JP2019147861A - Composition and molded body, and manufacturing method of them - Google Patents

Abstract

To provide a composition having high mechanical properties regardless of directional property for overcoming situation that conventional fiber-containing resin composition containing a cellulose fiber and an olefin resin has mechanical properties with anisotropy since the cellulose fiber has trend to be aligned in the same direction, or exhibits high mechanical properties in one direction, but the mechanical properties are not enough in another direction.SOLUTION: There is provided a composition containing a thermoplastic fiber, a cellulose fiber having aspect ratio of 30 or more, and a filler having aspect ratio of 10 or more.SELECTED DRAWING: None

Description

  The present invention relates to a composition, a molded body, and a method for producing them.

  In recent years, attention has been paid to the light weight and high strength performance of cellulose fibers, and studies have been conducted on compositions in which cellulose fibers are added to resins. A composition obtained by adding cellulose fibers to a resin exhibits high mechanical properties.

  For example, Patent Document 1 describes an invention relating to a fiber-containing resin composition containing cellulose fibers and an olefin resin. In this case, it is described that the cellulose constituting the cellulose fiber has a functional group having a linear or branched aliphatic hydrocarbon chain having 5 or more carbon atoms.

  In Patent Document 1, since cellulose fibers are hydrophilic, it is difficult to disperse them in a resin, various improvements have been made for dispersing cellulose fibers in a resin, It is described that by using cellulose fibers having a functional group having a branched aliphatic hydrocarbon chain, it is possible to remarkably increase mechanical properties while suppressing a decrease in transparency due to the blending of cellulose fibers. ing.

JP 2014-15512 A

  According to the fiber-containing resin composition described in Patent Document 1, high mechanical properties can be obtained because cellulose fibers are added to the olefin resin. However, when cellulose fibers tend to be arranged in the same direction, the mechanical properties are anisotropic, exhibiting high mechanical properties in one direction, but insufficient mechanical properties in another direction Turned out to be.

  Then, an object of this invention is to provide the composition which has a high mechanical characteristic irrespective of directionality.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by using a cellulose fiber having a predetermined aspect ratio and a filler having a predetermined aspect ratio, and has completed the present invention.

  That is, this invention relates to the composition containing a thermoplastic resin, the cellulose fiber whose aspect ratio is 30 or more, and the filler whose aspect ratio is 10 or more.

  According to the present invention, a composition having high mechanical properties regardless of directionality is provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

<Composition>
The composition includes a thermoplastic resin, cellulose fibers having an aspect ratio of 30 or more, and a filler having an aspect ratio of 10 or more.

  In a composition containing a conventional thermoplastic resin and cellulose fiber, in order to obtain mechanical properties, it is necessary to disperse the cellulose fiber in the thermoplastic resin. At this time, most of the cellulose fibers are usually oriented in substantially the same direction. For example, when manufacturing a composition by kneading | mixing, a cellulose fiber is orientated along the flow direction (MD direction) of resin. Thereby, high mechanical properties (elastic modulus, strength, etc.) can be realized in the MD direction. However, sufficient mechanical properties may not be realized in a direction perpendicular to the resin flow (TD direction). As a result, the obtained molded product may not have sufficient mechanical properties depending on the directionality.

  On the other hand, in the composition according to the present embodiment, the cellulose fibers are oriented in substantially the same direction (for example, arranged along the MD direction), and the filler used in combination is oriented in the substantially vertical direction with respect to the cellulose fibers (for example, , Arranged along the TD direction). As a result, a composition having high mechanical properties regardless of directionality can be obtained.

[Thermoplastic resin]
The thermoplastic resin means a resin that softens at the glass transition temperature (Tg) or the melting point.

  The thermoplastic resin is not particularly limited, but polyethylene (PE) resin (high density polyethylene (HDPE), low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), High molecular weight polyethylene (UHMW-PE), maleic anhydride modified polyethylene, etc., polypropylene (PP) resin, polyvinyl chloride (PVC) resin (polyvinylidene chloride, etc.), polystyrene (PS) resin (polystyrene, rubber modified polystyrene resin, etc.) ), Polyvinyl acetate (PVAc) resin, polyurethane (PU) resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, acrylic resin (polymethyl methacrylate resin (PMMA), etc.), polyamide resin (N Ron, etc.), polyacetal resin, polycarbonate resin, polyester resin (polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), etc.) , Polycarbonate (PC) resin, cyclic polyolefin resin, cellulose acetate propionate (CAP) resin, diacetyl cellulose (DAC) resin, polyphenylene sulfide (PPS) resin, polytetrafluoroethylene (PTFE) resin, polysulfone (PSF) resin, Polyethersulfone (PES) resin, polyetheretherketone (PEEK) resin, polyimide (PI) resin, polyamideimide (PAI) resin, polyether Ruimido (PEI) resins, polyketone resins. These thermoplastic resins may be used alone or in combination of two or more.

  Among the above, polyethylene (PE) resin, polypropylene (PP) resin, polyester resin, polyamide resin, and polycarbonate (PC) resin are preferably used, and polyethylene (PE) resin, polypropylene (PP) resin, and polyamide resin are used. Is more preferable.

  The content of the thermoplastic resin is preferably 50 to 99% by mass and more preferably 60 to 95% by mass with respect to the total mass of the thermoplastic resin, the cellulose fiber, and the filler. A thermoplastic resin content of 50% by mass or more is preferable because it can be molded into various shapes by heating and melting. On the other hand, the thermoplastic resin content of 99% by mass or less is preferable because various functions can be imparted by reinforcing the resin.

[Cellulose fiber]
Cellulose fiber is a material in which cellulose has a fibrous shape. The cellulose fiber has a function of imparting high mechanical properties in the direction by being oriented in the resin along the resin flow direction (MD direction or the like). In the present specification, the “cellulose fiber” means a fibrous fiber having a width of 1000 μm or less.

  As above-mentioned, the width | variety of a cellulose fiber is 1000 micrometers or less, Preferably it is 100 micrometers or less, More preferably, they are 4 nm-50 micrometers, More preferably, they are 4 nm-25 micrometers. It is preferable that the width of the cellulose fiber is 1000 μm or less because a composite effect appears and the reinforcing effect can be enhanced. In the present specification, the value measured by the following method is adopted as the “width of the cellulose fiber”. That is, the cellulose fibers are observed with a scanning electron microscope (SEM) (magnification: 5000 times), and a straight line intersecting 20 or more cellulose fibers is provided in one field of view. And about all the cellulose fibers which cross | intersected on the said straight line, the distance between two points with the smallest numerical value in an observation screen is measured, and let the average value be the width | variety of a cellulose fiber. In addition, the measurement cellulose fiber prepared by the following method is used for the measurement of the width | variety of the cellulose fiber which exists in a composition. That is, first, a sample of a composition of 1 cm × 1 cm × 0.1 mm is prepared. Next, the sample is immersed in an extraction solvent to extract the sample thermoplastic resin. In that case, you may boil by heating. And the cellulose fiber for a measurement can be obtained by drying the remaining cellulose fiber. In addition, the extraction solvent for extracting a thermoplastic resin changes with thermoplastic resins to be used. For example, when the thermoplastic resin is high density polyethylene (HDPE), polypropylene, or the like, xylene is used as the extraction solvent. When the thermoplastic resin is polyamide, polyester or the like, o-chlorophenol is used as the extraction solvent.

