WO2020050286A1 - Particules composites et composition de résine - Google Patents

Particules composites et composition de résine Download PDF

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Publication number
WO2020050286A1
WO2020050286A1 PCT/JP2019/034666 JP2019034666W WO2020050286A1 WO 2020050286 A1 WO2020050286 A1 WO 2020050286A1 JP 2019034666 W JP2019034666 W JP 2019034666W WO 2020050286 A1 WO2020050286 A1 WO 2020050286A1
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resin
cellulose
fine cellulose
mass
composite particles
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PCT/JP2019/034666
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English (en)
Japanese (ja)
Inventor
博文 小野
一文 河原
洋文 内村
三好　貴章
正広 大賀
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旭化成株式会社
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Priority to JP2020541249A priority Critical patent/JP6896946B2/ja
Publication of WO2020050286A1 publication Critical patent/WO2020050286A1/fr

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    • 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
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • One embodiment of the present invention relates to a composite particle containing fine cellulose and a thermoplastic resin, a resin composition containing the same, and a method for producing these.
  • cellulose is known to have a high modulus of elasticity comparable to aramid fibers and a lower coefficient of linear expansion than glass fibers.
  • the true density is as low as 1.56 g / cm 3 , which is lower than that of glass (density 2.4 to 2.6 g / cm 3 ) and talc (density 2.7 g / cm 3 ) which are used as general fillers. It is an overwhelmingly light material. It is present on Earth in large quantities as a natural resource, is regarded as an environmentally friendly material from the viewpoint of carbon neutrality, and is expected as a filler for thermoplastic resins.
  • Patent Documents 1 to 4 disclose techniques for dispersing fine cellulose having a high degree of fineness and a nanometer-sized fiber in a thermoplastic resin.
  • Patent Document 5 discloses a technique in which powdery cellulose is subjected to lipophilic treatment to obtain a mixture uniformly dispersed in a plasticizer, and then melt-kneaded with polyolefin. The technology to do this is described.
  • Patent Literature 6 describes a technique of mixing a resin, a vegetable fiber swollen in a special liquid, and an organic liquid.
  • Patent Document 7 discloses a technique in which water is separated from a mixed dispersion obtained by previously mixing a cellulose dispersion with a resin powder having a specific particle size to obtain a cellulose / resin mixture, and then the mixture is melt-kneaded. Has been described.
  • the mechanical properties and the thermal dimensional stability are inferior to the resin composition in which an equivalent amount of the fine cellulose is completely dispersed. Become. Therefore, in order to develop the same mechanical properties and thermal dimensional stability, the amount of fine cellulose added is undesirably increased.
  • a molded article formed from such a resin composition is likely to be broken starting from the aggregates. That is, since the aggregates cause a difference in mechanical strength depending on the portion of the molded body, the mechanical properties of the molded body including the aggregates vary greatly. In this case, the molded article partially has a strength defect, and significantly impairs the reliability as an actual product. For this reason, while fine cellulose has its excellent properties, it is not actually used in practice.
  • impurities such as hemicellulose and lignin remain in the cellulosic material, and these may be altered by heat received during processing in an extruder, which is a general resin processing method, and may cause coloring.
  • an extruder which is a general resin processing method
  • coloring may be altered by heat received during processing in an extruder, which is a general resin processing method, and may cause coloring.
  • Cellulose itself induces various side reactions such as hydrolysis with heat during extrusion processing and moisture in the system to induce a saccharification reaction and the like, which promotes thermal deterioration due to heat in the extruder and becomes a coloring factor.
  • the extruded pellets and the molded product gave a sweet smell of burnt sugar.
  • cellulose is expected to be used as a resin reinforcing material particularly in automotive applications because of its light weight.
  • the fine cellulose becomes a strong aggregate due to hydrogen bonding due to surface hydroxyl groups. At this time, the fine cellulose is hardly dispersed in the resin, and a part thereof is non-uniformly present as an aggregate.
  • one embodiment of the present disclosure provides a composite particle containing fine cellulose and a resin composition containing the composite particle, which impart sufficient mechanical properties to a molded article while providing sufficient physical property stability for practical use.
  • the purpose is to provide.
  • one embodiment of the present disclosure is a method in which a cellulose reinforced resin composition having excellent redispersibility even when a fine cellulose is in a dry state, and having very little coloring and having a suppressed odor can be used for general purposes. It is an object of the present invention to provide a manufacturing method for manufacturing with.
  • the present invention includes the following embodiments.
  • the viscosity ⁇ 10 at a liquid temperature of 25 ° C. and a shear rate of 10 s ⁇ 1 of a dispersion obtained by dispersing the composite particles in dimethyl sulfoxide so that the concentration of fine cellulose in the dispersion is 1% by mass is 10 mPa ⁇ s. s or more.
  • the thixotropic index (TI) which is the ratio of the viscosity ⁇ 10 at a shear rate of 10 s ⁇ 1 to the viscosity ⁇ 100 at a shear rate of 100 s ⁇ 1 at a liquid temperature of 25 ° C., ⁇ 10 / ⁇ 100 , is obtained.
  • the composite particle according to the above aspect 1 which is 2 or more.
  • the composite particles according to the above aspect 1 or 2 wherein the median particle diameter is 1 ⁇ m or more and 5000 ⁇ m or less.
  • thermoplastic resin is a cellulose derivative.
  • weight average molecular weight Mw of the cellulose derivative is 100,000 or less.
  • An aqueous dispersion of the fine cellulose is Fibrillation step of performing a fibrillation treatment of cellulose in an organic solvent to obtain a fine cellulose dispersion, and a purification step of substituting water for the organic solvent in the fine cellulose dispersion,
  • a resin composition comprising the composite particle according to any one of the above aspects 1 to 14 and a base resin.
  • a thermoplastic resin 0.1 to 40 parts by mass with respect to 100 parts by mass of the thermoplastic resin, fine cellulose fibers having a fiber diameter of 2 nm to less than 1000 nm, and 1 part by mass to 500 parts by mass with respect to 100 parts by mass of the fine cellulose fibers.
  • a resin composition comprising: [24] The above-mentioned aspect 23, wherein the fine cellulose fiber has a weight average molecular weight (Mw) of 100,000 or more and a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 6 or less. Resin composition. [25] The resin composition according to the above aspect 23 or 24, wherein the fine cellulose fibers have an average content of alkali-soluble polysaccharide of 12% by mass or less and a crystallinity of 60% or more. [26] The resin composition according to the above aspect 22, wherein the base resin is a thermoplastic resin.
  • the thermoplastic resin is selected from the group consisting of a polyolefin resin, a polyamide resin, a polyester resin, a polyacetal resin, a polyphenylene ether resin, a polyphenylene sulfide resin, and a mixture of any two or more thereof.
  • the thermoplastic resin is polypropylene, and a melt mass flow rate (MFR) of the polypropylene measured at 230 ° C in accordance with ISO1133 is 3 g / 10 min or more and 30 g / 10 min or less. 28.
  • MFR melt mass flow rate
  • the thermoplastic resin is a polyamide resin, and a ratio of a carboxyl terminal group to all terminal groups ([COOH] / [all terminal groups]) of the polyamide resin is 0.30 to 0.95. 28.
  • the thermoplastic resin is a polyester resin, and a ratio of a carboxyl terminal group to all terminal groups ([COOH] / [all terminal groups]) of the polyester resin is 0.30 to 0.95. 28.
  • thermoplastic resin is a polyacetal resin
  • polyacetal resin is a copolyacetal containing 0.01 to 4 mol% of a comonomer-derived structure.
  • thermoplastic resin is a crystalline thermoplastic resin having a melting point of 140 ° C. or higher.
  • base resin is a thermosetting resin or a photocurable resin.
  • base resin is a rubber.
  • a method comprising kneading the composite particles according to any one of the above aspects 1 to 12 in the form of a dry powder or an aqueous dispersion with a thermoplastic resin in a melt-kneading molding machine, and then molding.
  • a thermoplastic resin Composite particles composed of fine cellulose and a cellulose derivative
  • a method for producing a resin composition comprising: A first step of melt-kneading the thermoplastic resin in an extruder; A second step of adding the composite particles to the molten resin of the first step; Including, methods.
  • the above-mentioned aspect 36 wherein the fine cellulose has a weight average molecular weight (Mw) of 100,000 or more and a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 6 or less.
  • Method. [38] The method according to Aspect 36 or 37, wherein the fine cellulose has an average content of alkali-soluble polysaccharide of 12% by mass or less and a crystallinity of 60% or more.
  • the method comprises: A first step of melt-kneading the thermoplastic resin in an extruder; A second step of adding the composite particles to the molten resin of the first step; 36.
  • the method according to aspect 35 comprising: [40] The first step is performed in a melt-kneading zone in a cylinder provided in the extruder, 40.
  • the addition port is disposed downstream of the melt-kneading zone.
  • the composite particles and the resin composition containing the composite particles according to one embodiment of the present disclosure can impart sufficient mechanical properties to a molded article, and further, can impart sufficient physical property stability to withstand practical use.
  • cellulose reinforced resin having excellent redispersibility even when the fine cellulose is in a dry state, and having extremely little coloring and suppressed odor
  • the composition can be manufactured in a generally applicable manner.
  • FIG. 1 is a microscope image showing an example of fine cellulose fibers.
  • FIG. 2A is a microscope image showing an example of a cellulose whisker.
  • FIG. 2B is a microscope image showing an example of a cellulose whisker.
  • FIG. 3A is an explanatory diagram of a method for measuring the thermal decomposition onset temperature (T D ) and the 1% weight loss temperature.
  • FIG. 3B is an explanatory diagram of a method for measuring the thermal decomposition onset temperature (T D ) and the 1% weight loss temperature.
  • FIG. 4 is an explanatory diagram of a method of measuring the weight loss rate at 250 ° C.
  • FIG. 5 is an explanatory diagram of a method of calculating an IR index.
  • FIG. 1 is a microscope image showing an example of fine cellulose fibers.
  • FIG. 2A is a microscope image showing an example of a cellulose whisker.
  • FIG. 2B is a microscope image showing an example of a cellulose whisker.
  • FIG. 6 is a schematic view showing the shape of a fender manufactured for evaluation of the defect rate of the fender in the example and the comparative example.
  • FIG. 7 is a view of a fender showing a position where a test piece is taken out in order to measure a coefficient of variation of a linear expansion coefficient of an actual molded body in Examples and Comparative Examples.
  • One embodiment of the present invention provides a composite particle containing fine cellulose and a thermoplastic resin.
  • the proportion of fine cellulose in the composite particles is from 10% by mass to 95% by mass.
  • the lower limit of the proportion of fine cellulose in the composite particles is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and the upper limit is 95% by mass or less, preferably 90% by mass or less, more preferably Is 80% by mass or less.
  • the ratio of the fine cellulose is 10% by mass or more, in the production of the resin composition using the composite particles, the amount of the thermoplastic resin of the composite particles contained in the resin composition when the predetermined fine cellulose is added becomes too large.
  • the dispersion is obtained by dispersing the composite particles in dimethyl sulfoxide (DMSO in the present disclosure) so that the concentration of fine cellulose in the dispersion is 1% by mass.
  • the viscosity ⁇ 10 at a shear rate of 10 s ⁇ 1 (also simply referred to as “viscosity ⁇ 10 ” in the present disclosure) is 10 mPa ⁇ s or more, preferably 15 mPa ⁇ s or more, more preferably 20 mPa ⁇ s or more, and still more preferably. Is 25 mPa ⁇ s or more.
  • the dispersibility of fine cellulose in the resin composition is good, and the mechanical strength and dimensional stability can be improved, which is advantageous. It is.
  • the upper limit of the viscosity eta 10 for the higher viscosity eta 10 excellent dispersibility in DMSO rises no particular. The higher the viscosity eta 10 improves the dispersibility of the fine cellulose in the resin composition can achieve good improvement in mechanical strength and dimensional stability improvement.
  • the upper limit of the eta 10 is, 2000 mPa ⁇ s or less, or 1800 mPa ⁇ s or less, or 1500 mPa ⁇ s may be less.
  • the viscosity ⁇ 100 of a dispersion obtained by dispersing the composite particles in DMSO such that the concentration of fine cellulose in the dispersion is 1% by mass at a liquid temperature of 25 ° C. and a shear rate of 100 s ⁇ 1 is obtained.
  • the thixotropy index (TI) which is the ratio of the viscosity ⁇ 10 at a shear rate of 10 s ⁇ 1 to ⁇ 10 / ⁇ 100 , is 2 or more.
  • a dispersion in which fine cellulose is sufficiently dispersed has a structural viscosity that decreases as the shear rate increases. When the TI is 2 or more, the dispersibility of the fine cellulose in the composite particles is good.
  • TI is more preferably 3 or more, still more preferably 5 or more, and particularly preferably 7 or more.
  • the TI is preferably large from the viewpoint of dispersibility of the fine cellulose, but may be, for example, 50 or less, or 40 or less, or 30 or less from the viewpoint of ease of production of the composite particles.
  • a predetermined amount of composite particles is added to DMSO so that the fine cellulose is 1% by mass, and 100 ml of a DMSO dispersion liquid containing the composite particles is prepared.
  • the dispersion conditions are set so that the composite particles are dispersed in DMSO by stirring the dispersion liquid or the like. For example, stirring is performed with a magnetic stirrer at a rotation speed of 300 rpm or more for 1 minute or more (more specifically, with a magnetic stirrer at 1200 rpm. , Stirring for 1 hour).
  • the median particle size of the composite particles is a value measured by a laser diffraction type particle size distribution measuring device or an image analysis type particle size distribution measuring device.
  • the numerical value of the median particle size of the present disclosure is intended to be a numerical value obtained from at least one of these devices.
  • the lower limit of the median particle size is preferably at least 1 ⁇ m, more preferably at least 3 ⁇ m, further preferably at least 5 ⁇ m, particularly preferably at least 10 ⁇ m.
  • the upper limit is preferably 5000 ⁇ m or less, more preferably 3000 ⁇ m or less, further preferably 1000 ⁇ m or less, and particularly preferably 500 ⁇ m or less.
  • the median particle diameter is 1 ⁇ m or more, it is not necessary to use a special technique in production in order to prevent secondary aggregation of the primary particles, which is preferable from the viewpoint of the production process and cost.
  • the median particle diameter is 5000 ⁇ m or less, kneading of the composite particles and the base resin is stabilized in the production of the resin composition using an extruder or the like, and as a result, the dispersibility of the fine cellulose in the resin composition is good. It is preferable.
  • Fine cellulose of the present disclosure means cellulose having a number average diameter of 2 nm or more and less than 1000 nm, and includes cellulose fibers and cellulose whiskers.
  • the “length” (L) and the “diameter” (D) of the fine cellulose are, for example, the fiber length and the fiber diameter in a cellulose fiber (also referred to as a fine cellulose fiber in the present disclosure).
  • cellulose whiskers they correspond to the major axis and minor axis, respectively.
  • the number average diameter of the fine cellulose is, in one embodiment, 4 nm or more, 10 nm or more, or 20 nm or more, or 30 nm or more, and in one embodiment, 500 nm or less, or 500 nm. Or less than 450 nm, or 400 nm or less, or 350 nm or less, or 300 nm or less, or 100 nm or less, or less than 100 nm.
  • the number average diameter of the fine cellulose is less than 2 nm, the crystallinity is extremely low and the dispersibility in the resin composition is poor, so that the desired tensile breaking strength and thermal stability of the resin composition (specifically, Does not provide a low coefficient of linear thermal expansion and elastic retention at high temperatures).
  • the number average diameter of the fine cellulose is 1000 nm or more, the number of entangled points of the fine cellulose in the resin composition is small, and the desired tensile strength at break and thermal stability of the resin composition cannot be obtained.
  • Making the diameter of the fine cellulose within the above-mentioned range is advantageous from the viewpoint of improving the slidability of the molded article formed using the resin composition.
  • the fiber diameter of the cellulose fiber is preferably 4 nm or more, or 10 nm or more, or 20 nm or more, or 30 nm or more, preferably 500 nm or less, or less than 500 nm, or 450 nm or less, or 400 nm or less. , Or 350 nm or less, or 300 nm or less, or 100 nm or less, or less than 100 nm.
  • the minor axis of the cellulose whisker is preferably 4 nm or more, or 10 nm or more, 20 nm or more, or 30 nm or more, preferably 500 nm or less, or less than 500 nm, or 450 nm or less, or 400 nm or less, Or 350 nm or less, or 300 nm or less, or 100 nm or less, or less than 100 nm.
  • the ratio (L / D) of the fiber length (L) / fiber diameter (D) of the cellulose fiber is 30 or more, preferably 50 or more, more preferably 80 or more, more preferably 100 or more, more preferably. Is 120 or more, more preferably 150 or more, more preferably 200 or more, even more preferably 300 or more, and most preferably 500 or more, and also preferably 5000 or less, more preferably 4000 or less, and still more preferably 3000 or less. Preferably it is 1000 or less. It is advantageous that the L / D of the cellulose fiber is in the above-mentioned range in terms of improving the tensile strength at break and the thermal stability of the resin composition. In one embodiment, the L / D of the cellulose fiber of 1000 or less is advantageous from the viewpoint of not increasing the melt viscosity of the resin composition too much.
