JP2021155545A - Fibrous cellulose, fibrous cellulose composite resin, and method for producing fibrous cellulose - Google Patents

Abstract

To provide a fibrous cellulose having high reinforcing effect of a resin, a fibrous cellulose composite resin having high intensity, and a method for producing the fibrous cellulose having the high reinforcing effect of the resin.SOLUTION: A fibrous cellulose has an average fiber width of 0.1 μm or more, has some or all of hydroxyl groups substituted with carbamate groups, has a carbamate group substitution rate of 1.0 mmol/g or more, and has a fine rate of 10% or more and 35% or less. The fibrous cellulose composite resin comprises fibrous cellulose and a resin, the fibrous cellulose being the aforementioned fibrous cellulose. Moreover, when producing the fibrous cellulose, a cellulose raw material and urea or the like are heat-treated and some or all of the hydroxyl groups in the cellulose raw material are substituted by the carbamate groups, the fibers are separated until the average fiber width is 0.1 μm or more, the heat treatment is performed such that the carbamate group substitution rate reaches 1.0 mmol/g or more, and the fibers are separated until the fine rate is 10% or more and 35% or less.SELECTED DRAWING: None

Description

The present invention relates to a method for producing fibrous cellulose, fibrous cellulose composite resin and fibrous cellulose.

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 hydroxy group of the fine fiber with a carbamate group (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, even now, further improvement of the reinforcing effect is desired, and various studies are being continued.

Japanese Unexamined Patent Publication No. 2019-1876

A main problem to be solved by the present invention is to provide a fibrous cellulose having a high resin reinforcing effect, a high-strength fibrous cellulose composite resin, and a method for producing a fibrous cellulose having a high resin reinforcing effect.

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 a carbamate group among various modification methods such as esterification, etherification, amidation, and sulfidation. It was found that (carbamation) was excellent. On the other hand, the present invention does not focus on the introduction of a carbamate group, but solves the above-mentioned problems by pursuing the physical characteristics of fine fibers while conducting a number of tests on the premise of the introduction of a carbamate group. I learned that I could do it, and came up with the idea. More specifically, the cause of the insufficient reinforcing effect of the resin was investigated in detail, and first, it was found that one of the factors was the non-uniformity of the fine fibers. However, if the uniformity of the fine fibers is increased too much, the fluidity of the composite resin obtained by kneading the fine fibers and the resin decreases, and the homogeneity of the composite resin decreases due to this decrease in fluidity, resulting in a reinforcing effect. Was also found to be insufficient. The means that came to the fore through such knowledge are as follows.

(Means according to claim 1)
The average fiber width is 0.1 μm or more, and some or all of the hydroxyl groups are substituted with carbamate groups.
When the substitution rate of the carbamate group is 1.0 mmol / g or more,
The fine rate is 10% or more and 35% or less.
Fibrous cellulose characterized by that.

(Means according to claim 2)
The fine ratio of the cellulose raw material used as the raw material is 1% or more.
The fibrous cellulose according to claim 1.

(Means according to claim 3)
The cellulose raw material is not treated with an enzyme, or the amount of the enzyme added is in a range of 2% by mass or less of the cellulose raw material.
The fibrous cellulose according to claim 2.

(Means according to claim 4)
Pulp viscosity is 4 cps or more,
The fibrous cellulose according to any one of claims 1 to 3.

(Means according to claim 5)
Contains fibrous cellulose and resin,
The fibrous cellulose is
The average fiber width is 0.1 μm or more, and some or all of the hydroxyl groups are substituted with carbamate groups.
When the substitution rate of the carbamate group is 1.0 mmol / g or more,
The fine rate is 10% or more and 35% or less.
A fibrous cellulose composite resin characterized by this.

(Means according to claim 6)
The MFR measured according to JIS-K7210 (190 ° C., 2.16 kg) is 0.01 to 20 g / 10 minutes.
The fibrous cellulose composite resin according to claim 5.

(Means according to claim 7)
A step of heat-treating at least one of the cellulose raw material and urea and a derivative of urea to replace a part or all of the hydroxy groups of the cellulose raw material with a carbamate group.
It has a step of defibrating the cellulose raw material in a range where the average fiber width is 0.1 μm or more.
The heat treatment was carried out so that the substitution rate of the carbamate group was 1.0 mmol / g or more.
The defibration is performed so that the fine ratio is 10% or more and 35% or less.
A method for producing fibrous cellulose.

According to the invention, there is a method for producing a fibrous cellulose having a high resin reinforcing effect, a high-strength fibrous cellulose composite resin, and a fibrous cellulose having a high resin reinforcing effect.

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.

The fibrous cellulose of this embodiment (hereinafter, also referred to as “cellulose fiber”) has an average fiber width (diameter) of 0.1 μm or more, and a part or all of hydroxy groups (−OH groups) are replaced with carbamate groups. Has been done. In addition, the substitution rate of the carbamate group is 1.0 mmol / g or more, and the fine rate is 10% or more and 35% or less. Further, the fibrous cellulose composite resin is formed by containing the fibrous cellulose and the resin. Further, in the method for producing fibrous cellulose, a step of heat-treating at least one of the cellulose raw material and urea and a derivative of urea to replace a part or all of the hydroxy groups of the cellulose raw material with a carbamate group, and cellulose. It has a step of defibrating the raw material in a range where the average fiber width is 0.1 μm or more to obtain microfiber cellulose. Then, the heat treatment is performed so that the substitution rate of the carbamate group is 1.0 mmol / g or more, and the defibration is performed so that the fine rate is 10% or more and 35% or less. Hereinafter, a detailed description will be given.