  Moreover, it is preferable that the fiber length of a cellulose fiber is 100 nm or more, It is more preferable that it is 500 nm -10000 micrometers, It is further more preferable that it is 1-1000 micrometers. It is preferable that the fiber length of the cellulose fiber is 100 nm or more because the reinforcing effect can be enhanced by the composite effect. In the present specification, “the fiber length of the cellulose fiber” is a value measured by the following method. That is, the cellulose fibers are observed with a scanning electron microscope (SEM) (magnification: 1,000 times), 25 visual fields are synthesized, and 20 cellulose fibers whose start and end points are observed are selected. The distance between two points at which the value increases is measured, and the average value is taken as the fiber length of the cellulose fiber. In addition, also about the measurement of the fiber length of the cellulose fiber which exists in a composition, the cellulose fiber for a measurement obtained by the method similar to the measurement of the width | variety of the said cellulose fiber is used.

  And the aspect ratio of a cellulose fiber is 30 or more, Preferably it is 50 or more, More preferably, it is 50-20,000, More preferably, it is 100-2,000. It is preferable that the aspect ratio of the cellulose fiber is 30 or more because the cellulose fiber is easily oriented in the same direction (for example, MD direction) in the thermoplastic resin, and in particular, high mechanical properties can be obtained in the orientation direction. In the present specification, the “aspect ratio” means the fiber length of the cellulose fiber relative to the width of the cellulose fiber (the fiber length of the cellulose fiber / the width of the cellulose fiber).

  There is no restriction | limiting in particular as a cellulose fiber, A well-known thing is used.

  In one embodiment, examples of the cellulose fiber include pulp and synthetic fiber, and those obtained by defibrating them (defibrated material). In addition, the “width of cellulose fiber” of pulp and synthetic fiber is usually 10 to 50 μm, preferably 20 to 30 μm. Further, the “width of the cellulose fiber” of the defibrated material is usually less than 10 μm, preferably 50 nm to 5 μm.

  The pulp is a wood pulp such as a softwood pulp using fir, pine or the like, a hardwood pulp using eucalyptus, poplar or the like; a non-wood pulp such as a walla pulp, kenaf pulp, bagasse pulp, bamboo pulp, reed pulp, mulberry pulp or cotton linter pulp; Examples include waste paper pulp obtained by deinking waste paper and the like.

  Examples of the synthetic fiber include rayon, polynosic, cupra, lyocell, and cellophane.

  At this time, the pulp and the synthetic fiber may be subjected to a bleaching treatment (bleached pulp or the like) or may not be subjected to a bleaching treatment (unbleached pulp or the like).

  Of the above-mentioned pulps and synthetic fibers, pulp is preferred, wood pulp is more preferred, softwood unbleached kraft pulp (NUKP), softwood oxygen bleached kraft pulp (NOKP), softwood bleached kraft pulp (NBKP), More preferred are hardwood bleached kraft pulp (LBKP), hardwood unbleached kraft pulp (LUKP), hardwood oxygen bleached kraft pulp (LOKP), softwood unbleached kraft pulp (NUKP), coniferous oxygen bleached kraft pulp (NOKP), Particularly preferred is softwood bleached kraft pulp (NBKP).

  The defibrated material is not particularly limited, and examples thereof include cellulose microfibrils, cellulose nanofibers (CNF), and cellulose nanocrystals (CNC).

  Note that defibration for obtaining a defibrated material may be performed by mechanical treatment, chemical treatment, or a combination thereof. Examples of a method for obtaining a defibrated material by mechanical treatment include a high-pressure homogenizer method, an underwater facing collision method, a grinder method, and a ball mill method. Examples of a method for obtaining a defibrated material by chemical treatment include a TEMPO catalytic oxidation method. Further, the fiber may be defibrated by using a force applied when the composition is produced (for example, when melt-kneading). These defibrating may be applied alone or in combination of two or more.

  The cellulose fiber may contain hemicellulose, lignin and the like.

  The content of hemicellulose is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the cellulose fibers. In the present specification, the “hemicellulose content” is calculated using a value measured by a detergent analysis method.

  As a content rate of the said lignin, it is preferable that it is 40 mass% or less with respect to the total mass of a cellulose fiber, It is more preferable that it is 20 mass% or less, It is further more preferable that it is 5 mass% or less. In the present specification, the “lignin content” is calculated using a value measured by the Klason method.

  Although the above-mentioned cellulose fiber may be unmodified, it may be modified.

  “The cellulose fiber is modified” means that at least one of hydroxyl groups (—OH) at the C2, C3, and C6 positions of β-glucose molecules constituting cellulose is modified with an acyl group (—COR). Means an ester bond (—OCOR). In this case, the acyl group may be substituted on average at the C2-position, C3-position, and C6-position of the β-glucose unit, or may be substituted with a distribution.

  The R is not particularly limited, but is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms. Groups, substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, and the like.

  The alkyl group having 1 to 20 carbon atoms is not particularly limited, but is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 2-methylbutyl. Group, 3-methylbutyl group, 2,2-dimethylpropyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, pentadecyl group, hexadecyl group, cyclopropyl group, cyclobutyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like.

  Although it does not restrict | limit especially as a C2-C20 alkenyl group, A vinyl group, an allyl group, a propenyl group, an isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 2 -Hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1-methyl-2-propyl-3-hexenyl group and the like can be mentioned.

  Although it does not restrict | limit especially as a C2-C20 alkynyl group, An ethynyl group, 2-propynyl group, 2-butynyl group etc. are mentioned.

The alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, and the alkynyl group having 2 to 20 carbon atoms may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxy group, carboxy group, amino group, alkylamino group (—NHR ′ ₂ ), dialkylamino group (—NR ′ _2). ), A trialkylammonium group (—NR ′ ₃ ⁺ ), a nitro group, a thiol group, and the like. In this case, examples of R ′ include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms. These substituents may be used alone or in combination of two or more.

  The aromatic group having 6 to 20 carbon atoms is not particularly limited, but phenyl group, naphthyl group, anthracenyl group, pentarenyl group, indenyl group, indacenyl group, biphenylenyl group, acenaphthylenyl group, phenalenyl group, pyrrolyl group, furyl group, Thienyl, imidazolyl, imidazolidinyl, pyrazolyl, pyrazolidinyl, thiazolyl, thiazolidinyl, isothiazolyl, isothiazolidinyl, oxazolyl, oxazolidinyl, isoxazolyl, isoxazolidinyl, furazanyl, benzofuranyl Group, isobenzofuranyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, carbazolyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, Enajiniru group, phenothiazinyl group, a phenoxazinyl group, etc. Anchirijiniru group.

Although it does not restrict | limit especially as a substituent of the said C6-C20 aromatic group, A C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a halogen atom (Fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxy group, carboxy group, amino group, alkylamino group (—NHR ′ ₂ ), dialkylamino group (—NR ′ ₂ ), trialkylammonium group (— NR ′ ₃ ⁺ ), nitro group, thiol group and the like. These substituents may be used alone or in combination of two or more.

  Among the above, R is a methyl group, 1-carboxymethyl-2-propyl-3-hexenyl group, 2-carboxy-3-propyl-4-heptenyl group, 1-carboxymethyl-3-tridecenyl group, 2- A carboxy-4-tetradecenyl group, a 1-carboxymethyl-2-heptadecenyl group, and a 2-carboxy-3-octadecenyl group are preferable.

  In the case where the cellulose fiber is modified, when the cellulose fiber contains hemicellulose and lignin, at least one of the hydroxy groups of the hemicellulose and lignin may be modified.

  In addition, when a cellulose fiber has two or more above-mentioned R, each R may be the same or different.

