion liquid containing microfiber cellulose and the like and urea and the like obtained in the mixing treatment.
- 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. Specifically, for example, 6 to 24 hours.
- a mixture of microfiber cellulose or the like and urea or the like is heat-treated.
- a part or all of a hydroxy group such as microfiber cellulose reacts with urea or the like and is replaced with a carbamate group.
- urea or the like is heated, it is decomposed into isocyanic acid and ammonia as shown in the following reaction formula (1).
- Isocyanic acid is very reactive, and for example, it forms a carbamate group 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., microfiber cellulose or the like 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, particularly preferably 30 minutes, still more preferably 1 hour, and most preferably 2 hours.
- the upper limit of the heating time is preferably 15 hours, more preferably 10 hours. If the heating time exceeds 15 hours, it is not economical and sufficient carbamate can be achieved in 15 hours.
- 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. Under neutral conditions of pH 7 to 8, the average fiber length of the cellulose fibers becomes short, and the reinforcing effect of the resin may be inferior.
- 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 and the like remaining unreacted can be removed.
- 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 dispersion 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 dispersion liquid itself may decrease and uniform mixing may not be possible when a dispersant is used.
- the cellulose fiber-containing material of this embodiment contains a powder that does not interact with the cellulose fiber.
- the cellulose fiber can be in a form capable of exhibiting the reinforcing property of the resin. That is, when the cellulose fiber-containing material is a slurry, it is preferable to remove the aqueous medium contained in the slurry before compounding with the resin. However, when the aqueous medium is removed, 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 cellulose fiber-containing substance (slurry), hydrogen bonds between the celluloses are physically inhibited.
- non-interacting means that a strong bond is not formed by a covalent bond, an ionic bond, or a metal bond with a cellulose fiber (that is, a hydrogen bond or a van der Waals force bond is included in the concept that the bond does not interact. Is done.).
- 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.
- the cellulose fiber-containing material is combined with the resin or the like, the cellulose fiber and the powder that does not interact with the cellulose fiber can be easily dispersed in the resin or the like. Further, particularly when it is an inorganic powder, it is advantageous in terms of operation.
- a method for drying the composite resin for example, a method of directly applying an aqueous dispersion to a metal drum as a heat source (for example, drying with a yankee dryer or a cylinder dryer) and a method of drying with water as a heat source.
- a method of heating the dispersion without directly touching it that is, a method of drying in air (for example, drying with a constant temperature dryer).
- a heated metal plate for example, a Yankee dryer, a cylinder dryer, etc.
- Inorganic powders are advantageous in that such problems are unlikely to occur.
- the average particle size of the non-interacting powder is preferably 1 mm or less, more preferably 0.9 to 0.0001 mm, and particularly preferably 0.8 to 0.001 mm.
- the average particle size is within the above range, the effect of entering the gaps between the cellulose fibers and inhibiting aggregation is effectively exerted. Moreover, it is economical because it has excellent kneadability with a resin and does not require a large amount of energy.
- the average particle size exceeds 1 mm, when the aqueous medium is removed from the slurry of the cellulose fiber-containing material, the effect of entering the gaps between the cellulose fibers and inhibiting aggregation may not be exhibited.
- the average particle size is less than 0.0001 mm, hydrogen bonds between the microfiber celluloses may not be inhibited due to the fine particles.
- the particles may aggregate in the aqueous dispersion.
- the resin powder melts during kneading and does not affect the appearance as particles, a large particle size can be used relatively effectively.
- the resin powder is an inorganic powder, if the average particle size of the inorganic powder is within 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 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, 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, 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 powders 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 9900 to 1% by mass, more preferably 1900 to 5% by mass, and particularly preferably 900 to 10% by mass with respect to the cellulose fiber. 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.
- powders with a small particle size have a large surface area and are more susceptible to intramolecular forces than the effects of gravity, and as a result, they are more likely to aggregate.
- the powders will not loosen well in the slurry, or that the powders will aggregate when the aqueous medium is removed, and the effect of preventing the aggregation of microfiber cellulose will not be fully exhibited.
- the combined use of the inorganic powder and the resin powder can alleviate the aggregation 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, the powder does not loosen well in the slurry when mixing the powder and microfiber cellulose, or the powders do not loosen well when the aqueous medium is removed. It is considered that the effect of preventing the aggregation of the microfiber cellulose is sufficiently exhibited without causing the problem of aggregation.).
- 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 powder does not loosen well in the slurry when mixing the powder and microfiber cellulose, or the powders do not loosen well when the aqueous medium is removed. It is considered that the effect of preventing the aggregation of the microfiber cellulose is sufficiently exhibited without causing the problem of aggregation.).
- acid-modified resin As the non-interacting powder, it is preferable to use an acid-modified resin.
- the acid group may be ionically bonded to 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 can be selected and used from among maleic anhydrides, phthalic anhydrides, itaconic anhydrides, citraconic anhydrides, citrate anhydrides and the like.
- maleic anhydrides it is preferable to use maleic anhydrides. That is, it is preferable to use a maleic anhydride-modified polypropylene resin.
- the mixed 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 200,000, preferably 3,000 to 100,000.
- the acid value of maleic anhydride-modified polypropylene is preferably 1 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 10 mgKOH / g or more and 100 mgKOH / g or less.
- Dispersant Powders that do not interact with microfiber cellulose or cellulose fibers are more preferred when 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 acids, guaiacols, picric acids, phenolphthalenes, serotonins, dopamines, adrenaline, noradrenaline, timoles, tyrosine, salicylic acids, methyl salicylates, anis alcohols.
- Salicylic 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, eleidyl alcohols, oleyl alcohols, linoleil 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 cellulose fiber-containing material 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.
- polypropylene has a melting point of 160 ° C., so that the cellulose fiber-containing substance and the resin are kneaded 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 non-interacting powder physically intervenes between the microfiber celluloses to inhibit hydrogen bonds, thereby improving the dispersibility of the microfiber celluloses.
- the powder that does not interact is an acid-modified resin
- the compatibility is improved by ionic bonding the acid group and the carbamate group of the microfiber cellulose, thereby enhancing the reinforcing effect.
- the dispersant inhibits hydrogen bonds between microfiber celluloses, but the powders that do not interact with each other are micro-ordered, so that they physically intervene and suppress hydrogen bonds.
- the dispersibility is lower than that of the dispersant, in the case of the resin powder in particular, it melts into a matrix and does not contribute to the deterioration of the physical properties.
- the inorganic powder since the inorganic powder itself is rigid, it contributes to the improvement of the physical properties of the resin or the like when it is combined with the resin or the like.
- 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 mixture (slurry) preferably has a carbamate-modified microfiber cellulose concentration of 1.5% by mass or more, more preferably 1.8 to 5.0% by mass, and 2.0 to 4.0% by mass. Is particularly preferable.
- the concentration is less than 1.5% by mass
- the powder is mixed with a non-interacting powder and stirred, and then the density difference between the microfiber cellulose and the powder (for example, MFC is about 1.5 g / cm 3 and the powder).
- MFC density difference between the microfiber cellulose and the powder
- MFC and powder are gradually separated in the slurry due to 0.9 g / cm 3 ) or a difference in SP value described later, and the powder is already separated when the subsequent steps are started.
- the microfiber celluloses aggregate with each other.
- the concentration is 1.5% by mass or more
- the viscosity of the slurry becomes high, so that the fluidity of the slurry becomes low, and the separation due to the difference in density between the MFC and the powder and the difference in SP value is suppressed. That is, the method of reducing the difference in density and the difference in SP value also contributes to the suppression of aggregation, but since these methods have limitations, in this embodiment, the suppression of aggregation is to be completed by adjusting the concentration. be.
- the SP value of the powder is the same as that of the resin described later, and the details will be described later.
- the viscosity of the slurry is preferably adjusted to 1000 to 10000 cps, more preferably 1500 to 9000 cps, and particularly preferably 2000 to 8000 cps. ..
- this adjustment can also be performed using, for example, a thickener or the like.
- the viscosity of the slurry is a value measured according to the "method for measuring the viscosity of liquid" of JIS-Z8803 (2011).
- the density ratio of the non-interacting powder to the density of the carbamate-modified microfiber cellulose is preferably 0.4 to 2.2, more preferably 0.5 to 2.1. It is preferably 0.6 to 2.0, and is particularly preferable.
- the concentration of the acid-modified resin in the slurry is preferably 0.5% by mass or more, preferably 0.6 to 5.0. It is more preferably made by mass%, and particularly preferably 0.7 to 4.0% by mass.
- concentration of the acid-modified resin is 0.5% by mass or more, it is considered that the effect of preventing the aggregation of the carbamate-modified microfiber celluloses generated when the slurry is dried is sufficiently exhibited.
- the concentration ratio of the non-interacting powder is, for example, 50 to 0.1, preferably 20 to 0.5, and more preferably 10 to 1.0. be. If the concentration ratio is less than 0.1, the effect of suppressing the aggregation of microfiber cellulose during drying may not be sufficiently exhibited. On the other hand, if the concentration ratio exceeds 50, the blending ratio of the microfiber cellulose in the composite resin cannot be increased, and the effect of blending the microfiber cellulose may not be sufficiently exhibited.
- the mixture is made into a slurry and then dehydrated before drying to make it a dehydrated product.
- 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 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 drying, stirring drying. It can be performed 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 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 cellulose fibers 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 (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 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 powdery substance (cellulose fiber-containing substance) obtained as described above is kneaded with a resin to obtain a cellulose composite resin.
- This kneading can be performed, for example, by a method of mixing the pellet-shaped resin and the powdery substance, or by a method of first melting the resin and adding the powdery substance to the melt.
- the dispersant 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 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 a above (simply also referred to 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 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 blending ratio of the microfiber cellulose and the resin is preferably 1 part by mass or more for the microfiber cellulose, 99 parts by mass or less for the resin, more preferably 2 parts by mass or more for the microfiber cellulose, and 98 parts by mass or less for the resin, particularly preferably.
- the amount of microfiber cellulose is 3 parts by mass or more, and the amount of resin is 97 parts by mass or less.
- microfiber cellulose is 50 parts by mass or less
- resin is 50 parts by mass or more, more preferably microfiber cellulose is 40 parts by mass or less
- resin is 60 parts by mass or more, and particularly preferably microfiber cellulose is 30 parts by mass or less.
- the resin is 70 parts by mass or more.
- the amount of microfiber cellulose is 10 to 50 parts by mass, the strength of the resin composition, particularly the bending strength and the tensile elastic modulus can be remarkably improved.
- the content ratio of the microfiber cellulose and the resin contained in the finally obtained cellulose fiber composite resin is usually the same as the above-mentioned compounding ratio of the microfiber cellulose and the resin.
- the difference in SP value SP MFC value -Can be an SP POL value.
- 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 is not dispersed in the resin and the reinforcing effect cannot 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 the solute, the higher the solubility.
- the cellulose fiber-containing material and the kneaded product of the resin can be molded 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-like, pellet-like, powder-like, fibrous-like, 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 molding 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 molding 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 cellulose fiber-containing material 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 cellulose fiber-containing material 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.
- the resin composition includes kenaf, jute hemp, Manila hemp, sisal hemp, goose bark, sansho, ⁇ , banana, pineapple, coco palm, corn, sugar cane, bagasse, palm, etc. It can also contain fibers derived from plant materials obtained from various plants such as papyrus, reeds, esparto, survivorgrass, wheat, rice, bamboo, various coniferous trees (sugi and hinoki, etc.), broadleaf trees and cotton. May be.
- the resin composition for example, one or more selected from antistatic agents, flame retardants, antibacterial agents, colorants, radical scavengers, foaming agents, etc., and a range that does not impair the effects of the present invention. Can be added with. Whether these raw materials are added to the dispersion liquid of microfiber cellulose, added to the cellulose fiber-containing material (slurry), or added at the time of kneading the cellulose fiber-containing material and the resin, these kneaded products It may be added to or by other methods. However, from the viewpoint of production efficiency, it is preferable to add it at the time of kneading the cellulose fiber-containing material and the resin.
- the resin composition 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 agglomerates of microfiber cellulose are reduced (agglomeration reduction), and the merits of this are, for example, as follows.
- cracking of the cellulose fiber composite resin is reduced.
- the reduction of agglomerates reduces the risk of destruction and putrefaction of the cellulose fiber composite resin by external water and the like.
- the dispersibility of the microfiber cellulose is poor, agglomerates are exposed on the surface of the cellulose fiber composite resin. It is considered that the cellulose fiber composite resin is easily destroyed due to swelling and the like, and there is a risk of putrefaction.
- by improving the homogeneity of the surface of the cellulose fiber composite resin it becomes easier to obtain a uniform surface when performing surface secondary processing such as painting, and it is possible to reduce the amount of coating liquid used for painting and the processing time. can.
- the carbamate-modified microfiber-containing material was kneaded with a twin-screw kneader under the conditions of 180 ° C. and 200 rpm to obtain a carbamate-modified microfiber cellulose composite resin.
- This carbamate-modified microfiber cellulose composite resin was cut into a cylinder having a diameter of 2 mm and a length of 2 mm with a pelleter, and was injection-molded into a rectangular parallelepiped test piece (length 59 mm, width 9.6 mm, thickness 3.8 mm) at 180 ° C. .. For each test piece, the number of agglomerates, flexural modulus, and bending strength were examined.
- the test method was as follows.
- the composite resin was formed into a bending test piece, and the flexural modulus was examined according to JIS K 7171: 2008.
- the flexural modulus of the resin itself was set to 1, and the case where the flexural modulus (magnification) of the composite resin was greater than 1.50 times was marked with ⁇ , and the case of 1.50 times or less was marked with x.
- the bending strength was marked as ⁇ when it was greater than 1.20 times and x when it was 1.20 times or less.
- the bending test piece was observed with an optical microscope, and the number of agglomerates (aggregates) having a major axis of 1 mm or more in a field of view of 9 mm 2 was counted.
- the number of aggregates was 10 or more as x, 9 to 5 as ⁇ , and less than 5 as ⁇ . The smaller the number of agglomerates, the better the dispersibility.
- the present invention can be used as a method for producing a cellulose fiber-containing material and a method for producing a cellulose fiber composite resin.
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Abstract
[Problem] To provide a method for producing a cellulose-fiber-containing substance which can be combined with resins with reduced formation of agglomerates and a method for producing a cellulose-fiber composite resin having high strength. [Solution] Cellulose microfibers are mixed with a powder to give a slurry, from which a cellulose-fiber-containing substance is obtained. As the cellulose microfibers, use is made of carbamate-modified cellulose microfibers having an average fiber diameter of 0.1-19 μm. Used as the powder is a powder which does not interact with the cellulose fibers. The slurry has a concentration of the carbamate-modified cellulose microfibers of 1.5 mass% or higher. The thus-obtained cellulose-fiber-containing substance is mixed with a resin to produce a cellulose-fiber composite resin.
Description
本発明は、セルロース繊維含有物の製造方法、及びセルロース繊維複合樹脂の製造方法に関するものである。
The present invention relates to a method for producing a cellulose fiber-containing material and a method for producing a cellulose fiber composite resin.
近年、セルロースナノファイバー、マイクロ繊維セルロース(ミクロフィブリル化セルロース)等の微細繊維は、樹脂の補強材としての使用が脚光を浴びている。もっとも、微細繊維が親水性であるのに対し、樹脂は疎水性であるため、微細繊維を樹脂の補強材として使用するには、当該微細繊維の分散性に問題があった。そこで、本発明者等は、微細繊維のヒドロキシル基をカルバメート基で置換する(カルバメート変性、カルバメート化)ことを提案した(特許文献1参照)。この提案によると、微細繊維の分散性が向上し、もって樹脂の補強効果が向上する。もっとも、カルバメート変性した微細繊維も完全な疎水性ではないため、樹脂と複合化した際に凝集塊が生じるおそれがある。この点、凝集塊を減らすためには、カルバメート化率(カルバメート変性率)を上げることが考えられるが、カルバメート化率を上げるとセルロース繊維自体の強度が損なわれ、セルロース繊維複合樹脂の強度が不十分になるおそれがある。
In recent years, fine fibers such as cellulose nanofibers and microfiber cellulose (microfibrillated cellulose) have been in the limelight for use as reinforcing materials for resins. However, since the fine fibers are hydrophilic while the resin is hydrophobic, there is a problem in the dispersibility of the fine fibers in order to use the fine fibers as a reinforcing material for the resin. Therefore, the present inventors have proposed to replace the hydroxyl group of the fine fiber with a carbamate group (carbamate modification, carbamate formation) (see Patent Document 1). According to this proposal, the dispersibility of the fine fibers is improved, and thus the reinforcing effect of the resin is improved. However, since the carbamate-modified fine fibers are not completely hydrophobic, agglomerates may be formed when they are combined with the resin. In this respect, in order to reduce agglomerates, it is conceivable to increase the carbamate formation rate (carbamate modification rate), but if the carbamate formation rate is increased, the strength of the cellulose fiber itself is impaired, and the strength of the cellulose fiber composite resin is poor. May be sufficient.
発明が解決しようとする主たる課題は、樹脂と複合した際の凝集塊の発生を少なくすることができるセルロース繊維含有物の製造方法、及び強度の高いセルロース繊維複合樹脂の製造方法を提供することにある。
The main problem to be solved by the present invention is to provide a method for producing a cellulose fiber-containing material capable of reducing the generation of agglomerates when compounded with a resin, and a method for producing a high-strength cellulose fiber composite resin. be.
従来の開発、例えば、上記特許文献の開発においては、微細繊維の変性に主眼が置かれ、エステル化、エーテル化、アミド化、スルフィド化等、数々存在する変性方法の中で、カルバメートの導入(カルバメート化)が優れることを見出したものであった。これに対し、本発明は、カルバメートの導入を主眼とするものではなく、カルバメートの導入を前提に数々の試験を行うなかで、カルバメート変性マイクロ繊維セルロースの凝集を如何に抑えるかを追求し、もって想到するに至ったものである。このようにして想到するに至った手段は、次のとおりである。
In the conventional development, for example, in the development of the above patent document, the focus is on the modification of fine fibers, and the introduction of carbamate (introduction of carbamate) among various modification methods such as esterification, etherification, amidation, and sulfidation ( It was found that carbamate) was excellent. On the other hand, the present invention does not focus on the introduction of carbamate, but pursues how to suppress the aggregation of carbamate-modified microfiber cellulose by conducting a number of tests on the premise of the introduction of carbamate. It came to my mind. The means that led to this idea are as follows.
