WO2021075224A1 - セルロース複合体の製造方法、セルロース複合体/樹脂組成物の製造方法、セルロース複合体、及びセルロース複合体/樹脂組成物 - Google Patents
セルロース複合体の製造方法、セルロース複合体/樹脂組成物の製造方法、セルロース複合体、及びセルロース複合体/樹脂組成物 Download PDFInfo
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- WO2021075224A1 WO2021075224A1 PCT/JP2020/036244 JP2020036244W WO2021075224A1 WO 2021075224 A1 WO2021075224 A1 WO 2021075224A1 JP 2020036244 W JP2020036244 W JP 2020036244W WO 2021075224 A1 WO2021075224 A1 WO 2021075224A1
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- cellulose
- polymer
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/14—Copolymers of propene
Definitions
- the present invention relates to a method for producing a cellulose complex, a method for producing a cellulose complex / resin composition, a cellulose complex, and a cellulose complex / resin composition.
- the present invention relates to a method for producing a cellulose composite capable of substantially uniformly dispersing cellulose in a non-polar resin, a method for producing a cellulose composite / resin composition, a cellulose composite, and a cellulose composite /.
- resin composition Regarding resin composition.
- Cellulose and cellulose nanofibers are obtained by using pulp or the like as a raw material and undergoing mechanical defibration in water, and therefore exist in a state of containing a large amount of aqueous dispersion and water.
- CNF Cellulose and cellulose nanofibers
- the usual heat-drying treatment is applied to the cellulose or CNF, the cellulose or CNF becomes a strong aggregate due to the hydrogen bond of the cellulose or CNF. Even if this aggregate is crushed, the effect originally expected as cellulose or CNF is not exhibited. Therefore, various methods for taking out CNF capable of suppressing aggregation of cellulose and CNF and a method for dispersing cellulose in a resin for the purpose of suppressing aggregation have been studied.
- compositions containing cellulose and a dispersant, in which the dispersant has a resin affinity segment A and a cellulose affinity segment B, and has a block copolymer structure or a gradient copolymer structure.
- compositions are known (see, for example, Patent Document 1). According to the composition described in Patent Document 1, the dispersibility of cellulose in the resin can be improved.
- an object of the present invention is a method for producing a cellulose composite, which can disperse cellulose substantially uniformly in a resin without adding a compatibilizer (dispersant) while maintaining the characteristics of cellulose. It is an object of the present invention to provide a method for producing a cellulose composite / resin composition, a cellulose composite, and a cellulose composite / resin composition.
- the present invention comprises a mixing step of mixing a cellulose having a hydroxyl group and a polymer having a reactive group capable of reacting with the hydroxyl group and having a non-polar polymer in the molecular chain, and the hydroxyl group.
- a method for producing a cellulose composite which comprises a step of binding to a reactive group.
- the present invention comprises a step of kneading the cellulose composite obtained by the method for producing a cellulose composite described above with a predetermined non-polar resin. Manufacturing method is provided.
- the present invention provides a cellulose complex in which a non-polar polymer is bonded to a hydroxyl group of cellulose via a reactive group.
- the present invention provides a cellulose complex / resin composition containing the above-mentioned cellulose complex and a predetermined non-polar resin.
- a compatibilizer a compatibilizer () while maintaining the characteristics of cellulose.
- a resin composition can be provided.
- FIG. It is a figure of the micro X-ray CT observation result of the sample which concerns on Example 3.
- FIG. It is a figure of the micro X-ray CT observation result of the sample which concerns on Comparative Example 2. It is a figure of the micro X-ray CT observation result of the sample which concerns on Comparative Example 3. It is a figure of the SEM observation result of the sample which concerns on Example 3.
- FIG. It is a figure of the SEM observation result of the sample which concerns on Comparative Example 2. It is a figure of the SEM observation result of the sample which concerns on Comparative Example 3.
- the side chain By using a polymer as a side chain, the side chain also moves due to the movement of the main chain, improving the contact probability of cellulose with the hydroxyl group, and the "field" where the hydroxyl group and / or the reactive group easily collide with each other.
- a predetermined bond By reacting the hydroxyl group with the reactive group in the above, etc.), a predetermined bond can be formed without any treatment or step of activating the hydroxyl group.
- the present invention is based on such findings.
- the cellulose composite according to the embodiment of the present invention is formed by binding a non-polar polymer to a hydroxyl group of cellulose via a reactive group.
- the cellulose complex according to the present embodiment has a cellulose surface having a low molecular weight (for example, an organic compound having a weight average molecular weight of about 1,000 or less. However, for example, about a dodecadium of maleic anhydride (weight average molecular weight is 1,).
- a non-polar polymer is bonded to cellulose as a so-called "compatibility group" (conceptually).
- a high molecular weight compatibilizer is directly bound to cellulose.) This makes it unnecessary to add a compatibilizer (dispersant) when the cellulose complex according to the present embodiment is dispersed in a predetermined non-polar resin.
- the cellulose complex is a polymer trapped in the cellulose complex (that is, a polymer containing the above-mentioned reactive group and the above-mentioned non-polar polymer.
- the molecular chain is the above-mentioned non-polar polymer.
- it further contains a polymer in which a reactive group is attached to this molecular chain.
- captured means that the polymer is attached to the cellulose complex to the extent that it does not easily separate from the cellulose complex, is entangled with the cellulose complex, and is at least one of the cellulose complexes. It means at least one of coating the part. Since the cellulose complex contains the polymer trapped in the cellulose complex, the trapped polymer also exerts its function as a compatibilizer while being captured, so that the cellulose is dispersed in a non-polar resin. Will be easier.
- the “molecular chain” is a polymer, oligomer molecule, which is composed of a linear or branched structural unit between a terminal group, a branch point, or a boundary structural unit peculiar to a polymer. Or refers to a configuration including all or part of a block.
- the cellulose complex according to the present embodiment is a complex formed by binding a non-polar polymer to cellulose through a predetermined bond formed by reacting a hydroxyl group of cellulose with a predetermined reactive group.
- the cellulose complex can be obtained in powder form.
- As the cellulose cellulose fibers and / or cellulose nanofibers (CNF) can be used.
- cellulose fiber As the cellulose fiber according to the present embodiment, various cellulose fibers can be used as long as they have a hydroxyl group on the surface.
- the cellulose fiber include plant-derived cellulose fiber, animal-derived cellulose fiber (for example, cellulose fiber isolated from seaweed, seaweed, etc.), microorganism-derived cellulose fiber (for example, cellulose fiber produced by acetic acid bacteria, etc.).
- One or more kinds of cellulose fibers can be selected and used from the above. From the viewpoint of practicality, price, and / or availability, it is preferable to use plant-derived cellulose fiber as the cellulose fiber.
- raw materials for plant-derived cellulose fibers include plant fibers such as pulp obtained from natural plant raw materials such as wood, bamboo, hemp, jute, kenaf, cotton, beet, agricultural waste, and cloth. Further, as a raw material of cellulose fiber, used paper such as used newspaper, used corrugated cardboard, used magazine, and used copy paper can be mentioned. Examples of wood include sugi, cypress, eucalyptus, and acacia. Further, as a raw material for cellulose fibers, pulp or fibrillated cellulose obtained by fibrillating pulp can also be used. As the raw material of the cellulose fiber, one kind may be used alone or two or more kinds may be used in combination.
- the plant fiber has a structure in which the cellulose fibers are filled with lignin and hemicellulose, and a part or all of the periphery of the bundle of cellulose microfibrils is coated with hemicellulose and / or lignin. Then, it has a structure in which hemicellulose covers a bundle of cellulose microfibrils and / or a bundle of cellulose microfibrils, and hemicellulose is further coated with lignin.
- the plant fibers are formed in a state where the cellulose fibers are firmly adhered to each other by lignin. Therefore, from the viewpoint of suppressing the aggregation of cellulose fibers in the plant fibers, it is preferable to remove the lignin in the plant fibers.
- the amount of lignin in the raw material may be adjusted by subjecting the raw material of the cellulose fiber to a treatment such as delignin treatment or bleaching treatment, if necessary.
- the lignin content in the raw material of the cellulose fiber is not particularly limited, but from the viewpoint of suppressing the aggregation of the cellulose fiber, the lignin content in the plant fiber-containing material is about 40% by mass or less, and 10 It is preferably about mass% or less.
- the lower limit of lignin is not particularly limited, and the closer to 0% by mass is preferable.
- the lignin content can be measured by the Klason method.
- the average fiber length of cellulose fibers is not particularly limited. However, the longer the average fiber length of the cellulose fibers, the more the effect of improving the characteristics can be expected.
- CNF obtained by chemical treatment and defibration for example, TEMPO oxide CNF
- the aspect ratio of this CNF is about 1,000 (that is, the width of the cellulose fiber is 3 nm to 5 nm).