The above-described modification of cellulose fibers can be performed using a known compound. For example, when R is a methyl group (when a hydroxy group of cellulose fiber is modified with an acetyl group to form a methylcarbonyloxy group (—OCOCH ₃ )), acetic acid, acetic anhydride, or the like is used. Denaturation can be performed. Moreover, when R is an alkenyl group, modification | denaturation of a cellulose fiber can be performed by using alkenylcarboxylic acid. Furthermore, when R is an alkenyl group having a carboxy group as a substituent, cellulose fibers can be modified by using alkenyl succinic anhydride, alkenyl dicarboxylic acid, or the like.

  When the cellulose fiber is modified, the degree of substitution is preferably 0.05 to 2.0, more preferably 0.1 to 1.0, and 0.1 to 0.8. More preferably. When the degree of substitution is 0.05 or more, the cellulose fibers can be suitably dispersed in the resin, which is preferable. On the other hand, when the degree of substitution is 2.0 or less, the strength of the cellulose fiber is maintained, and high mechanical properties can be realized. In the present specification, the “degree of substitution” refers to the average number of the degree of substitution of hydroxyl groups per β-glucose unit, and means calculated by the following formula.

Degree of substitution = 3-DS
In this case, “DS” means the number of hydroxyl groups per β-glucose unit and can be measured by the following formula.

DS = 0.0113X-0.0122
In the above formula, X is a carbonyl (C) of an ester group in the vicinity of 1733 cm ⁻¹ of an infrared absorption spectrum measured by infrared spectroscopy (IR) using a Fourier transform infrared spectrophotometer (FT-IR). = O) absorption peak area. Since DS can be measured sequentially during the cellulose denaturation reaction, it can be used for tracking the reaction.

  As a specific example, when the hydroxyl groups at the C2, C3, and C6 positions of β-glucose are all substituted with acyl groups, the degree of substitution (maximum value) is 3.0.

  Among the above, the cellulose fiber is preferably unmodified cellulose or partially modified cellulose (with a substitution degree of 2 or less, preferably 0.1 to 1).

  In addition, the above-mentioned cellulose fiber may be used independently or may be used in combination of 2 or more type.

  As a content rate of a cellulose fiber, it is preferable that it is 0.1-20 mass% with respect to the total mass of the said thermoplastic resin, the said cellulose fiber, and the said filler, and it is 0.1-10 mass% Is more preferable, and it is further more preferable that it is 0.5-10 mass%. A cellulose fiber content of 0.1% by mass or more is preferable because high mechanical properties, particularly high physical properties (elastic modulus, strength) can be obtained in the resin flow direction (MD direction). On the other hand, when the content of the cellulose fiber is 20% by mass or less, the melt viscosity can be lowered and the handleability is excellent, which is preferable.

[Filler]
A filler is an additive added to a resin. The filler has a function of imparting high mechanical properties in the direction by being oriented in a direction substantially perpendicular to the resin flow direction (TD direction or the like) in the resin.

  The aspect ratio of the filler is 10 or more, preferably 10 to 75, more preferably 10 to 60, and still more preferably 20 to 50. It is preferable that the aspect ratio of the filler is 10 or more because high mechanical properties are obtained and mechanical properties (elastic modulus, strength, etc.) tend to be further enhanced. In addition, it is preferable that the aspect ratio of the filler is 75 or less because anisotropy can be less likely to occur with respect to the elastic modulus. In the present specification, the “aspect ratio of the filler” means the maximum diameter of the filler with respect to the minimum diameter of the filler (maximum diameter of the filler / minimum diameter of the filler). Here, the “maximum diameter of the filler” is the maximum length when the filler is sandwiched between a pair of parallel surfaces. Similarly, the “minimum diameter of the filler” is the minimum length when the filler is sandwiched between a pair of parallel surfaces. When the filler has a flat plate shape, the “minimum diameter of the filler” corresponds to a so-called thickness. “Maximum diameter of filler” is obtained by observing the filler with a scanning electron microscope (SEM) (magnification: 5,000 times), arbitrarily selecting 30 fillers existing in one field of view, and measuring the maximum diameter. . Similarly, the value of “minimum diameter of filler” is similarly observed by SEM (magnification: 10,000 times), and 30 fillers present in four fields of view are arbitrarily selected and the minimum diameter is measured. In addition, the measurement of the maximum diameter of the filler which exists in a composition and the minimum diameter of a filler is performed using the sample of a composition of 1 cm x 1 cm x 0.1 mm at 25 degreeC.

  The maximum diameter of the filler is preferably 50 μm or less, more preferably 30 μm or less, further preferably 10 μm or less, particularly preferably 0.01 to 10 μm, and preferably 0.1 to 10 μm. It is extremely preferable that it is 1 to 7.5 μm. When the maximum diameter of the filler is 50 μm or less, the volume effect as an additive is sufficiently exhibited, and as a result, mechanical properties (elastic modulus, strength, etc.) can be increased.

  The minimum diameter of the filler is preferably 0.001 μm or more, more preferably 0.01 μm or more, further preferably 0.05 to 5 μm, and 0.05 to 0.75 μm. It is particularly preferred. It is preferable that the minimum diameter of the filler is 0.001 μm or more because the aspect ratio of the filler is high and the mechanical properties of the composite material can be improved.

  There is no restriction | limiting in particular as a filler, Both an organic filler and an inorganic filler can be used.

  The organic filler is not particularly limited, and examples thereof include resin particles such as (meth) acrylic resin particles, silicone resin particles, styrene resin particles, and urethane resin particles; organic fibers such as aramid fibers.

  Although it does not restrict | limit especially as an inorganic filler, A metal compound, a silicate mineral, a carbon compound, an inorganic fiber, etc. are mentioned.

  The metal oxide is not particularly limited, but aluminum oxide, silicon oxide, titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, calcium hydroxide, Examples thereof include magnesium hydroxide, aluminum nitride, boron nitride, and magnesium chloride.

  Although it does not restrict | limit especially as said silicate mineral, Nesosilicate minerals (island tetrahedral silicate mineral), such as olivine, garnet, zircon, silicalite, kyanite, etc .; Solosilicate minerals (group structure type silicate minerals) such as olivine; Cyclosilicate minerals (annular silicate minerals) such as beryl, kiteite, and Osumiishi; pyroxeneite, iron silica Pyroxene, pigeonite, diopside, jadeite, wollastonite, clinopite, camingtonite, grünellite, diopside, and other inosilicate minerals (cyclic silicate minerals); kaolinite, hallolite, montmorillonite, hectorite Phytosilicate minerals (layered silicate minerals) such as talc, talc, mica, chlorite, vermiculite; tectoke such as orthofeldspar, anorthite, anorthite, meteorite, zeolite Salt minerals (network structure type silicate mineral), and the like.

  Although it does not restrict | limit especially as said carbon compound, Graphite, a carbon nanotube, carbon nanohawk, carbon black (soft carbon, hard carbon), carbon nanofiber, etc. are mentioned.

  Although it does not restrict | limit especially as said inorganic fiber, Glass fiber, carbon fiber, a boron fiber, etc. are mentioned.

  Among the above, the filler is preferably an inorganic filler, more preferably a silicate mineral or a carbon compound, more preferably a phyllosilicate mineral, a tectosilicate mineral or a carbon compound, and talc or mica. More preferred are sukumetite, graphite and graphene.

  Moreover, the above-mentioned filler may be surface-modified.

  Although it does not restrict | limit especially as a surface treating agent used for surface modification, A silane coupling agent is mentioned to an epoxy silane, aminosilane, (meth) acryl silane, vinyl silane, phenyl silane, mercapto silane, etc.

