WO2016148233A1 - Composition de résine renforcée par des fibres comprenant des nanofibres de cellulose chimiquement modifiées et résine thermoplastique - Google Patents

Composition de résine renforcée par des fibres comprenant des nanofibres de cellulose chimiquement modifiées et résine thermoplastique Download PDF

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WO2016148233A1
WO2016148233A1 PCT/JP2016/058481 JP2016058481W WO2016148233A1 WO 2016148233 A1 WO2016148233 A1 WO 2016148233A1 JP 2016058481 W JP2016058481 W JP 2016058481W WO 2016148233 A1 WO2016148233 A1 WO 2016148233A1
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chemically modified
cnf
fiber
thermoplastic resin
resin composition
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PCT/JP2016/058481
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English (en)
Japanese (ja)
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健 仙波
伊藤　彰浩
貴宏 上坂
和男 北川
文明 中坪
矢野　浩之
Original Assignee
国立大学法人京都大学
地方独立行政法人京都市産業技術研究所
日本製紙株式会社
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Priority claimed from JP2015240084A external-priority patent/JP6091589B2/ja
Application filed by 国立大学法人京都大学, 地方独立行政法人京都市産業技術研究所, 日本製紙株式会社 filed Critical 国立大学法人京都大学
Priority to US15/556,220 priority Critical patent/US10676615B2/en
Priority to CN201680016164.0A priority patent/CN107429071B/zh
Priority to EP16765062.1A priority patent/EP3272812B2/fr
Priority to KR1020177028689A priority patent/KR102405761B1/ko
Publication of WO2016148233A1 publication Critical patent/WO2016148233A1/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
    • C08L1/08—Cellulose derivatives
    • 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

  • the present invention relates to a fiber reinforced resin composition containing chemically modified cellulose nanofibers and a thermoplastic resin.
  • the weight of the plant fiber is as light as 1/5 of steel, the strength of the plant fiber is as strong as about 5 times that of steel, and the thermal expansion of the plant fiber is 1/50 of glass and has a low linear thermal expansion coefficient.
  • MFC microfibrillated plant fibers
  • MFC is a fiber having a fiber diameter of about 100 nm, a fiber length of about 5 ⁇ m or more, and a specific surface area of about 250 m 2 / g. MFC is higher in strength than unfiltrated plant fibers.
  • the cellulose contained in the plant fiber has three hydroxyl groups per repeating unit in the molecule, and the plant fiber as a whole has many hydroxyl groups. As a result, the cohesive force due to hydrogen bonding is strong between cellulose molecules.
  • Patent Document 1 discloses a composition comprising a polymer compound having a primary amino group, a polymer compound modified with maleic anhydride, microfibrillated plant fibers, and polyolefin.
  • Patent Document 2 discloses a resin composition containing a modified microfibrillated plant fiber esterified with an alkyl succinic anhydride and a thermoplastic resin.
  • Patent Document 3 discloses a dispersion containing cellulose nanofiber (CNF), a thermoplastic resin and a nonionic surfactant, and a resin composition obtained from this dispersion.
  • CNF cellulose nanofiber
  • a fiber-reinforced composite resin composition reinforced by fine cellulose fibers has been disclosed in which a fine cellulose fiber is dispersed in the resin.
  • a suitable combination of a fiber having good dispersibility and a resin in which the fiber is easily dispersed is necessary.
  • An object of the present invention is to provide a fiber-reinforced resin composition and a method for producing the same, in which a fiber having good dispersibility and a resin in which the fiber is easily dispersed are suitably combined. More specifically, an object of the present invention is to provide a fiber reinforced resin composition containing chemically modified CNF and a thermoplastic resin whose physical properties are improved by a suitable composite of fiber and resin, and a method for producing the same. .
  • SP value a solubility parameter
  • cellulose nanofiber used in the present invention means nanofabric composed of cellulose (cellulose nanofiber) and / or nanofabric composed of lignocellulose (lignocellulose nanofiber). Also referred to as “CNF”.
  • CNF may be used synonymously with microfibrillated cellulose fibers and / or microfibrillated lignocellulose fibers.
  • “Chemically modified cellulose nanofiber” means chemically modified CNF and / or chemically modified ligno CNF, and is also referred to as “chemically modified CNF”.
  • an alkanoyl group such as an acetyl group is introduced instead of the hydrogen atom of the hydroxyl group of the sugar chain constituting cellulose (that is, the hydroxyl group is chemically modified).
  • the hydroxyl groups of the cellulose molecules are blocked, the hydrogen bonding force of the cellulose molecules is suppressed, and the crystal structure originally possessed by the cellulose fibers is retained at a specific ratio. It is a feature.
  • the present invention is characterized in that such a chemically modified CNF and a resin having a specific SP value are combined (composited).
  • Such a feature of the present invention is that the SP value and the cellulose fiber or lignocellulose are changed by changing the degree of chemical modification of the sugar chain on the surface of the cellulose fiber or lignocellulose fiber (for example, substitution with an acetyl group or the like).
  • the knowledge that the degree of crystallinity originally possessed can be controlled, and the chemically modified CNF in which the SP value and the degree of crystallinity are controlled in this way, cellulose having a specific SP value is compared to the resin This is based on the result of obtaining knowledge such as improved compatibility.
  • the present invention relates to a fiber reinforced resin composition containing the following chemically modified CNF and a thermoplastic resin, and a method for producing the same.
  • the chemically modified cellulose nanofiber and the thermoplastic resin have the following conditions:
  • the ratio R (SP cnf / SP pol ) of the solubility parameter (SP cnf ) of (A) chemically modified cellulose nanofiber to the solubility parameter (SP pol ) of (a) (B) thermoplastic resin is in the range of 0.87 to 1.88.
  • Item 2 The fiber-reinforced resin composition according to item 1, wherein the ratio R (SP cnf / SP pol ) of the condition (a) is in the range of 1.03 to 1.88.
  • Item 3 The fiber-reinforced resin composition according to Item 1 or 2, wherein the crystallinity of the chemically modified cellulose nanofiber (A) in the condition (b) is 55.6% or more.
  • Item 4. The fiber-reinforced resin composition according to any one of Items 1 to 3, wherein (A) the chemically modified cellulose nanofiber is a cellulose nanofiber in which a hydroxyl group of a sugar chain constituting the cellulose nanofiber is modified with an alkanoyl group. .
  • thermoplastic resin is at least one resin selected from the group consisting of polyamide, polyacetal, polypropylene, maleic anhydride-modified polypropylene, polylactic acid, polyethylene, polystyrene, and ABS resin.
  • the fiber reinforced resin composition in any one.
  • thermoplastic resin is at least one resin selected from the group consisting of polyamide, polyacetal, and polylactic acid, the ratio R of the condition (a) is 1.03-1.32, and the chemical modification of (b) Item 5.
  • the fiber-reinforced resin composition according to any one of Items 1 to 4, wherein the crystallinity of the cellulose nanofiber is 55.6% or more.
  • thermoplastic resin (B) is at least one resin selected from the group consisting of polypropylene, maleic anhydride-modified polypropylene, polyethylene and polystyrene, and the ratio R in the condition (a) is 1.21 to 1.88, Item 5.
  • Item 8 The fiber-reinforced resin composition according to any one of Items 1 to 7, wherein the (A) chemically modified cellulose nanofiber is a cellulose nanofiber in which a hydroxyl group of a sugar chain constituting the cellulose nanofiber is modified with an acetyl group. .
  • Item 9 The fiber-reinforced resin composition according to any one of Items 1 to 8, wherein the chemically modified cellulose nanofiber and cellulose of the cellulose nanofiber are lignocellulose.
  • a method for producing a fiber-reinforced resin composition containing chemically modified cellulose nanofibers and (B) a thermoplastic resin the following steps: (1) The following conditions: The ratio R (SP cnf / SP pol ) of the solubility parameter (SP cnf ) of (A) chemically modified cellulose nanofiber to the solubility parameter (SP pol ) of (a) (B) thermoplastic resin is in the range of 0.87 to 1.88.
  • thermoplastic resin A method for producing a fiber-reinforced resin composition containing chemically modified cellulose nanofibers and (B) a thermoplastic resin, the following steps: (1) The following conditions: The ratio R (SP cnf / SP pol ) of the solubility parameter (SP cnf ) of (A) chemically modified cellulose nanofiber to the solubility parameter (SP pol ) of (a) (B) thermoplastic resin is in the range of 0.87 to 1.88.
  • thermoplastic resin to be (A) chemically modified cellulose nanofiber after defibration that satisfies the crystallinity of the chemically modified cellulose nanofiber of 42.7% or more Process of selecting, (2) a step of blending (A1) chemically modified pulp selected in step (1) and (B) a thermoplastic resin; and (3) (A1) chemically modified pulp and (B) thermoplastic resin blended in the above step (2) are kneaded, and at the same time, (A1) chemically modified pulp is defibrated, (A) chemically modified cellulose nanofiber And (B) a method for producing a resin composition containing a thermoplastic resin.
  • a method for producing a fiber-reinforced resin composition containing chemically modified cellulose nanofibers and (B) a thermoplastic resin the following steps: (1) (A1) a process of selecting chemically modified pulp and (B) thermoplastic resin, (2) a step of blending (A1) chemically modified pulp selected in step (1) and (B) a thermoplastic resin; and (3) (A1) chemically modified pulp and (B) thermoplastic resin blended in the above step (2) are kneaded, and at the same time, (A1) chemically modified pulp is defibrated, (A) chemically modified cellulose nanofiber And (B) obtaining a resin composition containing a thermoplastic resin, The (A) chemically modified cellulose nanofiber and the (B) thermoplastic resin are dissolved under the following conditions: (a) (B) the dissolution parameter (SP pol ) of the thermoplastic resin (A) The ratio R (SP cnf / SP pol ) of the parameter (SP cnf ) is in the range of 0.87
  • Item 13 The production method according to any one of Items 10 to 12, wherein the ratio R (SP cnf / SP pol ) of (a) is in the range of 1.03 to 1.82.
  • Item 14 Acetyl having a crystallinity of 42.7% or more, a hydroxyl group of a sugar chain substituted with an acetyl group, a substitution degree of 0.29 to 2.52, and a solubility parameter (SP cnf ) of 9.9 to 15 Cellulose nanofiber.
  • Item 15 A fiber-reinforced resin composition comprising (A2) acetylated cellulose nanofiber according to Item 14 and (B) a thermoplastic resin.
  • Item 16 The fiber-reinforced resin composition according to Item 15, wherein a content of the (A2) acetylated cellulose nanofibers is 0.1 to 30 parts by mass with respect to 100 parts by mass of the (B) thermoplastic resin.
  • thermoplastic resin is at least one resin selected from the group consisting of polyamide resin, polyacetal resin, polypropylene, maleic anhydride-modified polypropylene, polylactic acid, polyethylene, polystyrene, and ABS resin. 16. The fiber reinforced resin composition according to 16.
  • Item 18 The fiber-reinforced resin composition according to Item 15 or 16, wherein the acetylated cellulose nanofiber is an acetylated lignocellulose nanofiber.
