Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
  • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
  • C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
  • C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/02—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to polysaccharides

Definitions

• the present invention relates to a vinyl chloride resin composition, a method for producing the same, and a molded product.
• Plant fibers are not artificially synthesized, but are used by loosening plant-derived fibers. Since the plant fiber hardly remains as ash during combustion, there are no problems such as ash treatment in the incinerator and landfill treatment. For this reason, in recent years, research on the use of plant fibers as reinforcing materials for resins has been advanced, and in particular, cellulose nanofibers obtained by defibrating plant fibers to the nano level (hereinafter, also referred to as nanocellulose, fine cellulose fibers, or CNF). ) Is being studied.
• CNF nanocellulose, fine cellulose fibers
• Patent Document 1 describes a polyvinyl chloride resin composition containing a polyvinyl chloride resin, fine cellulose fibers or a modified product thereof, and a plasticizer. It is said that the polyvinyl chloride resin composition of Patent Document 1 maintains excellent strength even at high temperatures, does not lose its flexibility at low temperatures, and has excellent elasticity.
• Patent Document 2 describes a vinyl chloride resin composite for paste processing, which contains 0.002 to 0.9 parts by weight of fine cellulose fibers with respect to 100 parts by weight of the vinyl chloride resin for paste processing. Have been described. It is said that the complex of Patent Document 2 becomes a plastisol exhibiting high thixotropy property, and a paste PVC composition exhibiting good mechanical strength can be obtained.
• Patent Document 3 describes a cellulose fiber planar structure or cellulose fiber particles produced from a dispersion of fibers composed of cellulose having a cellulose type I crystal and having a specific repeating unit and / or a derivative thereof, and cellulose fiber particles other than cellulose.
• a structure, a substrate, a window material, and a vehicle body including a polymer cellulose composite obtained by combining a polymer with a polymer are disclosed.
• Patent Document 4 discloses that at least a part of a hollow window frame made of synthetic resin is formed from a composition containing a vinyl chloride resin and chemically modified cellulose nanofibers as main components.
• the chemically modified cellulose nanofibers used in Patent Document 4 are specifically obtained by chemically modifying commercially available pulp-derived cellulose with a propionyl group, and it is specifically a matter of using finely divided nanocellulose. Not disclosed.
• Patent Document 5 a cellulosic raw material is oxidized by using hypochloric acid having an effective chlorine concentration of 14% by mass to 43% by mass or a salt thereof as an oxidizing agent as a resin modifying agent having an excellent resin modifying effect.
• a resin modifier containing a polymer of cellulose nanofibers and an ethylenically unsaturated monomer obtained by defibrating the oxidized cellulose is disclosed.
• Patent Document 5 does not describe a polyvinyl chloride resin composition containing the above-mentioned cellulose nanofibers in a vinyl chloride resin.
• the vinyl chloride resin can improve its strength by containing CNF.
• the vinyl chloride resins of Patent Documents 1 and 2 include CNF obtained by TEMPO oxidation (also referred to as TEMPO oxide CNF).
• TEMPO Oxidized CNF is obtained by oxidizing a cellulosic raw material with 2,2,6,6-tetraalkylpiperidine-1-oxyl (TEMPO) and then applying a strong force using a device such as a high-pressure homogenizer to make it finer.
• TEMPO Oxidized CNF is obtained by oxidizing a cellulosic raw material with 2,2,6,6-tetraalkylpiperidine-1-oxyl (TEMPO) and then applying a strong force using a device such as a high-pressure homogenizer to make it finer.
• the fine cellulose fiber used in Patent Document 3 is obtained by mechanical defibration and ultrasonic treatment using a plant-derived raw material as a starting material.
• the vinyl chloride resin containing CNF also has problems of low productivity and high cost, and there is a demand for a means for efficiently obtaining a high-strength vinyl chloride resin.
• the present invention has been made in view of the above circumstances, and its main purpose is to efficiently obtain a vinyl chloride resin having excellent strength.
• the strength can be increased by containing the predetermined nanocellulose in the vinyl chloride resin, and that the vinyl chloride resin can be efficiently obtained.
• the invention was completed. Specifically, the present invention provides the following means.
• a vinyl chloride resin composition containing nanocellulose and a vinyl chloride resin A vinyl chloride resin composition in which the nanocellulose is derived from oxidized cellulose, which is an oxide of a cellulosic raw material due to hypochlorous acid or a salt thereof, and is substantially free of N-oxyl compounds.
• the method for producing a vinyl chloride resin composition according to any one of [1] to [10]. A production method comprising a step of polymerizing a raw material monomer of a vinyl chloride resin using a mixture containing nanocellulose and a raw material monomer of a vinyl chloride resin.
• Including the step of polymerizing the raw material monomer of vinyl chloride resin A production method, wherein the oxidized cellulose contains an oxide of a cellulosic raw material due to hypochlorous acid or a salt thereof.
• a step of obtaining a second mixture containing nanocellulose and a vinyl chloride resin by stirring the first mixture containing cellulose oxide and a vinyl chloride resin, and a step of drying the second mixture are included.
• a method for producing a vinyl chloride resin composition containing nanocellulose and a vinyl chloride resin A step of obtaining a mixture containing nanocellulose and a vinyl chloride resin by stirring the cellulose oxide and continuously adding a vinyl chloride resin, and a step of drying the mixture are included.
• a production method wherein the oxidized cellulose contains an oxide of a cellulosic raw material due to hypochlorous acid or a salt thereof.
• the vinyl chloride resin composition of the present invention has excellent strength and can be efficiently obtained.
• the present invention is not limited to the following embodiments.
• the components including element steps and the like are not essential unless otherwise specified.
• the term "process” includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
• the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
• each component may contain a plurality of applicable substances.
• the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified.
• a plurality of types of particles corresponding to each component may be contained.
• the particle size of each component means a value for a mixture of the plurality of particles present in the composition, unless otherwise specified.
• the vinyl chloride resin composition of the present invention contains nanocellulose.
• the nanocellulose is derived from oxidized cellulose which is an oxide of a cellulosic raw material by hypochloric acid or a salt thereof (in other words, a solution of cellulose oxide which is an oxide of a cellulosic raw material by hypochloric acid or a salt thereof. (Contains fibers) and is substantially free of N-oxyl compounds.
• the vinyl chloride resin composition of the present invention refers to a composition mainly containing a vinyl chloride resin as a constituent resin.
• "mainly containing a vinyl chloride resin as a constituent resin” means that the ratio of the vinyl chloride resin to the total amount of the constituent resins of the composition is usually in excess of 50% by mass. The above ratio may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. It may be 100% by mass.
• the form of the vinyl chloride resin composition of the present invention is not particularly limited, and may be, for example, powdery, pelletized, or lumpy.
• the vinyl chloride resin composition of the present invention may be used by molding powder, pellets, or lumps as they are. Further, the vinyl chloride resin composition of the present invention is used by mixing powder, pellets, or lumps with the vinyl chloride resin composition and the target resin to be blended (hereinafter, also referred to as raw material resin). May be good.
• the vinyl chloride resin composition is also referred to as a resin modification composition. That is, the vinyl chloride resin composition of the present invention includes both an embodiment in which the vinyl chloride resin composition itself is used as a resin and an embodiment in which the composition for modifying the resin is used.
• the vinyl chloride resin composition of the present invention contains nanocellulose, which is derived from oxidized cellulose which is an oxide of a cellulosic raw material by hypochlorous acid or a salt thereof, and which is substantially free of N-oxyl compound.
• Nanocellulose in the present invention is a general term for finely divided (also referred to as nanonized) cellulose, and includes fine cellulose fibers, cellulose nanocrystals, and the like, and also includes modified products thereof (details of the modified products will be described later). do).
• Fine cellulose fibers are also referred to as cellulose nanofibers (also referred to as CNF).
• the nanocellulose in the present invention is obtained by oxidizing a cellulose-based raw material with hypochlorous acid or a salt thereof and inducing it to oxidized cellulose (that is, corresponding to the oxide of the above-mentioned cellulose-based raw material).