(請求項1に記載の手段)
マイクロ繊維セルロース及び粉末を混合してスラリーとし、このスラリーからセルロース繊維含有物を得るものとし、
前記マイクロ繊維セルロースとして平均繊維径が0.1~19μmのカルバメート変性マイクロ繊維セルロースを使用し、
前記粉末としてセルロース繊維と相互作用しない粉末を使用し、
前記スラリーのカルバメート変性マイクロ繊維セルロース濃度を1.5質量%以上にする、
ことを特徴とするセルロース繊維含有物の製造方法。 (Means according to claim 1)
Microfiber cellulose and powder are mixed to form a slurry, and a cellulose fiber-containing substance is obtained from this slurry.
Carbamate-modified microfiber cellulose having an average fiber diameter of 0.1 to 19 μm was used as the microfiber cellulose.
Using a powder that does not interact with cellulose fibers as the powder,
Carbamate-modified microfiber cellulose concentration of the slurry is increased to 1.5% by mass or more.
A method for producing a cellulose fiber-containing material.
マイクロ繊維セルロース及び粉末を混合してスラリーとし、このスラリーからセルロース繊維含有物を得るものとし、
前記マイクロ繊維セルロースとして平均繊維径が0.1~19μmのカルバメート変性マイクロ繊維セルロースを使用し、
前記粉末としてセルロース繊維と相互作用しない粉末を使用し、
前記スラリーのカルバメート変性マイクロ繊維セルロース濃度を1.5質量%以上にする、
ことを特徴とするセルロース繊維含有物の製造方法。 (Means according to claim 1)
Microfiber cellulose and powder are mixed to form a slurry, and a cellulose fiber-containing substance is obtained from this slurry.
Carbamate-modified microfiber cellulose having an average fiber diameter of 0.1 to 19 μm was used as the microfiber cellulose.
Using a powder that does not interact with cellulose fibers as the powder,
Carbamate-modified microfiber cellulose concentration of the slurry is increased to 1.5% by mass or more.
A method for producing a cellulose fiber-containing material.
(請求項2に記載の手段)
前記カルバメート変性マイクロ繊維セルロースのカルバメート化率が、1.0~2.0mmol/gである、
請求項1に記載のセルロース繊維含有物の製造方法。 (Means according to claim 2)
The carbamate-modified microfiber cellulose has a carbamate conversion rate of 1.0 to 2.0 mmol / g.
The method for producing a cellulose fiber-containing material according to claim 1.
前記カルバメート変性マイクロ繊維セルロースのカルバメート化率が、1.0~2.0mmol/gである、
請求項1に記載のセルロース繊維含有物の製造方法。 (Means according to claim 2)
The carbamate-modified microfiber cellulose has a carbamate conversion rate of 1.0 to 2.0 mmol / g.
The method for producing a cellulose fiber-containing material according to claim 1.
(請求項3に記載の手段)
前記濃度を水で調整する、
請求項1又は請求項2に記載のセルロース繊維含有物の製造方法。 (Means according to claim 3)
Adjust the concentration with water,
The method for producing a cellulose fiber-containing product according to claim 1 or 2.
前記濃度を水で調整する、
請求項1又は請求項2に記載のセルロース繊維含有物の製造方法。 (Means according to claim 3)
Adjust the concentration with water,
The method for producing a cellulose fiber-containing product according to claim 1 or 2.
(請求項4に記載の手段)
前記スラリーの粘度を1000~10000cpsとする、
請求項1~3のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 4)
The viscosity of the slurry is 1000 to 10000 cps.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 3.
前記スラリーの粘度を1000~10000cpsとする、
請求項1~3のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 4)
The viscosity of the slurry is 1000 to 10000 cps.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 3.
(請求項5に記載の手段)
前記カルバメート変性マイクロ繊維セルロースの密度に対する前記相互作用しない粉体の密度比が0.4~2.2である、
請求項1~4のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 5)
The density ratio of the non-interacting powder to the density of the carbamate-modified microfiber cellulose is 0.4 to 2.2.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 4.
前記カルバメート変性マイクロ繊維セルロースの密度に対する前記相互作用しない粉体の密度比が0.4~2.2である、
請求項1~4のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 5)
The density ratio of the non-interacting powder to the density of the carbamate-modified microfiber cellulose is 0.4 to 2.2.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 4.
(請求項6に記載の手段)
前記相互作用しない粉末として酸変性樹脂を使用し、
前記カルバメート変性マイクロ繊維セルロースのカルバメート基の一部又は全部と、前記酸変性樹脂の酸基とをイオン結合させる、
請求項1~5のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 6)
An acid-modified resin was used as the non-interacting powder,
Ionic bonding a part or all of the carbamate group of the carbamate-modified microfiber cellulose with the acid group of the acid-modified resin.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 5.
前記相互作用しない粉末として酸変性樹脂を使用し、
前記カルバメート変性マイクロ繊維セルロースのカルバメート基の一部又は全部と、前記酸変性樹脂の酸基とをイオン結合させる、
請求項1~5のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 6)
An acid-modified resin was used as the non-interacting powder,
Ionic bonding a part or all of the carbamate group of the carbamate-modified microfiber cellulose with the acid group of the acid-modified resin.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 5.
(請求項7に記載の手段)
前記スラリーの酸変性樹脂の濃度を0.5質量%以上にする、
請求項1~6のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 7)
The concentration of the acid-modified resin in the slurry is set to 0.5% by mass or more.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 6.
前記スラリーの酸変性樹脂の濃度を0.5質量%以上にする、
請求項1~6のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 7)
The concentration of the acid-modified resin in the slurry is set to 0.5% by mass or more.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 6.
(請求項8に記載の手段)
前記相互作用しない粉末の平均粒子径が1mm以下である、
請求項1~7のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 8)
The average particle size of the non-interacting powder is 1 mm or less.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 7.
前記相互作用しない粉末の平均粒子径が1mm以下である、
請求項1~7のいずれか1項に記載のセルロース繊維含有物の製造方法。 (Means according to claim 8)
The average particle size of the non-interacting powder is 1 mm or less.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 7.
(請求項9に記載の手段)
請求項1~8のいずれか1項に記載の方法によって得たセルロース繊維含有物と、樹脂とを混合する、
ことを特徴とするセルロース繊維複合樹脂の製造方法。 (Means according to claim 9)
The cellulose fiber-containing material obtained by the method according to any one of claims 1 to 8 is mixed with the resin.
A method for producing a cellulose fiber composite resin.
請求項1~8のいずれか1項に記載の方法によって得たセルロース繊維含有物と、樹脂とを混合する、
ことを特徴とするセルロース繊維複合樹脂の製造方法。 (Means according to claim 9)
The cellulose fiber-containing material obtained by the method according to any one of claims 1 to 8 is mixed with the resin.
A method for producing a cellulose fiber composite resin.
発明によると、樹脂と複合した際の凝集塊の発生を少なくすることができるセルロース繊維含有物の製造方法、及び強度の高いセルロース繊維複合樹脂の製造方法になる。
According to the invention, it is a method for producing a cellulose fiber-containing material that can reduce the generation of agglomerates when compounded with a resin, and a method for producing a high-strength cellulose fiber composite resin.
次に、発明を実施するための形態を説明する。なお、本実施の形態は本発明の一例である。本発明の範囲は、本実施の形態の範囲に限定されない。
Next, a mode for carrying out the invention will be described. 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.
本形態のセルロース繊維含有物は樹脂と複合化されるものであり、セルロース繊維(以下、「繊維状セルロース」ともいう。)は平均繊維径が0.1~19μmのマイクロ繊維セルロースで、かつヒドロキシル基(-OH基)の一部又は全部がカルバメート基で置換されたカルバメート変性マイクロ繊維セルロースである。加えて、セルロース繊維含有物には、セルロース繊維と相互作用しない粉末が含まれる。また、このセルロース繊維含有物が樹脂に添加等され、複合化さることでセルロース複合樹脂が得られる。以下、詳細に説明する。
The cellulose fiber-containing material of this embodiment is compounded with a resin, and the cellulose fiber (hereinafter, also referred to as “fibrous cellulose”) is a microfiber cellulose having an average fiber diameter of 0.1 to 19 μm and is hydroxylated. Carbamate-modified microfiber cellulose in which a part or all of the group (-OH group) is substituted with a carbamate group. In addition, the cellulose fiber inclusions include powders that do not interact with the cellulose fibers. Further, the cellulose fiber-containing substance is added to the resin and the like, and the composite is obtained to obtain a cellulose composite resin. Hereinafter, it will be described in detail.
(セルロース繊維)
本形態のセルロース繊維複合樹脂は、セルロース繊維及びセルロース繊維と相互作用しない粉末を含むセルロース繊維含有物と、樹脂とを含む。本形態において微細繊維であるセルロース繊維は、平均繊維径が0.1~19μmのマイクロ繊維セルロース(ミクロフィブリル化セルロース、MFC)である。セルロース繊維がマイクロ繊維セルロースであると、樹脂の補強効果が著しく向上する。また、マイクロ繊維セルロースは、同じく微細繊維であるセルロースナノファイバーよりもカルバメート基で変性する(カルバメート化)のが容易である。ただし、微細化する前のセルロース繊維をカルバメート化するのがより好ましく、この場合においては、マイクロ繊維セルロース及びセルロースナノファイバーは同等である。 (Cellulose fiber)
The cellulose fiber composite resin of the present embodiment contains a cellulose fiber-containing material containing a cellulose fiber and a powder that does not interact with the cellulose fiber, and a resin. The cellulose fiber which is a fine fiber in this embodiment is a microfiber cellulose (microfibrillated cellulose, MFC) having an average fiber diameter of 0.1 to 19 μm. When the cellulose fiber is microfiber cellulose, the reinforcing effect of the resin is remarkably improved. In addition, microfiber cellulose is easier to denature (carbamate) with a carbamate group than cellulose nanofibers, which are also fine fibers. However, it is more preferable to carbamate the cellulose fibers before they are miniaturized, and in this case, the microfiber cellulose and the cellulose nanofibers are equivalent.
本形態のセルロース繊維複合樹脂は、セルロース繊維及びセルロース繊維と相互作用しない粉末を含むセルロース繊維含有物と、樹脂とを含む。本形態において微細繊維であるセルロース繊維は、平均繊維径が0.1~19μmのマイクロ繊維セルロース(ミクロフィブリル化セルロース、MFC)である。セルロース繊維がマイクロ繊維セルロースであると、樹脂の補強効果が著しく向上する。また、マイクロ繊維セルロースは、同じく微細繊維であるセルロースナノファイバーよりもカルバメート基で変性する(カルバメート化)のが容易である。ただし、微細化する前のセルロース繊維をカルバメート化するのがより好ましく、この場合においては、マイクロ繊維セルロース及びセルロースナノファイバーは同等である。 (Cellulose fiber)
The cellulose fiber composite resin of the present embodiment contains a cellulose fiber-containing material containing a cellulose fiber and a powder that does not interact with the cellulose fiber, and a resin. The cellulose fiber which is a fine fiber in this embodiment is a microfiber cellulose (microfibrillated cellulose, MFC) having an average fiber diameter of 0.1 to 19 μm. When the cellulose fiber is microfiber cellulose, the reinforcing effect of the resin is remarkably improved. In addition, microfiber cellulose is easier to denature (carbamate) with a carbamate group than cellulose nanofibers, which are also fine fibers. However, it is more preferable to carbamate the cellulose fibers before they are miniaturized, and in this case, the microfiber cellulose and the cellulose nanofibers are equivalent.
本形態において、マイクロ繊維セルロースは、セルロースナノファイバーよりも平均繊維径(幅)の太い繊維を意味する。具体的には、平均繊維径が、例えば0.1~19μm、好ましくは0.2~15μm、より好ましくは0.5~10μmである。マイクロ繊維セルロースの平均繊維径が0.1μmを下回ると(未満になると)、セルロースナノファイバーであるのと変わらなくなり、樹脂の強度(特に曲げ弾性率)向上効果が十分に得られないおそれがある。また、解繊時間が長くなり、大きなエネルギーが必要になる。さらに、セルロース繊維スラリーの脱水性が悪化する。脱水性が悪化すると、乾燥に大きなエネルギーが必要になり、乾燥に大きなエネルギーをかけるとマイクロ繊維セルロースが熱劣化して、強度が低下するおそれがある。他方、マイクロ繊維セルロースの平均繊維径が19μmを上回ると(超えると)、パルプであるのと変わらなくなり、補強効果が十分でなくなるおそれがある。
In this embodiment, microfiber cellulose means a fiber having an average fiber diameter (width) larger than that of cellulose nanofiber. Specifically, the average fiber diameter is, for example, 0.1 to 19 μm, preferably 0.2 to 15 μm, and more preferably 0.5 to 10 μm. When the average fiber diameter of the microfiber cellulose is less than 0.1 μm (less than 0.1 μm), 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. .. 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 the dehydration property deteriorates, a large amount of energy is required for drying, and when a large amount of energy is applied to drying, the microfiber cellulose is thermally deteriorated and the strength may decrease. On the other hand, if the average fiber diameter of the microfiber cellulose exceeds (exceeds) 19 μm, it is no different from pulp, and the reinforcing effect may not be sufficient.
マイクロ繊維セルロースの平均繊維径の測定方法は、次のとおりである。
まず、固形分濃度0.01~0.1質量%の微細繊維(マイクロ繊維セルロース)の水分散液100mlをテフロン(登録商標)製メンブレンフィルターでろ過し、エタノール100mlで1回、t-ブタノール20mlで3回溶媒置換する。次に、凍結乾燥し、オスミウムコーティングして試料とする。この試料について、構成する繊維の幅に応じて3,000倍~30,000倍のいずれかの倍率で電子顕微鏡SEM画像による観察を行う。具体的には、観察画像に二本の対角線を引き、対角線の交点を通過する直線を任意に三本引く。さらに、この三本の直線と交錯する合計100本の繊維の幅を目視で計測する。そして、計測値の中位径を平均繊維径とする。 The method for measuring the average fiber diameter of microfiber cellulose is as follows.
First, 100 ml of an aqueous dispersion of fine fibers (microfiber cellulose) 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 once with 100 ml of ethanol, 20 ml of t-butanol. Replace the solvent 3 times with. 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. Specifically, two diagonal lines are drawn on the observation image, and three straight lines passing through the intersections of the diagonal lines are arbitrarily drawn. Further, the width of a total of 100 fibers intersecting with these three straight lines is visually measured. Then, the medium diameter of the measured value is taken as the average fiber diameter.
まず、固形分濃度0.01~0.1質量%の微細繊維(マイクロ繊維セルロース)の水分散液100mlをテフロン(登録商標)製メンブレンフィルターでろ過し、エタノール100mlで1回、t-ブタノール20mlで3回溶媒置換する。次に、凍結乾燥し、オスミウムコーティングして試料とする。この試料について、構成する繊維の幅に応じて3,000倍~30,000倍のいずれかの倍率で電子顕微鏡SEM画像による観察を行う。具体的には、観察画像に二本の対角線を引き、対角線の交点を通過する直線を任意に三本引く。さらに、この三本の直線と交錯する合計100本の繊維の幅を目視で計測する。そして、計測値の中位径を平均繊維径とする。 The method for measuring the average fiber diameter of microfiber cellulose is as follows.
First, 100 ml of an aqueous dispersion of fine fibers (microfiber cellulose) 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 once with 100 ml of ethanol, 20 ml of t-butanol. Replace the solvent 3 times with. 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. Specifically, two diagonal lines are drawn on the observation image, and three straight lines passing through the intersections of the diagonal lines are arbitrarily drawn. Further, the width of a total of 100 fibers intersecting with these three straight lines is visually measured. Then, the medium diameter of the measured value is taken as the average fiber diameter.
マイクロ繊維セルロースは、セルロース原料(以下、「原料パルプ」ともいう。)を解繊(微細化)することで得ることができる。原料パルプとしては、例えば、広葉樹、針葉樹等を原料とする木材パルプ、ワラ・バガス・綿・麻・じん皮繊維等を原料とする非木材パルプ、回収古紙、損紙等を原料とする古紙パルプ(DIP)、植物由来の繊維、動物由来の繊維、微生物由来の繊維等の中から1種又は2種以上を選択して使用することができる。なお、以上の各種原料は、例えば、セルロース系パウダーなどと言われる粉砕物(粉状物)の状態等であってもよい。
Microfiber cellulose can be obtained by defibrating (miniaturizing) a cellulose raw material (hereinafter, also referred to as "raw material pulp"). The raw material pulp includes, for example, wood pulp made from broadleaf tree, coniferous tree, etc., non-wood pulp made from straw, bagasse, cotton, hemp, carrot fiber, etc., recovered waste paper, waste paper pulp made from waste paper, etc. One or more of (DIP), plant-derived fiber, animal-derived fiber, microbial-derived fiber and the like can be selected and used. 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.
ただし、不純物の混入を可及的に避けるために、原料パルプとしては、木材パルプを使用するのが好ましい。木材パルプとしては、例えば、広葉樹クラフトパルプ(LKP)、針葉樹クラフトパルプ(NKP)等の化学パルプ、機械パルプ(TMP)等の中から1種又は2種以上を選択して使用することができる。
However, in order to avoid contamination with impurities as much as possible, it is preferable to use wood pulp as the raw material pulp. As the 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.
広葉樹クラフトパルプは、広葉樹晒クラフトパルプであっても、広葉樹未晒クラフトパルプであっても、広葉樹半晒クラフトパルプであってもよい。同様に、針葉樹クラフトパルプは、針葉樹晒クラフトパルプであっても、針葉樹未晒クラフトパルプであっても、針葉樹半晒クラフトパルプであってもよい。
The hardwood kraft pulp may be hardwood bleached kraft pulp, hardwood unbleached kraft pulp, or hardwood semi-bleached kraft pulp. Similarly, the softwood kraft pulp may be softwood bleached kraft pulp, unbleached softwood kraft pulp, or semi-bleached softwood kraft pulp.
