WO2010131602A1 - セルロース繊維含有樹脂材料の製造方法 - Google Patents

セルロース繊維含有樹脂材料の製造方法 Download PDF

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WO2010131602A1
WO2010131602A1 PCT/JP2010/057805 JP2010057805W WO2010131602A1 WO 2010131602 A1 WO2010131602 A1 WO 2010131602A1 JP 2010057805 W JP2010057805 W JP 2010057805W WO 2010131602 A1 WO2010131602 A1 WO 2010131602A1
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cellulose fiber
cellulose
thermoplastic resin
resin
mixing step
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PCT/JP2010/057805
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English (en)
French (fr)
Japanese (ja)
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一仁 伊原
泰光 藤野
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コニカミノルタホールディングス株式会社
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Priority claimed from JP2009116529A external-priority patent/JP5613996B2/ja
Priority claimed from JP2009152276A external-priority patent/JP5621219B2/ja
Application filed by コニカミノルタホールディングス株式会社 filed Critical コニカミノルタホールディングス株式会社
Priority to CN201080020466.8A priority Critical patent/CN102421852B/zh
Publication of WO2010131602A1 publication Critical patent/WO2010131602A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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

Definitions

  • the present invention relates to a technique for uniformly dispersing hydrophilic cellulose fibers in a hydrophobic thermoplastic resin, and a technique for uniformly dispersing cellulose fibers in an organic solvent.
  • the fiber reinforced composite material whose strength and rigidity are greatly improved by blending various fibrous reinforcing materials with resin, is widely used in industrial fields such as electric / electronics, machinery, automobiles, and building materials.
  • fibrous reinforcing material blended in the fiber-reinforced composite material glass fibers having excellent strength and lightness are mainly used.
  • the specific gravity is increased, so that there is a limit to weight reduction.
  • fiber reinforcement made of organic materials such as polyester fiber, polyamide fiber, and aramid fiber has been studied as a fibrous reinforcement, but fiber reinforced composite materials containing these reinforcements are lightweight and thermally recyclable.
  • mechanical reinforcement effect was not sufficient.
  • Patent Document 1 discloses a resin composite material containing microfibrillated cellulose (MFC) surface-treated as a reinforcing material in a resin material, and after mixing an emulsion of MFC and a matrix resin, the matrix resin
  • MFC microfibrillated cellulose
  • the matrix resin emulsion only describes an example in which an aqueous solvent is used, and does not describe how to use a hydrophobic resin.
  • general-purpose resins there are many hydrophobic resins. For example, it is not possible to apply the production method described in Patent Document 1 to resins with a large production amount such as polyethylene terephthalate (PET) and polycarbonate (PC). Is possible.
  • PET polyethylene terephthalate
  • PC polycarbonate
  • Patent Document 2 includes a step of removing the solvent after mixing the microfibrillated cellulose (MFC) dispersibility and resin solubility with the dispersion of the microfibrillated cellulose and dissolving the resin, Although a method for producing a microfibrillated cellulose-containing resin molded product is described, the MFC and the resin are mixed only in one stage, and the MFC and the resin are not uniformly dispersed, and are particularly exposed to high temperatures. In mixing by kneading, the tensile strength and bending strength are reduced.
  • MFC microfibrillated cellulose
  • a melt mixing method is used to dissolve the resin at a high temperature.
  • the production method 2 cannot be applied to general-purpose resins.
  • the fibers in order to disperse these cellulose fibers uniformly in the resin and to make a highly functional material, the fibers must be microfibrillated and made uniform.
  • Patent Document 3 describes a production method in which cellulose is wet pulverized with water or a solvent.
  • wet pulverization only describes an example using water, and an organic solvent is used. There is no description of how to use it.
  • the aqueous suspension of microfibrillated cellulose fibers is in a gel-like or wet wheat flour state in a high concentration state and cannot be said to be a uniform dispersion.
  • Patent Document 4 describes a method for dispersing microfibrillated cellulose in an organic solvent, but water is used in the pulverization step for microfibrillating cellulose. For this reason, since the microfibrillated cellulose dispersed in the organic solvent contains water, it aggregates during the surface treatment of the cellulose or mixing with the resin.
  • MFC microfibrillated cellulose
  • thermoplastic resins since there are many thermoplastic resins in the hydrophobic resin, a melt mixing method is often used as a molding method, but this melt mixing method causes aggregation of MFC by exposure to high temperatures, Uniform dispersion cannot be achieved, and the target mechanical strength cannot be improved.
  • One of the problems to be solved by the present invention is that the MFC is uniformly dispersed in a thermoplastic resin typified by PET, which is widely demanded in the industry, and mechanical strength is improved. And a method for producing a cellulose fiber-containing resin material (composite material of cellulose fiber and thermoplastic resin) capable of maintaining transparency.
  • MFC microfibrillated cellulose
  • Another problem to be solved by the present invention is to produce a cellulose fiber dispersion which is pulverized into MFC at a high concentration and made into a uniform dispersed state without gelling cellulose.
  • it is to provide a cellulose fiber dispersion that maintains a uniform dispersion state even when mixed with a resin, improves the mechanical strength of the resin, and does not impair the transparency.
  • the object of the present invention is achieved by the following configuration.
  • a method for producing a resin material comprising a thermoplastic resin and a surface-treated cellulose fiber having an average fiber diameter of 2 nm or more and 200 nm or less, wherein the surface-treated cellulose fiber, an organic solvent, and a first thermoplastic resin
  • a method for producing a cellulose fiber-containing resin material comprising: a first mixing step of mixing, and a second mixing step of further mixing a second thermoplastic resin having a molecular weight larger than that of the first thermoplastic resin.
  • the molecular weight of the first thermoplastic resin mixed in the first mixing step is 500 or more and 50,000 or less, and the molecular weight of the second thermoplastic resin mixed in the second mixing step is 50,000 or more and 1,000,000 or less. 2.
  • a method for producing a cellulose fiber-containing resin material which is produced through a step of pulverizing cellulose fibers in an organic solvent by a wet pulverization method to 2 nm to 200 nm and a step of surface-treating the pulverized cellulose fibers.
  • cellulose fibers can be uniformly dispersed in a transparent thermoplastic resin, and the mechanical strength such as tensile strength, bending strength, and low linear expansion of the polymer film or the polymer composite alone while maintaining transparency.
  • the characteristics could be greatly improved.
  • the heat resistance of the resin could be remarkably improved.
  • the cellulose fiber dispersion can be uniformly dispersed at a high concentration without gelation, and the microfibrillated cellulose can be uniformly dispersed in a transparent resin.