  These surface treatment agents may be used alone or in combination of two or more.

  The above fillers may be used alone or in combination of two or more.

  As a content rate of a filler, it is preferable that it is 1-40 mass% with respect to the said thermoplastic resin, the said cellulose fiber, and the total mass of the said filler, and it is more preferable that it is 2-30 mass%. More preferably, it is -20 mass%. The filler content of 1% by mass or more is preferable because high mechanical properties, particularly high physical properties (elastic modulus and strength) can be obtained in a direction perpendicular to the resin flow (TD direction). On the other hand, the filler content of 40% by mass or less is preferable because the toughness of the composite material can be increased.

[Dispersant]
The composition may contain a dispersant. The said dispersing agent has a function etc. which disperse | distribute a cellulose fiber in a thermoplastic resin.

  Although it does not restrict | limit especially as a dispersing agent, At least 1 hydrophilic group selected from the group which consists of a hydroxyl group, a carboxy group, a quaternary ammonium group, a phosphoric acid group, a sulfonic acid group, and these salts is included. A hydrophilic group-containing compound, a glycol ether compound, the hydrophilic group-containing compound or a homopolymer of the glycol ether compound, at least one of the hydrophilic group-containing compound and the glycol ether compound, and / or a hydrophobic compound. 1 copolymer, a (meth) acrylic acid alkyl ester monomer having an alkyl group having 6 to 18 carbon atoms, an acrylic monomer having an amide group, and / or a second copolymer of other monomers, a choline compound, etc. Can be mentioned.

  Although it does not restrict | limit especially as a hydrophilic group containing compound, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, hydroxy group-containing compounds such as ethylene glycol mono (meth) acrylate, prolene glycol mono (meth) acrylate; (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Carboxy group-containing compounds such as itaconic anhydride, polyoxyethylene methyl ether carboxylic acid, N-acyl glutamic acid; hexadecyltrimethylammonium, myristyltrimethylammonium, dimethylaminoethyl (meth) acrylate Quaternary ammonium group-containing compounds such as zylates and [2-{(meth) acryloyloxy} ethyl] trimethylammonium; phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, metaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, Examples thereof include phosphoric acid group-containing compounds such as hexametaphosphoric acid and phosphonic acid; sulfonic acid group-containing compounds such as dodecyl sulfuric acid, dodecyl benzene sulfonic acid, styrene sulfonic acid, and dimethyl sulfosuccinic acid.

  In this case, when the hydrophilic group-containing compound is a salt, the counter ion of the salt is not particularly limited, but when it is an anion, a halide ion (fluoride ion, chloride ion, bromide ion, iodide ion) And the like. On the other hand, when it is a cation, it is preferably an alkali metal salt (sodium salt, potassium salt, lithium salt), a group 2 element salt (calcium salt, magnesium salt) or the like.

  The glycol ether compound is not particularly limited as long as it is other than the above-mentioned hydrophilic group-containing compound, but methoxyethylene glycol (meth) acrylate, ethylethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethylene Examples include glycol methacrylate.

  The homopolymer is not particularly limited, but poly (meth) acrylic acid, polyethylene glycol mono (meth) acrylate, polyprolene glycol mono (meth) acrylate, polyphosphoric acid, polystyrene sulfonic acid, methoxypolyethylene glycol (meth) acrylate , Ethyl polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and the like.

  As the hydrophilic group-containing compound and the glycol ether compound that can be used in the first copolymer, those described above are used. Under the present circumstances, the said hydrophilic group containing compound and the said glycol ether compound may be used independently, or may be used in combination of 2 or more type.

  The hydrophobic compound that can be used in the first copolymer is not particularly limited, but is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, capryl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate , (Meth) acrylic acid linolel, (meth) acrylic acid cyclohexyl, (meth) acrylic acid t-butylcyclohexyl, (meth) acrylic acid isobonyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid dicyclopentenyl (Meth) acrylic mono, such as oxyethyl and benzyl (meth) acrylate Chromatography; styrene, methyl styrene, ethyl styrene, styrene-based monomer such as dimethyl styrene, and the like. The hydrophobic compounds may be used alone or in combination of two or more.

  Specific examples of the first copolymer include a copolymer of a hydroxy group-containing compound and a (meth) acrylic monomer, a copolymer of a carboxy group-containing compound and a (meth) acrylic monomer, quaternary Examples include a copolymer of an ammonium group-containing compound and a (meth) acrylic monomer. More specifically, a copolymer of 2-hydroxyethyl (meth) acrylate and methyl (meth) acrylate, a copolymer of 2-hydroxyethyl (meth) acrylate and lauryl (meth) acrylate, 2- Copolymer of hydroxyethyl (meth) acrylate and cyclohexyl (meth) acrylate, copolymer of 2-hydroxyethyl (meth) acrylate and t-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) Copolymer of acrylate and isobornyl (meth) acrylate, copolymer of 2-hydroxyethyl (meth) acrylate and (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and dicyclo (meth) acrylate Copolymer with pentenyloxyethyl, (meth) acrylic acid and (meth) acrylic acid A copolymer of (meth) acrylic acid and lauryl (meth) acrylate, a copolymer of (meth) acrylic acid and cyclohexyl (meth) acrylate, (meth) acrylic acid and ( A copolymer of (meth) acrylic acid t-butylcyclohexyl, a copolymer of (meth) acrylic acid and isobornyl (meth) acrylate, a copolymer of (meth) acrylic acid and (meth) acrylic acid, ( Copolymers of (meth) acrylic acid and (meth) acrylic acid dicyclopentenyloxyethyl, copolymers of dimethylaminoethyl (meth) acrylate and methyl (meth) acrylate, (meth) acrylic acid Copolymer of dimethylaminoethyl benzylate and lauryl (meth) acrylate, benzylaminoethyl (meth) acrylate and (meth) acrylate Copolymer with cyclohexyl silylate, benzylated product of dimethylaminoethyl (meth) acrylate and t-butylcyclohexyl (meth) acrylate, benzylated product of dimethylaminoethyl (meth) acrylate and (meta ) Copolymer with isobornyl acrylate, benzylated (meth) acrylic acid dimethylaminoethyl and (meth) acrylic acid, dimethylated (meth) acrylic acid dimethylaminoethyl and (meth) acrylic acid Copolymer with dicyclopentenyloxyethyl, [2-{(meth) acryloyloxy} ethyl] copolymer with trimethylammonium and methyl (meth) acrylate, [2-{(meth) acryloyloxy} ethyl] A copolymer of trimethylammonium and lauryl (meth) acrylate, [2-{( (Meth) acryloyloxy} ethyl] trimethylammonium and (meth) acrylic acid cyclohexyl copolymer, [2-{(meth) acryloyloxy} ethyl] trimethylammonium and (meth) acrylic acid t-butylcyclohexyl copolymer A copolymer of [2-{(meth) acryloyloxy} ethyl] trimethylammonium and isobonyl (meth) acrylate, [2-{(meth) acryloyloxy} ethyl] trimethylammonium and (meth) acrylic acid, And a copolymer of [2-{(meth) acryloyloxy} ethyl] trimethylammonium and dicyclopentenyloxyethyl (meth) acrylate. At this time, the copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer, but may be a random copolymer or a block copolymer. preferable. In addition, the said hydrophobic compound can raise the hydrophobicity of a dispersing agent by incorporating in a dispersing agent by copolymerization, and can improve the affinity with a thermoplastic resin more.