  • a method for producing a fiber-reinforced resin composition comprising (A2) acetylated cellulose nanofibers and (B) a thermoplastic resin, the following steps: (1) (A3) Kneaded (A4) fiber assembly containing acetylated cellulose and (B) thermoplastic resin, and (A3) acetylated cellulose at the same time, (A2) acetylated cellulose nanofibers and (B) including a step of obtaining a resin composition containing a thermoplastic resin,
  • the crystallinity of the (A2) acetylated cellulose nanofiber is 42.7% or more, the hydroxyl group of the sugar chain is substituted with an acetyl group, the degree of substitution is 0.29 to 2.52, and the solubility parameter (SP cnf ) is A production method characterized by 9.9-15.
  • the hydroxyl group on the surface of the sugar chain in which the chemically modified CNF in the composition constitutes CNF is modified with, for example, an alkanoyl group such as an acetyl group (that is, chemically modified).
  • an alkanoyl group such as an acetyl group (that is, chemically modified).
  • the fiber-reinforced resin composition of the present invention is composed of a suitable combination of this matrix component (resin) and chemically modified CNF, the affinity between the chemically modified CNF in the resin and the resin is high, Dispersibility of chemically modified CNF is good. As a result, the fiber reinforced resin composition of the present invention exhibits optimum strength.
  • the fiber reinforced resin of the present invention when the fiber reinforced resin composition of the present invention containing 10% by mass of chemically modified CNF is compared with the fiber reinforced resin composition containing the same amount of unmodified CNF in the same resin, the fiber reinforced resin of the present invention is compared.
  • the modulus of elasticity of the composition is not present when the ratio R (SP cnf / SP pol ) of the solubility parameter (SP cnf ) of the chemically modified CNF to the solubility parameter (SP pol ) of the thermoplastic resin is in the range of 0.87 to 1.88. It is 1.05 times or more the elastic modulus of the fiber reinforced resin composition containing the modified CNF, and the chemically modified CNF and the resin can be designed so as to exhibit further optimum strength within the range of this ratio R. .
  • the fiber-reinforced resin composition of the present invention can be produced by kneading a chemically modified CNF and a resin.
  • a chemically modified CNF such as pulp
  • the fiber diameter is reduced in the process.
  • a tens to hundreds of ⁇ m chemically modified (for example, acetylated) pulp is easily defibrated to a chemically modified CNF having a fiber diameter of several tens to several hundreds of nm simultaneously with kneading, and the fiber reinforced resin composition of the present invention Things can be easily manufactured.
  • the chemically modified CNF used in the present invention a chemically modified CNF which is chemically modified with an inexpensive chemical modifier such as an acetylating agent can be used. And since the fiber reinforced resin composition of this invention can also be easily manufactured by the combination with optimal resin, it is low-cost and practical use is easy.
  • the fiber-reinforced resin composition of the present invention has good properties because the dispersibility of the chemically modified CNF in the resin is good.
  • an optimum amount for each resin depends on how many of the hydroxyl groups present in cellulose or lignocellulose are chemically modified (for example, replaced with a modifying group such as an acetyl group).
  • a chemically modified CNF such as acetylated CNF having a solubility parameter (SP) value can be easily selected and used for the production of a fiber reinforced resin composition.
  • the dispersibility of the chemically modified CNF in the resin is high by maintaining the crystallinity of the cellulose at about 42% or more and setting the appropriate solubility parameter (SP) value. Since the reinforcing effect on the resin is improved, a fiber-reinforced composite material having excellent mechanical properties can be obtained.
  • SP solubility parameter
  • polyamide 6 PA6
  • polyacetal polyoxymethylene, POM
  • polypropylene PP
  • maleic anhydride modified polypropylene MAPP
  • matrix matrix
  • chemical modification for example, Acetyl etc.
  • the fiber reinforced resin composition of the present invention containing a resin and chemically modified CNF has a higher flexural modulus than the resin-only embodiment.
  • PA6-chemically modified CNF is 2.2 times or more
  • POM-chemically modified CNF is 2.1 times or more
  • PP-chemically modified CNF is 1.2 times or more
  • MAPP-chemically modified CNF is 1.5 times or more It becomes the above bending elastic modulus.
  • the flexural modulus of the fiber reinforced resin composition containing the resin of the present invention and the chemically modified CNF is higher than that of the unmodified CNF-containing fiber reinforced resin composition.
  • the flexural modulus of the fiber reinforced resin composition containing the resin of the present invention and the chemically modified CNF is higher than that of the unmodified CNF-containing fiber reinforced resin composition.
  • it when containing 10% by mass of chemically modified CNF, it is at least 1.1 times or more.
  • PA6-chemically modified CNF is 1.4 times or more
  • POM-chemically modified CNF is 1.5 times or more
  • PP-chemically modified CNF is 1.1 times or more
  • MAPP-chemically modified CNF is 1.1 times or more
  • PS-chemically modified CNF is 1.1 times or more
  • PE-chemically modified CNF is 1.3 times.
  • the magnification value of this bending elastic modulus is a value obtained by rounding off the second decimal place.
  • the fiber reinforced resin composition has a high resin reinforcing effect by chemically modified CNF.
  • the fiber reinforced resin composition of the present invention contains (A) chemically modified cellulose nanofiber (chemically modified CNF) and (B) thermoplastic resin,
  • the chemically modified CNF and the thermoplastic resin satisfy the following conditions: (a) the ratio R (SP cnf / SP pol ) of the (A) chemically modified CNF solubility parameter (SP cnf ) to the thermoplastic resin solubility parameter (SP pol ) is in the range of 0.87 to 1.88; and (b) (A) The degree of crystallinity of the chemically modified CNF is 42.7% or more.
  • the ratio R (SP cnf / SP pol ) of (a) is preferably in the range of about 1.03 to 1.88, more preferably in the range of about 1.03 to 1.82.
  • a chemically modified CNF having an optimum solubility parameter (SP) value for each resin depending on how many of the hydroxyl groups present in the cellulose molecule are chemically modified (for example, replaced with acetyl groups or the like).
  • SP solubility parameter
  • acetylated CNF Due to the chemical modification treatment, the dispersibility of the chemically modified CNF in the resin of the fiber-reinforced resin composition of the present invention is promoted, the reinforcing effect of the chemically modified CNF on the resin is improved, and the CNF composite material having excellent mechanical properties Can be obtained.
  • the fiber reinforced resin composition of the present invention contains (A) chemically modified CNF.
  • the degree of crystallinity of chemically modified CNF is 42.7% or more.
  • Plant fibers used as raw materials for chemically modified CNF include fibers obtained from natural plant materials such as wood, bamboo, hemp, jute, kenaf, cotton, beet, agricultural waste, and cloth containing cellulose or / and lignocellulose. It is done. Examples of wood include Sitka spruce, cedar, cypress, eucalyptus, acacia, and examples of paper include, but are not limited to, deinked waste paper, corrugated waste paper, magazines, copy paper, and the like. . One kind of plant fiber may be used alone, or two or more kinds selected from these may be used.
  • Lignocellulose can also be used as a raw material for chemically modified CNF.
  • Lignocellulose is a complex hydrocarbon polymer that constitutes the cell walls of plants, and is known to be mainly composed of polysaccharide cellulose, hemicellulose, and lignin, which is an aromatic polymer.
  • Reference Example 1 Review Article Conversion of Lignocellulosic Biomass to Nanocellulose: Structure and Chemical Process HV Lee, SBA Hamid, and SK Zain, Scientific World Journal Volume 2014, Article ID 631013, 20 pages, http://dx.doi.org/ 10.1155 / 2014/631013
  • Reference example 2 New lignocellulose pretreatments using cellulose solvents: a review, Noppadon Sathitsuksanoh, Anthe George and YH Percival Zhang, J Chem Technol Biotechnol 2013; 88: 169-180
  • lignocellulose means a lignocellulose or / and lignocellulose mixture, artificially modified lignocellulose or / and lignocellulose mixture of chemical structure naturally present in plants.
  • the mixture is, for example, a lignocellulose or / and a lignocellulose mixture having chemical structures contained in various pulps obtained from natural plants and obtained by mechanically and / or chemically treating the wood.
  • Lignocellulose is not limited to lignocellulose having a chemical structure that exists in nature, and the lignin content in lignocellulose is not limited.
  • lignocellulose and lignopulp used in the present invention are interpreted as lignocellulose and lignopulp, respectively, even if the content of the lignin component is very small.
  • a fiber containing lignocellulose or a fiber aggregate containing lignocellulose can be used.
  • the fiber aggregate containing lignocellulose includes fiber aggregates containing lignocellulose of any shape in addition to plant-derived pulp, wood flour, wood chips and the like.
  • Plant-derived materials such as wood, bamboo, hemp, jute and kenaf, and agricultural residue such as bagasse, firewood and beet pomace can be used as plant raw materials.
  • These plant raw materials containing lignocellulose can be used in the form of flakes, powders, fibers, or the like.
  • the plant cell wall is mainly composed of lignocellulose.
  • cellulose microfibrils single CNF
  • cellulose microfibril bundles Cellulose fine fibers (cellulose microfibril bundles) are formed.
  • hemicellulose exists in the space
  • a typical example of a raw material for producing plant fiber or lignocellulose is pulp. Pulp is obtained by processing a plant-derived material such as wood chemically or / and mechanically and removing fibers contained therein. This is because the content of hemicellulose and lignin is lowered depending on the degree of chemical and biochemical treatment of the plant-derived material, and the fiber is mainly composed of cellulose.
  • wood for pulp production for example, Sitka spruce, cedar, cypress, eucalyptus, acacia and the like can be used.
  • waste paper such as deinked waste paper, corrugated waste paper, magazines, and copy paper can be used.
  • a raw material of the chemically modified CNF used in the fiber reinforced resin composition of the present invention one kind of plant fiber or two or more kinds of plant fibers can be used in combination.
  • fibrillated cellulose obtained by fibrillating pulp or pulp and fibrillated lignocellulose can be mentioned as preferable raw materials.
  • Pulp contains lignocellulose and is mainly composed of cellulose, hemicellulose, and lignin. Pulp can be obtained by treating plant raw materials by mechanical pulping, chemical pulping, or a combination of mechanical pulping and chemical pulping.
  • the mechanical pulping method is a method of pulping by mechanical force such as a grinder or refiner while leaving lignin.
  • the chemical pulping method is a method of pulping by adjusting the content of lignin using a chemical.
  • thermomechanical pulp TMP
  • CMP chemithermomechanical pulp
  • BCTMP bleached chemical thermomechanical pulp
  • chemimechanical pulp CMP
  • CGP chemiground pulp
  • SCP semi-chemical pulp
  • pulp produced by a sulfite method a cold soda method, a kraft method, a soda method, or the like can be used.
  • CP chemical pulp
  • SP sulfite pulp
  • AP soda pulp
  • KP kraft pulp
  • DKP dissolving kraft pulp
  • Deinked waste paper pulp, corrugated waste paper pulp, and magazine waste paper pulp mainly composed of mechanical pulp, chemical pulp, etc. can also be used as a raw material for chemically modified CNF.
  • These raw materials can be delignified or bleached as necessary to adjust the amount of lignin in the pulp.
  • various kraft pulps derived from conifers with strong fiber strength unbleached kraft pulps of conifers (NUKP), coniferous oxygen unexposed) Bleached kraft pulp (NOKP), conifer bleached kraft pulp (NBKP) is particularly preferred.