• the nanocellulose obtained by this production method can exhibit the property that oxidized cellulose is easily defibrated (easy defibration), and defibration proceeds sufficiently without applying a large energy load.
• Such nanocellulose can be obtained at low cost and can be efficiently produced. Therefore, the vinyl chloride resin composition of the present invention can also be efficiently obtained. Further, the nanocellulose in the present invention has high dispersibility.
• this nanocellulose When this nanocellulose is combined with a vinyl chloride resin, it is considered that a resin composition in which the nanocellulose is uniformly dispersed in the vinyl chloride resin can be obtained. As a result, a vinyl chloride resin having excellent strength, specifically, a flexural modulus can be obtained.
• the nanocellulose in the present invention is a miniaturized version of oxidized cellulose obtained by oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof.
• the oxidized cellulose can also be said to be an oxide of a cellulosic raw material. Therefore, the nanocellulose in the present invention is derived from the oxide of the cellulosic raw material by hypochlorous acid or a salt thereof.
• the main component of the plant is cellulose, and a bundle of cellulose molecules is called a cellulose microfibril. Cellulose in cellulosic raw materials is also contained in the form of cellulosic microfibrils.
• the nanocellulose in the present invention is required, for example, in a step of oxidizing a cellulosic raw material to produce oxidized cellulose using hypochlorous acid or a salt thereof having an effective chlorine concentration of 7% by mass or more and 43% by mass or less. Accordingly, it can be suitably produced by a production method including a step of defibrating the oxidized cellulose to make it finer.
• the nanocellulose in the present invention oxidizes a cellulosic raw material under the condition that the effective chlorine concentration of hypochlorous acid or a salt thereof in the reaction system is relatively high (for example, 14% by mass to 43% by mass). It is more preferable to obtain it by defibrating the oxidized cellulose, if necessary.
• the vinyl chloride resin composition of the present invention contains nanocellulose, it can also be produced by blending a defibrated cellulose oxide to be finely divided, and the vinyl chloride resin composition can be produced at the time of preparation. Can also be produced by using the above as a raw material and refining the oxidized cellulose into nanocellulose during preparation. Therefore, the nanocellulose in the vinyl chloride resin composition is refined at an appropriate time point.
• the above-mentioned oxidized cellulose can be obtained without using an N-oxyl compound such as TEMPO. Therefore, the oxidized cellulose and nanocellulose in the present invention are substantially free of N-oxyl compounds. Therefore, the vinyl chloride resin composition of the present invention is highly safe because the influence of the N-oxyl compound on the environment and the human body is sufficiently reduced.
• substantially free of N-oxyl compound means that the oxidized cellulose and the nanocellulose do not use the N-oxyl compound in producing the oxidized cellulose, or N-. It means that the content of the oxyl compound is 2.0 mass ppm or less with respect to the total amount of oxidized cellulose or nanocellulose, and is preferably 1.0 mass ppm or less.
• N-oxyl compound is substantially contained. It means "not included”.
• the content of the N-oxyl compound can be measured by a known means.
• a method using a trace total nitrogen analyzer can be mentioned.
• the nitrogen component derived from the N-oxyl compound in the oxidized cellulose or nanocellulose is the amount of nitrogen using a trace total nitrogen analyzer (for example, manufactured by Mitsubishi Chemical Analytech Co., Ltd., device name: TN-2100H, etc.). Can be measured as.
• the above-mentioned oxidized cellulose is excellent in defibration.
• the above-mentioned oxidized cellulose can be uniformly finely divided even when the defibration treatment is performed under mild conditions, and is excellent in defibration.
• the nanocellulose in the present invention can be produced through an oxidation reaction using hypochlorous acid or a salt thereof, as described in detail in [Method for producing nanocellulose] described later, and has the following zeta potential and light transmittance. It is preferable to satisfy.
• the zeta potential and the light transmittance can also be used as indicators of the nanocellulose.
• the nanocellulose in the present invention preferably has a zeta potential of ⁇ 30 mV or less.
• the zeta potential is -30 mV or less (that is, the absolute value is 30 mV or more)
• sufficient repulsion between microfibrils is obtained, and nanocellulose having a high surface charge density is likely to be generated when defibrated.
• the dispersion stability of nanocellulose is improved, and the viscosity stability and handleability of the slurry are excellent.
• the zeta potential is -100 mV or more (that is, the absolute value is 100 mV or less)
• oxidative cleavage in the fiber direction with the progress of oxidation tends to be suppressed, so that nanocellulose having a uniform size can be obtained.
• nanocellulose is stable and has high dispersibility in water, and the obtained vinyl chloride resin composition tends to contain nanocellulose uniformly. Therefore, there is a tendency that the vinyl chloride resin has less aggregation and is uniformly dispersed to increase the strength.
• the zeta potential of nanocellulose is preferably ⁇ 35 mV or less, more preferably ⁇ 40 mV or less, and even more preferably ⁇ 50 mV or less.
• the lower limit of the zeta potential -90 mV or more is preferable, -85 mV or more is more preferable, -80 mV or more is further preferable, -77 mV or more is further preferable, -70 mV or more is further preferable, and -65 mV or more is more preferable. More preferred.
• the range of the zeta potential can be appropriately combined with the above-mentioned lower limit and upper limit.
• the zeta potential is preferably ⁇ 90 mV or more and -30 mV or less, more preferably ⁇ 85 mV or more and -30 mV or less, still more preferably -80 mV or more and -30 mV or less, still more preferably ⁇ 77 mV or more and -30 mV or less. Yes, more preferably ⁇ 70 mV or more and ⁇ 30 mV or less, still more preferably ⁇ 65 mV or more and ⁇ 30 mV or less, and even more preferably ⁇ 65 mV or more and ⁇ 35 mV or less.
• the zeta potential is a value measured under the conditions of pH 8.0 and 20 ° C. for an aqueous dispersion having a concentration of nanocellulose of 0.1% by mass. Specifically, the measurement can be performed according to the conditions described in Examples described later.
• the nanocellulose dispersion in which nanocellulose having a narrow fiber width and few aggregates is dispersed in a dispersion medium has less light scattering of nanocellulose and can exhibit high light transmittance.
• the nanocellulose in the present invention has a light transmittance of 95% or more in a mixed solution having a solid content concentration of 0.1% by mass mixed with water.
• the light transmittance is more preferably 96% or more, still more preferably 97% or more.
• the light transmittance is a value measured by a spectrophotometer at a wavelength of 660 nm. Specifically, the measurement can be performed according to the conditions described in Examples described later.
• the degree of polymerization of the oxidized cellulose is preferably 600 or less.
• the degree of polymerization of cellulose oxide is 600 or less, a large amount of energy tends to be unnecessary for defibration, sufficient easy defibration can be exhibited, dispersibility is improved, and strength tends to be improved. It is in.
• the degree of polymerization of cellulose oxide is 600 or less, the amount of cellulose oxide that is insufficiently defibrated is reduced, so that light scattering and the like are reduced when the finely divided nanocellulose is dispersed in a dispersion medium. , Transparency tends to improve.
• the size of the obtained nanocellulose is less likely to vary, and the quality tends to be uniform.
• the viscosity of the slurry containing nanocellulose tends to be low, and the handleability of the slurry tends to be improved.
• the lower limit of the degree of polymerization of cellulose oxide is not particularly set.
• the degree of polymerization of cellulose oxide is 50 or more, the proportion of particulate cellulose rather than fibrous is reduced, the quality of the slurry becomes uniform, the viscosity becomes stable, and one of the characteristics of nanocellulose is. It becomes easy to obtain the viscosity property.
• the reinforcing effect when added to the resin tends to be improved.
• the degree of polymerization of cellulose oxide is preferably in the range of 50 or more and 600 or less.
• the degree of polymerization of the oxidized cellulose is more preferably 580 or less, further preferably 560 or less, still more preferably 550 or less, still more preferably 500 or less, still more preferably 450 or less. Even more preferably, it is 400 or less.
• the lower limit of the degree of polymerization is more preferably 60 or more, still more preferably 70 or more, still more preferably 80 or more, still more preferably, from the viewpoint of improving the viscosity stability and coatability of the slurry. Is 90 or more, more preferably 100 or more, even more preferably 110 or more, and most preferably 120 or more.