  Although it does not restrict | limit especially as a (meth) acrylic-acid alkylester monomer which has a C6-C18 alkyl group which can be used for a said 2nd copolymer, A cyclohexyl (meth) acrylate, a hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc. are mentioned. These (meth) acrylic acid alkyl ester monomers having an alkyl group having 6 to 18 carbon atoms may be used alone or in combination of two or more.

  The acrylic monomer having an amide group that can be used in the second copolymer is not particularly limited, but (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl ( (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-dodecylacrylamide, N-propoxy Methyl acrylamide, 6- (meth) acrylamide hexanoic acid, (meth) acryloylmorpholine, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide , N- 2,2-dimethyl-3- (dimethylamino) propyl] acrylamide. These acrylic monomers having an amide group may be used alone or in combination of two or more.

  Other monomers that can be used in the second copolymer are not particularly limited, but include the hydrophilic group-containing compound, the glycol ether compound, 2-methylaminoethyl (meth) acrylate, and (meth) acrylic acid. Tetrahydrofurfuryl, γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, glycidyl (meth) glycidyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) Examples include butyl acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, and the like. These other monomers may be used alone or in combination of two or more.

  Specific examples of the second copolymer include a copolymer of hexyl (meth) acrylate and (meth) acrylamide, a copolymer of hexyl (meth) acrylate and N-methyl (meth) acrylamide, and hexyl (meth) ) Copolymer of acrylate and N, N-dimethyl (meth) acrylamide, Copolymer of 2-ethylhexyl (meth) acrylate and (meth) acrylamide, 2-ethylhexyl (meth) acrylate and N-methyl (meth) Copolymer of acrylamide, copolymer of 2-ethylhexyl (meth) acrylate and N, N-dimethyl (meth) acrylamide, copolymer of lauryl (meth) acrylate and (meth) acrylamide, lauryl (meth) A copolymer of acrylate and N-methyl (meth) acrylamide, lauryl (me ) Copolymer of acrylate and N, N-dimethyl (meth) acrylamide, Copolymer of lauryl (meth) acrylate, (meth) acrylamide and (meth) acrylic acid, Lauryl (meth) acrylate and (meth) acrylamide And a copolymer of methyl (meth) acrylate. The second copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer, but is a random copolymer or a block copolymer. Is preferred.

  The choline compound is not particularly limited, but 2- (meth) acryloyloxymethyl phosphorylcholine, 2- (meth) acryloyloxyethyl phosphorylcholine, 2- (meth) acryloyloxymethyl phosphorylcholine-methyl (meth) acrylate copolymer 2- (meth) acryloyloxymethyl phosphorylcholine- (meth) acrylic acid ethyl copolymer, 2- (meth) acryloyloxymethyl phosphorylcholine- (meth) acrylic acid propyl copolymer, 2- (meth) acryloyloxymethyl phosphorylcholine -(Meth) acrylic acid butyl copolymer, 2- (meth) acryloyloxymethyl phosphorylcholine- (meth) acrylic acid capryl copolymer, 2- (meth) acryloyloxymethyl phosphorylcholine- (meth) acrylic Lauryl acid copolymer, 2- (meth) acryloyloxymethyl phosphorylcholine- (meth) acrylic acid myristyl copolymer, 2- (meth) acryloyloxymethyl phosphorylcholine- (meth) acrylic acid stearyl copolymer, 2- (meta ) Acrylyloxymethyl phosphorylcholine- (meth) acrylic acid oleyl copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine- (meth) acrylic acid methyl copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine- (meth) acrylic Ethyl acid copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine- (meth) propyl propyl copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine-butyl (meth) acrylate copolymer, 2- (meta Acu Royloxyethyl phosphorylcholine- (meth) acrylic acid capryl copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine- (meth) acrylic acid lauryl copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine- (meth) acrylic acid Examples include myristyl copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine- (meth) acrylic acid stearyl copolymer, 2- (meth) acryloyloxyethyl phosphorylcholine- (meth) acrylic acid oleyl copolymer, and the like.

  Among the above, the dispersant is preferably the first copolymer, the second copolymer, and the choline compound, and more preferably the second copolymer.

  The addition amount of the dispersant is preferably 10 to 200 parts by mass, preferably 20 to 150 parts by mass, when the total mass of the thermoplastic resin, the cellulose fiber, and the filler is 100 parts by mass. Is more preferable, and it is further more preferable that it is 30-100 mass parts. It is preferable that the addition amount of the dispersant is 10 parts by mass or more because cellulose fibers and fillers can be finely dispersed. On the other hand, when the added amount of the dispersant is 200 parts by mass or less, it is preferable because performance deterioration of the composite material due to thermal deterioration or bleed out can be suppressed.

[solvent]
In one embodiment, the composition may include a solvent.

  Although it does not restrict | limit especially as said solvent, Water and an organic solvent are mentioned.

  The organic solvent is not particularly limited, but alcohols such as methanol, ethanol, propanol, isopropyl alcohol, and butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol Acetic esters such as monomethyl ether acetate, carbitol acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate; alcohols such as isopropyl alcohol, butanol, cellosolve, butyl carbitol; aromatic hydrocarbons such as toluene and xylene; Examples include amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Among these, as the organic solvent, alcohols and ketones are preferably used, and butanol, acetone, and methyl ethyl ketone are more preferably used. In addition, these organic solvents may be used independently or may be used in combination of 2 or more type.

  As content of a solvent, it is preferable that it is 1000 parts or less with respect to 100 parts of solid content mass of a composition, and it is more preferable that it is 200 parts or less. In the present specification, the “solid content of the composition” means the total mass of the components excluding the solvent in the composition. Therefore, when the composition does not contain a solvent, the total mass of the composition becomes a solid content.

[Additive]
In one embodiment, the composition may include an additive.

  The additive is not particularly limited, but is a defibration aid such as urea, urea derivative, sugar, sugar alcohol, organic acid, organic acid salt, etc .; a decomposition product of the above defibration aid; phosphorus flame retardant, nitrogen-based Flame retardants such as flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants; plasticizers; antioxidants; ultraviolet absorbers; light stabilizers; antistatic agents; Release agent; Crystallization accelerator; Hydrolysis inhibitor; Lubricant; Impact imparting agent; Sliding property improver; Nucleating agent; Reinforcer; Reinforcer; Flow modifier; Dye; Pigments; rubbery polymers; thickeners; anti-settling agents; anti-sagging agents; antifoaming agents; coupling agents; rust inhibitors; antibacterial / antifungal agents; . These additives may be used alone or in combination of two or more.

<Method for producing composition>
The composition is not particularly limited and can be produced by a known method.

  For example, a cellulose fiber and a filler may be mixed, and this may be mixed with a thermoplastic resin to produce a composition, or a thermoplastic resin and a filler may be mixed and a cellulose fiber mixed with this to produce a composition. Alternatively, a thermoplastic resin and cellulose fiber may be mixed and a filler may be mixed therewith to produce a composition, or a thermoplastic resin and cellulose fiber may be mixed and a thermoplastic resin and filler mixed. In addition, the composition may be produced by mixing individually prepared mixtures. In this case, when the cellulose fiber is a modified cellulose fiber, it may further include a step of modifying the cellulose fiber to prepare a cellulose dispersion.

  According to a preferred embodiment, the method for producing a composition includes a step of melt-kneading a mixture containing a thermoplastic resin, cellulose fibers, and a filler.

  Hereinafter, the preferable embodiment will be described in detail.