  • NUKP unbleached kraft pulps of conifers
  • NOKP coniferous oxygen unexposed
  • NNKP conifer bleached kraft pulp
  • lignin derived from plant raw materials is not completely removed and pulp produced by a pulping method in which lignin is appropriately present in the pulp can be applied without limitation.
  • a mechanical pulping method in which plant raw materials are mechanically pulped is preferable.
  • the pulp used for the production of the chemically modified CNF used in the fiber reinforced resin composition of the present invention include groundwood pulp (GP), refiner GP (RGP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP) and the like. It is preferable to use mechanical pulp (MP).
  • the content of lignin in the lignocellulosic fibers or this fiber aggregate is such that the lignin can be chemically modified in these raw materials.
  • the content of lignin is preferably about 1 to 40% by mass, more preferably about 3 to 35% by mass, and still more preferably about 5 to 35% by mass from the viewpoint of the strength of the chemically modified lignocellulose obtained and the thermal stability. .
  • the lignin content can be measured by the Klason method.
  • Lignocellulose and lignopulp are simpler in production process and have a better yield from the raw material (for example, wood) than cellulose and pulp not containing lignin. Moreover, since it can manufacture with little energy, it is advantageous from the point of cost, and it is useful as a raw material of the fiber reinforced resin composition of this invention.
  • cellulose fiber-containing materials such as pulp are defibrated.
  • a method is mentioned.
  • the defibrating method for example, an aqueous suspension or slurry of a cellulose fiber-containing material is mechanically ground by a refiner, a high-pressure homogenizer, a grinder, a uniaxial or multiaxial kneader (preferably a biaxial kneader), a bead mill or the like.
  • a method of defibration by crushing or beating can be used. You may process combining the said defibrating method as needed.
  • a known defibrating method or the like may be used as the defibrating method.
  • Chemically modified cellulose fiber-containing materials are defibrated when the resin is melted and kneaded under heating in a uniaxial or multiaxial kneader (preferably a multiaxial kneader) together with a thermoplastic resin.
  • a uniaxial or multiaxial kneader preferably a multiaxial kneader
  • a thermoplastic resin preferably a multiaxial kneader
  • the fiber-reinforced resin composition of the present invention it can be made into a nanofibrillated and can be chemically modified CNF or / and chemically modified ligno CNF in a thermoplastic resin. It is advantageous to defibrate the material in a molten thermoplastic resin.
  • CNF and MFLC are also referred to as CNF.
  • CNF is a material (for example, wood pulp) containing cellulose fibers obtained by unraveling (defibrating) the fibers to the nano-size level.
  • the average CNF fiber diameter (fiber width) is preferably about 4 to 200 nm, and the average fiber length is preferably about 5 ⁇ m or more.
  • the average value of the CNF fiber diameter is more preferably about 4 to 150 nm, and further preferably about 4 to 100 nm.
  • the preferred range and further preferred range of the average fiber length and average fiber diameter of the chemically modified CNF used in the present invention are the same as those of the CNF.
  • Fiber diameter and fiber length can be measured using a Kajaani fiber length measuring instrument manufactured by Metso.
  • the average fiber diameter (average fiber diameter) and average fiber length (average fiber length) of CNF and chemically modified CNF are measured for at least 50 or more CNF or chemically modified CNF within the field of view of the electron microscope. Obtained as an average value.
  • the object of the present invention is achieved (for example, the bending elastic modulus of the chemically modified CNF / or chemically modified ligno CNF reinforced composition is 1.1 times or more than the bending elastic modulus of the unmodified CNF / or unmodified ligno CNF reinforced composition)
  • the bending elastic modulus of the chemically modified CNF / or chemically modified ligno CNF reinforced composition is 1.1 times or more than the bending elastic modulus of the unmodified CNF / or unmodified ligno CNF reinforced composition
  • the specific surface area of the chemical modification CNF is preferably about 70 ⁇ 300m 2 / g, more preferably about 70 ⁇ 250m 2 / g, more preferably about 100 ⁇ 200m 2 / g.
  • the hydroxyl group present on the surface of the CNF is hydrophobized according to the resin used.
  • Examples of the chemically modified CNF include a hydrophobic CNF in which the hydroxyl group present on the surface of the nanofiber is hydrophobized by modification with an acyl group or an alkyl group; a silane coupling agent having an amino group, glycidyl trialkylammonium halide or the like Modified CNF in which the hydroxyl group present on the surface of the nanofiber is cation-modified by modification of halohydrin type compound; monoesterification with cyclic acid anhydride such as succinic anhydride, alkyl or alkenyl succinic anhydride, carboxyl group Modified CNF or the like in which the hydroxyl group present on the surface of the nanofiber is anion-modified can be used by modification with a silane coupling agent.
  • a silane coupling agent having an amino group, glycidyl trialkylammonium halide or the like
  • Modified CNF in which the hydroxyl group present on the surface of the nanofiber is
  • CNF alkanoyl modified CNF
  • the chemically modified CNF is more preferably CNF (lower alkanoyl modified CNF) in which the hydroxyl group of the sugar chain constituting the CNF is modified with a lower alkanoyl group.
  • the chemically modified CNF used in the present invention includes CNF in which the hydroxyl group of the sugar chain constituting CNF is modified with an acetyl group (also referred to as Ac-CNF). More preferred.
  • the chemically modified CNF can be obtained by chemically modifying the above-mentioned CNF or fibrillating a fiber assembly such as chemically modified pulp or chemically modified cellulose by a known defibrating method. Also, when preparing a composite with a resin (matrix material, described later), the resin and a fiber assembly such as chemically modified pulp or chemically modified cellulose are kneaded and microscopically dispersed in the resin by shearing force during kneading. It can also be fibrillated.
  • Chemically modified CNF is a saturated fatty acid, unsaturated carboxylic acid, monounsaturated fatty acid, diunsaturated fatty acid having a hydroxyl group (that is, a hydroxyl group of a sugar chain) present in at least one of cellulose and hemicellulose (including lignocellulose).
  • the hydroxyl group of the sugar chain of cellulose and lignocellulose is acylated with a residue (acyl group) obtained by removing the hydroxyl group from the carboxy group of the carboxylic acid.
  • saturated fatty acids examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecyl Acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid and arachidic acid are preferred.
  • unsaturated carboxylic acid acrylic acid, methacrylic acid and the like are preferable.
  • monounsaturated fatty acid crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, ricinoleic acid and the like are preferable.
  • diunsaturated fatty acid sorbic acid, linoleic acid, eicosadienoic acid and the like are preferable.
  • triunsaturated fatty acid linolenic acid, pinolenic acid, eleostearic acid and the like are preferable.
  • the tetraunsaturated fatty acid is preferably selected from stearidonic acid and arachidonic acid.
  • boseopentaenoic acid As the pentaunsaturated fatty acid, boseopentaenoic acid, eicosapentaenoic acid and the like are preferable.
  • hexaunsaturated fatty acid docosahexaenoic acid, nisic acid and the like are preferable.
  • Aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid (3,4,5-trihydroxybenzenecarboxylic acid), cinnamic acid (3-phenylprop-2-enoic acid) Etc.) are preferred.
  • dicarboxylic acid oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid and the like are preferable.
  • amino acid glycine, ⁇ -alanine, ⁇ -aminocaproic acid (6-aminohexanoic acid) and the like are preferable.
  • the chemically modified CNF used in the present invention includes a CNF in which the sugar chain hydroxyl group constituting the CNF is modified with a lower alkanoyl group (a sugar constituting the CNF).
  • CNF in which the hydroxyl group of the chain is lower alkanoylated and referred to as lower alkanoylated CNF (corresponding to CNF having a chemical structure in which the hydroxyl group of the sugar chain constituting CNF is substituted with a lower alkanoyloxy group) is preferable because it is easy to produce. .
  • Branched alkyl carboxylic acids e.g., pivalic acid, 3,5,5-trimethylhexanoic acid, etc.
  • cyclic alkane carboxylic acids cyclohexane carboxylic acid, t-butyl cyclohexane carboxylic acid, etc.
  • substituted or unsubstituted phenoxyalkyl carboxylic acids Acylated with a residue (acyl group) obtained by removing a hydroxyl group from the carboxy group of an acid (phenoxyacetic acid, 1,1,3,3-tetramethylbutylphenoxyacetic acid, bornanephenoxyacetic acid, bornanephenoxyhexanoic acid, etc.)
  • CNF and ligno-CNF can be advantageously used because they have a strong reinforcing effect even with respect to resins (in particular, resins with low olefinic SP values such as PP and PE).
  • the chemically modified CNF used in the present invention includes CNF in which the hydroxyl group of the sugar chain constituting CNF is modified with an acetyl group (the sugar chain constituting CNF).
  • Chemically modified CNF having a hydroxyl group acetylated, also referred to as Ac-CNF) is more preferred.
  • the chemically modified CNF used in the present invention is a state in which the hydroxyl structure (sugar chain hydroxyl group) of cellulose and hemicellulose in the raw material is retained as much as possible in the crystal structure of the cellulose present in the raw cellulose or / and lignocellulose fiber. And is preferably acylated. That is, the chemically modified CNF used in the present invention is originally a hydroxyl group present on the surface of the raw fiber so as not to break the cellulose crystal structure present in the raw cellulose or / and lignocellulose fiber, such as a hydroxyl group of cellulose, hemicellulose. It is preferable to acylate a hydroxyl group or the like. Through the chemical modification treatment, chemically modified CNF with excellent mechanical properties inherent to CNF can be obtained, and the dispersibility of chemically modified CNF in the resin is promoted, improving the effect of chemically modified CNF on the resin. To do.
  • the raw material is suspended in an anhydrous aprotic polar solvent capable of swelling the raw fiber (CNF or pulp), for example, N-methylpyrrolidone, N, N-dimethylformamide, and the anhydrous carboxylic acid is added.
  • an acid chloride preferably in the presence of a base.
  • a base pyridine, N, N-dimethylaniline, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the like are preferable.
  • This acylation reaction is preferably performed with stirring at room temperature to 100 ° C., for example.
  • the degree of acylation of the sugar chain hydroxyl group of the chemically modified CNF used in the present invention (also referred to as DS, sometimes referred to as substitution degree or modification degree) will be described.
  • the acylation degree (modification degree, DS) at the sugar chain hydroxyl group of chemically modified CNF obtained by acylation reaction is preferably about 0.05 to 2.5, more preferably about 0.1 to 1.7, and further preferably about 0.15 to 1.5.
  • the maximum value of the degree of substitution (DS) depends on the sugar chain hydroxyl amount of CNF, but is about 2.7.
  • a chemically modified CNF having an appropriate degree of crystallinity and SP value can be obtained.
  • the preferred DS is 0.29 to 2.52, and with a DS in that range, the crystallinity can be kept at about 42.7% or more.
  • the degree of substitution can be analyzed by various analysis methods such as elemental analysis, neutralization titration method, FT-IR, two-dimensional NMR ( 1 H and 13 C-NMR).
  • Crystallinity of chemically modified CNF The crystallinity of chemically modified CNF contained in the fiber reinforced resin composition is about 42.7% or more.
  • the chemically modified CNF has a high crystallinity of about 42.7% or more, and the crystal type thereof preferably has a cellulose type I crystal.