• the preferable range of the degree of polymerization can be determined by appropriately combining the above-mentioned upper limit and lower limit.
• the degree of polymerization of cellulose oxide is more preferably 60 to 600, still more preferably 70 to 600, still more preferably 80 to 600, still more preferably 80 to 550, and even more preferably 80 to 80. It is 500, more preferably 80 to 450, and particularly preferably 80 to 400.
• the degree of polymerization of the oxidized cellulose can be adjusted by changing the reaction time, the reaction temperature, the pH, and the effective chlorine concentration of the hypochlorous acid or a salt thereof at the time of the oxidation reaction. Specifically, since the degree of polymerization tends to decrease as the degree of oxidation increases, for example, a method of increasing the reaction time and / or the reaction temperature of oxidation can be mentioned in order to reduce the degree of polymerization. As another method, the degree of polymerization of cellulose oxide can be adjusted by the stirring conditions of the reaction system at the time of the oxidation reaction.
• the degree of polymerization of cellulose oxide is the average degree of polymerization (viscosity average degree of polymerization) measured by the viscosity method. For details, follow the method described in Examples described later.
• the amount of carboxy groups of the nanocellulose and the oxidized cellulose is preferably 0.10 mmol / g or more.
• the amount of the carboxy group is 0.10 mmol / g or more, sufficient friability can be imparted to the oxidized cellulose.
• the amount of carboxy group is preferably less than 2.0 mmol / g.
• the carboxy group amount of the nanocellulose and the oxidized cellulose is more preferably 0.35 mmol / g or more, further preferably 0.40 mmol / g or more, still more preferably 0.42 mmol / g or more.
• the upper limit of the amount of carboxy group is more preferably 1.5 mmol / g or less, further preferably 1.2 mmol / g or less, still more preferably 1.0 mmol / g or less, and even more preferably 0. It is 9.9 mmol / g or less.
• the preferable range of the amount of carboxy group can be determined by appropriately combining the above-mentioned upper limit and lower limit.
• the carboxy group amount of the nanocellulose and the oxidized cellulose is more preferably 0.35 to 2.0 mmol / g, still more preferably 0.35 to 1.5 mmol / g, still more preferably 0.40 to 0.40 to g. It is 1.5 mmol / g, more preferably 0.50 to 1.2 mmol / g, still more preferably more than 0.50 to 1.2 mmol / g, and even more preferably 0.55 to 1. It is 0 mmol / g.
• the amount of carboxy group (mmol / g) is 0.05 N after adding 0.1 M (also referred to as mol / L) aqueous hydrochloric acid solution to an aqueous solution of nanocellulose or oxidized cellulose mixed with water to adjust the pH to 2.5. From the amount of sodium hydroxide (a) consumed in the neutralization step of a weak acid in which the change in electrical conductivity is moderate, the electric conductivity is measured by dropping the aqueous sodium hydroxide solution of the above (11.0) until the pH reaches 11.0. It is a value calculated using the following formula. For details, follow the method described in Examples described later.
• the amount of carboxy group can be adjusted by changing the reaction time of the oxidation reaction, the reaction temperature, the pH of the reaction solution, and the like.
• Amount of carboxy group a (ml) x 0.05 / mass of nanocellulose or oxidized cellulose (g)
• the average fiber diameter of the oxidized cellulose in the present invention is not particularly limited, but may be 0.1 ⁇ m or more and 200 ⁇ m or less.
• the nanocellulose or oxidized cellulose in the present invention preferably has a structure in which at least two of the hydroxyl groups of the glucopyranose ring constituting the cellulose are oxidized. More specifically, it has a structure in which the hydroxyl groups at the 2- and 3-positions of the glucopyranose ring are oxidized and a carboxy group is introduced. Further, it is preferable that the hydroxyl group at the 6-position of the glucopyranose ring in the nanocellulose or oxidized cellulose is not oxidized and remains as a hydroxyl group.
• the position of the carboxy group in the glucopyranose ring can be analyzed by comparing the solution NMR spectrum using rayon oxide as a model molecule and the solid 13 C-NMR spectrum of cellulose oxide.
• Rayon has the same chemical structure as cellulose, and its oxide (rayon oxide) is water-soluble.
• rayon oxide By dissolving rayon oxide in heavy water and performing one-dimensional 13 C-NMR measurement of the solution, a peak of carbon attributed to the carboxy group is observed at 165 to 185 ppm.
• the oxidized cellulose or nanocellulose used in the present invention obtained by oxidizing the raw material cellulose with hypochlorous acid or a salt thereof, two signals appear in this chemical shift range. Further, by solution two-dimensional NMR measurement, it can be determined that the carboxy group is introduced at the 2-position and the 3-position.
• the carboxy group is introduced at the 2-position and the 3-position by evaluating the spread of the peak appearing at 165 to 185 ppm. That is, two peak area values obtained by vertically dividing the area value at the peak top after drawing a baseline on the peak in the range of 165 ppm to 185 ppm in the solid 13 C-NMR spectrum to obtain the total area value. A ratio (large area value / small area value) is obtained, and if the ratio of the peak area values is 1.2 or more, it can be said that the peak is broad.
• the presence or absence of the broad peak can be determined by the ratio of the baseline length L in the range of 165 ppm to 185 ppm and the perpendicular length L'from the peak top to the baseline. That is, if the ratio L'/ L is 0.1 or more, it can be determined that a broad peak exists.
• the ratio L'/ L may be 0.2 or more, 0.3 or more, 0.4 or more, or 0.5 or more.
• the upper limit of the ratio L'/ L is not particularly limited, but usually it may be 3.0 or less, 2.0 or less, or 1.0 or less.
• the structure of the glucopyranose ring can also be determined by analysis according to the method described in Sustainable Chem. Eng. 2020, 8, 48, 17800-17806.
• Nanocellulose in the present invention is an aggregate of fibers in units of one.
• the nanocellulose in the present invention contains carboxylated nanocellulose, it suffices to contain at least one carboxylated nanocellulose, and it is preferable that the carboxylated nanocellulose is the main component.
• the main component of the carboxylated nanocellulose is that the ratio of the carboxylated nanocellulose to the total amount of nanocellulose exceeds 50% by mass, preferably exceeds 70% by mass, and more preferably 80% by mass. Refers to being in excess.
• the upper limit of the above ratio is 100% by mass, but it may be 98% by mass or 95% by mass.
• the average fiber length of nanocellulose in the present invention is preferably 100 nm or more and 700 nm or less.
• the average fiber width of nanocellulose in the present invention is preferably 2.0 nm or more and 5.0 nm or less.
• the average fiber length of nanocellulose is more preferably in the range of 100 nm or more and 600 nm or less, and further preferably in the range of 100 nm or more and 400 nm or less.
• the average fiber length is 700 nm or less, it is possible to avoid a situation in which the slurry is violently thickened and handling becomes difficult. Further, when the average fiber length is 100 nm or more, the viscosity characteristic of nanocellulose is easily developed.
• the average fiber width of nanocellulose is more preferably in the range of 2.0 nm or more and 4.5 nm or less, and more preferably in the range of 2.5 nm or more and 4.0 nm or less.
• the average fiber width is 2.0 nm or more, the strength improvement of the resin composition containing nanocellulose is likely to occur. Further, when the average fiber width is 5.0 nm or less, the strength improvement is likely to occur.
• nanocellulose and water are mixed so that the concentration of nanocellulose is approximately 1 to 10 ppm, and a sufficiently diluted nanocellulose aqueous dispersion is naturally dried on a mica substrate.
• the shape of nanocellulose was observed using a scanning probe microscope, and an arbitrary number of fibers were randomly selected from the obtained images.
• the average fiber width and the average fiber length may be measured using an aqueous dispersion of nanocellulose, or may be measured using an aqueous dispersion containing nanocellulose and a vinyl chloride monomer. Specifically, the average fiber length and the average fiber width are obtained by diluting an aqueous dispersion of nanocellulose with pure water, for example, 1000 to 1000000 times, and naturally drying it on a mica substrate.
• the shape of nanocellulose can be observed in AC mode using a probe microscope "MFP-3D infinity”.