[blend]
The mixture includes a thermoplastic resin, cellulose fibers, and a filler.

(Thermoplastic resin)
Since the thermoplastic resin described above can be used, the description thereof is omitted here.

  The content of the thermoplastic resin in the mixture is preferably 50 to 99% by mass and more preferably 70 to 95% by mass with respect to the total mass of the solid content of the mixture. The amount of the thermoplastic resin added is preferably 50% by mass or more because it can be molded into various shapes by heating and melting in the resulting composition. On the other hand, it is preferable that the addition amount of the thermoplastic resin is 99% by mass or less because various functions can be imparted by reinforcing the resin in the obtained composition. In the present specification, the “solid content of the mixture” means a non-volatile component excluding the solvent contained in the mixture. When the mixture does not contain a solvent, the total mass of the mixture becomes the solid content of the mixture.

(Cellulose fiber)
Since the above-mentioned cellulose fibers can be used, description thereof is omitted here.

  The content of the cellulose fiber raw material in the mixture is preferably 0.1 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total mass of the solid content of the mixture. It is preferable that the addition amount of the cellulose fiber is 0.1% by mass or more because high mechanical properties in the obtained composition, in particular, high physical properties (elastic modulus, strength) in the resin flow direction (MD direction) can be obtained. . On the other hand, when the addition amount of the cellulose fiber is 20% by mass or less, the melt viscosity can be lowered in the resulting composition, and it is preferable because the handleability is excellent.

(Filler)
Since the filler described above can be used, the description thereof is omitted here.

  It is preferable that the content rate of the filler in a mixture is 2-30 mass% with respect to the total mass of the solid content of a mixture, and it is more preferable that it is 5-20 mass%. When the added amount of the filler is 2% by mass or more, high mechanical properties in the obtained composition, particularly high physical properties (elastic modulus, strength) in a direction perpendicular to the resin flow (TD direction) can be obtained. To preferred. On the other hand, when the added amount of the filler is 30% by mass or less, it is preferable because the toughness of the composite material can be increased in the obtained composition.

(Dispersant)
The mixture may contain a dispersant. When the mixture contains a dispersant, the cellulose fibers can be particularly preferably dispersed in the thermoplastic resin when melt kneading described later.

  Since the above-mentioned dispersants can be used as the dispersant, description thereof is omitted here.

  It is preferable that the content rate of the dispersing agent in a mixture is 1-20 mass% with respect to the total mass of solid content of a mixture, and it is more preferable that it is 2-15 mass%. It is preferable that the addition ratio of the dispersant is 1% by mass or more because cellulose fibers and fillers can be finely dispersed. On the other hand, when the addition ratio of the dispersant is 20% by mass or less, it is preferable because deterioration in performance of the composite material due to thermal deterioration or bleed-out can be suppressed.

(Fibering aid)
The mixture may contain a defibrating aid. When the mixture contains a fibrillation aid, at least a part of the cellulose fibers can be defibrated particularly when melt-kneading described later. Thereby, higher mechanical properties can be expressed.

  For example, when cellulose fibers having a relatively large cellulose fiber width and / or fiber length are used, a cellulose fiber is defibrated by adding a defibrating aid to the mixture and utilizing the pressure generated during melt kneading described later. In addition, it is possible to produce a composition containing cellulose fibers having a small width and / or fiber length, or cellulose fiber defibrated material.

  Such advantages are more effective when the cellulose fiber is unmodified. If the cellulose fiber is unmodified, the cellulose fiber has a large number of hydroxy groups, and therefore is difficult to be defibrated by intramolecular and / or intermolecular hydrogen bonding. For this reason, normally, the unmodified cellulose fiber is defibrated in water, dehydrated and dried, and then mixed with the thermoplastic resin. However, according to the present embodiment, defibration can be performed in melt-kneading without performing steps such as defibration in water, dehydration, and drying that are separately required. As a result, a composition in which the fibrillated unmodified cellulose fibers are suitably dispersed in the thermoplastic resin can be obtained. Therefore, in a more preferred embodiment, the method for producing a composition includes a step of melt-kneading a mixture containing a thermoplastic resin, unmodified cellulose fibers, a filler, and a defibrating aid.

  As the defibrating aid, those described above can be used, and the description thereof is omitted here.

  The content of the defibrating aid in the mixture is preferably 0.1 to 10% by mass and more preferably 0.5 to 5% by mass with respect to the total mass of the solid content of the mixture. It is preferable that the addition rate of the defibrating aid is 0.1% by mass or more because cellulose fibers can be defibrated more finely. On the other hand, when the addition rate of the fibrillation aid is 10% by mass or less, it is preferable because deterioration of mechanical properties in the resulting composition can be suppressed.

(Solvent, additive)
The mixture may further contain a solvent and an additive.

  Since the solvent and additives are the same as described above, description thereof is omitted here.

  However, it is preferable not to use a solvent from the viewpoint of production cost, composition performance, and the like.

(Method for preparing the mixture)
The method for preparing the mixture is not particularly limited. For example, it may be prepared by mixing a cellulose fiber with a filler and mixing it with a thermoplastic resin, or may be prepared by independently mixing a cellulose fiber and a filler with a thermoplastic resin.

[Melting and kneading]
A composition can be manufactured by melt-kneading the above-mentioned mixture. In addition, a thermoplastic resin, a cellulose fiber, a filler, etc. can be added during melt-kneading as needed, and the composition of a composition can be adjusted. In addition, since cellulose fibers can be defibrated during melt-kneading, the cellulose fibers contained in the mixture and the cellulose fibers contained in the resulting composition have a cellulose fiber width, fiber length, aspect ratio, etc. May be different. Also, since force is applied to the filler during melt-kneading, the filler contained in the mixture and the filler contained in the resulting composition are different in maximum diameter, minimum diameter, aspect ratio, average particle diameter, etc. There is.

  The temperature for melt kneading varies depending on the thermoplastic resin used, but is preferably 100 to 380 ° C, more preferably 120 to 280 ° C.

  The melt kneading time varies depending on the thermoplastic resin to be used, but is preferably 1 to 20 minutes, and more preferably 3 to 10 minutes.

<Molded body>
According to one form of this invention, a molded object is provided. Under the present circumstances, the said molded object shape | molds the above-mentioned composition.

  In the composition described above, the cellulose fibers tend to be oriented in the resin flow direction (MD direction and the like), and the filler tends to be oriented in the direction perpendicular to the resin flow direction (TD direction and the like). As a result, it has high mechanical properties regardless of directionality. For this reason, the molded object obtained by shape | molding the said composition also has a high mechanical characteristic irrespective of directionality.

  In one embodiment, since the molded body has high mechanical characteristics with respect to external forces from all directions, interior materials, exterior materials, structural materials, etc. for automobiles, trains, ships, airplanes, etc .; personal computers, televisions, watches Suitable for telephones, mobile phones, portable music playback equipment, video playback equipment, printing equipment, copying equipment, sports equipment, etc., structural materials, internal parts, etc .; building materials; office equipment such as stationery, containers, containers, etc. Can be applied to.

<Method for producing molded body>
According to one form of this invention, the manufacturing method of a molded object is provided. Under the present circumstances, the manufacturing method of the said molded object includes shape | molding the composition manufactured by the above-mentioned method.

  The molding method of the composition is not particularly limited, and examples thereof include compression molding, injection molding, extrusion molding, hollow molding, and foam molding. These molding methods may be applied singly or in combination of two or more.