  • the ratio (L / D) of the major axis (L) / minor axis (D) of the cellulose whisker is less than 30, preferably 25 or less, more preferably 20 or less, more preferably 15 or less, more preferably. It is 10 or less, more preferably 5 or less.
  • the L / D of the cellulose whisker is 1 or more, preferably 1.1 or more, more preferably 1.2 or more, and further preferably 1.5 or more. Having the L / D ratio of the cellulose whiskers within the above-described range is advantageous in one aspect in that a suitable fluidity can be imparted to the resin composition.
  • the fine cellulose is a cellulose fiber, a cellulose whisker, or a mixture thereof.
  • the fine cellulose is a cellulose fiber or a mixture of cellulose fibers and cellulose whiskers in that the advantages of the composite particles of the present disclosure are significant.
  • the cellulose fiber / cellulose whisker ratio (by mass) of the above mixture is preferably 90/10 to 10/90, more preferably 80/20 to 20/80, and further preferably 70/30 to 30/70.
  • the cellulose whiskers can improve the dispersibility of the cellulose fibers by being mixed with the cellulose fibers, and as a result, can improve the mechanical properties of the resin composition.
  • the cellulose whisker may be chemically modified, and the aspect of the chemical modification may be the same as that of the cellulose fiber.
  • the amount of cellulose whiskers is preferably from 10 to 500 parts by mass, more preferably from 20 to 300 parts by mass, even more preferably from 30 to 200 parts by mass based on 100 parts by mass of the cellulose fibers. . From the viewpoint of the balance between processability and mechanical properties, it is desirable that the amount of cellulose whisker be within the above range.
  • the number average diameter, number average length, and L / D of fine cellulose can be determined by using an aqueous dispersion of fine cellulose in a water-soluble solvent (eg, water, ethanol, tert-butanol, etc.). And then diluted with a high shear homogenizer (eg, Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, manufactured by IKA, trade name “Ultra Turrax T18”).
  • a high shear homogenizer eg, Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, manufactured by IKA, trade name “Ultra Turrax T18”.
  • the cellulose whiskers and the cellulose fibers may be distinguished from each other by classifying cellulose whiskers having a ratio (L / D) of less than 30 as cellulose whiskers and those having a ratio (L / D) of 30 or more as cellulose fibers.
  • a ratio (L / D) of less than 30 when the fine cellulose is a mixture of cellulose whiskers and cellulose fibers, a total of 200 cellulose fibers of 100 or more cellulose fibers having an L / D of 30 or more and 100 or more cellulose whiskers having an L / D of less than 30 are used. The above measurement is performed.
  • FIG. 1 is a microscope image showing an example of fine cellulose as a cellulose fiber. It can be seen that any cellulose has a fibrous structure and has a high L / D of 30 or more.
  • 2A and 2B are microscopic images showing examples of cellulose whiskers.
  • FIG. 2B is a partially enlarged view of FIG. 2A. It can be seen that all celluloses have a needle-like crystal particle structure and have a low L / D of less than 30.
  • the length, diameter, and L / D ratio of fine cellulose (for example, each of cellulose whiskers and cellulose fibers) in the resin composition or the composite particles are determined using the solid resin composition or the composite particles as a measurement sample. It may be confirmed by measuring according to the measurement method described above.
  • a solvent in which the thermoplastic resin is dissolved for example, 1,2,4-trichlorobenzene or 1,2-dichlorobenzene for polyolefin,
  • 1,2-dichlorobenzene for polyolefin
  • the resin dissolving agent is not limited to these.
  • aqueous dispersion can be taken out by dispersing at a processing condition of 25,000 rpm for 5 minutes.
  • the number average diameter of the fine cellulose of the present embodiment may be a specific surface area equivalent diameter calculated from the specific surface area. That is, in one embodiment, the equivalent diameter of the specific surface area of the fine cellulose may be in the range of the present disclosure.
  • the specific surface area equivalent diameter is a diameter calculated from the specific surface area obtained by the BET method using nitrogen adsorption.
  • the specific surface area equivalent diameter is obtained by preparing a porous sheet by replacing the aqueous dispersion of fine cellulose with tBuOH and then drying it, and measuring the specific surface area of the porous sheet using the BET method by nitrogen adsorption. Value.
  • the fine cellulose has a crystalline structure of cellulose type I and / or II.
  • crystalline forms of cellulose type I, type II, type III, type IV and the like are known. While type I and type II celluloses are commonly used, type III and type IV celluloses are obtained on a laboratory scale but not on an industrial scale.
  • a fine cellulose a resin composition having relatively high structural mobility, dispersing the fine cellulose into a resin, having a lower coefficient of linear thermal expansion, and having higher strength and elongation at the time of tensile and bending deformation. From the viewpoint of obtaining a product, fine cellulose containing cellulose type I crystal or cellulose type II crystal is preferable.
  • the crystallinity of the fine cellulose (particularly, each of cellulose fiber and cellulose whisker) of the present embodiment is preferably 50% or more.
  • the mechanical properties (particularly strength and dimensional stability) of the fine cellulose (for example, cellulose fiber) itself increase, so that the strength and dimensional stability of the resin composition obtained by dispersing the fine cellulose in the resin are increased.
  • the crystallinity of the fine cellulose of the present embodiment is more preferably 55% or more, or 60% or more, or 65% or more, or 70% or more, or 80% or more. Since the higher the degree of crystallinity of the fine cellulose, the more preferable it is. Therefore, the upper limit is not particularly limited, but 99% is a preferable upper limit from the viewpoint of production.
  • Crystallinity (%) h1 / h0 ⁇ 100
  • the degree of polymerization (DP) of the fine cellulose is preferably 100 or more and 12,000 or less.
  • the degree of polymerization is the number of repetitions of an anhydrous glucose unit forming a cellulose molecular chain.
  • the degree of polymerization of the fine cellulose is 100 or more, the tensile strength at break and the elastic modulus of the fine cellulose itself are improved, and the high tensile strength at break and the thermal stability of the resin composition are preferably exhibited.
  • cellulose having a degree of polymerization exceeding 12,000 is practically difficult to obtain and tends to be difficult to use industrially.
  • the degree of polymerization of the fine cellulose is preferably from 150 to 8000.
  • the intrinsic viscosity (JIS P 8215: 1998) of a dilute cellulose solution using a copper ethylenediamine solution is determined, and then the intrinsic viscosity of the cellulose and the polymerization degree DP have a relationship represented by the following formula (1).
  • Intrinsic viscosity [ ⁇ ] K x DPa (1)
  • K and a are constants determined by the type of polymer. In the case of cellulose, K is 5.7 ⁇ 10 ⁇ 3 and a is 1.
  • the degree of polymerization of the cellulose whiskers is preferably 600 or less, more preferably 300 or less, and preferably 100 or more, and more preferably 150 or more.
  • the weight average molecular weight (Mw) of the fine cellulose is 100,000 or more, more preferably 200,000 or more.
  • the ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight (Mn) is 6 or less, preferably 5.4 or less. The higher the weight average molecular weight, the smaller the number of terminal groups of the cellulose molecule. Further, since the ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight indicates the width of the molecular weight distribution, the smaller the Mw / Mn, the smaller the number of the terminal of the cellulose molecule.
  • the weight average molecular weight (Mw) of the fibrous cellulose may be, for example, 600,000 or less or 500,000 or less from the viewpoint of availability of the cellulose raw material.
  • the ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight (Mn) may be, for example, 1.5 or more, or 2 or more, from the viewpoint of easy production of fibrous cellulose.
  • Mw can be controlled in the above range by selecting a cellulose raw material having Mw according to the purpose, appropriately performing physical treatment and / or chemical treatment on the cellulose raw material within an appropriate range, and the like.
  • Mw / Mn is also in the above range by selecting a cellulose raw material having Mw / Mn according to the purpose, appropriately performing physical treatment and / or chemical treatment on the cellulose raw material in an appropriate range, and the like.
  • the physical treatment includes dry or wet pulverization using a microfluidizer, a ball mill, a disk mill, etc., a crusher, a homomixer, a high-pressure homogenizer, and an ultrasonic device. And the like.
  • Examples of the physical treatment for applying a mechanical force such as impact, shear, shear, friction and the like due to the above-mentioned chemical treatment include digestion, bleaching, acid treatment, regenerated cellulose and the like.
  • the weight-average molecular weight and number-average molecular weight of the cellulose used herein are defined as the values obtained by dissolving cellulose in N, N-dimethylacetamide to which lithium chloride has been added and then performing gel permeation chromatography using N, N-dimethylacetamide as a solvent. This is the calculated value.
  • the fine cellulose of the present embodiment may be chemically modified (in the present disclosure, chemically modified fine cellulose is also referred to as chemically modified fine cellulose).
  • the chemical modification is performed on the hydroxyl groups of the cellulose molecules inside and / or on the surface of the fine cellulose, and the hydroxyl groups are replaced with desired functional groups by the cellulose modifying agent.
  • hydroxyl groups present on the surface of fine cellulose are esterified to acetate, nitrate, sulfate, phosphate, etc. (esterified fine cellulose), alkyl ethers such as methyl ether, and carboxymethyl ether.
  • Such chemical modification is preferably esterification, more preferably acetylation, from the viewpoint of simplifying the reaction process and improving the heat resistance of the fine cellulose itself.
  • Chemical modification may occur on a portion (eg, inside or on the surface) of the microcellulose or on all (eg, both inside and on the surface).
  • the cellulose skeleton can be left in the fine cellulose. For example, it is possible to chemically modify only the surface of the fine cellulose and leave a cellulose skeleton (particularly, a cellulose I-type or II-type crystal structure) in the center.
  • the microcellulose When a part of the microcellulose is chemically modified and the microcellulose has a crystal structure (typically type I and / or type II, preferably type I), high tensile breaking strength and size derived from cellulose It is more preferable because the stability can be maintained, the heat resistance can be improved by chemical modification, the affinity with the resin at the time of resin composite can be improved, and the dimensional stability of the resin composition can be improved.
  • the presence of a chemically modified group in the chemically modified fine cellulose can be confirmed by 1 HNMR.
  • the thermal decomposition onset temperature (Td) of the fine cellulose is not particularly limited, but when discoloration or thermal degradation of the fine cellulose by heating becomes a problem, the higher the thermal decomposition onset temperature, the more preferable.
  • the thermal decomposition onset temperature (Td) is preferably at least 270 ° C, more preferably at least 275 ° C, further preferably at least 280 ° C, particularly preferably at least 285 ° C.
  • the thermal decomposition onset temperature is, as shown in the explanatory diagrams of FIGS. 3A and 3B, a thermogravimetric (TG) analysis from a graph in which the horizontal axis represents temperature and the vertical axis represents weight retention%. This is the calculated value (FIG. 3B is an enlarged view of FIG. 3A).
  • TG thermogravimetric
  • the temperature at the point where this straight line intersects with the horizontal line (base line) passing through the starting point of the weight loss of 0 wt% is defined as the thermal decomposition onset temperature (Td).
  • the TG analysis is composed of two steps: (1) a sample drying step and (2) a measurement step that follows the drying step.
  • (1) the sample is heated from room temperature to 150 ° C. at a rate of 10 ° C./min in a nitrogen flow of 100 ml / min, kept at 150 ° C. for 1 hour, and then cooled to 30 ° C. Cooling.
  • the measurement step (2) the temperature is increased from 30 ° C. to 450 ° C.
  • a circularly cut-out piece of the above-mentioned porous sheet of chemically modified fine cellulose is used, and 10 mg of the sample is placed in an aluminum sample pan and measured.
  • the 1% weight loss temperature is the temperature at the time of 1% weight loss starting from the weight of 150 ° C. when the temperature is raised by the method of the above-mentioned thermal decomposition onset temperature (Td).
  • the weight reduction rate of the fine cellulose of the present embodiment at 250 ° C. was determined by thermogravimetric (TG) analysis when the fine cellulose was kept at 250 ° C. under a nitrogen flow for 2 hours. Rate.
  • the TG analysis is composed of two steps: (1) a sample drying step and (2) a measurement step that follows the drying step. (1) In the sample drying step, the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C./min in a nitrogen flow of 100 ml / min, and maintained at 150 ° C. for 1 hour. Subsequently, in the measurement step (2), the temperature is increased from 150 ° C. to 250 ° C.
  • a circularly cut-out piece of the above-mentioned porous sheet of chemically modified fine cellulose is used, and 10 mg of the sample is placed in an aluminum sample pan and measured.
  • the zeta potential of the fine cellulose is preferably -5 mV or less.
  • the zeta potential is more preferably -10 mV or less, further preferably -20 mV or less, particularly preferably -25 mV or less, and most preferably -30 mV or less.
  • the zeta potential of the chemically modified fine cellulose may be outside the above range.
  • the zeta potential can be measured by the following method.
  • a suspension of pure water having a concentration of 1% by mass of fine cellulose was mixed with a high-shear homogenizer (for example, Nippon Seiki Co., Ltd., trade name "Excel Auto Homogenizer ED-7", IKA, trade name "Ultra Turrax T18”).
  • Processing conditions A water dispersion obtained by dispersing at 25,000 rpm for 5 minutes at a rotation speed was diluted with pure water to 0.01 to 0.5% by mass, and a zeta potentiometer (for example, an apparatus manufactured by Malvern Co., Ltd. It is measured at 25 ° C. and pH 7 using the name Zetasizer Nano ZS).
  • the fine cellulose of the present embodiment may contain an acid-insoluble component containing lignin and / or an alkali-soluble polysaccharide containing hemicellulose and the like.
  • the contents of the acid-insoluble component and the alkali-soluble polysaccharide affect the heat resistance of fine cellulose and the dispersibility in the resin composition, and may be adjusted according to the purpose. In general, when the content of the acid-insoluble component and the alkali-soluble polysaccharide is large, the heat resistance of the fine cellulose is reduced, the discoloration accompanying the content is reduced, and the mechanical properties of the fine cellulose are reduced.
  • the average content of the acid-insoluble component and the alkali-soluble polysaccharide in the cellulose raw material is preferably smaller. is there.
  • the average content of the acid-insoluble component in the fine cellulose is preferably less than 10% by mass, more preferably 8% by mass or less, still more preferably 7% by mass or less, and still more preferably 6% by mass. %, Most preferably 5% by mass or less.
  • the average content of the acid-insoluble component may be 0% by mass, but from the viewpoint of easy production of fine cellulose, for example, 0.1% by mass or more, or 0.5% by mass or more, or 1% by mass or more, or It may be 2% by mass or more, or 3% by mass or more.
  • the quantitative determination of the acid-insoluble component is performed as the quantitative determination of the acid-insoluble component using the Klason method described in Non-Patent Document (Wood Science Experiment Manual, edited by The Japan Wood Science Society, pp. 92-97, 2000).
  • This method is understood in the art as a method for measuring the amount of lignin.
  • the sample is stirred in a sulfuric acid solution to dissolve cellulose, hemicellulose, and the like, and then filtered through a glass fiber filter, and the obtained residue corresponds to the acid-insoluble component.
  • the content of the acid-insoluble component is calculated from the weight of the acid-insoluble component, and the number average of the content of the acid-insoluble component calculated for the three samples is defined as the average content of the acid-insoluble component.
  • the average content of alkali-soluble polysaccharides in fine cellulose is preferably 13% by mass or less, more preferably 12% by mass or less, more preferably 8% by mass or less, further preferably 5% by mass or less. % By mass or less.
  • the alkali-soluble polysaccharide average content may be 0% by mass, but from the viewpoint of easy production of fine cellulose, for example, may be 1% by mass or more, or 3% by mass or more, or 6% by mass or more. Good.
  • the fine cellulose has a value in the above range as the average content of the alkali-soluble polysaccharide, and has a value in the range of the present disclosure (particularly preferably 60% or more) as the crystallinity.
  • the alkali-soluble polysaccharide in the present disclosure includes ⁇ -cellulose and ⁇ -cellulose in addition to hemicellulose.
  • the alkali-soluble polysaccharide is a component obtained as an alkali-soluble polysaccharide from holocellulose obtained by subjecting a plant (eg, wood) to solvent extraction and chlorination (ie, a component obtained by removing ⁇ -cellulose from holocellulose).
  • a plant eg, wood
  • solvent extraction and chlorination ie, a component obtained by removing ⁇ -cellulose from holocellulose.
  • Alkali-soluble components are polysaccharides containing hydroxyl groups and have poor heat resistance, decompose when heated, cause yellowing during thermal aging, and cause inconvenience such as a decrease in the strength of cellulose fibers. It is preferable that the content of the alkali-soluble polysaccharide in the fine cellulose is small, because it can cause the occurrence.
  • the content of the alkali-soluble polysaccharide can be determined by the method described in Non-Patent Document (Wood Science Experiment Manual, edited by The Japan Wood Science Society, pp. 92-97, 2000), and is calculated from the holocellulose content (Wise method). It is determined by subtracting the cellulose content. This method is understood in the art as a method for measuring the amount of hemicellulose.
  • the alkali-soluble polysaccharide content is calculated three times for one sample, and the number average of the calculated alkali-soluble polysaccharide content is defined as the alkali-soluble polysaccharide average content.