• the fiber length can be binarized and analyzed using the image processing software "ImageJ”.
• the nanocellulose in the present invention contains fine cellulose fibers, cellulose nanocrystals, and the like, and also includes modified products thereof.
• modified product of nanocellulose refers to a product in which nanocellulose is modified with an arbitrary compound.
• the compound for modifying nanocellulose is not particularly limited, and metal soap, amine or quaternary ammonium can be preferably mentioned. It is considered that the reaction between the carboxy group on the surface of the nanocellulose and the arbitrary compound portion modifies the nanocellulose, improves the hydrophobicity of the nanocellulose, and improves the affinity for the vinyl chloride resin.
• the amine is not particularly limited and may be any of primary, secondary and tertiary.
• the number of carbon atoms of the hydrocarbon group or aromatic group bonded to the nitrogen atom of the amine or quaternary ammonium salt compound (if two or more hydrocarbon groups or aromatic groups are bonded to the nitrogen atom, the total carbon number)
• the number is not particularly limited and may be selected from 1 to 100 carbon atoms.
• Specific examples of the amine include monododecylamine.
• an amine having a polyalkylene oxide structure such as an ethylene oxide / propylene oxide (EO / PO) copolymer may be used. From the viewpoint of imparting sufficient hydrophobicity to nanocellulose, the number of carbon atoms is preferably 3 or more, and more preferably 5 or more.
• the quaternary ammonium salt compound that modifies nanocellulose is not particularly limited.
• the quaternary ammonium salt compound includes a quaternary ammonium hydroxide such as tetrabutylammonium hydroxide, a quaternary ammonium chloride such as tetrabutylammonium chloride, and a quaternary ammonium bromide such as tetrabutylammonium bromide.
• a quaternary ammonium iodide such as tetrabutylammonium iodide can be considered.
• the metal soap that modifies nanocellulose is not particularly limited, and is, for example, a metal salt of a long-chain fatty acid such as a magnesium salt of a long-chain fatty acid, a calcium salt of a long-chain fatty acid, or a zinc salt of a long-chain fatty acid; Examples thereof include a mixture of a calcium salt and a zinc salt of a long-chain fatty acid, and a lead-based metal soap, and among these, a metal salt of a long-chain fatty acid is preferable.
• the metal salt of the long-chain fatty acid is preferably a polyvalent metal salt of the long-chain fatty acid.
• long-chain fatty acids examples include buty acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecic acid, palmitic acid, isostearic acid, stearic acid, oleic acid and linole.
• examples thereof include acid, ricinoleic acid, octyl acid, arachidic acid, arachidonic acid, behenic acid, lignoseric acid, montanic acid and the like.
• the metal soap magnesium stearate, a mixture of calcium stearate salt and zinc stearate salt, and lead-based thermometal soap are more preferable.
• metal soaps may be used alone or in combination of two or more.
• a commercially available product containing the above-mentioned metal soap may be used, and examples of the commercially available product include RZ-161, RZ-162, MDZ-CP-102, FTZ-111, and SCI-HSA manufactured by San Ace.
• a modified nanocellulose can be obtained, for example, by refining oxidized cellulose that has been reacted with an arbitrary compound. Specifically, an acid, preferably hydrochloric acid, is added to an aqueous dispersion containing oxidized cellulose obtained from hypochlorous acid or a salt thereof as a cellulose-based raw material to make the carboxy group H-type, and further any compound is added. Then, if necessary, the dispersion medium can be removed to obtain a modified form of cellulose oxide, and the modified form of nanocesulose can be obtained by appropriately refining the mixture.
• an acid preferably hydrochloric acid
• the content of nanocellulose in the vinyl chloride resin composition of the present invention is preferably 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. It is 15 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less. When the content of nanocellulose is 0.5 parts by mass or more and 20 parts by mass or less, the strength of the vinyl chloride resin tends to be further improved.
• the vinyl chloride resin composition may further contain an arbitrary additive in an arbitrary content.
• the additive include the above-mentioned metal soap, lubricant, gelling improver, antistatic agent, heat stabilizer, stabilizing aid, processing aid, filler, antioxidant, light stabilizer, pigment and the like. Can be appropriately blended as long as the object of the present invention is not impaired, and a plasticizer can also be appropriately used as needed.
• the lubricant is not particularly limited, and examples thereof include stearyl alcohol and the like.
• the nanocellulose in the present invention is produced by a method including a step A of oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof to obtain oxidized cellulose and a step B of defibrating the oxidized cellulose as necessary. Can be done.
• the nanocellulose in the present invention can also be obtained without performing step B. That is, the nanocellulose in the present invention is produced by a production method including a step of oxidizing a cellulosic raw material with hypochlorous acid or a salt thereof, and after the oxidation, obtaining nanocellulose without substantially performing a defibration treatment. Can also be manufactured.
• the nanocellulose in the present invention can also be obtained by a method of defibrating the oxidized cellulose in the presence of a vinyl chloride resin or a raw material monomer of a vinyl chloride resin. That is, nanocellulose may be used during the production of the vinyl chloride resin.
• the cellulosic raw material is not particularly limited as long as it is a material mainly composed of cellulose, and examples thereof include pulp, natural cellulose, regenerated cellulose, and fine cellulose depolymerized by mechanically treating cellulose.
• a commercially available product such as crystalline cellulose made from pulp can be used as it is.
• unused biomass containing a large amount of cellulose components such as okara and soybean skin may be used as a raw material.
• the cellulosic raw material may be treated with an alkali having an appropriate concentration in advance.
• hypochlorous acid or a salt thereof used for oxidation of cellulose-based raw materials examples include hypochlorous acid water, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, and ammonium hypochlorite. Can be mentioned. Of these, sodium hypochlorite is preferable from the viewpoint of ease of handling.
• Examples of the method for producing oxidized cellulose by oxidizing a cellulosic raw material include a method of mixing a cellulosic raw material with a reaction solution containing hypochlorous acid or a salt thereof.
• the solvent contained in the reaction solution is preferably water because it is easy to handle and side reactions are unlikely to occur.
• the effective chlorine concentration of hypochlorous acid or a salt thereof in the reaction solution is preferably 14 to 43% by mass. When the effective chlorine concentration of the reaction solution is in the above range, the amount of carboxy groups in the oxidized cellulose can be sufficiently increased, and defibration can be easily performed.
• the effective chlorine concentration of the reaction solution is more preferably 15% by mass or more, further preferably 18% by mass or more, still more preferably 20% by mass or more. Is. Further, from the viewpoint of suppressing excessive decomposition of cellulose during defibration, the effective chlorine concentration of the reaction solution is more preferably 40% by mass or less, still more preferably 38% by mass or less.
• the range of the effective chlorine concentration of the reaction solution can be appropriately combined with the above-mentioned lower limit and upper limit.
• the range of the effective chlorine concentration is more preferably 16 to 43% by mass, still more preferably 18 to 40% by mass.
• hypochlorous acid is a weak acid that exists as an aqueous solution
• hypochlorite is a compound in which hydrogen of hypochlorous acid is replaced with another cation.
• sodium hypochlorite which is a hypochlorite
• the concentration is measured not as the concentration of sodium hypochlorite but as the amount of effective chlorine in the solution. ..
• sodium hypochlorite since the oxidizing power of the divalent oxygen atom generated by the decomposition of sodium hypochlorite corresponds to the diatomic equivalent of monovalent chlorine, sodium hypochlorite is used.
• the sample is first weighed, water, potassium iodide and acetic acid are added and left to stand, and the free iodine solution is titrated with a sodium thiosulfate solution using an aqueous starch solution as an indicator to measure the effective chlorine concentration. do.
• the oxidation reaction of the cellulosic raw material with hypochlorous acid or a salt thereof should be carried out while adjusting the pH in the range of 5.0 to 14.0. Within this range, the oxidation reaction of the cellulosic raw material can be sufficiently promoted, and the amount of carboxy groups in the oxidized cellulose can be sufficiently increased. This makes it possible to easily defibrate the oxidized cellulose.
• the pH of the reaction system is more preferably 7.0 or higher, still more preferably 8.0 or higher.