  • the “crystallinity” is an abundance ratio of crystals (mainly cellulose I-type crystals) in the total cellulose.
  • the crystallinity of the chemically modified CNF (preferably cellulose I type crystals) is preferably about 50% or more, more preferably about 55% or more, more preferably about 55.6% or more, more preferably about 60% or more, Still more preferably, about 69.5% or more.
  • the upper limit of crystallinity of chemically modified CNF is generally about 80%. Chemically modified CNF maintains the crystal structure of cellulose type I and exhibits properties such as high strength and low thermal expansion.
  • the cellulose type I crystal structure is, for example, as described in “The Cellulose Dictionary”, the first edition of the first edition, pages 81-86, or pages 93-99, published by Asakura Shoten. Cellulose type I crystal structure.
  • cellulose fibers of, for example, cellulose II, III, and IV type are derived from cellulose having cellulose I type crystal structure.
  • the I-type crystal structure has a higher crystal elastic modulus than other structures.
  • the crystal structure is an I-type crystal
  • a composite material having a low coefficient of linear expansion and a high elastic modulus can be obtained when a composite material of CNF and resin (matrix material) is used.
  • the degree of polymerization of cellulose is about 500 to 10,000 for natural cellulose and about 200 to 800 for regenerated cellulose.
  • Cellulose is a bundle of several celluloses linearly stretched by ⁇ -1,4 bonds, fixed by hydrogen bonds within or between molecules to form crystals that are extended chains. . It has been clarified by X-ray diffraction and solid state NMR analysis that many crystal forms exist in cellulose crystals, but the natural cellulose crystal form is only type I. From the X-ray diffraction and the like, it is estimated that the ratio of the crystalline region in cellulose is about 50 to 60% for wood pulp and about 70% higher for bacterial cellulose. Cellulose has not only a high elastic modulus due to being an extended chain crystal, but also exhibits a strength five times that of steel and a linear thermal expansion coefficient of 1/50 or less that of glass.
  • the fiber reinforced resin composition of the present invention contains (B) a thermoplastic resin in addition to (A) the chemically modified CNF. Using this fiber reinforced resin composition, a molded article having excellent strength can be produced.
  • the fiber-reinforced resin composition of the present invention contains (A) an acylated cellulose nanofiber (acylated CNF) as the chemically modified CNF, and is preferably a lower alkanoyl cellulose nanofiber (lower alkanoyl) from the viewpoint of production method and cost.
  • CNF acylated cellulose nanofiber
  • acetylated cellulose nanofiber acetylated CNF
  • Thermoplastic resins include polyethylene (PE), polypropylene (PP), polyvinyl chloride, polystyrene, polyvinylidene chloride, fluororesin, (meth) acrylic resin, polyamide resin (nylon resin, PA), polyester, polylactic acid resin Polylactic acid and polyester copolymer resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate, polyphenylene oxide, (thermoplastic) polyurethane, polyacetal (POM), vinyl ether resin, polysulfone resin, cellulose resin (for example, A thermoplastic resin such as triacetylated cellulose or diacetylated cellulose can be preferably used.
  • Homopolymers or copolymers such as fluororesin tetrachloroethylene, hexpropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and perfluoroalkyl vinyl ether can be preferably used.
  • (meth) acrylic resins (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylic acid esters, (meth) acrylamides can be preferably used.
  • (meth) acryl means “acryl and / or methacryl”.
  • (Meth) acrylic acid includes acrylic acid or methacrylic acid.
  • (Meth) acrylonitrile includes acrylonitrile or methacrylonitrile.
  • (meth) acrylic acid esters examples include (meth) acrylic acid alkyl esters, (meth) acrylic acid monomers having a cycloalkyl group, and (meth) acrylic acid alkoxyalkyl esters.
  • Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) Examples include benzyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, hydroxyethyl (meth) acrylate, and the like.
  • Examples of the (meth) acrylic acid monomer having a cycloalkyl group include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.
  • (meth) acrylic acid alkoxyalkyl esters examples include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and 2-butoxyethyl (meth) acrylate.
  • (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -N-substituted (meth) acrylamides such as isopropyl (meth) acrylamide and Nt-octyl (meth) acrylamide, and copolymers of these (meth) acrylic resins.
  • Polyester aromatic polyester, aliphatic polyester, unsaturated polyester and the like can be preferably used.
  • aromatic polyester examples include copolymers of diols described later such as ethylene glycol, propylene glycol, and 1,4-butanediol with aromatic dicarboxylic acids such as terephthalic acid.
  • aliphatic polyester examples include copolymers of diols described below and aliphatic dicarboxylic acids such as succinic acid and valeric acid, homopolymers or copolymers of hydroxycarboxylic acids such as glycolic acid and lactic acid, and diols described below. And copolymers of aliphatic dicarboxylic acids and the above hydroxycarboxylic acids.
  • unsaturated polyester examples include diols described later, unsaturated dicarboxylic acids such as maleic anhydride, and copolymers with vinyl monomers such as styrene as necessary.
  • a reaction product of polycarbonate bisphenol A or its derivative bisphenol and phosgene or phenyl dicarbonate can be preferably used.
  • a copolymer such as polysulfone resin 4,4′-dichlorodiphenylsulfone or bisphenol A can be preferably used.
  • Copolymers such as polyphenylene sulfide p-dichlorobenzene and sodium sulfide can be preferably used.
  • a copolymer of polyurethane diisocyanates and diols can be preferably used.
  • Diisocyanates include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, 2,4-tolylene diisocyanate, 2,6- Examples include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, and the like.
  • Diols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Relatively low molecular weight diols such as 1,6-hexanediol, neopentyl glycol, diethylene glycol, trimethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexanedimethanol, polyester diol, poly Examples include ether diol and polycarbonate diol.
  • Amide resin Nylon 66 (polyamide 66, PA66), nylon 6 (polyamide 6, PA6), nylon 11 (polyamide 11, PA11), nylon 12 (polyamide 12, PA12), nylon 46 (polyamide 46, PA46), nylon 610 (polyamide 610) PA610), nylon 612 (polyamide 612, PA612), and other aliphatic amide resins, aromatic diamines such as phenylene diamine, aromatic dicarboxylic acids such as terephthaloyl chloride and isophthaloyl chloride, or derivatives thereof. It can be preferably used.
  • Polymers and copolymers such as polyacetal trioxane, formaldehyde, and ethylene oxide can be preferably used.
  • thermoplastic resins may be used alone or as a mixed resin of two or more.
  • thermoplastic resins in terms of excellent mechanical properties, heat resistance, surface smoothness and appearance, polyamide, polyacetal, polypropylene, maleic anhydride modified polypropylene, polyethylene, polylactic acid, polylactic acid and polyester copolymer resin, At least one resin selected from the group consisting of ABS resin and polystyrene is preferred.
  • Polyamide resin (PA) having a highly polar amide bond in the molecular structure has high affinity with cellulosic materials, so PA6 (a ring-opening polymer of ⁇ -caprolactam), PA66 (polyhexamethylene adipone) Amide), PA11 (polyamide obtained by ring-opening polycondensation of undecane lactam), PA12 (polyamide obtained by ring-opening polycondensation of lauryl lactam), and polyamide copolymer resins are preferably used.
  • PA6 a ring-opening polymer of ⁇ -caprolactam
  • PA66 polyhexamethylene adipone Amide
  • PA11 polyamide obtained by ring-opening polycondensation of undecane lactam
  • PA12 polyamide obtained by ring-opening polycondensation of lauryl lactam
  • polyamide copolymer resins are preferably used.
  • polypropylene PP
  • polyethylene PE, particularly high-density polyethylene: HDPE
  • maleic anhydride-modified polypropylene having high compatibility with these versatile polyolefins are preferable as the structural member.
  • (A) The ratio R (SP cnf / SP pol ) of the chemically modified CNF solubility parameter (SP cnf ) is about 0.87 to 1.88, preferably in the range of 1.03 to 1.88, more preferably about 1.03 to 1.82. It is a range.
  • polyamide (PA), polyacetal (POM), polylactic acid (PLA) or a mixed resin thereof can be suitably used as the (B) thermoplastic resin, and in this case, the ratio R ( SP cnf / SP pol ) is preferably about 1.04 to 1.32, and the crystallinity of the chemically modified CNF is preferably about 69.5% or more.
  • thermoplastic resin having a lower polarity than the thermoplastic resin for example, polypropylene (PP), polyethylene (PE), maleic anhydride modified polypropylene (MAPP) and polystyrene (PS)
  • PP polypropylene
  • PE polyethylene
  • MAPP maleic anhydride modified polypropylene
  • PS polystyrene
  • the ratio R (SP cnf / SP pol ) between the SP cnf of the chemically modified CNF and the SP pol of the thermoplastic resin is preferably about 1.21 to 1.88, more preferably 1.21 to 1.82, and the crystal of the chemically modified CNF
  • the degree of conversion is preferably 42.7% or more.
  • the general-purpose (B) thermoplastic resin includes, for example, olefin resins such as polypropylene (PP) and polyethylene (PE), and modified polyolefins having good compatibility with these olefin resins, for example, It is preferable to use maleic anhydride-modified polypropylene (MAPP).
  • MAPP maleic anhydride-modified polypropylene
  • the ratio R (SP cnf / SP pol ) between SP cnf of the chemically modified CNF and SP pol of the thermoplastic resin is about 1.21 to 1.88, More preferably, it is preferably about 1.21 to 1.82, and the crystallinity of the chemically modified CNF is preferably about 42.7% or more.
  • the SP value of acetylated cellulose obtained by the above linear approximation was considered to be a reasonable value because it was within ⁇ 10% of the calculated value obtained by the Fedors calculation method.
  • lignopulp 150-1 As an example of lignopulp, the composition of lignopulp 150-1 (GP150-1) obtained by digesting groundwood pulp (GP) for 1 hour at 150 ° C. is roughly composed of cellulose (Cel): 66%, hemicellulose (molar ratio) HCel): 12% (mannan (Man): 7% and xylan (Xyl): 5%) and lignin (Lig): 22%) will be described as an example.
  • This lignin is assumed to consist only of ⁇ -O-4 type lignin in the present invention. When this is acetylated, it becomes acetylated lignin, and the maximum DS of lignopulp is 2.73. This lignin contains two hydroxyl groups and the lignin has a maximum DS of 2.
  • lignopulp 150-3 obtained by digesting ground pulp (GP) at 150 ° C. for 3 hours, cellulose containing 3 hydroxyl groups and hemicellulose were 87.4% (mass%), and lignin containing 2 hydroxyl groups were Since it is 12.6% (mass%), the maximum DS of lignopulp is 2.87.
  • lignopulp 150-1: cooking at 150 ° C. for 1 hour
  • LP lignopulp
  • the DS value (0.88) is based on cellulose contained in lignopulp, and the acetyl content (g / mol) is 0.88 mol / 162 g (g / mol of cellulose).
  • SP cel SP value of cellulose
  • Sp celac3 SP value of cellulose triacetate was determined using SP cel (SP value of cellulose, literature value) and SP celac2 (SP value of cellulose diacetate, literature value).
  • SP xy SP value of xylan
  • SP lig SP value of lignin
  • SP xylac SP value of xylan diacetate
  • SP ligac SP value of lignin diacetate
  • lignocellulose having a lignin content of less than 1% by mass has virtually no problem even if lignin is ignored (calculated assuming a lignin content of 0).
