Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

• the present invention relates to a fibrous cellulose composite resin.
• the fibrous cellulose composite resin using fine fibers as a filler has as high a filler content as possible so that it can be diluted to any filler content depending on the application. .
• the filler compounding ratio exceeds, for example, 50% by mass, when the fibrous cellulose composite resin is discharged from a twin-screw extruder, etc. in the process of pelletizing, the so-called strands discharged from the twin-screw extruder, etc., will be weighed down by their own weight. It may break.
• conventional fibrous cellulose composite resins have a problem of poor processing suitability when the filler compounding ratio is increased.
• the main problem to be solved by the present invention is to provide a fibrous cellulose composite resin that has excellent processability even with a high blending ratio of fibrous cellulose as a filler.
• the present inventors first focused on resin components other than the filler and conducted extensive studies regarding the fact that the strands break under their own weight when the fibrous cellulose (filler) is incorporated at a high proportion. As a result, it was found that when high molecular weight polyethylene (PE) is used, the strands do not break under their own weight even when the filler content is 66.7% by mass, and stable cutting is possible. Based on this knowledge, we came up with the following method.
• PE polyethylene
• fibrous cellulose composite resin characterized by containing fibrous cellulose having an average fiber width of 0.1 ⁇ m or more, maleic anhydride-modified polypropylene, and polyethylene having a molecular weight of 1 million g/mol or more.
• a fibrous cellulose composite resin has excellent processability even when the fibrous cellulose filler is added at a high blending rate.
• the fibrous cellulose composite resin of this embodiment includes fibrous cellulose with an average fiber width of 0.1 ⁇ m or more, maleic anhydride-modified polypropylene (MAPP), and polyethylene (PE) with a molecular weight of 1 million g/mol or more. It is characterized by Preferably, in the fibrous cellulose, some or all of the hydroxy groups (-OH groups) are substituted with carbamate groups. This will be explained in detail below.
• the carbamate group is more hydrophilic than the hydroxyl group, it is more likely to interact with the hydrophilic side chain of MAPP. Furthermore, since MAPP has both hydrophilic and hydrophobic properties within its molecules, it becomes difficult to align and crystallize. Furthermore, the carbamate group also contributes to suppressing aggregation of fibers. From the above, MAPP and the carbamate cellulose fibers that interact with this MAPP have very excellent dispersibility in the resin. As a result, as is clear from the examples described later, when MAPP, cellulose fibers that interact with MAPP, preferably carbamate cellulose fibers (microfiber cellulose), and PE or PP are kneaded, they do not separate but are compatible with each other. This results in improved processing suitability and, in addition, improved strength.
• the fibrous cellulose that is the fine fibers is microfiber cellulose (microfibrillated cellulose) with an average fiber diameter of 0.1 ⁇ m or more.
• Microfiber cellulose significantly improves the reinforcing effect of the resin.
• microfiber cellulose is easier to modify with carbamate groups (carbamate formation) than cellulose nanofibers, which are also fine fibers.
• carbamate groups carbamate formation
• cellulose nanofibers which are also fine fibers.
• Microfiber cellulose can be obtained by defibrating (refining) cellulose raw material (hereinafter also referred to as "raw material pulp”).
• Raw material pulp includes, for example, wood pulp made from hardwoods, coniferous trees, etc., non-wood pulp made from straw, bagasse, cotton, linen, bark fiber, etc., and waste paper pulp made from recycled waste paper, waste paper, etc. (DIP) and the like, one or more types can be selected and used.
• DIP waste paper pulp made from recycled waste paper, waste paper, etc.
• the various raw materials mentioned above may be in the form of a pulverized material (powdered material) called, for example, cellulose powder.
• wood pulp As the raw material pulp, one or more types can be selected and used from, for example, chemical pulps such as hardwood kraft pulp (LKP) and softwood kraft pulp (NKP), mechanical pulp (TMP), and the like.
• the hardwood kraft pulp may be a bleached hardwood kraft pulp, an unbleached hardwood kraft pulp, or a semi-bleached hardwood kraft pulp.
• the softwood kraft pulp may be a bleached softwood kraft pulp, an unbleached softwood kraft pulp, or a semi-bleached softwood kraft pulp.
• Mechanical pulps include, for example, stone ground pulp (SGP), pressurized stone ground pulp (PGW), refiner ground pulp (RGP), chemical ground pulp (CGP), thermoground pulp (TGP), ground pulp (GP),
• SGP stone ground pulp
• PGW pressurized stone ground pulp
• RGP refiner ground pulp
• CGP chemical ground pulp
• TGP thermoground pulp
• GGP ground pulp
• TMP ground pulp
• TMP thermomechanical pulp
• CMP chemi-thermomechanical pulp
• RMP refiner mechanical pulp
• BTMP bleached thermomechanical pulp
• the raw material pulp can be pretreated by chemical methods prior to defibration.
• pretreatments using chemical methods include hydrolysis of polysaccharides with acids (acid treatment), hydrolysis of polysaccharides with enzymes (enzyme treatment), swelling of polysaccharides with alkalis (alkali treatment), and oxidation of polysaccharides with oxidizing agents ( Examples include oxidation treatment), reduction of polysaccharide with a reducing agent (reduction treatment), and the like.
• it is preferable to perform enzyme treatment it is preferable to perform enzyme treatment, and in addition, it is more preferable to perform one or more treatments selected from acid treatment, alkali treatment, and oxidation treatment.
• the enzyme treatment will be explained in detail below.
• the enzyme used for the enzyme treatment it is preferable to use at least one of a cellulase enzyme and a hemicellulase enzyme, and it is more preferable to use both in combination.
• the use of these enzymes makes it easier to defibrate cellulosic raw materials.
• cellulase enzymes cause the decomposition of cellulose in the presence of water.
• hemicellulase enzymes cause the decomposition of hemicellulose in the presence of water.
• cellulase enzymes include Trichoderma, Acremonium, Aspergillus, Phanerochaete, and Trametes. It is produced by the genus Humicola, the genus Bacillus, the genus Schizophyllum, the genus Streptomyces, and the genus Pseudomonas. Enzymes can be used. These cellulase enzymes can be purchased as reagents or commercial products.
• EG encodedoglucanase
• CBH cellobiohydrolase
• hemicellulase enzymes examples include xylanase, an enzyme that decomposes xylan, mannase, an enzyme that decomposes mannan, and arabanase, an enzyme that decomposes alaban. can.