• the upper limit of the pH of the reaction system is more preferably 13.5 or less, still more preferably 13.0 or less.
• the pH range of the reaction system is more preferably 7.0 to 14.0, and even more preferably 8.0 to 13.5.
• hypochlorite sodium hypochlorite is used as hypochlorous acid or a salt thereof.
• the reaction solution is preferably an aqueous solution of sodium hypochlorite.
• a method of adjusting the effective chlorine concentration of the aqueous sodium hypochlorite solution to the target concentration for example, target concentration: 14% by mass to 43% by mass
• sodium hypochlorite having a lower effective chlorine concentration than the target concentration is used.
• a method for concentrating an aqueous solution, a method for diluting an aqueous solution of sodium hypochlorite having an effective chlorine concentration higher than the target concentration, and a method using crystals of sodium hypochlorite (for example, sodium hypochlorite pentahydrate) as a solvent for example, sodium hypochlorite pentahydrate
• Examples thereof include a method of dissolving.
• adjusting the concentration of effective chlorine as an oxidizing agent by a method of diluting an aqueous solution of sodium hypochlorite or a method of dissolving crystals of sodium hypochlorite in a solvent has less self-decomposition (that is,). There is little decrease in the effective chlorine concentration), and it is preferable because it is easy to adjust the effective chlorine concentration.
• the method of mixing the cellulosic raw material and the sodium hypochlorite aqueous solution is not particularly limited, but from the viewpoint of ease of operation, it is preferable to add the cellulosic raw material to the sodium hypochlorite aqueous solution and mix them.
• the stirring method include a magnetic stirrer, a stirring rod, a stirring machine with a stirring blade (three-one motor), a homomixer, a dispenser type mixer, a homogenizer, and external circulation stirring.
• shear stirrers such as homomixers and homogenizers, stirrers with stirring blades, and stirrers with stirring blades are available because the oxidation reaction of the cellulosic raw material proceeds smoothly and the degree of polymerization of the oxidized cellulose can be easily adjusted to a predetermined value or less.
• a method using one or more of the disper type mixers is preferable, and a method using a stirrer with a stirring blade is particularly preferable.
• a stirrer with a stirrer blade a device equipped with a known stirrer blade such as a propeller blade, a paddle blade, and a turbine blade can be used as the stirrer.
• a stirrer with a stirring blade it is preferable to perform stirring at a rotation speed of 50 to 300 rpm.
• the reaction temperature in the oxidation reaction is preferably 15 ° C to 100 ° C, more preferably 20 ° C to 90 ° C.
• an alkaline agent for example, sodium hydroxide or the like
• an acid for example, hydrochloric acid or the like
• the reaction time of the oxidation reaction can be set according to the degree of progress of oxidation, but is preferably about 15 minutes to 50 hours.
• the pH of the reaction system is 10 or more, it is preferable to set the reaction temperature to 30 ° C. or higher and / or the reaction time to 30 minutes or longer.
• the zeta potential and light transmittance of nanocellulose can be adjusted to desired values by adjusting the reaction time, reaction temperature, stirring conditions, etc. of the oxidation reaction. Specifically, as the reaction time is lengthened and / or the reaction temperature is increased, oxidation of the cellulosic raw material to the surface of the cellulose microfibrils progresses, and electrostatic repulsion and osmotic pressure cause repulsion between the fibrils. By strengthening, the average fiber width becomes smaller, which tends to increase the light transmission rate.
• the zeta potential is set by setting one or more of the reaction time, reaction temperature, and stirring conditions of oxidation (for example, lengthening the reaction time) on the side where oxidation is further promoted (that is, the side where the degree of oxidation is increased). It tends to be expensive.
• a known isolation treatment such as filtration is performed, and further purification is performed as necessary to obtain an oxide of the cellulosic raw material by hypochlorous acid or a salt thereof.
• Oxidized cellulose can be obtained as.
• the solution containing the oxidized cellulose obtained by the above reaction may be directly subjected to the defibration treatment.
• a cellulose-based raw material is oxidized using hypochlorous acid or a salt thereof, and after the oxidation, nanocellulose is produced without substantially performing a defibration treatment. It may include the step of obtaining.
• substantially no defibration treatment means a step of isolating the obtained oxidized cellulose after oxidation and refining the oxidized cellulose using a mechanical defibrating device or the like. Means not to do.
• the reaction time of the oxidation reaction is preferably 30 minutes or more.
• the reaction time of the oxidation reaction is more preferably 2 hours or more, still more preferably 3 hours or more, from the viewpoint of further advancing the defibration.
• the upper limit of the reaction time of the oxidation reaction is not particularly limited and may be appropriately adjusted.
• the upper limit of the reaction time is usually 15 days or less, may be 10 days or less, or may be 7 days or less. From the viewpoint of productivity, the upper limit of the reaction time is preferably 30 hours or less, more preferably 20 hours or less.
• the concentration of the cellulosic raw material during the oxidation reaction is preferably 30 with respect to the total amount of the reaction mixture during the oxidation reaction from the viewpoint of improving workability such as facilitating stirring during the oxidation reaction and from the viewpoint of advancing defibration. It is mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less.
• the lower limit of the concentration of the cellulosic raw material in the oxidation reaction is usually 0.1% by mass or more, and from the viewpoint of productivity, it is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably. 3% by mass or more.
• the concentration of the cellulosic raw material in the oxidation reaction is preferably in the range of 0.1% by mass or more and 30% by mass or less, more preferably in the range of 1% by mass or more and 20% by mass or less, and further preferably 1% by mass. It is in the range of% or more and 10% by mass or less.
• the treatment for stopping the oxidation reaction is not particularly limited, and examples thereof include a method of adding an acid or a metal catalyst. Further, a method of reducing hypochlorous acid or a salt thereof is preferably mentioned. Specific examples of the treatment for stopping the oxidation reaction include a method of adding a reducing agent such as sodium sulfite. The amount of the reducing agent added may be appropriately adjusted according to the amount of hypochlorous acid or a salt thereof (effective chlorine concentration).
• nanocellulose can be obtained by appropriately performing a post-treatment after oxidizing the cellulosic raw material without performing the defibration treatment.
• a solution obtained by oxidation it is preferable to use known solid-liquid separation such as filtration, if necessary. Therefore, one aspect of the production method of the present invention is a reaction mixture obtained by oxidizing a cellulosic raw material with hypochloric acid or a salt thereof, and after the oxidation, substantially without performing a defibration treatment. Is required to be solid-liquid separated to obtain a dispersion containing nanocellulose.
• the solid-liquid separation referred to here means an operation of separating the solid content and the liquid phase, and the dispersion liquid containing nanocellulose corresponds to the liquid phase.
• unrefined cellulose oxide can be recovered as a solid content.
• the unrefined cellulose oxide (that is, the solid content obtained by solid-liquid separation) may be reused for further oxidation reaction, or may be subjected to a defibration treatment step to be refined.
• the obtained reaction mixture may be solid-liquid separated as necessary to obtain a dispersion containing nanocellulose, and the dispersion may be purified as necessary.
• the purification method is not particularly limited as long as it is a means for removing impurities other than nanocellulose in the dispersion liquid.
• the impurities include salt components derived from the oxidation reaction and the like, particulate cellulose obtained as a result of excessive progress of the oxidation reaction, soluble components and the like.
• Specific methods for purification include general methods such as a method of putting a dispersion in a dialysis tube and extracting impurities into water, electrodialysis, and various types of chromatography (distribution chromatography, adsorption chromatography, size). Chromatography such as exclusion chromatography and ion exchange chromatography) and the like can be mentioned.
• the nanocellulose in the present invention may be obtained by defibrating and refining the oxidized cellulose obtained above.
• Examples of the method for defibrating cellulose oxide include a method by weak stirring using a magnetic stirrer and the like, a method by mechanical defibration, and the like.
• a screw type mixer for example, a screw type mixer, a paddle mixer, a disper type mixer, a turbine type mixer, a homomixer under high speed rotation, a high pressure homogenizer, an ultrahigh pressure homogenizer, a double cylindrical homogenizer, and an ultrasonic homogenizer are used.