  • the SP value of lignocellulose whose total content of cellulose and glucomannan is 92 mass% or more and whose lignin content is 0.5 mass% or less
  • the SP value of acetylated lignocellulose, the components of this lignocellulose are: Assuming that it is composed entirely of cellulose, the SP can be calculated using the above-mentioned cellulose SP literature values and cellulose diacetate SP literature values.
  • the optimum range of the solubility parameter (SP cnf ) of the chemically modified CNF depends on the solubility parameter (SP pol ) of the resin (matrix) combined with the chemically modified CNF, but is preferably about 9.9-15.
  • the optimum range of the solubility parameter (SP cnf ) of the chemically modified CNF is more preferably 11.5 to 15 for a hydrophilic resin having a resin (matrix) solubility parameter (SP pol ) of about 11 to 13.
  • the optimum range of the solubility parameter (SP cnf ) of chemically modified CNF is about 9.9 to 15 for a hydrophobic resin having a solubility parameter (SP pol ) of the resin (matrix) of about 8 to 9.
  • the solubility parameter (SP cnf ) of the chemically modified CNF is preferably determined depending on the solubility parameter SP pol of the resin (matrix), and the solubility parameter (SP cnf ) of the chemically modified CNF with respect to the solubility parameter (SP pol ) of the resin ) Ratio R (SP cnf / SP pol ) is preferably in the range of about 0.87 to 1.88.
  • the ratio R (SP cnf / SP pol ) is more preferably in the range of about 1.03 to 1.88, and further preferably in the range of about 1.03 to 1.82.
  • the ratio R is within this range, the dispersibility of the chemically modified CNF in the resin (matrix) is improved, and the strength of the resin composition containing the chemically modified CNF is improved.
  • thermoplastic resin (SP pol ) Solubility parameter of thermoplastic resin (SP pol ) Regarding the solubility parameter (SP pol ) value of the thermoplastic resin, it is possible to refer to the SP value described by Fumio Ide, “Practical Polymer Alloy Design” (Industry Research Committee First Edition, issued on September 1, 1996). SP values of typical thermoplastic resins are as follows.
  • the average value in this numerical range is used as the SP value of the material in the present invention.
  • the average value 12.2 (rounded to the first decimal place) of 11.6 and 12.7 was used as the SP value for nylon 6 (PA6).
  • thermoplastic resin used for the fiber reinforced resin composite depends on the application of the fiber reinforced composite using the thermoplastic resin.
  • range of the solubility parameter (SP pol ) of the thermoplastic resin is unique to the resin.
  • solubility parameter (SP pol ) of polyamides frequently used in engine covers, automobile parts such as manifolds, and home appliance parts is about 12 to 13
  • the SP pol of nylon 6 (PA6) is 12.2.
  • the SP pol of polyacetal (POM) which is frequently used for the exterior, casing, and mechanical parts of electrical and electronic products that require strength, is about 11.1.
  • the SP pol of maleic anhydride-modified polypropylene (MAPP) used for improving dispersibility is about 8.2.
  • a chemically modified CNF having SP cnf such that the ratio R (SP cnf / SP pol ) is about 1.03 to 1.32 is selected to produce the fiber reinforced resin composition of the present invention.
  • the ratio R (SP cnf / SP pol ) must be 1.03 to 1.32. Is preferred.
  • the ratio R (SP cnf / SP pol ) Is preferably 1.21 to 1.82.
  • MAPP maleic anhydride-modified polypropylene
  • acetylated cellulose having a DS of about 0.32 to 2.52, a SP of about 15.0 to 9.9, and a crystallinity of about 42.7% or more is preferable. More preferred is acetylated cellulose having a DS of about 0.32 to 1.57, a SP of about 15.0 to 12.1, and a crystallinity of about 55.6% or more.
  • acetylated cellulose having a DS of about 0.30 to 2.02, SP of about 15.0 to 11.1, and a crystallinity of about 42.7% or more is preferable. Good bending properties can be obtained.
  • acetylated cellulose having a DS of about 0.30 to 2.02, a SP of about 15.0 to 11.0, and a crystallinity of about 42.7% or more is preferable. Good bending properties can be obtained.
  • polar materials such as polyamide (PA6) and polyacetal (POM)
  • PA6 polyamide
  • POM polyacetal
  • a material having the highest bending characteristics can be obtained by maintaining the strength of the cellulose fiber at about% or higher, that is, by maintaining the strength of the cellulose fiber at a high level.
  • the fiber reinforced resin composition of the present invention contains (A) a chemically modified CNF and (B) a thermoplastic resin.
  • the content of (A) chemically modified CNF in the fiber reinforced resin composition is preferably about 1 to 300 parts by weight, more preferably about 1 to 200 parts by weight, with respect to 100 parts by weight of the thermoplastic resin (B). About 100 parts by mass is more preferable.
  • the content ratio of (A) chemically modified CNF (preferably acetylated CNF) in the fiber reinforced resin composition is preferably about 0.1 to 30 parts by mass.
  • thermoplastic resin A fiber-reinforced resin composition excellent in mechanical properties, heat resistance, surface smoothness and appearance can be obtained by blending (B) thermoplastic resin with (A) chemically modified CNF.
  • (A) Chemically modified CNF like plant fibers, is lightweight, has strength, and has a low linear thermal expansion coefficient. Even if the composition contains (A) chemically modified CNF, the composition has the property (thermoplasticity) that softens when heated and becomes easy to mold, and becomes hard again when cooled (thermoplasticity), as in general-purpose plastics. Can be expressed.
  • the fiber-reinforced resin composition of the present invention includes, for example, a compatibilizing agent; a surfactant; a starch, a polysaccharide such as alginic acid, gelatin, glue, Natural proteins such as casein; inorganic compounds such as tannins, zeolites, ceramics, metal powders; colorants; plasticizers; fragrances; pigments; flow regulators; leveling agents; conductive agents; antistatic agents; An additive such as a deodorant may be blended. As a content ratio of an arbitrary additive, it may be appropriately contained within a range not impairing the effects of the present invention.
  • the fiber reinforced resin composition of the present invention includes (A) chemically modified CNF, (A) the chemically modified CNFs can be prevented from aggregating due to hydrogen bonding. Therefore, in the mixing process of (A) chemically modified CNF and thermoplastic resin (matrix material), aggregation of (A) chemically modified CNF is suppressed, and (A) chemically modified CNF is uniformly dispersed in the thermoplastic resin. Thus, a fiber reinforced resin composition containing (A) chemically modified CNF having excellent mechanical properties, heat resistance, surface smoothness and appearance can be obtained.
  • the fiber reinforced resin composition containing (A) chemically modified CNF of the present invention can improve the mechanical properties in a balanced manner, such as static properties such as bending tests and dynamic properties such as impact tests.
  • the chemically modified CNF contained in the fiber reinforced resin composition is preferably (A2) acetylated cellulose nanofiber (acetylated CNF).
  • Acetylated CNF has a crystallinity of about 42.7% or more, the hydroxyl group of the sugar chain is substituted with an acetyl group, the degree of substitution is about 0.29 to 2.52, and the solubility parameter (SP cnf ) is 9.9 to 15 It is preferable that it is a grade.
  • acetylated CNF has a crystallinity of about 42.7% or higher and a degree of substitution (DS) of 0.29. It is preferable that the solubility parameter (SP cnf ) is about 9.9 to 15.0.
  • acetylated CNF has a crystallinity of about 55.6% or higher, a degree of substitution (DS) of about 0.29 to 1.84, and a solubility parameter (SP cnf ) of 11.5 to It is preferably about 15.0.
  • the acetylated CNF can withstand melt kneading with a high melting point resin of 200 ° C. or higher and repeated melt kneading.
  • the crystallinity is about 65% or more, and the degree of substitution (DS) is about 0.4 to 1.2.
  • chemically modified CNF having a solubility parameter (SP cnf ) of about 12-15 .
  • SP cnf solubility parameter
  • NBKP a raw material pulp from which the chemically modified CNF can be prepared.
  • the degree of crystallinity is about 40% or more
  • the degree of substitution (DS) is about 1.2 or more
  • a chemically modified CNF having a solubility parameter (SP cnf ) of about 8-12 is preferable to use.
  • SP cnf solubility parameter
  • the fiber reinforced resin composition can be produced by mixing (A) a chemically modified CNF and (B) a thermoplastic resin (matrix material). Furthermore, a molded body can be produced by molding the fiber reinforced resin composition.
  • the fiber reinforced resin composition of the present invention can be produced by kneading a chemically modified CNF and a resin, but using a kneader or the like, a chemically modified pulp (a material that becomes a chemically modified CNF) and (B) a thermoplastic resin It can also be produced by kneading and compounding them.
  • the fibrillation of the chemically modified pulp proceeds due to the shear stress during the kneading, and a uniform mixed composition of (A) the chemically modified CNF and (B) the thermoplastic resin can be obtained.
  • thermoplastic resin (B) When chemically modified CNF or chemically modified pulp and (B) thermoplastic resin are mixed, both components are mixed without heating at room temperature, and then mixed with heating. May be.
  • the mixing temperature can be adjusted according to the thermoplastic resin (B) to be used. Heating set temperature is the minimum processing temperature recommended by the thermoplastic resin supplier (225 to 240 ° C for PA6, 170 to 190 ° C for POM, 160 to 180 ° C for PP and MAPP) to 20 ° C from this recommended processing temperature A high temperature range is preferred. By setting the mixing temperature within this temperature range, (A) chemically modified CNF or chemically modified pulp and (B) thermoplastic resin can be uniformly mixed.
  • the mixing is preferably performed by a kneading method such as a bench roll, a Banbury mixer, a kneader, or a planetary mixer, a mixing method using a stirring blade, a mixing method using a revolving / spinning type stirrer, or the like.
  • a kneading method such as a bench roll, a Banbury mixer, a kneader, or a planetary mixer, a mixing method using a stirring blade, a mixing method using a revolving / spinning type stirrer, or the like.
  • chemically modified CNF (acetylated CNF, etc.) having an optimum SP value for each resin depending on how many of the hydroxyl groups present in the cellulose molecule are chemically modified (replaced with acetyl groups, etc.)
  • acetylated CNF etc.
  • the degree of crystallinity of cellulose is maintained at about 42% or more, and by making it an appropriate SP value, the dispersibility of the cellulose in the resin is high, and the reinforcing effect of the cellulose resin is improved.
  • CNF composites with excellent mechanical properties can be obtained.
  • the kneading process and the mixing process are also referred to as “composite”.
  • the fiber reinforced resin composition contains (A) a chemically modified CNF and (B) a thermoplastic resin, and the following steps: (1) The following conditions: (a) the ratio R (SP cnf / SP pol ) of the (A) chemically modified CNF solubility parameter (SP cnf ) to the thermoplastic resin solubility parameter (SP pol ) is in the range of 0.87 to 1.88; and (b) (A) a step of selecting a chemically modified CNF and (B) a thermoplastic resin that satisfy the crystallinity of the chemically modified CNF of 42.7% or more, (2) a step of blending (A) the chemically modified CNF selected in the step (1) and (B) a thermoplastic resin, and (3) The method includes a step of kneading (A) the chemically modified CNF and (B) the thermoplastic resin blended in the step (2) to obtain a resin composition.