  • the average content of the acid-insoluble component and the average content of the alkali-soluble polysaccharide of the fine cellulose in the present embodiment are calculated from the average content of the acid-insoluble component and the average content of the alkali-soluble polysaccharide of the cellulose raw material used for the production of the fine cellulose. May be.
  • a method for producing fine cellulose will be exemplified.
  • a cellulose fiber also referred to as a cellulose raw material
  • natural cellulose wood pulp obtained from wood species (hardwood or conifer), non-wood pulp obtained from non-wood species (cotton, bamboo, hemp, bagasse, kenaf, cotton linter, sisal, straw, etc.), animals (for example, Cellulose fiber aggregates derived from sea squirts), algae, microorganisms (for example, acetic acid bacteria), and microbial products can be used.
  • regenerated cellulose examples include cut yarns of regenerated cellulose fibers (such as viscose, cupra, and Tencel), cut yarns of cellulose derivative fibers, and ultrafine yarns of regenerated cellulose or cellulose derivatives obtained by electrospinning. These raw materials may be used to adjust the fiber diameter, fiber length, degree of fibrillation, etc. by beating, fibrillation, or refining by mechanical force of a beater or refiner, etc., or bleaching, refining using chemicals, and lignin And the content of non-cellulose such as hemicellulose and the like can be adjusted.
  • cut yarns of regenerated cellulose fibers such as viscose, cupra, and Tencel
  • cut yarns of cellulose derivative fibers such as viscose, cupra, and Tencel
  • ultrafine yarns of regenerated cellulose or cellulose derivatives obtained by electrospinning These raw materials may be used to adjust the fiber diameter, fiber length, degree of fibrillation, etc. by beating, fibrillation, or
  • Acid-insoluble components and alkali-soluble polysaccharides can be mentioned as components other than cellulose remaining in the pulp, but in a usual embodiment, these components remain even after the production of fine cellulose.
  • the acid-insoluble component and the alkali-soluble polysaccharide contained in the fine cellulose all affect the dispersibility, heat resistance and the like of the fine cellulose in the resin composition, and may be adjusted according to the purpose. As described above, when improvement in heat resistance or the like of fine cellulose is required, it is preferable that the content of the acid-insoluble component and the alkali-soluble polysaccharide in the cellulose raw material is small and the cellulose purity ( ⁇ -cellulose content) is high. There are cases.
  • cellulose having a cellulose purity ( ⁇ -cellulose content) of 80% by mass or more to suppress the discoloration of the resin composition and maintain the properties of the composition.
  • cellulose purity is more preferably at least 85% by mass, still more preferably at least 90% by mass, particularly preferably at least 95% by mass.
  • the cellulose purity can be determined by the ⁇ -cellulose content measuring method described in Non-Patent Document (Wood Science Experiment Manual, edited by The Japan Wood Science Society, pp. 92-97, 2000).
  • the ⁇ -cellulose content measuring method is a raw material of the cellulose I crystal, such as wood.
  • the cellulose purity is originally high. Therefore, even if the cellulose purity is less than 85% by mass, it is preferable as the raw material of the fine cellulose of the present embodiment.
  • Fine cellulose is obtained by applying shear to the cellulose raw material to make it finer.
  • shearing in a liquid is preferable.
  • a method of performing fibrillation by a method other than strong mechanical fibrillation such as pulverization (TEMPO oxidation, chemical modification of cellulose hydroxyl group in an organic solvent, etc.).
  • the fibrillation solvent water, aprotic solvent and the like are useful.
  • a fibrillation solvent containing an aprotic solvent is impregnated into a cellulose raw material (preferably a cellulose raw material having a cellulose purity of 80% by mass or more), the cellulose swells in a short time. In this state, a finer treatment can be performed by applying shear energy.
  • refinement with aprotic solvent is simpler in process because it can be defibrated with low energy and chemical modification can be performed simultaneously with or after defibration. Is more preferable.
  • aprotic solvent examples include alkyl sulfoxides, alkyl amides, and pyrrolidones. These solvents can be used alone or in combination of two or more.
  • alkyl sulfoxides examples include, for example, di C 1-4 alkyl sulfoxides such as dimethyl sulfoxide (DMSO), methyl ethyl sulfoxide, and diethyl sulfoxide.
  • DMSO dimethyl sulfoxide
  • methyl ethyl sulfoxide methyl ethyl sulfoxide
  • diethyl sulfoxide diethyl sulfoxide
  • alkylamides examples include N, N-diC1-4alkylformamides such as N, N-dimethylformamide (DMF) and N, N-diethylformamide; N, N-dimethylacetamide (DMAc), N, N N, N-diC1-4alkylacetamides such as -diethylacetamide and the like.
  • pyrrolidones include, for example, pyrrolidone such as 2-pyrrolidone and 3-pyrrolidone; and N-C1-4 alkylpyrrolidone such as N-methyl-2-pyrrolidone (NMP).
  • pyrrolidone such as 2-pyrrolidone and 3-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • aprotic solvents can be used alone or in combination of two or more.
  • the number in parentheses is the number of donors
  • DMSO dimethyl methacrylate
  • DMF dimethyl methacrylate
  • DMAc dimethyl methacrylate
  • NMP NMP
  • a method of applying agitation or shearing energy for example, a device to which impact shear is applied such as a planetary ball mill and a bead mill, a device to which a rotary shear field which induces fibrillation of cellulose such as a disc refiner and a grinder is added, or various kneaders and The kneading, stirring, and dispersing functions, such as a planetary mixer, can be obtained by using an apparatus capable of performing the functions with high efficiency.
  • a disintegrator a beater, a refiner, a low-pressure homogenizer, a high-pressure homogenizer, an ultra-high-pressure homogenizer, a homomixer, a grinder, a mass colloider, a cutter mill, a ball mill, a jet mill, a single-screw extruder, a twin-screw extruder, Examples thereof include an ultrasonic stirrer and a household juicer mixer.
  • Cellulose whiskers can be obtained with high efficiency by hydrolyzing cellulose raw materials and dissolving the amorphous part of cellulose.
  • the method of hydrolysis is not particularly limited, and examples thereof include acid hydrolysis, alkali oxidative decomposition, hydrothermal decomposition, steam explosion, and microwave decomposition. These methods may be used alone or in combination of two or more.
  • acid hydrolysis for example, a suitable amount of protonic acid, carboxylic acid, Lewis acid, heteropoly acid, etc. is added in a state where a cellulose raw material is dispersed in an aqueous medium, and the mixture is heated with stirring to easily perform average polymerization. You can control the degree.
  • the reaction conditions such as temperature, pressure, and time vary depending on the type of cellulose, the concentration of cellulose, the type of acid, and the concentration of acid, but are appropriately adjusted so as to achieve the desired average polymerization degree. For example, there is a condition that the cellulose is treated at 100 ° C. or more and under pressure for 10 minutes or more using a 2% by mass or less aqueous mineral acid solution. Under these conditions, a catalyst component such as an acid penetrates into the inside of the cellulose, hydrolysis is promoted, the amount of the catalyst component used is reduced, and subsequent purification is also facilitated.
  • the dispersion of the cellulose raw material at the time of hydrolysis may contain a small amount of an organic solvent in addition to water as long as the effects of the present invention are not impaired.
  • the method for chemically modifying the fine cellulose is not particularly limited.For example, a method of adding a chemical modifier at the same time as miniaturization, and performing a chemical modification at the same time as the miniaturization, or adding a chemical modifier after the miniaturization is performed. A method of separately performing chemical modification by a chemical method, or a method of performing fine modification after chemically modifying a cellulose raw material.
  • the solvent used in the chemical modification is not particularly limited. In particular, when an aprotic solvent is used, the cellulose quickly swells into the microfibril gap of cellulose, swells the cellulose, and the microfibrils enter a finely fibrillated state. By performing the chemical modification after creating this state, the chemical modification proceeds uniformly throughout the fine cellulose, and as a result, the variation in the degree of modification is reduced, and high heat resistance can be obtained.
  • a compound which reacts with the hydroxyl group of cellulose can be used, and examples thereof include an esterifying agent, an etherifying agent, and a silylating agent. Particularly, an esterifying agent is preferable from the viewpoint of improving heat resistance.
  • an esterifying agent an acid halide, an acid anhydride and a vinyl carboxylate are preferred.
  • the acid halide may be at least one selected from the group consisting of compounds represented by the following formula (1).
  • acid halides include acetyl chloride, acetyl bromide, acetyl iodide, propionyl chloride, propionyl bromide, propionyl iodide, butyryl chloride, butyryl bromide, butyryl iodide, benzoyl chloride, benzoyl bromide, iodine But not limited thereto.
  • one or more alkaline compounds may be added for the purpose of neutralizing the acidic substance which is a by-product while acting as a catalyst.
  • the alkaline compound include, but are not limited to, tertiary amine compounds such as triethylamine and trimethylamine; and nitrogen-containing aromatic compounds such as pyridine and dimethylaminopyridine.
  • any appropriate acid anhydrides can be used.
  • saturated aliphatic monocarboxylic anhydrides such as acetic acid, propionic acid, (iso) butyric acid, and valeric acid
  • unsaturated aliphatic monocarboxylic anhydrides such as (meth) acrylic acid and oleic acid
  • cyclohexanecarboxylic acid tetrahydro Alicyclic monocarboxylic acid anhydrides
  • aromatic monocarboxylic acid anhydrides such as benzoic acid and 4-methylbenzoic acid
  • dibasic carboxylic acid anhydrides such as succinic anhydride and adipic acid
  • Unsaturated aliphatic dicarboxylic anhydrides such as saturated aliphatic dicarboxylic acid, maleic anhydride and itaconic anhydride
  • 1-cyclohexene-1,2-dicarboxylic anhydride such as hexahydrophthalic anhydride
  • one or more acidic compounds such as sulfuric acid, hydrochloric acid, and phosphoric acid, or Lewis acids such as metal chlorides and metal triflates, or alkaline compounds such as triethylamine and pyridine are used as catalysts. It may be added.
  • R-COO-CH CH 2
  • R is an alkyl group having 1 to 24 carbon atoms, an alkylene group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, or an aryl group having 6 to 24 carbon atoms.
  • Vinyl carboxylate represented by ⁇ is preferred.
  • Vinyl carboxylate includes vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl cyclohexanecarboxylate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, pivalin More preferably, it is at least one selected from the group consisting of vinyl acrylate, vinyl octylate divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl pivalate, vinyl octylate, vinyl benzoate, and vinyl cinnamate. .
  • a catalyst such as an alkali metal hydroxide, an alkaline earth metal hydroxide, a primary to tertiary amine, a quaternary ammonium salt, imidazole and its derivatives, pyridine and its derivatives, and an alkoxide Or one or more selected from the group consisting of:
  • alkali metal hydroxide and alkaline earth metal hydroxide examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide and the like.
  • the primary to tertiary amines are primary amines, secondary amines, and tertiary amines, and specific examples include ethylenediamine, diethylamine, proline, N, N, N ', N'-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, tris (3-dimethylaminopropyl) amine, N, N-dimethylcyclohexylamine, triethylamine and the like can be mentioned.
  • imidazole and its derivatives examples include 1-methylimidazole, 3-aminopropylimidazole, carbonyldiimidazole and the like.
  • pyridine and derivatives thereof include N, N-dimethyl-4-aminopyridine, picoline and the like.
  • alkoxide examples include sodium methoxide, sodium ethoxide, potassium-t-butoxide and the like.
  • esterifying agents in particular, acetic anhydride, propionic anhydride, butyric anhydride, vinyl acetate, vinyl propionate, and at least one selected from the group consisting of vinyl butyrate, among them, acetic anhydride and vinyl acetate, the reaction efficiency of Preferred from a viewpoint.
  • the peak position of the absorption band changes depending on the type of the chemically modified group. From the change in the peak position, it can be determined what absorption band the peak is based on, and the modifying group can be identified.
  • Ratio of peak intensity (peak height of C O absorption band based on acyl group) of peak intensity of absorption band based on chemical modifying group to peak intensity (height) of absorption band of CO based on cellulose backbone (chemical modification)
  • the degree of modification (modification ratio) (IR index 1030) defined by the peak height of the absorption band based on the group / the peak height of the absorption band of the cellulose backbone C—O) is preferably 0.0024 or more, and 0.1. 50 or less. When the IR index 1030 is 0.0024 or more, a resin composition containing chemically modified fine cellulose having a high thermal decomposition onset temperature can be obtained.
  • the IR index 1030 is more preferably 0.012 or more, further preferably 0.024 or more, still more preferably 0.048 or more, particularly preferably 0.72 or more, and most preferably 0.1 or more, and more preferably It is 0.44 or less, more preferably 0.37 or less, particularly preferably 0.30 or less, and most preferably 0.25 or less.
  • Reading of the peak heights of 1730 cm -1 and 1030 cm -1 used to calculate the IR index 1730 and IR index 1030 is carried out as follows.
  • the peak intensity of 1730 cm -1, drawing a base line which connects a straight line other peak is not located near 1550 cm -1 and near 1850 cm -1, a peak of 1730 cm -1 to the height of the baseline in 1730 cm -1
  • the value subtracted from the height shall be read.
  • the peak intensity of 1030 cm -1, drawing a base line which connects a straight line other peaks is no position near 820 cm -1 and near 1530 cm -1, a peak of 1030 cm -1 to the height of the baseline in 1030 cm -1
  • the value subtracted from the height shall be read.
  • the unmodified cellulose skeleton remains in the chemically modified fine cellulose, and therefore, a chemical having both high tensile strength and dimensional stability derived from cellulose and high thermal decomposition initiation temperature derived from the chemical modification.
  • a resin composite containing the modified fine cellulose can be obtained.
  • DS is more preferably 0.05 or more, further preferably 0.1 or more, particularly preferably 0.2 or more, most preferably 0.3 or more, more preferably 1.8 or less, and still more preferably 1. 5 or less, particularly preferably 1.2 or less, most preferably 1.0 or less.
  • the fine cellulose or the chemically modified fine cellulose is washed and concentrated by filtration or centrifugation using water, and finally can be used as a water slurry or a dried product for producing composite particles.
  • thermoplastic resin that can be used for the composite particles of the present embodiment will be described in detail.
  • specific examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymer; vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; polyvinyl acetate and ethylene-vinyl acetate copolymer.
  • a vinyl resin such as polyvinyl alcohol; a polyacetal resin; a fluororesin such as polyvinylidene fluoride; a polyester resin such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polystyrene, styrene-butadiene block copolymer, styrene-isoprene Polystyrene resins such as block copolymers; Nitrile resins such as polyacrylonitrile, styrene-acrylonitrile copolymer, ABS resin; polyphenylene ether resins; polyamides; Polyimide; Polyamide imide; Acrylic resin such as polymethacrylic acid and polyacrylic acid; Polycarbonate; Polyphenylene sulfide; Polysulfone; Polyether sulfone; Polyether nitrile; Polyether ketone; Polyketone; Liquid crystal polymer; Silicone resin; Natural celluloses such as wood
  • the thermoplastic is soluble in DMSO.
  • being soluble in DMSO means that 0.1 g or more is dissolved in 100 g of DMSO at 25 ° C.
  • Thermoplastic resins that are soluble in DMSO contribute to increasing the viscosities ⁇ 10 and ⁇ 100 of the present disclosure.
  • the thermoplastic resin soluble in DMSO include a cellulose derivative (particularly, a cellulose ester), a polystyrene resin, and a vinyl chloride resin.
  • the thermoplastic resin dissolves more preferably in an amount of 0.5 g or more, further preferably 1.0 g or more, particularly preferably 2.0 g or more, in 100 g of DMSO at 25 ° C.
  • thermoplastic resin is 100 g or less of DMSO at 25 ° C., for example, 100 g or less, or 70 g or less, or Dissolve in an amount of 50 g or less.
  • the cellulose derivative has a high affinity for fine cellulose because it is a cellulosic material, and also because it is a thermoplastic resin, it can contribute to stabilizing the dispersion of fine cellulose in the resin composition. Therefore, it is more preferable as the thermoplastic resin used for the composite particles.
  • the mechanical properties of the resin composition are improved by improving and controlling the dispersion state of the fine cellulose in the base resin in the resin composition due to the presence of the cellulose derivative.
  • the presence of the cellulose derivative can have a property that the fine cellulose is soluble and redispersible in the thermoplastic resin.
  • the composite particles as a filler are in a dry state.
  • fine cellulose having a nanometer size ie, less than 1 ⁇ m
  • the cellulose derivative interacts with the surface of the fine cellulose, and can also function as a binder showing an affinity for the base resin. Redistribution is feasible.
  • the fact that the surface of the fine cellulose is chemically modified is effective for strengthening the interaction between the cellulose derivative and the fine cellulose.
  • the cellulose derivative is bound to the surface of the fine cellulose.
  • Cellulose derivatives are preferably cellulose acetate, cellulose acetate propionate, cellulose esters such as cellulose acetate butyrate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, cellulose ethers such as cyanoethyl cellulose, and hydroxypropyl.