(Fibrous cellulose)
The fibrous cellulose composite resin of the present embodiment contains fibrous cellulose (hereinafter, also referred to as “cellulose fiber”), a resin, and preferably an acid-modified resin. When the acid-modified resin is contained, a part or all of the carbamate groups are ionically bonded to the acid group of the acid-modified resin.

The fibrous cellulose which is a fine fiber in this embodiment is a microfiber cellulose (microfibrillated cellulose) having an average fiber diameter of 0.1 μm or more. When it 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 raw material before it is miniaturized, and in this case, the microfiber cellulose and the cellulose nanofiber are equivalent.

In this embodiment, microfiber cellulose means fibers having an average fiber width wider than that of cellulose nanofibers. Specifically, the average fiber diameter is, for example, 0.1 to 20 μm, preferably 0.2 to 19 μm, and more preferably more than 0.5 to 18 μm. If 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 flexural 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 for 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) 20 μm, it is no different from pulp, and the reinforcing effect may not be sufficient.

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 trees, coniferous trees, etc., non-wood pulp made from straw, bagasse, cotton, hemp, carrot fiber, etc., recycled paper pulp made from recovered waste paper, waste paper, etc. One type or two or more types can be selected and used from (DIP) and the like. The above-mentioned various raw materials may be in the state of a crushed product (powder) called, for example, a cellulosic powder.

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 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. Similarly, the softwood kraft pulp may be softwood bleached kraft pulp, softwood unbleached kraft pulp, or softwood semi-bleached kraft pulp.

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), ground pulp (GP), and the like. 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.

Raw pulp can be pretreated by chemical methods prior to defibration. Pretreatments by chemical methods include, for example, hydrolysis of polysaccharides with acid (acid treatment), hydrolysis of polysaccharides with enzymes (enzyme treatment), swelling of polysaccharides with alkali (alkali treatment), and oxidation of polysaccharides with oxidizing agents (alkaline treatment). Oxidation treatment), reduction of polysaccharides with a reducing agent (reduction treatment), and the like can be exemplified. However, as the pretreatment by the 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.

As the enzyme used for the enzyme treatment, it is preferable to use at least one of a cellulase-based enzyme and a 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 induces the decomposition of cellulose in the coexistence of water. In addition, hemicellulose-based enzymes induce the decomposition of hemicellulose in the presence of water.

Examples of cellulase-based enzymes include the genus Trichoderma, the genus Acremonium, the genus Aspergillus, the genus Fanerochaete, the genus Trametes, and the genus Trametes. Bacteria, Humicola, filamentous fungi, Bacillus, bacteria, Schizophyllum, Streptomyces, bacteria, Pseudomonas, bacteria, etc. Enzymes can be used. These cellulase-based enzymes can be purchased as reagents or commercially available products. Commercially available products include, for example, cell leucine T2 (manufactured by HPI), Meicerase (manufactured by Meiji Seika), Novozyme 188 (manufactured by Novozyme), Multifect CX10L (manufactured by Genencore), and cellulase enzyme GC220 (manufactured by Genecore). Manufactured by) and the like can be exemplified.

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. Alternatively, it may be used in combination with a hemicellulase-based enzyme.

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.

Hemicellulose is a polysaccharide excluding pectins located between cellulose microfibrils in 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 softwoods, 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.

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 adding the enzyme may not be sufficiently obtained. On the other hand, if the amount of the enzyme added exceeds 3% by mass, cellulose may be saccharified and the yield of fine fibers may decrease. In addition, there is also a problem that the improvement of the effect corresponding to the increase in the addition amount cannot be recognized.

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).

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 unlikely to decrease, and it is possible to prevent a long treatment time. 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.

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.

After the enzyme treatment, it is preferable to inactivate the enzyme. 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.

Next, the method of alkali treatment will be described.
When alkali treatment is performed prior to defibration, some of the hydroxyl groups of hemicellulose and cellulose contained in pulp are dissociated, and the molecules are anionized, weakening the intramolecular and intermolecular hydrogen bonds and promoting the dispersion of the cellulose raw material in defibration. NS.

Examples of the alkali used for the alkali treatment include sodium hydroxide, lithium hydroxide, potassium hydroxide, aqueous ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide and the like. Organic alkali or the like can be used. However, from the viewpoint of manufacturing cost, it is preferable to use sodium hydroxide.

When an enzyme treatment, an acid treatment, or an oxidation treatment is performed prior to the defibration, the water retention degree of the microfiber cellulose can be lowered, the crystallinity 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.

When the raw material pulp is subjected to enzyme treatment, acid treatment, or oxidation treatment, hemicellulose and the amorphous region of cellulose contained in the pulp 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 reduces 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.

For defibration of raw pulp, for example, beaters, high-pressure homogenizers, homogenizers such as high-pressure homogenizers, stone mill type friction machines such as grinders and grinders, single-screw kneaders, multi-screw kneaders, kneader refiners, jet mills, etc. It can be done by beating the raw material pulp in use. However, 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. be. If the average fiber length is less than 0.10 mm, a three-dimensional network of fibers cannot be formed, and the flexural modulus of the composite resin may decrease. However, it may be said that the reinforcing effect is not improved. On the other hand, if the average fiber length exceeds 2.00 mm, the reinforcing effect may be insufficient because the length is the same as that of the raw material pulp.