• Pectinase which is an enzyme that degrades pectin, can also be used.
• Hemicellulose is a polysaccharide excluding pectin, which is present between cellulose microfibrils in plant cell walls. Hemicellulose is diverse and varies depending on the type of wood and the wall layers of the cell wall. In the secondary wall of softwood, glucomannan is the main component, and in the secondary wall of hardwood, 4-O-methylglucuronoxylan is the main component. Therefore, when obtaining fine fibers from softwood bleached kraft pulp (NBKP), it is preferable to use mannase. Moreover, when obtaining fine fibers from hardwood bleached kraft pulp (LBKP), it is preferable to use xylanase.
• NNKP softwood bleached kraft pulp
• LLKP hardwood bleached kraft pulp
• the amount of enzyme added to the cellulose raw material is determined by, for example, the type of enzyme, the type of wood used as the raw material (softwood or hardwood), the type of mechanical pulp, etc.
• the amount of enzyme added to the cellulose raw material is preferably 0.1 to 3% by mass, more preferably 0.3 to 2.5% by mass, particularly preferably 0.5 to 2% by mass. If the amount of the enzyme added is less than 0.1% by mass, there is a risk that the effect of the addition of the enzyme may not be sufficiently obtained. On the other hand, if the amount of enzyme added exceeds 3% by mass, cellulose may be saccharified and the yield of fine fibers may decrease. Another problem is that it is not possible to recognize an improvement in the effect commensurate with the increase in the amount added.
• the temperature during the enzyme treatment is preferably 30 to 70°C, more preferably 35 to 65°C, particularly preferably 40 to 60°C, regardless of whether a cellulase enzyme or a hemicellulase enzyme is used as the enzyme. . If the temperature during the enzyme treatment is 30° C. or higher, the enzyme activity will be less likely to decrease, and the treatment time can be prevented from becoming longer. On the other hand, if the temperature during enzyme treatment is 70° C. or lower, deactivation of the enzyme can be prevented.
• the time for enzyme treatment is determined by, for example, the type of enzyme, the temperature of enzyme treatment, the pH at the time of enzyme treatment, etc.
• the general enzyme treatment time is 0.5 to 24 hours.
• Examples of methods for inactivating enzymes include adding an alkaline aqueous solution (preferably pH 10 or higher, more preferably pH 11 or higher), adding hot water at 80 to 100°C, and the like.
• alkali used in the alkali treatment examples include sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia aqueous solution, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, etc.
• Organic alkalis and the like can be used. However, from the viewpoint of manufacturing cost, it is preferable to use sodium hydroxide.
• the degree of water retention of microfiber cellulose can be lowered, the degree of crystallinity can be increased, and the homogeneity can be increased.
• the water retention degree of microfiber cellulose is low, it becomes easy to dehydrate, and the dehydration property of the cellulose fiber slurry improves.
• a beater For defibration of raw material pulp, for example, a beater, a high-pressure homogenizer, a homogenizer such as a high-pressure homogenizer, a grinder, a stone mill friction machine such as a mill, a single-shaft kneader, a multi-shaft kneader, a kneader refiner, a jet mill, etc.
• a homogenizer such as a high-pressure homogenizer
• a grinder a stone mill friction machine such as a mill
• a single-shaft kneader a multi-shaft kneader
• a kneader refiner a jet mill
• microfiber cellulose means fibers with an average fiber width thicker than cellulose nanofibers.
• the average fiber diameter is, for example, 0.1 to 15 ⁇ m, preferably 0.2 to 10 ⁇ m, and more preferably more than 0.5 to 10 ⁇ m. If the average fiber diameter of microfiber cellulose is less than (below) 0.1 ⁇ m, it will not be different from cellulose nanofibers, and there is a possibility that the effect of improving the strength (especially flexural modulus) of the resin will not be sufficiently obtained. . Furthermore, the defibration time becomes longer and a large amount of energy is required. Furthermore, the dehydration properties of the cellulose fiber slurry deteriorate.
• the microfiber cellulose may be thermally degraded and its strength may be reduced.
• the average fiber diameter of the microfiber cellulose exceeds (exceeds) 15 ⁇ 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, 100ml of an aqueous dispersion of fine fibers with a solid content concentration of 0.01 to 0.1% by mass was filtered through a Teflon (registered trademark) membrane filter, and the solvent was replaced once with 100ml of ethanol and three times with 20ml of t-butanol. do. Next, it is freeze-dried, coated with osmium, and used as a sample. This sample is observed using an electron microscope SEM image at a magnification of 3,000 times to 30,000 times depending on the width of the constituent fibers. Specifically, two diagonal lines are drawn on the observed image, and three straight lines passing through the intersections of the diagonals are arbitrarily drawn. Furthermore, the widths of a total of 100 fibers that intersect with these three straight lines are visually measured. Then, the median diameter of the measured value is taken as the average fiber diameter.
• the average fiber length (average length of single fibers) of microfiber cellulose is preferably 0.10 to 2.00 mm, more preferably 0.12 to 1.50 mm, 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 (especially flexural modulus) of the composite resin may be reduced. 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 microfiber cellulose can be arbitrarily adjusted, for example, by selecting the raw material pulp, pretreatment, fibrillation, etc.
• the average fiber length of the cellulose raw material that is the raw material for microfiber cellulose is preferably 0.50 to 5.00 mm, more preferably 1.00 to 3.00 mm, particularly preferably 1.50 to 2.50 mm. If the average fiber length of the cellulose raw material is less than 0.50 mm, there is a possibility that the reinforcing effect of the resin will not be sufficiently obtained during defibration treatment. On the other hand, if the average fiber length exceeds 5.00 mm, it may be disadvantageous in terms of manufacturing cost during defibration.
• the fiber length of microfiber cellulose and the fibrillation rate described below are measured using a fiber analyzer "FS5" manufactured by Valmet.
• the proportion of microfiber cellulose fibers exceeding 0.02 mm is preferably 20% or more, more preferably 40% or more, particularly preferably 60% or more. If the ratio is less than 20%, there is a possibility that the reinforcing effect of the resin will not be sufficiently obtained. On the other hand, the fiber length of microfiber cellulose does not have an upper limit of more than 0.02 mm, and may all 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, so even if the average fiber length exceeds 0.01 mm, the reinforcing effect may be insufficient. On the other hand, when the aspect ratio exceeds 15,000, the microfiber cellulose becomes highly entangled with each other, and there is a possibility that the dispersion in the resin becomes insufficient.