- Fiber length is about 3 ⁇ m).
- the cellulose nanofiber (CNF) according to the present embodiment is a nanofiber obtained by refining (defibrating) a material containing cellulose fibers (for example, the raw material of the cellulose fibers) to a nano-size level.
- a material containing cellulose fibers for example, the raw material of the cellulose fibers
- various CNFs can be used as long as they have a hydroxyl group on the surface.
- CNF can be prepared by defibrating a raw material of cellulose fibers (for example, pulp).
- a raw material of cellulose fibers for example, pulp
- the defibration method first, an aqueous suspension or slurry of cellulose fibers is prepared, and the prepared aqueous suspension or slurry is used in a refiner, a high-pressure homogenizer, a grinder, a kneader (extruder), a bead mill or the like.
- CNF can be prepared by defibrating cellulose fibers by mechanically grinding or the like.
- the average value of the fiber diameter of CNF may be 4 nm or more and 200 nm or less, 150 nm or less, 100 nm or less, or 50 nm or less.
- the average value of the fiber length of CNF may be about 3 ⁇ m or more, about 5 ⁇ m or more, about 100 ⁇ m or less, or about 500 ⁇ m or less.
- the fiber diameter and the fiber length of CNF of a predetermined number or more (for example, 50 or more) observed in a predetermined field of view of an electron microscope are measured. It may be the calculated average value.
- the specific surface area of the CNF is preferably at least 70m 2 / g, more preferably at least 100 m 2 / g, preferably the degree 300 meters 2 / g or less, more preferably the extent 250 meters 2 / g or less, 200 meters 2 / g lower than about Is more preferable, and about 150 m 2 / g or less is most preferable.
- the specific surface area of carboxymethyl cellulose (CMC, chemically treated CNF), which is CNF is about 300 m 2 / g.
- the specific surface area can be measured by the BET method.
- the polymer according to the present embodiment (that is, a polymer composed of a predetermined molecular chain having a reactive group) has a reactive group capable of reacting with a hydroxyl group, and the molecular chain is substantially non-polar or hydrophobic. It is a polymer.
- the reactive group reacts with the hydroxyl group of cellulose to form a predetermined bond, whereby the molecular chain of the polymer is bonded to cellulose.
- the polymer only needs to have a reactive group in the molecular chain, and the chain length of the reactive group does not have to be controlled.
- the non-polar polymer of the molecular chain may have another group different from the reactive group.
- the reactive group that reacts with the hydroxyl group of cellulose may be at least a part of the reactive groups in the polymer, and it is not always necessary that all the reactive groups and the hydroxyl group of cellulose form a bond. ..
- the reactive group according to the present embodiment is a group having an oxygen atom bonded to a carbon atom and can be crosslinked by forming a predetermined bond with a hydroxyl group of cellulose.
- the predetermined bond formed by the reaction of the hydroxyl group of cellulose with the reactive group is at least one bond selected from the group consisting of an ether bond, an ester bond, an amide bond, and a urethane bond.
- the reactive group includes at least one group selected from the group consisting of an acid anhydride group, a carbonyl group (for example, a methoxycarbonyl group), and a carboxyl group.
- the acid anhydride group for example, a succinic anhydride group, a maleic anhydride group, a glutaric anhydride group, and a phthalic anhydride group are preferable, and a succinic anhydride group is more preferable from the viewpoint of easy handling.
- non-polar polymer is a polymer substance that does not have a permanent dipole, and is a case where it contains impurities that are mixed under normal usage conditions and permanent dipoles derived from additives that are usually added. Is also a non-polar polymer. Examples of the non-polar polymer include polyethylene resin, polypropylene resin, tetrafluoroethylene resin and the like.
- non-polar polymer having a molecular chain in the present embodiment examples include a substantially non-polar or hydrophobic olefin resin.
- Olefin resins include polypropylene, polyethylene, ethylene / vinyl acetate copolymer resins, vinyl chloride resins, styrene resins, (meth) acrylic resins, vinyl ether resins, polyamide resins, polycarbonate resins, polysulfone resins, polyester resins, Examples thereof include polyvinyl acetal-based resins, polyvinylidene chloride-based resins, and polyurethane-based resins.
- the reactive group may be a methoxycarbonyl group or the like contained in the molecular chain.
- the non-polar polymer in the present embodiment refers to the molecular structure of a portion containing a methoxycarbonyl group or the like (in this case, the molecular chain is a structure in which the molecular chain itself contains a reactive group).
- the molecular chain portion excluding the reactive group is non-polar, it is assumed to be a non-polar polymer).
- another reactive group reactive group different from the methoxycarbonyl group
- non-polar polymer at least one selected from the group consisting of polypropylene, ethylene / vinyl acetate copolymer resin, and acrylic resin from the viewpoint of easy availability, low specific gravity, versatility, and / or processability. It is preferably a non-polar polymer. Of these, polypropylene is more preferred. In addition, these olefin-based resins may contain other copolymerizable units. Further, these olefin resins may be used alone or in combination of two or more.
- Examples of the polymer containing the above-mentioned molecular chain and reactive group include various polymers in which the above-mentioned molecular chain and the above-mentioned reactive group are combined.
- polypropylene, ethylene / vinyl acetate copolymer resin, and acrylic resin having at least one of the above reactive groups can be mentioned.
- the polymer a polymer in which a reactive group is bonded to a molecular chain such as a pendant group is more preferable, and for example, a graft copolymer is preferable.
- maleic anhydride-modified polypropylene having a maleic anhydride group as the reactive group and having a polypropylene molecular chain is used. Most preferably used.
- the weight average molecular weight of the polymer containing the reactive group and the non-polar polymer is preferably 5,000 or more, more preferably 10,000 or more, further preferably 15,000 or more, and 200,000 or less. Is preferable, 150,000 or less is more preferable, and 100,000 or less is further preferable. If the weight average molecular weight is less than 5,000, the mechanical properties of the cellulose complex tend to decrease, and if it exceeds 200,000, the reactive groups are insufficient, and a cellulose complex exhibiting the desired physical properties can be produced. It tends to be difficult.
- the weight average molecular weight can be calculated by polystyrene conversion using high temperature gel permeation chromatography (high temperature GPC) and then by polypropylene conversion using the Q factor.
- the graft ratio is low (that is, when the graft copolymer has a high molecular weight and MA is low), it is difficult to emulsify the polymer, and when the graft ratio is high, the molecular weight of the graft copolymer is high. Extremely low. Further, when the molecular weight of the graft copolymer is reduced, the graft copolymer captured by the cellulose composite is also reduced in molecular weight, so that the characteristics (for example, strength, etc.) of the cellulose composite itself are deteriorated. May decrease.
- the graft ratio is preferably 0.2% or more, preferably 1.0%, from the viewpoint of facilitating the formation of an emulsion of the polymer.
- the above is more preferable.
- the graft ratio is preferably 4.0% or less, more preferably 3.0% or less, from the viewpoint of suppressing the decrease in the molecular weight of the polymer and the deterioration of the characteristics of the cellulose complex / resin composition.
- the method for calculating the graft ratio of the graft copolymer is as follows. First, a sample is prepared by purifying the graft copolymer (sample preparation step). Next, the reactive group-derived component of the sample is quantified by 1 1 H-NMR measurement (quantification step of the reactive group-derived component). In addition, the absorbance ratio of the characteristic absorber of the sample (for example, each of the molecular chain and the reactive group) is determined by FT-IR measurement (absorbance ratio calculation step). Then, a calibration curve is prepared from the quantitative value of 1 H-NMR and the absorbance ratio of FT-IR (calibration curve preparation step). Subsequently, using the prepared calibration curve, the graft ratio is calculated from the absorbance ratio of FT-IR of the graft copolymer (graft ratio calculation step).
- the graft copolymer is purified to prepare a sample from which noise components have been removed.
- the purification process of MAPP is carried out through the following steps. First, a predetermined amount of MAPP and a predetermined amount of a first organic solvent (for example, xylene) are put into an eggplant flask, and the MAPP is dissolved by heating. Next, after cooling the solution in which MAPP is dissolved, a predetermined amount of a second organic solvent (for example, acetone) is added to the eggplant flask to recrystallize MAPP.
- a first organic solvent for example, xylene
- a predetermined amount of a second organic solvent for example, acetone
- the solid component is separated by filtering the liquid that becomes cloudy due to recrystallization of MAPP under reduced pressure. Subsequently, the solid component is rinsed by adding an organic solvent (for example, acetone). Then, the rinsed solid component is dried under heating and reduced pressure (for example, heating and reduced pressure drying at 140 ° C. for 1 hour is performed). After the drying is completed, the obtained solid component is heat-pressed (for example, pressed at 200 ° C.) to prepare a sample transparent film (for example, a transparent film having a thickness of about 0.1 mm).