The average fiber length of the cellulose raw material used as the raw material for the 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 the microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration and the like.

The fine ratio of the microfiber cellulose is preferably 10% or more and 35% or less, more preferably 11 to 33%, and particularly preferably 13 to 31%. When the fine ratio is 10% or more, the proportion of homogeneous fibers is secured to some extent, and the homogeneity of the composite resin is ensured. As a result, the flexural modulus is secured. However, if the fine ratio exceeds 35%, the fluidity of the composite resin may decrease, and the homogeneity of the composite resin may decrease due to this decrease in fluidity, resulting in insufficient reinforcing effect. .. In this regard, the present inventors have found that when the fine ratio is 35% or less, the fluidity of the composite resin is high, and the strands can be drawn even when the fiber content is 55%.

The above is the fine ratio of the microfiber cellulose, but it is more preferable that the fine ratio of the cellulose raw material which is the raw material of the microfiber cellulose is also within a predetermined range. Specifically, the fine ratio of the cellulose raw material, which is the raw material of the microfiber cellulose, is preferably 1% or more, more preferably 3 to 20%, and particularly preferably 5 to 18%. If the fine ratio of the cellulose raw material before defibration is within the above range, it is considered that the fiber damage after defibration is small and the reinforcing effect of the resin is improved.

The fine ratio can be adjusted by pretreatment such as enzyme treatment. However, especially in the case of enzymatic treatment, the fibers themselves may become tattered and the reinforcing effect of the resin may be reduced. Therefore, the amount of the enzyme added from this viewpoint is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. Further, it is also one of the selection frames that the enzyme treatment is not performed (addition amount: 0% by mass).

In the present embodiment, the "fine ratio" refers to a mass-based ratio of pulp fibers having a fiber length of 0.2 mm or less.

The aspect ratio of the microfiber cellulose is preferably 2 to 15,000, more preferably 10 to 10,000. If the aspect ratio is less than 2, the three-dimensional network cannot be sufficiently constructed, and therefore, even if the average fiber length is 0.10 mm or more, the reinforcing effect may be insufficient. On the other hand, if the aspect ratio exceeds 15,000, the entanglement of the microfiber celluloses becomes high, and the dispersion in the resin may be insufficient.

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 risk that a strong three-dimensional network cannot be formed.

In the present embodiment, the fibrillation rate refers to the dissociation of cellulose fibers in accordance with JIS-P-8220: 2012 "Pulp-Dissolution Method", and the obtained dissociated pulp is referred to as FiberLab. (Kajaani) means a value measured using.

The crystallinity of the microfiber cellulose is preferably 50% or more, more preferably 55% or more, and particularly preferably 60% or more. When the crystallinity is less than 50%, the mixability with pulp and cellulose nanofibers is improved, but the strength of the fibers themselves is lowered, so that the strength 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.

The crystallinity of the microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, and micronization treatment.

The pulp viscosity of the microfiber cellulose is preferably 4 cps or more, more preferably 5 cps or more. If the pulp viscosity of the microfiber cellulose is less than 4 cps, it may be difficult to suppress the aggregation of the microfiber cellulose. In this respect, when the pulp viscosity is 4 cps or more, the fine ratio of the microfiber cellulose is set to 35% or less, and therefore, even if long fibers may be present, the aggregation of the long fibers is suppressed and the resin reinforcing effect is obtained. It can be played reliably.

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 20 μm, and the effect of improving the strength of the resin may not be sufficiently obtained.

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 water retention rate exceeds 400%, the dehydration property tends to be inferior and the water retention tends to be agglomerated. In this respect, the water retention of the microfiber cellulose can be lowered by substituting the hydroxy group of the fiber with a carbamate group, and the dehydration property and the drying property can be improved.

The water retention degree of the microfiber cellulose can be arbitrarily adjusted by, for example, selection of raw material pulp, pretreatment, defibration and the like.

Microfiber cellulose 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 carbamateized to have a carbamate group, or the microfiber cellulose (finely divided cellulose raw material) may be carbamate to have a carbamate group. ..

In addition, having a carbamate group means a state in which a carbamate group (ester of carbamic acid) is introduced into fibrous cellulose. The carbamate group is a group represented by -O-CO-NH-, for example, a group represented by -O-CO-NH ₂ , -O-CONHR, -O-CO-NR _{2, and the} like. That is, the carbamate group can be represented by the following structural formula (1).

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. It is an aromatic group and at least one of these inducing groups.

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.

Examples of the saturated branched chain hydrocarbon group include a branched 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.

Examples of the saturated cyclic hydrocarbon group 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 a −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 propen-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.

Examples of the aromatic group include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group and the like.

Examples of the inducing group include the above-mentioned saturated linear hydrocarbon group, saturated branched chain hydrocarbon group, saturated cyclic hydrocarbon group, unsaturated linear hydrocarbon group, unsaturated branched chain hydrocarbon group and aromatic. Examples thereof include a group in which one or more hydrogen atoms contained in the group are substituted with a substituent (for example, a hydroxy group, a carboxy group, a halogen atom, etc.).