• Aspect ratio is the value obtained by dividing the average fiber length by the average fiber width. As the aspect ratio increases, the number of places where snags occur increases, so the reinforcing effect increases, but on the other hand, it is thought that the more snags occur, the more the ductility of the resin decreases.
• the fibrillation rate of microfiber cellulose is preferably 1.0 to 30.0%, more preferably 1.5 to 20.0%, particularly preferably 2.0 to 15.0%. If the fibrillation rate exceeds 30.0%, the contact area with water becomes too large, so even if the fibers are defibrated within a range where the average fiber width remains at 0.1 ⁇ m or more, dehydration may become difficult. be. On the other hand, if the fibrillation rate is less than 1.0%, there are few hydrogen bonds between fibrils, and a strong three-dimensional network may not be formed.
• the crystallinity of the microfiber cellulose is preferably 50% or more, more preferably 55% or more, particularly preferably 60% or more.
• the degree of crystallinity is less than 50%, although the mixability with pulp and cellulose nanofibers is improved, the strength of the fibers themselves decreases, so there is a possibility that the strength of the resin cannot be improved.
• the crystallinity of the microfiber cellulose is preferably 95% or less, more preferably 90% or less, particularly preferably 85% or less.
• the degree of crystallinity exceeds 95%, the proportion of strong intramolecular hydrogen bonds increases, the fiber itself becomes rigid, and its dispersibility becomes poor.
• the degree of crystallinity of microfiber cellulose can be arbitrarily adjusted, for example, by selecting the raw material pulp, pretreatment, and refining treatment.
• the crystallinity is a value measured in accordance with JIS K 0131 (1996).
• the pulp viscosity of the microfiber cellulose is preferably 2 cps or more, more preferably 4 cps or more. When the pulp viscosity of the microfiber cellulose is less than 2 cps, it may be difficult to suppress aggregation of the microfiber cellulose.
• the pulp viscosity is a value measured according to TAPPI T230.
• the freeness of the microfiber cellulose is preferably 500 ml or less, more preferably 300 ml or less, particularly preferably 100 ml or less. If the freeness of the microfiber cellulose exceeds 500 ml, the average fiber diameter of the microfiber cellulose will exceed 10 ⁇ m, and there is a possibility that the effect of improving the strength of the resin will not be sufficiently obtained.
• microfiber cellulose The freeness of microfiber cellulose is a value measured in accordance with JIS P8121-2 (2012).
• the zeta potential of microfiber cellulose is preferably -150 to 20 mV, more preferably -100 to 0 mV, particularly preferably -80 to -10 mV. If the zeta potential is less than -150 mV, the compatibility with the resin may decrease significantly and the reinforcing effect may become insufficient. On the other hand, if the zeta potential exceeds 20 mV, there is a risk that the dispersion stability will decrease.
• the water retention degree of microfiber cellulose is preferably 80 to 400%, more preferably 90 to 350%, particularly preferably 100 to 300%. If the water retention is less than 80%, the reinforcing effect may be insufficient because it is no different from the raw material pulp. On the other hand, when the degree of water retention exceeds 400%, dehydration properties tend to be poor and agglomeration tends to occur. In this regard, the water retention of microfiber cellulose can be lowered by substituting the hydroxy groups of the fibers with carbamate groups, and the dehydration and drying properties can be improved.
• the water retention degree of microfiber cellulose can be arbitrarily adjusted, for example, by selecting the raw material pulp, pretreatment, fibrillation, etc.
• the microfiber cellulose has a carbamate group.
• the microfiber cellulose adheres to the maleic anhydride-modified polypropylene during melt-kneading, and the maleic anhydride-modified polypropylene is compatible with the base resin, thereby increasing the homogeneity of the composite resin.
• the strand In order for the strand to be stably discharged from the kneader without breaking, it is important that there are few non-uniform parts in the strand, and microfiber cellulose with carbamate groups has high compatibility, Since the homogeneity of the composite resin increases, the processability of the composite resin improves.
• microfiber cellulose is made to have carbamate groups.
• a cellulose raw material may have a carbamate group due to carbamate treatment, or a microfiber cellulose (finely divided cellulose raw material) may have a carbamate group due to carbamate conversion. .
• having a carbamate group means that a carbamate (carbamic acid ester) is introduced into the fibrous cellulose.
• the carbamate group is a group represented by -O-CO-NH-, for example, a group represented by -O-CO-NH 2 , -O-CONHR, -O-CO-NR 2 and the like. That is, the carbamate group can be represented by the following structural formula (1).
• R each independently represents hydrogen, a saturated linear hydrocarbon group, a saturated branched hydrocarbon group, a saturated cyclic hydrocarbon group, an unsaturated linear hydrocarbon group, an unsaturated branched hydrocarbon group, At least one of an aromatic group and a group derived therefrom.
• saturated linear hydrocarbon group examples include linear alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, and propyl group.
• saturated branched hydrocarbon group examples include branched alkyl groups having 3 to 10 carbon atoms such as isopropyl group, sec-butyl group, isobutyl group, and tert-butyl group.
• saturated cyclic hydrocarbon group examples include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a norbornyl group.
• Examples of the unsaturated linear hydrocarbon group include linear alkenyl groups having 2 to 10 carbon atoms such as ethenyl group, propen-1-yl group, propen-3-yl group, ethynyl group, propyn-1
• Examples include straight-chain alkynyl groups having 2 to 10 carbon atoms such as -yl group and propyn-3-yl group.
• Examples of the unsaturated branched hydrocarbon group include branched alkenyl groups having 3 to 10 carbon atoms such as propen-2-yl group, buten-2-yl group, buten-3-yl group, butyn-3 Examples include branched alkynyl groups having 4 to 10 carbon atoms such as -yl group.
• aromatic group examples include phenyl group, tolyl group, xylyl group, and naphthyl group.
• Examples of the derivative group include the above-mentioned saturated linear hydrocarbon group, saturated branched hydrocarbon group, saturated cyclic hydrocarbon group, unsaturated linear hydrocarbon group, unsaturated branched hydrocarbon group, and aromatic group.
• Examples include groups in which one or more hydrogen atoms are substituted with a substituent (for example, a hydroxy group, a carboxy group, a halogen atom, etc.).