  • Cellulose ether esters such as methylcellulose acetate and hydroxypropylmethylcellulose acetate succinate (in the present disclosure, cellulose ether esters are intended to be included in the concept of both cellulose ethers and cellulose esters). At least one type. Among them, cellulose ester is excellent in terms of heat resistance and is preferred.
  • the cellulose derivative is preferably soluble in a solvent used for defibrating cellulose.
  • the cellulose derivative preferably has a melting point between 100 ° C. and 350 ° C. from the viewpoint of miscibility with the resin.
  • cellulose derivatives having two or more substituents in one derivative such as cellulose acetate propionate and cellulose acetate butyrate, often have a melting point, and are more preferable.
  • the weight average molecular weight (Mw) of the cellulose derivative is preferably 1,000 or more, or 5,000 or more, or 10,000 or more, or 20,000 or more, preferably 100,000 or less, or 80,000 or less, or 60,000 or less. is there. Mw is a value measured by a method of calculating in terms of standard polystyrene by size exclusion chromatography.
  • the alkyl substituent of the cellulose ether is preferably an alkyl group having 1 to 18 carbon atoms.
  • One or more ether substituents per anhydroglucose unit ie, mixed esters
  • Preferred examples of the ether substituent are a methyl group, an ethyl group, and a propyl group.
  • the ether substituent is preferably an ethyl group in view of moldability, transparency and flexural modulus of the resin composition.
  • the total degree of substitution of the cellulose ether (the sum of the degree of methyl group substitution and the degree of ethyl group substitution in the case of a co-substituted product such as cellulose methyl ethyl ether) is preferably 1 from the viewpoint of compatibility between the resin and the fine cellulose. It is from 2.5 to 3.0, more preferably from 2.1 to 2.95, even more preferably from 2.6 to 2.90.
  • the degree of ether substitution is a value measured by 1 H-NMR (nuclear magnetic resonance apparatus).
  • the viscosity of a solution obtained by dissolving 5 parts by mass of cellulose ether in a mixed solvent of 80 parts by mass of toluene and 20 parts by mass of ethanol has a lower limit of 1 mPa ⁇ s or more under a temperature condition of 25 ° C. It is preferably at least 3 mPa ⁇ s, more preferably at least 5 mPa ⁇ s, even more preferably at least 8 mPa ⁇ s, particularly preferably at least 12 mPa ⁇ s, most preferably at least 20 mPa ⁇ s.
  • the upper limit of the degree of polymerization is preferably 500 mPa ⁇ s or less, more preferably 350 mPa ⁇ s or less, further preferably 250 mPa ⁇ s or less, further preferably 110 mPa ⁇ s or less, particularly preferably 70 mPa ⁇ s or less, and 55 mPa ⁇ s or less. s or less are most preferred.
  • the degree of polymerization of the cellulose ethers by inhibiting aggregation of the fine cellulose in the composite particles (which are reflected in the dispersion viscosity eta 10 of the composite particles is a high value), the fine cellulose in the resin composition
  • it is preferably not less than the lower limit, and the fineness is increased by increasing the binding point at the interface between the fine cellulose and the cellulose derivative.
  • the content is preferably not more than the above upper limit.
  • the cellulose ether may be a commercially available product, or a product obtained by adjusting the degree of substitution of the commercially available product to a desired range.
  • Commercially available products include, for example, those available from The Dow Chemical Company under the name ETHOCEL TM. ETHOCEL (TM) Standard @ 4, ETHOCEL (TM) Standard # 7, ETHOCEL (TM) Standard @ 10, ETHOCEL (TM) Standard @ 20, ETHOCEL (TM) Standard @ 45, or ETHOCyl @ Shd @ rd @ Shd. Have been.
  • the ester substituent of the cellulose ester is preferably an acyl group having 1 to 18 carbon atoms.
  • One or more ester substituents per anhydroglucose unit ie, mixed esters
  • Preferred examples of ester substituents are acetyl, propionyl, and butyryl.
  • the ester substituent is preferably an acetyl group from the viewpoint of moldability and flexural modulus of the resin composition.
  • the cellulose ester has a degree of polymerization of 50 to 1000, and preferably has a total degree of substitution (ester substitution of 1.5 to 2.6.
  • the average degree of polymerization of the cellulose ester can be measured by the limiting viscosity method of Uda et al. (Kazuo Uda, Hideo Saito, Journal of the Fiber Society, Vol. 18, No. 1, pp. 105-120, 1962).
  • the total degree of substitution of the cellulose ester is preferably from the viewpoint of compatibility between the resin and the fine cellulose. Is from 1.5 to 3.0, more preferably from 2.1 to 2.95, even more preferably from 2.6 to 2.90.
  • the degree of ester substitution is a value measured by 1 H-NMR (nuclear magnetic resonance apparatus).
  • the cellulose ester may be a commercially available product, or a product obtained by adjusting the total substitution degree of the commercially available product to a desired range.
  • Commercially available products include cellulose diacetate (manufactured by Daicel, product names: L-30 and L-70), cellulose triacetate (manufactured by Daicel, product name: LT-105), and cellulose acetate propionate (Eastman Chemical Co., Ltd.) And product name: CAP504-2.0), cellulose acetate butyrate (manufactured by Eastman Chemical Company, product name: CAB321-0.1), and the like.
  • the combination of the cellulose derivative and the chemical modification in the fine cellulose is preferably a combination in which the cellulose derivative has at least an acetyl substituent and the chemical modification is acetylation, and more preferably, the cellulose derivative is a cellulose diacetate (DAC), cellulose triacetate (TAC), cellulose acetate butyrate (CAB), and cellulose acetate propionate (CAP), and the chemical modification is acetylation.
  • DAC cellulose diacetate
  • TAC cellulose triacetate
  • CAB cellulose acetate butyrate
  • CAP cellulose acetate propionate
  • the chemical modification is acetylation.
  • the hydrophobicity and affinity of the cellulose derivative and the fine cellulose tend to be good, and the fine dispersion of the fine cellulose in the resin composition is good. It is preferred in terms of.
  • the ratio of the fine cellulose to 100% by mass of the composite particles is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, particularly preferably 15% by mass, from the viewpoint of obtaining a good effect as a filler. At least 20% by mass, most preferably at least 20% by mass, and preferably at most 90% by mass, more preferably at most 90% by mass, from the viewpoint of obtaining an excellent dispersion improving effect of fine cellulose by using a thermoplastic resin (in one embodiment, a cellulose derivative). It is at most 85% by mass, more preferably at most 80% by mass.
  • the lower limit of the ratio of the thermoplastic resin (in one aspect, a cellulose derivative) in the composite particles is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably from the viewpoint of obtaining a good dispersion improving effect of fine cellulose. Is not less than 20% by mass, and the upper limit is preferably not more than 90% by mass, more preferably not more than 85% by mass, and still more preferably not more than 80% by mass, from the viewpoint of obtaining a good filler action by using fine cellulose.
  • the lower limit of the amount of the cellulose derivative per 100 parts by mass of fine cellulose (fine cellulose fibers in one embodiment) is preferably 1 part by mass or more, or 5 parts by mass or more, or 10 parts by mass or more, or 20 parts by mass or more,
  • the upper limit is preferably 500 parts by mass or less, or 300 parts by mass or less, or 200 parts by mass or less. From the viewpoint of improving the tensile rupture strength and thermal stability of the resin composition and reducing the variation in performance, it is desirable that the amount of fine cellulose (fine cellulose fiber in one embodiment) be within the above range.
  • the ratio (by mass) of fine cellulose / cellulose derivative in the composite particles is preferably 10/90 to 90/10, more preferably 15/85 to 85/15, and still more preferably 20/80 to 80/20. .
  • the method for producing the composite particles is not particularly limited, and examples thereof include the following methods. According to these methods, the composite particles can be collected as a slurry or a dried product.
  • An aqueous dispersion (slurry) of fine cellulose (fine cellulose fibers in one embodiment) and thermoplastic resin particles (cellulose derivative powder in one embodiment) are mixed, and then optionally dried (ie, powdered), A method for recovering composite particles.
  • a thermoplastic resin is added to an organic solvent dispersion of fine cellulose (fine cellulose fiber in one embodiment) to disperse the fine cellulose and dissolve the thermoplastic resin (cellulose derivative in one embodiment). Obtaining an organic solvent dispersion (fine cellulose / resin dispersion).
  • This organic solvent dispersion is mixed with a poor solvent for a thermoplastic resin (in one embodiment, a cellulose derivative) to precipitate the thermoplastic resin (that is, to deposit composite particles containing fine cellulose and the thermoplastic resin), thereby dispersing the composite particles.
  • a thermoplastic resin in one embodiment, a cellulose derivative
  • a purification step of replacing the organic solvent of the composite particle dispersion with water and optionally, a step of separating and collecting the composite particles by filtration, centrifugation, etc., washing with pure water, and / or drying,
  • Fine cellulose can be preferably prepared by a defibration step of performing a defibration treatment of cellulose in an organic solvent to obtain a fine cellulose dispersion, and optionally a purification step of replacing the organic solvent in the fine cellulose dispersion with water.
  • the addition of the thermoplastic resin in the method (3) may be performed before or during defibration.
  • the fine cellulose is chemically modified, it is preferable to provide a chemical modification step for chemically modifying the fine cellulose at the same time as or after the fibrillation step (preferably, before the purification step).
  • the organic solvent in which the thermoplastic resin (in one embodiment, a cellulose derivative) dissolves is not particularly limited, but may be a halogenated hydrocarbon, an ester, a ketone, an ether, an alcohol, an alkylsulfoxide, an alkylamide, or a pyrrolidone.
  • the solvent may be a single type of compound or a mixed solvent obtained by mixing a plurality of compounds.
  • halogenated hydrocarbons eg, dichloromethane, etc.
  • esters eg, methyl acetate, methyl formate, ethyl acetate, amyl acetate, butyl acetate, etc.
  • ketones eg, acetone, methyl ethyl ketone, cyclohexanone, etc.
  • Ethers eg, dioxane, dioxolan, tetrahydrofuran, diethyl ether, methyl-t-butyl ether, etc.
  • alcohols eg, methanol, ethanol, hexafluoroisopropanol, resorcinol, etc.
  • aprotic solvents described above in the present disclosure Alkylsulfoxides, alkylamides, pyrrolidones
  • the above-mentioned aprotic solvents are also excellent in producing fine cellulose. It is preferable in terms of process efficiency to continuously perform the production of fine cellulose and the production of composite particles using an aprotic solvent.
  • the thermoplastic resin is a cellulose derivative
  • a poor solvent for a thermoplastic resin is a solvent that does not dissolve the thermoplastic resin. More preferably, it is a solvent that does not dissolve the thermoplastic resin and is miscible with the organic solvent in which the thermoplastic resin dissolves.
  • the poor solvent for the thermoplastic resin in one embodiment, a cellulose derivative
  • examples of the poor solvent for the thermoplastic resin include water having a pH of 1 to 14, water containing an inorganic salt (eg, sodium chloride, calcium chloride, sodium silicate, etc.), and alcohol (eg, methanol, ethanol, and the like). Isopropanol, 1-hexanol, etc.), and a mixed solvent of water / alcohol.
  • the method of stirring or shearing necessary to promote the compositing of the fine cellulose and the cellulose derivative is not particularly limited, but, for example, a device to which collision shear is applied such as a planetary ball mill and a bead mill, a disc refiner
  • a device capable of performing kneading, stirring, and dispersing functions with high efficiency can be used, such as a device that adds a rotary shear field that induces fibrillation of cellulose, such as a grinder, and a grinder, or various kneaders and a planetary mixer. .
  • the proportion of water in the composite particles is preferably not more than 95% by mass, more preferably 0.01 to 95% by mass, still more preferably 0.1 to 50% by mass, particularly preferably 0 to 50% by mass, based on the total amount of the composite particles. It can be controlled to 1 to 20% by mass, most preferably 0.1 to 10% by mass.
  • the drying operation may be appropriately performed in a constant temperature chamber or the like so that the proportion of water in the composite particles falls within a desired range.
  • a resin composition including the above-described composite particles and a base resin.
  • a base resin a thermoplastic resin, a thermosetting resin, a photocurable resin, rubber, or the like can be used.
  • the thermoplastic resin derived from the composite particles forms a matrix together with the base resin (preferably by mixing the thermoplastic resin and the base resin) in the resin composition, and the fine cellulose is contained in the matrix.
  • the base resin is a thermoplastic resin
  • the base resin is a resin different from the thermoplastic resin contained in the composite particles.
  • “different resins” means resins having different component compositions and / or molecular structures (for example, molecular weights) of the resins.
  • One embodiment of the present invention also provides a resin composition containing a thermoplastic resin (as a base resin), fine cellulose having a fiber diameter of 2 nm or more and less than 1000 nm, and a cellulose derivative.
  • a thermoplastic resin as a base resin
  • fine cellulose having a fiber diameter of 2 nm or more and less than 1000 nm and a cellulose derivative.
  • Specific embodiments include a thermoplastic resin (as a base resin), 0.1 to 40 parts by mass per 100 parts by mass of the thermoplastic resin, fine cellulose having a fiber diameter of 2 nm or more and less than 1000 nm, and fine cellulose 100
  • a resin composition containing 1 to 900 parts by mass of a cellulose derivative with respect to parts by mass.
  • thermoplastic resin examples include, but are not particularly limited to, for example, polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer; polyvinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride; Vinyl resins such as polyvinyl acetate, ethylene-vinyl acetate copolymer and polyvinyl alcohol; polyacetal resins; fluororesins such as polyvinylidene fluoride; polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; Polystyrene resins such as styrene-butadiene block copolymer and styrene-isoprene block copolymer; nitrile resins such as polyacrylonitrile, styrene-acrylonitrile copolymer and ABS resin; polyphenylene-butadiene block copolymer and polyethylene
  • thermoplastic resins a crystalline resin having a melting point in the range of 100 ° C. to 350 ° C. or an amorphous resin having a glass transition temperature in the range of 100 to 250 ° C.
  • a polyolefin resin for example, a polyolefin resin, a polyamide resin , Polyester-based resin, polyacetal-based resin, polyphenylene ether-based resin, polyphenylene sulfide-based resin and a mixture of two or more thereof, preferably polyolefin-based resin, polyamide-based resin, polyester from the viewpoint of handleability and cost Resins, polyacetal resins and the like.
  • the melting point of the thermoplastic resin is preferably 140 ° C or higher, or 150 ° C or higher, or 160 ° C or higher, or 170 ° C or higher, or 180 ° C or higher. Or at least 190 ° C, or at least 200 ° C, or at least 210 ° C, at least 220 ° C, or at least 230 ° C, or at least 240 ° C, or at least 245 ° C, or at least 250 ° C.
  • the melting point of the crystalline resin as used herein refers to the peak top temperature of an endothermic peak that appears when the temperature is raised from 23 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the enthalpy of the endothermic peak is preferably at least 10 J / g, more preferably at least 20 J / g.
  • the glass transition temperature of the amorphous resin as used herein means that the temperature is measured at an applied frequency of 10 Hz using a dynamic viscoelasticity measuring apparatus while increasing the temperature from 23 ° C. at a rate of 2 ° C./min.
  • the measurement frequency at this time is desirably at least once every 20 seconds in order to increase the measurement accuracy.
  • the method of preparing the measurement sample is not particularly limited. From the viewpoint of eliminating the influence of molding distortion, it is preferable to use a cut piece of a hot press molded product, and the size (width and thickness) of the cut piece is as small as possible. Smaller is more desirable from the viewpoint of heat conduction.
  • thermoplastic resins that are preferable as thermoplastic resins are polymers obtained by polymerizing olefins (for example, ⁇ -olefins) or alkenes as a monomer unit.
  • polyolefin resin include ethylene (co) polymers exemplified by low-density polyethylene (for example, linear low-density polyethylene), high-density polyethylene, ultra-low-density polyethylene, ultra-high-molecular-weight polyethylene, polypropylene, and ethylene.
  • -Polypropylene (co) polymers exemplified by ethylene-propylene copolymer, ethylene-propylene-diene copolymer, etc., ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer Copolymers of ⁇ -olefins such as ethylene typified by coalescence are exemplified.
  • the most preferable polyolefin resin is polypropylene.
  • polypropylene having a melt mass flow rate (MFR) of 3 g / 10 min or more and 30 g / 10 min or less measured at 230 ° C. under a load of 21.2 N according to ISO 1133 is preferable.
  • the lower limit of the MFR is more preferably 5 g / 10 minutes, still more preferably 6 g / 10 minutes, and most preferably 8 g / 10 minutes.
  • the upper limit is more preferably 25 g / 10 minutes, still more preferably 20 g / 10 minutes, and most preferably 18 g / 10 minutes.
  • the MFR desirably does not exceed the above upper limit from the viewpoint of improving the toughness of the composition, and desirably does not exceed the above lower limit from the viewpoint of the fluidity of the composition.
  • an acid-modified polyolefin-based resin can be suitably used.
  • the acid at this time can be appropriately selected from maleic acid, fumaric acid, succinic acid, phthalic acid, anhydrides thereof, and polycarboxylic acids such as citric acid.
  • maleic acid or its anhydride is preferred because of its high modification rate.
  • the modification method is not particularly limited, but is generally a method of melting and kneading by heating to the melting point or higher in the presence or absence of a peroxide.