In microfiber cellulose having a carbamate group (in which a carbamate group is introduced), some or all of the highly polar hydroxy groups are replaced with relatively less polar carbamate groups. Therefore, the microfiber cellulose having a carbamate group has low hydrophilicity and high affinity with a resin having low polarity. As a result, the microfiber cellulose having a carbamate group is excellent in uniform dispersibility with the resin. Further, the slurry of microfiber cellulose having a carbamate group has low viscosity and good handleability.

The substitution rate of the carbamate group with respect to the hydroxy group of the microfiber cellulose is preferably 1.0 to 5.0 mmol / g, more preferably 1.2 to 3.0 mmol / g, and particularly preferably 1.5 to 2.0 mmol / g. g. When the substitution rate is 1.0 mmol / g or more, the effect of introducing the carbamate group, particularly the effect of improving the flexural modulus of the resin can be surely exhibited. On the other hand, if the substitution rate exceeds 5.0 mmol / g, the cellulose fibers may not be able to maintain the shape of the fibers, and the resin reinforcing effect may not be sufficiently obtained. Further, when the substitution rate of the carbamate group exceeds 2.0 mmol / g, the average fiber length of the pulp becomes short when the raw material pulp is carbamate, and as a result, the average fiber length of the microfiber cellulose becomes less than 0.1 mm. There is a risk that sufficient resin reinforcement effect cannot be obtained.

In this embodiment, 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. The substitution rate of the carbamate group is determined by measuring the N atoms present in the carbamate pulp by the Kjeldahl method and calculating the carbamate rate per unit weight. Cellulose is a polymer having anhydrous glucose as a structural unit, and has three hydroxy groups per structural unit.

<Carbamate>
As described above, the point of introducing a carbamate group (carbamate) into microfiber cellulose (in the case of carbamate before defibration, it is a cellulose raw material. The same applies hereinafter, and is also referred to as "microfiber cellulose or the like"). There are two methods, one is to carbamate the cellulose raw material and then refine it, and the other is to miniaturize the cellulose raw material and then carbamate it. In this regard, in the present specification, the defibration of the cellulose raw material will be described first, and then the carbamate formation (degeneration) will be described. However, either defibration or carbamate can be done 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.

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.

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 or a derivative of urea (hereinafter, also simply referred to as “urea or the like”) are mixed in a dispersion medium. Mix.

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 or derivatives of urea can be used alone or in combination of two or more. However, it is preferable to use urea.

The lower limit of the mixed mass ratio of urea or the like to microfiber cellulose or the like (urea or the like / 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 carbamate formation reaches a plateau.

The dispersion medium is usually water. However, other dispersion media such as alcohol and ether, or a mixture of water and another dispersion medium may be used.

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.

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.

The dispersion medium is preferably removed 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.

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. The dispersion medium can be efficiently volatilized (removed) by setting the heating temperature to 50 ° C. or higher. 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 reacts with urea, and 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.

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 the hydroxy groups such as microfiber cellulose react with urea and the like and are replaced with carbamate groups. More specifically, when urea or the like is heated, it is decomposed into isocyanic acid and ammonia as shown in the following reaction formula (1). Isocyanic acid is very reactive, and for example, a carbamate group is formed at the hydroxyl group of cellulose as shown in the following reaction formula (2).
NH _2- CO-NH ₂ → H-N = C = O + NH ₃ ... (1)
Cell-OH + H-N = C = O → Cell-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 greater than or equal to the melting point of urea (about 134 ° C.), 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.

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 15 hours is sufficient for carbamate formation.

However, a long heating time causes deterioration of the cellulose fibers. Therefore, the pH condition in the heat treatment is 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 reaction is carried out efficiently. Therefore, 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-forming reaction is carried out 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.

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.

As an apparatus for heating in the heat treatment, for example, a hot air dryer, a paper machine, a dry pulp machine and the like can be used.

The mixture after heat treatment may be washed. This cleaning may be performed with water or the like. By this washing, urea and the like remaining unreacted can be removed.

(slurry)
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.

The solid content concentration of the slurry is preferably 2 to 10% by mass, more preferably 3 to 8% by mass. If the solid content concentration is less than 2% by mass, excessive energy may be required for dehydration and drying. On the other hand, if the solid content concentration exceeds 10% by mass, the fluidity of the slurry itself is lowered, and even when a dispersant is used, it may not be possible to mix uniformly. In this respect, for example, when the fine ratio exceeds 35%, the upper limit of the slurry solid content concentration is 4.0% by mass from the viewpoint of ensuring fluidity. On the other hand, when the fine ratio is 35% or less, the upper limit is 10 (preferably 6.0) mass% as described above. Therefore, if the fine ratio is 35% or less and the slurry solid content concentration is 10% by mass or less, the amount of the aqueous medium that needs to be removed from the slurry can be reduced, and the solid content concentration can be increased. There are also advantages such as cost reduction.

(Acid-modified resin)
In the acid-modified resin, as described above, the acid group ionically bonds with a part or all of the carbamate group. This ionic bond improves the reinforcing effect of the resin.

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.

As the polyolefin component, for example, one 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.

As the unsaturated carboxylic acid component, for example, one or more of maleic anhydride, phthalic anhydride, itaconic anhydride, citraconic anhydride, citric acid anhydride and the like can be selected and used. However, 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. 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.