機械パルプとしては、例えば、ストーングランドパルプ(SGP)、加圧ストーングランドパルプ(PGW)、リファイナーグランドパルプ(RGP)、ケミグランドパルプ(CGP)、サーモグランドパルプ(TGP)、グランドパルプ(GP)、サーモメカニカルパルプ(TMP)、ケミサーモメカニカルパルプ(CTMP)、リファイナーメカニカルパルプ(RMP)、漂白サーモメカニカルパルプ(BTMP)等の中から1種又は2種以上を選択して使用することができる。
Examples of the mechanical pulp 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). One or more of the thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), refiner mechanical pulp (RMP), bleached thermomechanical pulp (BTMP) and the like can be selected and used.
原料パルプは、解繊するに先立って化学的手法によって前処理することができる。化学的手法による前処理としては、例えば、酸による多糖の加水分解(酸処理)、酵素による多糖の加水分解(酵素処理)、アルカリによる多糖の膨潤(アルカリ処理)、酸化剤による多糖の酸化(酸化処理)、還元剤による多糖の還元(還元処理)等を例示することができる。ただし、化学的手法による前処理としては、酵素処理を施すのが好ましく、加えて酸処理、アルカリ処理、及び酸化処理の中から選択された1又は2以上の処理を施すのがより好ましい。以下、酵素処理について詳細に説明する。
Raw 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. However, as 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. Hereinafter, the enzyme treatment will be described in detail.
酵素処理に使用する酵素としては、セルラーゼ系酵素及びヘミセルラーゼ系酵素の少なくともいずれか一方を使用するのが好ましく、両方を併用するのがより好ましい。これらの酵素を使用すると、セルロース原料の解繊がより容易になる。なお、セルラーゼ系酵素は、水共存下でセルロースの分解を惹き起こす。また、ヘミセルラーゼ系酵素は、水共存下でヘミセルロースの分解を惹き起こす。
As 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. In addition, hemicellulose-based enzymes induce the decomposition of hemicellulose in the presence of water.
セルラーゼ系酵素としては、例えば、トリコデルマ(Trichoderma、糸状菌)属、アクレモニウム(Acremonium、糸状菌)属、アスペルギルス(Aspergillus、糸状菌)属、ファネロケエテ(Phanerochaete、担子菌)属、トラメテス(Trametes、担子菌)属、フーミコラ(Humicola、糸状菌)属、バチルス(Bacillus、細菌)属、スエヒロタケ(Schizophyllum、担子菌)属、ストレプトミセス(Streptomyces、細菌)属、シュードモナス(Pseudomonas、細菌)属などが産生する酵素を使用することができる。これらのセルラーゼ系酵素は、試薬や市販品として購入可能である。市販品としては、例えば、セルロイシンT2(エイチピィアイ社製)、メイセラ-ゼ(明治製菓社製)、ノボザイム188(ノボザイム社製)、マルティフェクトCX10L(ジェネンコア社製)、セルラーゼ系酵素GC220(ジェネンコア社製)等を例示することができる。
Examples of the cellulase-based enzymes include Trichoderma (Filamentous fungus), Acremonium (Filamentous fungus), Aspergillus (Filamentous fungus), Fanerochaete (Phanerochaete), Tramethes (Tra). Genus Humicola, genus Humicola, genus Bacillus, genus Schizophyllum, genus Streptomyces, genus Pseudomonas, bacteria produced by Pseudomonas, etc. Enzymes can be used. These cellulase-based enzymes can be purchased as reagents or commercial products. Commercially available products include, for example, cellulosein T2 (manufactured by HPI), Meicerase (manufactured by Meiji Seika), Novozyme 188 (manufactured by Novozyme), Multifect CX10L (manufactured by Genencore), and cellulase-based enzyme GC220 (manufactured by Genecore). Manufactured by) and the like can be exemplified.
また、セルラーゼ系酵素としては、EG(エンドグルカナーゼ)及びCBH(セロビオハイドロラーゼ)のいずれかもを使用することもできる。EG及びCBHは、それぞれを単体で使用しても、混合して使用してもよい。また、ヘミセルラーゼ系酵素と混合して使用してもよい。
Further, as the cellulase-based enzyme, either EG (endoglucanase) or CBH (cellobiohydrolase) can be used. EG and CBH may be used alone or in combination. Further, it may be used in combination with a hemicellulase-based enzyme.
ヘミセルラーゼ系酵素としては、例えば、キシランを分解する酵素であるキシラナーゼ(xylanase)、マンナンを分解する酵素であるマンナーゼ(mannase)、アラバンを分解する酵素であるアラバナーゼ(arabanase)等を使用することができる。また、ペクチンを分解する酵素であるペクチナーゼも使用することができる。
As the 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 alabang, can be used. can. In addition, pectinase, which is an enzyme that decomposes pectin, can also be used.
ヘミセルロースは、植物細胞壁のセルロースミクロフィブリル間にあるペクチン類を除いた多糖類である。ヘミセルロースは多種多様で木材の種類や細胞壁の壁層間でも異なる。針葉樹の2次壁では、グルコマンナンが主成分であり、広葉樹の2次壁では4-O-メチルグルクロノキシランが主成分である。そこで、針葉樹晒クラフトパルプ(NBKP)から微細繊維を得る場合は、マンナーゼを使用するのが好ましい。また、広葉樹晒クラフトパルプ(LBKP)から微細繊維を得る場合は、キシラナーゼを使用するのが好ましい。
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.
セルロース原料に対する酵素の添加量は、例えば、酵素の種類、原料となる木材の種類(針葉樹か広葉樹か)、機械パルプの種類等によって決まる。ただし、セルロース原料に対する酵素の添加量は、好ましくは0.1~3質量%、より好ましくは0.3~2.5質量%、特に好ましくは0.5~2質量%である。酵素の添加量が0.1質量%を下回ると、酵素の添加による効果が十分に得られないおそれがある。他方、酵素の添加量が3質量%を上回ると、セルロースが糖化され、繊維の収率が低下するおそれがある。また、添加量の増量に見合う効果の向上を認めることができないとの問題もある。
The amount of enzyme added to the cellulose raw material is determined by, for example, the type of enzyme, the type of wood used as the raw material (conifer or hardwood), the type of mechanical pulp, and the like. However, 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, the cellulose may be saccharified and the yield of the fiber 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.
酵素としてセルラーゼ系酵素を使用する場合、酵素処理時のpHは、酵素反応の反応性の観点から、弱酸性領域(pH=3.0~6.9)であるのが好ましい。他方、酵素としてヘミセルラーゼ系酵素を使用する場合、酵素処理時のpHは、弱アルカリ性領域(pH=7.1~10.0)であるのが好ましい。
When a cellulase-based enzyme is used as the enzyme, the pH at the time of enzyme treatment is preferably in a weakly acidic region (pH = 3.0 to 6.9) from the viewpoint of the reactivity of the enzyme reaction. On the other hand, when a hemicellulase-based enzyme is used as the enzyme, the pH at the time of enzyme treatment is preferably in a weak alkaline region (pH = 7.1 to 10.0).
酵素処理時の温度は、酵素としてセルラーゼ系酵素及びヘミセルラーゼ系酵素のいずれを使用する場合においても、好ましくは30~70℃、より好ましくは35~65℃、特に好ましくは40~60℃である。酵素処理時の温度が30℃以上であれば、酵素活性が低下し難くなり、処理時間の長期化を防止することができる。他方、酵素処理時の温度が70℃以下であれば、酵素の失活を防止することができる。
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. .. When 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. On the other hand, if the temperature at the time of enzyme treatment is 70 ° C. or lower, inactivation of the enzyme can be prevented.
酵素処理の時間は、例えば、酵素の種類、酵素処理の温度、酵素処理時のpH等によって決まる。ただし、一般的な酵素処理の時間は、0.5~24時間である。
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. However, the general enzyme treatment time is 0.5 to 24 hours.
酵素処理した後には、酵素を失活させるのが好ましい。酵素を失活させる方法としては、例えば、アルカリ水溶液(好ましくはpH10以上、より好ましくはpH11以上)を添加する方法、80~100℃の熱水を添加する方法等が存在する。
It is preferable to inactivate the enzyme after the enzyme treatment. As 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.
次に、アルカリ処理の方法について説明する。
解繊に先立ってアルカリ処理すると、パルプが持つヘミセルロースやセルロースの水酸基が一部解離し、分子がアニオン化することで分子内及び分子間水素結合が弱まり、解繊におけるセルロース原料の分散が促進される。 Next, the method of alkali treatment will be described.
When alkali treatment is performed prior to defibration, the hydroxyl groups of hemicellulose and cellulose in pulp are partially dissociated, and the molecules are anionized, weakening intramolecular and intermolecular hydrogen bonds and promoting dispersion of cellulose raw materials in defibration. Ru.
解繊に先立ってアルカリ処理すると、パルプが持つヘミセルロースやセルロースの水酸基が一部解離し、分子がアニオン化することで分子内及び分子間水素結合が弱まり、解繊におけるセルロース原料の分散が促進される。 Next, the method of alkali treatment will be described.
When alkali treatment is performed prior to defibration, the hydroxyl groups of hemicellulose and cellulose in pulp are partially dissociated, and the molecules are anionized, weakening intramolecular and intermolecular hydrogen bonds and promoting dispersion of cellulose raw materials in defibration. Ru.
アルカリ処理に使用するアルカリとしては、例えば、水酸化ナトリウム、水酸化リチウム、水酸化カリウム、アンモニア水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化テトラブチルアンモニウム、水酸化ベンジルトリメチルアンモニウム等の有機アルカリ等を使用することができる。ただし、製造コストの観点からは、水酸化ナトリウムを使用するのが好ましい。
Examples of the alkali used for the alkali treatment include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia solution, 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.
解繊に先立って酵素処理や酸処理、酸化処理を施すと、マイクロ繊維セルロースの保水度を低く、結晶化度を高くすることができ、かつ均質性を高くすることができる。この点、マイクロ繊維セルロースの保水度が低いと脱水し易くなり、セルロース繊維スラリーの脱水性が向上する。
When enzyme treatment, acid treatment, and oxidation treatment are performed prior to defibration, 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.
原料パルプを酵素処理や酸処理、酸化処理すると、パルプが持つヘミセルロースやセルロースの非晶領域が分解される。結果、解繊のエネルギーを低減することができ、セルロース繊維の均一性や分散性を向上することができる。ただし、前処理は、マイクロ繊維セルロースのアスペクト比を低下させるため、樹脂の補強材として使用する場合には、過度の前処理を避けるのが好ましい。
When the raw material pulp is subjected to enzyme treatment, acid treatment, or oxidation treatment, the hemicellulose and the amorphous region of cellulose that the pulp has are decomposed. As a result, the energy of defibration can be reduced, and the uniformity and dispersibility of the cellulose fibers can be improved. However, since the pretreatment lowers the aspect ratio of the microfiber cellulose, it is preferable to avoid excessive pretreatment when it is used as a reinforcing material for the resin.
原料パルプの解繊(微細化)は、例えば、ビーター、高圧ホモジナイザー、高圧均質化装置等のホモジナイザー、グラインダー、摩砕機等の石臼式摩擦機、単軸混練機、多軸混練機、ニーダーリファイナー、ジェットミル等を使用して原料パルプを叩解することによって行うことができる。ただし、リファイナーやジェットミルを使用して行うのが好ましい。
For defibration (miniaturization) of raw pulp, for example, beaters, high-pressure homogenizers, homogenizers such as high-pressure homogenizers, millstone friction machines such as grinders and grinders, single-screw kneaders, multi-screw kneaders, kneader refiners, etc. This can be done by beating the raw pulp using a jet mill or the like. However, it is preferable to use a refiner or a jet mill.
マイクロ繊維セルロースの平均繊維長(単繊維の長さの平均)は、好ましくは0.10~2.00mm、より好ましくは0.12~1.50mm、特に好ましくは0.15~1.00mmである。平均繊維長が0.10mm以下であると、繊維同士の三次元ネットワークを形成できず、複合樹脂の補強効果(特に曲げ弾性率)が低下するおそれがある。他方、平均繊維長が2.00mmを上回ると、原料パルプと変わらない長さのため補強効果が不十分となるおそれがある。
The average fiber length (average length of single fibers) of the microfiber cellulose is preferably 0.10 to 2.00 mm, more preferably 0.12 to 1.50 mm, and particularly preferably 0.15 to 1.00 mm. be. If the average fiber length is 0.10 mm or less, a three-dimensional network of fibers cannot be formed, and the reinforcing effect (particularly, flexural modulus) of the composite resin may decrease. 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.
マイクロ繊維セルロースの原料となるセルロース原料の平均繊維長は、好ましくは0.50~5.00mm、より好ましくは1.00~3.00mm、特に好ましくは1.50~2.50mmである。セルロース原料の平均繊維長が0.50mmを下回ると、解繊処理した際の、樹脂の補強効果が十分得られない可能性がある。他方、平均繊維長が5.00mmを上回ると、解繊時の製造コストの面で不利となるおそれがある。
The average fiber length of the cellulose raw material as a raw material for microfiber cellulose 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 of the cellulose raw material is less than 0.50 mm, the effect of reinforcing the resin during the defibration treatment may not be sufficiently obtained. 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.
マイクロ繊維セルロースの平均繊維長は、例えば、原料パルプの選定、前処理、解繊等で任意に調整可能である。
The average fiber length of microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
マイクロ繊維セルロースの平均繊維長は、平均繊維径の場合と同様にして、各繊維の長さを目視で計測する。計測値の中位長を平均繊維長とする。
For the average fiber length of microfiber cellulose, the length of each fiber is visually measured 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.
マイクロ繊維セルロースの繊維長は、0.02mm超の割合が、好ましくは20%以上、より好ましくは40%以上、特に好ましくは60%以上である。当該割合が20%を下回ると、樹脂の補強効果が十分に得られない可能性がある。他方、マイクロ繊維セルロースの繊維長は、0.02mm超の割合の上限がなく、全てが0.02mm超であっても良い。
The fiber length of the microfiber cellulose is preferably 20% or more, more preferably 40% or more, and particularly preferably 60% or more in a ratio of more than 0.02 mm. If the ratio is less than 20%, the reinforcing effect of the resin may not be sufficiently obtained. On the other hand, the fiber length of the microfiber cellulose has no upper limit of the ratio of more than 0.02 mm, and all of them may be more than 0.02 mm.
マイクロ繊維セルロースのアスペクト比は、好ましくは2~15,000、より好ましくは10~10,000である。アスペクト比が2を下回ると、三次元ネットワークを構築できないため、たとえ平均繊維長が0.01mmを超えたとしても、補強効果が不十分となるおそれがある。他方、アスペクト比が15,000を上回ると、マイクロ繊維セルロース同士の絡み合いが高くなり、樹脂中での分散が不十分となるおそれがある。
The aspect ratio of the microfiber cellulose is preferably 2 to 15,000, more preferably 10 to 10,000. If the aspect ratio is less than 2, a three-dimensional network cannot be constructed, and even if the average fiber length exceeds 0.01 mm, 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.
アスペクト比は、平均繊維長を平均繊維幅で除した値である。アスペクト比が大きいほど引っかかりが生じる箇所が多くなるため補強効果が上がるが、他方で引っかかりが多くなる分、樹脂の延性が低下するものと考えられる。
The aspect ratio is the 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.
マイクロ繊維セルロースのフィブリル化率は、好ましくは1.0~30.0%、より好ましくは1.5~20.0%、特に好ましくは2.0~15.0%である。フィブリル化率が30.0%を上回ると、水との接触面積が広くなり過ぎるため、たとえ平均繊維幅が0.1μm以上に留まる範囲で解繊したとしても、脱水が困難になる可能性がある。他方、フィブリル化率が1.0%下回ると、フィブリル同士の水素結合が少なく、強固な三次元ネットワークを形成することができなくなるおそれがある。
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 μm 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.
フィブリル化率は、微細繊維をJIS-P-8220:2012「パルプ-離解方法」に準拠して離解し、得られた離解パルプをFiberLab.(Kajaani社)を用いて測定した値をいう。
The fibrillation rate was determined by dissociating fine fibers in accordance with JIS-P-8220: 2012 "Pulp-Dissolution Method", and dissociating the obtained dissociated pulp in FaberLab. (Kajaani) means a value measured using.
マイクロ繊維セルロースの結晶化度は、好ましくは50%以上、より好ましくは55%以上、特に好ましくは60%以上である。結晶化度が50%を下回ると、パルプやセルロースナノファイバーとの混合性は向上するものの、繊維自体の強度が低下するため、樹脂の強度を向上することができなくなるおそれがある。他方、マイクロ繊維セルロースの結晶化度は、好ましくは95%以下、より好ましくは90%以下、特に好ましくは85%以下である。結晶化度が95%を上回ると、分子内の強固な水素結合割合が多くなり、繊維自体が剛直となり、分散性が劣るようになる。
The crystallinity of the microfiber cellulose is preferably 50% or more, more preferably 55% or more, and particularly preferably 60% or more. When the crystallinity is less than 50%, the mixing property with 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. On the other hand, the crystallinity of the microfiber cellulose is preferably 95% or less, more preferably 90% or less, and particularly preferably 85% or less. When the crystallinity exceeds 95%, the ratio of strong hydrogen bonds in the molecule increases, the fiber itself becomes rigid, and the dispersibility becomes inferior.
マイクロ繊維セルロースの結晶化度は、例えば、原料パルプの選定、前処理、微細化処理で任意に調整可能である。
The crystallinity of microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, and micronization treatment.
結晶化度は、JIS-K0131(1996)の「X線回折分析通則」に準拠して、X線回折法により測定した値である。なお、微細繊維は、非晶質部分と結晶質部分とを有しており、結晶化度は微細繊維全体における結晶質部分の割合を意味する。
The crystallinity is a value measured by the X-ray diffraction method in accordance with the "general rule of X-ray diffraction analysis" of JIS-K0131 (1996). The fine fiber has an amorphous portion and a crystalline portion, and the crystallinity means the ratio of the crystalline portion to the entire fine fiber.