  • the ratio R (SP cnf / SP pol ) of (a) is preferably in the range of about 1.03 to 1.88, and more preferably in the range of about 1.03 to 1.82.
  • CNF in various states is chemically modified to enable compounding with a thermoplastic resin.
  • the fiber reinforced resin composition contains (A) a chemically modified CNF and (B) a thermoplastic resin, and the following steps: (1) The following conditions: (a) the ratio R (SP cnf / SP pol ) of the (A) chemically modified CNF solubility parameter (SP cnf ) to the thermoplastic resin solubility parameter (SP pol ) is in the range of 0.87 to 1.88; and (b) a step of selecting (A) chemically modified pulp and (B) thermoplastic resin to be (A) chemically modified CNF after defibration that satisfies the degree of crystallinity of chemically modified CNF being 42.7% or more, (2) a step of blending (A1) chemically modified pulp selected in step (1) and (B) a thermoplastic resin; and (3) (A1) chemically modified pulp and (B) thermoplastic resin blended in the above step (2) are kneaded, and simultaneously (A1) chemically modified pulp is defib
  • the ratio R (SP cnf / SP pol ) of (a) is preferably in the range of about 1.03 to 1.88, and more preferably in the range of about 1.03 to 1.82.
  • the fiber reinforced resin composition contains (A) a chemically modified CNF and (B) a thermoplastic resin, and the following steps: (1) (A1) a process of selecting chemically modified pulp and (B) thermoplastic resin, (2) a step of blending (A1) chemically modified pulp selected in step (1) and (B) a thermoplastic resin; and (3) (A1) chemically modified pulp and (B) thermoplastic resin blended in the above step (2) are kneaded, and simultaneously (A1) chemically modified pulp is defibrated, (A) chemically modified CNF and ( B) including a step of obtaining a resin composition containing a thermoplastic resin,
  • the (A) chemically modified CNF and (B) thermoplastic resin are subjected to the following conditions: (A) (B) the solubility parameter (SP cnf ) of the chemically modified CNF relative to the solubility parameter (SP pol ) of the thermoplastic resin ) Ratio R (SP cnf /
  • the ratio R (SP cnf / SP pol ) of (a) is preferably in the range of about 1.03 to 1.88, and more preferably in the range of about 1.03 to 1.82.
  • the fiber reinforced resin composition contains (A2) acetylated CNF and (B) a thermoplastic resin, and the following steps: (1) (A3) Kneaded (A4) fiber assembly containing (A3) acetylated cellulose and (B) thermoplastic resin, and simultaneously (A3) deflated cellulose and (A2) acetylated CNF and (B ) Including a step of obtaining a resin composition containing a thermoplastic resin,
  • the crystallinity of the (A2) acetylated CNF is 42.7% or more, the hydroxyl group of the sugar chain is substituted with an acetyl group, the degree of substitution is 0.29 to 2.52, and the solubility parameter (SP cnf ) is 9.9 to It is characterized by being 15.
  • molding material and molded body using fiber reinforced resin composition
  • a molding material and a molded body (a molding material and a molded body) can be produced.
  • the shape of the molded body include molded bodies having various shapes such as various shapes such as a film shape, a sheet shape, a plate shape, a pellet shape, a powder shape, and a three-dimensional structure.
  • mold molding, injection molding, extrusion molding, hollow molding, foam molding and the like can be used.
  • the molded product can be used not only in the field of fiber reinforced plastics where a matrix molded product (molded product) containing plant fibers is used, but also in fields where thermoplasticity and mechanical strength (such as tensile strength) are required.
  • Interior materials, exterior materials, structural materials, etc. for transportation equipment such as automobiles, trains, ships, airplanes, etc .; casings, structural materials, internal parts, etc. for electrical appliances such as personal computers, televisions, telephones, watches; mobile communications such as mobile phones Housings such as equipment, structural materials, internal parts, etc .; portable music playback equipment, video playback equipment, printing equipment, copying equipment, sports equipment, etc .; construction materials; office equipment such as stationery, etc. It can be used effectively as a container, container, and the like.
  • the component content of pulp, chemically modified pulp, chemically modified CNF, thermoplastic resin, etc. represents mass%.
  • Test Method Test methods used in the following examples and comparative examples are as follows.
  • the DS of esterified cellulose / lignocellulose can also be determined by measuring the infrared (IR) absorption spectrum.
  • IR infrared
  • a calibration curve is created by plotting the DS values obtained by the method on the horizontal axis.
  • the DS value of the sample is obtained by measuring the intensity of the absorption band and obtaining the DS of the sample from this value and a calibration curve. In this way, DS can be measured quickly and easily.
  • NUKP softwood-derived unbleached softwood forest pulp
  • Pulp containing refiner-treated lignocellulose (ligno pulp, LP): Preparation of GP-150-1 ⁇ Conifer grinder-treated pulp (GP, source : Nippon Paper Industries Co., Ltd.), 20 g of chemical solution for 1 g of pulp (0.8M-NaOH, 0.2M-Na 2 S) was reacted in an autoclave at 150 ° C. for 1 hour to obtain a pulp slurry.
  • the obtained slurry (pulp slurry concentration 3 mass% water suspension) is passed through a single disc refiner (manufactured by Aikawa Tekko Co., Ltd.) and repeatedly refined until the Canadian Standard Freeness (CSF) value reaches 50 mL. Defibration was performed.
  • the obtained slurry (pulp slurry concentration 3 mass% water suspension) is passed through a single disc refiner (manufactured by Aikawa Tekko Co., Ltd.) and repeatedly refined until the Canadian Standard Freeness (CSF) value reaches 50 mL. Defibration was performed.
  • lignocellulose-containing pulp (ligno pulp, LP) was used.
  • the composition is shown in Table 2.
  • GP150-1-a, GP150-3 and GP150- obtained by digesting softwood-derived unbleached kraft pulp (NUKP) and groundwood pulp (GP) at 150 ° C for 1 hour or 3 hours and treating with refiner 3-a.
  • GP150-1-a was prepared in the same manner as GP150-1 described in the above-mentioned raw material (pulp) preparation section.
  • GP150-3 and GP150-3-a are digested and refined under the same processing conditions as GP150-3 described in the above section of raw material (pulp) preparation. Appears.
  • Tables 3 and 4 show the synthesis procedure of acetylated pulp and acetylated lignopulp.
  • DS was calculated by adding an alkali to acetylated NBKP and acetylated lignopulp and titrating the amount of acetic acid generated by hydrolyzing the ester bond.
  • Acetylated NBKP / resin and lignopulp / resin composite matrix resins include commercially available polyamide 6 (PA6, NYRON RESIN manufactured by Unitika Ltd.), polyacetal (POM, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) (Iupital)), polypropylene (PP, manufactured by Nippon Polypro Co., Ltd. (Novatec PP)), polypropylene modified with maleic anhydride (MAPP, manufactured by Toyobo Co., Ltd.
  • Table 5 shows the characteristics of each resin (MI: Melt Index).
  • Acetylated NBKP was complexed with PA6, POM, PP, MAPP, PLA, ABS, PS and PE.
  • Acetylated lignopulp was complexed with PA6, POM, PP and MAPP.
  • Acetylated NBKP or acetylated lignopulp and a resin were charged into a twin screw extruder and melt kneaded.
  • the melt kneading temperature was adjusted to 215 ° C for PA6, 170 ° C for POM, PP, MAPP and PLA, 195 ° C for ABS and PS, and 140 ° C for PE.
  • the Izod impact test of the obtained acetylated NBKP / resin composite material and acetylated lignopulp / resin composite material was performed.
  • a V-notch with a depth of 2 mm was inserted into the center of the test piece and struck with a hammer with a capacity of 2.75 J.
  • melt kneading was performed at a high set temperature of 215 ° C. for PA6 and 170 ° C. for POM and PP. It is considered that the temperature is high. Since cellulose is exposed under such conditions, the thermogravimetric properties of acetylated pulp are important.
  • Table 6 shows the crystallinity of some DS acetylated NBKP.
  • Table 7 shows the crystallinity of some DS acetylated lignopulps.
  • NUKP has a crystallinity of 78.3%, and the crystallinity decreased as the DS value of acetylation increased, with DS0.85 reaching 74.4%.
  • GP150-1-a had a crystallinity of 78.7%, and the crystallinity decreased with an increase in the DS value of acetylation, and the DS0.97 was 73.1%.
  • GP150-3-a had a crystallinity of 83.1%, and the crystallinity decreased with an increase in the DS value of acetylation, reaching 75.4% in DS0.95.
  • the fiber amount is described as 10% by mass for both untreated fibers and acetylated fibers for convenience.
  • Tables 8 and 9 show the mechanical properties of the PA6 matrix PA6 resin (polyamide) matrix composite.
  • Table 8 shows the characteristics of the material with NBKP added.
  • Table 9 shows the characteristics of the material to which lignopulp was added.
  • NBKP reinforced PA6 material (Table 8) showed significant improvement in flexural modulus and flexural strength.
  • DS 0.64 acetylated NBKP-added composite material (No.PA6-225) has a flexural modulus of 5430 MPa, 2.5 times that of neat PA6 (No.PA6), untreated NBKP-added PA6 (No.PA6-15) The value was 1.6 times that of.
  • DS 0.46 acetylated NBKP-added composite material (No.PA6-216) has a bending strength of 159 MPa, 1.8 times that of neat PA6 (No.PA6), untreated NBKP-added PA6 (No.PA6-15) The value was 1.4 times.
  • DS 0.41 acetylated NUKP-added composite material (No.PA6-263) has a bending strength of 154 MPa, 1.7 times that of neat PA6 (No.PA6), untreated NUKP-added PA6 (No.PA6-265) The value was 1.2 times.
  • the DS 0.57 acetylated GP (150-3) -added composite material (No.PA6-237) has a flexural modulus of 5380 MPa, and the neat PA6 (No.PA6) The value was 2.4 times that of untreated GP (150-3) added PA6 (No. PA6-266).
  • DS 0.57 acetylated GP (150-3) added composite material (No.PA6-237) has a flexural strength of 161 MPa, 1.8 times that of neat PA6 (No.PA6), untreated GP (150-3) The value was 1.3 times that of added PA6 (No. PA6-266).
  • Table 10 shows the mechanical properties of the POM matrix polyacetal resin (POM) matrix composite.
  • DS 1.17 acetylated NBKP-added composite material (No.POM-134) has a flexural modulus of 5590 MPa, 2.5 times that of neat POM (No.POM), untreated NBKP-added POM (No.POM-148) The value was 1.8 times the value.
  • DS 1.17 acetylated NBKP-added composite material (No.POM-134) has a bending strength of 129 MPa, 1.7 times that of neat POM (No.POM), untreated NBKP-added POM (No.POM-148) It was 1.4 times the value.
  • the Izod impact strength decreased about 1 kJ / m 2 with respect to the neat POM, but the decrease rate was lower than that of the untreated NBKP-added POM (No. POM-148).
  • the elastic modulus was reduced by about 10%.
  • the POM matrix resin NBKP composite material provides an acetylated cellulose composite material excellent in bending elastic modulus, bending strength and impact resistance in the region of about DS 1.17, and also has a high reinforcing effect in lignopulp.