- an organic solvent for example, acetone
- the rinsed solid component is dried under heating and reduced pressure (for example, heating and reduced pressure drying at 140 ° C. for 1 hour is performed). After the drying is completed, the obtained solid component is heat-pressed (for example, pressed at 200 ° C.) to prepare a sample transparent film (for example, a transparent film having a thickness of about 0.1 mm).
- 1 H-NMR measurement and FT-IR measurement are carried out using the prepared sample.
- the maleic anhydride (MA) -derived component of the sample is quantified by 1 1 H-NMR.
- the absorbance ratio of the characteristic absorption band (PP, MA) of the sample is determined using FT-IR.
- a calibration curve is prepared from the ratio of 1 H-NMR quantitative value and FT-IR absorbance.
- the graft ratio is calculated from the absorbance ratio of FT-IR using the following equation.
- A is the absorbance of the polypropylene-derived methyl group of 4240 cm -1
- B is the absorbance of the reverse target expansion and contraction absorption of the ring-closed carbonyl of 1865 cm -1.
- the coefficient is 1.2.
- B / A is the absorbance (abs) ratio of maleic anhydride and polypropylene.
- the melting point of the polymer depends on the melting point of the non-polar polymer used for the molecular chain. For example, when a polypropylene-based polymer is used for the molecular chain, the melting point of the polymer is about 80 ° C. or higher and 175 ° C. or lower.
- the polymer trapped in the cellulose complex is the same as the above polymer.
- the non-polar polymer bonded to the hydroxyl group of cellulose via a reactive group that is, the polymer having the non-polar polymer having this reactive group, and the captured polymer are the same. It is a polymer of.
- the extracted insoluble component contains the cellulose complex
- the extracted soluble component contains a polymer. If so, the polymer is "captured" by the cellulose complex.
- the cellulose complex is Soxhlet-extracted to separate the insoluble and soluble components.
- FT-IR measurement, 1 H-NMR measurement, and / or 13 C-NMR measurement are carried out for each of the extract-insoluble component and the extract-soluble component.
- a complex formed by binding MAPP to CNF as a cellulose complex will be given as an example.
- CNF itself is insoluble in xylene
- MAPP itself is soluble.
- xylene is used as the organic solvent for Soxhlet extraction
- an extraction-insoluble component and an extraction-soluble component can be obtained.
- the amount of the extracted insoluble component (wt%) is larger than the amount of CNF used for the synthesis of the cellulose composite (wt%), and the presence of the ester bond is confirmed by NMR measurement. , It is shown that MAPP was attached to CNF via an ester bond.
- a peak based on polypropylene (PP) skeleton is observed by 13 C-NMR measurement of the extracted soluble component, FT-IR measurement, and a peak based on MA backbone by 1 H-NMR measurement was observed, 1 with a peak based on the cellulose backbone by H-NMR measurement is observed, extracted FT-IR measurement of the insoluble component, and 13 C-NMR carbonyl peak based on MA backbone by measurement is observed, cellulose backbone by 13 C-NMR measurement If a peak based on is observed, it can be estimated that the polymer is trapped in the cellulose complex.
- PP polypropylene
- the cellulose complex / resin composition according to the present embodiment is a composition obtained by dispersing the cellulose complex in a predetermined non-polar resin. Since the cellulose complex is in a state in which a non-polar polymer is bonded to cellulose, it can be dispersed substantially uniformly in a non-polar resin. Further, when the polymer trapped in the cellulose complex is present, the cellulose complex can be more easily dispersed in the non-polar resin.
- resin As the resin in the cellulose complex / resin composition, various resins can be used.
- the resin include a thermoplastic resin, a thermosetting resin, and / or a photocurable resin. Then, it is preferable to use a non-polar or hydrophobic resin as the resin in the cellulose complex / resin composition.
- thermoplastic resin examples include styrene resins, acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, and olefin resins (for example, aliphatic polyolefin resins, Cyclic olefin resin), polyamide resin, polyphenylene ether resin, thermoplastic polyimide resin, polyacetal resin, polysulfone resin, amorphous fluorine resin and the like.
- styrene resins acrylic resins, aromatic polycarbonate resins, aliphatic polycarbonate resins, aromatic polyester resins, aliphatic polyester resins, and olefin resins (for example, aliphatic polyolefin resins, Cyclic olefin resin), polyamide resin, polyphenylene ether resin, thermoplastic polyimide resin, polyacetal resin, polysulfone resin, amorphous fluorine resin and the like.
- thermosetting resin examples include epoxy resin, acrylic resin, oxetane resin, phenol resin, urea resin, polyimide resin, melamine resin, unsaturated polyester resin, silicon resin, polyurethane resin, allyl ester resin, and diallyl phthalate resin. Be done.
- photocurable resin examples include epoxy resin, acrylic resin, and oxetane resin.
- thermoplastic resin for example, an olefin resin (polypropylene or the like) from the viewpoint that it can be applied to various industries and is relatively easy to mold.
- olefin resin polypropylene or the like
- the cellulose composite and / or the cellulose composite / resin composition according to the present embodiment is added to the cellulose composite and / or the cellulose composite / resin composition as long as the physical properties of the cellulose composite and / or the cellulose composite / resin composition are not impaired.
- Various additives such as pigments, dyes, fillers and diluents may be added.
- the cellulose complex / resin composition according to this embodiment can be used for various purposes. Specifically, it can be used for various products such as automobile parts, home appliances, housing / building materials, and packaging materials.
- the method for producing a cellulose complex generally includes the following steps. That is, the method for producing a cellulose composite includes a mixing step of mixing cellulose having a hydroxyl group and a polymer having a reactive group to prepare a mixture, and a step of binding the hydroxyl group and the reactive group (bonding step). To be equipped.
- the bonding step may be a heating step of heating the mixture.
- the method for producing a cellulose complex may further include a drying step of drying the cellulose complex obtained after the heating step. The heating step can be executed after the mixing step, or the mixing step and the heating step can be executed at the same time (execution while heating the mixing step).
- cellulose having a hydroxyl group that is, a predetermined amount of cellulose fiber and / or cellulose nanofiber (CNF), and a predetermined amount of polymer (that is, having a reactive group capable of reacting with the hydroxyl group, and the molecular chain is non-polar.
- a mixture is prepared by mixing each of them.
- the mixing method is not particularly limited, and manual mixing, mixing using a stirrer or a mixer, or the like can be appropriately selected.
- CNF aqueous dispersion As the CNF of the CNF aqueous dispersion, the above-mentioned various CNFs can be used. It is also possible to use cellulose fibers that have been hydrophobized in advance by chemical treatment. However, when the cellulose fibers are hydrophobized in advance by chemical treatment, the number of steps such as purification associated with the chemical treatment increases, which increases cost and labor. On the other hand, in the present embodiment, since chemically untreated cellulose fibers and / or an aqueous dispersion of cellulose can be used, it is not necessary to go through the above steps, which is very advantageous in terms of cost and the like.
- the amount of water contained in the cellulose fibers varies depending on the method for producing the cellulose fibers.
- the method for producing cellulose fibers is 10 nm by mechanical defibration, which uses a grinder or ultra-high pressure water to defibrate cellulose to a fiber width of several tens to 200 nm, or by TEMPO oxidation or phosphoric acid esterification.
- chemical treatment defibration that defibrates to the level of fiber width.
- mechanical defibration heat is generated
- chemical defibration chemical treatment in an aqueous solution is required, so both are aqueous dispersions.
- the solid content concentration of the cellulose fiber is usually about 2 wt% or more and 10 wt% or less (note that the shape of the cellulose fiber is about 10 wt%, although it varies depending on the degree of defibration. It becomes sherbet-like.)
- the solid content concentration of the cellulose fiber is about 0.5 wt% or more and 2 wt% or less (Note that 2 wt% is the upper limit of the solid content concentration for maintaining the gel state).
- the solid content concentration of the CNF aqueous dispersion is preferably a concentration at which the viscosity can be stirred even when mixed with the polymer emulsion.
- the solid content concentration of the CNF aqueous dispersion is 0.5 wt% or more, preferably 2 wt% or more, 5 wt% or more, and 15 wt% or less from the viewpoint of facilitating mixing with the polymer. It is preferably 10 wt% or less.
- the viscosity of the CNF aqueous dispersion (for example, a typical value of the viscosity when measured at 25 ° C.
- polymer used for mixing As the polymer used in the mixing step, it is preferable to use a polymer aqueous emulsion in which fine particles of the polymer are dispersed in water.
- the polymer constituting the aqueous emulsion of the polymer the above-mentioned various polymers can be used.