マイクロ繊維セルロースのパルプ粘度は、好ましくは2cps以上、より好ましくは4cps以上である。マイクロ繊維セルロースのパルプ粘度が2cpsを下回ると、マイクロ繊維セルロースの凝集を抑制するのが困難になるおそれがある。
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.
パルプ粘度は、TAPPI T 230に準拠して測定した値である。
The pulp viscosity is a value measured according to TAPPI T 230.
マイクロ繊維セルロースのフリーネスは、好ましくは500ml以下、より好ましくは300ml以下、特に好ましくは100ml以下である。マイクロ繊維セルロースのフリーネスが500mlを上回ると、マイクロ繊維セルロースの平均繊維径が19μmを超え、樹脂の強度向上効果が十分に得られなくなるおそれがある。
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 average fiber diameter of the microfiber cellulose exceeds 19 μm, and the effect of improving the strength of the resin may not be sufficiently obtained.
フリーネスは、JIS P8121-2(2012)に準拠して測定した値である。
Freeness is a value measured in accordance with JIS P8121-2 (2012).
マイクロ繊維セルロースのゼータ電位は、好ましくは-150~20mV、より好ましくは-100~0mV、特に好ましくは-80~-10mVである。ゼータ電位が-150mVを下回ると、樹脂との相溶性が著しく低下し補強効果が不十分となるおそれがある。他方、ゼータ電位が20mVを上回ると、分散安定性が低下するおそれがある。
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.
マイクロ繊維セルロースの保水度は、好ましくは80~400%、より好ましくは90~350%、特に好ましくは100~300%である。保水度が80%を下回ると、原料パルプと変わらないため補強効果が不十分となるおそれがある。他方、保水度が400%を上回ると、脱水性が劣る傾向にあり、また、凝集し易くなる。この点、マイクロ繊維セルロースの保水度は、当該セルロース繊維のヒドロキシ基がカルバメート基に置換されていることで、より低くすることができ、脱水性や乾燥性を高めることができる。
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%, dehydration tends to be inferior, and aggregation tends to occur. In this respect, the degree of water retention of the microfiber cellulose can be lowered by substituting the hydroxy group of the cellulose fiber with a carbamate group, and the dehydration property and the drying property can be improved.
マイクロ繊維セルロースの保水度は、例えば、原料パルプの選定、前処理、解繊等で任意に調整可能である。
The water retention level of the microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration, and the like.
保水度は、JAPAN TAPPI No.26(2000)に準拠して測定した値である。
The degree of water retention is JAPAN TAPPI No. It is a value measured according to 26 (2000).
本形態のマイクロ繊維セルロースは、カルバメート基を有する。どのようにしてカルバメート基を有するものとされているかは特に限定されない。例えば、セルロース原料がカルバメート化されていることでカルバメート基を有するものであっても、マイクロ繊維セルロース(微細化されたセルロース原料)がカルバメート化されることでカルバメート基を有するものであってもよい。
The microfiber cellulose of this embodiment has a carbamate group. How it is supposed to have a carbamate group is not particularly limited. For example, 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. ..
なお、カルバメート基を有するとは、繊維状セルロースにカルバメート(カルバミン酸のエステル)が導入された状態を意味する。カルバメート基は、-O-CO-NH-で表される基であり、例えば、-O-CO-NH2、-O-CONHR、-O-CO-NR2等で表わされる基である。つまり、カルバメート基は、下記の構造式(1)で示すことができる。
In addition, having a carbamate group means a state in which carbamate (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).
ここでRは、それぞれ独立して、飽和直鎖状炭化水素基、飽和分岐鎖状炭化水素基、飽和環状炭化水素基、不飽和直鎖状炭化水素基、不飽和分岐鎖状炭化水素基、芳香族基、及びこれらの誘導基の少なくともいずれかである。
Here, 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. An aromatic group and at least one of these inducing groups.
飽和直鎖状炭化水素基としては、例えば、メチル基、エチル基、プロピル基等の炭素数1~10の直鎖状のアルキル基を挙げることができる。
Examples of the saturated linear hydrocarbon group include a linear alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group.
飽和分岐鎖状炭化水素基としては、例えば、イソプロピル基、sec-ブチル基、イソブチル基、tert-ブチル基等の炭素数3~10の分岐鎖状アルキル基を挙げることができる。
Examples of the saturated branched chain hydrocarbon group 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.
飽和環状炭化水素基としては、例えば、シクロペンチル基、シクロヘキシル基、ノルボルニル基等のシクロアルキル基を挙げることができる。
Examples of the saturated cyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group and norbornyl group.
不飽和直鎖状炭化水素基としては、例えば、エテニル基、プロペン-1-イル基、プロペン-3-イル基等の炭素数2~10の直鎖状のアルケニル基、エチニル基、プロピン-1-イル基、プロピン-3-イル基等の炭素数2~10の直鎖状のアルキニル基等を挙げることができる。
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.
不飽和分岐鎖状炭化水素基としては、例えば、プロペン-2-イル基、ブテン-2-イル基、ブテン-3-イル基等の炭素数3~10の分岐鎖状アルケニル基、ブチン-3-イル基等の炭素数4~10の分岐鎖状アルキニル基等を挙げることができる。
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 alkynyl group having 4 to 10 carbon atoms such as an yl group can be mentioned.
芳香族基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基等を挙げることができる。
Examples of the aromatic group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.
誘導基としては、上記飽和直鎖状炭化水素基、飽和分岐鎖状炭化水素基、飽和環状炭化水素基、不飽和直鎖状炭化水素基、不飽和分岐鎖状炭化水素基及び芳香族基が有する1又は複数の水素原子が、置換基(例えば、ヒドロキシ基、カルボキシ基、ハロゲン原子等。)で置換された基を挙げることができる。
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 group. Examples thereof include a group in which one or more hydrogen atoms having one or more hydrogen atoms are substituted with a substituent (for example, a hydroxy group, a carboxy group, a halogen atom, etc.).
カルバメート基を有する(カルバメート基が導入された)マイクロ繊維セルロースにおいては、極性の高いヒドロキシ基の一部又は全部が、相対的に極性の低いカルバメート基に置換されている。したがって、カルバメート基を有するマイクロ繊維セルロースは、親水性が低く、極性の低い樹脂等との親和性が高い。結果、カルバメート基を有するマイクロ繊維セルロースは、樹脂との均一分散性に優れる。また、カルバメート基を有するマイクロ繊維セルロースのスラリーは、ハンドリング性が良い。
In 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 polar 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 good handleability.
マイクロ繊維セルロースのヒドロキシ基に対するカルバメート基の置換率は、好ましくは1.0~2.0mmol/g、より好ましくは1.1~1.9mmol/g、特に好ましくは1.2~1.8mmol/gである。置換率を1.0mmol/g以上にすると、カルバメートを導入した効果、特に樹脂の曲げ伸び向上効果が確実に奏せられる。他方、置換率が2.0mmol/gを超えると、セルロース繊維が繊維の形状を保てなくなり、樹脂の補強効果が十分得られなくなる可能性と、疎水性になりすぎることで、水分散体中で十分に分散せず、樹脂粉末等と混合する際に凝集の原因となるおそれがある。
The substitution rate of the carbamate group with respect to the hydroxy group of the microfiber cellulose is preferably 1.0 to 2.0 mmol / g, more preferably 1.1 to 1.9 mmol / g, and particularly preferably 1.2 to 1.8 mmol / g. g. When the substitution rate is 1.0 mmol / g or more, the effect of introducing the carbamate, particularly the effect of improving the bending elongation of the resin can be surely exhibited. On the other hand, if the substitution rate exceeds 2.0 mmol / g, the cellulose fibers may not be able to maintain the shape of the fibers, and the reinforcing effect of the resin may not be sufficiently obtained. It does not disperse sufficiently and may cause aggregation when mixed with resin powder or the like.
なお、カルバメート基の置換率(mmol/g)とは、カルバメート基を有するセルロース原料1gあたりに含まれるカルバメート基の物質量をいう。また、セルロースは、無水グルコースを構造単位とする重合体であり、一構造単位当たり3つのヒドロキシ基を有する。
The carbamate group substitution rate (mmol / g) refers to the amount of substance of the carbamate group contained in 1 g of the cellulose raw material having a carbamate group. Cellulose is a polymer having anhydrous glucose as a structural unit, and has three hydroxy groups per structural unit.
<カルバメート化>
マイクロ繊維セルロース(解繊前にカルバメート化する場合は、セルロース原料。以下、同様であり、「マイクロ繊維セルロース等」ともいう。)にカルバメートを導入する(カルバメート化)点については、前述したようにセルロース原料をカルバメート化してから微細化する方法と、セルロース原料を微細化してからカルバメート化する方法とがある。この点、本明細書においては、先にセルロース原料の解繊について説明し、その後にカルバメート化(変性)について説明している。しかしながら、解繊及びカルバメート化は、どちらを先に行うこともできる。ただし、先にカルバメート化を行い、その後に、解繊をする方が好ましい。解繊する前のセルロース原料は脱水効率が高く、また、カルバメート化に伴う加熱によってセルロース原料が解繊され易い状態になるためである。 <Carbamate>
As described above, the point of introducing carbamate (carbamate) into microfiber cellulose (cellulose raw material when carbamate before defibration. The same applies hereinafter, also referred to as "microfiber cellulose, etc."). There are a method of carbamating the cellulose raw material and then making it finer, and a method of making the cellulose raw material finer and then making it into carbamate. In this regard, in the present specification, the defibration of the cellulose raw material will be described first, and then the carbamate formation (modification) will be described. However, either fibrillation or carbamate can be performed first. However, it is preferable to carry out 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.
マイクロ繊維セルロース(解繊前にカルバメート化する場合は、セルロース原料。以下、同様であり、「マイクロ繊維セルロース等」ともいう。)にカルバメートを導入する(カルバメート化)点については、前述したようにセルロース原料をカルバメート化してから微細化する方法と、セルロース原料を微細化してからカルバメート化する方法とがある。この点、本明細書においては、先にセルロース原料の解繊について説明し、その後にカルバメート化(変性)について説明している。しかしながら、解繊及びカルバメート化は、どちらを先に行うこともできる。ただし、先にカルバメート化を行い、その後に、解繊をする方が好ましい。解繊する前のセルロース原料は脱水効率が高く、また、カルバメート化に伴う加熱によってセルロース原料が解繊され易い状態になるためである。 <Carbamate>
As described above, the point of introducing carbamate (carbamate) into microfiber cellulose (cellulose raw material when carbamate before defibration. The same applies hereinafter, also referred to as "microfiber cellulose, etc."). There are a method of carbamating the cellulose raw material and then making it finer, and a method of making the cellulose raw material finer and then making it into carbamate. In this regard, in the present specification, the defibration of the cellulose raw material will be described first, and then the carbamate formation (modification) will be described. However, either fibrillation or carbamate can be performed first. However, it is preferable to carry out 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.
マイクロ繊維セルロース等をカルバメート化する工程は、例えば、混合処理、除去処理、及び加熱処理に、主に区分することができる。なお、混合処理及び除去処理は合わせて、加熱処理に供される混合物を調製する調整処理ということもできる。また、カルバメート化においては、有機溶剤を使用する必要がない。
The step of carbamate microfiber cellulose or the like can be mainly classified into, for example, a mixing treatment, a removal treatment, and a heat treatment. The mixing treatment and the removing treatment can also be referred to as an adjustment treatment for preparing a mixture to be subjected to the heat treatment. Moreover, it is not necessary to use an organic solvent for carbamate formation.
混合処理においては、マイクロ繊維セルロース等(前述したようにセルロース原料の場合もある。以下、同様。)と尿素及び/又は尿素の誘導体(以下、単に「尿素等」ともいう。)とを分散媒中で混合する。
In the mixing treatment, microfiber cellulose or the like (which may be a cellulose raw material as described above; the same applies hereinafter) and urea and / or a derivative of urea (hereinafter, also simply referred to as “urea or the like”) are used as a dispersion medium. Mix in.
尿素や尿素の誘導体としては、例えば、尿素、チオ尿素、ビウレット、フェニル尿素、ベンジル尿素、ジメチル尿素、ジエチル尿素、テトラメチル尿素、尿素の水素原子をアルキル基で置換した化合物等を使用することができる。これらの尿素や尿素の誘導体は、それぞれを単独で又は複数を組み合わせて使用することができる。ただし、尿素を使用するのが好ましい。
As the derivative of 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. can. These ureas and urea derivatives can be used alone or in combination of two or more. However, it is preferable to use urea.
マイクロ繊維セルロース等に対する尿素等の混合質量比(尿素等/マイクロ繊維セルロース等)の下限は、好ましくは10/100、より好ましくは20/100である。他方、上限は、好ましくは300/100、より好ましくは200/100である。混合質量比を10/100以上にすることで、カルバメート化の効率が向上する。他方、混合質量比が300/100を上回っても、カルバメート化は頭打ちになる。
The lower limit of the mixed mass ratio of urea or the like (urea or the like / microfiber cellulose or the like) to the microfiber cellulose or the like is preferably 10/100, more preferably 20/100. On the other hand, the upper limit is preferably 300/100, more preferably 200/100. By setting the mixed mass ratio to 10/100 or more, the efficiency of carbamate formation is improved. On the other hand, even if the mixed mass ratio exceeds 300/100, the carbamation reaches a plateau.
分散媒は、通常、水である。ただし、アルコール、エーテル等の他の分散媒や、水と他の分散媒との混合物を用いてもよい。
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.
混合処理においては、例えば、水にマイクロ繊維セルロース等及び尿素等を添加しても、尿素等の水溶液にマイクロ繊維セルロース等を添加しても、マイクロ繊維セルロース等を含むスラリーに尿素等を添加してもよい。また、均一に混合するために、添加後、攪拌してもよい。さらに、マイクロ繊維セルロース等と尿素等とを含む分散液には、その他の成分が含まれていてもよい。
In the mixing treatment, for example, even if microfiber cellulose or the like and urea or the like are added to water, or microfiber cellulose or the like is added to an aqueous solution of urea or the like, urea or the like is added to a slurry containing microfiber cellulose or the like. You may. Further, in order to mix uniformly, the mixture may be stirred after the addition. Further, the dispersion liquid containing microfiber cellulose or the like and urea or the like may contain other components.
除去処理においては、混合処理において得られたマイクロ繊維セルロース等及び尿素等を含む分散液から分散媒を除去する。分散媒を除去することで、これに続く加熱処理において効率的に尿素等を反応させることができる。
In the removal treatment, the dispersion medium is removed from the dispersion liquid containing microfiber cellulose and the like and urea and the like obtained in the mixing treatment. By removing the dispersion medium, urea and the like can be efficiently reacted in the subsequent heat treatment.
分散媒の除去は、加熱によって分散媒を揮発させることで行うのが好ましい。この方法によると、尿素等の成分を残したまま分散媒のみを効率的に除去することができる。
It is preferable to remove the 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.
除去処理における加熱温度の下限は、分散媒が水である場合は、好ましくは50℃、より好ましくは70℃、特に好ましくは90℃である。加熱温度を50℃以上にすることで効率的に分散媒を揮発させる(除去する)ことができる。他方、加熱温度の上限は、好ましくは120℃、より好ましくは100℃である。加熱温度が120℃を上回ると、分散媒と尿素が反応し、尿素が単独分解するおそれがある。
When the dispersion medium is water, the lower limit of the heating temperature in the removal treatment is preferably 50 ° C, more preferably 70 ° C, and particularly preferably 90 ° C. By setting the heating temperature to 50 ° C. or higher, the dispersion medium can be efficiently volatilized (removed). On the other hand, 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.
除去処理における加熱時間は、分散液の固形分濃度等に応じて適宜調節することができる。具体的には、例えば、6~24時間である。
The heating time in the removal treatment can be appropriately adjusted according to the solid content concentration of the dispersion liquid and the like. Specifically, for example, 6 to 24 hours.
除去処理に続く加熱処理においては、マイクロ繊維セルロース等と尿素等との混合物を加熱処理する。この加熱処理において、マイクロ繊維セルロース等のヒドロキシ基の一部又は全部が尿素等と反応してカルバメート基に置換される。より詳細には、尿素等が加熱されると下記の反応式(1)に示すようにイソシアン酸及びアンモニアに分解される。そして、イソシアン酸はとても反応性が高く、例えば、下記の反応式(2)に示すようにセルロースの水酸基にカルバメート基を形成する。
NH2-CO-NH2 → H-N=C=O + NH3 …(1)
Cell-OH + H-N=C=O → Cell-O-CO-NH2 …(2)
加熱処理における加熱温度の下限は、好ましくは120℃、より好ましくは130℃、特に好ましくは尿素の融点(約134℃)以上、さらに好ましくは140℃、最も好ましくは150℃である。加熱温度を120℃以上にすることで、カルバメート化が効率的に行われる。加熱温度の上限は、好ましくは200℃、より好ましくは180℃、特に好ましくは170℃である。加熱温度が200℃を上回ると、マイクロ繊維セルロース等が分解し、補強効果が不十分となるおそれがある。 In the heat treatment following the removal treatment, a mixture of microfiber cellulose or the like and urea or the like is heat-treated. In this heat treatment, a part or all of a hydroxy group such as microfiber cellulose reacts with urea or the like and is replaced with a carbamate group. More specifically, when urea or the like is heated, it is decomposed into isocyanic acid and ammonia as shown in the following reaction formula (1). Isocyanic acid is very reactive, and for example, it forms a carbamate group at the hydroxyl group of cellulose as shown in the following reaction formula (2).
NH 2 -CO-NH 2 → H-N = C = O + NH 3 ... (1)
Cell-OH + HN = C = O → Cell-O-CO-NH 2 … (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. By setting the heating temperature to 120 ° C. or higher, carbamate formation is efficiently performed. 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., microfiber cellulose or the like may be decomposed and the reinforcing effect may be insufficient.