  • mixing with the matrix resin was facilitated, and the mechanical properties such as tensile strength and low linear expansion of the polymer film or polymer composite could be greatly improved while maintaining the transparency of the resin.
  • Sectional drawing of an extensional flow kneading chamber is shown.
  • One aspect of the present invention is a method for producing a resin material comprising a thermoplastic resin and a surface-treated cellulose fiber having an average fiber diameter of 2 nm to 200 nm, the surface-treated cellulose fiber and an organic solvent. And a first mixing step of mixing the first thermoplastic resin and a second mixing step of further mixing a second thermoplastic resin having a molecular weight higher than that of the first thermoplastic resin.
  • the cellulose fiber of the present invention only needs to be defibrated to a state where the average fiber diameter is 2 nm or more and 200 nm or less, and the fiber surface may be further subjected to surface treatment by chemical modification or physical modification.
  • Examples of the raw material cellulose fiber used in the present invention include plant-derived pulp, wood, cotton, hemp, bamboo, cotton, kenaf, hemp, jute, banana, coconut, seaweed, tea leaves, and other fibers separated from plant fibers, marine animals Examples include fibers separated from animal fibers produced by sea squirts, and bacterial cellulose produced from acetic acid bacteria. Among these, fibers separated from plant fibers can be preferably used, but fibers obtained from plant fibers such as pulp and cotton are more preferable.
  • these fibers are defibrated using a homogenizer, a grinder or the like to obtain a microfibrillated cellulose fiber, but as long as the contained cellulose maintains the fiber state, There is no restriction
  • hard materials such as wood may need to be pulverized with a dry pulverizer as pre-crushing if they cannot be processed directly with a homogenizer.
  • cellulose fibers such as pulp are put into a dispersion vessel containing water so as to be 0.1 to 3% by mass, and this is defibrated with a high-pressure homogenizer to obtain an average fiber diameter of 0.1.
  • An aqueous dispersion of cellulose fibers defibrated to about 10 ⁇ m microfibrils is obtained.
  • nano-order cellulose fibers having an average fiber diameter of about 2 to 200 nm can be obtained.
  • Examples of the grinder used for the grinding treatment include a pure fine mill (manufactured by Kurita Machinery Co., Ltd.). As another method, there is a method using a high-pressure homogenizer in which cellulose fiber dispersion is jetted from a pair of nozzles at a high pressure of about 250 MPa, and the jet fibers collide with each other at a high speed to pulverize the cellulose fibers.
  • Examples of the apparatus used include “Homogenizer” manufactured by Sanwa Machinery Co., Ltd., “Artemizer System” manufactured by Sugino Machine Co., Ltd., and the like.
  • the average fiber diameter of the cellulose fibers obtained by fibrillation in this manner is preferably 2 nm or more and 200 nm or less, more preferably 2 nm or more and 100 nm or less, and further preferably 4 nm or more and 40 nm or less.
  • the average fiber diameter shown here is an average value of the diameters of the fibers dispersed in the resin.
  • the average fiber diameter and the measurement of the average fiber length to be described later are measured for the obtained fibers with a transmission electron microscope. , H-1700FA type (manufactured by Hitachi, Ltd.) was used to observe at a magnification of 10000 times, and 100 fibers were randomly selected from the obtained images, and each image was selected using image processing software (WINROOF). The fiber diameter and the fiber length are analyzed, and their simple number average value is obtained.
  • the strength of the fiber composite material may be insufficient. Furthermore, when mixed with a transparent resin, the transparency of the resin is adversely affected.
  • the length of the cellulose fiber is not particularly limited, but the average fiber length is preferably 50 nm or more, and more preferably 100 nm or more.
  • surface treatment method of cellulose In order to maintain good dispersibility of cellulose fibers having an average fiber diameter of 2 nm or more and 200 nm or less, surface modification is preferably performed.
  • the surface modification of the cellulose fiber includes chemical modification or physical modification, but is preferably a chemical modification method, and the chemical modification will be described more specifically.
  • the hydroxyl group of the cellulose fiber is chemically modified using a modifying agent such as an acid, an alcohol, a halogenating reagent, an acid anhydride, an isocyanate, a silane coupling agent, or a polymer.
  • a modifying agent such as an acid, an alcohol, a halogenating reagent, an acid anhydride, an isocyanate, a silane coupling agent, or a polymer.
  • the chemical modification can be carried out according to a known method. For example, after cellulose fiber that has been defibrated is added to water or an appropriate solvent and dispersed, then a chemical modifier is added to the reaction to perform an appropriate reaction. What is necessary is just to make it react on conditions. In this case, in addition to the chemical modifier, a reaction catalyst can be added as necessary.
  • pyridine N, N-dimethylaminopyridine, triethylamine, sodium methoxide, sodium ethoxide, sodium hydroxide, etc.
  • a basic catalyst or an acidic catalyst such as acetic acid, sulfuric acid, or perchloric acid can be used, but a basic catalyst such as pyridine is preferably used in order to prevent a decrease in reaction rate and degree of polymerization.
  • the reaction temperature is preferably about 40 to 100 ° C. from the viewpoint of suppressing the deterioration of cellulose fibers such as yellowing and lowering of the degree of polymerization and ensuring the reaction rate.
  • the reaction time may be appropriately selected depending on the modifier used and the processing conditions.
  • Examples of the functional group introduced into the cellulose fiber by chemical modification include, for example, acetyl group, methacryloyl group, propanoyl group, butanoyl group, iso-butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, methyl group, ethyl group, Examples include propyl group, iso-propyl group, butyl group, iso-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like.
  • the cellulose chain forming the regenerated cellulose is at the molecular chain level, and only the primary hydroxyl group at the C6 position in the glucopyranose ring, which is a constituent monomer unit of the cellulose chain, is selectively oxidized and passes through the aldehyde. It is oxidized to a carboxyl group.
  • the method of this report (Article entitled “Preparation of polyuronic acid from cellulose by TEMPO catalyzed oxidation” by A. Isogai and Y. Kato in “Cellulose” Vol. 5, 1998, pages 153-164) It is also possible to use it for the cellulose fiber produced by this method for producing the nanofiber. Nanofibers of cellulose fibers prepared by this method can also be used as cellulose fibers having surface hydroxyl groups modified in the same manner as the above chemical modification method.
  • the concentration of the cellulose fiber with respect to the solvent can be 1% by mass or more and 30% by mass or less. Moreover, it is also possible to make it 5 mass% or more and 30 mass% or less preferably, and a yield can be raised.
  • the cellulose fiber defibrating treatment is preferably performed at a cellulose fiber concentration of 0.1% by mass or more and 3% by mass or less with respect to water as a solvent.