  • Table 11 shows the mechanical properties of the PP matrix polypropylene (PP) matrix composite.
  • the degree of reinforcement by cellulose is low, as can be seen by comparing neat PP (No. PP) and untreated NBKP additive material (PP-116).
  • PP-116 untreated NBKP additive material
  • the DS 0.6 acetylated lignopulp [GP (150-3)]-added composite material (No.PP-450) exhibited a reinforcing effect with a flexural modulus of 2620 MPa and a flexural strength of 66 MPa.
  • MAPP matrix maleic anhydride modified PP (MAPP) matrix composite The mechanical properties of MAPP matrix maleic anhydride modified PP (MAPP) matrix composite are shown in Table 12.
  • DS 0.88 acetylated NBKP-added composite material (No.PP-382) has a flexural modulus of 3070 MPa, 1.8 times that of neat MAPP (No.MAPP), untreated NBKP-added MAPP (No.PP-309) It was 1.3 times the value.
  • DS 0.88 acetylated NBKP-added composite material (No.PP-382) has a bending strength of 76.3 MPa, 1.5 times that of neat MAPP (No.MAPP), untreated NBKP-added MAPP (No.PP-309) ) was 1.3 times the value.
  • the Izod impact strength was equal to or greater than neat MAPP.
  • the DS 0.56 acetylated lignopulp [GP (150-3-a)]-added composite material (No. PP-451) showed a reinforcement effect with a flexural modulus of 2730 MPa and a flexural strength of 70.2 MPa.
  • Table 13 shows the mechanical properties of PLA matrix polylactic acid (PLA) matrix composites.
  • DS 0.88 acetylated NBKP-added composite material (No.PLA-2) has a flexural modulus of 6400 MPa, 1.9 times that of neat PLA (No.PLA-5), untreated NBKP-added PLA (No.PLA- The value was 1.5 times that of 6).
  • DS 0.88 acetylated NBKP-added composite material (No.PLA-2) has a bending strength of 119 MPa, 1.1 times that of neat PLA (No.PLA-5), untreated NBKP-added PLA (No.PLA- The value was 1.2 to 1.3 times that of 6).
  • the Izod impact strength was equal to or greater than that of neat PLA.
  • Table 14 shows the mechanical properties of the ABS matrix acrylonitrile-butadiene-styrene copolymer (ABS) matrix composite.
  • DS 0.87 acetylated NBKP-added composite material (No.ABS-70) has a flexural modulus of 3780 MPa, 1.9 times that of neat ABS (No.ABS), untreated NBKP-added ABS (No.ABS-63) It was 1.4 times the value.
  • DS 0.87 acetylated NBKP-added composite material (No.ABS-70) has a bending strength of 87.3 MPa, 1.4 times that of neat ABS (No.ABS), untreated NBKP-added ABS (No.ABS-63) ) Was 1.2 times the value.
  • Table 15 shows the mechanical properties of PS matrix polystyrene (PS) matrix composites.
  • DS 0.86 acetylated NBKP-added composite material (No.PS-3) has a flexural modulus of 4110 MPa, 1.3 to 1.4 times that of neat PS (No.PS), untreated NBKP-added PS (No.PS- The value was 1.2 times that of 1).
  • Table 16 shows the mechanical properties of PE matrix polyethylene (PE) matrix composites.
  • DS 0.86 acetylated NBKP-added composite material (No.PE-184) has a flexural modulus of 2390 MPa, 2.2 times that of neat PE (No.PE), untreated NBKP-added PE (No.PE-182) The value was 1.5 times greater than that.
  • DS 0.86 acetylated NBKP-added composite material (No. PE-184) has a bending strength of 42.4 MPa, 1.8 times that of neat PE (No. PE), and untreated NBKP-added PE (No. PE-182). ) 1.4 times the value.
  • Table 17 shows the mechanical properties of the PA6 matrix PA6 resin matrix composite.
  • the material (No.PA6-242, -243, -244, -15) to which 1, 3, 5, 10% by weight of untreated NBKP was added was compared with neat PA6 (No.PA6).
  • the improvement was about 120, 310, 410, and 1230 MPa, respectively.
  • the material (No. PA6-234, -235, -236, -226) to which 1, 3, 5, 10 mass% of acetylated NBKP was added significant improvements of 310, 820, 1410, and 3120 MPa were observed, respectively.
  • Table 18 shows the mechanical properties of the POM matrix POM resin matrix composite.
  • the acetylated NBKP-added material showed a higher value than the untreated NBKP.
  • the acetylated NBKP reinforced composite material is superior to the conventional cellulose-based composite material, and can be effectively reinforced with a very small addition amount. It became clear.
  • Table 19 shows the mechanical properties of the PA6 matrix PA6 resin matrix composite.
  • Kneading was performed up to twice at 215 ° C.
  • the bending elastic modulus decreased to 5120 MPa in the first kneading (No.PA6-220-1) and 4780 MPa in the second kneading (No.PA6-220-2).
  • the decrease rate was 6.60%, which was the same as that of Toray's 30 mass% reinforced PA6 glass fiber.
  • the bending strength decreased to 154 MPa by the first kneading (No.PA6-220-1) and 150 MPa by the second kneading (No.PA6-220-2).
  • the decrease rate was 2.60%, which was smaller than the decrease rate of about 5% for Toray's 30 mass% reinforced PA6 glass fiber.
  • Izod impact strength was not significantly changed with 3.60kJ / m 2 at 3.41kJ / m 2 in the first kneading (No.PA6-220-1), 2 th kneading (No.PA6-220-2).
  • the reduction rate of 30% by mass glass fiber reinforced PA6 from Toray Industries, Inc. is about 20%.
  • the impact properties of new materials are very good and cannot be compared.
  • Table 20 shows the mechanical properties of the POM matrix POM resin matrix composite.
  • Kneading was performed up to 3 times at 170 ° C.
  • the flexural modulus improved to 5170 MPa for the first kneading (No. POM129), 5270 MPa for the second kneading (No. POM130), and 5290 MPa for the third kneading (No. POM131).
  • the improvement rate was about 2% for the first time ⁇ second time and the first time ⁇ third time.
  • the bending strength was constant at 122 MPa for the first kneading (No. POM129), 117 MPa for the second kneading (No. POM130), and 120 MPa for the third kneading (No. POM131).
  • the kneading temperature is high, and the heat resistance of acetylated NBKP is higher than that of normal NBKP due to repeated molding (melt kneading, etc.), but deteriorates.
  • the kneading temperature is low, so the acetylated NBKP with improved heat resistance hardly deteriorates.
  • the refining property is improved by repeated molding processing, and the flexural modulus and impact resistance are improved. it is conceivable that.
  • Glass fiber (GF) and carbon fiber (CF) and resin composite materials which are general-purpose reinforcing fibers, are generally cascade-recycled because the fiber breaks during fiber recycling or the fibers become shorter. Can only be used for low-grade applications).
  • this acetylated cellulose fiber is resistant to repeated molding in polypropylene, polyethylene, polystyrene, ABS, thermoplastic elastomer, and other low melting point resin materials that are below the molding temperature range such as POM. It is considered to be a material with excellent recyclability.
  • FIG. 1 shows an SEM photograph of NBKP as a raw material.
  • NBKP fibers with submicron order diameters can be seen, but there are many fibers having a coarse fiber diameter of several tens to several hundreds of micrometers.
  • Acetylated NBKP is more defibrated than NBKP, but there are coarse fibers of several tens of ⁇ m or more.
  • FIG. 3 shows an X-CT image of untreated NBKP-added PA6 (No. PA6-15).
  • FIG. 4 shows an SEM photograph of cellulose obtained by extracting PA6 of the untreated NBKP-added PA6.
  • FIG. 5 shows an X-CT image of acetylated NBKP-added PA6 (NO.PA6-216).
  • FIG. 6 shows an SEM photograph of cellulose obtained by extracting PA6 of the acetylated NBKP-added PA6.
  • untreated NBKP-added PA6 (No. PA6-15) has many fibers with a thickness of several tens of ⁇ m, and there are few sub-micron and tens of nanometer order cellulose.
  • PA6 No. PA6-216
  • cellulose of about 3 ⁇ m was scattered, but most of them were dispersed as acetylated CNF of several tens to several hundreds of nm.
  • the POM matrix POM has a small density difference from cellulose, the contrast difference between the POM matrix and cellulose is small in X-CT imaging, and it is difficult to distinguish cellulose.
  • FIG. 7 shows a SEM photograph of cellulose obtained by extracting the POM of untreated NBKP-added POM (No. POM-148).
  • FIG. 8 shows an SEM photograph of cellulose obtained by extracting POM of acetylated NBKP-added POM (No. POM-134).
  • PP matrix Fig. 11 shows an X-CT image of untreated NBKP-added PP (No. PP-116).
  • FIG. 12 shows an SEM photograph of cellulose obtained by extracting PP of the untreated NBKP-added PP.
  • FIG. 14 shows a SEM photograph of cellulose obtained by extracting PP of the acetylated NBKP-added PP.
  • untreated NBKP-added PP No. PP-116 had coarse fibers of several tens of ⁇ m and fibers that were being defibrated more than several ⁇ m. However, the fiber that is being defibrated has a remarkably reduced fiber length and has been shortened.
  • FIG. 16 shows an SEM photograph of cellulose obtained by extracting PP of the low DS acetylated NBKP-added PP.
  • the SP value of acetylated cellulose was calculated by linear approximation from the SP values of the literature values of cellulose and diacetylated cellulose.
  • the crystallinity was calculated by wide-angle X-ray scattering by pressing each cellulose into tablets.
  • Resin SP quoted Fumio Ide's Practical Polymer Alloy Design published in 1996.
  • resin SP is described in the range of SP value, the average value of the upper limit value and the lower limit value is used as SP of the resin, and the relational expression between DS (x) and SP (y) of AcCNF is obtained. It was.
  • Tables 25 to 28 the physical property values in Tables 21 to 24 are shown as indices based on the unmodified NBKP-resin composition.
  • the SP value of acetylated lignopulp is calculated according to the method of Fedors (Robert F. Fedors, Polymer Engineering and Science, February, 1974, vol.14, No.2 147-154) ( Refer to the above - mentioned “ Method for calculating SP value of acetylated lignopulp (LP)”) .
  • Table 31 the numerical values of the PA6 reinforced materials in Table 29 are shown as indices based on the unmodified lignopulp-resin composition.
  • Table 32 summarizes Table 25 to Table 28.
  • Table 33 summarizes Table 31.
  • the material having the highest bending properties can be obtained by keeping the strength of the cellulose fibers at a high level.
  • PP which is a nonpolar material
  • acetylated cellulose with high crystallinity and high fiber strength up to about DS1.0 has insufficient bending properties because the interfacial strength is too low. It can be said that the acetylated NBKP / PP composite material needs to have a high DS even when the crystallinity is lowered.
  • PP can be said to be difficult to obtain high bending properties unless high DS acetylated lignopulp is used.
  • acylated NUKP-containing polypropylene (PP) composition and its strength test (1) Preparation of acylated NUKP In a four-necked 1L flask equipped with a stirring blade, the above-mentioned “unrefined coniferous pulp derived from refiner-treated conifers” The pulp slurry (NUKP) obtained in “Preparation of” was added (corresponding to 5 g of NUKP solid content). N-methyl-2-pyrrolidone (NMP) 500 mL and toluene 250 mL were added and stirred to disperse NUKP in NMP / toluene.