• Water flow counter-collision type disperser beater, disc type refiner, conical type refiner, double disc type refiner, grinder, single-screw or multi-screw kneader, rotation / revolution stirrer, vibration type stirrer, etc.
• the method can be mentioned.
• a method using an ultra-high pressure homogenizer may be used in that nanocellulose with more advanced defibration can be produced.
• the pressure during the defibration treatment is preferably 100 MPa or more, more preferably 120 MPa or more, still more preferably 150 MPa or more.
• the number of times of defibration treatment is not particularly limited, but is preferably 2 times or more, more preferably 3 times or more, from the viewpoint of sufficiently advancing defibration.
• the above-mentioned oxidized cellulose can be sufficiently defibrated by mild stirring with a rotation / revolution stirrer, a vibration type stirrer or the like.
• the vibration type agitator include a vortex mixer (touch mixer). That is, according to the above-mentioned oxidized cellulose, uniformized nanocellulose can be obtained even when the defibration treatment is performed under mild defibration conditions.
• the defibration of the cellulose oxide may be an operation of stirring the cellulose oxide to make it finer.
• the defibration of cellulose oxide is not particularly limited as long as it is an operation for dispersing the components constituting the nanocellulose-containing composition, and for example, a velocity field and velocity fluctuation of arbitrary intensity; collision with inclusions and obstacles; ultrasound. Sound waves; pressure loads; etc. can be used.
• a liquid disperser can be preferably used for such a dispersion operation.
• the liquid disperser is not particularly limited, and for example, a homomixer, a magnetic stirrer, a stirring rod, a stirrer with a stirring blade, a disper type mixer, a homogenizer, an external circulation stirrer, a rotating / revolving stirrer, a vibrating stirrer, and the like.
• a method using an ultrasonic disperser or the like can be mentioned.
• a rotary shear type agitator, a colloidal mill, a roll mill, a pressure homogenizer, a container-driven mill, a medium agitation mill and the like can be mentioned.
• a kneader can be used as the liquid disperser.
• the rotary shear type agitator is a device that disperses by passing an object to be agitated through the gap between the rotary blade and the outer cylinder, and disperses by the shear flow in the gap and the strong velocity fluctuation before and after.
• a colloid mill is a device that disperses by shear flow in the gap between a rotating disc and a fixed disc. The roll mill disperses by a shearing force and a compressive force utilizing the gap between a plurality of rotating rolls.
• the pressure homogenizer is used as a disperser that discharges a slurry or the like from a pore at a high pressure, and is also called a pressure injection disperser.
• a high pressure homogenizer is preferable.
• the high-pressure homogenizer refers to a homogenizer having an ability to discharge a slurry at a pressure of, for example, 10 MPa or more, preferably 100 MPa or more.
• Examples of the high-pressure homogenizer include a counter-collision type high-pressure homogenizer such as a microfluidizer and a wet jet mill.
• the container-driven mill is a device that disperses by collision and friction of a medium such as a ball in the container, and specifically, there are a rotary mill, a vibration mill, a planetary mill, and the like.
• the medium stirring mill is a device that uses a medium such as a ball or a bead and disperses it by the impact force and the shearing force of the medium. Specific examples thereof include an attritor and a bead mill (sand mill).
• a kneader is a device that wets powder or the like with a liquid (also called kneading or kneading). Specifically, it is a double-armed kneader (biaxial in two semi-cylindrical containers). (It is a device that disperses by the mixing blades of These devices may be used alone or in combination of two or more.
• the defibration treatment is preferably carried out in a state where the above-mentioned cellulose oxide is mixed with a dispersion medium.
• the dispersion medium is not particularly limited and may be appropriately selected depending on the intended purpose. Specific examples of the dispersion medium include water, alcohols, ethers, ketones, cyclic carbonates, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethylsulfoxide and the like. As the solvent, one of these may be used alone, or two or more of them may be used in combination.
• alcohols include methanol, ethanol, isopropanol, isobutanol, sec-butyl alcohol, tert-butyl alcohol, methyl cellosolve, ethylene glycol, glycerin and the like.
• ethers include ethylene glycol dimethyl ether, 1,4-dioxane and tetrahydrofuran.
• ketone include acetone, methyl ethyl ketone and the like.
• cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate and the like.
• an organic solvent as a dispersion medium during the defibration treatment, it becomes easy to isolate the oxidized cellulose and the nanocellulose obtained by defibrating the oxidized cellulose. Further, since nanocellulose dispersed in an organic solvent can be obtained, it becomes easy to mix with a resin that dissolves in the organic solvent, a resin raw material monomer, or the like.
• the nanocellulose dispersion obtained by dispersing the nanocellulose obtained by defibration in a dispersion medium of water and / or an organic solvent can be used for mixing with various components such as resin, rubber, and solid particles. ..
• vinyl chloride resin examples of the vinyl chloride resin contained in the vinyl chloride resin composition of the present invention include polyvinyl chloride, chlorinated polyvinylidene chloride, polyvinylidene chloride, chlorinated polyethylene, and a copolymer of vinyl chloride and another vinyl monomer. Can be mentioned. Examples of other vinyl monomers include ⁇ -olefins such as ethylene, propylene and butene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; acrylic acid, methacrylic acid and the like.
• Unsaturated carboxylic acids acrylic acid or methacrylic acid esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, phenyl acrylate, phenyl methacrylate; vinylidene chloride, Vinyl halides other than vinyl chloride such as vinyl fluoride; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide can be mentioned.
• copolymer examples include vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, and vinyl chloride-isobutylene.
• Polymer vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile ternary copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene Polymers, vinyl chloride-chlorinated propylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride -Acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers and the like can be mentioned.
• the ratio of the vinyl chloride monomer unit in these copolymers is preferably 60% by mass or more, more preferably 80% by mass or more, from the viewpoint of strength at high temperature, flexibility at low temperature, and high elasticity. , More preferably 90% by mass or more, still more preferably 95% by mass or more.
• these polyvinyl chloride resins commercially available products or those prepared according to known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. Further, a rubber-modified vinyl chloride resin such as an acrylic rubber-modified vinyl chloride resin is also included.
• the vinyl chloride resin may be used alone or in combination of two or more.
• the average degree of polymerization of the vinyl chloride resin is preferably 500 to 3000, more preferably 500 to 2000, and even more preferably 500 to 1500.
• the average degree of polymerization of the vinyl chloride resin is 500 or more, the mechanical properties of the obtained molded product tend to be further improved.
• the average degree of polymerization of the vinyl chloride resin is 3000 or less, the processability of the vinyl chloride resin composition tends to be better.
• the value of the average degree of polymerization of the vinyl chloride resin is a value obtained by using a manufacturer's catalog, a known Mark-Houwink-Sakurada formula, or the like.
• the vinyl chloride resin composition of the present invention can be produced, for example, by blending nanocellulose derived from an oxide of a cellulosic raw material with hypochlorous acid or a salt thereof and a vinyl chloride resin, and the production method is as follows. There are no particular restrictions. Further, the vinyl chloride resin composition of the present invention can be produced by using oxidized cellulose containing an oxide of a cellulosic raw material by hypochlorous acid or a salt thereof.
• the vinyl chloride resin composition containing nanocellulose can be produced by polymerizing the raw material monomer of the vinyl chloride resin in the presence of nanocellulose. That is, one aspect of the present invention is a method for producing a vinyl chloride resin composition containing nanocellulose, which is obtained by stirring the first mixture containing the oxidized cellulose and the raw material monomer of the vinyl chloride resin. A step of obtaining a second mixture containing cellulose and a raw material monomer of a vinyl chloride resin, a step of polymerizing using the second mixture, and the oxidation of the cellulosic raw material by the hypochlorous acid or a salt thereof. It is a manufacturing method including products.
• the vinyl chloride resin composition containing nanocellulose nanocellulose derived from an oxide of a cellulosic raw material due to hypochlorous acid or a salt thereof is obtained, and the raw material monomer of the vinyl chloride resin is used in the presence of the nanocellulose. It may be produced by polymerization, and by obtaining oxidized cellulose containing an oxide of a cellulosic raw material by hypochloric acid or a salt thereof and polymerizing a raw material monomer of a vinyl chloride resin in the presence of the nanocellulose. It may be manufactured.