  • the cellulose fiber after the fiber treatment may be once dried by means of air drying, oven drying, vacuum drying, freeze drying or the like, and then dispersed in a solvent at a concentration necessary for the surface treatment.
  • concentration of the cellulose fiber immediately after defibration is 0.1 mass% or more and 3 mass% or less
  • concentration with respect to the solvent of a cellulose fiber is 1 mass% or more and 30 mass%. You may concentrate by concentration methods, such as an evaporator and a membrane separation method, so that it may become the following.
  • the concentration of cellulose fibers immediately after defibration is such that a cellulose dispersion of 0.1% by mass or more and 3% by mass or less is concentrated by a concentration method such as an evaporator or a membrane separation method, followed by surface treatment. Also good. Before surface treatment, many hydroxyl groups are exposed on the cellulose surface and cause gelation. Therefore, a concentration method after surface treatment is preferable.
  • a silane coupling agent may be used as a surface treatment method for cellulose.
  • Silazanes vinylsilazane, hexamethyldisilazane, tetramethyldisilazanechlorosilanes: trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, vinyltrichlorosilane alkoxysilanes: trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, vinyl Trimethoxysilane silane coupling agents: vinyltriacetoxysilane, vinyltris (methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, etc. are applicable, trimethylmethoxysilane, dimethyldimethoxysilane, Methy
  • a silane coupling agent capable of introducing a reactive group is preferably used.
  • silane coupling agents may be appropriately diluted with hexane, toluene, methanol, ethanol, acetone, methyl ethyl ketone (MEK), pyridine, water or the like.
  • silane coupling agents may be used alone or in combination, and cellulose fibers treated with a silane coupling agent may be further treated with a silane coupling agent.
  • the ratio of the silane coupling agent is not particularly limited, but the ratio of the silane coupling agent is preferably 10% by mass or more and 99% by mass or less, and 30% by mass or more and 98% by mass with respect to the cellulose fiber. The following is more preferable.
  • the amphiphilic polymer is a polymer having both a hydrophilic component and a lipophilic component in a polymer unit, and has a property of being dissolved and dispersed in both an organic solvent and water.
  • the polymer may be a homopolymer composed of a single monomer having both a hydrophilic component and a lipophilic component in the side chain, or may be a copolymer polymer obtained by copolymerizing a hydrophilic component monomer and a lipophilic component monomer.
  • (polyoxyalkylene) acrylate and methacrylate are commercially available hydroxypoly (oxyalkylene) materials such as “Pluronic” (Pluronic (Asahi Denka Kogyo Co., Ltd.)).
  • Adeka Polyether Adeka Polyether (Asahi Denka Kogyo Co., Ltd.), Carbowax [Carbowax (Glico Products)], Triton [Toriton (Rohm and Haas)] and P.I. E. Those generally sold as G (Daiichi Kogyo Seiyaku Co., Ltd.) can be used.
  • an amphiphilic polymer may be prepared by copolymerizing a hydrophilic component monomer and a lipophilic component monomer.
  • an acrylic resin that is easy to polymerize and has a wide variety of monomers is preferred.
  • the acrylic resin may be a homopolymer based only on the acrylic monomer, or may be copolymerized with other monomers based on the acrylic monomer. May be.
  • acrylic monomer examples include general acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylic acid chloride, methacrylic acid chloride, and acrylic acid anhydride.
  • Blemmer 50POEP-800B Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-400, Blemmer PSE-1300, Blemmer ASE series, Blemmer PKEP series, Blemmer AKEP series, Blemmer AE-300 , Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANE -500, BLEMMER 70ANEP-550, etc., and Kyoeisha Chemical Co., Ltd.
  • light ester MC light ester 130MA, light ester 041MA, light acrylate BO-A, light acrylate EC-A, light acrylate MTG-A, light acrylate 130A, light Acrylate DPM-A, light acrylate P-200A, light acrylate NP-4EA, light acrylate NP-8EA and the like can be mentioned, and these can be selected and used.
  • acrylimides typically include diacetone acrylamide, acrylamide, N-isopropyl acrylamide (NIPAM), N-ethyl acrylamide, N-pyrrolidinyl acrylamide, N-cyclopropyl acrylamide, N -Diethyl acrylamide, N-methyl, N-isopropyl acrylamide, N-propyl acrylamide, N-methyl, N-isopropyl acrylamide, N-piperidinyl acrylamide, N-propyl acrylamide and the like.
  • NIPAM N-isopropyl acrylamide
  • NIPAM N-ethyl acrylamide
  • N-pyrrolidinyl acrylamide N-cyclopropyl acrylamide
  • N-Diethyl acrylamide N-methyl, N-isopropyl acrylamide, N-propyl acrylamide, N-methyl, N-isopropyl acrylamide, N-piperidinyl acrylamide, N-prop
  • vinyl monomers other than acrylic monomers include vinyl alcohol and vinyl acetate.
  • the hydrophilicity and hydrophobicity of the polymer can be controlled by copolymerizing these monomers at an arbitrary ratio.
  • the molecular weight of the polymer is not particularly limited, but is preferably from 10,000 to 500,000.
  • thermoplastic resin Next, the thermoplastic resin used in the present invention will be described.
  • Thermoplastic resin is a resin that becomes soft when heated to the glass transition temperature or melting point and can be molded into the desired shape.
  • thermoplastic resins are often difficult to machine such as cutting and grinding, and when heated and softened, they are widely used for injection molding, etc., which is pushed into a mold and cooled and solidified to make the final product. ing.
  • thermoplastic resin As the thermoplastic resin, the following are examples of general-purpose plastics that are generally available in a wide variety. Polyethylene (PE), high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), Teflon (registered trademark) (Polytetrafluoroethylene, PTFE), ABS resin (acrylonitrile butadiene styrene resin), AS resin, acrylic resin (PMMA), and the like.
  • PE Polyethylene
  • PVC polyvinyl chloride
  • PS polyvinylidene chloride
  • PS polystyrene
  • PVAc polyvinyl acetate
  • Teflon registered trademark
  • AS resin acrylic resin
  • PMMA acrylic resin
  • PA Polyamide
  • nylon polyacetal
  • PC polycarbonate
  • m-PPE modified polyphenylene ether
  • PPO polybutylene terephthalate
  • PET polyethylene terephthalate
  • GF-PET glass fiber reinforced polyethylene terephthalate
  • COP cyclic polyolefin
  • PPS Polyphenylene sulfide
  • PTFE polytetrafluoroethylene
  • PI thermoplastic polyimide
  • PAI polyamideimide
  • thermoplastic resins include polyethylene terephthalate (PET), polycarbonate (PC), and acrylic resin (PMMA).