NH2-CO-NH2 → H-N=C=O + NH3 …(1)
Cell-OH + H-N=C=O → Cell-O-CO-NH2 …(2)
加熱処理における加熱温度の下限は、好ましくは120℃、より好ましくは130℃、特に好ましくは尿素の融点(約134℃)以上、さらに好ましくは140℃、最も好ましくは150℃である。加熱温度を120℃以上にすることで、カルバメート化が効率的に行われる。加熱温度の上限は、好ましくは200℃、より好ましくは180℃、特に好ましくは170℃である。加熱温度が200℃を上回ると、マイクロ繊維セルロース等が分解し、補強効果が不十分となるおそれがある。 In the heat treatment following the removal treatment, a mixture of microfiber cellulose or the like and urea or the like is heat-treated. In this heat treatment, a part or all of a hydroxy group such as microfiber cellulose reacts with urea or the like and is replaced with a carbamate group. More specifically, when urea or the like is heated, it is decomposed into isocyanic acid and ammonia as shown in the following reaction formula (1). Isocyanic acid is very reactive, and for example, it forms a carbamate group at the hydroxyl group of cellulose as shown in the following reaction formula (2).
NH 2 -CO-NH 2 → H-N = C = O + NH 3 ... (1)
Cell-OH + HN = C = O → Cell-O-CO-NH 2 … (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. By setting the heating temperature to 120 ° C. or higher, carbamate formation is efficiently performed. 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., microfiber cellulose or the like may be decomposed and the reinforcing effect may be insufficient.
加熱処理における加熱時間の下限は、好ましくは1分、より好ましくは5分、特に好ましくは30分、更に好ましくは1時間、最も好ましくは2時間である。加熱時間を1分以上にすることで、カルバメート化の反応を確実に行うことができる。他方、加熱時間の上限は、好ましくは15時間、より好ましくは10時間である。加熱時間が15時間を上回ると、経済的ではなく、15時間で十分カルバメート化を行うことができる。
The lower limit of the heating time in the heat treatment is preferably 1 minute, more preferably 5 minutes, particularly preferably 30 minutes, still more preferably 1 hour, and most preferably 2 hours. By setting the heating time to 1 minute or more, the carbamate-forming reaction can be surely carried out. On the other hand, the upper limit of the heating time is preferably 15 hours, more preferably 10 hours. If the heating time exceeds 15 hours, it is not economical and sufficient carbamate can be achieved in 15 hours.
もっとも、加熱時間の長期化は、セルロース繊維の劣化を招く。そこで、加熱処理におけるpH条件が重要となる。pHは、好ましくはpH9以上、より好ましくはpH9~13、特に好ましくはpH10~12のアルカリ性条件である。また、次善の策として、pH7以下、好ましくはpH3~7、特に好ましくはpH4~7の酸性条件又は中性条件である。pH7~8の中性条件であると、セルロース繊維の平均繊維長が短くなり、樹脂の補強効果に劣る可能性がある。これに対し、pH9以上のアルカリ性条件であると、セルロース繊維の反応性が高まり、尿素等への反応が促進され、効率良くカルバメート化反応するため、セルロース繊維の平均繊維長を十分に確保することができる。他方、pH7以下の酸性条件であると、尿素等からイソシアン酸及びアンモニアに分解する反応が進み、セルロース繊維への反応が促進され、効率良くカルバメート化反応するため、セルロース繊維の平均繊維長を十分に確保することができる。ただし、可能であれば、アルカリ性条件で加熱処理する方が好ましい。酸性条件であるとセルロースの酸加水分解が進行するおそれがあるためである。
However, prolonged heating time causes deterioration of cellulose fibers. Therefore, 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. Further, as the next best measure, 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. Under neutral conditions of pH 7 to 8, the average fiber length of the cellulose fibers becomes short, and the reinforcing effect of the resin may be inferior. On the other hand, under alkaline conditions of pH 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, so that the average fiber length of the cellulose fibers should be sufficiently secured. Can be done. On the other hand, under acidic conditions of pH 7 or less, 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. However, if possible, it is preferable to heat-treat under alkaline conditions. This is because acid hydrolysis of cellulose may proceed under acidic conditions.
pHの調整は、混合物に酸性化合物(例えば、酢酸、クエン酸等。)やアルカリ性化合物(例えば、水酸化ナトリウム、水酸化カルシウム等。)を添加すること等によって行うことができる。
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.
加熱処理において加熱する装置としては、例えば、熱風乾燥機、抄紙機、ドライパルプマシン等を使用することができる。
As a device for heating in the heat treatment, for example, a hot air dryer, a paper machine, a dry pulp machine, or the like can be used.
加熱処理後の混合物は、洗浄してもよい。この洗浄は、水等で行えばよい。この洗浄によって未反応で残留している尿素等を除去することができる。
The mixture after heat treatment may be washed. This washing may be performed with water or the like. By this washing, urea and the like remaining unreacted can be removed.
マイクロ繊維セルロースは、必要により、水系媒体中に分散して分散液(スラリー)にする。水系媒体は、全量が水であるのが特に好ましいが、一部が水と相溶性を有する他の液体である水系媒体も使用することができる。他の液体としては、炭素数3以下の低級アルコール類等を使用することができる。
If necessary, 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.
分散液の固形分濃度は、好ましくは0.1~10.0質量%、より好ましくは0.5~5.0質量%である。固形分濃度が0.1質量%を下回ると、脱水や乾燥する際に過大なエネルギーが必要となるおそれがある。他方、固形分濃度が10.0質量%を上回ると、分散液自体の流動性が低下してしまい分散剤を使用する場合において均一に混合できなくなるおそれがある。
The solid content concentration of the dispersion 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 dispersion liquid itself may decrease and uniform mixing may not be possible when a dispersant is used.
(相互作用しない粉末)
本形態のセルロース繊維含有物は、セルロース繊維と相互作用しない粉末を含む。セルロース繊維含有物がセルロース繊維と相互作用しない粉末を含むことで、セルロース繊維を樹脂の補強性を発揮できる形態とすることができる。すなわち、セルロース繊維含有物がスラリーである場合は、樹脂と複合化する前にスラリーに含まれる水系媒体を除去するのが好ましい。しかしながら、水系媒体を除去する際にセルロース同士が水素結合により不可逆的に凝集し、繊維としての補強効果を十分に発揮できなくなる可能性がある。そこで、セルロース繊維含有物(スラリー)に相互作用しない粉末を含むことで、セルロース同士の水素結合を物理的に阻害するものである。 (Powder that does not interact)
The cellulose fiber-containing material of this embodiment contains a powder that does not interact with the cellulose fiber. By containing the powder in which the cellulose fiber-containing material does not interact with the cellulose fiber, the cellulose fiber can be in a form capable of exhibiting the reinforcing property of the resin. That is, when the cellulose fiber-containing material is a slurry, it is preferable to remove the aqueous medium contained in the slurry before compounding with the resin. However, when the aqueous medium is removed, 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 cellulose fiber-containing substance (slurry), hydrogen bonds between the celluloses are physically inhibited.
本形態のセルロース繊維含有物は、セルロース繊維と相互作用しない粉末を含む。セルロース繊維含有物がセルロース繊維と相互作用しない粉末を含むことで、セルロース繊維を樹脂の補強性を発揮できる形態とすることができる。すなわち、セルロース繊維含有物がスラリーである場合は、樹脂と複合化する前にスラリーに含まれる水系媒体を除去するのが好ましい。しかしながら、水系媒体を除去する際にセルロース同士が水素結合により不可逆的に凝集し、繊維としての補強効果を十分に発揮できなくなる可能性がある。そこで、セルロース繊維含有物(スラリー)に相互作用しない粉末を含むことで、セルロース同士の水素結合を物理的に阻害するものである。 (Powder that does not interact)
The cellulose fiber-containing material of this embodiment contains a powder that does not interact with the cellulose fiber. By containing the powder in which the cellulose fiber-containing material does not interact with the cellulose fiber, the cellulose fiber can be in a form capable of exhibiting the reinforcing property of the resin. That is, when the cellulose fiber-containing material is a slurry, it is preferable to remove the aqueous medium contained in the slurry before compounding with the resin. However, when the aqueous medium is removed, 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 cellulose fiber-containing substance (slurry), hydrogen bonds between the celluloses are physically inhibited.
ここで、相互作用しないとは、セルロース繊維と共有結合、イオン結合、金属結合による強固な結合をしないことを意味する(つまり、水素結合、ファンデルワールス力による結合は相互作用しないという概念に含まれる。)。好ましくは、強固な結合は、結合エネルギーが100kJ/molを超える結合である。
Here, "non-interacting" means that a strong bond is not formed by a covalent bond, an ionic bond, or a metal bond with a cellulose fiber (that is, a hydrogen bond or a van der Waals force bond is included in the concept that the bond does not interact. Is done.). Preferably, the strong bond is a bond having a binding energy of more than 100 kJ / mol.
相互作用しない粉末は、好ましくは、スラリー中で共存した際に、セルロース繊維の持つ水酸基を水酸化物イオンへ解離させる作用の少ない無機粉末及び樹脂粉末の少なくともいずれか一方である。この形態によると、セルロース繊維含有物とした後に樹脂等と複合化した際に、セルロース繊維と、セルロース繊維と相互作用しない粉末とを樹脂等へ容易に分散することができるようになる。また、特に無機粉末であると、操業上有利である。具体的には、複合樹脂の乾燥方法としては、例えば、熱源である金属ドラムに水分散体を直接あてる方法で乾燥(例えば、ヤンキードライヤーやシリンダードライヤーによる乾燥等。)する方法と、熱源に水分散体を直接触れさせずに加温する方法、つまり空気中で乾燥(例えば、恒温乾燥機による乾燥等。)する方法とが存在する。しかるに、樹脂粉末を使用すると、加温した金属板(例えば、ヤンキードライヤー、シリンダードライヤー等。)に接触させて乾燥した際に、金属板表面に皮膜ができ熱伝導が悪化し、乾燥効率が著しく低下する。このような問題が生じ難い点で、無機粉末は有利である。
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. According to this form, when the cellulose fiber-containing material is combined with the resin or the like, the cellulose fiber and the powder that does not interact with the cellulose fiber can be easily dispersed in the resin or the like. Further, particularly when it is an inorganic powder, it is advantageous in terms of operation. Specifically, as a method for drying the composite resin, for example, a method of directly applying an aqueous dispersion to a metal drum as a heat source (for example, drying with a yankee dryer or a cylinder dryer) and a method of drying with water as a heat source. There is a method of heating the dispersion without directly touching it, that is, a method of drying in air (for example, drying with a constant temperature dryer). However, when resin powder is used, when it is brought into contact with a heated metal plate (for example, a Yankee dryer, a cylinder dryer, etc.) and dried, a film is formed on the surface of the metal plate, the heat conduction deteriorates, and the drying efficiency becomes remarkable. descend. Inorganic powders are advantageous in that such problems are unlikely to occur.
相互作用しない粉末の平均粒子径は、1mm以下が好ましく、0.9~0.0001mmがより好ましく、0.8~0.001mmが特に好ましい。平均粒子径が以上の範囲内であると、セルロース繊維同士の間隙に入って凝集を阻害する効果が効果的に発揮されるようになる。しかも、樹脂との混練性に優れ、大きなエネルギーが不要となり経済的である。これに対し、平均粒子径が1mmを超えると、セルロース繊維含有物のスラリーから水系媒体を除去する際に、セルロース繊維同士の間隙に入って凝集を阻害する効果が発揮されないおそれがある。ただし、平均粒子径が0.0001mm未満であると、微細なためにマイクロ繊維セルロース同士の水素結合を阻害することができないおそれがある。また、水分散体中で粒子同士が凝集するおそれがある。
The average particle size of the non-interacting powder is preferably 1 mm or less, more preferably 0.9 to 0.0001 mm, and particularly preferably 0.8 to 0.001 mm. When the average particle size is within the above range, the effect of entering the gaps between the cellulose fibers and inhibiting aggregation is effectively exerted. Moreover, it is economical because it has excellent kneadability with a resin and does not require a large amount of energy. On the other hand, if the average particle size exceeds 1 mm, when the aqueous medium is removed from the slurry of the cellulose fiber-containing material, the effect of entering the gaps between the cellulose fibers and inhibiting aggregation may not be exhibited. However, if the average particle size is less than 0.0001 mm, hydrogen bonds between the microfiber celluloses may not be inhibited due to the fine particles. In addition, the particles may aggregate in the aqueous dispersion.
なお、樹脂粉末は混練時に溶融し粒として外観に影響を与えなくなるため、大きな粒子径のものも比較的効果的に使用することができる。他方、樹脂粉末が無機粉末である場合においても無機粉末の平均粒子径が上記範囲内にあることでセルロース繊維同士の間隙に入って凝集を阻害する効果が発揮されるが、無機粉末は混練してもサイズは大きく変わらないため、粒径が大きすぎると粒として外観に影響を与える可能性がある。
Since the resin powder melts during kneading and does not affect the appearance as particles, a large particle size can be used relatively effectively. On the other hand, even when the resin powder is an inorganic powder, if the average particle size of the inorganic powder is within the above range, the effect of entering the gaps between the cellulose fibers and inhibiting aggregation is exhibited, but the inorganic powder is kneaded. However, the size does not change significantly, so if the particle size is too large, it may affect the appearance as grains.
本明細書において、相互作用しない粉末の平均粒子径は、粉体をそのまま又は水分散体の状態で粒度分布測定装置(例えば株式会社堀場製作所のレーザー回折・散乱式粒度分布測定器)を用いて測定される体積基準粒度分布から算出される中位径である。
In the present specification, 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, 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.
無機粉末としては、例えば、Fe、Na、K、Cu、Mg、Ca、Zn、Ba、Al、Ti、ケイ素元素等の周期律表第I族~第VIII族中の金属元素の単体、酸化物、水酸化物、炭素塩、硫酸塩、ケイ酸塩、亜硫酸塩、これらの化合物よりなる各種粘土鉱物等を例示することができる。具体的には、例えば、硫酸バリウム、硫酸カルシウム、硫酸マグネシウム、硫酸ナトリウム、亜硫酸カルシウム、酸化亜鉛、重質炭酸カルシウム、軽質炭酸カルシウム、ほう酸アルミニウム、アルミナ、酸化鉄、チタン酸カルシウム、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化ナトリウム、炭酸マグネシウム、ケイ酸カルシウム、クレー、ワラストナイト、ガラスビーズ、ガラスパウダー、シリカゲル、乾式シリカ、コロイダルシリカ、珪砂、硅石、石英粉、珪藻土、ホワイトカーボン、ガラスファイバー等を例示することができる。これらの無機粉末は、複数が含有されていてもよい。また、古紙パルプに含まれるものであってもよいし、製紙スラッジ中の無機物を再生した所謂再生填料等であってもよい。
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 powders 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.
ただし、製紙用の填料や顔料として好適に使用される炭酸カルシウム、タルク、ホワイトカーボン、クレー、焼成クレー、二酸化チタン、水酸化アルミニウム及び再生填料等の中から選択される少なくとも1種以上の無機粉末を使用するのが好ましく、炭酸カルシウム、タルク、クレーの中からから選択される少なくとも1種以上を使用するのがより好ましく、軽質炭酸カルシウム及び重質炭酸カルシウムの少なくともいずれか一方を使用するのが特に好ましい。炭酸カルシウム、タルク、クレーを使用すると、樹脂等のマトリックスとの複合化が容易である。また、汎用的な無機材料であるため、用途の制限が生じることが少ないとのメリットがある。さらに、炭酸カルシウムは下記の理由から特に好ましい。軽質炭酸カルシウムを使用する場合は、粉末のサイズや形状を一定に制御しやすくなる。このため、セルロース繊維のサイズや形状に合わせて、間隙に入り込んでセルロース繊維同士の凝集を抑制する効果を生じやすくするようにサイズや形状を調整して、ピンポイントで効果を発揮しやすくできるメリットがある。また、重質炭酸カルシウムを使用すると、重質炭酸カルシウムが不定形であることから、スラリー中に様々なサイズの繊維が存在する場合でも、水系媒体除去時に繊維が凝集する過程において、間隙に入り込んでセルロース繊維同士の凝集を抑制することができるとのメリットがある。
However, 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. When calcium carbonate, talc, or clay is used, 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. When light calcium carbonate is used, it becomes easier to control the size and shape of the powder to be constant. For this reason, there is a merit that the size and shape can be adjusted so as to easily generate the effect of suppressing the aggregation of the cellulose fibers by entering the gap according to the size and shape of the cellulose fibers, and the effect can be easily exerted in a pinpoint manner. There is. In addition, when heavy calcium carbonate is used, since the heavy calcium carbonate is irregular, even if fibers of various sizes are present in the slurry, they enter the gap in the process of agglomeration of the fibers when the aqueous medium is removed. There is a merit that the aggregation of cellulose fibers can be suppressed.
一方、樹脂粉末としては、複合樹脂を得る際に使用する樹脂と同様のものを使用することができる。もちろん、異種であってもよいが、同種である方が好ましい。
On the other hand, as the resin powder, the same resin as that used when obtaining the composite resin can be used. Of course, they may be different, but they are preferably the same.
相互作用しない粉末の配合量は、セルロース繊維に対して、好ましくは9900~1質量%、より好ましくは1900~5質量%、特に好ましくは900~10質量%である。配合量が1質量%を下回ると、セルロース繊維の間隙に入って凝集抑制する作用が不足となるおそれがある。他方、配合量が9900質量%を上回ると、セルロース繊維としての機能が発揮されなくなるおそれがある。なお、相互作用しない粉末が無機粉末である場合は、サーマルリサイクルに支障が出ない割合で配合するのが好ましい。
The blending amount of the non-interacting powder is preferably 9900 to 1% by mass, more preferably 1900 to 5% by mass, and particularly preferably 900 to 10% by mass with respect to the cellulose fiber. 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.
相互作用しない粉末としては、無機粉末及び樹脂粉末を併用することもできる。無機粉末及び樹脂粉末を併用すると、無機粉体同士や樹脂粉末同士が凝集する条件で混合した場合でも無機粉末及び樹脂粉末がお互いに凝集を防ぐような効果を発揮する。また、粒径が小さい粉体は表面積が大きく重力の影響よりも分子間力の影響を受けやすく、その結果として凝集しやすくなるため、粉体とマイクロ繊維セルロースとを混合する際に粉体がスラリー中でうまくほぐれなかったり、水系媒体の除去時に粉体同士が凝集することで、マイクロ繊維セルロースの凝集を防ぐ効果が十分に発揮されなくなったりするおそれがある。しかしながら、無機粉末及び樹脂粉末を併用すると、自身の凝集を緩和することができると考えられる。
Inorganic powder and resin powder can be used in combination as the non-interacting powder. When the inorganic powder and the resin powder are used in combination, 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. In addition, powders with a small particle size have a large surface area and are more susceptible to intramolecular forces than the effects of gravity, and as a result, they are more likely to aggregate. There is a risk that the powders will not loosen well in the slurry, or that the powders will aggregate when the aqueous medium is removed, and the effect of preventing the aggregation of microfiber cellulose will not be fully exhibited. However, it is considered that the combined use of the inorganic powder and the resin powder can alleviate the aggregation of the powder itself.