  • the polyolefin resin to be acid-modified all of the above-mentioned polyolefin resins can be used, but polypropylene is particularly preferably used.
  • the acid-modified polypropylene may be used alone, but it is more preferable to use it in combination with unmodified polypropylene in order to adjust the modification rate of the whole resin.
  • the ratio of the acid-modified polypropylene to all the polypropylenes is 0.5% by mass to 50% by mass.
  • a more preferred lower limit is 1% by mass, further preferably 2% by mass, still more preferably 3% by mass, particularly preferably 4% by mass, and most preferably 5% by mass.
  • a more preferable upper limit is 45% by mass, further preferably 40% by mass, still more preferably 35% by mass, particularly preferably 30% by mass, and most preferably 20% by mass.
  • the lower limit is preferably greater than or equal to the lower limit.
  • the upper limit is preferably equal to or less than the upper limit.
  • the melt mass flow rate (MFR) of the acid-modified polypropylene measured at 230 ° C. under a load of 21.2 N according to ISO 1133 is preferably 50 g / 10 min or more in order to increase the affinity with the cellulose interface. .
  • a more preferred lower limit is 100 g / 10 minutes, still more preferably 150 g / 10 minutes, and most preferably 200 g / 10 minutes.
  • aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,11 and polyamide 6,12, polyamide 6, C, polyamide 2M5, C
  • the alicyclic polyamide is more preferable.
  • the terminal carboxyl group concentration of the polyamide resin is not particularly limited, but the lower limit is preferably 20 ⁇ mol / g, and more preferably 30 ⁇ mol / g.
  • the upper limit of the terminal carboxyl group concentration is preferably 150 ⁇ mol / g, more preferably 100 ⁇ mol / g, and still more preferably 80 ⁇ mol / g.
  • the ratio of the carboxyl terminal group to all terminal groups is more preferably 0.30 to 0.95.
  • the lower limit of the carboxyl end group ratio is more preferably 0.35, even more preferably 0.40, and most preferably 0.45.
  • the upper limit of the carboxyl terminal group ratio is more preferably 0.90, still more preferably 0.85, and most preferably 0.80.
  • the carboxyl terminal group ratio is desirably 0.30 or more from the viewpoint of dispersibility of the fine cellulose in the composition, and desirably 0.95 or less from the viewpoint of the color tone of the obtained composition.
  • a known method can be used to adjust the terminal group concentration of the polyamide resin.
  • a diamine compound, a monoamine compound, a dicarboxylic acid compound, a monocarboxylic acid compound, an acid anhydride, a monoisocyanate, a monoacid halide, a monoester, a monoalcohol, etc. so as to have a predetermined terminal group concentration during polymerization of polyamide.
  • a method in which a terminal adjuster that reacts with a terminal group is added to the polymerization solution may be used.
  • Aliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid A carboxylic acid; and a plurality of mixtures arbitrarily selected from these.
  • at least one terminal adjuster selected from the group consisting of benzoic acid and benzoic acid, and acetic acid is most preferred.
  • Examples of a terminal adjuster that reacts with a terminal carboxyl group include aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Monoamines; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine, and any mixtures thereof.
  • At least one terminal selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline from the viewpoints of reactivity, boiling point, stability of a sealed terminal, and price. Modifiers are preferred.
  • the concentration of these amino terminal groups and carboxyl terminal groups is preferably determined from the integrated value of the characteristic signal corresponding to each terminal group by 1 H-NMR from the viewpoint of accuracy and simplicity.
  • a method for determining the concentrations of these terminal groups a method described in JP-A-7-228775 is specifically recommended. When this method is used, deuterated trifluoroacetic acid is useful as a measuring solvent. Further, the number of times of integration of 1 H-NMR requires at least 300 scans even when measured by an instrument having a sufficient resolution.
  • the concentration of the terminal group can be measured by a titration measurement method as described in JP-A-2003-055549. However, in order to minimize the influence of mixed additives, lubricants, and the like, quantification by 1 H-NMR is more preferable.
  • the intrinsic viscosity [ ⁇ ] of the polyamide resin measured in concentrated sulfuric acid at 30 ° C. is preferably 0.6 to 2.0 dL / g, and 0.7 to 1.4 dL / g. Is more preferably 0.7 to 1.2 dL / g, and particularly preferably 0.7 to 1.0 dL / g.
  • Use of the polyamide having an intrinsic viscosity in a preferable range, and particularly preferable range among them, can significantly increase the fluidity in a mold at the time of injection molding of the resin composition, and give an effect of improving the appearance of a molded piece. it can.
  • intrinsic viscosity has the same meaning as viscosity generally called intrinsic viscosity.
  • a specific method for obtaining this viscosity is to measure ⁇ sp / c of several measuring solvents having different concentrations in 96% concentrated sulfuric acid under a temperature condition of 30 ° C., and to determine the respective ⁇ sp / c and the concentration (c ) And extrapolating the concentration to zero. The value extrapolated to zero is the intrinsic viscosity. Details of these are described, for example, in Polymer Process Engineering (Prentice-Hall, Inc. 1994), pages 291 to 294. At this time, it is desirable from the viewpoint of accuracy that the number of the measurement solvents having different concentrations be at least four.
  • the recommended concentrations of the different viscosity measurement solutions are preferably at least four points of 0.05 g / dL, 0.1 g / dL, 0.2 g / dL, and 0.4 g / dL.
  • polyester resins as thermoplastic resins include polyethylene terephthalate (hereinafter sometimes simply referred to as PET), polybutylene succinate (a polyester resin comprising an aliphatic polyvalent carboxylic acid and an aliphatic polyol (hereinafter referred to as PBS). ), Polybutylene succinate adipate (hereinafter sometimes simply referred to as PBSA), polybutylene adipate terephthalate (hereinafter sometimes simply referred to as PBAT), polyhydroxyalkanoic acid (3-hydroxyalkanoic acid).
  • PET polyethylene terephthalate
  • PBS aliphatic polyvalent carboxylic acid and an aliphatic polyol
  • PBSA Polybutylene succinate adipate
  • PBAT polybutylene adipate terephthalate
  • polyhydroxyalkanoic acid (3-hydroxyalkanoic acid).
  • a polyester resin comprising: PHA; polylactic acid (hereinafter, sometimes simply referred to as PLA); polybutylene terephthalate (hereinafter, sometimes simply referred to as PBT); polyethylene naphthalate (hereinafter, simply referred to as PBT) , May be referred to as PEN), polyarylate (hereinafter sometimes simply referred to as PAR), polycarbonate (hereinafter sometimes simply referred to as PC), or one or more kinds selected therefrom. .
  • PLA polylactic acid
  • PBT polybutylene terephthalate
  • PAR polyarylate
  • PC polycarbonate
  • polyester-based resins include PET, PBS, PBSA, PBT, and PEN, and more preferably, PBS, PBSA, and PBT.
  • the end groups of the polyester resin can be freely changed depending on the monomer ratio at the time of polymerization and the presence / absence of the terminal stabilizer, and the amount of the carboxyl end group relative to all end groups of the polyester resin.
  • the ratio ([COOH] / [all terminal groups]) is more preferably 0.30 to 0.95.
  • the lower limit of the carboxyl end group ratio is more preferably 0.35, even more preferably 0.40, and most preferably 0.45.
  • the upper limit of the carboxyl terminal group ratio is more preferably 0.90, still more preferably 0.85, and most preferably 0.80.
  • the carboxyl terminal group ratio is desirably 0.30 or more from the viewpoint of dispersibility of the fine cellulose in the composition, and desirably 0.95 or less from the viewpoint of the color tone of the obtained composition.
  • thermoplastic resins preferred as thermoplastic resins include homopolyacetals using formaldehyde as a raw material and copolyacetals containing trioxane as a main monomer and 1,3-dioxolane as a comonomer component, and both are usable.
  • copolyacetal can be preferably used.
  • the amount of the structure derived from a comonomer component is more preferably in the range of 0.01 to 4 mol%.
  • a preferred lower limit of the amount of the structure derived from the comonomer component is 0.05 mol%, more preferably 0.1 mol%, and even more preferably 0.2 mol%.
  • a preferred upper limit is 3.5 mol%, more preferably 3.0 mol%, still more preferably 2.5 mol%, and most preferably 2.3 mol%.
  • the lower limit is preferably within the above range
  • the upper limit is preferably within the above range from the viewpoint of mechanical strength.
  • thermosetting resin Specific examples of the thermosetting resin are not particularly limited.
  • the thermosetting resin are not particularly limited.
  • Phenol resin such as resol type phenol resin such as phenol resin, phenoxy resin, urea (urea) resin, triazine ring-containing resin such as melamine resin, unsaturated polyester resin, bismaleimide resin, diallyl phthalate resin, silicone resin, benzoxazine ring Resin, norbornene resin, cyanate resin, isocyanate resin, urethane resin, benzocyclobutene resin, maleimide resin, bismaleimide triazine resin, polyazomethine resin, thermosetting resin Imide and the like.
  • These thermosetting resins may be used alone or as a blend of two or more. The blending ratio when blending may be appropriately selected according to various uses.
  • Photocurable resin Specific examples of the photocurable resin include, but are not particularly limited to, known general (meth) acrylate resins, vinyl resins, and epoxy resins. These are roughly classified into a radical reaction type in which a monomer reacts by radicals generated by light and a cation reaction type in which a monomer cationically polymerizes, according to a reaction mechanism.
  • the radical reaction type monomers include (meth) acrylate compounds, vinyl compounds (for example, certain vinyl ethers), and the like. Epoxy compounds, certain vinyl ethers and the like correspond to the cation reaction type.
  • an epoxy compound that can be used as a cation reaction type can be a monomer of both a thermosetting resin and a photocurable resin.
  • (Meth) acrylate compound refers to a compound having one or more (meth) acrylate groups in a molecule.
  • Specific examples of the (meth) acrylate compound include monofunctional (meth) acrylate, polyfunctional (meth) acrylate, epoxy acrylate, polyester acrylate, and urethane acrylate.
  • Examples of the vinyl compound include vinyl ether, styrene and styrene derivatives, and vinyl compounds.
  • Examples of the vinyl ether include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether.
  • Examples of the styrene derivative include methyl styrene and ethyl styrene.
  • Examples of the vinyl compound include triallyl isocyanurate and trialmethallyl isocyanurate.
  • a so-called reactive oligomer may be used as a raw material of the photocurable resin.
  • the reactive oligomer an oligomer having any combination selected from a (meth) acrylate group, an epoxy group, a urethane bond, and an ester bond in the same molecule, for example, a (meth) acrylate group and a urethane bond in the same molecule Urethane acrylate, a polyester acrylate having a (meth) acrylate group and an ester bond in the same molecule, an epoxy acrylate derived from an epoxy resin and having an epoxy group and a (meth) acrylate group in the same molecule, and the like.
  • the photocurable resin may be used alone, or two or more kinds may be used as a blend.
  • the blending ratio in the case of blending may be appropriately selected according to various uses.
  • elastomer that is, rubber
  • elastomer are not particularly limited, and include, for example, natural rubber (NR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), isoprene rubber (IR) Butyl rubber (IIR), acrylonitrile-butadiene rubber (NBR), acrylonitrile-styrene-butadiene copolymer rubber, chloroprene rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer Combined rubber, chlorosulfonated polyethylene rubber, modified natural rubber (epoxidized natural rubber (ENR), hydrogenated natural rubber, deproteinized natural rubber, etc.), ethylene-propylene copolymer rubber, acrylic rubber, epichlorohydrin rubber, polysulf
  • the resin composition of the present embodiment may further include an additive as needed in order to improve its performance.
  • the additive is not particularly limited, but includes, for example, a dispersion stabilizer; a fine fiber filler component (eg, fibrillated fiber or fine fiber of aramid fiber) composed of a high heat-resistant organic polymer other than fine cellulose; Agents; polysaccharides such as starches and alginic acid; natural proteins such as gelatin, glue and casein; inorganic compounds such as zeolites, ceramics, talc, silica, metal oxides and metal powders; coloring agents; fragrances; pigments; Leveling agent; conductive agent; antistatic agent; ultraviolet absorber; ultraviolet dispersant;
  • the content ratio of the optional additive in the resin composition is appropriately selected within a range that does not impair the desired effect of the present invention, and is, for example, 0.01 to 50% by mass, or 0.1 to 30% by mass. May be.
  • a dispersion stabilizer having a function of stably dispersing fine cellulose in the resin composition may be used.
  • the dispersion stabilizer can improve the mechanical properties of the resin composition by improving and controlling the dispersion state of the fine cellulose in the resin composition.
  • the dispersion stabilizer can be at least one selected from the group consisting of a surfactant, an organic compound having a boiling point of 160 ° C. or higher, and a resin having a chemical structure capable of highly dispersing fine cellulose.
  • the lower limit of the mass ratio of the dispersion stabilizer to the total mass of the resin composition is preferably 0.01% by mass or more, or 0%, from the viewpoint of favorably improving the mechanical properties and thermal stability of the resin composition. 0.5% by mass or more, or 0.1% by mass or more, or 0.5% by mass or more, or 1% by mass or more, and the upper limit is in terms of favorably maintaining the desired properties of the base resin in the resin composition. Therefore, it is preferably 20% by mass or less, or 10% by mass or less, or 5% by mass or less, or 3% by mass or less.
  • the surfactant only needs to have a chemical structure in which a site having a hydrophilic substituent and a site having a hydrophobic substituent are covalently bonded.
  • the following can be used alone or in combination of two or more.
  • any of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be used.
  • an anionic surfactant and a nonionic surfactant are preferable, and a nonionic surfactant is more preferable.
  • a surfactant having a polyoxyethylene chain as a hydrophilic group, a carboxylic acid group, or a hydroxyl group is preferable, and a polyoxyethylene-based surfactant having a polyoxyethylene chain as a hydrophilic group.
  • Agents are more preferred, and nonionic polyoxyethylene derivatives are even more preferred.
  • the polyoxyethylene chain length of the polyoxyethylene derivative is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 15 or more.
  • the upper limit is preferably 60 or less, more preferably 50 or less, still more preferably 40 or less, and particularly preferably 30 or less. Most preferred is 20 or less.
  • alkyl ether type alkyl phenyl ether type, rosin ester type, bisphenol A type, ⁇ naphthyl type, styrenated phenyl type, and hardened castor oil type
  • the preferred alkyl chain length is preferably 5 or more, more preferably 10 or more, still more preferably 12 or more, and particularly preferably 16 or more.
  • the base resin is a polyolefin
  • the upper limit is preferably 30 or less, more preferably 25 or less.
  • hydrophobic groups those having a cyclic structure or those having a bulky and multifunctional structure are preferable.
  • Those having a cyclic structure are preferably alkylphenyl ether type, rosin ester type, bisphenol A type, ⁇ -naphthyl type, and styrenated phenyl type, and those having a polyfunctional structure are preferably hardened castor oil type.
  • the rosin ester type and the hardened castor oil type are particularly preferable.
  • an organic compound having a boiling point of 160 ° C. or higher may be effective as a non-surfactant-based dispersion medium in some cases.
  • a high-boiling organic solvent such as liquid paraffin or decalin is effective.
  • the base resin is a polar resin such as a nylon-based resin and a polyacetate-based resin, it is effective to use a solvent similar to an aprotic solvent that can be used in producing fine cellulose, for example, DMSO. It may be.
  • the lower limit of the amount of the composite particles relative to 100 parts by mass of the base resin is at least 0.1 part by mass, preferably at least 1 part by mass, more preferably at least 2 parts by mass, even more preferably at least 3 parts by mass, and the upper limit is 100 parts by mass. Parts by mass, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, particularly preferably 50 parts by mass or less. From the viewpoint of the balance between the fluidity of the resin composition at the time of melting and the mechanical properties, it is desirable that the amount of fine cellulose be within the above range.
  • the lower limit of the mass ratio of the fine cellulose to the total mass of the resin composition is preferably 0.05% by mass or more, or 0. 0 mass% from the viewpoint of favorably improving the mechanical properties and thermal stability of the resin composition.
  • 1% by mass or more, or 1% by mass or more, and the upper limit is preferably 50% by mass or less, or 40% by mass or less, from the viewpoint of favorably maintaining desired properties of the base resin in the resin composition. 30% by mass or less, or 20% by mass or less.
  • the mass ratio of the base resin (thermoplastic resin in one embodiment) to the total mass of the resin composition is preferably 50 from the viewpoint of exhibiting thermal stability (reduction of linear thermal expansion coefficient and retention of elasticity at high temperatures). % By mass or more, or 60% by mass or more, or 70% by mass or more, or 80% by mass or more, from the viewpoint of imparting functions such as a high elastic modulus and a decrease in thermal expansion coefficient to the resin composition. Is 99.5% by mass or less, or 90% by mass or less.
  • the amount of fine cellulose is preferably 0.1 parts by mass or more, or 1 part by mass or more, or 2 parts by mass or more based on 100 parts by mass of the base resin (the thermoplastic resin in one embodiment). Or 3 parts by mass or more, and the upper limit is preferably 40 parts by mass or less, or 30 parts by mass or less, or 20 parts by mass or less, or 10 parts by mass or less. From the viewpoint of the balance between the fluidity of the resin composition at the time of melting and the mechanical properties, it is desirable that the amount of fine cellulose be within the above range.