  • the molecular weight of the thermoplastic resin can be measured by a conventionally known method.
  • GPC measurement conditions are measured by stabilizing the column at 40 ° C., flowing THF (tetrahydrofuran) at a flow rate of 1 ml / min, and injecting about 100 ⁇ l of a sample having a concentration of 1 mg / ml.
  • the column it is preferable to use a combination of commercially available polystyrene gel columns.
  • a refractive index detector (RI detector) or a UV detector is preferably used.
  • the molecular weight distribution of the sample is calculated using a calibration curve created using monodisperse polystyrene standard particles. About 10 points are preferably used as polystyrene for preparing a calibration curve.
  • molecular weight was measured under the following measurement conditions.
  • the molecular weight was measured by the above method.
  • the molecular weight by a mass spectrometer was adopted.
  • the molecular weight can be obtained from the mass number of the parent peak in measurement with a mass spectrometer (manufactured by Shimadzu Corporation, GCMS-QP2010 Plus).
  • the cellulose fiber-containing resin material production method includes a cellulose fiber defibrating step in which one type of cellulose fiber or one or more types of cellulose fibers are uniformly dispersed in a fiber diameter nanometer order in a solvent, and defibration. It is composed of a surface treatment step for hydrophobizing the surface of the cellulose fiber after the step, and a kneading step for kneading the surface-treated and hydrophobic cellulose fiber and the thermoplastic resin.
  • the kneading step of kneading the resin includes the first mixing step of mixing the surface-treated cellulose fiber, the organic solvent and the first thermoplastic resin, and the second thermoplastic having a molecular weight larger than that of the first thermoplastic resin.
  • the content of the surface-treated cellulose fiber with respect to the thermoplastic resin is 1% or more and 60% or less, preferably 2% or more and 50% or less, more preferably 3% or more and 40% or less by volume.
  • the surface-treated cellulose fiber used in the present invention is mixed with a first thermoplastic resin having a molecular weight lower than that of the second thermoplastic resin used in the second mixing step in advance as a second (final)
  • the compatibility with the thermoplastic resin is improved, and uniform dispersion becomes possible.
  • the step of mixing the low-molecular-weight first thermoplastic resin as a binder before mixing with the second (final) thermoplastic resin is referred to as a first mixing step.
  • What is used as a binder is suitably used in consideration of the affinity with the final second thermoplastic resin and the dispersibility of cellulose fibers.
  • the molecular weight of the first plastic resin used in the first mixing step is preferably 500 or more and 50000 or less, more preferably 1500 or more and 50000 or less.
  • the (first) thermoplastic resin in the first mixing step is usually the second mixture. It is preferable to use the same composition as that of the (second) thermoplastic resin in the step. However, as long as the affinity with the second thermoplastic resin (the thermoplastic resin used in the second mixing step) and the dispersibility of the cellulose fibers are good, the thermoplastic resin in the first mixing step and the second mixing step The compositions need not be similar.
  • the wet mixing method is desirable from the viewpoint that the thermoplastic resin and the surface-treated cellulose fiber are less damaged and can be uniformly mixed.
  • Other advantages of the wet mixing method include prevention of powder scattering, operational convenience, and improved dispersibility.
  • the amount of solvent or solution specifically used is appropriately selected depending on the thermoplastic resin used and the surface-treated cellulose fiber.
  • the applicable solvent may be any solvent that can dissolve the first thermoplastic resin in the first mixing step and maintain the dispersibility of the surface-treated cellulose fiber, such as benzene, toluene, xylene, and the like.
  • Halogenated hydrocarbons such as chlorobenzene, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane
  • a protic solvent is a proton-donating solvent, and many proton solvents have relatively highly acidic hydrogen bonded to oxygen or nitrogen atoms. At the same time, oxygen or nitrogen is an unshared electron pair. It is a solvent that also has the property of accepting protons (Lewis basic).
  • Protic solvents are also solvents that form hydrogen bonds between solvent molecules. Specific examples include glycols such as water, methanol, ethanol, propanol, butanol, acetic acid, ethylene glycol, and propylene glycol (glycolic acid, glyoxylic acid, diethylene glycol, polyethylene glycol, glycol aldehyde, glyoxal) and the like. These solvents can be used alone or in admixture of two or more.
  • an organic solvent containing a hydroxyl group is preferable, and water, methanol, ethanol, propanol, butanol, acetic acid, ethylene glycol, propylene glycol and other glycols are preferable in that cellulose fibers are uniformly dispersed in the resin.
  • the boiling point at atmospheric pressure of the solvent used is preferably 30 ° C. or higher and 200 ° C. or lower, more preferably 50 ° C. or higher and 150 ° C. or lower.
  • the boiling point is less than 30 ° C., it is dangerous in handling.
  • the boiling point is higher than 200 ° C., it is difficult to remove the solvent, and the final product is adversely affected by the residue of the decomposition product and heating.
  • the amount of the solvent used when carrying out the first mixing step of the present invention is not particularly limited as long as the thermoplastic resin in the first mixing step is dissolved, but 100 mass of the thermoplastic resin in the first mixing step.
  • the solvent is preferably 100 to 2000 parts by mass with respect to parts. When the solvent is less than 100 parts by mass, the thermoplastic resin in the first mixing step is not completely dissolved, and the composition of the cellulose fiber thermoplastic resin composite material in the first mixing step may be nonuniform. In the case of over 2000 parts by mass, productivity is lowered and sufficient torque cannot be obtained during wet mixing, and the composition of the cellulose fiber thermoplastic resin composite material may become non-uniform.
  • the solvent may be removed in the solvent removal step after the completion of the first mixing step, it is preferable to remove the solvent during the first mixing step from the viewpoint of increasing production time and drying equipment.
  • twin-screw kneader such as a twin-screw kneader, tumbler mixer, super mixer, Henschel mixer, screw blender, and ribbon blender can be used as the first mixing device while removing the solvent. It is desirable to use a twin-screw kneader that is easy and can continuously produce materials. Moreover, when performing by a batch type, when high torque type kneaders, such as TK high vis mix by a Primix company, are used, it is possible to mix a high-viscosity substance from a powder, and solvent removal is also easy.
  • high torque type kneaders such as TK high vis mix by a Primix company
  • the temperature during the first mixing step is preferably 20 ° C. or higher and 300 ° C. or lower, more preferably 40 ° C. or higher and 250 ° C. or lower.
  • thermoplastic resin to be added is preferably 0.1% by mass to 50% by mass of the cellulose fiber, and preferably 0.1% by mass to 50% by mass of the thermoplastic resin added in the second mixing step.