• microfiber cellulose having carbamate groups In microfibrous cellulose having carbamate groups (introduced with carbamate groups), some or all of the highly polar hydroxy groups are substituted with relatively less polar carbamate groups. Therefore, microfiber cellulose having carbamate groups has low hydrophilicity and high affinity with resins and the like with low polarity. As a result, microfiber cellulose having carbamate groups has excellent uniform dispersibility with resin. Further, the microfiber cellulose slurry having carbamate groups has low viscosity and good handling properties.
• the amount of carbamate groups introduced into the hydroxyl groups of microfiber cellulose is preferably 0.3 to 2.0 mmol/g, more preferably 0.4 to 1.8 mmol/g, particularly preferably 0.5 to 1.5 mmol/g. It is g.
• the amount introduced is 0.3 mmol/g or more, the effect of introducing carbamate, especially the effect of improving the bending elongation of the resin, can be reliably achieved.
• the amount introduced exceeds 2.0 mmol/g, the cellulose fibers may not be able to maintain their fiber shape, and the reinforcing effect of the resin may not be sufficiently obtained.
• the amount of carbamate groups introduced refers to the amount of carbamate groups contained per gram of cellulose raw material having carbamate groups. Further, cellulose is a polymer having anhydroglucose as a structural unit, and has three hydroxy groups per structural unit.
• carbamate formation it is preferable to carry out carbamate formation first and then defibrate. This is because the cellulose raw material before being defibrated has a high dehydration efficiency, and the cellulose raw material is in a state where it is easily defibrated by heating accompanying carbamate formation.
• the process of carbamateing microfiber cellulose etc. can be mainly divided into, for example, mixing treatment, removal treatment, and heat treatment.
• the mixing treatment and the removal treatment can also be collectively referred to as a preparation treatment for preparing a mixture to be subjected to heat treatment.
• microfiber cellulose, etc. (as mentioned above, it may be a cellulose raw material. The same applies hereinafter) and urea and/or a derivative of urea (hereinafter also simply referred to as "urea etc.”) are mixed in a dispersion medium. Mix inside.
• urea and urea derivatives examples include urea, thiourea, biuret, phenylurea, benzylurea, dimethylurea, diethylurea, tetramethylurea, and compounds in which the hydrogen atom of urea is replaced with an alkyl group. can. These urea and urea derivatives can be used alone or in combination. However, it is preferred to use urea.
• the lower limit of the mixing mass ratio of urea, etc. to microfiber cellulose, etc. 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 also be used.
• microfiber cellulose, etc. and urea, etc. may be added to water, microfiber cellulose, etc. may be added to an aqueous solution of urea, etc., or urea, etc. may be added to a slurry containing microfiber cellulose, etc. It's okay. Further, in order to mix uniformly, it may be stirred after addition. Furthermore, the dispersion containing microfiber cellulose and the like and urea and the like may contain other components.
• the dispersion medium is removed from the dispersion containing microfiber cellulose, etc., urea, etc. obtained in the mixing treatment.
• urea and the like can be efficiently reacted in the subsequent heat treatment.
• the removal of the dispersion medium is preferably performed by volatilizing the dispersion medium by heating. According to this method, only the dispersion medium can be efficiently removed while leaving components such as urea.
• the lower limit of the heating temperature in the removal treatment is preferably 50°C, more preferably 70°C, particularly preferably 90°C when the dispersion medium is water.
• the upper limit of the heating temperature is preferably 120°C, more preferably 100°C. If the heating temperature exceeds 120° C., the dispersion medium and urea may react, and urea may decompose alone.
• the heating time in the removal treatment can be adjusted as appropriate depending on the solid content concentration of the dispersion. Specifically, it is, for example, 6 to 24 hours.
• a mixture of microfiber cellulose, etc., and urea, etc. is heat treated.
• part or all of the hydroxyl groups of microfiber cellulose etc. react with urea etc. and are substituted with carbamate groups.
• urea or the like is heated, it is decomposed into isocyanic acid and ammonia as shown in reaction formula (1) below.
• Isocyanic acid has very high reactivity, and forms carbamate groups on the hydroxyl groups of cellulose, for example, as shown in reaction formula (2) below.
• the lower limit of the heating temperature in the heat treatment is preferably 120°C, more preferably 130°C, particularly preferably at least the melting point of urea (about 134°C), even more preferably 140°C, and most preferably 150°C.
• the upper limit of the heating temperature is preferably 200°C, more preferably 180°C, particularly preferably 170°C. If the heating temperature exceeds 200° C., the microfiber cellulose etc. may be decomposed and the reinforcing effect may become 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. By setting the heating time to 1 minute or more, the carbamate reaction can be carried out reliably.
• 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 15 hours is enough to carry out carbamate formation.
• the pH is preferably pH 9 or higher, more preferably pH 9 to 13, particularly preferably pH 10 to 12, which is an alkaline condition.
• acidic conditions or neutral conditions with a pH of 7 or less, preferably a pH of 3 to 7, particularly preferably a pH of 4 to 7 are preferred. Under neutral pH conditions of 7 to 8, the average fiber length of cellulose fibers becomes short, and the reinforcing effect of the resin may be poor.
• the pH can be adjusted by adding an acidic compound (for example, acetic acid, citric acid, etc.) or an alkaline compound (for example, sodium hydroxide, calcium hydroxide, etc.) to the mixture.
• an acidic compound for example, acetic acid, citric acid, etc.
• an alkaline compound for example, sodium hydroxide, calcium hydroxide, etc.
• a hot air dryer for example, a paper machine, a dry pulp machine, etc. can be used.
• the mixture after heat treatment may be dehydrated and washed. This dehydration and washing may be performed using water or the like. This dehydration and washing can remove unreacted urea and the like.
• the microfiber cellulose is dispersed in an aqueous medium to form a dispersion (slurry).
• aqueous medium consists entirely of water, but an aqueous medium that is partially composed of other liquids that are compatible with water can also be used.
• other liquids lower alcohols having 3 or less carbon atoms can be used.
• the solid content concentration of the slurry is preferably 0.1 to 10.0% by mass, more preferably 0.5 to 5.0% by mass.
• the solid content concentration is less than 0.1% by mass, excessive energy may be required during dehydration and drying.
• the solid content concentration exceeds 10.0% by mass, the fluidity of the slurry itself will decrease, and there is a possibility that uniform mixing will not be possible.
• the fibrous cellulose composite resin of this embodiment contains maleic anhydride-modified polypropylene (MAPP).