- a system (emulsion) in which polymer fine particles (dispersant) are stably dispersed in water (dispersion medium) is called “latex”.
- the system is referred to as an "emulsion" in accordance with practice.
- the proportion of the solid content in the aqueous emulsion of the polymer is 5 wt% or more, preferably 10 wt% or more, more preferably 15 wt% or more, further preferably 20 wt% or more, still more preferably 25 wt% or more, from the viewpoint of reactivity with cellulose. There may be. Further, the ratio of the solid content in the aqueous emulsion of the polymer is 45 wt% or less, preferably 30 wt% or less, from the viewpoint of facilitating the preparation of the emulsion.
- emulsions can be used as the polymer aqueous emulsion.
- a maleic anhydride-modified polypropylene (MAPP) emulsion it is preferable to use a maleic anhydride-modified polypropylene (MAPP) emulsion, an ethylene-vinyl acetate copolymer resin (EVA) emulsion, and an acrylic emulsion of an acrylic resin.
- MAPP maleic anhydride-modified polypropylene
- EVA ethylene-vinyl acetate copolymer resin
- acrylic emulsion of an acrylic resin acrylic resin.
- the MAPP emulsion is most preferable because the reactive group is hung from the molecular chain, so that the reactive group can easily approach the hydroxyl group of cellulose and the frequency of collision of the reactive group with the hydroxyl group can be improved.
- the mixing ratio of cellulose and polymer can be defined by the solid content ratio of cellulose and polymer. That is, the solid content ratio of the cellulose (cellulose fiber or CNF) of the mixture is 3 wt% or more, may be 5 wt% or more, preferably 10 wt% or more, may be 20 wt% or more, and may be cellulose (cellulosic fiber or CNF). Typically, it is 50 wt% or less, preferably 40 wt% or less, from the viewpoint of suppressing aggregation of CNF) and appropriately forming a complex with a polymer.
- the solid content ratio of the cellulose (cellulose fiber or CNF) of the mixture is 3 wt% or more, may be 5 wt% or more, preferably 10 wt% or more, may be 20 wt% or more, and may be cellulose (cellulosic fiber or CNF). Typically, it is 50 wt% or less, preferably 40 wt% or less, from the viewpoint of suppressing
- the solid content ratio of the polymer of the mixture may be a ratio equal to or higher than the solid content ratio of cellulose, preferably a higher ratio, for example, 10 wt% or more, 15 wt% or more, 25 wt%. It may be more than or equal to 45 wt% or more.
- the ratio of the solid content ratio of cellulose to the solid content ratio of the polymer in the mixture that is, the solid content ratio of cellulose: the solid content ratio of the polymer is , 1: x (however, x ⁇ 1), typically about 1: 1 to 1:10, preferably about 1: 2 to 1: 9, cellulose (cellulose fiber containing water, or CNF aqueous dispersion) and polymer (polymer aqueous emulsion) are weighed and mixed.
- the bonding step is a step of bonding the hydroxyl group of cellulose and the reactive group of the polymer.
- the bonding step may be, for example, a heating step of heating a mixture of cellulose having a hydroxyl group and a polymer having a reactive group and having a non-polar molecular chain at a predetermined temperature or lower.
- the bonding step may be a step of adding (or while adding) cellulose having a hydroxyl group to a polymer aqueous emulsion in which polymer fine particles are dispersed in water and heating the emulsion.
- the heating step the mixture obtained in the mixing step is controlled to a predetermined temperature or lower and heated for a predetermined time.
- the hydroxyl group of the cellulose reacts with the reactive group of the polymer to form a predetermined bond, and the polymer is bonded to the cellulose through this bond.
- the reactive group is at least one reactive group selected from the group consisting of a succinic anhydride group, a carbonyl group, and a carboxyl group
- the bond formed by the hydroxyl group of cellulose and the reactive group is an ester. It is a bond. That is, in this case, the esterification reaction proceeds in the heating step.
- the reaction temperature in the heating step is preferably 50 ° C. or higher from the viewpoint of enabling the formation of a predetermined bond (for example, an ester bond), preferably 70 ° C. or higher from the viewpoint of improving the reactivity, and further improves the reactivity. From the viewpoint, it may be 80 ° C. or higher. Further, the reaction temperature is 200 ° C. or lower in order to suppress thermal deterioration of cellulose, preferably 160 ° C. or lower from the viewpoint of facilitating temperature control, and may be 145 ° C. or lower from the viewpoint of facilitating quality control. ..
- the heating step it is preferable to heat the mixture under reduced pressure.
- the pressure during heating may be less than normal pressure.
- the pressure in the heating step may be about 0.09 MPa or less. Heating under reduced pressure facilitates the removal of moisture from the system.
- a cellulose complex powder is obtained.
- the reaction product obtained after the heating step may be filtered under reduced pressure (vacuum filtration step). That is, the above-mentioned reaction product according to the present embodiment can be dehydrated. By going through the vacuum filtration step, the reaction product can be subjected to a stronger dehydration treatment.
- an apparatus such as a planetary stirring type heating / vacuum drying device can be used.
- the heating step is a step of heating the mixture in a normal pressure open system kettle and then performing a primary dehydration treatment with a centrifuge, a filter press or the like (primary dehydration treatment step), followed by a dryer to which a shearing force is applied. May include a step of drying under reduced pressure (secondary dehydration treatment step).
- the heating step is preferably a step in which the primary dehydration treatment step and the secondary dehydration treatment step are combined.
- this cellulose complex contains a polymer trapped in the cellulose complex.
- cellulose cellulose fiber containing water or CNF aqueous dispersion
- a polymer aqueous emulsion By using cellulose (cellulose fiber containing water or CNF aqueous dispersion) and a polymer aqueous emulsion, not only a cellulose complex is formed, but also a polymer is formed into a non-polar polymer bonded to cellulose. It is presumed that the polymer is easily entangled and the polymer is easily trapped in the cellulose complex.
- the drying step dries the moisture remaining in the cellulose complex obtained after the heating step.
- the drying step is a step of drying the cellulose complex with warm air.
- the temperature of the warm air is, for example, about 80 ° C., and the drying time is about 8 hours.
- the temperature and drying time are not limited to this as long as the thermal deterioration of the cellulose contained in the cellulose complex can be suppressed.
- the cellulose complex / resin composition can be adjusted by undergoing a kneading step of kneading the cellulose complex obtained above into a predetermined non-polar resin at a predetermined temperature for a predetermined time. After the kneading step, a curing step of curing the obtained cellulose complex / resin composition may be further carried out.
- the kneading step is a step of kneading the cellulose complex and a predetermined non-polar resin in a predetermined temperature environment, and the kneading method is not particularly limited, and the kneading can be performed in one step or a plurality of times. It can also be divided into processes.
- the kneading step can be performed using, for example, a kneader, a twin-screw kneader, and / or an injection molding machine, which are devices for kneading the charged materials by rotating the blade in the container.
- the cellulose complex used in the kneading step may be in the form of powder or in the form of pellets from the viewpoint of ease of handling at the time of compounding.
- the shape of the non-polar resin is not particularly limited, and may be in the form of pellets or powder.
- the amount of the cellulose complex added to the resin is not particularly limited.
- a: b is 1: 1 to 1.
- the cellulose (CNF) content of the cellulose complex is preferably 5 wt% or more, more preferably 10 wt% or more, further preferably 15 wt% or more, further preferably 20 wt% or more, preferably 40 wt% or less, and preferably 35 wt%. The following is more preferable, and 30 wt% or less is further preferable.
- the cellulose (CNF) content in the cellulose complex / resin composition is preferably 2 wt% or more, more preferably 3 wt% or more, and preferably 15 wt% or less from the viewpoint of ensuring mechanical physical characteristics and raw material cost. It is considered that 10 wt% or less is more preferable, and 5 wt% or less is further preferable.
- the heating temperature at the time of kneading is a temperature equal to or higher than the temperature at which the resin melts from the viewpoint of melting the resin and dispersing the cellulose composite in the melted resin (that is, adding the cellulose composite to the melt of the resin).
- the temperature is 175 ° C. or higher from the viewpoint of not applying excessive heat to the cellulose composite while keeping the resin in a molten state. It is preferable to control the heating temperature, and it is preferable to control the heating temperature to 190 ° C. or 220 ° C. or lower.
- the kneading step for example, it is preferable to melt the resin first using a twin-screw extrusion molding machine or the like, add the cellulose complex to the melted resin, and knead the resin.
- the heat (heat amount) applied to the cellulose complex can be reduced, and the thermal deterioration of the cellulose contained in the cellulose complex can be suppressed.
- the cellulose complex / resin composition obtained through the kneading step the cellulose complex is substantially uniformly dispersed in the resin.