  • a cellulose fiber thermoplastic resin composite material prepared in the first mixing step is added to the target thermoplastic resin and kneaded to produce a composite material, or a thermoplastic dissolved in a solvent.
  • a preferred embodiment is a production method in which a composite material is prepared by mixing a resin and a cellulose fiber thermoplastic resin composite material and then removing the organic solvent.
  • the second mixing step it is particularly desirable to prepare the final composite material by a kneading method.
  • the second mixing step it is possible to use an organic solvent. In that case, it is preferable to deaerate after kneading to remove the organic solvent from the composite material.
  • Examples of the apparatus that can be used for kneading in the second mixing step include a closed kneading apparatus such as a lab plast mill, a Brabender, a Banbury mixer, a kneader, and a roll, or a batch kneading apparatus. Moreover, it can also manufacture using a continuous kneading apparatus like a single screw extruder, a twin screw extruder, etc.
  • the second thermoplastic resin in the second mixing step is melted, After the prepared cellulose fiber thermoplastic resin composite material is added and melt kneaded to disperse it in the second thermoplastic resin in the second mixing step, the molten composite material is extruded into a strand and pellets There is also a way to make it.
  • thermoplastic resin and the cellulose fiber thermoplastic resin composite material prepared in the first mixing step may be added and kneaded all at once, or added in stages. And may be kneaded.
  • a kneading apparatus such as an extruder
  • the cellulose fiber thermoplastic resin composite material prepared in the first mixing step is powdered or agglomerated. It can be added as it is. Alternatively, the cellulose fiber thermoplastic resin composite material prepared in the first mixing step can be added in a state of being dispersed in the liquid. In the case where the cellulose fiber thermoplastic resin composite material prepared in the first mixing step is added in a state dispersed in a liquid, it is preferable to perform deaeration after kneading.
  • thermoplastic resins may be added by the same method as in the second mixing step.
  • the thermoplastic resin in the second mixing step corresponds to a thermoplastic resin having a large molecular weight, and a molecular weight of 50,000 to 1,000,000 is preferably used from the viewpoint of resin strength and moldability.
  • the temperature during the second mixing step is preferably 20 ° C. or more and 300 ° C. or less, and more preferably 40 ° C. or more and 250 ° C. or less.
  • concentration of a cellulose fiber is 1 mass% or more and 30 mass% with respect to the total amount of the 1st thermoplastic resin of a 1st mixing process, and the 2nd thermoplastic resin of a 2nd mixing process. It is preferable that More preferably, they are 3 mass% or more and 20 mass% or less.
  • the ratio of the molecular weight of the first thermoplastic resin in the first mixing step and the second thermoplastic resin in the second mixing step is (molecular weight of the first thermoplastic resin / molecular weight of the second thermoplastic resin) is 1. / 1000 or more and 1/1 or less is preferable. In the case of 1/1000 or less, uniform dispersion of cellulose fibers becomes difficult. On the other hand, when the ratio is 1/1 or more, the molding of the base resin becomes worse. The ratio is more preferably 1/1000 or more and 1/2 or less. In this case, the effect of the present invention, which can significantly improve the mechanical properties of the resin, is obtained.
  • additives when using the composite material which concerns on this invention for the optical resin material, and when using it as an optical element, you may add various additives as needed.
  • additives include antioxidants, light stabilizers, heat stabilizers, weather stabilizers, stabilizers such as ultraviolet absorbers and near infrared absorbers, lubricants, resin modifiers such as plasticizers, soft polymers, , Anti-clouding agents such as alcoholic compounds, colorants such as dyes and pigments, other antistatic agents, flame retardants and the like. They may be used alone or in combination.
  • antioxidants examples include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. By blending these antioxidants, coloring and strength reduction due to oxidative degradation during molding of the composite material can be prevented without reducing transparency, heat resistance, and the like.
  • phenolic antioxidant conventionally known ones can be applied.
  • 2-t-butyl-6- (3-t-butyl-2-hydroxy-deoxysilane described in JP-A No. 63-179953 is available.
  • Acrylate compounds such as octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate described in JP-A-1-168463, and 2,2′-methylene-bis (4-methyl) -6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6- Lis (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenylpropionate)) methane, , Pentaerythrimethyl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenylpropionate)), triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5- Alkyl-substituted phenol
  • the phosphorus-based antioxidant is not particularly limited as long as it is a substance that is usually used in the general resin industry.
  • monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable.
  • sulfur-based antioxidant examples include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodiprote.
  • Pionate pentaerythritol-tetrakis- ( ⁇ -lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc. Can be mentioned.
  • amine-based antioxidants such as diphenylamine derivatives, nickel or zinc thiocarbamates, and the like are also applicable as antioxidants.
  • the above-mentioned antioxidants can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention.
  • the amount is preferably in the range of 0.001 to 20 parts by weight, and more preferably in the range of 0.01 to 10 parts by weight with respect to parts.
  • ⁇ Anti-clouding agent> As the cloudiness inhibitor, a compound having the lowest glass transition temperature of 30 ° C. or less can be blended. This prevents the cloudiness of the thin film in the long-time high-temperature and high-humidity environment without degrading various properties such as transmittance, heat resistance, and mechanical strength, and in the long-time high-temperature and high-humidity environment. it can.
  • Light-resistant stabilizers are roughly classified into quenchers and radical scavengers. Benzophenone light stabilizers, benzotriazole light stabilizers, and triazine light stabilizers are classified as quenchers, and hindered amine light stabilizers are classified as radical scavengers.
  • HALS hindered amine light stabilizer
  • Specific examples of such HALS can be selected from low molecular weight to medium molecular weight and high molecular weight.
  • LA-77 (manufactured by Asahi Denka), Tinuvin 765 (manufactured by Ciba Japan), Tinuvin 123 (manufactured by Ciba Japan), Tinuvin 440 (manufactured by Ciba Japan), Tinuvin 144 (manufactured by Ciba Japan) Hostavin N20 (Hoechst) medium molecular weight LA-57 (Asahi Denka), LA-52 (Asahi Denka), LA-67 (Asahi Denka), LA-62 (Asahi Denka), Large molecular weights include LA-68 (Asahi Denka), LA-63 (Asahi Denka), Hostavin N30 (Hoechst), Chimassorb 944 (Ciba Japan), Chimassorb 2020 (Ciba Japan), Chimassorb 119 (Ciba). ⁇ Made in Japan), Tinuv n622 (manufactured by Ciba Japan), Cyasorb
  • HALS is also preferably used in combination with a benzotriazole-based light-resistant stabilizer.