• the amount of maleic anhydride-modified polypropylene mixed is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts by weight, particularly preferably 40 to 60 parts by weight, based on 100 parts by weight of microfiber cellulose. If the amount of maleic anhydride-modified polypropylene mixed is less than 1 part by mass, the strength will not be improved sufficiently. On the other hand, if the mixing amount exceeds 200 parts by mass, it becomes excessive and the strength tends to decrease.
• the weight average molecular weight of the maleic anhydride-modified polypropylene is, for example, 1,000 to 100,000, preferably 3,000 to 90,000, particularly preferably 5,000 to 80,000. If the weight average molecular weight is less than 1000, although it adheres to the microfiber cellulose, it may not be compatible with the resin that serves as the base material, resulting in poor homogeneity. Further, since the strength of the maleic anhydride-modified polypropylene itself is too low, the physical properties as a whole may be insufficient even though it is reinforced with fibers.
• the weight average molecular weight exceeds 100,000, the viscosity increases when melted, and there are areas where the fibers are not sufficiently bonded to the microfiber cellulose, and the fibers do not participate in reinforcing the entire resin, resulting in poor physical properties as a composite resin. It may be sufficient.
• the ratio of the molecular weight of the maleic anhydride-modified polypropylene to the molecular weight of polyethylene is preferably 1:10 to 1:1000, more preferably 1:15 to 1:500, particularly preferably 1:25 to 1:300. and is suitable. If the ratio of the molecular weight of the maleic anhydride-modified polypropylene to the molecular weight of polyethylene is outside the above range, the maleic anhydride-modified polypropylene and polyethylene will not be well compatible with each other during kneading, and the strands will not form when discharged from the kneader. There may be a lack of homogeneity and the strands may not draw consistently.
• the acid value of the maleic anhydride-modified polypropylene is preferably 10 to 90 mgKOH/g, more preferably 20 to 80 mgKOH/g, particularly preferably 30 to 70 mgKOH/g. If the acid value is less than 10 mgKOH/g, the adhesion to microfiber cellulose may become insufficient and the dispersibility may deteriorate. On the other hand, if the acid value exceeds 90 mgKOH/g, although the adhesion with microfiber cellulose is sufficient, the compatibility with the base resin may deteriorate, and conversely, the dispersibility in the composite resin may deteriorate. There is sex.
• the fibrous cellulose composite resin of this embodiment contains polyethylene with a molecular weight of 1 million g/mol or more.
• the molecular weight of polyethylene is more preferably 1 million to 10 million g/mol, particularly preferably 2 million to 8 million g/mol.
• the molecular weight is 1,000,000 g/mol or more, it becomes possible for the resins to interact with each other while interacting with the fibers during melting, making it easier for the composite resin to move as a unit within the kneader.
• the composite resin is discharged from the nozzle outlet or the like, it is thought to be continuously discharged as a single piece, making it easier to form a strand.
• UHMW-PE ultra high molecular weight polyethylene
• the melting point of polyethylene is preferably 125°C or higher, more preferably 130 to 160°C, particularly preferably 135 to 155°C. If the melting point is less than 125°C, it will melt immediately at the inlet of the kneader and adhere to the wall surface, and the polyethylene will not be uniformly dispersed in the kneaded material, resulting in a lower MFC blending ratio at the moment it is discharged from the nozzle outlet. It is thought that the blurring becomes larger and the strand breaks. On the other hand, if the melting point exceeds 160°C, it is necessary to raise the kneading temperature more than necessary, and the microfiber cellulose may become colored due to thermal decomposition or the like.
• Polyethylene can be in the form of powder, pellets, sheets, blocks, etc., for example. However, it is preferable that the polyethylene is in powder form.
• polyethylene when polyethylene is in powder form, when it is added to an aqueous dispersion of microfiber cellulose, mixed, and dried, it partially enters the gaps where the microfiber cellulose aggregates, making it easier to knead than when nothing is added. This can be suppressed by agglomeration to the extent that it can be redispersed by shearing by a machine.
• the average particle diameter of the polyethylene is preferably 10 to 1000 ⁇ m, more preferably 15 to 100 ⁇ m, particularly preferably 20 to 80 ⁇ m. If the average particle diameter is less than 10 ⁇ m, the polyethylene powders will aggregate and float together in the aqueous dispersion of microfiber cellulose, and will not be able to enter the gaps between the microfiber celluloses, so that the effect of suppressing aggregation will be sufficient. There is a possibility that you will not be able to perform effectively.
• the average particle diameter is a value measured in accordance with ISO13320.
• the durometer hardness of polyethylene is preferably 30 or more, more preferably 50 or more, particularly preferably 60 or more.
• the discharged strand is cooled with water or air, and then cut into granules using a strand cutter.
• the durometer hardness of polyethylene at room temperature is 30 or more, it is thought that the discharged strand will be difficult to cut during the process of being transferred to a strand cutter.
• the durometer hardness is a value measured using a type A measuring machine in accordance with JIS K 7215 (1986).
• Maleic anhydride-modified polypropylene and polyethylene are contained in a dry mass ratio of preferably 10:90 to 90:10, more preferably 15:85 to 85:15, particularly preferably 50:50 to 80:20. It is preferable that the If the content ratio of maleic anhydride-modified polypropylene is small, polyethylene may enter between the adhesion of microfiber cellulose and maleic anhydride-modified polypropylene, which may inhibit adhesion between maleic anhydride-modified polypropylene and microfiber cellulose.
• the fibrous cellulose composite resin of this embodiment preferably contains an inorganic powder that does not interact with fibrous cellulose.
• the purpose is to physically inhibit hydrogen bonding between cellulose fibers by including inorganic powder that does not interact with each other.
• not interacting means not forming strong bonds with cellulose through covalent bonds, ionic bonds, or metal bonds (in other words, bonds due to hydrogen bonds and van der Waals forces are included in the concept of not interacting). ).
• a strong bond is one with a binding energy greater than 100 kJ/mol.
• the non-interacting inorganic powder is preferably an inorganic powder that has little effect of dissociating the hydroxyl groups of cellulose fibers into hydroxide ions when they coexist in the slurry.
• inorganic powder is advantageous in terms of operation.
• methods for drying composite resins include, for example, drying by applying the water dispersion directly to a metal drum that is a heat source (for example, drying with a Yankee dryer or cylinder dryer, etc.), and drying by applying water dispersion to a metal drum that is a heat source There is a method of heating the dispersion without directly touching it, that is, a method of drying it in air (for example, drying with a constant temperature dryer).