- This dispersed state can be confirmed by, for example, an infrared imaging method, a three-dimensional TEM, or the like.
- a non-polar polymer is bonded to a hydroxyl group of cellulose via a reactive group. Therefore, when the cellulose composite is added to a non-polar resin, a compatibilizer (dispersion) The cellulose complex can be dispersed in this resin substantially uniformly without adding an agent). Therefore, according to the cellulose composite according to the present embodiment, for example, the cellulose resin and / or CNF can be uniformly dispersed in an olefin resin such as polyethylene or polypropylene, so that the raw material cost and the manufacturing equipment cost are reduced. On top of that, high-performance structural materials can be manufactured.
- the cellulose complex uses an aqueous dispersion of cellulose and a high molecular weight aqueous emulsion, the cellulose complex can be prepared while suppressing thermal deterioration of cellulose. As a result, the cellulose complex / resin composition can exhibit the characteristics in which the original characteristics of cellulose are added.
- the cellulose complex can be prepared in a state of capturing the polymer used for preparing the cellulose complex.
- the cellulose complex according to the present embodiment when it is added to a non-polar resin, it becomes easier to disperse in the resin.
- Examples 1 and 2 Cellulose complex
- each compounding substance was mixed at the compounding ratio shown in Table 1 to obtain a mixture.
- the obtained mixture was heated under reduced pressure using a vertical kneading / stirring machine (Trimix TX-15, manufactured by Inoue Seisakusho).
- the decompression heating conditions were a set temperature of 145 ° C., a heating time of 30 minutes, and an internal pressure of 0.09 MPa.
- a powder of the cellulose complex (hereinafter referred to as "CNFem") according to Example 1 was prepared.
- the obtained CNFem powder according to Example 1 was dried using a warm air dryer. The drying conditions were set at 80 ° C. for 8 hours.
- the CNFem according to Example 2 was also prepared in the same manner.
- the unit of the compounding amount of each compounding substance is "wt%".
- the details of the compounded substances are as follows. -Cellulose nanofiber (CNF) slurry (BiNFi-s WFo-10010: solid content 10%, manufactured by Sugino Machine Limited) -MAPP emulsion (Aqueous emulsion of maleic anhydride-modified polypropylene (MAPP): prepared to a solid content of 25% using water)
- the blending amount of the CNF slurry is represented by the amount of CNF contained in the CNF slurry
- the blending amount of the MAPP emulsion is represented by the amount of MAPP contained in the MAPP emulsion.
- the measurement result of Example 1 is shown, but the same measurement result was obtained in Example 2.
- the soluble and insoluble parts used in the NMR spectroscopy measurement were measured by the total internal reflection measurement method (ATR method) using a Fourier transform infrared spectroscopic analyzer (FT / IR-4200typeA, manufactured by Nippon Spectroscopy Co., Ltd.). did.
- CNFem contains a soluble part soluble in xylene and an insoluble part insoluble in xylene may be due to the amount of MAPP captured by CNFem. That is, it is presumed that the amount of MAPP captured by CNFem in the soluble portion and the amount of MAPP captured by CNFem in the insoluble portion may differ.
- the filtrate obtained when the cellulose complex trapping MAPP as described above is dissolved in an organic solvent (for example, xylene, toluene, etc.) and filtered contains CNF which is originally insoluble in the organic solvent. If the insoluble portion contains a PP-derived component that is originally soluble in an organic solvent, it can be presumed that the cellulose composite is produced by the production method described in this embodiment.
- an organic solvent for example, xylene, toluene, etc.
- Example 3 Comparative Examples 1 to 4: Cellulose complex / resin composition
- Each compounding substance was mixed at the compounding ratio shown in Table 2 to prepare a cellulose complex / resin composition having a CNF content of 5 wt%.
- the prepared cellulose complex / resin composition and polypropylene were mixed at a blending ratio of 3 wt% to prepare the cellulose complex / resin composition according to Example 3.
- pelletized polypropylene (PP) J107G, manufactured by Prime Polymer Co., Ltd.
- PP pelletized polypropylene
- a predetermined amount of CNFem according to Example 1 was added and melt-kneaded for 5 minutes.
- this sample obtained by melt-kneading was cooled and then pulverized using a cutting mill P-15 (manufactured by Fritsch Japan). As a result, a sample (Sample 1) having a CNF content of 5 wt% was obtained.
- sample 1 whose CNF content was adjusted to 5 wt% by a lab plast mill so that the CNF content after kneading was 3 wt%, and pelletized PP (J107G, manufactured by Prime Polymer Co., Ltd.). was mixed to obtain a dry blend.
- the temperature of the kneading zone of the twin-screw extruder was set to 190 ° C. and the rotation speed was set to 200 rpm, and the dry blend was added from the hopper.
- the extruded strands were air-cooled on a conveyor, passed through a water bath, and pelletized with a pelletizer.
- the prepared pellets were dried for 3 days in a dryer set at 70 ° C.
- the cellulose complex / resin composition according to Example 3 having a CNF content of 3 wt% was obtained.
- Comparative Example 1 is a sample using only PP (prepared using Sample 2)
- Comparative Example 2 is a sample using CNF powder and MAPP instead of CNFem (prepared using Sample 3).
- Comparative Example 3 is a sample using CNF powder instead of CNFem (prepared using sample 4)
- Comparative Example 4 is a sample using MAPP without using CNFem and CNF powder (prepared using sample 5). ).
- Table 3 shows the CNF content of each sample according to Example 3 and Comparative Examples 1 to 4.
- test piece was prepared in accordance with JIS K6921-2 using each of the cellulose complex / resin composition according to Example 3 and the samples according to Comparative Examples 1 to 4, and the prepared test piece was prepared.
- JIS K6921-2 JIS K6921-2
- each test piece was prepared by pre-drying the sample at 80 ° C. for 4 hours, using ISO multipurpose type A as a mold, and injection molding using an injection molding machine FE80S12ASE (manufactured by Nissei Resin Industry Co., Ltd.). did.
- the molten resin temperature is set to 200 ° C.
- the cylinder set temperature is set to 175 ° C. to 195 ° C.
- the mold temperature is set to 40 ° C.
- the average injection speed is set to 200 ⁇ 20 (mm / s)
- the screw rotation speed is set to 110 (rpm). did.
- a tensile test piece for a tensile test (test piece shape: 1A type) and a bending test piece for a bending test (test piece shape: 80 mm ⁇ 10 mm).
- ⁇ 4 mm (cut from the parallel part of the 1A type dumbbell)
- Charpy impact test piece for impact test (without notch)
- test piece shape: 80 mm ⁇ 10 mm ⁇ 4 mm (cut from the parallel part of the 1A type dumbbell)
- the tensile test conforms to JIS K7161-1 and 2, and uses Strograph APII (manufactured by Toyo Seiki Seisakusho) as a test device, with a test speed of 50 mm / min, a distance between marked lines of 50 mm, and a distance between chucks of 115 mm.
- the bending test conforms to JIS K7171 and uses Bentgraph II (manufactured by Toyo Seiki Seisakusho) as a test device, test speed is 2 mm / min, test temperature and humidity is 23 ° C, 50% RH, span spacing is 64 mm, and indenter.
- Table 3 shows the results of each test.
- Micro X-ray CT observation was performed on each of the sample according to Example 3, Comparative Example 2 and Comparative Example 3. Specifically, an X-ray analysis microscope nano 3DX (manufactured by Rigaku) was used as a test apparatus, a high-magnification lens (L0270) was used as the lens, and Cu (40 kV, 30 mA) was used as the X-ray source (target). The resolution is 0.825 ⁇ m / pixel.
- the observation result of the sample according to Example 3 is shown in FIG. 1, the observation result of the sample according to Comparative Example 2 is shown in FIG. 2, and the observation result of the sample according to Comparative Example 3 is shown in FIG.
- Example 3 As can be seen with reference to FIGS. 1 to 3, it was shown that the aggregation of CNF was significantly suppressed in Example 3 as compared with Comparative Example 2 and Comparative Example 3.
- SEM observation SEM observation was performed on each of the sample according to Example 3, the sample according to Comparative Example 2 and the sample according to Comparative Example 3. Specifically, in order to observe the dispersed state of CNF in the sample, a sample was prepared with a Focused Ion Beam (FIB) device and observed by SEM.
- FIB Focused Ion Beam
- the test piece prepared above is cut to a predetermined size, Pt coating is applied to the sample surface by sputtering, and then about 1 ⁇ m of carbon is vapor-deposited at the processing site in the FIB device to cross-section the sample.
- a cross-section SEM sample was prepared.
- an XVision 200TB focused ion beam device (acceleration voltage 30 kV) manufactured by SII Nanotechnology Inc. was used.