The weight average molecular weight of maleic anhydride-modified polypropylene is, for example, 1,000 to 100,000, preferably 3,000 to 50,000.

The acid value of maleic anhydride-modified polypropylene is preferably 0.5 mgKOH / g or more and 100 mgKOH / g or less, and more preferably 1 mgKOH / g or more and 50 mgKOH / g or less.

Further, the MFR (melt flow rate) of the acid-modified resin is preferably 2000 g / 10 minutes (190 ° C. / 2.16 kg) or less, more preferably 1500 g / 10 minutes or less, and 500 g / 10 minutes or less. Is particularly preferable. If the MFR exceeds 2000 g / 10 minutes, the dispersibility of the cellulose fibers may decrease.

The acid value is measured in accordance with JIS-K2501 and titrated with potassium hydroxide. The MFR measurement is based on JIS-K7210, and is determined by the weight of the sample flowing out in 10 minutes with a load of 2.16 kg at 190 ° C.

(Dispersant)
Cellulose feedstock or microfiber cellulose becomes more preferred when mixed with a dispersant. As the dispersant, a compound having an amine group and / or a hydroxyl group in the aromatic and a compound having an amine group and / or a hydroxyl group in the aliphatic are preferable.

Examples of compounds having an amine group and / or a hydroxyl group in aromatics include aniline, toluidine, trimethylaniline, anicidin, tyramine, histamine, tryptamine, phenol, dibutylhydroxytoluene, and bisphenol A. Classes, cresols, eugenols, gallic acids, guaiacols, picric acids, phenolphthalines, serotonins, dopamines, adrenalines, noradrenalines, timols, tyrosine, salicylic acids, methyl salicylates, anis alcohols. , Salicylic alcohols, cinapyl alcohols, diphenidols, diphenylmethanol, 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, ellaidyl alcohols, oleyl alcohols, linoleyl alcohols, methylamines, dimethylamines, trimethylamines, ethylamines, diethylamines, ethylenediamine , Triethanolamines, N, N-diisopropylethylamines, tetramethylethylenediamines, hexamethylenediamines, spermidins, spermins, amantazines, 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, margaric acids, stearic acids, oleic acids, linoleic acids, linoleyl acids, arachidonic acids, eicosapentaenoic acids, docosahexaenoic acids, sorbin Acids and the like can be mentioned.

The above dispersant inhibits hydrogen bonds between cellulose fibers. Therefore, when the microfiber cellulose and the resin are kneaded, the microfiber cellulose is surely dispersed in the resin. Further, the above dispersant also has a role of improving the compatibility between the microfiber cellulose and the resin. In this respect, the dispersibility of the microfiber cellulose in the resin is improved.

It is conceivable to add a phase solvent (drug) separately when kneading the fibrous cellulose and the resin, but the fibrous cellulose and the dispersant (drug) are mixed in advance rather than adding the chemical at this stage. In this case, the chemicals are more uniformly attached to the fibrous cellulose, and the effect of improving the compatibility with the resin is enhanced.

Further, for example, polypropylene has a melting point of 160 ° C., and therefore, kneading of fibrous cellulose and resin is performed 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, resins with a low melting point generally have low strength. Therefore, according to this method, the strength of the composite resin may decrease.

The mixing amount of the dispersant 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, it becomes excessive and the resin strength tends to decrease.

In this respect, the above-mentioned acid-modified resin is for improving compatibility by ionic bonding between an acid group and a carbamate group of microfiber cellulose, thereby enhancing a reinforcing effect, and since it has a large molecular weight, it is easy to be compatible with a 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 celluloses 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 an acid-modified resin 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.

To explain this point in more detail, the resin powder physically intervenes between the microfiber celluloses to inhibit hydrogen bonds, thereby improving the dispersibility of the microfiber celluloses. On the other hand, the acid-modified resin improves compatibility by ionic bonding an acid group and a carbamate group of microfiber cellulose, thereby enhancing a reinforcing effect. In this respect, the dispersant inhibits hydrogen bonds between microfiber celluloses in the same manner, but since the resin powder is in the micro order, it physically intervenes and suppresses hydrogen bonds. Therefore, although the dispersibility is lower than that of the dispersant, the resin powder itself melts into a matrix, which does not contribute to deterioration of physical properties. 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.

(Production method)
The mixture of fibrous cellulose, acid-modified resin, dispersant and the like can be dried and pulverized before kneading with the resin to form a powder. According to this form, it is not necessary to dry the fibrous cellulose when kneading with the resin, and the thermal efficiency is good. Further, when a dispersant is mixed in the mixture, there is a low possibility that the fibrous cellulose (microfiber cellulose) will not be redispersed even if the mixture is dried.

If necessary, the mixture is dehydrated to dehydration prior to drying. For this dehydration, for example, one 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.

The 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 carried out by selectively using one type or two or more types from the above.

The dried mixture (dried product) is crushed into a powder. The pulverization of the dried product can be carried out by selecting or using one or more of, for example, a bead mill, a kneader, a disper, a twist mill, a cut mill, a hammer mill and the like.

The average particle size of the powder is preferably 1 to 10,000 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 reduce the average particle size of the powder to less than 1 μm.

The average particle size of the powder can be controlled by controlling the degree of pulverization and 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. When the bulk specific density exceeds 1.0, it means that the hydrogen bonds between the fibrous celluloses are stronger and it is not easy to disperse them in the resin. On the other hand, setting the bulk specific density to less than 0.03 is disadvantageous in terms of transfer cost.