• the average particle diameter of the non-interacting inorganic 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 diameter exceeds 10,000 ⁇ m, the particles may enter the gaps between cellulose fibers during removal of the aqueous medium and may not be effective in inhibiting agglomeration. On the other hand, if the average particle diameter is less than 1 ⁇ m, the particles may be too fine to inhibit hydrogen bonding between microfiber celluloses.
• the average particle diameter of non-interacting inorganic powder is measured using a particle size distribution measuring device (for example, a laser diffraction/scattering particle size distribution measuring device manufactured by Horiba, Ltd.) using the powder as it is or in the state of an aqueous dispersion.
• a particle size distribution measuring device for example, a laser diffraction/scattering particle size distribution measuring device manufactured by Horiba, Ltd.
• inorganic powders include simple substances and oxides of metal elements in Groups I to VIII of the periodic table, such as Fe, Na, K, Cu, Mg, Ca, Zn, Ba, Al, Ti, and silicon elements. , hydroxides, carbon salts, sulfates, silicates, sulfites, and various clay minerals made of these compounds.
• a plurality of these inorganic fillers may be contained. Moreover, it may be contained in waste paper pulp, or it may be a so-called recycled filler obtained by recycling inorganic substances in papermaking 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 paper manufacturing. 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. Particularly preferred.
• calcium carbonate, talc, or clay it is easy to form a composite with a matrix such as a resin.
• it is a general-purpose inorganic material it has the advantage that there are few restrictions on its uses.
• calcium carbonate is particularly preferred for the following reasons.
• the size and shape of the powder When using light calcium carbonate, it becomes easier to control the size and shape of the powder to a constant level. For this reason, the size and shape can be adjusted according to the size and shape of the cellulose fibers so that the effect of inhibiting agglomeration between cellulose fibers can be easily produced by entering the gaps, making it easier to exert the effect in a pinpoint manner. There is.
• ground calcium carbonate since it has an amorphous shape, even if fibers of various sizes are present in the slurry, they will enter the gaps in the process of agglomeration during the removal of the aqueous medium. This has the advantage of being able to suppress aggregation of cellulose fibers.
• the blending amount of the non-interacting inorganic powder is preferably 1 to 9900% by mass, more preferably 5 to 1900% by mass, particularly preferably 10 to 900% by mass, based on the fibrous cellulose. If the blending amount is less than 1% by mass, the effect of entering the gaps between cellulose fibers and inhibiting agglomeration may be insufficient. On the other hand, if the blending amount exceeds 9900% by mass, there is a risk that the cellulose fibers will not be able to function as cellulose fibers.
• maleic anhydride-modified polypropylene and non-interacting inorganic powder are used together as in this embodiment, even if they are mixed under conditions that cause each to coagulate, the maleic anhydride-modified polypropylene and non-interacting inorganic powder will prevent each other from agglomerating. It has a great effect.
• powder with a small particle size has a large surface area and is more susceptible to intermolecular forces than gravity, and as a result, it is more likely to aggregate, so when mixing the powder and microfiber cellulose slurry, If the particles are not loosened properly in the slurry, or if the powders aggregate together when the aqueous medium is removed, the effect of preventing the microfiber cellulose from agglomerating may not be sufficiently exerted.
• maleic anhydride-modified polypropylene and non-interacting inorganic powder are used together, the agglomeration of the polypropylene itself can be alleviated.
• the average particle diameter ratio of maleic anhydride-modified polypropylene:non-interacting inorganic powder is preferably 1:0.1 to 1:10,000, and 1:1. ⁇ 1:1000 is more preferable. Within this range, problems caused by the strength of its own cohesive force (for example, the powder does not loosen properly in the slurry, or the powders aggregate when removing the aqueous medium) will not occur. It is thought that the effect of preventing agglomeration of microfiber cellulose can be fully exhibited.
• the ratio of the mass % of the inorganic powder to the mass % of the maleic anhydride-modified polypropylene is preferably 1:0.01 to 1:100, and 1:0. More preferably 1 to 1:10. It is considered that within this range, different types of powders can inhibit their own aggregation. In other words, if it is within this range, problems will occur due to the strength of its own cohesive force (for example, the powder will not loosen properly in the slurry, or the powder will coagulate with each other when the aqueous medium is removed). It is thought that the effect of preventing agglomeration of microfiber cellulose can be fully exhibited without the need for agglomeration.
• the fibrous cellulose composite resin of this embodiment becomes more preferable 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 hydroxyl group in the aromatic group include anilines, toluidines, trimethylanilines, anisidines, tyramines, histamines, tryptamines, phenols, dibutylhydroxytoluenes, and bisphenol A.
• cresols cresols, eugenols, gallic acids, guaiacols, picric acids, phenolphthaleins, serotonins, dopamines, adrenaline, noradrenaline, thymol, tyrosine, salicylic acids, methyl salicylate, anis alcohols , salicyl alcohols, sinapyl alcohols, diphenidols, diphenylmethanols, cinnamyl alcohols, scopolamines, tryptofols, vanillyl alcohols, 3-phenyl-1-propanols, phenethyl alcohols, phenoxyethanols , veratryl alcohols, benzyl alcohols, benzoins, mandelic acids, mandelonitriles, benzoic acids, phthalic acids, isophthalic acids, terephthalic acids, mellitic acids, cinnamic acids, and the like.
• examples of compounds having an amine group and/or hydroxyl group in the aliphatic group include caprylic alcohols, 2-ethylhexanols, pelargon alcohols, capric alcohols, undecyl alcohols, lauryl alcohols, and tridecyl alcohols.
• myristyl alcohols pentadecyl alcohols, cetanols, stearyl alcohols, elaidyl alcohols, oleyl alcohols, linoleyl alcohols, methylamines, dimethylamines, trimethylamines, ethylamines, diethylamines, ethylenediamine triethanolamines, N,N-diisopropylethylamines, tetramethylethylenediamines, hexamethylenediamines, spermidines, spermines, amantadines, formic acids, acetic acids, propionic acids, butyric acids, valeric acids, Caproic acids, enanthic acids, caprylic acids, pelargonic acids, capric acids, lauric acids, myristic acids, palmitic acids, margaric acids, stearic acids, oleic acids, linoleic acids, linolenic acids, arachidonic acids,
• the above dispersants inhibit hydrogen bonding between cellulose fibers. Therefore, the microfiber cellulose is reliably dispersed in the resin during kneading. Moreover, the above-mentioned dispersant also has the role of improving the compatibility between microfiber cellulose and resin. In this respect, the dispersibility of microfiber cellulose in the resin is improved.