  The physical properties may be adjusted by further adding a thermoplastic resin, cellulose fiber, filler, or the like to the composition before or during molding.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

[Example 1]
(Production of composition)
80 parts high-density polyethylene (HDPE) which is a thermoplastic resin, softwood bleached kraft pulp (NBKP) which is a cellulose fiber raw material (width: 50 μm, fiber length: 2 mm, manufactured by Howe Sound Pulp and Paper), 4.8 parts, filler 15.2 parts of graphite (aspect ratio: 45, average particle size: 11 μm) and 3 parts of a dispersant were mixed. The obtained mixture was melt-kneaded at 140 ° C. using a KZW25 (manufactured by Technobell Co., Ltd.), which is a kneading apparatus, to produce a composition.

The width of the cellulose fiber in the obtained composition was measured by the following method. Specifically, after sandwiching between polyethylene terephthalate sheets and pressing at 160 ° C. to a thickness of 1 mm, the center part is cut out by 1 cm ² and wrapped in a metal mesh, and after extracting the resin with hot xylene (heating reflux using a mantle heater), Cellulose fibers remaining on the wire mesh were dried. And the SEM observation was carried out by the following method about the obtained dry cellulose fiber. That is, the observation was made at a magnification of 5,000 times, and a straight line intersecting 20 or more cellulose fibers was provided in one visual field. And about all the cellulose fibers cross | intersected on the said straight line, the distance between 2 points | pieces in which the numerical value becomes the smallest among the cellulose fibers in an observation screen was measured, and the average value was made into the width | variety of a cellulose fiber. As a result, the width of the cellulose fiber was 0.7 μm. In addition, from this, it can be said that the cellulose fiber in the composition is an NBKP defibrated material.

Moreover, the fiber length of the cellulose fiber in the obtained composition was measured with the following method. Specifically, the composition was sandwiched between polyethylene terephthalate sheets, pressed at 160 ° C. to a thickness of 1 mm, the center portion was cut out by 1 cm ² , wrapped in a metal mesh, the resin was extracted with hot xylene, and the cellulose remaining in the wire mesh The fiber was dried. And about the obtained dry cellulose fiber, it observed by SEM with the following method. That is, observed at a magnification of 500 times, synthesized 25 fields of view, selected 20 cellulose fibers in which the starting point and the ending point were observed, measured the distance between the two points where the numerical value was the largest, and the average value thereof Was defined as the fiber length of the cellulose fiber. As a result, the fiber length of the cellulose fiber was 88 μm.

  And when the aspect-ratio (fiber length / width) of the cellulose fiber in a composition was computed, it was 126.

  Moreover, the maximum diameter of the filler of the obtained composition was measured by the following method. Specifically, the composition was cut into 1 cm × 1 cm × 0.1 mm, and the obtained sample was observed by SEM by the following method. That is, observation was performed at a magnification of 5000 times, 30 fillers present in one visual field were arbitrarily selected, the maximum diameter of each filler was measured, and the average value was calculated. As a result, the maximum diameter of the filler was 4.5 μm.

  Further, the minimum diameter of the filler was observed by SEM by the following method using the sample. That is, the magnification was 10,000 times, 30 fillers present in the four visual fields were arbitrarily selected, the minimum diameter was measured, and the average value was calculated. As a result, it was 0.1 μm.

  The aspect ratio of the filler was calculated by (maximum diameter / minimum diameter). The resulting aspect ratio was 45.

(Manufacture of molded products)
The manufactured composition was molded into an ISO D2 shape (flat plate shape) at 160 ° C. using SE-75D (manufactured by Sumitomo Heavy Industries, Ltd.) which is an injection molding machine.

[Example 2]
A composition and a molded body were produced in the same manner as in Example 1 except that talc (aspect ratio: 20, average particle diameter: 5 μm) was used instead of graphite as the filler.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.7 μm, 95 μm, and 135, respectively.

  Moreover, when the maximum diameter, the minimum diameter, and the aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 3.6 μm, 0.15 μm, and 24, respectively.

[Example 3]
A composition and a molded body were produced in the same manner as in Example 1 except that mica (aspect ratio: 80, average particle size: 25 μm) was used instead of graphite as the filler.

  In addition, when the width | variety of the cellulose fiber in a composition, fiber length, and an aspect-ratio were measured and calculated by the method similar to Example 1, they were 0.7 micrometer, 85 micrometers, and 121, respectively.

  Moreover, when the maximum diameter, minimum diameter, and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 13 μm, 0.15 μm, and 86, respectively.

[Example 4]
The same method as in Example 1 except that the addition amount of the thermoplastic resin was changed to 73.5 parts, the addition amount of the cellulose fiber raw material was changed to 10.3 parts, and the addition amount of the filler was changed to 16.2 parts. Compositions and molded bodies were produced.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.7 μm, 88 μm, and 126, respectively.

  Moreover, when the maximum diameter, minimum diameter, and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 4.5 μm, 0.1 μm, and 45, respectively.

[Example 5]
The same method as in Example 1 except that the addition amount of the thermoplastic resin was changed to 84.0 parts, the addition amount of the cellulose fiber raw material was changed to 0.8 parts, and the addition amount of the filler was changed to 15.1 parts. Compositions and molded bodies were produced.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.7 μm, 89 μm, and 127, respectively.

  Moreover, when the maximum diameter, minimum diameter, and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 4.5 μm, 0.1 μm, and 45, respectively.

[Example 6]
Instead of high density polyethylene (HDPE) as the thermoplastic resin, polypropylene (PP) is used, the added amount of the thermoplastic resin is 84.7 parts, the added amount of the cellulose fiber raw material is 5.1 parts, and the added amount of the filler is A composition and a molded body were produced in the same manner as in Example 1 except that the amount was changed to 10.2 parts.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.8 μm, 77 μm, and 96, respectively.

  Moreover, when the maximum diameter, minimum diameter, and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 4.5 μm, 0.1 μm, and 45, respectively.

[Example 7]
Instead of high-density polyethylene (HDPE) as the thermoplastic resin, polyamide (PA) PA6 (manufactured by Ube Industries, Ltd.) is used, the amount of thermoplastic resin added is 84.7 parts, and the amount of cellulose fiber raw material added is A composition and a molded body were produced in the same manner as in Example 1 except that 5.1 parts and the amount of filler added were changed to 10.2 parts.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.9 μm, 68 μm, and 76, respectively.

  Moreover, when the maximum diameter, minimum diameter, and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 4.5 μm, 0.1 μm, and 45, respectively.

[Comparative Example 1]
The composition and molded body were prepared in the same manner as in Example 1 except that the amount of thermoplastic resin added was 83.3 parts, the amount of cellulose fiber raw material added was 16.7 parts, and no filler was added. Manufactured.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.7 μm, 88 μm, and 126, respectively.

[Comparative Example 2]
A composition and a molded body were produced in the same manner as in Example 1 except that the amount of thermoplastic resin added was 84.7 parts, the amount of filler added was 15.3 parts, and no cellulose fiber was added. did.

  In addition, when the maximum diameter, the minimum diameter, and the aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 4.5 μm, 0.1 μm, and 45, respectively.

[Comparative Example 3]
A composition and a molded body were produced in the same manner as in Comparative Example 2, except that talc (aspect ratio: 20, average particle size: 5 μm) was used instead of graphite as the filler.

  In addition, when the maximum diameter, the minimum diameter, and the aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 3.6 μm, 0.15 μm, and 24, respectively.

[Comparative Example 4]
A composition and a molded body were produced in the same manner as in Comparative Example 2, except that mica (aspect ratio: 80, average particle size: 25 μm) was used instead of graphite as the filler.