  • NMP N-methyl-2-pyrrolidone
  • a cooler was attached, and the dispersion was heated to 150 ° C. in a nitrogen atmosphere, and water contained in the dispersion was distilled off together with toluene. Thereafter, the dispersion was cooled to 40 ° C., and 15 mL of pyridine (about 2 equivalents to the NUKP hydroxyl group) and myristoyl chloride (denaturing agent, esterification reagent): 16.2 mL (about 1 equivalent to the NUKP hydroxyl group) were added. .
  • the increase in the number of ester groups formed was measured sequentially by infrared absorption spectrum (Note), the reaction was followed, and the reaction was carried out for 90 minutes in a nitrogen atmosphere.
  • NUKP acylated NUKP modified with various modifying groups as shown in the following table (Table 34) was prepared in the same manner as described above. Reaction conditions and the resulting acylated NUKP are shown in Table 34.
  • the crystallinity of pulp and lignopulp was NBKP: 77.4%
  • NUKP 78.3%
  • GP150-1-a 78.7%
  • GP150-3-a 83.1%
  • the range was approximately 77 to 83% (see Table 6 and Table 7 above).
  • Correction coefficient (SP literature value of cellulose diacetate 11.13) ⁇ (SP value of cellulose diacetate determined by Fedors method 12.41)
  • SP ligac SP value of lignin diacetate
  • the content of Myristoyl NUKP in the resin composition is 10% by mass.
  • the resin composition obtained above was injection molded under the following injection molding conditions to prepare a test piece (myristoyl NUKP-containing PP molded body).
  • Table 36 shows the agglomerated part% of the acylated NUKP-containing PP molded product.
  • Table 36 The numerical values of the elastic moduli of the acylated NUKP-containing molded products in Table 35 are shown in Table 36 as indices based on the elasticity of the PP single molded product or the unmodified NUKP-containing molded product. Furthermore, Table 36 also shows the ratio R of the solubility parameter of each acylated NUKP to the solubility parameter [SP: 8.1 (cal / cm 3 ) 1/2 ] of polypropylene (PP) (SP of acylated NUKP / SP of PP). To do.
  • myristoylated NUKP has the highest defibration properties, followed by bornanphenoxyhexanoyl NUKP, hornanphenoxyacetyl NUKP, 1,1,3,3-tetramethylphtylphenoxyacetyl NUKP, 3, The order was 5,5-trimethylhexanenoyl NUKP. And phenoxyacetyl NUKP has the lowest defibration property. Even in this case, it can be said that about 95% is defibrated to a fiber width of about 700 nm or less.
  • Table 36 shows the modulus of elasticity of any acylated NUKP-containing PP molded product, compared with the modulus of elasticity of a single PP molded product when the ratio R (SP of acylated NUKP / SP of PP) is 1.72-1.76. It is about 1.3 to 1.9 times, showing an increase of about 1.1 to 1.6 times the elastic modulus of the unmodified NUKP-containing PP molding.
  • acetylated NUKP containing HDE composition, PS composition and ABS composition Use acetylated NUKP (AcNUKP, DS: 0.41, crystallinity about 75%) prepared in the same manner as described above.
  • HDPE high density polyethylene
  • GPPS general-purpose polystyrene
  • ABS acrylonitrile / butadiene / styrene resin
  • the ratio of fiber (acetylated NUKP) SP / resin SP is 1.31-1.84
  • the elasticity of the acetylated NUKP-containing composition is higher than the elastic modulus of the NUKP-containing resin composition that is not chemically modified. The rate was over 1.1 times.
  • acylated NBKP-containing high-density polyethylene (HDPE) composition and its strength test (1) Preparation of acylated NBKP-0 Softwood bleached kraft pulp containing no lignin (chemical composition cellulose 80% by mass, glucomannan: 12% by mass) Xylan: 6% by mass, arabinan / galactan: 2% by mass, lignin: 0% by mass, which is referred to as “NBKP-0” to distinguish it from NBKP containing the above lignin (slurry concentration: 2 (Mass%) was passed through a single disk refiner (manufactured by Kumagai Riki Kogyo Co., Ltd.), and refiner treatment was repeated until the Canadian Standard Freeness (CSF) was 100 mL or less.
  • CSF Canadian Standard Freeness
  • NBKP-0 solid content: 150 g
  • aqueous suspension having a pulp slurry concentration of 0.75% by mass.
  • the slurry obtained was mechanically defibrated using a bead mill (NVM-2, manufactured by IMEX Co., Ltd.) (zirconia bead diameter 1 mm, bead filling 70%, rotation speed 2,000 rpm, number of treatments twice)
  • NVM-2 bead mill
  • a slurry of NBKP-0 nanofibrils was obtained. This was concentrated using a centrifuge (manufactured by Kokusan Co., Ltd.) to prepare NBKP-0 nanofibril slurry having a concentration of 20% by mass.
  • NBKP-0 nanofibril slurry (solid content 5 g) was charged into a four-necked 1 L flask equipped with a stirring blade.
  • NMP N-methyl-2-pyrrolidone
  • 500 mL and toluene 250 mL were added and stirred to disperse NBKP-0 nanofibrils in NMP / toluene.
  • a condenser was attached, and the dispersion was heated to 150 ° C. in a nitrogen atmosphere, and water contained in the dispersion was distilled off together with toluene. Thereafter, the dispersion was cooled to 40 ° C., 15 mL of pyridine (2 equivalents relative to the hydroxyl group of NBKP-0), myristoyl chloride (denaturing agent, esterification reagent): 16.2 mL (1 equivalent relative to the hydroxyl group of NBKP-0) ) was added and reacted for 120 minutes in a nitrogen atmosphere to obtain chemically modified NBKP-0 nanofibrils (myristoylated NBKP-0 nanofibrils).
  • the degree of substitution (DS) of the ester group of the product is sequentially measured by infrared absorption spectrum and the reaction is traced.
  • the reaction suspension is diluted with 200 mL of ethanol after 90 minutes.
  • the mixture was centrifuged at 7,000 rpm for 20 minutes, the supernatant was removed, and the precipitate was taken out.
  • the above operation (addition of ethanol, dispersion, centrifugation, and removal of the supernatant) was repeated by changing ethanol to acetone. Further, acetone was changed to NMP and repeated twice to obtain an esterified NBKP-0 nanofibril slurry.
  • NBKP-0 nanofibrils modified with various modifying groups were prepared in the same manner as described above.
  • acylated NBKP-0 As described above, the constituent components of NBKP-0 are 80% by mass of cellulose, 12% by mass of glucomannan, 6% by mass of xylan, and 2% by mass of arabinan / galactan.
  • the chemical formula (-C 6 H 10 O 5- ) of the repeating unit of the glucomannan sugar chain is the same as that of cellulose, and the proportion of this chemical formula is 92% of the whole. And other contained sugar sugar chains also have a repeating unit having a structure similar to that of cellulose.
  • SP of NBKP-0 used the SP value of cellulose (document value).
  • the SP value of acylated NBKP-0 was determined as follows.
  • the content of myristoyl NBKP-0 nanofibrils in the resin composition is 10% by mass.
  • a resin composition and a test piece containing the acylated NBKP-0 nanofibril were similarly prepared, and their elastic modulus and tensile strength were measured.
  • Table 40 shows the measurement results.
  • Table 41 shows the relationship between the increase in elastic modulus of acylated NBKP-0 nanofibril-containing resin (HPDE) and the ratio of resin (HDPE) SP to SP of acylated NBKP-0 nanofibrils.
  • SP value ratio of acylated NBKP-0 to resin (HDPE) (indicated in the table as fiber SP / resin SP)
  • elastic modulus increase rate (each acylated NBKP-0 containing composition relative to HDPE elastic modulus)
  • the elastic modulus increase rate (a) and the elastic modulus increase rate (b) of each acylated NBKP-0-containing composition relative to the elastic modulus of the unmodified NBKP-0-containing HDPE composition are shown.
  • the elastic modulus of the HDPE composition containing the same is the elastic modulus of HDPE alone, unmodified NBKP- Compared with the elastic modulus of the 0-containing HDPE composition, it increased by 2 times or more and 1.15 times or more, respectively.

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  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention vise à procurer une composition de résine renforcée par des fibres dans laquelle des fibres dispersibles de manière satisfaisante et une résine dans laquelle les fibres sont facilement dispersées ont été convenablement combinées ; et un procédé de production de la composition de résine renforcée par des fibres. Plus précisément, le but est de fournir : une composition de résine renforcée par des fibres qui comprend des nanofibres de cellulose (NFC) chimiquement modifiées et une résine thermoplastique et qui a des propriétés physiques améliorées en raison de la composition appropriée des fibres avec la résine ; et un procédé de production de la composition de résine renforcée par des fibres. La composition de résine renforcée par des fibres comprend (A) des NFC chimiquement modifiées et (B) une résine thermoplastique, les NFC chimiquement modifiées et la résine thermoplastique satisfaisant les exigences suivantes : (a) le rapport R du paramètre de solubilité (SPcnf) des NFC chimiquement modifiées (A) au paramètre de solubilité (SPpol) de la résine thermoplastique (B), SPcnf/SPpol, est dans la plage de 0,87 à 1,88 et (b) les NFC chimiquement modifiées (A) ont un degré de cristallinité de 42,7 % ou plus.
PCT/JP2016/058481 2015-03-19 2016-03-17 Composition de résine renforcée par des fibres comprenant des nanofibres de cellulose chimiquement modifiées et résine thermoplastique WO2016148233A1 (fr)

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US15/556,220 US10676615B2 (en) 2015-03-19 2016-03-17 Fiber-reinforced resin composition comprising chemically modified cellulose nanofibers and thermoplastic resin
CN201680016164.0A CN107429071B (zh) 2015-03-19 2016-03-17 含有化学修饰纤维素纳米纤维和热塑性树脂的纤维强化树脂组合物
EP16765062.1A EP3272812B2 (fr) 2015-03-19 2016-03-17 Composition de résine renforcée par des fibres comprenant des nanofibres de cellulose chimiquement modifiées et résine thermoplastique
KR1020177028689A KR102405761B1 (ko) 2015-03-19 2016-03-17 화학적으로 개질된 셀룰로오스 나노섬유 및 열가소성 수지를 포함하는 섬유 강화 수지 조성물

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JP2018115292A (ja) * 2017-01-20 2018-07-26 国立大学法人京都大学 エチレングリコール誘導体を含有するアセチル化パルプ組成物、ミクロフィブリル化されたアセチル化パルプを含有する樹脂組成物、及びそれらの製造方法
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WO2020095845A1 (fr) * 2018-11-05 2020-05-14 国立大学法人京都大学 Composition de résine renforcée par des fibres et son procédé de production
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JP2020196783A (ja) * 2019-05-31 2020-12-10 旭化成株式会社 化学修飾されたセルロース微細繊維、及び化学修飾されたセルロース微細繊維を含む高耐熱性樹脂複合体
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JP2020152925A (ja) * 2020-06-26 2020-09-24 旭化成株式会社 セルロース含有樹脂組成物
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