  • a benzotriazole-based light-resistant stabilizer examples include ADK STAB LA-32, LA-36, LA-31 (Asahi Denka Kogyo), Tinuvin 326, Tinuvin 571, Tinuvin 234, Tinuvin 1130 (Ciba Japan), and the like.
  • HALS is preferably used in combination with the above-mentioned various antioxidants.
  • antioxidants There are no particular restrictions on the combination of HALS and antioxidant, and combinations of phenols, phosphorus, sulfur and the like are possible, but combinations of phosphorus and phenols are particularly preferred.
  • antioxidants and light stabilizers heat stabilizers, weather stabilizers, stabilizers such as near infrared absorbers, resin modifiers such as lubricants and plasticizers, soft polymers, white turbidity such as alcoholic compounds Inhibitors, coloring agents such as dyes and pigments, antistatic agents, flame retardants and the like can be mentioned.
  • stabilizers such as near infrared absorbers
  • resin modifiers such as lubricants and plasticizers
  • soft polymers soft polymers
  • white turbidity such as alcoholic compounds Inhibitors
  • coloring agents such as dyes and pigments, antistatic agents, flame retardants and the like can be mentioned.
  • the final composite material produced in this way may be used as a molded body such as an optical lens or may be used in a film-like film form.
  • the cellulose fiber of the present invention can ensure transparency, but even if it is used as a colored molded body or film, the heat resistance and mechanical strength can be drastically improved compared to a single resin, Deployment is also possible.
  • a cellulose fiber dispersion which is another embodiment of the present invention is uniformly dispersed at a high concentration without gelation, and a cellulose fiber dispersion is provided without impairing transparency.
  • the method for producing the cellulose fiber-containing resin material will be described in detail. This makes it possible to uniformly disperse the microfibrillated cellulose in the transparent resin, and as a result, facilitates mixing with the matrix resin and maintains the transparency of the resin while maintaining the transparency of the polymer film or polymer composite. The mechanical properties such as tensile strength and low linear expansion were greatly improved.
  • cellulose derived from natural products is hydrophilic and agglomerates in an organic solvent and cannot be dispersed.
  • the present invention has found that the fiber diameter of cellulose can be maintained and dispersed in a general organic solvent by wet-pulverizing the fiber diameter of cellulose to nanoscale microfibrils with an organic solvent.
  • Any organic solvent that can disperse cellulose fibers may be used as long as the fibers can be dispersed in the solvent.
  • Alcohols include methanol, ethanol, 2-propanol, ketones include acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone, ethers include tetrahydrofuran and diethyl ether, aromatic hydrocarbons include toluene and xylene, Halogenated hydrocarbons can be used. These solvents can be used alone or in combination of two or more. Preferred are ketones.
  • these fibers are microfibrillated by a grinder, a high speed mixer, a homogenizer, a high speed impact mill, a Banbury mixer, a homomixer, a kneader, a ball mill, a vibration ball mill, a planetary ball mill, an attritor, a sand mill, a bead mill, and a colloid mill.
  • a grinder a high speed mixer, a homogenizer, a high speed impact mill, a Banbury mixer, a homomixer, a kneader, a ball mill, a vibration ball mill, a planetary ball mill, an attritor, a sand mill, a bead mill, and a colloid mill.
  • a jet mill a roller mill, a tron mill, a high-speed stone mill, a high-pressure homogenizer, etc.
  • mechanically pulverizing cellulose fibers together with the organic solvent described above to obtain finely divided microfibri
  • the concentration at the time of defibration can be 0.1% by mass to 50% by mass with respect to the organic solvent, but preferably 0.5% by mass to 30% by mass.
  • the following high shear mechanical pulverization methods are preferable.
  • a media disperser is preferable, and mills such as a ball mill, a sand mill, and a bead mill can be specifically mentioned. These dispersers may be arranged in series and dispersed in one pass, and there may be a storage process or the like between the first and second units.
  • Distributing in one pass by arranging in series means that material is introduced from the sample inlet of one disperser, and the dispersion liquid that has come out from the outlet is not stored in a stock tank or the like, but is stored in the sample inlet of the next disperser. Indicates that they are connected directly or via piping. This simplifies the process, reduces adhesion loss in the process, and has many advantages as a production process.
  • beads of 1 mm or less, preferably 0.5 mm or less, more preferably 0.3 mm or less are preferable. Ceramic beads are preferred as the beads.
  • the front disperser uses beads having a larger particle diameter as the particle diameter of the front and rear dispersers.
  • Ceramics used for the ceramic beads used in the media disperser include, for example, Al 2 O 3 , BaTiO 3 , SrTiO 3 , MgO, ZrO, BeO, Cr 2 O 3 , SiO 2 , SiO 2 —Al 2 O 3.
  • Cr 2 O 3 MgO, MgO—CaO, MgO—C, MgO—Al 2 O 3 (spinel), SiC, TiO 2 , K 2 O, Na 2 O, BaO, PbO, B 2 O 3 , SrTiO 3 (Strontium titanate), BeAl 2 O 4 , Y 3 Al 5 O 12 , ZrO 2 —Y 2 O 3 (cubic zirconia), 3BeO—Al 2 O 3 -6SiO 2 (synthetic emerald), C (synthetic diamond) Si 2 O—nH 2 O, silicon nitride, yttrium stabilized zirconia, zirconia reinforced alumina and the like are preferable.
  • Yttrium-stabilized zirconia and zirconia-reinforced alumina are particularly preferably used because of the low generation of impurities due to friction with beads and dispersers during dispersion.
  • a pulverization method in which fine dispersion is performed by pressurizing the dispersion liquid at a high pressure to pass through a fine slit and then causing a rapid pressure drop can be preferably exemplified.
  • a “shearing force” generated when the dispersoid passes through a narrow gap (about 75 ⁇ m to 350 ⁇ m) at high pressure and high speed (b) liquid-liquid collision or wall collision in a narrow space under high pressure. It is considered that uniform and efficient dispersion can be achieved by further increasing the cavitation force due to the subsequent pressure drop without changing the impact force generated in.
  • Dispersing devices using this type of pulverization method have long been known as gorin homogenizers.
  • the liquid to be dispersed sent at a high pressure is converted into a high-speed flow through a narrow gap on the cylindrical surface, It collides with the wall surface and emulsifies and disperses by the impact force.
  • the liquid-liquid collision include a Y-type chamber of a microfluidizer, a spherical chamber using a spherical check valve as described in JP-A-8-103642, and the liquid-wall collision includes Examples include a Z-type chamber of a microfluidizer.
  • a device that has been devised such as making the high-speed flow part into a saw blade shape and increasing the number of collisions has been devised.