- a field emission scanning electron microscope (acceleration voltage 3 kV) manufactured by ZEISS was used for SEM observation.
- FIG. 4 shows a cross-sectional SEM image of the sample according to Example 3.
- a contrast presumed to be CNF was observed in the sample.
- the size of the observed CNF was about 10 ⁇ m or less, and many relatively small CNFs of 1 ⁇ m or less were observed.
- FIG. 5 shows a cross-sectional SEM image of the sample according to Comparative Example 2.
- a contrast presumed to be CNF was observed in the sample.
- the observed size of CNF was about 0.5 to 10 ⁇ m.
- FIG. 6 shows a cross-sectional SEM image of the sample according to Comparative Example 3.
- a contrast presumed to be CNF was observed in the sample.
- the size of the observed CNF was about 0.5 ⁇ m to 20 ⁇ m, and a relatively large CNF was also observed.
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Abstract
Description
<セルロース複合体着想の背景>
これまで、セルロースやセルロースナノファイバー(CNF)の水酸基に所定の反応性基を反応させて結合させる場合、セルロースの水酸基を反応活性にすることが必要であると認識される場合があった。しかしながら、本発明者は、水酸基と反応性を有する反応性基であれば、例えば、水酸基と反応性基との接触確率を向上させること(例えば、所定以上の分子量の主鎖に反応性基を側鎖として有する高分子を用いることで主鎖の運動等により側鎖も移動してセルロースの水酸基への接触確率が向上することや、水酸基及び/又は反応性基が互いに衝突しやすい「場」において水酸基と反応性基とを反応させること等)で、水酸基を活性化させる処理や工程を設けなくても所定の結合を形成し得るという逆転の発想により、セルロース水分散体と無水マレイン酸変性ポリプロピレン(MAPP)エマルジョンとを用いてセルロースへのMAPPの導入を試みた。その結果、驚くべきことにセルロースの水酸基とMAPPの無水コハク酸基との間で比較的低温での加熱でエステル結合が容易に生じることを見出した。本発明は、係る知見に基づくものである。
本発明の実施の形態に係るセルロース複合体は、セルロースの水酸基に反応性基を介して無極性高分子が結合されて形成される。本実施形態に係るセルロース複合体は、セルロース表面を低分子量(例えば、重量平均分子量が1,000以下程度の有機化合物。但し、例えば、無水マレイン酸の12量体前後(重量平均分子量が1,200程度)のMAオリゴマーは除く。)の有機化合物を用いて疎水化する従来の処理とは異なり、セルロースに無極性高分子を、いわば「相溶化基」として結合させている(概念的には、セルロースに高分子量の相溶化剤を直接結合させている。)。これにより、本実施形態に係るセルロース複合体を所定の無極性の樹脂に分散させる場合に、相溶化剤(分散剤)を添加することが不要となる。
本実施形態に係るセルロース複合体は、セルロースの水酸基に所定の反応性基が反応して形成される所定の結合を介して無極性高分子がセルロースに結合されて形成される複合体である。セルロース複合体は、粉末状で得ることができる。そして、セルロースとしては、セルロース繊維及び/又はセルロースナノファイバー(CNF)を用いることができる。
本実施形態に係るセルロース繊維は、表面に水酸基を有している形態であれば各種のセルロース繊維を用いることができる。セルロース繊維としては、植物由来のセルロース繊維、動物由来のセルロース繊維(例えば、ホヤ、海草等から単離されるセルロース繊維)、微生物由来のセルロース繊維(例えば、酢酸菌が産出するセルロース繊維等)等の中から1種以上のセルロース繊維を選択して用いることができる。実用性、価格、及び/又は入手の容易性等の観点から、セルロース繊維としては植物由来のセルロース繊維を用いることが好ましい。
本実施形態に係るセルロースナノファイバー(CNF)は、セルロース繊維を含む材料(例えば、上記セルロース繊維の原料)をナノサイズレベルまで微細化処理(解繊処理)して得られるナノファイバーである。本実施形態に係るCNFは、表面に水酸基を有している形態であれば各種のCNFを用いることができる。
本実施形態に係る高分子(つまり、反応性基を有する所定の分子鎖からなる高分子)は、水酸基と反応可能な反応性基を有し、分子鎖が実質的に無極性若しくは疎水性の高分子である。この反応性基とセルロースの水酸基とが反応し、所定の結合を形成することで、高分子の分子鎖がセルロースに結合される。本実施形態において高分子は、分子鎖が反応性基を有していればよく、反応性基の鎖長を制御しなくてよい。また、反応性基と水酸基との反応を阻害しない限り、分子鎖中の一部に他の構造単位が含まれていてもよい。更に、分子鎖の無極性高分子は、反応性基とは異なる他の基を有していてもよい。また、セルロースの水酸基と反応する反応性基は、高分子中の少なくとも一部の反応性基であってよく、必ずしも全ての反応性基とセルロースの水酸基とが結合を形成することを要さない。
本実施形態に係る反応性基は、炭素原子に結合した酸素原子を有する基であって、セルロースの水酸基との間で所定の結合を形成することで架橋し得る基である。そして、セルロースの水酸基と反応性基とが反応して形成される所定の結合は、エーテル結合、エステル結合、アミド結合、及びウレタン結合からなる群から選択される少なくとも1つの結合である。例えば、反応性基としては、酸無水物基、カルボニル基(例えば、メトキシカルボニル基)、及びカルボキシル基からなる群から選択される少なくとも1つの基が挙げられる。酸無水物基としては、例えば、無水コハク酸基、無水マレイン酸基、無水グルタル酸基、無水フタル酸基が好ましく、取り扱いが容易である観点から、無水コハク酸基がより好ましい。
無極性高分子とは、永久双極子を有さない高分子物質であり、通常の使用状況において混入する不純物や、通常添加される添加剤等に由来する永久双極子を含んだ場合であっても無極性高分子とする。無極性高分子としては、例えば、ポリエチレン樹脂、ポリプロピレン樹脂、テトラフルオロエチレン樹脂等が挙げられる。
上記の分子鎖及び反応性基を含んでなる高分子としては、上記の分子鎖と上記の反応性基とを組み合わせた種々の高分子が挙げられる。例えば、上記の反応性基のうち少なくとも1種の反応性基を有するポリプロピレン、エチレン・酢酸ビニル共重合樹脂、及びアクリル樹脂が挙げられる。高分子としては、反応性基がペンダント基のように分子鎖に結合した高分子がより好ましく、例えば、グラフト共重合体が好ましい。上記の高分子の中では、分子鎖に対する反応性基の運動を活発にし得る観点から、反応性基として無水マレイン酸基を有し、分子鎖がポリプロピレンである無水マレイン酸変性ポリプロピレン(MAPP)を用いることが最も好ましい。
反応性基と無極性高分子とを含んでなる上記高分子の重量平均分子量としては、5,000以上が好ましく、10,000以上がより好ましく、15,000以上が更に好ましく、200,000以下が好ましく、150,000以下がより好ましく、100,000以下が更に好ましい。重量平均分子量が5,000未満であるとセルロース複合体の機械的物性が低下する傾向があり、200,000を超えると反応性基が不足し、所望の物性を発揮するセルロース複合体の作製が困難になる傾向がある。なお、重量平均分子量は、高温ゲル浸透クロマトグラフィー(高温GPC)を用いて、ポリスチレン換算により求めた後、Qファクターを用いてポリプロピレン換算として算出できる。
例えば、MAPPを得るためにポリプロピレンに無水マレイン酸をグラフトさせる場合、グラフト反応においてポリプロピレン鎖上にポリマーラジカルが生じ、このポリマーラジカルへ無水マレイン酸がグラフト反応する。一方、グラフト反応の競争反応として、ポリプロピレン鎖の分子切断反応が起こる。ここで、分子切断反応の方がグラフト反応より優位であることから、グラフト率を高くすると得られるMAPPの分子量が低下するというように、グラフト率と分子量とはトレードオフの関係にある。