• the amount of the dispersant mixed is preferably 0.1 to 1,000 parts by weight, more preferably 1 to 500 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of microfiber cellulose. If the amount of the dispersant mixed is less than 0.1 part by mass, there is a possibility that the resin strength will not be improved sufficiently. On the other hand, if the mixing amount exceeds 1,000 parts by mass, it becomes excessive and the resin strength tends to decrease.
• the aforementioned maleic anhydride-modified polypropylene improves compatibility by bonding acid groups with the carbamate groups of microfiber cellulose, thereby increasing the reinforcing effect. It is thought that it is easy to get used to it and contributes to the improvement of strength.
• the above-mentioned dispersant intervenes between the hydroxyl groups of microfiber cellulose to prevent agglomeration, thereby improving dispersibility in the resin, and also has a molecular weight that is lower than that of maleic anhydride-modified polypropylene. Because it is small, it can enter the narrow spaces between microfiber cellulose that maleic anhydride-modified polypropylene cannot enter, and plays a role in improving dispersibility and strength.
• the molecular weight of the maleic anhydride-modified polypropylene is preferably 2 to 2000 times, preferably 5 to 1000 times, the molecular weight of the dispersant.
• the non-interacting inorganic powder physically intervenes between the microfiber cellulose and inhibits hydrogen bonding, thereby improving the dispersibility of the microfiber cellulose.
• maleic anhydride-modified polypropylene improves compatibility by bonding acid groups and carbamate groups of microfiber cellulose, thereby increasing the reinforcing effect.
• the dispersant inhibits hydrogen bonding between microfiber celluloses, but since the inorganic powder that does not interact is on the micro-order, it physically intervenes and suppresses hydrogen bonding.
• the inorganic powder itself is rigid, when it is combined with a resin or the like, it contributes to improving the physical properties of the resin or the like.
• the dispersant since the dispersant is at the molecular level and is extremely small, it covers the microfiber cellulose to inhibit hydrogen bonding and is highly effective in improving the dispersibility of the microfiber cellulose. However, it may remain in the resin and deteriorate its physical properties.
• Microfiber cellulose (or an aqueous dispersion of microfiber cellulose) is mixed with maleic anhydride-modified polypropylene and polyethylene. This mixture (liquid) is preferably dried into a dry product before being kneaded to form a composite resin. If it is dried, there is no need to dry the fibrous cellulose during kneading, resulting in good thermal efficiency.
• the mixture can be dried by, for example, rotary kiln drying, disc drying, air flow drying, medium fluidized drying, spray drying, drum drying, screw conveyor drying, paddle drying, uniaxial kneading drying, multi-screw kneading drying, vacuum drying, stirring drying. This can be carried out by selectively using one or more of these.
• one or more types of dehydration equipment is selected from among the following dehydration equipment: belt press, screw press, filter press, twin roll, twin wire former, valveless filter, center disk filter, membrane treatment, centrifugal separator, etc. It can be done using:
• the dry material can be pulverized by selecting one or more of a bead mill, a kneader, a disperser, a twist mill, a cut mill, a hammer mill, etc., for example.
• the average particle diameter of the powder is preferably 1 to 10,000 ⁇ m, more preferably 10 to 5,000 ⁇ m, particularly preferably 100 to 1,000 ⁇ m. If the average particle diameter of the powder exceeds 10,000 ⁇ m, the kneading properties may be poor. On the other hand, it is not economical to make the powder material have an average particle size of less than 1 ⁇ m since it requires a large amount of energy.
• the average particle diameter of the powdered material can be controlled not only by controlling the degree of pulverization but also by classification using a classification device such as a filter or cyclone.
• the bulk specific gravity of the mixture (powder) is preferably 0.03 to 1.0, more preferably 0.04 to 0.9, particularly preferably 0.05 to 0.8.
• a bulk specific gravity of more than 1.0 means that the hydrogen bonds between fibrous cellulose are stronger and it is not easy to disperse the cellulose in the resin.
• having a bulk specific gravity of less than 0.03 is disadvantageous in terms of transportation costs.
• the bulk specific gravity is a value measured according to JIS K7365.
• the moisture content of the mixture (powder) is preferably 50% or less, more preferably 30% or less, particularly preferably 10% or less. If the moisture content exceeds 50%, the energy required for kneading with the resin will be enormous, making it uneconomical.
• the moisture content is a value calculated using the following formula, using a constant temperature dryer to maintain the sample at 105° C. for 6 hours or more, and using the mass at which no change in mass is observed as the mass after drying.
• Fiber moisture content (%) [(mass before drying - mass after drying) ⁇ mass before drying] x 100
• This dry and pulverized product is kneaded to form a fibrous cellulose composite resin.
• the composite resin of this embodiment even when the blending ratio of fibrous cellulose is as high as, for example, 50% by mass or more, it has excellent processability and can be drawn into strands.
• the blending ratio of fibrous cellulose to the total amount of the composite resin is, for example, 50% by mass or more, preferably 50 to 70% by mass, and more preferably 55 to 68% by mass. If the blending ratio exceeds 70% by mass, the processing suitability of the composite resin may be insufficient even in this embodiment.
• the dry powder can be kneaded, for example, in the same manner as in the case of adding and kneading a further resin as described below. Therefore, the explanation is omitted here.
• the fibrous cellulose composite resin of this embodiment can be used after being kneaded with a further resin and diluted until the blending ratio of fibrous cellulose becomes, for example, 10%.
• This kneading can be carried out, for example, by mixing the composite resin of the present form in the form of a powder with the additional resin in the form of pellets, or by first melting the additional resin and adding the powder into the melt. It is also possible to add the composite resin of this embodiment.
• one or more types are selected and used from, for example, a single-screw or multi-screw kneader with two or more shafts, a mixing roll, a kneader, a roll mill, a Banbury mixer, a screw press, a disperser, etc. be able to.
• a multi-screw kneader having two or more shafts it is preferable to use.
• Two or more multi-shaft kneaders having two or more shafts may be used in parallel or in series.
• the temperature of the kneading treatment is 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 more preferably 100 to 240°C. is particularly preferred.
• thermoplastic resin As the further resin, at least one of a thermoplastic resin and a thermosetting resin can be used.
• thermoplastic resins 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, polyamide resins, One or more types can be selected and used from polycarbonate resins, polyacetal resins, etc.