The bulk relative 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, with the mass at the time when the sample is held at 105 ° C. for 6 hours or more at 105 ° C. and no change in mass is observed using a constant temperature dryer as the mass after drying.
Fiber moisture content (%) = [(mass before drying-mass after drying) / mass before drying] x 100

The dehydrated and dried microfiber cellulose may contain a resin. When the resin is contained, the hydrogen bonds between the dehydrated and dried microfiber celluloses are inhibited, and the dispersibility in the resin at the time of kneading can be improved.

Examples of the form of the resin contained in the dehydrated / dried microfiber cellulose include powder, pellet, and sheet. However, powder (powdered resin) is preferable.

In the case of powder, the average particle size of the resin powder contained in the dehydrated and dried microfiber cellulose 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 exceeds 10,000 μm, it may not enter the kneading device due to the large particle size. On the other hand, if the average particle size is less than 1 μm, hydrogen bonds between microfiber celluloses may not be inhibited due to the fineness. The resin such as the powder resin used here may be the same type as or different from the resin (resin as the main raw material) kneaded with the microfiber cellulose, but it is preferable that the resin is the same type.

The resin powder having an average particle size of 1 to 10,000 μm is preferably mixed in an aqueous dispersion state before dehydration and drying. By mixing in an aqueous-based dispersion state, the resin powder can be uniformly dispersed between the microfiber celluloses, and the microfiber celluloses can be uniformly dispersed in the composite resin after kneading, further improving the strength and physical characteristics. Can be done.

The powdery substance (resin reinforcing material) obtained as described above is kneaded with a resin to obtain a fibrous cellulose composite resin. This kneading can be performed by, for example, a method of mixing the pellet-shaped resin and the powdery material, or a method of first melting the resin and then adding the powdery material to the melted material. The acid-modified resin, dispersant and the like can also be added at this stage.

For the kneading process, for example, one or two or more kinds are selected and used from a single-screw or two-screw or more 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 them, it is preferable to use a multi-screw kneader with 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.

As the resin, at least one of a thermoplastic resin and a thermosetting resin can be used.

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 type or two or more types can be selected and used from polycarbonate resin, polyacetal resin and the like.

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 (also referred to simply as "biodegradable resin").

As the biodegradable resin, for example, one or more of hydroxycarboxylic acid-based aliphatic polyesters, caprolactone-based aliphatic polyesters, dibasic acid polyesters and the like can be selected and used.

As the hydroxycarboxylic acid-based aliphatic polyester, for example, a homopolymer of hydroxycarboxylic acid such as lactic acid, malic acid, glucose acid, 3-hydroxybutyric acid, or at least one of these hydroxycarboxylic acids is used. One kind or two or more kinds can be selected and used from the polymer and the like. However, it is preferable to use polylactic acid, a polymer of lactic acid and the above-mentioned hydroxycarboxylic acid excluding lactic acid, polycaprolactone, or a polymer of at least one of the above-mentioned hydroxycarboxylic acids and caprolactone, and polylactic acid is used. Especially preferred to use.

As the 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.

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 above-mentioned hydroxycarboxylic acid, and the like. ..

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.

As the biodegradable resin, one type may be used alone, or two or more types may be used in combination.

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.

The resin may preferably contain an inorganic filler in a proportion that does not interfere with thermal recycling.

Examples of the inorganic filler include simple substances and oxidation of metal elements in Groups I to VIII of the Periodic Table of the Periodic Table, such as Fe, Na, K, Cu, Mg, Ca, Zn, Ba, Al, Ti, and silicon elements. Examples thereof include substances, hydroxides, carbon salts, sulfates, silicates, sulfites, and various clay minerals composed of these compounds.

Specifically, for example, barium sulfate, calcium sulfate, magnesium sulfate, sodium sulfate, calcium sulfite, zinc oxide, silica, heavy calcium carbonate, light calcium carbonate, aluminum borate, alumina, iron oxide, calcium titanate, hydroxylation. Examples of aluminum, magnesium hydroxide, calcium hydroxide, sodium hydroxide, magnesium carbonate, calcium silicate, clay walastonite, glass beads, glass powder, silica sand, silica stone, quartz powder, diatomaceous earth, white carbon, glass fiber and the like are exemplified. be able to. A plurality of these inorganic fillers may be contained. Further, it may be contained in used paper pulp.

The blending ratio of the fibrous cellulose and the resin is preferably 1 part by mass or more for the fibrous cellulose, 99 parts by mass or less for the resin, more preferably 2 parts by mass or more for the fibrous cellulose, and 98 parts by mass or less for the resin, particularly preferably. The amount of fibrous cellulose is 3 parts by mass or more, and the amount of resin is 97 parts by mass or less. Further, preferably, fibrous cellulose is 50 parts by mass or less, resin is 50 parts by mass or more, more preferably fibrous cellulose is 40 parts by mass or less, resin is 60 parts by mass or more, and particularly preferably fibrous cellulose is 30 parts by mass or less. , The resin is 70 parts by mass or more. In particular, when the fibrous 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 fibrous cellulose and the resin finally obtained in the resin composition is usually the same as the above-mentioned compounding ratio of the fibrous cellulose and the resin.