無機粉末及び樹脂粉末を併用する場合、無機粉末の平均粒子径:樹脂粉末の平均粒子径の比は、1:0.1~1:10000が好ましく、1:1~1:1000がより好ましい。この範囲にあると、自身の凝集力の強さから生じる問題(例えば、粉体とマイクロ繊維セルロースとを混合する際に粉体がスラリー中でうまくほぐれなかったり、水系媒体の除去時に粉体同士が凝集したりする問題。)が発生せずに、マイクロ繊維セルロースの凝集を防ぐ効果が十分に発揮されるようになると考えられる。
When the inorganic powder and the resin powder are used in combination, 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. Within this range, problems arise from the strength of its own cohesive force (for example, the powder does not loosen well in the slurry when mixing the powder and microfiber cellulose, or the powders do not loosen well when the aqueous medium is removed. It is considered that the effect of preventing the aggregation of the microfiber cellulose is sufficiently exhibited without causing the problem of aggregation.).
無機粉末及び樹脂粉末を併用する場合、無機粉末の質量%:樹脂粉末の質量%の比は、1:0.01~1:100が好ましく、1:0.1~1:10がより好ましい。この範囲にあると、異種粉体同士が自身の凝集を阻害することが可能になると考えられる。この範囲にあると、自身の凝集力の強さから生じる問題(例えば、粉体とマイクロ繊維セルロースとを混合する際に粉体がスラリー中でうまくほぐれなかったり、水系媒体の除去時に粉体同士が凝集したりする問題。)が発生せずに、マイクロ繊維セルロースの凝集を防ぐ効果が十分に発揮されるようになると考えられる。
When the inorganic powder and the resin powder are used in combination, 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. Within this range, it is considered possible for dissimilar powders to inhibit their own aggregation. Within this range, problems arise from the strength of its own cohesive force (for example, the powder does not loosen well in the slurry when mixing the powder and microfiber cellulose, or the powders do not loosen well when the aqueous medium is removed. It is considered that the effect of preventing the aggregation of the microfiber cellulose is sufficiently exhibited without causing the problem of aggregation.).
(酸変性樹脂)
相互作用しない粉末としては、酸変性樹脂を使用すると好適である。酸変性樹脂は、前述したように、酸基がカルバメート基の一部又は全部とイオン結合し得る。このイオン結合により、樹脂の補強効果が向上する。 (Acid-modified resin)
As the non-interacting powder, it is preferable to use an acid-modified resin. In the acid-modified resin, as described above, the acid group may be ionically bonded to a part or all of the carbamate group. This ionic bond improves the reinforcing effect of the resin.
相互作用しない粉末としては、酸変性樹脂を使用すると好適である。酸変性樹脂は、前述したように、酸基がカルバメート基の一部又は全部とイオン結合し得る。このイオン結合により、樹脂の補強効果が向上する。 (Acid-modified resin)
As the non-interacting powder, it is preferable to use an acid-modified resin. In the acid-modified resin, as described above, the acid group may be ionically bonded to a part or all of the carbamate group. This ionic bond improves the reinforcing effect of the resin.
酸変性樹脂としては、例えば、酸変性ポリオレフィン樹脂、酸変性エポキシ樹脂、酸変性スチレン系エラストマー樹脂等を使用することができる。ただし、酸変性ポリオレフィン樹脂を使用するのが好ましい。酸変性ポリオレフィン樹脂は、不飽和カルボン酸成分とポリオレフィン成分との共重合体である。
As the acid-modified 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.
ポリオレフィン成分としては、例えば、エチレン、プロピレン、ブタジエン、イソプレン等のアルケンの重合体の中から1種又は2種以上を選択して使用することができる。ただし、好適には、プロピレンの重合体であるポリプロピレン樹脂を用いることが好ましい。
As the polyolefin component, for example, one or two or more of alkene polymers such as ethylene, propylene, butadiene, and isoprene can be selected and used. However, it is preferable to use a polypropylene resin which is a polymer of propylene.
不飽和カルボン酸成分としては、例えば、無水マレイン酸類、無水フタル酸類、無水イタコン酸類、無水シトラコン酸類、無水クエン酸類等の中から1種又は2種以上を選択して使用することができる。ただし、好適には、無水マレイン酸類を使用するのが好ましい。つまり、無水マレイン酸変性ポリプロピレン樹脂を用いることが好ましい。
As the unsaturated carboxylic acid component, for example, one or more can be selected and used from among maleic anhydrides, phthalic anhydrides, itaconic anhydrides, citraconic anhydrides, citrate anhydrides and the like. However, it is preferable to use maleic anhydrides. That is, it is preferable to use a maleic anhydride-modified polypropylene resin.
酸変性樹脂の混合量は、マイクロ繊維セルロース100質量部に対して、好ましくは0.1~1,000質量部、より好ましくは1~500質量部、特に好ましくは10~200質量部である。特に酸変性樹脂が無水マレイン酸変性ポリプロピレン樹脂である場合は、好ましくは1~200質量部、より好ましくは10~100質量部である。酸性変性樹脂の混合量が0.1質量部を下回ると強度の向上が十分ではない。他方、混合量が1,000質量部を上回ると、過剰となり強度が低下する傾向となる。
The mixed 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. In particular, when 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.
無水マレイン酸変性ポリプロピレンの重量平均分子量は、例えば1,000~200,000、好ましくは3,000~100,000である。
The weight average molecular weight of maleic anhydride-modified polypropylene is, for example, 1,000 to 200,000, preferably 3,000 to 100,000.
また、無水マレイン酸変性ポリプロピレンの酸価は、1mgKOH/g以上、200mgKOH/g以下が好ましく、10mgKOH/g以上、100mgKOH/g以下がより好ましい。
The acid value of maleic anhydride-modified polypropylene is preferably 1 mgKOH / g or more and 200 mgKOH / g or less, and more preferably 10 mgKOH / g or more and 100 mgKOH / g or less.
(分散剤)
マイクロ繊維セルロースやセルロース繊維と相互作用しない粉末は、分散剤と混合するとより好ましいものになる。分散剤としては、芳香族類にアミン基及び/又は水酸基を有する化合物、脂肪族類にアミン基及び/又は水酸基を有する化合物が好ましい。 (Dispersant)
Powders that do not interact with microfiber cellulose or cellulose fibers are more preferred when mixed with a dispersant. As the 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.
マイクロ繊維セルロースやセルロース繊維と相互作用しない粉末は、分散剤と混合するとより好ましいものになる。分散剤としては、芳香族類にアミン基及び/又は水酸基を有する化合物、脂肪族類にアミン基及び/又は水酸基を有する化合物が好ましい。 (Dispersant)
Powders that do not interact with microfiber cellulose or cellulose fibers are more preferred when mixed with a dispersant. As the 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.
芳香族類にアミン基及び/又は水酸基を有する化合物としては、例えば、アニリン類、トルイジン類、トリメチルアニリン類、アニシジン類、チラミン類、ヒスタミン類、トリプタミン類、フェノール類、ジブチルヒドロキシトルエン類、ビスフェノールA類、クレゾール類、オイゲノール類、没食子酸類、グアイアコール類、ピクリン酸類、フェノールフタレイン類、セロトニン類、ドーパミン類、アドレナリン類、ノルアドレナリン類、チモール類、チロシン類、サリチル酸類、サリチル酸メチル類、アニスアルコール類、サリチルアルコール類、シナピルアルコール類、ジフェニドール類、ジフェニルメタノール類、シンナミルアルコール類、スコポラミン類、トリプトフォール類、バニリルアルコール類、3-フェニル‐1-プロパノール類、フェネチルアルコール類、フェノキシエタノール類、ベラトリルアルコール類、ベンジルアルコール類、ベンゾイン類、マンデル酸類、マンデロニトリル類、安息香酸類、フタル酸類、イソフタル酸類、テレフタル酸類、メリト酸類、ケイ皮酸類などが挙げられる。
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 acids, guaiacols, picric acids, phenolphthalenes, serotonins, dopamines, adrenaline, noradrenaline, timoles, tyrosine, salicylic acids, methyl salicylates, anis alcohols. , Salicylic 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.
また、脂肪族類にアミン基及び/又は水酸基を有する化合物としては、例えば、カプリルアルコール類、2-エチルヘキサノール類、ペラルゴンアルコール類、カプリンアルコール類、ウンデシルアルコール類、ラウリルアルコール類、トリデシルアルコール類、ミリスチルアルコール類、ペンタデシルアルコール類、セタノール類、ステアリルアルコール類、エライジルアルコール類、オレイルアルコール類、リノレイルアルコール類、メチルアミン類、ジメチルアミン類、トリメチルアミン類、エチルアミン類、ジエチルアミン類、エチレンジアミン類、トリエタノールアミン類、N,N-ジイソプロピルエチルアミン類、テトラメチルエチレンジアミン類、ヘキサメチレンジアミン類、スペルミジン類、スペルミン類、アマンタジン類、ギ酸類、酢酸類、プロピオン酸類、酪酸類、吉草酸類、カプロン酸類、エナント酸類、カプリル酸類、ペラルゴン酸類、カプリン酸類、ラウリン酸類、ミリスチン酸類、パルミチン酸類、マルガリン酸類、ステアリン酸類、オレイン酸類、リノール酸類、リノレン酸類、アラキドン酸類、エイコサペンタエン酸類、ドコサヘキサエン酸類、ソルビン酸類などが挙げられる。
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, eleidyl alcohols, oleyl alcohols, linoleil 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, arachidonic acids, eicosapentaenoic acids, docosahexaenoic acids, sorbins. Examples include acids.
以上の分散剤は、セルロース繊維同士の水素結合を阻害する。したがって、セルロース繊維含有物及び樹脂の混練に際してマイクロ繊維セルロースが樹脂中において確実に分散するようになる。また、以上の分散剤は、マイクロ繊維セルロース及び樹脂の相溶性を向上させる役割も有する。この点でマイクロ繊維セルロースの樹脂中における分散性が向上する。
The above dispersants inhibit hydrogen bonds between cellulose fibers. Therefore, when the cellulose fiber-containing material 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.
なお、セルロース繊維含有物及び樹脂の混練に際して、別途、相溶剤(薬剤)を添加することも考えられるが、この段階で薬剤を添加するよりも、予めマイクロ繊維セルロースと分散剤(薬剤)を混合する方が、マイクロ繊維セルロースに対する薬剤の纏わりつきが均一になり、樹脂との相溶性向上効果が高くなる。
It is conceivable to add a phase solvent (drug) separately when kneading the cellulose fiber-containing material and the resin, but rather than adding the chemical at this stage, the microfiber cellulose and the dispersant (drug) are mixed in advance. By doing so, the binding of the drug to the microfiber cellulose becomes uniform, and the effect of improving the compatibility with the resin becomes higher.
また、例えば、ポリプロピレンは融点が160℃であり、したがってセルロース繊維含有物及び樹脂の混練は、180℃程度で行う。しかるに、この状態で分散剤(液)を添加すると、一瞬で乾燥してしまう。そこで、融点の低い樹脂を使用してマスターバッチ(マイクロ繊維セルロースの濃度の濃い複合樹脂)を作製し、その後に通常の樹脂で濃度を下げる方法が存在する。しかしながら、融点の低い樹脂は一般的に強度が低い。したがって、当該方法によると、複合樹脂の強度が下がるおそれがある。
Further, for example, polypropylene has a melting point of 160 ° C., so that the cellulose fiber-containing substance and the resin are kneaded at about 180 ° C. However, if a dispersant (liquid) is added in this state, it dries in an instant. Therefore, there is a method of producing a masterbatch (composite resin having a high concentration of microfiber cellulose) using a resin having a low melting point, and then lowering the concentration with a normal resin. However, 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.
分散剤の混合量は、マイクロ繊維セルロース100質量部に対して、好ましくは0.1~1,000質量部、より好ましくは1~500質量部、特に好ましくは10~200質量部である。分散剤の混合量が0.1質量部を下回ると、樹脂強度の向上が十分ではないとされるおそれがある。他方、混合量が1,000質量部を上回ると、過剰となり樹脂強度が低下する傾向となる。
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.
この点、前述した酸変性樹脂は酸基とマイクロ繊維セルロースのカルバメート基とがイオン結合することで相溶性を向上し、もって補強効果を上げるためのものであり、分子量が大きいため樹脂とも馴染み易く、強度向上に寄与していると考えられる。一方、上記の分散剤は、マイクロ繊維セルロース同士の水酸基同士の間に介在して凝集を防ぎ、もって樹脂中での分散性を向上するものであり、また、分子量が酸変性樹脂に比べ小さいため、酸変性樹脂が入り込めないようなマイクロ繊維セルロース間の狭いスペースに入ることができ、分散性を向上して強度向上する役割を果たす。以上のような観点から、上記酸変性樹脂の分子量は、分散剤の分子量の2~2,000倍、好ましくは5~1,000倍であると好適である。
In this respect, 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. On the other hand, 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. , It can enter a narrow space between microfiber celluloses that acid-modified resins cannot enter, and plays a role of improving dispersibility and strength. From the above viewpoint, 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.
以上をより詳細に説明すると、相互作用しない粉末は物理的にマイクロ繊維セルロース同士の間に介在することで水素結合を阻害し、もってマイクロ繊維セルロースの分散性を向上する。ただし、相互作用しない粉末が酸変性樹脂である場合は、酸基とマイクロ繊維セルロースのカルバメート基とをイオン結合することで相溶性を向上し、もって補強効果を上げる。この点、分散剤がマイクロ繊維セルロース同士の水素結合を阻害する点は同じであるが、相互作用しない粉末はマイクロオーダーであるため、物理的に介在して水素結合を抑制する。したがって、分散性が分散剤にくらべ低いものの、特に樹脂粉末の場合は自身が溶融してマトリックスになるため物性低下に寄与しない。他方、無機粉末の場合は、無機粉末自体が剛直であるため、樹脂等と複合化した場合に樹脂等の物性向上に寄与する。一方、分散剤は分子レベルであり、極めて小さいためマイクロ繊維セルロースを覆うようにして水素結合を阻害し、マイクロ繊維セルロースの分散性を向上する効果は高い。しかしながら、樹脂中に残り、物性低下に働く可能性がある。
Explaining the above in more detail, the non-interacting powder physically intervenes between the microfiber celluloses to inhibit hydrogen bonds, thereby improving the dispersibility of the microfiber celluloses. However, when the powder that does not interact is an acid-modified resin, the compatibility is improved by ionic bonding the acid group and the carbamate group of the microfiber cellulose, thereby enhancing the reinforcing effect. In this respect, the dispersant inhibits hydrogen bonds between microfiber celluloses, but the powders that do not interact with each other are micro-ordered, so that they physically intervene and suppress hydrogen bonds. Therefore, although the dispersibility is lower than that of the dispersant, in the case of the resin powder in particular, it melts into a matrix and does not contribute to the deterioration of the physical properties. On the other hand, in the case of the inorganic powder, since the inorganic powder itself is rigid, it contributes to the improvement of the physical properties of the resin or the like when it is combined with the resin or the like. On the other hand, 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.
(製造方法)
マイクロ繊維セルロースや相互作用しない粉末等の混合物は、樹脂と混練するに先立って、スラリーとし、乾燥及び粉砕して粉状物にする。この形態によると、樹脂との混練に際してセルロース繊維を乾燥させる必要がなく、熱効率が良い。また、混合物に相互作用しない粉末や分散剤等が混合されている場合は、当該混合物を乾燥したとしても、繊維状セルロース(マイクロ繊維セルロース)が再分散しなくなるおそれが低い。 (Production method)
Mixtures such as microfiber cellulose and non-interacting powders are made into slurries, dried and pulverized into powders prior to kneading with the resin. According to this form, it is not necessary to dry the cellulose fibers when kneading with the resin, and the thermal efficiency is good. Further, when a powder or a dispersant that does not interact with the mixture is mixed, there is a low possibility that the fibrous cellulose (microfiber cellulose) will not be redispersed even if the mixture is dried.
マイクロ繊維セルロースや相互作用しない粉末等の混合物は、樹脂と混練するに先立って、スラリーとし、乾燥及び粉砕して粉状物にする。この形態によると、樹脂との混練に際してセルロース繊維を乾燥させる必要がなく、熱効率が良い。また、混合物に相互作用しない粉末や分散剤等が混合されている場合は、当該混合物を乾燥したとしても、繊維状セルロース(マイクロ繊維セルロース)が再分散しなくなるおそれが低い。 (Production method)
Mixtures such as microfiber cellulose and non-interacting powders are made into slurries, dried and pulverized into powders prior to kneading with the resin. According to this form, it is not necessary to dry the cellulose fibers when kneading with the resin, and the thermal efficiency is good. Further, when a powder or a dispersant that does not interact with the mixture is mixed, there is a low possibility that the fibrous cellulose (microfiber cellulose) will not be redispersed even if the mixture is dried.