• 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 polyamide resins
• One or more types can be selected and used from polycarbonate resins, polyacetal resins, etc.
• polyester resin examples include aliphatic polyester resins such as polylactic acid and polycaprolactone, and examples of aromatic polyester resins such as polyethylene terephthalate. It is preferable to use a polyester resin (also simply referred to as "biodegradable resin") having the following.
• biodegradable resin one or more types can be selected and used from, for example, hydroxycarboxylic acid-based aliphatic polyesters, caprolactone-based aliphatic polyesters, dibasic acid polyesters, and the like.
• hydroxycarboxylic acid-based aliphatic polyesters include homopolymers of hydroxycarboxylic acids such as lactic acid, malic acid, glucose acid, and 3-hydroxybutyric acid, and copolymers using at least one of these hydroxycarboxylic acids.
• hydroxycarboxylic acids such as lactic acid, malic acid, glucose acid, and 3-hydroxybutyric acid
• copolymers using at least one of these hydroxycarboxylic acids One type or two or more types can be selected and used from polymers and the like.
• polylactic acid, a copolymer of lactic acid and the above-mentioned hydroxycarboxylic acids other than lactic acid, polycaprolactone, and a copolymer of at least one of the above-mentioned hydroxycarboxylic acids and caprolactone Particularly preferred is the use of
• lactic acid for example, L-lactic acid, D-lactic acid, etc. can be used, and these lactic acids may be used alone or two or more types may be selected and used.
• caprolactone-based aliphatic polyester one or more types can be selected and used from, for example, a homopolymer of polycaprolactone, a copolymer of polycaprolactone, etc., and the above-mentioned hydroxycarboxylic acid, etc. .
• one or more types can be selected and used from, for example, polybutylene succinate, polyethylene succinate, polybutylene adipate, and the like.
• the biodegradable resins may be used alone or in combination of two or more.
• thermosetting resins 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, etc. can be used. These resins can be used alone or in combination of two or more.
• the blending ratio of the total amount of fibrous cellulose and resin is preferably 1 part by mass or more for fibrous cellulose and 99 parts by mass or less for resin, more preferably 2 parts by mass or more for fibrous cellulose and 98 parts by mass or less for resin, particularly preferably.
• the content of fibrous cellulose is 3 parts by mass or more, and the content of resin is 97 parts by mass or less.
• the fibrous cellulose is 50 parts by mass or less
• the resin is 50 parts by mass or more, more preferably the fibrous cellulose is 40 parts by mass or less
• the resin is 60 parts by mass or more, and particularly preferably the fibrous cellulose is 30 parts by mass or less.
• the resin is 70 parts by mass or more.
• the strength of the resin composition particularly the flexural strength and tensile modulus, can be significantly improved.
• the content ratio of fibrous cellulose and resin contained in the finally obtained resin composition is usually the same as the above-mentioned blending ratio of fibrous cellulose and resin.
• the fibrous cellulose composite resin or a composite resin obtained by diluting this composite resin can be kneaded again if necessary, and then molded into a desired shape.
• 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 above 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.
• the kneaded product can be shaped by, for example, die molding, injection molding, extrusion molding, blow molding, foam molding, or the like. Further, the kneaded material can be spun into fibers and mixed with the above-mentioned plant materials, etc., to form a mat shape or a board shape.
• the mixed fibers can be mixed, for example, by a method of simultaneous deposition using air lay.
• the device for molding the kneaded product for example, one or two types from injection molding machines, blow molding machines, blow molding machines, blow molding machines, compression molding machines, extrusion molding machines, vacuum molding machines, pressure molding machines, etc. can be used. More than one species can be selected and used.
• the above molding can be performed after kneading, or by cooling the kneaded material and turning it into chips using a crusher, etc., and then feeding the chips into a molding machine such as an extrusion molding machine or an injection molding machine. You can also do this. Of course, shaping is not an essential requirement of the invention.
• the obtained carbamate-modified pulp was diluted with distilled water and stirred, and dehydration and washing were repeated twice to adjust the solid content concentration to 3.0% by mass, thereby obtaining a carbamate-modified pulp after washing.
• the carbamate-modified pulp is beaten using a beating machine until the fine ratio (proportion of fibers of 0.2 mm or less as measured by fiber length distribution by FS5) is 40% or more to produce carbamate-modified microfiber cellulose (CAMFC). I got it.
• the carbamate-modified microfiber cellulose-containing material was kneaded in a twin-screw kneader at 170°C and 75 rpm, and cut into cylinders with a diameter of 2 mm and a length of 2 mm using a pelleter, resulting in carbamate with a fiber content of 66.7%.
• a modified microfiber cellulose composite resin was obtained. It was confirmed whether or not strands could be drawn with this composite resin.
• carbamate-modified microfiber cellulose composite resin with a fiber content ratio of 66.7% and PP pellets were dry-blended at a dry mass ratio of 9:51, and a twin-screw kneader was used at 170°C and 75 rpm.
• the mixture was kneaded and cut into cylinders with a diameter of 2 mm and a length of 2 mm using a pelleter to obtain pellets of carbamate-modified microfiber cellulose composite resin with a fiber blending ratio of 10%.
• This pellet (fiber blend ratio 10%) was injection molded at 180° C. into a rectangular parallelepiped specimen (length 59 mm, width 9.6 mm, thickness 3.8 mm), and the bending elastic modulus and bending strength were examined.
• Test Example 2 A test similar to Test Example 2 was conducted by changing carbamate-modified microfiber cellulose to non-carbamate-modified microfiber cellulose (MFC), replacing part of MAPP with a different type of PE, and using a flow improver. Ta. Details and results are shown in Tables 1 to 3.
• the physical properties of the PE powder were measured as described above. Furthermore, the blending ratio of MFC also includes CAMFC. Furthermore, regarding the availability of strands, the following was determined.
• ⁇ When the length that can be drawn from the extruder outlet is 150 cm or more ⁇ : When the length that can be drawn from the extruder outlet is 10 cm or more and less than 150 cm ⁇ : When the length that can be drawn from the extruder outlet is less than 10 cm
• the present invention can be used as a fibrous cellulose composite resin.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=88100881

Family Applications (1)

Country Status (2)

Cited By (1)

Citations (7)

• 2022
  • 2022-03-24 JP JP2022049139A patent/JP7449323B2/ja active Active
  • 2022-12-20 WO PCT/JP2022/046809 patent/WO2023181538A1/ja not_active Ceased

Patent Citations (7)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events