• one aspect of the present invention is a method for producing a vinyl chloride resin composition containing nanocellulose, which comprises a step of polymerizing using a mixture containing nanocellulose and a raw material monomer of vinyl chloride resin.
• Nanocellulose is a production method containing an oxide of a cellulosic raw material by hypochlorous acid or a salt thereof.
• one aspect of the present invention is a method for producing a vinyl chloride resin composition containing nanocellulose, wherein the oxidized cellulose is stirred and the raw material monomer of the vinyl chloride resin is continuously added.
• the method of polymerizing the raw material monomer of the vinyl chloride resin in the presence of nanocellulose is not particularly limited. Emulsion polymerization or suspension polymerization is preferable from the viewpoint of efficiently obtaining a vinyl chloride resin composition.
• nanocellulose and the above raw material monomer are dispersed in a solvent such as water, and a polymerization initiator is added.
• a method of heating can be mentioned.
• the polymerization initiator a general polymerization initiator such as a persulfate, an organic peroxide, or an azo compound can be used, but the persulfate is preferable in terms of excellent polymerization reaction rate and productivity. Ammonium persulfate is more preferable because the obtained resin has excellent water resistance.
• persulfate examples include ammonium persulfate, potassium persulfate, sodium persulfate and the like.
• organic peroxide examples include t-butylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-butylhydroperoxide, cumenehydroperoxide, and dicumyl peroxide.
• azo compound examples include 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-i-butylnitrile, and 2,2'-azobis-4-methoxy-2,4-dimethyl. Valeronitrile and the like can be mentioned.
• persulfate or peroxide may be used as a redox-based polymerization initiator in combination with the reducing agent sodium bisulfite or sodium ascorbate.
• an emulsifier may be used in the polymerization reaction.
• the emulsifier include anionic surfactants such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl phosphate ester salts, dialkyl sulfosuccinates and partially saponified polyvinyl acetate; polyoxyethylene alkyl ethers and polys.
• Nonionic surfactants such as oxyethylene fatty acid esters, sorbitanic acid fatty esters and glycerin fatty acid esters; cationic surfactants such as alkylamine salts and the like can be mentioned.
• These emulsifiers may be used alone or in combination of two or more.
• the temperature during the polymerization reaction is not particularly limited. For example, it is preferably in the range of 30 ° C to 180 ° C, and more preferably in the range of 50 ° C to 150 ° C.
• the reaction time of the polymerization reaction is not particularly limited, and is usually in the range of 30 minutes to 48 hours, preferably in the range of 1 hour to 24 hours.
• the nanocellulose in the production method of the present invention is preferably treated as an aqueous dispersion.
• the concentration of nanocellulose in the nanocellulose aqueous dispersion is preferably 1% by mass to 40% by mass, more preferably 3% by mass to 20% by mass, and 5% by mass to 15% by mass as the solid content concentration. It is more preferably by mass%.
• the ratio of nanocellulose to the above-mentioned raw material monomer when polymerizing the raw material monomer of vinyl chloride resin in the presence of nanocellulose is not particularly limited.
• the amount of the raw material monomer with respect to 100 parts by mass of nanocellulose may be 5 parts by mass to 1000 parts by mass, or 10 parts by mass to 100 parts by mass.
• the vinyl chloride resin composition containing nanocellulose can also be produced by using a vinyl chloride resin, for example, nanocellulose and a vinyl chloride resin containing an oxide of a cellulosic raw material by hypochlorous acid or a salt thereof. Can be produced by blending. That is, one aspect of the present invention is a method for producing a vinyl chloride resin composition containing nanocellulose, which comprises a step of drying a mixture containing nanocellulose and vinyl chloride resin, wherein the nanocellulose is hypochlorous acid or It is a production method containing an oxide of a cellulosic raw material due to the salt.
• one aspect of the present invention is a method for producing a vinyl chloride resin composition containing nanocellulose, wherein the first mixture containing oxidized cellulose and vinyl chloride resin is stirred to cause nanocellulose and vinyl chloride resin. It is a production method including a step of obtaining a second mixture containing and, and a step of drying the second mixture, wherein the cellulosic oxide contains an oxide of a cellulosic raw material by hypochlorous acid or a salt thereof. Further, one aspect of the present invention is a method for producing a vinyl chloride resin composition containing nanocellulose, in which the oxidized cellulose is stirred and the vinyl chloride resin is continuously added to obtain the nanocellulose and vinyl chloride.
• the drying method is not particularly limited, and examples thereof include hot air drying and spray drying.
• the oxidized cellulose used in the production method of the present invention may be any embodiment of the oxidized cellulose described in the above [nanocellulose], but specifically, it is preferable that the N-oxyl compound is substantially not contained. Further, the degree of polymerization of the oxidized cellulose used in the production method of the present invention is preferably 600 or less.
• the definition of "substantially free of N-oxyl compound", the definition of the degree of polymerization of oxidized cellulose, its preferred embodiment, and the like are as described in the above-mentioned [Nanocellulose].
• the nanocellulose used in the production method of the present invention may be any embodiment of the nanocellulose described in the above [nanocellulose].
• the monomer of the resin described in the above [polyvinyl chloride resin] can be mentioned.
• the operation is not particularly limited as long as it is an operation for dispersing the components constituting the nanocellulose-containing composition, and for example, it has an arbitrary strength. Velocity field and velocity fluctuation; collision with inclusions and obstacles; ultrasonic waves; pressure load; etc. can be utilized.
• a liquid disperser can be preferably used for such a dispersion operation. Therefore, in one aspect of the production method of the present invention, stirring is performed by a liquid disperser. Examples of the liquid disperser include those described in the above (step B: defibration treatment).
• the miniaturization of the oxidized cellulose can be promoted by stirring using such an apparatus, stirring may be performed until the constituent components of the nanocellulose-containing composition are homogenized or emulsified. Thereby, the nanocellulose is uniformly dispersed in the nanocellulose-containing composition, and the nanocellulose-containing composition can be obtained as an emulsion.
• cellulose oxide is stirred and a vinyl chloride resin or a raw material monomer of a vinyl chloride resin is continuously added. More specifically, one aspect of the production method of the present invention is a production method in which cellulose oxide is stirred to refine at least a part thereof, and then a vinyl chloride resin or a raw material monomer of a vinyl chloride resin is continuously added. ..
• "continuously” means that at least a part of the oxidized cellulose is refined by stirring and the compound is added in a series.
• the user of cellulose oxide can obtain nanocellulose by micronizing the cellulose oxide by himself and use it.
• the vinyl chloride resin composition obtained by the production method of the present invention can be recovered by appropriate post-treatment to obtain a vinyl chloride resin composition.
• the method of post-treatment is not particularly limited as long as it can recover the vinyl chloride resin composition.
• a post-treatment of dehydrating the slurry after the reaction and drying it in the range of 30 ° C to 100 ° C for 30 minutes to 48 hours can be mentioned. ..
• the vinyl chloride resin composition obtained by the production method of the present invention may be used as it is or may be formed into a desired shape (powder, bead, pellet, etc.).
• the vinyl chloride resin composition may further contain any additive as described above. Therefore, the production method of the present invention may include a step of further adding an additive and kneading the vinyl chloride resin composition obtained by the above production method.
• the additive used in the production method of the present invention include the additive described in the above ⁇ vinyl chloride resin composition>.
• the method of kneading the vinyl chloride resin composition and the additive is not particularly limited, and the additive is added to the vinyl chloride resin composition obtained by the above method, and the mixture is preferably heated in the range of 50 ° C to 300 ° C. However, it is preferable to knead.
• a known kneader can be used for kneading, and for example, a plast mill or the like can be used.
• the vinyl chloride resin composition kneaded with the additive may be used as it is or may be formed into a desired shape (powder, bead, pellet, etc.).
• the vinyl chloride resin composition of the present invention can be appropriately molded according to the purpose such as use to produce a molded product.
• One aspect of the present invention is a molded product made from the vinyl chloride resin composition of the present invention.