  • the composite particles in a dry state are highly redispersed after being mixed into the base resin, sufficient mechanical properties can be realized even if the amount of fine cellulose relative to the resin is small.
  • the ratio of the fine cellulose can be preferably 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the base resin.
  • excellent mechanical properties can be realized even when the amount is 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the base resin, problems such as moisture absorption of the composition as well as coloring and odor are minimized. can do.
  • the content of the composite particles in the resin composition may be 0.5 to 40% by mass, more preferably 10 to 20% by mass.
  • a resin composition using the composite particles of the present disclosure is a comparative resin composition using fine cellulose alone (ie, not as composite particles) and having the same fine cellulose ratio in the resin composition.
  • the tensile breaking strength is preferably 1.03 or more, more preferably 1.05 or more, still more preferably 1.10 or more, and most preferably 1.15 or more, and / or the tensile breaking elongation is preferably 1 or more.
  • 05 or more more preferably 1.10 or more, most preferably 1.15 or more, and / or the coefficient of linear expansion is preferably 0.90 or less, more preferably 0.85 or less, and still more preferably 0.80 or less. Or less, most preferably 0.75 or less.
  • the change in storage modulus of the resin composition is preferably 0.98 or less, more preferably 0.95, even more preferably 0.90 or less, and most preferably 0.85 or less.
  • the change in storage modulus is calculated according to the following equation.
  • Change in storage modulus storage modulus at low temperature / storage modulus at high temperature
  • the low / high temperature is 0 ° C / 150 ° C
  • polypropylene is -50 ° C / 100 ° C.
  • the storage elastic modulus decreases as the temperature increases, so that the change in the storage elastic modulus becomes 1 or more. The closer this value is to 1, the smaller the change in storage modulus at high temperature and the higher the heat resistance (the higher the rigidity at high temperature).
  • the dispersibility of the fine cellulose is improved as compared with the resin composition in which fine cellulose is directly added to the base resin.
  • a state in which the dispersibility of the fine cellulose is poor means that the fine cellulose exists as a coarse aggregate. Since coarse aggregates serve as fracture starting points at the time of a tensile test, the presence of coarse aggregates is not preferable in the production of a resin composition because the tensile strength at break and elongation are reduced when compared with an ideal dispersion state.
  • the presence of coarse aggregates means a decrease in the amount of fine cellulose that effectively contributes as a filler, lowers the flexural modulus when compared to the ideal dispersion state, and changes the linear expansion coefficient and the storage modulus. It is not preferable in the production of the resin composition because it deteriorates.
  • the resin composition of the present disclosure can have improved dispersibility of fine cellulose, it can exhibit lower linear expansion than a conventional resin composition containing fine cellulose.
  • the linear expansion coefficient of the resin composition in a temperature range of 0 ° C. to 60 ° C. is preferably 80 ppm / k or less, more preferably 70 ppm / k or less, further preferably 60 ppm / k or less, and further preferably 55 ppm / k. Or less, particularly preferably 50 ppm / k or less, most preferably 45 ppm / k or less.
  • the linear expansion coefficient is preferably as low as possible, but may be, for example, 10 ppm / k or more, or 15 ppm / k or more from the viewpoint of ease of production of the resin composition.
  • the variation coefficient CV of tensile strength at break of the resin composition is preferably 15% or less.
  • the coefficient of variation referred to here is a value expressed as a percentage obtained by dividing the standard deviation ( ⁇ ) by the arithmetic mean ( ⁇ ) and multiplying by 100, and is a number without a unit representing relative variation.
  • CV ( ⁇ / ⁇ ) ⁇ 100
  • ⁇ and ⁇ are given by the following equations.
  • xi is a single piece of data of the tensile breaking strength among the n pieces of data x1, x2, x3,... Xn.
  • the number of samples (n) for calculating the coefficient of variation CV of the tensile rupture strength is desirably at least 10 or more in order to easily find defects in the resin composition. More preferably, it is 15 or more.
  • the coefficient of variation in the above range can be realized by using a combination of fine cellulose (particularly fine cellulose fibers) and a cellulose derivative.
  • the fine cellulose fiber can be present in the resin composition at a higher dispersibility and a higher concentration than the fine cellulose fiber alone. This breakthrough eliminates the occurrence of partial strength defects found in resin molded products made of conventional resin compositions containing fine cellulose fibers, and significantly improves the reliability as actual products. Effects can be obtained.
  • the partial strength defect as described above of a conventional resin molded product is caused by the aggregation of fine cellulose (fine cellulose fibers in one embodiment) in a base resin (thermoplastic resin in one embodiment), and the vicinity of the aggregate. It is considered that the formation of voids (voids) occurs.
  • voids voids
  • As an index for evaluating the easiness of formation of the strength defect there is a method in which a tensile test is performed on a plurality of test pieces and the presence / absence and the number of variations in the breaking strength are confirmed.
  • the material has a homogeneous internal structure and does not have voids and the like, even when a tensile break test of a plurality of samples is performed, the stress at the time of breakage is between the plurality of samples. The values are almost the same, and the coefficient of variation is very small. However, in a material having a non-uniform portion or a void inside, the stress leading to fracture in one sample has a great difference from the stress of another sample. Such a degree of the number of samples exhibiting stress different from the stress of other samples can be clarified by using a scale called a coefficient of variation.
  • a sample having an internal defect leads to fracture at a lower strength than other samples.
  • a material having a yield strength after the yield, it often breaks on the way to necking, and the sample having a defect inside has a higher strength than the other samples. The tendency to reach.
  • the dispersion state of the fine cellulose in the composition greatly affects the coefficient of variation of the tensile strength at break.
  • various techniques for improving the dispersion state For example, a method for optimizing the ratio of fine cellulose to a cellulose derivative, a method for optimizing the diameter and / or L / D of fine cellulose, optimizing screw arrangement during melt kneading in an extruder, Method of giving sufficient shearing to fine cellulose by optimizing resin viscosity by control, method of strengthening interface between resin and fine cellulose by adding an optimal organic component (for example, surfactant) additionally,
  • an optimal organic component for example, surfactant
  • There are various approaches such as a method for forming some kind of chemical bond with cellulose, a method for chemically modifying the surface of fine cellulose, and a method for optimizing a method for preparing a composite of fine cellulose and a cellulose derivative.
  • the tensile yield strength tends to be dramatically improved as compared to the thermoplastic resin alone in the resin composition.
  • the ratio of the tensile yield strength of the resin composition when the tensile yield strength of the composition containing no fine cellulose or the thermoplastic resin alone is set to 1.0 is preferably 1.05 times or more, more preferably It is at least 1.10 times, still more preferably at least 1.15 times, particularly preferably at least 1.20 times, and most preferably at least 1.3 times.
  • the upper limit of the ratio is not particularly limited, but is preferably, for example, 5.0 times, and more preferably 4.0 times, from the viewpoint of ease of production.
  • the resin composition has excellent dispersion uniformity in the composition of fine cellulose, and thus also has a feature that the variation in linear expansion coefficient in a large molded product is small. Specifically, the characteristic is that the variation of the coefficient of linear expansion measured using the test pieces collected from different portions of the large molded body is extremely low.
  • the magnitude of the variation of the linear expansion coefficient can be expressed by using the variation coefficient of the linear expansion coefficient of the measurement sample obtained from a different portion of the site.
  • the coefficient of variation here is the same as that described in the section on the coefficient of variation of tensile strength at break.
  • the coefficient of variation of the linear expansion coefficient obtained from the resin composition is preferably 15% or less.
  • a more preferred upper limit of the variation coefficient is 13%, further preferably 11%, more preferably 10%, still more preferably 9%, and most preferably 8%.
  • the lower limit is preferably 0%, but is preferably 0.1% from the viewpoint of ease of production.
  • the number of samples (n) for calculating the coefficient of variation of the linear expansion coefficient is desirably at least 10 or more in order to reduce the influence of data errors and the like.
  • the resin composition can be produced by mixing the composite particles and the base resin, and performing hot-melt kneading, thermosetting, light curing, vulcanization, and the like. Further, a molded article can be produced by molding the resin composition.
  • the form in which the composite particles are added in the production of the resin composition is not particularly limited, and may be a slurry containing water as well as the dry powder.
  • the slurry containing water can be prepared by a method of stopping the drying in the course of the drying process of the above-described method for producing composite particles, a method of once drying, and a method of adding water.
  • the method for producing a resin composition comprises melt-kneading the composite particles in the form of a dry powder or an aqueous dispersion with a thermoplastic resin (in one embodiment, a thermoplastic resin different from the thermoplastic resin in the composite particles). Kneading inside a molding machine and then molding.
  • a method for producing a resin composition comprises mixing the composite particles with a thermosetting resin, then molding and then performing a thermosetting treatment, or mixing the composite particles with a photocurable resin, Molding and then photo-curing.
  • a method for producing a resin composition includes the steps of mixing the composite particles with a rubber, molding, and then vulcanizing.
  • the method for producing the resin composition when the base resin is a thermoplastic resin is not particularly limited, for example, 1.
  • a single-screw or twin-screw extruder after melt-kneading a mixture of composite particles (dry powder or aqueous dispersion) and a thermoplastic resin, (1) a method of extruding into a strand, cooling and solidifying in a water bath to obtain a pellet-shaped molded product of the resin composition, (2) a method of obtaining an extruded product of the resin composition by extruding and cooling into a rod or a tube, or (3) a method of extruding from a T-die to obtain a sheet or film of the resin composition, or 2 .
  • the composite particles (dry powder or aqueous dispersion) and a thermoplastic resin monomer are mixed, and a polymerization reaction (specifically, solid-phase polymerization, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like) is performed, and the obtained mixture is obtained.
  • a polymerization reaction specifically, solid-phase polymerization, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like
  • a more specific method for producing a resin composition can include the following. 1. After mixing the base resin, the dried fine cellulose, the cellulose derivative powder, and the dispersant in a desired ratio as needed, a method of collective melt kneading, 2. After mixing the base resin, the fine cellulose water slurry, the cellulose derivative powder, and the dispersant in a desired ratio as needed, a method of melt-kneading all at once, 3. After preparing a composite of fine cellulose and a cellulose derivative in advance, after mixing the base resin and the dispersant as required in a desired ratio, a method of melt-kneading all at once, 4.
  • melt-kneading the base resin and, if necessary, the dispersant After melt-kneading the base resin and, if necessary, the dispersant, adding a dried fine cellulose and cellulose derivative powder mixed in a desired ratio, and further melt-kneading, 5. After melt-kneading the base resin and the dispersant as necessary, adding a fine cellulose water slurry and cellulose derivative powder mixed in a desired ratio, and further melt-kneading, 6. After melt-kneading the base resin and the dispersant if necessary, adding a composite of fine cellulose and a cellulose derivative prepared in advance at a desired ratio, and further melt-kneading, And the like.
  • the heating temperature when melt-kneading the mixture of the composite particles and the base resin can be adjusted according to the resin used.
  • the minimum processing temperature recommended by the thermoplastic resin supplier is 255 to 270 ° C for nylon 66, 225 to 240 ° C for nylon 6, 170 to 190 ° C for polyacetal resin, and 160 to 180 ° C for polypropylene.
  • the heating set temperature is preferably in the range of 20 ° C. higher than these recommended minimum processing temperatures. By setting the mixing temperature within this temperature range, the mixed components can be uniformly mixed.
  • the moisture content of the resin composition is not particularly limited.
  • it is preferably 10 ppm or more in order to suppress an increase in the molecular weight of the polyamide during melting, and 1200 ppm in order to suppress hydrolysis of the polyamide during melting. It is preferably at most 900 ppm, more preferably at most 900 ppm, most preferably at most 700 ppm.
  • the moisture content is a value measured using a Karl Fischer moisture meter by a method based on ISO # 15512.
  • the resin composition of the present embodiment can be provided in various shapes. Specific examples include resin pellets, sheets, fibers, plates, and rods. Among them, the resin pellet shape is more preferable from the viewpoint of easiness of post-processing and transportation. Preferable pellet shapes at this time include a round shape, an elliptical shape, a cylindrical shape, and the like, and these differ depending on a cutting method at the time of extrusion. Pellets cut by a cutting method called underwater cut are often round, and pellets cut by a cutting method called hot cut are often round or oval, and cuts called strand cuts The pellets cut by the method often have a columnar shape.
  • the preferred size is 1 mm or more and 3 mm or less as a pellet diameter.
  • a preferred diameter is 1 mm or more and 3 mm or less, and a preferred length is 2 mm or more and 10 mm or less.
  • the above-mentioned diameter and length are desirably not less than the lower limit from the viewpoint of operation stability during extrusion, and desirably not more than the upper limit from the viewpoint of biting into a molding machine in post-processing.
  • the resin composition may be a composite of a nonwoven fabric (which is also simply referred to as a nonwoven fabric) made of fine cellulose fibers to which a cellulose derivative is attached, and a thermoplastic resin.
  • a resin composition can be produced by, for example, the following operation.
  • A A method of impregnating a non-woven fabric with a thermoplastic resin precursor and polymerizing the precursor.
  • B A nonwoven fabric is impregnated or coated with a solution containing a thermoplastic resin or a thermoplastic resin precursor, dried, adhered by a hot press or the like, and polymerized and cured as necessary. How to let.
  • thermoplastic resin sheet and a non-woven fabric are alternately arranged and closely adhered by a hot press or the like.
  • the method for obtaining the nonwoven fabric composed of the fine cellulose fibers to which the cellulose derivative is attached is not particularly limited.
  • the fine cellulose fiber water slurry to which the cellulose derivative is attached is dried after papermaking or coating.
  • a method in which a nonwoven fabric is first obtained by using fine cellulose fibers alone, an organic solvent in which a cellulose derivative is dissolved is applied to the nonwoven fabric, and then dried.
  • the resin composition using a thermoplastic resin as a base resin can be molded into a resin molded article having various shapes (for example, a film shape, a sheet shape, a fiber shape, a plate shape, a pellet shape, a powder shape, and a three-dimensional structure).
  • injection molding for example, injection compression molding, injection press molding, gas assist injection molding, and ultra high speed injection molding
  • various extrusion molding cold runner method or hot runner method
  • Examples include foam molding (including by injection of supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating / cooling mold molding, and various shape extrusion molding (eg, two-color molding and sandwich molding). it can.
  • extrusion moldings are suitable for molding sheets, films, fibers and the like.
  • an inflation method, a calendar method, a casting method, or the like can be used.
  • the injection molding method is particularly preferable from the viewpoint of design and cost.
  • the method for producing the resin composition in which the base resin is a thermosetting resin or a photocurable resin is not particularly limited.
  • the composite particles are sufficiently dispersed in a base resin solution or a base resin powder dispersion and dried.
  • various polymerization initiators, curing agents, curing accelerators, polymerization inhibitors and the like can be blended.
  • a resin composition containing a thermosetting resin or a photocurable resin as a base resin can be used as various resin molded articles. There is no particular limitation on the method for producing the resin molded body.
  • thermosetting resin if a plate-like product is to be manufactured, an extrusion molding method is generally used, but a flat press can also be used.
  • a profile extrusion method, a blow molding method, a compression molding method, a vacuum molding method, an injection molding method, or the like can be used.
  • a solution casting method can be used in addition to a melt extrusion method.
  • melt molding method blown film molding, cast molding, extrusion lamination molding, calender molding, sheet molding.
  • a method may be used in which after a sheet called an uncured or semi-cured prepreg is produced, the prepreg is formed into a single layer or a laminate, and the resin is cured and molded by applying pressure and heat.
  • the method of applying heat and pressure includes a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, an internal pressure molding method, and the like, but is not limited to these molding methods.
  • a method of impregnating a filament or preform of a reinforcing fiber such as a carbon fiber with a resin composition before the base resin is cured, and then curing the base resin to obtain a molded product for example, RTM, VaRTM, filament winding, RFI etc.
  • a molded product for example, RTM, VaRTM, filament winding, RFI etc.
  • a molded article can be manufactured by various curing methods using active energy rays.
  • the method for producing the resin composition when the base resin is rubber is not particularly limited.For example, a method of kneading the composite particles and the rubber in a dry manner, dispersing or dissolving the composite particles and the rubber in a dispersion medium. And then kneading by drying.
  • a mixing method a high shearing force and pressure are applied, and a mixing method using a homogenizer is preferable in that the dispersion can be promoted.
  • a method can also be used.
  • the obtained resin composition is molded into a desired shape and can be used as a molding material. Examples of the shape of the molding material include a sheet, a pellet, and a powder.
  • Resin compositions using rubber as a base resin can be used as various resin molded articles.
  • the molding material is molded using a desired molding method such as, for example, mold molding, injection molding, extrusion molding, hollow molding, foam molding, or the like.
  • a molded product of sulfur can be obtained.
  • the unvulcanized molded body can be vulcanized by heat treatment or the like as necessary.