混合物(スラリー)は、カルバメート変性マイクロ繊維セルロース濃度を1.5質量%以上にするのが好ましく、1.8~5.0質量%にするのがより好ましく、2.0~4.0質量%にするのが特に好ましい。この点、濃度が1.5質量%を下回ると、相互作用しない粉末と混合して攪拌等した後に、マイクロ繊維セルロースと粉末との密度差(例えば、MFCは約1.5g/cm3、粉末がPPである場合は0.9g/cm3。)や、後述するSP値の差などによって徐々にスラリー内でMFC及び粉末が分離し、続く工程に入る際に既に分離した状態になる。結果として、マイクロ繊維セルロース同士が凝集する。しかしながら、濃度を1.5質量%以上とすれば、スラリーの粘度が高くなることからスラリーの流動性が低くなり、MFC及び粉末の密度差、SP値の差による分離が抑制される。つまり、密度差やSP値の差を減らす方法も凝集抑制には資するが、これらの方法には限界があるため、本形態においては濃度の調節によって凝集抑制を完全なものにしようとするものである。なお、粉末のSP値は後述する樹脂の場合と同様であり、詳細は後述する。
The mixture (slurry) preferably has a carbamate-modified microfiber cellulose concentration of 1.5% by mass or more, more preferably 1.8 to 5.0% by mass, and 2.0 to 4.0% by mass. Is particularly preferable. In this regard, when the concentration is less than 1.5% by mass, the powder is mixed with a non-interacting powder and stirred, and then the density difference between the microfiber cellulose and the powder (for example, MFC is about 1.5 g / cm 3 and the powder). When is PP, MFC and powder are gradually separated in the slurry due to 0.9 g / cm 3 ) or a difference in SP value described later, and the powder is already separated when the subsequent steps are started. As a result, the microfiber celluloses aggregate with each other. However, when the concentration is 1.5% by mass or more, the viscosity of the slurry becomes high, so that the fluidity of the slurry becomes low, and the separation due to the difference in density between the MFC and the powder and the difference in SP value is suppressed. That is, the method of reducing the difference in density and the difference in SP value also contributes to the suppression of aggregation, but since these methods have limitations, in this embodiment, the suppression of aggregation is to be completed by adjusting the concentration. be. The SP value of the powder is the same as that of the resin described later, and the details will be described later.
以上の観点から、スラリーの粘度は、1000~10000cpsとなるように調整するのが好ましく、1500~9000cpsとなるように調整するのがより好ましく、2000~8000cpsとなるように調整するのが特に好ましい。この調整は、MFCの濃度を調整することの他、例えば、増粘剤等を使用して行うこともできる。
From the above viewpoint, the viscosity of the slurry is preferably adjusted to 1000 to 10000 cps, more preferably 1500 to 9000 cps, and particularly preferably 2000 to 8000 cps. .. In addition to adjusting the concentration of MFC, this adjustment can also be performed using, for example, a thickener or the like.
スラリーの粘度は、JIS-Z8803(2011)の「液体の粘度測定方法」に準拠して測定した値である。
The viscosity of the slurry is a value measured according to the "method for measuring the viscosity of liquid" of JIS-Z8803 (2011).
また、以上の観点からは、カルバメート変性マイクロ繊維セルロースの密度に対する相互作用しない粉体の密度比が0.4~2.2であるのが好ましく、0.5~2.1であるのがより好ましく、0.6~2.0であるのが特に好ましい。
From the above viewpoint, the density ratio of the non-interacting powder to the density of the carbamate-modified microfiber cellulose is preferably 0.4 to 2.2, more preferably 0.5 to 2.1. It is preferably 0.6 to 2.0, and is particularly preferable.
さらに、MFCの濃度は、水で調整すると好適である。水で調整すると、溶媒自体のコストが安価であり、有機溶媒の際に必要な処理や回収設備が不要のため、環境負荷を最小限に抑えることができるメリットがある。
Furthermore, it is preferable to adjust the concentration of MFC with water. When adjusted with water, the cost of the solvent itself is low, and the treatment and recovery equipment required for the organic solvent are not required, so that there is an advantage that the environmental load can be minimized.
一方、前述したように、相互作用しない粉末として酸変性樹脂を使用する場合においては、スラリー中における酸変性樹脂の濃度を0.5質量%以上にするのが好ましく、0.6~5.0質量%にするのがより好ましく、0.7~4.0質量%にするのが特に好ましい。酸変性樹脂の濃度が0.5質量%以上であれば、スラリーを乾燥させた際に生じるカルバメート変性マイクロ繊維セルロース同士の凝集を防ぐ効果が十分に発揮されるようになると考えられる。
On the other hand, as described above, when the acid-modified resin is used as the powder that does not interact with each other, the concentration of the acid-modified resin in the slurry is preferably 0.5% by mass or more, preferably 0.6 to 5.0. It is more preferably made by mass%, and particularly preferably 0.7 to 4.0% by mass. When the concentration of the acid-modified resin is 0.5% by mass or more, it is considered that the effect of preventing the aggregation of the carbamate-modified microfiber celluloses generated when the slurry is dried is sufficiently exhibited.
また、マイクロ繊維セルロースの濃度(質量%)を1としたときの相互作用しない粉末の濃度比は、例えば50~0.1、好ましくは20~0.5、より好ましくは10~1.0である。濃度比が0.1を下回ると、乾燥時にマイクロ繊維セルロースの凝集を抑制する効果が十分に発揮されないおそれがある。他方、濃度比が50を上回ると、複合樹脂中のマイクロ繊維セルロースの配合率を上げられなくなり、マイクロ繊維セルロースの配合による効果が充分に発揮されなくなるおそれがある。
When the concentration (% by mass) of the microfiber cellulose is 1, the concentration ratio of the non-interacting powder is, for example, 50 to 0.1, preferably 20 to 0.5, and more preferably 10 to 1.0. be. If the concentration ratio is less than 0.1, the effect of suppressing the aggregation of microfiber cellulose during drying may not be sufficiently exhibited. On the other hand, if the concentration ratio exceeds 50, the blending ratio of the microfiber cellulose in the composite resin cannot be increased, and the effect of blending the microfiber cellulose may not be sufficiently exhibited.
混合物は、スラリーとした後、乾燥するに先立って脱水して脱水物にする。この脱水は、例えば、ベルトプレス、スクリュープレス、フィルタープレス、ツインロール、ツインワイヤーフォーマ、バルブレスフィルタ、センターディスクフィルタ、膜処理、遠心分離機等の脱水装置の中から1種又は2種以上を選択使用して行うことができる。
The mixture is made into a slurry and then dehydrated before drying to make it a dehydrated product. For this dehydration, for example, one or two or more types are selected from 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.
混合物の乾燥は、例えば、ロータリーキルン乾燥、円板式乾燥、気流式乾燥、媒体流動乾燥、スプレー乾燥、ドラム乾燥、スクリューコンベア乾燥、パドル式乾燥、一軸混練乾燥、多軸混練乾燥、真空乾燥、攪拌乾燥等の中から1種又は2種以上を選択使用して行うことができる。
Drying of the mixture 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 drying, stirring drying. It can be performed by selectively using one type or two or more types from the above.
乾燥した混合物(乾燥物)は、粉砕して粉状物にする。乾燥物の粉砕は、例えば、ビーズミル、ニーダー、ディスパー、ツイストミル、カットミル、ハンマーミル等の中から1種又は2種以上を選択使用して行うことができる。
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 disper, a twist mill, a cut mill, a hammer mill and the like.
粉状物の平均粒子径は、好ましくは1~10,000μm、より好ましくは10~5,000μm、特に好ましくは100~1,000μmである。粉状物の平均粒子径が10,000μmを上回ると、樹脂との混練性に劣るものになるおそれがある。他方、粉状物の平均粒子径が1μmを下回るものにするには大きなエネルギーが必要になるため、経済的でない。
The average particle size of the powder is preferably 1 to 10,000 μm, more preferably 10 to 5,000 μm, and particularly preferably 100 to 1,000 μm. If the average particle size of the powdery substance exceeds 10,000 μm, 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 μm.
粉状物の平均粒子径の制御は、粉砕の程度を制御することのほか、フィルター、サイクロン等の分級装置を使用した分級によることができる。
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.
混合物(粉状物)の嵩比重は、好ましくは0.03~1.0、より好ましくは0.04~0.9、特に好ましくは0.05~0.8である。嵩比重が1.0を超えるということはセルロース繊維同士の水素結合がより強固であり、樹脂中で分散させることは容易ではなくなることを意味する。他方、嵩比重が0.03を下回るものにするのは、移送コストの面から不利である。
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. When the bulk specific density exceeds 1.0, it means that the hydrogen bonds between the cellulose fibers are stronger and it is not easy to disperse them in the resin. On the other hand, making the bulk specific density less than 0.03 is disadvantageous in terms of transfer cost.
嵩比重は、JIS K7365に準じて測定した値である。
The bulk specific density is a value measured according to JIS K7365.
混合物(粉状物)の水分率は、好ましくは50%以下、より好ましくは30%以下、特に好ましくは10%以下である。水分率が50%を上回ると、樹脂と混練する際のエネルギーが膨大になり、経済的でない。
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.
水分率は、定温乾燥機を用いて、試料を105℃で6時間以上保持し質量の変動が認められなくなった時点の質量を乾燥後質量とし、下記式にて算出した値である。
水分率(%)=[(乾燥前質量-乾燥後質量)÷乾燥前質量]×100 The water 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
水分率(%)=[(乾燥前質量-乾燥後質量)÷乾燥前質量]×100 The water 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
以上のようにして得た粉状物(セルロース繊維含有物)は、樹脂と混練し、セルロース複合樹脂を得る。この混練は、例えば、ペレット状の樹脂と粉状物とを混ぜ合わす方法によることのほか、樹脂をまず溶融し、この溶融物の中に粉状物を添加するという方法によることもできる。なお、分散剤は、この段階で添加することもできる。
The powdery substance (cellulose fiber-containing substance) obtained as described above is kneaded with a resin to obtain a cellulose composite resin. This kneading can be performed, for example, by a method of mixing the pellet-shaped resin and the powdery substance, or by a method of first melting the resin and adding the powdery substance to the melt. The dispersant can also be added at this stage.
混練処理には、例えば、単軸又は二軸以上の多軸混練機、ミキシングロール、ニーダー、ロールミル、バンバリーミキサー、スクリュープレス、ディスパーザー等の中から1種又は2種以上を選択して使用することができる。これらの中では、二軸以上の多軸混練機を使用することが好ましい。二軸以上の多軸混練機を2機以上、並列又は直列にして、使用しても良い。
For the 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. Among these, it is preferable to use 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.
混練処理の温度は、樹脂のガラス転移点以上であり、樹脂の種類によって異なるが、80~280℃とするのが好ましく、90~260℃とするのがより好ましく、100~240℃とするのが特に好ましい。
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.
樹脂としては、熱可塑性樹脂又は熱硬化性樹脂の少なくともいずれか一方を使用することができる。
As the resin, at least one of a thermoplastic resin and a thermosetting resin can be used.
熱可塑性樹脂としては、例えば、ポリプロピレン(PP)、ポリエチレン(PE)等のポリオレフィン、脂肪族ポリエステル樹脂や芳香族ポリエステル樹脂等のポリエステル樹脂、ポリスチレン、メタアクリレート、アクリレート等のポリアクリル樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリアセタール樹脂等の中から1種又は2種以上を選択して使用することができる。
Examples of the thermoplastic resin 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. One kind or two or more kinds can be selected and used from the polycarbonate resin, the polyacetal resin and the like.
ただし、ポリオレフィン及びポリエステル樹脂の少なくともいずれか一方を使用するのが好ましい。また、ポリオレフィンとしては、ポリプロピレンを使用するのが好ましい。さらに、ポリエステル樹脂としては、脂肪族ポリエステル樹脂として、例えば、ポリ乳酸、ポリカプロラクトン等を例示することができ、芳香族ポリエステル樹脂として、例えば、ポリエチレンテレフタレート等を例示することができるが、生分解性を有するポリエステル樹脂(単に「生分解性樹脂」ともいう。)を使用するのが好ましい。
However, it is preferable to use at least one of polyolefin and polyester resin. Moreover, it is preferable to use polypropylene as the polyolefin. Further, as the 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”).
生分解性樹脂としては、例えば、ヒドロキシカルボン酸系脂肪族ポリエステル、カプロラクトン系脂肪族ポリエステル、二塩基酸ポリエステル等の中から1種又は2種以上を選択して使用することができる。
As the 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.
ヒドロキシカルボン酸系脂肪族ポリエステルとしては、例えば、乳酸、リンゴ酸、グルコース酸、3-ヒドロキシ酪酸等のヒドロキシカルボン酸の単独重合体や、これらのヒドロキシカルボン酸のうちの少なくとも1種を用いた共重合体等の中から1種又は2種以上を選択して使用することができる。ただし、ポリ乳酸、乳酸と乳酸を除く上記ヒドロキシカルボン酸との共重合体、ポリカプロラクトン、上記ヒドロキシカルボン酸のうちの少なくとも1種とカプロラクトンとの共重合体を使用するのが好ましく、ポリ乳酸を使用するのが特に好ましい。
As the 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. One type or two or more types can be selected and used from the polymers and the like. However, it is preferable to use 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. Especially preferred to use.
この乳酸としては、例えば、L-乳酸やD-乳酸等を使用することができ、これらの乳酸を単独で使用しても、2種以上を選択して使用してもよい。
As this 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.
カプロラクトン系脂肪族ポリエステルとしては、例えば、ポリカプロラクトンの単独重合体や、ポリカプロラクトン等と上記ヒドロキシカルボン酸との共重合体等の中から1種又は2種以上を選択して使用することができる。
As the 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. ..
二塩基酸ポリエステルとしては、例えば、ポリブチレンサクシネート、ポリエチレンサクシネート、ポリブチレンアジペート等の中から1種又は2種以上を選択して使用することができる。
As the dibasic acid polyester, for example, one or more of polybutylene succinate, polyethylene succinate, polybutylene adipate and the like can be selected and used.
生分解性樹脂は、1種を単独で使用しても、2種以上を併用してもよい。
The biodegradable resin may be used alone or in combination of two or more.
熱硬化性樹脂としては、例えば、フェノール樹脂、尿素樹脂、メラミン樹脂、フラン樹脂、不飽和ポリエステル、ジアリルフタレート樹脂、ビニルエステル樹脂、エポキシ樹脂、ウレタン系樹脂、シリコーン樹脂、熱硬化性ポリイミド系樹脂等を使用することができる。これらの樹脂は、単独で又は二種以上組み合わせて使用することができる。
Examples of the thermosetting resin 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.
マイクロ繊維セルロース及び樹脂の配合割合は、好ましくはマイクロ繊維セルロースが1質量部以上、樹脂が99質量部以下、より好ましくはマイクロ繊維セルロースが2質量部以上、樹脂が98質量部以下、特に好ましくはマイクロ繊維セルロースが3質量部以上、樹脂が97質量部以下である。また、好ましくはマイクロ繊維セルロースが50質量部以下、樹脂が50質量部以上、より好ましくはマイクロ繊維セルロースが40質量部以下、樹脂が60質量部以上、特に好ましくはマイクロ繊維セルロースが30質量部以下、樹脂が70質量部以上である。特にマイクロ繊維セルロースが10~50質量部であると、樹脂組成物の強度、特に曲げ強度及び引張り弾性率の強度を著しく向上させることができる。
The blending ratio of the microfiber cellulose and the resin is preferably 1 part by mass or more for the microfiber cellulose, 99 parts by mass or less for the resin, more preferably 2 parts by mass or more for the microfiber cellulose, and 98 parts by mass or less for the resin, particularly preferably. The amount of microfiber cellulose is 3 parts by mass or more, and the amount of resin is 97 parts by mass or less. Further, preferably, microfiber cellulose is 50 parts by mass or less, resin is 50 parts by mass or more, more preferably microfiber cellulose is 40 parts by mass or less, resin is 60 parts by mass or more, and particularly preferably microfiber cellulose is 30 parts by mass or less. , The resin is 70 parts by mass or more. In particular, when the amount of microfiber cellulose is 10 to 50 parts by mass, the strength of the resin composition, particularly the bending strength and the tensile elastic modulus can be remarkably improved.
なお、最終的に得られセルロース繊維複合樹脂に含まれるマイクロ繊維セルロース及び樹脂の含有割合は、通常、マイクロ繊維セルロース及び樹脂の上記配合割合と同じとなる。
The content ratio of the microfiber cellulose and the resin contained in the finally obtained cellulose fiber composite resin is usually the same as the above-mentioned compounding ratio of the microfiber cellulose and the resin.
マイクロ繊維セルロース及び樹脂の溶解パラメータ(cal/cm3)1/2(SP値)の差、つまり、マイクロ繊維セルロースのSPMFC値、樹脂のSPPOL値とすると、SP値の差=SPMFC値-SPPOL値とすることができる。SP値の差は10~0.1が好ましく、8~0.5がより好ましく、5~1が特に好ましい。SP値の差が10を超えると、樹脂中でマイクロ繊維セルロースが分散せず、補強効果を得ることはできない。他方、SP値の差が0.1未満であるとマイクロ繊維セルロースが樹脂に溶解してしまい、フィラーとして機能せず、補強効果が得られない。この点、樹脂(溶媒)のSPPOL値とマイクロ繊維セルロース(溶質)のSPMFC値の差が小さい程、補強効果が大きい。
If the difference in solubility parameter (cal / cm 3 ) 1/2 (SP value) between microfiber cellulose and resin, that is, the SP MFC value of microfiber cellulose and the SP POL value of resin, the difference in SP value = SP MFC value -Can be an SP POL value. 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 is not dispersed in the resin and the reinforcing effect cannot 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.
溶解パラメータ(cal/cm3)1/2(SP値)とは、溶媒-溶質間に作用する分子間力を表す尺度であり、SP値が近い溶媒と溶質であるほど、溶解度が増す。
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 the solute, the higher the solubility.
(成形処理)
セルロース繊維含有物及び樹脂の混練物は、必要により再度混練する等した後、所望の形状に成形することができる。この成形の大きさや厚さ、形状等は、特に限定されず、例えば、シート状、ペレット状、粉末状、繊維状等とすることができる。 (Molding process)
The cellulose fiber-containing material and the kneaded product of the resin can be molded 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-like, pellet-like, powder-like, fibrous-like, or the like.
セルロース繊維含有物及び樹脂の混練物は、必要により再度混練する等した後、所望の形状に成形することができる。この成形の大きさや厚さ、形状等は、特に限定されず、例えば、シート状、ペレット状、粉末状、繊維状等とすることができる。 (Molding process)
The cellulose fiber-containing material and the kneaded product of the resin can be molded 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-like, pellet-like, powder-like, fibrous-like, or the like.