• the use of the molded product of the present invention is not particularly limited, and examples thereof include known uses of vinyl chloride resin.
• building materials such as window frames, pipes, rain gutters, deformed molded products, automobile materials, toys, etc. It is useful as a material for miscellaneous goods such as stationery, OA equipment, and home appliances.
• the vinyl chloride resin composition of the present invention is suitable for window frames.
• ⁇ Production Example 1> Preparation of Oxidized Cellulose Put 350 g of sodium hypochlorite pentahydrate crystal having an effective chlorine concentration of 42% by mass in a beaker, add pure water and stir to adjust the effective chlorine concentration to 21% by mass. And said. To this, 35% by mass hydrochloric acid was added and stirred to obtain an aqueous sodium hypochlorite solution having a pH of 11. The above sodium hypochlorite aqueous solution is heated to 30 ° C. in a constant temperature water bath while stirring at 200 rpm using a propeller type stirring blade with a stirrer (Three-One Motor, BL600) manufactured by Shinto Kagaku Co., Ltd., and then cellulose.
• a propeller type stirring blade with a stirrer (Three-One Motor, BL600) manufactured by Shinto Kagaku Co., Ltd.
• the solid content concentration is determined from the formula of (mass of dried product / mass of dispersion of cellulose oxide) ⁇ 100 from the mass of the dried product obtained by drying the obtained dispersion of cellulose oxide at 110 ° C. for 2 hours. Calculated.
• the effective chlorine concentration in the sodium hypochlorite aqueous solution was measured by the following method. (Measurement of effective chlorine concentration in sodium hypochlorite aqueous solution) Precisely weigh 0.582 g of an aqueous solution of sodium hypochlorite pentahydrate crystals in pure water, add 50 mL of pure water, add 2 g of potassium iodide and 10 mL of acetic acid, immediately seal and place in the dark for 15 minutes. I left it.
• Table 1 shows the physical characteristics of the oxidized cellulose of Production Example 1.
• the fact that the cellulose oxide obtained in Production Example 1 has a structure in which the hydroxyl groups at the 2- and 3-positions of the glucopyranose ring are oxidized and a carboxy group is introduced means that the model molecule of the oxidized cellulose is used as a sample. It was also confirmed from the results of measuring two-dimensional NMR. Further, since there was no change in the spectral data between the cellulosic raw material solid 13 C-NMR and the oxidized cellulose solid 13 C-NMR according to the 6th position, the hydroxyl group at the 6th position was not oxidized. , It was judged that the hydroxyl group remained as a hydroxyl group in the oxidized cellulose.
• Example 1 After degassing a 25-liter stainless steel polymerization reactor equipped with a jacket and a stirrer, 150 parts of warm water at 40 ° C. and 20 parts of the dispersion liquid of cellulose oxide A (solid content concentration 10%) of Production Example 1 were charged. After that, the temperature inside the polymerization reactor was raised to 30 ° C. by passing warm water through the jacket, and the mixture was stirred at a rotation speed of 9000 rpm for 10 minutes. A part was taken out and it was confirmed that the oxidized cellulose A was defibrated into nanocellulose (also referred to as nanocellulose A) by measuring the light transmittance and the zeta potential.
• nanocellulose also referred to as nanocellulose A
• the light transmittance of nanocellulose A was 95.03%, and the zeta potential was ⁇ 42.3 mV.
• 100 parts of vinyl chloride monomer was charged.
• the stirring can also be performed in the presence of a vinyl chloride monomer, that is, a mixture containing the vinyl chloride monomer and the dispersion liquid of cellulose oxide A of Production Example 1 is passed through a jacket with warm water to heat the temperature inside the polymerization reactor.
• a mixture of the vinyl chloride monomer and nanocellulose A was also obtained by raising the temperature to 30 ° C. and stirring at a rotation rate of 9000 rpm for 10 minutes.
• Example 2 20 parts of the dispersion liquid of cellulose oxide A (solid content concentration 10%) used in Production Example 1 and 150 parts of water were mixed by stirring with a homomixer at a rotation speed of 9000 rpm for 10 minutes. A part was taken out and it was confirmed by measuring the light transmittance and the zeta potential that the oxidized cellulose A was defibrated into nanocellulose (also referred to as nanocellulose A). The light transmittance of nanocellulose A was 95.03%, and the zeta potential was ⁇ 42.3 mV.
• thermometal soap (NSP-R: manufactured by NI Chemitec Co., Ltd.), which is a metal soap, and a lubricant (Calcol 86: Kao).
• 1.0 part of stearyl alcohol (manufactured by Co., Ltd.) was mixed and kneaded by heating using a plastic mill.
• the kneading temperature with a plast mill was 190 ° C., and the kneading time was 2 minutes. Then, it was pressurized at 190 ° C. for 2 minutes using a pressurizing machine to form a flat plate of the kneaded product.
• the pressure was 10 MPa for the first minute and 15 MPa for the next minute.
• a test piece having the shape of a No. 3 dumbbell (thickness 4 mm) specified in JIS K 6251: 2010 was prepared. The results of the three-point bending test using this test piece are shown in Table 2.
• Example 3 The dispersion liquid of cellulose oxide A was changed to the dispersion liquid of cellulose oxide B (solid content concentration 10%), and a mixture of calcium stearate salt and zinc stearate salt using metal soap in Example 1 (manufactured by Sun Ace Co., Ltd.). ), A test piece was prepared in the same manner as in Example 2. The results of the three-point bending test using this test piece are shown in Table 2.
• Example 4 20 parts of the dispersion of cellulose oxide A was changed to 2 parts of cellulose oxide C (solid content concentration 99%), and a mixture of calcium stearate salt and zinc stearate salt using metal soap in Example 1 (stock). A test piece was prepared in the same manner as in Example 2 except that it was changed to (manufactured by San Ace). The results of the three-point bending test using this test piece are shown in Table 2.
• various physical properties of nanocellulose were measured by the following methods.
• Pure water was added to the aqueous dispersion of nanocellulose to dilute the nanocellulose concentration to 0.1%.
• a 0.05 mol / L sodium hydroxide aqueous solution was added to the diluted nanocellulose aqueous dispersion to adjust the pH to 8.0, and the zeta potential was adjusted to 20 ° C. using a zeta potential meter (ELSZ-1000) manufactured by Otsuka Electronics Co., Ltd. Measured at.
• ELSZ-1000 zeta potential meter
• test piece was evaluated by the following method.
• (3-point bending test) A three-point bending test was performed using the test piece. Specifically, the bending test (test speed: 5 mm / min, distance between fulcrums: 30 mm) specified in JIS K 7171: 2016 was performed using the test pieces of Examples 1 to 4 to determine the flexural modulus (MPa). It was measured. A test piece to which cellulose oxide and nanocellose were not added was used as a blank, and a test piece having an improved flexural modulus of 20% or more was designated as ⁇ .
• coniferous pulp (SIGMA-ALDRICH NIST RM 8495, bleached kraft pulp) is cut into 5 mm squares with scissors and treated with Osaka Chemical's "Wonder Blender WB-1" for 1 minute at 25,000 rpm. Then, it was mechanically defibrated into a cotton-like shape. 0.048 g of TEMPO and 0.3 g of sodium bromide were placed in a beaker, pure water was added and stirred to form an aqueous solution, and 3.0 g of the mechanically defibrated coniferous kraft pulp was added. The above aqueous solution was heated to 25 ° C.
• a dispersion liquid of oxidized cellulose D ( A solid content concentration of 10%) was obtained in an amount of about 30 g.
• the amount of carboxy group of cellulose oxide D was 1.55 mmol / g.
• the nitrogen component derived from the N-oxyl compound in the oxidized cellulose D was measured as the amount of nitrogen using a trace total nitrogen analyzer (manufactured by Mitsubishi Chemical Analytech Co., Ltd., device name: TN-2100H), and increased from the raw material pulp. As a result of calculating the minute, it was 5 ppm.
• the vinyl chloride resin composition of the present invention is useful as a material for building materials such as window frames, pipes, rain gutters, deformed molded products, automobile materials, toys, miscellaneous goods such as stationery, OA equipment, home appliances and the like.

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