  • thermoplastic resin as a base resin and composite particles of the present disclosure (for example, composite particles composed of fine cellulose and a cellulose derivative),
  • a method for producing a resin composition comprising: A first step of melt-kneading the thermoplastic resin in an extruder; A second step of adding the composite particles to the molten resin of the first step;
  • a method comprising:
  • the phrase “the composite particle is composed of fine cellulose and a cellulose derivative” means that the composite particle is composed mainly of the fine cellulose and the cellulose derivative (that is, the total amount of the fine cellulose and the cellulose derivative is the composite particle 100). (To be more than 50% by mass with respect to% by mass), and does not exclude inclusion of a third component such as an additive.
  • Pulp which is an aggregate of fine cellulose having a high elastic modulus, is defibrated at a beating level and used as a resin filler. Since pulp with a low degree of defibration has a relatively good dispersion in the resin, kneading is possible even if the dried pulp is added to the thermoplastic resin, and a constant quality level is maintained in the subsequent extruded product. be able to.
  • the fine cellulose capable of forming the above network structure can form a highly elastic gel state in, for example, an aqueous dispersion medium before kneading with a thermoplastic resin.
  • the cellulose derivative controls the interaction between the fine celluloses, and thus contributes to controlling the state of dispersion between the fine celluloses in the base resin.
  • the diameter of fine cellulose (particularly cellulose whiskers and / or cellulose fibers) alone be nanometer-sized (that is, less than 1 ⁇ m) from the viewpoint of effectively forming a cellulose aggregate in the second step.
  • a single-screw extruder, a twin-screw extruder, or the like can be used as an extruder, but a twin-screw extruder is preferable in controlling the dispersibility of cellulose.
  • L / D obtained by dividing the cylinder length (L) of the extruder by the screw diameter (D) is preferably 40 or more, and particularly preferably 50 or more.
  • the screw rotation speed during kneading is preferably in the range of 100 to 800 rpm, more preferably in the range of 150 to 600 rpm. These vary depending on the screw design.
  • Each screw in the cylinder of the extruder is optimized by combining an elliptical two-wing screw-shaped full flight screw, a kneading element called a kneading disk, and the like.
  • an addition port is provided in the middle of the cylinder of the extruder, and the raw material charged into the addition port is guided to a screw in the cylinder.
  • the position of the addition port is located downstream of the melt-kneading zone where the first step is performed.
  • the first resin melting zone is the region where the shearing is most intense.
  • the filler is finely dispersed by the shearing force below.
  • cellulose is finely dispersed in a resin as a reinforcing filler, if cellulose is added before the resin melting zone, the cellulose may deteriorate due to strong shearing force in the resin melting zone.
  • the composite particles of the present disclosure can have excellent redispersibility even in a dry state, they can be finely dispersed without exposing the composite particles under the above-mentioned shearing. That is, the composite particles can be added in the second step to the thermoplastic resin melted in the first step.
  • the composite particles composed of fine cellulose and a cellulose derivative are rapidly and finely dispersed in a resin already in a molten state, and the amount thereof is extremely small, for example, 10 parts by mass with respect to 100 parts by mass of a thermoplastic resin as a base resin. Parts or less, it can exhibit a good function as a reinforcing filler, can reliably improve the mechanical properties of the finally obtained resin composition, and can also satisfactorily suppress problems such as coloring and odor.
  • the addition port is preferably designed downstream of the melt-kneading zone of the extruder for the purpose of reducing the heat history received when passing through the inside of the cylinder.
  • the length (L2) from the outlet of the cylinder to the addition port is preferably designed to be 1 / or less of the total length (L1) of the cylinder. Note that the entire length of the cylinder includes a portion not involved in kneading (for example, a transport zone).
  • Composite particles composed of fine cellulose and a cellulose derivative are introduced from the addition port and mixed into the thermoplastic resin melt-kneaded in the extruder. Since the composite particles of this embodiment are excellent in redispersibility, they can be highly dispersed in the resin even when introduced in a subsequent step in an extruder.
  • thermoplastic resin is an engineered plastic having excellent heat resistance, its melting temperature is extremely high, so that during processing, a strong heat history is applied to the fine cellulose, and coloring and odor problems due to burning are likely to occur.
  • this strong thermal history partially loses the excellent mechanical properties of cellulose (particularly natural cellulose), the mechanical properties of the resin composition are improved when cellulose is added as a filler to the thermoplastic resin. Decrease the effect.
  • the resin melted in the first step (Preferably downstream of the melt kneading zone of the extruder, more preferably L2 / L1 is 1 / or less, further preferably L2 / L1 is 1 / or less, most preferably L2 / L1 is 1 / or less.
  • L2 / L1 is 1 / or less
  • L2 / L1 is 1 / or less
  • most preferably L2 / L1 is 1 / or less.
  • a degas cylinder Downstream of the extruder including the addition port (side feeder), a degas cylinder, a vacuum vent, etc. are provided as appropriate to degas air and a small amount of water (water vapor) mixed when the composite particles are charged. it can.
  • a gear pump can be installed downstream for the purpose of controlling the resin pressure and reducing the rise in resin temperature.
  • the distance in which the composite particles composed of the fine cellulose and the cellulose derivative are conveyed in the extruder can be shortened as compared with the thermoplastic resin, so that the configuration of the screw in the cylinder after mixing the composite particles is reduced.
  • the present invention is not limited to this.
  • the fine cellulose is removed. Advanced dispersion can be realized more reliably.
  • the molded article obtained from the resin composition of the present embodiment may have any shape depending on the application, and may have a three-dimensional three-dimensional shape, a sheet shape, a film shape, or a fibrous shape.
  • a part (for example, several places) of the molded body may be melted by heat treatment, and may be used by being adhered to a resin or metal substrate, for example.
  • the molded body may be a coating film applied to a resin or metal substrate, or may form a laminate with the substrate.
  • the sheet, film, or fibrous formed body may be subjected to secondary processing such as annealing, etching, corona processing, plasma processing, grain transfer, cutting, and surface polishing.
  • the resin composition of the present embodiment has high heat resistance and light weight, it can be substituted for a steel plate, or a fiber reinforced plastic such as a carbon fiber reinforced plastic or a glass fiber reinforced plastic, or a resin composite containing an inorganic filler.
  • industrial machine parts for example, electromagnetic equipment housing, roll material, transfer arm, medical equipment members, etc.
  • general machine parts for example, automobile / railway / vehicle parts (for example, outer plates, chassis, aerodynamic members, seats, Frictional material inside the transmission, etc.), marine components (for example, hull, seat, etc.), aviation-related parts (for example, fuselage, main wing, tail wing, rotor blade, fairing, cowl, door, seat, interior materials, etc.), spacecraft, Satellite members (motor case, main wing, structure, antenna, etc.), electronic and electric parts (for example, personal computer housing, mobile phone housing, OA equipment, AV equipment, telephone, facsimile, home appliances, toy supplies, etc.), architecture ⁇ Civil engineering materials (for example, reinfor
  • automotive members that require resin molding can exhibit advantages due to higher heat resistance and lighter weight than existing resin compositions.
  • it is useful for gears, engine covers, radiator tanks, intake manifolds and the like, which are members around the engine used in a high temperature environment.
  • gears, engine covers, radiator tanks, intake manifolds and the like which are members around the engine used in a high temperature environment.
  • the resin composition of the present embodiment having excellent high-temperature stiffness is most suitable for a member used in a high-temperature environment.
  • the resin composition of the present embodiment has high heat resistance, light weight and high strength, as well as low linear expansion, because the fine cellulose is satisfactorily dispersed, and also has excellent surface properties and sliding properties.
  • the resin composition according to one aspect of the present disclosure can have high mechanical properties and low linear expansion, and / or can have high fluidity that can accommodate large parts, and / or have a partial fluidity. Since it is possible to provide a molded article substantially free of high strength defects, the molded article may be various large parts.
  • the dispersion ⁇ 10 at a liquid temperature of 25 ° C. and a shear rate of 10 s ⁇ 1 has a viscosity ⁇ 10 of 10 mPa ⁇ s, obtained by dispersing the composite particles in DMSO such that the concentration of fine cellulose in the dispersion becomes 1% by mass. That is the composite particle.
  • the thixotropic index (TI) which is the ratio of the viscosity ⁇ 10 at a shear rate of 10 s ⁇ 1 to the viscosity ⁇ 100 at a shear rate of 100 s ⁇ 1 at a liquid temperature of 25 ° C., ⁇ 10 / ⁇ 100 , is obtained.
  • the composite particle according to the above aspect 1 which is 2 or more.
  • the composite particles according to the above aspect 1 or 2 wherein the median particle diameter is 1 ⁇ m or more and 5000 ⁇ m or less.
  • thermoplastic resin is a cellulose derivative.
  • the fine cellulose has a specific surface area equivalent diameter of 2 nm or more and less than 1000 nm.
  • the chemical modification is acetylation.
  • the method for producing a composite particle according to any one of the above aspects 1 to 8, A method comprising a powdering step of mixing an aqueous dispersion of fine cellulose and particles of a thermoplastic resin and then drying to collect the composite particles.
  • the aqueous dispersion of the fine cellulose is Fibrillation step of performing a fibrillation treatment of cellulose in an organic solvent to obtain a fine cellulose dispersion, and a purification step of substituting water for the organic solvent in the fine cellulose dispersion,
  • the production method according to the above aspect 9 which is prepared by the following method.
  • the method according to the above aspect 10 further comprising a chemical modification step of performing a chemical modification of the fine cellulose simultaneously with the defibration step or after the defibration step and before the purification step.
  • the method for producing a composite particle according to any one of the above aspects 1 to 8, Preparation of fine cellulose / resin dispersion by adding thermoplastic resin to organic solvent dispersion of fine cellulose to obtain fine cellulose / resin dispersion in which fine cellulose is dispersed in organic solvent and thermoplastic resin is dissolved Process, A precipitation step of obtaining a composite particle dispersion by mixing the fine cellulose / resin dispersion with a poor solvent for the thermoplastic resin and precipitating composite particles containing the fine cellulose and the thermoplastic resin; A purification step of replacing the organic solvent in the composite particle dispersion with water to obtain an aqueous dispersion, and a powdering step of drying the aqueous dispersion to collect composite particles, Including, methods.
  • thermoplastic resin 0.1 to 40 parts by mass based on 100 parts by mass of the thermoplastic resin, fine cellulose fibers having a fiber diameter of 2 nm or more and less than 1 ⁇ m, and 1 part by mass to 500 parts by mass based on 100 parts by mass of the fine cellulose fibers Of a cellulose derivative
  • a resin composition comprising: [2] The thermoplastic resin is selected from the group consisting of polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyphenylene ether resins, polyphenylene sulfide resins, and mixtures of any two or more of these.
  • thermoplastic resin is polypropylene
  • melt mass flow rate (MFR) of the polypropylene measured at 230 ° C. based on ISO1133 is 3 g / 10 min or more and 30 g / 10 min or less.
  • the resin composition according to 1. [4] The thermoplastic resin is a polyamide resin, and a ratio of a carboxyl terminal group to all terminal groups ([COOH] / [all terminal groups]) of the polyamide resin is 0.30 to 0.95.
  • the thermoplastic resin is a polyester resin, and the ratio of carboxyl terminal groups to all terminal groups ([COOH] / [all terminal groups]) of the polyester resin is 0.30 to 0.95.
  • thermoplastic resin is a polyacetal resin
  • polyacetal resin is a copolyacetal containing 0.01 to 4 mol% of a comonomer-derived structure.
  • the cellulose derivative is at least one selected from the group consisting of cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.
  • the fine cellulose fiber has a fiber diameter of 500 nm or less.
  • thermoplastic resin Composite particles composed of fine cellulose and a cellulose derivative
  • a method for producing a resin composition comprising: A first step of melt-kneading the thermoplastic resin in an extruder; A second step of adding the composite particles to the molten resin of the first step; And a manufacturing method.
  • the first step is performed in a melt-kneading zone in a cylinder provided in the extruder, The manufacturing method according to the above aspect 1, wherein the second step is performed by supplying the composite particles from an addition port provided in the cylinder.
  • the production method according to the above aspect 2 wherein the addition port is disposed downstream of the melt-kneading zone.
  • the resin composition contains the fine cellulose in an amount of 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the thermoplastic resin.
  • the manufacturing method as described.
  • Example A >> ⁇ Production of fine cellulose> Fine cellulose slurries used in the production of the composite particles and the single particles of the fine cellulose alone were produced according to the compositions shown in Table 1 by the following Production Examples A to E2.
  • CNC Cellulose whisker
  • Commercial DP pulp (average degree of polymerization: 1600) was cut and hydrolyzed in a 10% by mass aqueous hydrochloric acid solution at 105 ° C. for 30 minutes. The obtained acid-insoluble residue was filtered, washed and pH-adjusted to prepare a crystalline cellulose dispersion having a solid content of 14% by mass and a pH of 6.5. The crystalline cellulose dispersion was spray-dried to obtain a dried crystalline cellulose.
  • the dried product obtained above was supplied to an air-flow type pulverizer (STJ-400, manufactured by Seishin Enterprise Co., Ltd.) at a supply rate of 10 kg / hr and pulverized to obtain cellulose whiskers as crystalline cellulose fine powder. .
  • the properties of the obtained cellulose whiskers were evaluated by the methods described below. The results are shown below.
  • the obtained beaten water dispersion was directly subjected to micronization treatment at an operating pressure of 100 MPa for 15 times using a high-pressure homogenizer (NSO15H manufactured by Niro Soavi Co., Ltd. (Italy)) to obtain a fine cellulose slurry (solid content: 1.5%). % By mass). Then, the mixture was concentrated to a solid content of 10% by mass with a dehydrator to obtain 30 parts by mass of slurry A (aqueous solvent).
  • a high-pressure homogenizer NSO15H manufactured by Niro Soavi Co., Ltd. (Italy)
  • the rotation speed of the bead mill was 2500 rpm
  • the peripheral speed was 12 m / s
  • the beads used were made of zirconia, ⁇ 2.0 mm
  • the filling rate was 70% (the slit gap of the bead mill was 0.6 mm).
  • the slurry temperature was controlled at 40 ° C. by a chiller in order to absorb heat generated by friction.
  • Nylon 6 powder was added to the slurry C2, and the mixture was kneaded with a planetary mixer at a rotation speed of 50 rpm at room temperature for 2 hours, followed by vacuum drying at 40 ° C. to obtain dried composite particles.
  • Table 1 shows the physical properties of the fine celluloses of Production Examples A, B1, C1, C2, D1, and E1. These physical properties were evaluated using the aqueous slurries of Production Examples A, B1, C1, C2, D1, and E1 and the porous sheet prepared by the following method.
  • the wet paper obtained by the filtration is in a state where the filter paper is stuck, and is sandwiched between two filter papers of 150 mm in diameter, and the circumference of the wet paper is suppressed by a cylindrical weight (inner diameter 110 mm) of about 300 g. Heating was performed at 150 ° C. for 5 minutes to obtain a dried sheet. At this time, a sheet having an air permeability resistance of 100 sec / 100 ml or less per 10 g / m 2 of sheet weight was defined as a porous sheet and used as a measurement sample. After measuring the basis weight W (g / m 2 ) of the sample which was allowed to stand for 1 day in an environment of 23 ° C.
  • IR index H1730 / H1030 (1) It calculated according to.
  • H1730 and H1030 are absorbances at 1730 cm ⁇ 1 and 1030 cm ⁇ 1 (absorption band of cellulose backbone chain CO stretching vibration).
  • the line connecting 1900 cm -1 and 1500 cm -1 and the line connecting 800 cm -1 and 1500 cm -1 are used as the baseline, and the absorbance is defined as the absorbance of which is 0.
  • TI thixotropic index
  • the temperature of the apparatus was previously adjusted to 25 ° C.
  • a cycle in which the shear rate was decreased from 100 s -1 to 1 s -1 over 100 seconds and then increased to 100 s -1 over 100 seconds was repeated twice. And finally, it was lowered from 100 s -1 to 1 s -1 over 100 seconds, and viscosity data was acquired every 1 second.
  • the viscosities at a shear rate of 10 s -1 and 100 s -1 were defined as ⁇ 10 and ⁇ 100 , respectively.
  • ⁇ Measurement method-resin composition> A multipurpose test piece based on ISO294-3 was molded using an injection molding machine.
  • Polyamide-based material Conditions according to JIS K6920-2
  • Polypropylene-based material Conditions according to JIS K6921-2
  • the storage elastic modulus decreases as the temperature increases, so that the change in the storage elastic modulus becomes 1 or more. The closer this value is to 1, the smaller the change in storage modulus at high temperatures and the better the heat resistance (high temperature rigidity).
  • Example B >> ⁇ Manufacture of fine cellulose fiber (hereinafter may be abbreviated as CNF)>
  • CNF fine cellulose fiber
  • the obtained beaten water dispersion was directly subjected to micronization treatment 15 times under an operating pressure of 100 MPa using a high-pressure homogenizer (NSO15H manufactured by Niro Soavi Co., Ltd. (Italy)) to obtain a fine cellulose slurry (solid content: 1). 0.5% by mass). Then, the mixture was concentrated to a solid content of 10% by mass with a dehydrator to obtain 30 parts by mass of slurry a (aqueous solvent).