グラフト共重合体のグラフト率の算出方法は以下のとおりである。まず、グラフト共重合体を精製処理することでサンプルを作製する(サンプル作製工程)。次に、1H-NMR測定によりサンプルの反応性基由来成分を定量する(反応性基由来成分の定量工程)。また、FT-IR測定によりサンプルの特性吸収体(例えば、分子鎖及び反応性基それぞれ)の吸光度の比を求める(吸光度比算出工程)。そして、1H-NMRの定量値とFT-IRの吸光度比とから検量線を作成する(検量線作成工程)。続いて、作成した検量線を用い、グラフト共重合体のFT-IRの吸光度比からグラフト率を算出する(グラフト率算出工程)。
上記高分子の融点としては、分子鎖に採用する無極性高分子の融点に依存する。例えば、分子鎖にポリプロピレン系高分子を採用した場合、高分子の融点は80℃以上175℃以下程度である。
セルロース複合体に捕捉される高分子は、上記高分子と同様である。ただし、セルロースの水酸基に反応性基を介して結合している無極性高分子、つまり、この反応性基を有する無極性高分子を有してなる高分子と、捕捉される高分子とは同一の高分子である。
本実施形態に係るセルロース複合体/樹脂組成物は、所定の無極性の樹脂にセルロース複合体を分散させて得られる組成物である。セルロース複合体は、セルロースに無極性高分子が結合した状態であるので、無極性の樹脂に実質的に均一に分散させることができる。また、セルロース複合体に捕捉された高分子が存在する場合、セルロース複合体をより容易に無極性の樹脂に分散させることができる。
セルロース複合体/樹脂組成物における樹脂としては、各種の樹脂を用いることができる。例えば、樹脂としては、熱可塑性樹脂、熱硬化性樹脂、及び/又は光硬化性樹脂等が挙げられる。そして、セルロース複合体/樹脂組成物における樹脂としては無極性若しくは疎水性の樹脂を用いることが好ましい。
本実施形態に係るセルロース複合体、及び/又はセルロース複合体/樹脂組成物に、セルロース複合体及び/又はセルロース複合体/樹脂組成物の物性等を損なわない範囲で必要に応じ、増量剤、可塑剤、水分吸収剤、物性調整剤、補強剤、着色剤、難燃剤、酸化防止剤、老化防止剤、導電剤、帯電防止剤、紫外線吸収剤、紫外線分散剤、溶剤、香料、消臭剤、顔料、染料、フィラー、希釈剤等の各種添加剤を加えてもよい。
本実施形態に係るセルロース複合体/樹脂組成物は、様々な用途に利用できる。具体的に、自動車用部品、家電、住宅・建材、包装材料等の様々な製品に利用できる。
本実施形態に係るセルロース複合体の製造方法は、概略、以下の各工程を備える。すなわち、セルロース複合体の製造方法は、水酸基を有するセルロースと反応性基を有する高分子とを混合して混合物を調製する混合工程と、水酸基と反応性基とを結合させる工程(結合工程)とを備える。当該結合させる工程は、混合物を加熱する加熱工程であってよい。また、セルロース複合体の製造方法は、加熱工程後に得られるセルロース複合体を乾燥する乾燥工程を更に備えることもできる。なお、混合工程後に加熱工程を実行することも、混合工程と加熱工程とを同時に実行すること(混合工程を加熱しながら実行すること)もできる。
まず、水酸基を有するセルロース、すなわち、所定量のセルロース繊維及び/又はセルロースナノファイバー(CNF)、及び所定量の高分子(つまり、水酸基と反応可能な反応性基を有し、分子鎖が無極性高分子である高分子)それぞれを混合することで混合物を調製する。混合方法には特に限定はなく、手動での混合、撹拌機や混合機を用いた混合等を適宜選択できる。
ここで、セルロースとしてセルロール繊維を用いる場合、セルロース繊維が水分を含んだ状態で用いる。また、セルロースとしてCNFを用いる場合、セルロースの水分散体、すなわち、CNFの水分散体(以下、「CNF水分散体」と称する。)を用いることが好ましい。CNF水分散体のCNFとしては上記の各種のCNFを用いることができる。なお、予め化学処理で疎水化したセルロース繊維を用いることもできる。ただし、セルロース繊維を予め化学処理で疎水化する場合、化学処理に付随する精製等の工程が増加することから、コストや手間が増加する。一方、本実施形態においては、化学未処理のセルロース繊維、及び/又はセルロースの水分散体を用いることができるので、上記工程を経ることを要さず、コスト面等において非常に有利である。
混合工程で用いる高分子は、高分子の微粒子を水に分散させた高分子の水系エマルジョンを用いることが好ましい。高分子の水系エマルジョンを構成する高分子としては、上記の各種の高分子を用いることができる。なお、水(分散媒)中に高分子の微粒子(分散質)が安定に分散している系(乳濁液)を「ラテックス」という。ただし、本実施形態においては、慣行に従って、係る系を「エマルジョン」と称するものとする。
セルロースと高分子との混合比は、セルロース及び高分子の固形分比率で定義できる。すなわち、混合物のセルロース(セルロース繊維、又はCNF)の固形分比率は、3wt%以上であり、5wt%以上であってもよく、10wt%以上が好ましく、20wt%以上であってもよく、セルロース(典型的にはCNF)の凝集を抑制し、高分子との複合体を適切に形成させる観点から、50wt%以下であり、40wt%以下であることが好ましい。
結合工程は、セルロースの水酸基と高分子の反応性基とを結合させる工程である。結合工程は、例えば、水酸基を有するセルロースと、反応性基を有し分子鎖が無極性高分子である高分子との混合物を所定の温度以下に制御して加熱する加熱工程であってよい。また、結合工程は、高分子の微粒子を水に分散させた高分子の水系エマルジョンに、水酸基を有するセルロースを添加して(若しくは添加しつつ)加熱する工程であってもよい。
加熱工程は、混合工程で得られた混合物を所定の温度以下に制御して所定時間、加熱する。この加熱工程により、セルロースの水酸基と高分子の反応性基とが反応し、所定の結合が形成され、この結合を介してセルロースに高分子が結合される。ここで、反応性基が無水コハク酸基、カルボニル基、及びカルボキシル基からなる群から選択される少なくとも1つの反応性基である場合、セルロースの水酸基と反応性基とにより形成される結合はエステル結合である。すなわち、この場合、加熱工程においてエステル化反応が進行することになる。
乾燥工程は、加熱工程後に得られるセルロース複合体に残存する水分を乾燥させる。例えば、乾燥工程は、セルロース複合体を温風で乾燥させる工程である。温風の温度は、一例として80℃程度であり、乾燥時間は8時間程度である。ただし、セルロース複合体に含まれるセルロースの熱劣化を抑制できる範囲であれば、温度及び乾燥時間はこれに限られない。乾燥工程は、例えば、セルロース複合体に含まれる水分量が5wt%程度以下になるまで乾燥を継続することが好ましい。
セルロース複合体/樹脂組成物は、所定の無極性の樹脂に上記で得られるセルロース複合体を所定時間、所定の温度で混練する混練工程を経ることにより調整できる。なお、混練工程後、得られるセルロース複合体/樹脂組成物を養生する養生工程を更に実施してもよい。
混練工程は、セルロース複合体と所定の無極性の樹脂とを所定の温度環境下で混練する工程であり、混練方法に特に限定はなく、混練を一度の工程で実行することも、複数回の工程に分割することもできる。混練工程は、例えば、容器の中でブレードを回転させることにより投入された材料を混練する装置であるニーダー、二軸混練機、及び/又は射出成型機等を用いて実行できる。なお、混練工程に用いるセルロース複合体は粉末状であっても、若しくはコンパウンド時の取り扱い容易性の観点からペレット状であってもよい。一方、無極性の樹脂の形状に特に制限はなく、ペレット状であってもパウダー状であってもよい。
樹脂に添加されるセルロース複合体の量に特に限定はない。例えば、セルロース複合体/樹脂組成物のセルロース複合体の固形分比率をa(wt%)とし、樹脂の固形分比率をb(wt%)とした場合、a:bが、1:1~1:9、好ましくは1:2~1:5程度の比となるように秤量した樹脂とセルロース複合体とを混練することができる。なお、セルロース複合体のセルロース(CNF)含有率は、5wt%以上が好ましく、10wt%以上がより好ましく、15wt%以上が更に好ましく、20wt%以上が更により好ましく、40wt%以下が好ましく、35wt%以下がより好ましく、30wt%以下が更に好ましい。そして、セルロース複合体/樹脂組成物におけるセルロース(CNF)含有率は、機械的物性の確保及び原料コスト等の観点から、2wt%以上が好ましく、3wt%以上がより好ましく、15wt%以下が好ましく、10wt%以下がより好ましく、5wt%以下が更に好ましいと考えられる。