  • Typical examples of such devices include Gorin homogenizers, microfluidizers manufactured by Microfluidics International Corporation, microfluidizers manufactured by Mizuho Industry Co., Ltd., nanomizers manufactured by Special Machine Industries, Inc., and Sugino Machine And high pressure crushing system “Ultimizer HJP-25005”, etc. Further, there are also descriptions in JP-A-8-238848, JP-A-8-103642, and US Pat. No. 4,533,254.
  • the degree of dispersion is not particularly limited as long as the average fiber diameter is 2 nm or more and 200 nm or less, but the average fiber diameter is preferably within 30%, particularly preferably the average fiber diameter is 10% or less. It is also preferable from the viewpoint of tensile strength, transmittance and the like than the polydispersed one.
  • the cellulose fiber of the present invention only needs to be defibrated to an average fiber diameter of 2 nm or more and 200 nm or less, and the fiber surface may be further subjected to surface treatment by chemical modification or physical modification.
  • the standard deviation of the average fiber diameter can be known by the following procedure. First, a microfibrillated cellulose film coated on a support is attached to an appropriate holder with an adhesive, and an ultrathin film having a thickness of 0.1 to 0.2 ⁇ m is used with a diamond knife in a direction substantially parallel to the support surface. Make sections. At this time, the upper and lower ends of the microfibrillated cellulose film are observed with an optical microscope to confirm that the cutting is performed substantially parallel to the support surface, that is, the cutting angle is 1 degree or less.
  • the prepared ultrathin slice was supported on a copper mesh, transferred onto a carbon film hydrophilized by glow discharge, and cooled to ⁇ 130 ° C. or lower with liquid nitrogen, while being transmitted through an electron microscope (hereinafter referred to as TEM).
  • TEM electron microscope
  • a bright field image is observed at a magnification of 5,000 to 40,000, and the image is quickly recorded on a film, an imaging plate, a CCD camera or the like.
  • the carbon film it is preferable to use a film supported by an organic film such as a very thin collodion or form bar, and more preferably, the carbon film is formed on a rock salt substrate and dissolved and removed, or the organic film is formed of an organic film. It is a carbon-only film obtained by solvent and ion etching.
  • Acceleration voltage of TEM is preferably 80 to 400 kV, particularly preferably 80 to 200 kV.
  • a TEM image recorded on a suitable medium is decomposed into at least 1024 pixels ⁇ 1024 pixels, preferably 2048 pixels ⁇ 2048 pixels or more, and image processing by a computer is performed.
  • an analog image recorded on a film is converted into a digital image by a scanner or the like, and shading correction, contrast / edge enhancement, etc. are performed as necessary. Thereafter, a histogram is prepared, and a portion corresponding to microfibrillated cellulose that is 2 nm or more and 200 nm or less is extracted from the image by binarization processing.
  • the aggregated particles are cut by an appropriate algorithm, and particles having an equivalent circle diameter (HEYWOOD) of less than 2 nm are deleted (ELIMINATE).
  • the center point of each particle is obtained (SHLINK), and each pixel is expanded (EXTEND) by the center point until it touches each other to form a cell around the center point.
  • the cell that has taken the measurement frame is deleted (EDGEPROCESS REJECT), and the equivalent circle diameter (HEYWOOD) of each cell is obtained.
  • an average value and a standard deviation are calculated from values obtained for at least 500, preferably 1000 or more cells, and the degree of dispersion is obtained by the following equation.
  • Dispersity (standard deviation of equivalent circle diameter of cell) / (average value of equivalent circle diameter of cell) ⁇ 100
  • a standard sample Uniform latex particles (DULP) marketed by US Dow Chemical Company are suitable as the standard sample, and polystyrene particles having a coefficient of variation of less than 10% for a particle size of 0.1 to 0.3 ⁇ m are used. Specifically, a lot having a particle size of 0.212 ⁇ m and a standard deviation of 0.0029 ⁇ m is available.
  • image processing technology can be referred to “Image Processing Application Technology (Industry Research Committee)” edited by Hiroshi Tanaka, and the image processing program or device is not particularly limited as long as the above operation is possible.
  • Image Processing Application Technology Industry Research Committee
  • An example is Luzex-III manufactured by Nireco.
  • PE Polyethylene
  • PP polypropylene
  • PVC polyvinyl chloride
  • PS polyvinylidene chloride
  • PS polystyrene
  • PVA polyvinyl alcohol
  • PVAc polyvinyl acetate
  • Teflon registered trademark
  • AS resin acrylic resin
  • PMMA acrylic resin
  • PA Polyamide
  • nylon polyacetal
  • PC polycarbonate
  • m-PPE modified polyphenylene ether
  • PPO polybutylene terephthalate
  • PET polyethylene terephthalate
  • GF-PET glass fiber reinforced polyethylene terephthalate
  • COP cyclic polyolefin
  • PPS Polyphenylene sulfide
  • PTFE polytetrafluoroethylene
  • PI thermoplastic polyimide
  • PAI polyamideimide
  • thermoplastic resins include polyethylene terephthalate (PET), polycarbonate (PC), and acrylic resin (PMMA).
  • Method for producing cellulose fiber-containing resin material As a method for producing the cellulose fiber-containing resin material of the present invention, one type of cellulose fiber or one or more types of cellulose fibers are uniformly dispersed in an organic solvent, and then the matrix resin is dissolved, and the film is obtained by a solvent casting method. There is a way to make it.
  • the cellulose fiber dispersion is dried once by a drying method that does not aggregate, such as freeze drying, and then a powder is added to the molten resin to form a molded body
  • a drying method that does not aggregate, such as freeze drying
  • a powder is added to the molten resin to form a molded body
  • the mixing method is not limited to this.
  • the resin molding is a variety of fiber reinforced composite materials widely used in industrial fields such as electric / electronics, machinery, automobiles, and building materials, and includes film-shaped ones.
  • the content of the cellulose fiber with respect to the matrix resin is 1% to 60% by volume, preferably 2% to 50%, and more preferably 3% to 40%.
  • the bending elastic modulus and bending strength were measured at 2 mm / min and 20 ° C.
  • (3) Linear expansion coefficient The molded body was measured for the linear expansion coefficient by changing the temperature within the range of 40 to 80 ° C.
  • SII Seiko Instruments
  • EXSTAR6000 TMA / SS6100 was used as a measuring device.
  • the test piece was 1 cm in length, 1 cm in width, and 2 mm in thickness.
  • Heat resistance (measurement of glass transition point (Tg)
  • the glass transition point of the composite material was measured using a high-sensitivity differential scanning calorimeter (DSC SII Nanotechnology Inc.).