If the difference between the solubility parameters (cal / cm ³ ) ^1/2 (SP value) of 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 It can be a −SP _{POL value.} The difference in SP value is preferably 10 to 0.1, more preferably 8 to 0.5, and particularly preferably 5 to 1. If the difference in SP value exceeds 10, the microfiber cellulose may not be dispersed in the resin, and the reinforcing effect may not be obtained. On the other hand, if the difference in SP value is less than 0.1, the microfiber cellulose dissolves in the resin and does not function as a filler, so that a 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 intermolecular force acting between the solvent and the solute, and the closer the SP value is to the solvent and solute, the higher the solubility. ..

(Molding process)
The kneaded product of fibrous cellulose and 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-shaped, pellet-shaped, powder-shaped, fibrous-shaped, or the like.

The temperature during the molding process is equal to or higher than the glass transition point of the resin and varies depending on the type of resin, but is, for example, 90 to 260 ° C, preferably 100 to 240 ° C.

The kneaded product can be molded 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 produced by, for example, a method of simultaneously depositing with an air ray.

The device for molding the kneaded product is, 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, pressure molding machines, and the like. More than a species can be selected and used.

The above molding can be performed after kneading, or the kneaded product is once cooled and made into chips by using a crusher or the like, and then the chips are put into a molding machine such as an extrusion molding machine or an injection molding machine. You can also do it. Of course, molding is not an essential requirement of the present invention.

(Other compositions)
The fibrous cellulose may contain cellulose nanofibers together with microfiber cellulose. Cellulose nanofibers are fine fibers like microfiber cellulose, and have a role of complementing microfiber cellulose for improving the strength of the resin. 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.

Further, the fibrous cellulose may contain pulp. Pulp has a role of significantly improving the dehydration property of the cellulose fiber slurry. However, as in the case of cellulose nanofibers, it is most preferable that pulp is not blended, that is, the content is 0% by mass.

In addition to fine fibers and pulp, the resin composition includes kenaf, jute hemp, Manila hemp, sisal hemp, ganpi, sansho, 楮, banana, pineapple, coco palm, corn, sugar cane, bagasse, palm, papyrus, reeds, esparto, etc. Fibers derived from plant materials obtained from various plants such as survivorgrass, wheat, rice, bamboo, various coniferous trees (sugi and hinoki, etc.), broadleaf trees and cotton may be included.

For the resin composition, for example, one or more selected from antistatic agents, flame retardants, antibacterial agents, colorants, radical scavengers, foaming agents, etc., within a range that does not impair the effects of the present invention. Can be added with. These raw materials may be added to the dispersion of fibrous cellulose, added at the time of kneading the fibrous cellulose and the resin, added to these kneaded products, or added by other methods. good. However, from the viewpoint of production efficiency, it is preferable to add it at the time of kneading the fibrous cellulose and the resin.

The 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.

The MFR (melt flow rate) of the resin composition (preferably when the fiber content is 55%) is preferably 0.01 to 20 g / 10 minutes, more preferably 0.02 to 10 g / 10 minutes, and particularly preferably. Is 0.03 to 5 g / 10 minutes. If the MFR is 0.01 g / 10 minutes or more, the strands can be reliably pulled. However, if the MFR exceeds 1.0 g / 10 minutes, the molecular weight of the base resin may be reduced too much, and the required strength and physical characteristics may not be satisfied.

The measurement of MFR is the same as that for the acid-modified resin described above. Further, in the present specification, whether or not the strands can be pulled is determined by a small experimental machine (small biaxial kneading having a shaft length L, a shaft diameter D of D = 15 mm, and an axial ratio L / D = 15). It can be said that if a simple device with L / D = about 15 can pull the strands without any problem, a normal device can also pull the strands. In addition, the fact that a small testing machine can be used means that any device can be used, which has the advantage of eliminating the need for additional capital investment. Incidentally, when the L / D is large, the composite resin is kneaded more, so that the dispersion of MFC and the homogenization of the composite resin proceed, and the fluidity of the composite resin is improved. According to the knowledge of the present inventors, the strand can be drawn by any of the devices of D = 48 and L / D = 48 and the devices of D = 30 and L / D = 60.

(Definition, measurement method, etc.)
(Average fiber diameter)
The method for measuring the average fiber diameter of fine fibers (microfiber cellulose and cellulose nanofibers) is as follows.
First, 100 ml of an aqueous dispersion of fine fibers having a solid content concentration of 0.01 to 0.1% by mass is filtered through a membrane filter made of Teflon (registered trademark), and the solvent is replaced once with 100 ml of ethanol and three times with 20 ml of t-butanol. do. Next, it is freeze-dried and coated with osmium to prepare a sample. This sample is observed by 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 median diameter of the measured value is taken as the average fiber diameter.

(aspect ratio)
The aspect ratio is a value obtained by dividing the average fiber length by the average fiber width. It is considered that the larger the aspect ratio, the more places where the resin is caught, so that the reinforcing effect is improved, but on the other hand, the greater the number of catches, the lower the ductility of the resin.

(Water retention)
The degree of water retention is determined by JAPAN TAPPI No. It is a value measured according to 26 (2000).

(Fiber analysis)
The fine rate (fine rate), fibrillation rate, average fiber length and the like are values measured by a fiber analyzer "FS5" manufactured by Valmet.