  • a high-pressure homogenizer NSO15H manufactured by Niro Soavi Co., Ltd. (Italy)
  • the rotation speed of the bead mill was 2500 rpm
  • the peripheral speed was 12 m / s
  • the beads used were made of zirconia, ⁇ 2.0 mm
  • the filling rate was 70% (the slit gap of the bead mill was 0.6 mm).
  • the slurry temperature was controlled at 40 ° C. by a chiller in order to absorb heat generated by friction.
  • the obtained wet cake is again dispersed in 30 parts by mass of pure water, and the washing operation of stirring and concentrating is repeated a total of 5 times to remove DMSO, and to remove 10 parts by mass of the water-containing composite Y (solid content: 10% by mass). ) Manufactured.
  • a measurement sample was prepared in the same procedure as in Example A using 4 g of a concentrated cellulose fiber or a chemically modified fine cellulose fiber concentrated slurry having a solid content of 10% by mass.
  • Table 4 shows the physical properties of the fine cellulose fibers and the chemically modified fine cellulose fibers in Examples and Comparative Examples. These physical properties were evaluated using the aqueous slurries of Production Examples A, B2, and C2, and the porous sheet produced by the following method.
  • the fine cellulose fibers / chemically modified fine cellulose fibers obtained in Production Examples B1 and C1 were regarded as equivalent to those obtained in Production Examples B2 and C2.
  • Thermal decomposition start temperature The thermal analysis of the porous sheet was evaluated by the following measurement method.
  • T D calculation method Determined from a graph in which the horizontal axis represents temperature and the vertical axis represents weight retention%. Starting from the weight of the porous sheet at 150 ° C. (in a state where moisture is almost removed) (weight loss: 0 wt%), the temperature is further increased, and the temperature when the weight is reduced by 1 wt% and the temperature when the weight is reduced by 2 wt% To get a straight line. The temperature at the point where this straight line intersected with the horizontal line (base line) passing through the starting point where the weight loss amount was 0 wt% was defined as the thermal decomposition onset temperature (T D ).
  • Equipment Thermo plus EVO2 manufactured by Rigaku Sample: A circular sheet cut from a porous sheet was placed in an aluminum sample pan in an amount of 10 mg. Sample size: 10mg Measurement conditions: In a nitrogen flow of 100 ml / min, the temperature was raised from room temperature to 150 ° C. at a rate of 10 ° C./min, maintained at 150 ° C. for 1 hour, and then increased from 150 ° C. to 250 ° C. at a rate of 10 ° C. / Min, and kept at 250 ° C. for 2 hours.
  • N, N-dimethylacetamide and the solid content were separated again by centrifugation, 20 mL of N, N-dimethylacetamide was added, and the mixture was lightly stirred and allowed to stand for 1 day.
  • the N, N-dimethylacetamide and the solid content were separated by centrifugation, and 19.2 g of an N, N-dimethylacetamide solution prepared by adjusting the solid content to 8% by mass of lithium chloride was added, followed by stirring with a stirrer. Dissolution was confirmed visually.
  • the solution in which cellulose was dissolved was filtered through a 0.45 ⁇ m filter, and the filtrate was used as a sample for gel permeation chromatography.
  • the equipment used and the measurement conditions are as follows.
  • the acid-insoluble component was quantified by the Clerson method described in Non-Patent Document (Wood Science Experiment Manual, edited by The Japan Wood Research Society, pp. 92-97, 2000) for fine cellulose fiber raw materials.
  • the raw material of the absolutely dried fine cellulose fiber is precisely weighed, put in a predetermined container, added with 72% by mass of concentrated sulfuric acid, and appropriately pressed with a glass rod so that the contents become uniform. Was dissolved in the acid solution. After allowing to cool, the content was filtered through a glass fiber filter paper to obtain an acid-insoluble component as a residue.
  • the acid-insoluble component content was calculated from the weight of the acid-insoluble component, and the number average of the acid-insoluble component content calculated for the three samples was defined as the acid-insoluble component average content.
  • alkali-soluble polysaccharide content The content of alkali-soluble polysaccharide is determined by the method described in Non-Patent Document (Wood Science Experiment Manual, edited by The Wood Science Society of Japan, pp. 92-97, 2000) for the raw material of fine cellulose fiber (Wise method). From the ⁇ -cellulose content. The alkali-soluble polysaccharide content was calculated three times for one sample, and the number average of the calculated alkali-soluble polysaccharide content was defined as the average alkali-soluble polysaccharide content of the fine cellulose fibers.
  • the cylinder temperature of an injection molding machine with a maximum clamping pressure of 4000 tons was set to 250 ° C., and a predetermined mold capable of molding a fender having the shape shown in the schematic diagram of FIG. (Cavity volume: about 1400 cm 3 , average thickness: 2 mm, projected area: about 7000 cm 2 , number of gates: 5 gates, hot runner: a runner is shown in FIG. 6 to clarify the runner position of the molded body. (The relative position 1 of the (hot runner) is shown.), The mold temperature was set to 60 ° C., and 20 fenders were formed.
  • the obtained fender was placed on the floor, and a bag containing 5 kg of sand was dropped from the height of about 50 cm to the center of the fender, and the state of destruction of the fender was confirmed. The number destroyed out of 20 was counted.
  • the lateral portion of the rectangular parallelepiped sample at this time is in the thickness direction of the fender.
  • the sample Prior to the measurement, the sample was left standing at 120 ° C. for 5 hours to perform annealing, thereby obtaining a sample for measurement.
  • the obtained sample was measured in a measurement temperature range of ⁇ 10 ° C. to + 80 ° C. in accordance with ISO 11359-2, and an expansion coefficient between 0 ° C. and 60 ° C. was calculated, and a total of 10 measurement results were obtained.
  • ⁇ represents a standard deviation
  • ⁇ represents an arithmetic mean of tensile breaking strength.
  • Examples B1 to B21, Comparative Examples B1 to B4> The polyamide, the cellulose derivative composite, and the cellulose whisker were mixed such that the fine cellulose fiber or the chemically modified fine cellulose fiber, the cellulose derivative, the cellulose whisker, and the polyamide had the ratios shown in Tables 6 to 8, and were mixed with Toshiba Machine Co., Ltd. ), The mixture was melt-kneaded at a screw rotation speed of 350 rpm and a discharge rate of 140 kg / hr, devolatilized in vacuum, extruded from a die into a strand, cooled in a water bath, and pelletized. The pellet had a columnar shape, a diameter of 2.3 mm and a length of 5 mm. These were evaluated based on the above-mentioned evaluation method.
  • Examples B22 to B23 Comparative Examples B5 to B6> Pellets were obtained using the procedure of Example B1 with the composition shown in Table 9 except that the resin was changed to polypropylene or acid-modified polypropylene, or cellulose whiskers were added.
  • the defect rate of the fender and the expansion rate of the molded piece are greatly improved by the fact that not only the fine cellulose fiber or the chemically modified fine cellulose fiber but also the cellulose derivative is contained in the polypropylene resin. Further, by using the acid-modified polypropylene in combination, the affinity between the thermoplastic resin and the fine cellulose fibers is improved, the dispersibility of the fine cellulose fibers in the resin is also improved, and the physical properties are generally improved.
  • Example C >> ⁇ Evaluation method> [Fiber diameter D, fiber length L / fiber diameter D of cellulose fiber] A part of the cellulose fiber slurry is repeatedly washed with pure water to obtain a cellulose fiber water slurry.
  • the cellulose fiber water slurry was diluted with tert-butanol to 0.01% by mass, and treated with a high shear homogenizer (trade name “Ultra Turrax T18” manufactured by IKA) under the following conditions: 25,000 rpm for 5 minutes.
  • a sample that is dispersed, cast on mica, and air-dried is used as a measurement sample, and measured by a high-resolution scanning microscope.
  • the diameter D and the length L of 100 randomly selected microcellulose are measured in an observation visual field whose magnification is adjusted so that 100 or more microcellulose are observed.
  • the average value of the obtained 100 diameters D is defined as the number average diameter of the fine cellulose.
  • the number average diameter is 20 nm or more and less than 450 nm, it is defined as a cellulose nanofiber (CNF) described later.
  • the L / D of 100 fine celluloses is calculated, and the average value is defined as the average L / D of the fine cellulose.
  • the average L / D is 30 or more and less than 1000, it is defined as a cellulose nanofiber (CNF) described later.
  • the fiber diameter D and L / D of the cellulose fiber are also preserved in the fiber diameter and L / D of the chemically modified cellulose fiber, and even when the cellulose fiber is chemically modified, the fine cellulose before the chemical modification is removed. It should be evaluated.
  • a vent port is provided at the upper part of the cylinder 12 so that vacuum suction can be performed, and vacuum suction is performed.
  • the screw configuration of the extruder is such that the cylinders 1 and 2 are transport zones composed of only transport screws, and one clockwise kneading disk (feed type kneading disk: hereinafter simply referred to as RKD) is provided on the cylinder 3 from the upstream side. 2) Neutral kneading disk (non-conveying type kneading disk: hereinafter may be simply referred to as NKD), 1 counterclockwise screw (reverse feed type kneading disk: hereinafter) , May be simply referred to as RKD.).
  • the cylinders 4 to 8 are used as a transport zone, and two NKD and one LKD are arranged in the cylinder 9 in this order.
  • the subsequent cylinder 10 is a transport zone, two NKDs and one LKD are arranged in this order on the cylinder 11, and the cylinders 12 and 13 are transport zones.
  • Cylinder temperature of this extruder is set to 200 ° C. for cylinder 1 with water cooling, cylinder 2 for 160 ° C. and cylinder 3 to die when resin is PP.
  • the resin is PA6
  • the cylinder 1 is water-cooled
  • the cylinder 2 is set at 230 ° C.
  • the cylinders 3 to dies are set at 250 ° C.
  • a resin is supplied from the addition port of the cylinder 4 to the composite particles at a ratio shown in Tables 10 and 11, melt kneading is performed at a screw rotation speed of the extruder of 250 rpm, extruded into a strand, and water-cooled. Pelletize. The obtained pellets are subjected to vacuum drying for 12 hours using a vacuum dryer set at 80 ° C. in order to reduce moisture.
  • Preparations were made in the same manner as in Embodiment 1, except that the composite particles were supplied from.
  • Preparations were made in the same manner as in Embodiment 1, except that the composite particles were supplied from.
  • the forcible push-in port is closed from the extrusion side of the cylinders 4, 8, and 10, and the screw configuration is such that the cylinders 1 to 8 are formed as a conveyance zone composed of only conveyance screws, and two cylinders are provided in the cylinder 9. NKD and one LKD are arranged in this order.
  • the subsequent cylinder 10 serves as a transfer zone, two NKDs and one subsequent LKD are arranged on the cylinder 11 in this order, and the cylinders 12 and 13 serve as transfer zones.
  • a vent port is provided in the upper portion of the cylinder 12 so that vacuum suction can be performed, and vacuum suction is performed. All preparations are made in the same manner as in Embodiment 1, except that a possible feeder can be installed.
  • Both the resin and the composite particles are supplied from the main throat at the ratios shown in Tables 10 and 11, melt-kneaded at a screw rotation speed of the extruder of 250 rpm, extruded into strands, water-cooled, and pelletized.
  • the obtained pellets are subjected to vacuum drying for 12 hours using a vacuum dryer set at 80 ° C. in order to reduce moisture.
  • the resin and the composite particles are supplied from different supply devices from the main throat.
  • DMSO dimethyl sulfoxide
  • ⁇ Measurement method> [Preparation of measurement sample of chemically modified fine cellulose] A part of the chemically modified fine cellulose slurry is repeatedly washed with pure water to obtain a chemically modified fine cellulose water slurry. Subsequently, the water slurry is dispersed in tert-butanol (solid content: less than 0.4% by mass and moisture content: less than 5% by mass), and further subjected to dispersion treatment with a homogenizer until no aggregates are present. The obtained tert-butanol dispersion is filtered on filter paper (5C, Advantech, diameter 90 mm), and the obtained wet paper is dried by heating to obtain a sheet. A sheet having an air resistance of 100 sec / 100 ml or less per 10 g / m 2 of sheet weight is defined as a porous sheet and used as a measurement sample.
  • Crystallinity of chemically modified fine cellulose In the same procedure as in Example A, the X-ray diffraction measurement of the porous sheet is performed to calculate the crystallinity.
  • a material having a crystallinity of 55% or more can exhibit good mechanical properties as a filler, and is evaluated as satisfying the requirements in this example.
  • the minimum filling pressure is measured as an index of fluidity close to actual molding. Specifically, an injection molding machine with a mold clamping pressure of 200 tons, a flat plate mold having a film gate in the width direction, a length of 200 mm, a width of 150 mm, and a thickness varying from 3 mm to 1.5 mm at the center of the plate. Attach, set the cylinder temperature and the mold temperature as follows, and measure the bare pressure of the test piece. At this time, the holding pressure is not switched, and the injection pressure and the speed are set to only one stage. Further, after molding by full filling for 20 consecutive shots, the injection pressure is gradually lowered, and the injection pressure immediately before unfilling occurs or immediately before sink occurs is defined as the minimum filling pressure.
  • Colorability is evaluated as an index of the ease of coloring. In general, when coloring a resin, an operation of adding a dye and pigment necessary for a desired color and then toning is performed after whitening the resin once. The easiness of turning to white greatly affects the colorability.
  • the coloring property is evaluated by measuring the whiteness when a predetermined amount of titanium oxide is added.
  • a master batch containing 50 parts by mass of titanium oxide was dry-blended at a ratio of 3 parts by mass with respect to 100 parts by mass of pellets containing fine cellulose prepared in the example, and an injection molding machine with a mold clamping pressure of 200 tons was used. Then, using the same flat mold as that used for fluidity (minimum filling pressure), the cylinder temperature and the mold temperature are set as follows, and molding is performed at a pressure sufficient for filling the test piece.
  • a masterbatch using polypropylene as a base resin for a polypropylene material and a polyamide as a base resin for a polyamide material is used as the masterbatch used at this time. Cylinder temperature / Mold temperature Polypropylene material 210 °C / 40 °C Polyamide material 260 ° C / 70 ° C
  • the L * value was measured with a color difference meter (CM-2002, manufactured by Konica Minolta) under a D65 light and a 10 ° visual field, and the coloring property was evaluated according to the following evaluation criteria. Perform an evaluation. L * value of flat plate Colorability 85 or more Excellent 80 or more and less than 85 Good 75 or more and less than 80 Acceptable Less than 75 Poor
  • Odor The odor is evaluated by a sensory test and the following three levels. A: No odor. B: There is a slight sugar smell (sweet smell). C: There is a strong sugar odor. D: There is a burning smell together with a sugar smell.
  • the odor test is performed at each of the following stages. (1) resin composition pellets immediately after extrusion, (2) atmosphere during injection molding, (3) molded body immediately after injection molding, (4) molded body one hour after injection molding
  • Molding piece expansion rate In the same procedure as in Example B, molding, measurement, and calculation of the molding piece expansion rate are performed. Mold piece expansion rate Degree of expansion suppression 0.2% or less Excellent 0.3% or less Good 0.4% or less Acceptable More than 0.4% Poor
  • Example 10 shows the composition ratio of each component and the evaluation results.
  • the acetylated microcellulose has a fiber diameter D and a fiber length L / fiber diameter D falling under the definition of the cellulose nanofiber described above (excluding the cellulose whiskers used in Example C13).
  • the crystallinity and average degree of substitution (DS) satisfy the above requirements.
  • the median particle size of the composite particles with the cellulose derivative also satisfies the above requirements.
  • the resin composition of the present invention can be suitably used, for example, in the field of exterior materials for automobiles, which are large parts requiring high strength and low linear expansion and stable performance.

Abstract

Un mode de réalisation de la présente invention concerne : des particules composites qui contiennent de la cellulose fine et confèrent à un corps moulé une stabilité de propriété physique qui est suffisamment bonne pour une utilisation pratique, tout en conférant au corps moulé des caractéristiques mécaniques suffisantes ; et une composition de résine qui contient les particules composites. Un mode de réalisation de la présente invention concerne des particules composites qui contiennent de la cellulose fine et une résine thermoplastique et est conçu de telle sorte que : le rapport de la cellulose fine dans les particules composites est de 10 % en masse à 95 % en masse (valeurs extrêmes incluses) ; et un liquide de dispersion, qui est obtenu par dispersion des particules composites dans du diméthylsulfoxyde, de telle sorte que la concentration en cellulose fine dans le liquide de dispersion est de 1 % en masse, présente une viscosité η10, à une température de liquide de 25°C et à une vitesse de cisaillement de 10 s-1, de 10 mPa·s ou plus.
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JP2020079356A (ja) * 2018-11-13 2020-05-28 凸版印刷株式会社 塗工用組成物
CN114479389A (zh) * 2022-03-28 2022-05-13 金发科技股份有限公司 一种纳米纤维改性pbt复合材料及其制备方法和应用
EP4011955A4 (fr) * 2020-05-29 2022-12-14 LG Chem, Ltd. Complexe polymère
JP7444669B2 (ja) 2020-03-25 2024-03-06 旭化成株式会社 微細セルロース繊維を含む複合粒子、及び複合粒子を含む樹脂組成物

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