  • An ultrathin section having a thickness of 0.1 to 0.2 ⁇ m is prepared using a diamond knife, and the ultrathin section is supported on a copper mesh and transferred onto a carbon film that has been hydrophilized by glow discharge. While cooling to ⁇ 130 ° C. or lower with nitrogen, a bright field image was observed with a TEM at a magnification of 5,000 to 40,000 times and quickly recorded on a CCD camera.
  • the carbon film was an extremely thin collodion organic film, the TEM acceleration voltage was 150 kV, and a TEM image recorded was visually observed to evaluate dispersibility. ⁇ was classified as good dispersibility, ⁇ was slightly aggregated, and ⁇ was severely aggregated. The two listed are judged to be intermediate states.
  • Example 1 ⁇ About cellulose fiber> (Comparative Example 1) Sulfuric acid bleached pulp obtained from conifers is added to pure water so as to be 1.0% by mass, and cellulose fibers are defibrated using an Excel auto homogenizer manufactured by Nippon Seiki Seisakusho Co., Ltd. for 15 minutes at 3000 rpm. did. This aqueous dispersion was designated as cellulose fiber A. From the observation result of the scanning electron microscope, it was confirmed that the obtained cellulose fiber was fibrillated to an average fiber diameter of 250 nm and was microfibrillated.
  • Comparative Example 2 The cellulose fiber A aqueous dispersion prepared in Comparative Example 1 was filtered, washed with pure water, and dried at 70 ° C. to obtain cellulose fiber B.
  • cellulose fiber C To 100 parts by mass of acetone, 5 parts by mass of cellulose fiber B is added and dispersed. While stirring this dispersion at the boiling reflux temperature, a mixture of 5 parts by mass of acetic anhydride is added over 60 minutes, and then further. Stir for 2 hours. From the result of observation with a scanning electron microscope, the obtained cellulose fiber was kept at an average fiber diameter of 250 nm. The obtained sample was designated as cellulose fiber C.
  • cellulose fiber E To 100 parts by mass of ethanol and 1 part by mass of pure water, 5 parts by mass of cellulose fiber E is added and dispersed. While stirring this dispersion at 50 ° C., a mixture of 5 parts by mass of tetraethoxysilane is taken over 60 minutes. And then stirred for another 2 hours. From the result of observation with a scanning electron microscope, the obtained cellulose fiber was kept at an average fiber diameter of 200 nm. The obtained sample was designated as cellulose fiber F.
  • the cellulose fiber D produced in Production Example 1 was pulverized 180 times at 200 MPa with a high pressure pulverization system Altemizer HJP-2005 (manufactured by Sugino Machine Co., Ltd.).
  • the cellulose fiber D was adjusted with water so that the cellulose fiber D might be 1 mass%, and the cellulose fiber J was obtained.
  • the obtained cellulose fiber had an average fiber diameter of 10 nm.
  • the reaction product is filtered through a glass filter, washed with a sufficient amount of water and filtered five times, so that the cellulose fiber D is 0.1% by mass. Diluted with water. Furthermore, it processed with the ultrasonic disperser for 1 hour and the cellulose fiber L was obtained. It was the average fiber diameter of 4 nm.
  • thermoplastic resin used for a cellulose fiber and a 2nd mixing process was adjusted so that it might become a mixing
  • the second mixing step was performed by first melting the thermoplastic resin and then adding the sample prepared in the first mixing step. Further, as a high-torque type kneader, a kneader equipped with the extension flow kneading chamber shown in FIG. 1 is used in the molten resin discharge section, and melt kneading is performed at a barrel temperature of 250 ° C. and a discharge rate of 10 kg / h.
  • the resin discharged from the tip was cut into pellets to obtain final composite material pellets.
  • the obtained pellets were vacuum-dried at 70 ° C. for 24 hours and then used for measuring physical properties of the above-mentioned sizes, for example, 140 mm ⁇ 12 mm ⁇ , using an injection molding machine (IS-80G type manufactured by Toshiba Machine Co., Ltd.). 2 mm was produced and used for various measurements.
  • the evaluation results are shown in Table 1.
  • the solvent is volatilized from the vent port in the middle of mixing in the kneading machine in the second mixing step (vent exhaust), and the resin discharged from the tip of the extruder is solvent Was not left behind.
  • Table 1 shows the composition of the composite material sample, each condition of the first mixing step and the second mixing step, and Table 2 shows the evaluation result of each composite material sample.
  • Each evaluation method is as described above.
  • TEOS Tetraethoxysilane EG: Ethylene glycol PET: Polyethylene terephthalate PC: Polycarbonate 1 and 30 are single polymers.
  • the present invention can improve the mechanical strength of the base resin while maintaining transparency and reduce the linear expansion. Furthermore, it was surprisingly found that as a composite material, the glass transition temperature of the matrix resin can be raised to impart heat resistance. As a result, a low-priced resin represented by PET can be made highly functional, and a great contribution to the industrial field can be expected.
  • Example 2 Examples for another problem to be solved by the present invention will be shown below, but the present invention is not limited to these examples.
  • the cellulose fiber dispersion of the present invention is a dispersion having a high concentration without gelling in a dispersion with a high concentration even in a small fiber diameter, and a dispersion with a small dispersion (equal average fiber diameter). It turns out that it is a liquid.
  • ⁇ Creation of composite material 100 g of each of the dispersions prepared in the comparative example and the production example are weighed, polyvinyl alcohol (PVA) is used for water, polyvinyl chloride (PVC) is used for acetone, and ethanol is used for ethanol.
  • PVA polyvinyl alcohol
  • PVC polyvinyl chloride
  • ethanol is used for ethanol.
  • PP polypropylene
  • methylene dichloride 50 g of triacetyl cellulose (TAC) was dissolved. This was transferred to a petri dish and dried in a drying box at 100 ° C. for 24 hours to prepare a composite material film.
  • test specimens for measuring physical properties of the above sizes for example, 1 cm in length, 1 cm in width, and 2 mm in thickness were prepared. (Samples 1 to 56) were subjected to various measurements. Tables 5 and 6 show the cellulose fibers (dispersion) used for the prepared composite materials 1 to 56, the resin type used, and the evaluation of the prepared composite materials.
  • the tensile strength is high, the linear expansion coefficient is low, and the transmittance It turns out that it is also favorable. That is, it was found that the mechanical strength of the base resin can be improved while maintaining the transparency, and the linear expansion can be reduced.

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PCT/JP2010/057805 2009-05-13 2010-05-07 セルロース繊維含有樹脂材料の製造方法 WO2010131602A1 (ja)

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