また、混練工程は、加熱しつつ混練を実行することが好ましい。混練時における加熱温度は、樹脂を溶融させ、溶融した樹脂にセルロース複合体を分散させる(つまり、樹脂の融液にセルロース複合体を添加する)観点から、樹脂が溶融する温度以上の温度であり、セルロース複合体に含まれるセルロースが熱劣化しにくい温度以下の温度に制御することが好ましい。具体的に、混練工程は、混練に用いる無極性樹脂、例えば無極性の樹脂としてポリプロピレン系樹脂を用いる場合、樹脂を溶融状態にしつつ過剰な熱をセルロース複合体にかけない観点から、175℃以上の加熱温度に制御することが好ましく、190℃若しくは220℃以下の加熱温度に制御することが好ましい。
本実施形態に係るセルロース複合体は、セルロースの水酸基に反応性基を介して無極性高分子が結合しているので、セルロース複合体を無極性の樹脂に添加した場合に、相溶化剤(分散剤)を添加しなくても、実質的に均一にこの樹脂中にセルロース複合体を分散させることができる。したがって、本実施形態に係るセルロース複合体によれば、例えば、ポリエチレンやポリプロピレン等のオレフィン樹脂にセルロース樹脂及び/又はCNFを均一に分散させることができることから、原材料費及び製造設備費を低減させたうえで、高性能な構造材料を製造することができる。
まず、表1に示す配合割合で各配合物質を混合して混合物を得た。続いて、竪型混練・撹拌機(トリミックスTX-15、井上製作所製)を用い、得られた混合物を減圧下で加熱した。減圧加熱条件は、設定温度145℃、加熱時間30分間、内部圧力0.09MPaにした。これにより、実施例1に係るセルロース複合体(以下、「CNFem」と称する。)の粉末を調製した。続いて、温風乾燥機を用い、得られた実施例1に係るCNFemの粉末を乾燥させた。乾燥条件は、80℃、8時間に設定した。実施例2に係るCNFemについても同様にして調製した。
・セルロースナノファイバー(CNF)スラリー(BiNFi-s WFo-10010:固形分10%、株式会社スギノマシン製)
・MAPPエマルジョン(無水マレイン酸変性ポリプロピレン(MAPP)の水系エマルジョン:水を用いて固形分25%に調製。)
実施例1に係るCNFemをキシレン中で還流し、キシレンに可溶な部分(以下、「可溶部」と称する)と、不溶な部分(以下、「不溶部」と称する)とを得た。そして、可溶部の乾燥物について、フーリエ変換核磁気共鳴装置(JNM-EX400、日本電子株式会社製)を用い、1H-NMR、13C-NMR測定を実施した。測定溶媒はオルトジクロロベンゼンとベンゼンとの混合溶媒を用いた。また、不溶部の乾燥物について、フーリエ変換核磁気共鳴装置(JNM-ECA400、日本電子株式会社製)を用い、13C-NMR測定を実施した。
NMR分光法測定で用いた可溶部及び不溶部について、フーリエ変換赤外分光分析装置(FT/IR-4200typeA、日本分光株式会社製)を用い、全反射測定法(ATR法)による測定を実施した。なお、測定条件は、赤外吸収スペクトルの測定範囲:400~4000cm-1、分解能:4cm-1、積算回数:32回とした。
表2に示す配合割合で各配合物質を混合し、CNF含有率を5wt%に調製したセルロース複合体/樹脂組成物を作製した。続いて、作製したセルロース複合体/樹脂組成物とポリプロピレンとをCNF含有量が3wt%になる配合割合で混合することにより実施例3に係るセルロース複合体/樹脂組成物を作製した。
以下、実施例3に係るセルロース複合体/樹脂組成物、及び比較例1~4に係る試料の物性試験について説明する。物性試験においては、実施例3に係るセルロース複合体/樹脂組成物、及び比較例1~4に係る試料のそれぞれを用い、JIS K6921-2に準拠して試験片を作製し、作製した試験片を用いた。具体的に、各試験片は、試料の予備乾燥処理を80℃で4時間実施し、金型としてISO多目的タイプAを用い、射出成形機FE80S12ASE(日精樹脂工業製)を用いて射出成型により作製した。ここで、溶融樹脂温度を200℃、シリンダ設定温度を175℃~195℃、金型温度を40℃、平均射出速度を200±20(mm/s)、スクリュー回転数を110(rpm)に設定した。
引張試験は、JIS K7161-1,2に準拠し、試験装置としてストログラフAPII(東洋精機製作所製)を用い、試験速度を50mm/min、標線間距離を50mm、チャック間距離を115mm、試験温湿度を23℃、50%RHに設定し、試験数n=5で実施した。
曲げ試験は、JIS K7171に準拠し、試験装置としてベントグラフII(東洋精機製作所製)を用い、試験速度を2mm/min、試験温湿度を23℃、50%RH、スパン間を64mm、圧子、支持台半径を5.0mmに設定し、試験数n=5で実施した。
シャルピー衝撃試験は、JIS K7111-1に準拠し、試験装置としてデジタルインパクトテスター(東洋精機製作所製)を用い、打撃方向をエッジワイズ、試験温湿度を23℃、50%RH、ハンマひょう量を15Jに設定し、試験数n=10で実施した。
実施例3に係る試料、比較例2及び比較例3に係る試料のそれぞれについてマイクロX線CT観察をした。具体的に、試験装置としてX線分析顕微鏡 nano 3DX(Rigaku製)を用い、レンズに高倍率レンズ(L0270)を用い、X線源(ターゲット)にCu(40kV、30mA)を用いた。また、解像度は0.825μm/pixelである。実施例3に係る試料の観察結果を図1、比較例2に係る試料の観察結果を図2、及び比較例3に係る試料の観察結果を図3に示す。
実施例3に係る試料、比較例2及び比較例3に係る試料のそれぞれについてSEM観察をした。具体的に、試料中におけるCNFの分散状態を観察するため、Focused Ion Beam(FIB)装置で試料を作製し、SEM観察した。
Claims (17)
- 水酸基を有するセルロースと、前記水酸基と反応可能な反応性基を有し、分子鎖が無極性高分子である高分子とを混合する混合工程と、
前記水酸基と前記反応性基とを結合させる工程と
を備えるセルロース複合体の製造方法。 - 前記混合工程が、前記セルロースと前記高分子との混合物を得る工程であり、
前記結合させる工程が、前記混合物を所定の温度以下に制御して加熱する加熱工程である請求項1に記載のセルロース複合体の製造方法。 - 前記混合工程が、前記セルロースの水分散体と、前記高分子の水系エマルジョンとを混合する請求項1又は2に記載のセルロース複合体の製造方法。
- 前記セルロースが、セルロース繊維又はセルロースナノファイバー(CNF)である請求項1~3のいずれか1項に記載のセルロース複合体の製造方法。
- 前記反応性基が、炭素原子に結合した酸素原子を有する基であって、前記セルロースの前記水酸基との間で所定の結合を形成することで架橋し得る基であって、
前記無極性高分子が、ポリプロピレン、エチレン・酢酸ビニル共重合樹脂、及びアクリル樹脂からなる群から選択される少なくとも1つの無極性高分子である請求項1~4のいずれか1項に記載のセルロース複合体の製造方法。 - 前記高分子が、重量平均分子量が5,000以上200,000以下の無水マレイン酸変性ポリプロピレン(MAPP)である請求項1~4のいずれか1項に記載のセルロース複合体の製造方法。
- 前記加熱工程が、減圧下で前記混合物を加熱する請求項2に記載のセルロース複合体の製造方法。
- 前記加熱工程が、50℃以上200℃以下の温度で前記混合物を加熱する請求項2に記載のセルロース複合体の製造方法。
- 前記加熱工程を経て得られるセルロース複合体が、前記セルロース複合体に捕捉された、前記反応性基を側鎖に有し、主鎖が無極性高分子である高分子を含む請求項2に記載のセルロース複合体の製造方法。
- 請求項1~9のいずれかに1項に記載のセルロース複合体の製造方法により得られるセルロース複合体と、所定の無極性の樹脂とを混練する工程を備えるセルロース複合体/樹脂組成物の製造方法。
- セルロースの水酸基に反応性基を介して無極性高分子が結合されてなるセルロース複合体。
- 前記セルロースが、セルロース繊維又はセルロースナノファイバー(CNF)である請求項11に記載のセルロース複合体。
- 前記反応性基が、無水コハク酸基、カルボニル基、及びカルボキシル基からなる群から選択される少なくとも1つの反応性基であって、
前記結合が、エステル結合であって、
前記無極性高分子が、ポリプロピレン、エチレン・酢酸ビニル共重合樹脂、及びアクリル樹脂からなる群から選択される少なくとも1つの無極性高分子である請求項11又は12に記載のセルロース複合体。 - 前記反応性基と前記無極性高分子とを含んでなる高分子の重量平均分子量が5,000以上200,000以下である請求項11~13のいずれか1項に記載のセルロース複合体。
- 前記セルロース複合体に捕捉された、前記反応性基と前記無極性高分子とを含んでなる高分子を更に含む請求項11~14のいずれか1項に記載のセルロース複合体。
- 請求項11~15のいずれか1項に記載のセルロース複合体と、所定の無極性の樹脂とを含むセルロース複合体/樹脂組成物。
- 請求項16に記載のセルロース複合体/樹脂組成物を含む製品。
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