成形処理の際の温度は、樹脂のガラス転移点以上であり、樹脂の種類によって異なるが、例えば90~260℃、好ましくは100~240℃である。
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.
混練物の成形は、例えば、金型成形、射出成形、押出成形、中空成形、発泡成形等によることができる。また、混練物を紡糸して繊維状にし、前述した植物材料等と混繊してマット形状、ボード形状とすることもできる。混繊は、例えば、エアーレイにより同時堆積させる方法等によることができる。
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.
混練物を成形する装置としては、例えば、射出成形機、吹込成形機、中空成形機、ブロー成形機、圧縮成形機、押出成形機、真空成形機、圧空成形機等の中から1種又は2種以上を選択して使用することができる。
As an apparatus for molding 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 molding machines, pneumatic molding machines and the like. You can select and use more than one species.
以上の成形は、混練に続いて行うことも、混練物をいったん冷却し、破砕機等を使用してチップ化した後、このチップを押出成形機や射出成形機等の成形機に投入して行うこともできる。もちろん、成形は、本発明の必須の要件ではない。
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. Of course, molding is not an essential requirement of the present invention.
(その他)
セルロース繊維含有物には、マイクロ繊維セルロースと共にセルロースナノファイバーが含まれていてもよい。セルロースナノファイバーは、マイクロ繊維セルロースと同様に微細繊維であり、樹脂の強度向上にとってマイクロ繊維セルロースを補完する役割を有する。ただし、可能であれば、微細繊維としてセルロースナノファイバーを含むことなくマイクロ繊維セルロースのみによる方が好ましい。なお、セルロースナノファイバーの平均繊維径(平均繊維幅。単繊維の直径平均。)は、好ましくは4~100nm、より好ましくは10~80nmである。 (others)
The cellulose fiber-containing material 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. However, if possible, it is preferable to use only microfiber cellulose without containing cellulose nanofibers as fine fibers. The average fiber diameter (average fiber width; average diameter of single fibers) of the cellulose nanofibers is preferably 4 to 100 nm, more preferably 10 to 80 nm.
セルロース繊維含有物には、マイクロ繊維セルロースと共にセルロースナノファイバーが含まれていてもよい。セルロースナノファイバーは、マイクロ繊維セルロースと同様に微細繊維であり、樹脂の強度向上にとってマイクロ繊維セルロースを補完する役割を有する。ただし、可能であれば、微細繊維としてセルロースナノファイバーを含むことなくマイクロ繊維セルロースのみによる方が好ましい。なお、セルロースナノファイバーの平均繊維径(平均繊維幅。単繊維の直径平均。)は、好ましくは4~100nm、より好ましくは10~80nmである。 (others)
The cellulose fiber-containing material 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. However, if possible, it is preferable to use only microfiber cellulose without containing cellulose nanofibers as fine fibers. The average fiber diameter (average fiber width; average diameter of single fibers) of the cellulose nanofibers is preferably 4 to 100 nm, more preferably 10 to 80 nm.
また、セルロース繊維含有物には、パルプが含まれていてもよい。パルプは、セルロース繊維スラリーの脱水性を大幅に向上する役割を有する。ただし、パルプについてもセルロースナノファイバーの場合と同様に、配合しないのが、つまり含有率0質量%であるのが最も好ましい。
Further, the cellulose fiber-containing material 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.
樹脂組成物(セルロース繊維複合樹脂)には、微細繊維やパルプ等のほか、ケナフ、ジュート麻、マニラ麻、サイザル麻、雁皮、三椏、楮、バナナ、パイナップル、ココヤシ、トウモロコシ、サトウキビ、バガス、ヤシ、パピルス、葦、エスパルト、サバイグラス、麦、稲、竹、各種針葉樹(スギ及びヒノキ等)、広葉樹及び綿花などの各種植物体から得られた植物材料に由来する繊維を含ませることもでき、含まれていてもよい。
In addition to fine fibers and pulp, the resin composition (cellulose fiber composite resin) includes kenaf, jute hemp, Manila hemp, sisal hemp, goose bark, sansho, 楮, banana, pineapple, coco palm, corn, sugar cane, bagasse, palm, etc. It can also contain fibers derived from plant materials obtained from various plants such as papyrus, reeds, esparto, survivorgrass, wheat, rice, bamboo, various coniferous trees (sugi and hinoki, etc.), broadleaf trees and cotton. May be.
樹脂組成物には、例えば、帯電防止剤、難燃剤、抗菌剤、着色剤、ラジカル捕捉剤、発泡剤等の中から1種又は2種以上を選択して、本発明の効果を阻害しない範囲で添加することができる。これらの原料は、マイクロ繊維セルロースの分散液に添加しても、セルロース繊維含有物(スラリー)に添加しても、セルロース繊維含有物及び樹脂の混練の際に添加しても、これらの混練物に添加しても、その他の方法で添加してもよい。ただし、製造効率の面からは、セルロース繊維含有物及び樹脂の混練の際に添加するのが好ましい。
For the resin composition, for example, one or more selected from antistatic agents, flame retardants, antibacterial agents, colorants, radical scavengers, foaming agents, etc., and a range that does not impair the effects of the present invention. Can be added with. Whether these raw materials are added to the dispersion liquid of microfiber cellulose, added to the cellulose fiber-containing material (slurry), or added at the time of kneading the cellulose fiber-containing material and the resin, these kneaded products It may be added to or by other methods. However, from the viewpoint of production efficiency, it is preferable to add it at the time of kneading the cellulose fiber-containing material and the resin.
樹脂組成物には、ゴム成分として、エチレン-αオレフィン共重合エラストマー又はスチレン-ブタジエンブロック共重合体が含有されていてもよい。α-オレフィンの例としては、例えば、ブテン、イソブテン、ペンテン、ヘキセン、メチル-ペンテン、オクテン、デセン、ドデセン等が挙げられる。
The resin composition may contain an ethylene-α-olefin copolymer elastomer or a styrene-butadiene block copolymer as a rubber component. Examples of α-olefins include butene, isobutene, pentene, hexene, methyl-pentene, octene, decene, dodecene and the like.
なお、以上、本形態によるとマイクロ繊維セルロースの凝集塊が減る(凝集塊減少)ことになるが、このことによるメリットとしては、例えば、次のものがある。まず、セルロース繊維複合樹脂のひび割れが低減される。また、凝集塊減少により、外部の水等によるセルロース繊維複合樹脂の破壊、腐敗のリスクが減る。この点、マイクロ繊維セルロースの分散性が悪いと、セルロース繊維複合樹脂の表面に凝集塊が露出し、例えば湿度の高い場所で使用された場合、凝集塊から水分が侵入し、吸水した凝集塊が膨張する等してセルロース繊維複合樹脂が破壊し易くなり、また、腐敗するリスクがあると考えられる。さらに、セルロース繊維複合樹脂表面の均質性の向上により、塗装等の表面二次加工を行う場合に均一な表面とし易くなり、塗装に用いる塗装液量の低減、加工時間の低減等を図ることができる。
As described above, according to this embodiment, the agglomerates of microfiber cellulose are reduced (agglomeration reduction), and the merits of this are, for example, as follows. First, cracking of the cellulose fiber composite resin is reduced. In addition, the reduction of agglomerates reduces the risk of destruction and putrefaction of the cellulose fiber composite resin by external water and the like. In this respect, if the dispersibility of the microfiber cellulose is poor, agglomerates are exposed on the surface of the cellulose fiber composite resin. It is considered that the cellulose fiber composite resin is easily destroyed due to swelling and the like, and there is a risk of putrefaction. Furthermore, by improving the homogeneity of the surface of the cellulose fiber composite resin, it becomes easier to obtain a uniform surface when performing surface secondary processing such as painting, and it is possible to reduce the amount of coating liquid used for painting and the processing time. can.
次に、本発明の実施例を説明する。
水分率10%以下の針葉樹クラフトパルプと濃度10%の尿素水溶液とpH調整液とを用いて、固形分換算の質量比で表に記載の配合となるように混合した後、105℃で乾燥させ、反応時間3時間、反応温度140℃で加熱処理し、カルバメート変性パルプを得た。得られたカルバメート変性パルプを蒸留水で希釈攪拌して、脱水洗浄を2回繰り返し、洗浄したカルバメート変性パルプを得た。 Next, an embodiment of the present invention will be described.
Using coniferous kraft pulp with a water content of 10% or less, an aqueous urea solution with a concentration of 10%, and a pH adjusting solution, they are mixed so as to have the composition shown in the table in terms of mass ratio in terms of solid content, and then dried at 105 ° C. , The reaction time was 3 hours and the reaction temperature was 140 ° C. to obtain a carbamate-modified pulp. The obtained carbamate-modified pulp was diluted with distilled water and stirred, and dehydration washing was repeated twice to obtain washed carbamate-modified pulp.
水分率10%以下の針葉樹クラフトパルプと濃度10%の尿素水溶液とpH調整液とを用いて、固形分換算の質量比で表に記載の配合となるように混合した後、105℃で乾燥させ、反応時間3時間、反応温度140℃で加熱処理し、カルバメート変性パルプを得た。得られたカルバメート変性パルプを蒸留水で希釈攪拌して、脱水洗浄を2回繰り返し、洗浄したカルバメート変性パルプを得た。 Next, an embodiment of the present invention will be described.
Using coniferous kraft pulp with a water content of 10% or less, an aqueous urea solution with a concentration of 10%, and a pH adjusting solution, they are mixed so as to have the composition shown in the table in terms of mass ratio in terms of solid content, and then dried at 105 ° C. , The reaction time was 3 hours and the reaction temperature was 140 ° C. to obtain a carbamate-modified pulp. The obtained carbamate-modified pulp was diluted with distilled water and stirred, and dehydration washing was repeated twice to obtain washed carbamate-modified pulp.
以上のカルバメート変性パルプに水を添加して固形分濃度3.0%に調製し、ナイヤガラビーターで4時間叩解してカルバメート変性マイクロ繊維セルロースを得た(平均繊維径14μm)。
Water was added to the above carbamate-modified pulp to prepare a solid content concentration of 3.0%, and the pulp was beaten with a niagar beater for 4 hours to obtain carbamate-modified microfiber cellulose (average fiber diameter 14 μm).
固形分濃度3重量%のカルバメート変性マイクロ繊維セルロース水分散体333gに、無水マレイン酸変性ポリプロピレン5g及びポリプロピレン粉末85gを添加した後に、繊維濃度が1.3質量%、1.7質量%、2.0質量%、3.0質量%となるようにそれぞれ水を添加し、それぞれ1000rpmで5分間撹拌することで、繊維濃度の異なるカルバメート変性マイクロ繊維セルロース含有スラリーを得た。これを、105℃で加熱乾燥しカルバメート変性マイクロ繊維セルロース含有物を得た。当該カルバメート変性マイクロ繊維セルロース含有物の含水率は10%未満であった。
After adding 5 g of maleic anhydride-modified polypropylene and 85 g of polypropylene powder to 333 g of a carbamate-modified microfiber cellulose aqueous dispersion having a solid content concentration of 3% by weight, the fiber concentration was 1.3% by mass%, 1.7% by mass, 2. Water was added so as to be 0% by mass and 3.0% by mass, respectively, and the mixture was stirred at 1000 rpm for 5 minutes to obtain carbamate-modified microfiber cellulose-containing slurrys having different fiber concentrations. This was dried by heating at 105 ° C. to obtain a carbamate-modified microfiber cellulose-containing product. The water content of the carbamate-modified microfiber cellulose-containing material was less than 10%.
カルバメート変性マイクロ繊維含有物は、180℃、200rpmの条件で二軸混練機にて混練し、カルバメート変性マイクロ繊維セルロース複合樹脂を得た。このカルバメート変性マイクロ繊維セルロース複合樹脂は、ペレッターで2mm径、2mm長の円柱状にカットし、180℃で直方体試験片(長さ59mm、幅9.6mm、厚さ3.8mm)に射出成形した。各試験片について、凝集塊の数、曲げ弾性率、曲げ強度を調べた。
The carbamate-modified microfiber-containing material was kneaded with a twin-screw kneader under the conditions of 180 ° C. and 200 rpm to obtain a carbamate-modified microfiber cellulose composite resin. This carbamate-modified microfiber cellulose composite resin was cut into a cylinder having a diameter of 2 mm and a length of 2 mm with a pelleter, and was injection-molded into a rectangular parallelepiped test piece (length 59 mm, width 9.6 mm, thickness 3.8 mm) at 180 ° C. .. For each test piece, the number of agglomerates, flexural modulus, and bending strength were examined.
試験の方法は、次のとおりとした。
複合樹脂を曲げ試験片に成形し、JIS K 7171:2008に準拠して曲げ弾性率を調べた。ただし、表中には、樹脂自体の曲げ弾性率を1とし複合樹脂の曲げ弾性率(倍率)が1.50倍より大きい場合を○、1.50倍以下の場合を×とした。 The test method was as follows.
The composite resin was formed into a bending test piece, and the flexural modulus was examined according to JIS K 7171: 2008. However, in the table, the flexural modulus of the resin itself was set to 1, and the case where the flexural modulus (magnification) of the composite resin was greater than 1.50 times was marked with ◯, and the case of 1.50 times or less was marked with x.
複合樹脂を曲げ試験片に成形し、JIS K 7171:2008に準拠して曲げ弾性率を調べた。ただし、表中には、樹脂自体の曲げ弾性率を1とし複合樹脂の曲げ弾性率(倍率)が1.50倍より大きい場合を○、1.50倍以下の場合を×とした。 The test method was as follows.
The composite resin was formed into a bending test piece, and the flexural modulus was examined according to JIS K 7171: 2008. However, in the table, the flexural modulus of the resin itself was set to 1, and the case where the flexural modulus (magnification) of the composite resin was greater than 1.50 times was marked with ◯, and the case of 1.50 times or less was marked with x.
曲げ強度は、1.20倍より大きい場合を○、1.20倍以下の場合を×とした。
The bending strength was marked as ◯ when it was greater than 1.20 times and x when it was 1.20 times or less.
曲げ試験片を光学顕微鏡で観察し、9mm2の視野における長径1mm以上の凝集(凝集塊)の個数をカウントした。凝集の個数が10個以上を×、9個~5個を〇、5個未満を◎とした。凝集塊の数が少ないほど分散性が良いことを意味する。
The bending test piece was observed with an optical microscope, and the number of agglomerates (aggregates) having a major axis of 1 mm or more in a field of view of 9 mm 2 was counted. The number of aggregates was 10 or more as x, 9 to 5 as 〇, and less than 5 as ⊚. The smaller the number of agglomerates, the better the dispersibility.
本発明は、セルロース繊維含有物の製造方法、セルロース繊維複合樹脂の製造方法として利用可能である。
The present invention can be used as a method for producing a cellulose fiber-containing material and a method for producing a cellulose fiber composite resin.
Claims (9)
- マイクロ繊維セルロース及び粉末を混合してスラリーとし、このスラリーからセルロース繊維含有物を得るものとし、
前記マイクロ繊維セルロースとして平均繊維径が0.1~19μmのカルバメート変性マイクロ繊維セルロースを使用し、
前記粉末としてセルロース繊維と相互作用しない粉末を使用し、
前記スラリーのカルバメート変性マイクロ繊維セルロース濃度を1.5質量%以上にする、
ことを特徴とするセルロース繊維含有物の製造方法。 Microfiber cellulose and powder are mixed to form a slurry, and a cellulose fiber-containing substance is obtained from this slurry.
Carbamate-modified microfiber cellulose having an average fiber diameter of 0.1 to 19 μm was used as the microfiber cellulose.
Using a powder that does not interact with cellulose fibers as the powder,
Carbamate-modified microfiber cellulose concentration of the slurry is increased to 1.5% by mass or more.
A method for producing a cellulose fiber-containing material. - 前記カルバメート変性マイクロ繊維セルロースのカルバメート化率が、1.0~2.0mmol/gである、
請求項1に記載のセルロース繊維含有物の製造方法。 The carbamate-modified microfiber cellulose has a carbamate conversion rate of 1.0 to 2.0 mmol / g.
The method for producing a cellulose fiber-containing material according to claim 1. - 前記濃度を水で調整する、
請求項1又は請求項2に記載のセルロース繊維含有物の製造方法。 Adjust the concentration with water,
The method for producing a cellulose fiber-containing product according to claim 1 or 2. - 前記スラリーの粘度を1000~10000cpsとする、
請求項1~3のいずれか1項に記載のセルロース繊維含有物の製造方法。 The viscosity of the slurry is 1000 to 10000 cps.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 3. - 前記カルバメート変性マイクロ繊維セルロースの密度に対する前記相互作用しない粉体の密度比が0.4~2.2である、
請求項1~4のいずれか1項に記載のセルロース繊維含有物の製造方法。 The density ratio of the non-interacting powder to the density of the carbamate-modified microfiber cellulose is 0.4 to 2.2.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 4. - 前記相互作用しない粉末として酸変性樹脂を使用し、
前記カルバメート変性マイクロ繊維セルロースのカルバメート基の一部又は全部と、前記酸変性樹脂の酸基とをイオン結合させる、
請求項1~5のいずれか1項に記載のセルロース繊維含有物の製造方法。 An acid-modified resin was used as the non-interacting powder,
Ionic bonding a part or all of the carbamate group of the carbamate-modified microfiber cellulose with the acid group of the acid-modified resin.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 5. - 前記スラリーの酸変性樹脂の濃度を0.5質量%以上にする、
請求項1~6のいずれか1項に記載のセルロース繊維含有物の製造方法。 The concentration of the acid-modified resin in the slurry is set to 0.5% by mass or more.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 6. - 前記相互作用しない粉末の平均粒子径が1mm以下である、
請求項1~7のいずれか1項に記載のセルロース繊維含有物の製造方法。 The average particle size of the non-interacting powder is 1 mm or less.
The method for producing a cellulose fiber-containing material according to any one of claims 1 to 7. - 請求項1~8のいずれか1項に記載の方法によって得たセルロース繊維含有物と、樹脂とを混合する、
ことを特徴とするセルロース繊維複合樹脂の製造方法。 The cellulose fiber-containing material obtained by the method according to any one of claims 1 to 8 is mixed with the resin.
A method for producing a cellulose fiber composite resin.
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