(Crystallinity)
The crystallinity is a value measured according to JIS K 0131 (1996).

(viscosity)
The pulp viscosity is a value measured according to TAPPI T 230.

(B type viscosity)
The B-type viscosity (solid content concentration 1%) of the dispersion liquid is a value measured in accordance with "Method for measuring liquid viscosity" of JIS-Z8803 (2011). The B-type viscosity is the resistance torque when the dispersion liquid is stirred, and the higher it is, the more energy is required for stirring.

(Freeness)
Freeness is a value measured in accordance with JIS P8121-2 (2012).

Next, examples of the present invention will be described.
Using coniferous kraft pulp with a water content of 10% or less, a urea aqueous solution with a solid content concentration of 10%, and various pH adjusting solutions, the formulations shown in Table 1 in terms of mass ratio in terms of solid content (the amount of the pH adjusting solution is described. Since urea is a weak base, the pH adjusting solution is mixed so that the amount is small (about 0.02 to 0.2 g / urea g), and then dried at 105 ° C. .. Then, 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. The washed carbamate-modified pulp was beaten with a Niagara beater for 1 hour to obtain carbamate-modified microfiber cellulose having a Fine ratio of 24%.

27.5 g of maleic anhydride-modified polypropylene and 17.5 g of polypropylene powder were added to 2750 g of a carbamate-modified microfiber cellulose aqueous dispersion having a solid content concentration of 2% by mass, and the mixture was heated and dried at 105 ° C. to obtain a carbamate-modified microfiber cellulose-containing substance. Obtained. The water content of this carbamate-modified microfiber cellulose-containing material was less than 20%.

The carbamate-modified microfiber-containing material obtained as described above 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 having a fiber content of 55%. To this carbamate-modified microfiber cellulose composite resin, polypropylene pellets are added and mixed so that carbamate-modified microfibers: other components = 10:90, and kneaded at 180 ° C. and 200 rpm with a twin-screw kneader to make the fibers. A carbamate-modified microfiber cellulose composite resin having a blending ratio of 10% was obtained.

The carbamate-modified microfiber cellulose composite resin having a fiber content of 10% is cut into a columnar shape having a diameter of 2 mm and a length of 2 mm with a pelleter, and a rectangular parallelepiped test piece (length 59 mm, width 9.6 mm, thickness 3.8 mm) at 180 ° C. ) Was injection molded. It was visually confirmed whether or not the strands could be pulled with respect to the composite resin having a fiber compounding ratio of 55%, and the flexural modulus was examined for the composite resin having a fiber compounding ratio of 10%. The results are shown in Table 1.

The flexural modulus was measured in accordance with JIS K7171: 2008. In the table, when the flexural modulus (1.38 GPa) of the resin itself (blank) is 1, and the flexural modulus (magnification) of the composite resin is 1.40 times or more, it is "○", and it is less than 1.40 times. The case is shown as "x". Further, the strands were tested with the above-mentioned small experimental aircraft, and the case where they could be closed was marked with "○" and the case where they could not be closed was marked with "x".

The present invention can be used as a method for producing fibrous cellulose, fibrous cellulose composite resin and fibrous cellulose. For example, fibrous cellulose composite resin is used for interior materials, exterior materials, structural materials, etc. of transportation equipment such as automobiles, trains, ships, and airplanes; Parts, etc .; Housings for mobile communication equipment such as mobile phones, structural materials, internal parts, etc .; Housings for portable music playback equipment, video playback equipment, printing equipment, copying equipment, sports equipment, office equipment, toys, sports equipment, etc. Structural materials, internal parts, etc .; Interior materials such as buildings and furniture, exterior materials, structural materials, etc .; Office equipment such as stationery; It is available.

Claims (7)

The average fiber width is 0.1 μm or more, and some or all of the hydroxyl groups are substituted with carbamate groups.
When the substitution rate of the carbamate group is 1.0 mmol / g or more,
The fine rate is 10% or more and 35% or less.
Fibrous cellulose characterized by that. The fine ratio of the cellulose raw material used as the raw material is 1% or more.
The fibrous cellulose according to claim 1. The cellulose raw material is not treated with an enzyme, or the amount of the enzyme added is in a range of 2% by mass or less of the cellulose raw material.
The fibrous cellulose according to claim 2. Pulp viscosity is 4 cps or more,
The fibrous cellulose according to any one of claims 1 to 3. Contains fibrous cellulose and resin,
The fibrous cellulose is
The average fiber width is 0.1 μm or more, and some or all of the hydroxyl groups are substituted with carbamate groups.
When the substitution rate of the carbamate group is 1.0 mmol / g or more,
The fine rate is 10% or more and 35% or less.
A fibrous cellulose composite resin characterized by this. The MFR measured according to JIS-K7210 (190 ° C., 2.16 kg) is 0.01 to 20 g / 10 minutes.
The fibrous cellulose composite resin according to claim 5. A step of heat-treating at least one of the cellulose raw material and urea and a derivative of urea to replace a part or all of the hydroxy groups of the cellulose raw material with a carbamate group.
It has a step of defibrating the cellulose raw material in a range where the average fiber width is 0.1 μm or more.
The heat treatment was carried out so that the substitution rate of the carbamate group was 1.0 mmol / g or more.
The defibration is performed so that the fine ratio is 10% or more and 35% or less.
A method for producing fibrous cellulose.