  In addition, when the average particle diameter and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 13 μm, 0.15 μm, and 86, respectively.

[Comparative Example 5]
A composition and a molded body were produced in the same manner as in Example 1 except that talc (aspect ratio: 5, average particle diameter: 5 μm) was used instead of graphite as the filler.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.7 μm, 86 μm, and 125, respectively.

  Moreover, when the average particle diameter, minimum diameter, and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 0.8 μm, 0.16 μm, and 5, respectively.

[Comparative Example 6]
Instead of softwood bleached kraft pulp (NBKP) as a raw material for cellulose fibers, hardwood bleached kraft pulp (LBKP) (width: 50 μm, fiber length: 0.8 mm, manufactured by Howe Sound Pulp and Paper) is used, and graphite is used as a filler. Using talc (aspect ratio: 20, average particle size: 5 μm), the amount of thermoplastic resin added is 78.1 parts, the amount of cellulose fiber raw material added is 7.8 parts, and the amount of filler added is 14.1. A composition and a molded body were produced in the same manner as in Example 1 except that the parts were changed to parts.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 1.5 μm, 30 μm, and 20, respectively.

  Moreover, when the average particle diameter, minimum diameter, and aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 3.6 μm, 0.15 μm, and 24, respectively.

[Comparative Example 7]
A composition and a molded body were produced in the same manner as in Comparative Example 1 except that polypropylene (PP) was used instead of high-density polyethylene (HDPE) as the thermoplastic resin.

  In addition, when the width, fiber length, and aspect ratio of the cellulose fiber in the composition were measured and calculated in the same manner as in Example 1, they were 0.7 μm, 98 μm, and 140, respectively.

[Comparative Example 8]
A composition and a molded body were produced in the same manner as in Comparative Example 3 except that polypropylene (PP) was used instead of high density polyethylene (HDPE) as the thermoplastic resin.

  In addition, when the average particle diameter, the minimum diameter, and the aspect ratio of the filler in the composition were measured and calculated in the same manner as in Example 1, they were 3.6 μm, 0.15 μm, and 24, respectively.

  The compositions of the compositions produced in Examples 1-7 and Comparative Examples 1-8 are shown in Table 1 below.

[Evaluation of the physical properties]
Various physical properties of the compositions or molded bodies produced in Examples 1 to 7 and Comparative Examples 1 to 8 were evaluated.

(Melt flow rate (MFR))
5 g of the produced composition was put into a cylinder and heated to a predetermined temperature. Then, under a load condition of 2.16 kgf, the resin extruded from the die at the bottom of the cylinder (caliber (maximum diameter): 2 mm) was manually cut off twice every minute. The resin amount per 10 minutes was calculated, the average value was calculated, and evaluated according to the following criteria. The obtained results are shown in Table 2 below.

  In addition, about Examples 1-6 and Comparative Examples 1-8, the said predetermined temperature is 190 degreeC, and about Example 7, the said predetermined temperature is 230 degreeC.

○: 4 g / 10 min or more Δ: 1 g / 10 min or more and less than 4 g / 10 min x: less than 1 g / 10 min

(MD flexural modulus)
The manufactured molded body was cut out in a width of 25 mm in the MD direction to produce an MD direction test piece. Using the obtained test piece, the bending elastic modulus in the MD direction was measured by a bending test according to ISO 178. The obtained flexural modulus was evaluated according to the following criteria. The obtained results are shown in Table 2 below.

○: Flexural modulus in MD direction is 2.5 GPa or more Δ: Flexural modulus in MD direction is 2.0 GPa or more and less than 2.5 GPa ×: Flexural modulus in MD direction is less than 2.0 GPa

(TD flexural modulus)
The manufactured molded body was cut out in a width of 25 mm in the TD direction to prepare a TD direction test piece. Using the obtained test piece, the bending elastic modulus in the TD direction was measured by a bending test according to ISO 178. The obtained flexural modulus was evaluated according to the following criteria. The obtained results are shown in Table 2 below.

○: Flexural modulus in TD direction is 2.5 GPa or more Δ: Flexural modulus in TD direction is 2.0 GPa or more and less than 2.5 GPa ×: Flexural modulus in TD direction is less than 2.0 GPa

(MD / TD elastic modulus ratio)
A value obtained by dividing the measured value of the MD flexural modulus by the measured value of the TD flexural modulus (MD flexural modulus / TD flexural modulus) was calculated as the MD / TD elastic modulus ratio and evaluated according to the following criteria. The obtained results are shown in Table 2 below.

○: MD / TD elastic modulus ratio is 0.9 to 1.1
X: MD / TD elastic modulus ratio is less than 0.9 or more than 1.1

(MD / TD intensity ratio)
Using the MD direction test piece and the TD direction test piece, the strength in the MD direction (MD strength) and the strength in the TD direction (TD strength) were measured by a bending test according to ISO 178. And the value (MD intensity / TD intensity) which divided the measured value of MD intensity by the measured value of TD intensity was computed as MD / TD intensity ratio, and evaluated according to the following standards. The obtained results are shown in Table 2 below.

○: MD / TD intensity ratio is 0.9 to 1.0
X: MD / TD intensity ratio is less than 0.9 or more than 1.0

(Specific modulus)
The specific gravity was measured by Archimedes method using the MD direction test piece. And the value (MD bending elastic modulus / specific gravity) which divided MD bending elastic modulus by specific gravity was computed as specific elastic modulus, and it evaluated in accordance with the following references | standards. The obtained results are shown in Table 2 below.

○: Specific elastic modulus is 2.5 GPa or more Δ: Specific elastic modulus is 2.0 GPa or more and less than 2.5 GPa X: Specific elastic modulus is less than 2.0 GPa

(Specific strength)
The specific gravity was measured by Archimedes method using the MD direction test piece. And the value (strength of MD direction / specific gravity) which divided the measured value of the intensity | strength of MD direction by specific gravity was computed as a specific elastic modulus, and evaluated according to the following references | standards. The obtained results are shown in Table 2 below.

○: Specific strength is 40 N · m / kg or more Δ: Specific strength is 30 N · m / kg or more and less than 40 N · m / kg ×: Specific strength is less than 30 N · m / kg

  When Examples 1-7 are compared with Comparative Examples 1-8, it can be seen that Examples 1-7 are excellent in the flexural modulus in both the MD direction and the TD direction, and the elastic modulus ratio is at the same level. That is, it turns out that Examples 1-7 have a high mechanical characteristic irrespective of directionality.

  In Comparative Example 5, the MD flexural modulus and the TD flexural modulus are both “Δ”, but when the MD / TD elastic modulus ratio is calculated using the measured values, the evaluation result of “x” It became.

Claims (6)

  A composition comprising a thermoplastic resin, cellulose fibers having an aspect ratio of 30 or more, and fillers having an aspect ratio of 10 or more.   The composition according to claim 1, wherein a maximum diameter of the filler is 50 μm or less.   The composition of Claim 1 or 2 whose content rate of the said cellulose fiber is 0.1-20 mass% with respect to the total mass of the said thermoplastic resin, the said cellulose fiber, and the said filler.   The molded object formed by shape | molding the composition of any one of Claims 1-3. It is a manufacturing method of the composition of any one of Claims 1-3, Comprising:
The manufacturing method including the process of melt-kneading the mixture containing the said thermoplastic resin, the said cellulose fiber, and the said filler.   The manufacturing method of a molded object further including the process of shape | molding the composition manufactured by the method of Claim 5.