JP2019189758A - Manufacturing method of resin composition, and manufacturing method of molded body using the resin composition - Google Patents

Abstract

To provide a method for manufacturing a resin composition excellent in manufacturing cost, under a condition that various methods for dispersing a cellulose fiber in a thermoplastic resin or the like are considered conventionally, for example a method using an ion liquid is known, however the method needs a large amount of the ion liquid for dissolving the cellulose fiber in the ion liquid, it has high cost and is not suitable for industrial production.SOLUTION: There is provided a manufacturing method of a resin composition including melting and mixing a mixture containing a thermoplastic resin and a cellulose fiber in presence of an ion liquid, in which the added amount of the ion liquid is less than 20 pts.mass based on 100 pts.mass of the cellulose fiber.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a resin composition, and a method for producing a molded body using the resin composition.

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

  However, it is known that cellulose fibers are difficult to disperse in hydrophobic thermoplastic resins and the like because they exhibit hydrophilicity. Thus, various methods for dispersing cellulose fibers in a thermoplastic resin and the like have been studied.

  For example, Patent Document 1 includes cellulose crystals formed by reprecipitating cellulose in a polar solvent using an ionic liquid in which cellulose is dissolved, and the cellulose I type crystal component fraction of the cellulose crystals, cellulose The sum of the fraction of the type II crystal component and the fraction of the amorphous cellulose component is 1, the fraction of the cellulose type I crystal component is 0.4 or more, and the fraction of the cellulose type II crystal component is 0 An invention relating to a cellulose / resin composite characterized by being 1 or more is described. Patent Document 1 describes that according to the cellulose / resin composite, cellulose can be uniformly dispersed in the resin.

  In Patent Document 1, as a method for producing the cellulose / resin composite, a step of dissolving cellulose in an ionic liquid and an ionic liquid in which the cellulose is dissolved in a polar solvent in which resin fine particles are dispersed are disclosed. Adding and reprecipitating cellulose; filtering and washing the solution in which the resin fine particles are dispersed and reprecipitating cellulose to form cellulose / resin powder; heating the cellulose / resin powder; And pressurizing and melting the resin to form a cellulose / resin composite.

  Patent Document 1 discloses that cellulose is soluble in ionic liquid, and cellulose solubilized in ionic liquid is added to a polar liquid that can dissolve ionic liquids such as alcohol and water. As a result, it is known that the ionic liquid is dissolved in the polar solvent and that cellulose insoluble in the liquid such as alcohol and water is reprecipitated.

JP 2010-195996 A

  According to the method described in Patent Document 1, cellulose fibers can be dispersed in a resin. However, since a large amount of ionic liquid is required to dissolve the cellulose fiber in the ionic liquid, the cost is high and it is not suitable for industrial production.

  Then, an object of this invention is to provide the method of manufacturing the resin composition excellent in manufacturing cost.

  The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using a predetermined amount of ionic liquid together when melt-kneading cellulose fibers in a thermoplastic resin, and the present invention has been completed.

  That is, a method for producing a resin composition comprising melt-kneading a mixture containing a thermoplastic resin and cellulose fibers in the presence of an ionic liquid, wherein the added amount of the ionic liquid is 100 parts by mass of cellulose fibers. On the other hand, it is related with the manufacturing method which is less than 20 mass parts.

  According to this invention, the method of manufacturing the resin composition excellent in manufacturing cost is provided.

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

<Method for producing resin composition>
The manufacturing method of the resin composition which concerns on this form includes melt-kneading the mixture containing a thermoplastic resin and a cellulose fiber in presence of an ionic liquid. Under the present circumstances, the addition amount of the said ionic liquid is less than 20 mass parts with respect to 100 mass parts of cellulose fibers.

  The production method is to disperse cellulose fibers and / or their defibrated material in a thermoplastic resin while defibrating at least a part of the cellulose fibers in the process of melt kneading (that is, in the process of melt kneading). , Cellulose fiber defibration and dispersion can occur simultaneously). In this case, when a predetermined amount of ionic liquid is used in combination, surprisingly, the defibration and dispersion of the cellulose fiber proceed suitably. As a result, a resin composition in which cellulose fibers are suitably defibrated and dispersed in the thermoplastic resin can be obtained.

  The reason why the above effect is obtained is not necessarily clear, but it is considered to be due to the following mechanism, for example. That is, the ionic liquid swells at least a part of the cellulose fiber by interacting with the cellulose fiber in the thermoplastic resin. The swollen cellulose fiber can easily be defibrated and dispersed by the force applied during melt-kneading. As a result, cellulose fibers can be suitably defibrated and dispersed in the thermoplastic resin. In addition, the mechanism by which the said effect is acquired is a presumption, and even if it is a case where the said effect is acquired by mechanisms other than the said mechanism, it is contained in the technical scope of this invention.

  According to the above production method, defibration and dispersion are performed in the course of melt-kneading, so steps such as dissolution and reprecipitation of cellulose are unnecessary, and the production cost is excellent. Moreover, since the addition amount of an ionic liquid is small, it is excellent in manufacturing cost.

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

(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 and the cellulose fiber. It is preferable for the content of the thermoplastic resin to be 50% by mass or more because the resin composition obtained can be suitably molded into various shapes by heating and melting. On the other hand, when the thermoplastic resin content is 99% by mass or less, it is preferable because high mechanical properties can be imparted by reinforcing the resin composition obtained.

(Cellulose fiber)
Cellulose fiber is a material in which cellulose has a fibrous shape. In the present specification, the “cellulose fiber” means a fibrous fiber having a width of 100 μm or less.

  As described above, the width of the cellulose fiber is 100 μm or less, preferably 75 μm or less, more preferably 4 nm to 50 μm, and further preferably 4 nm to 25 μm. It is preferable that the width of the cellulose fiber is 100 μm or less because a composite effect appears and the reinforcing effect can be increased. 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), 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 2 points | pieces where a numerical value becomes the smallest in an observation screen is measured, and let the average value be the width | variety of a cellulose fiber.

  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, a cellulose fiber is observed with a scanning electron microscope (SEM), 25 visual fields are synthesized, 20 cellulose fibers whose start point and end point are observed are selected, and the distance between two points where the numerical value is the largest Are measured, and the average value is defined as the fiber length of the cellulose fiber.

  The aspect ratio of the cellulose fiber is preferably 30 or more, more preferably 50 or more, further preferably 50 to 20,000, and particularly preferably 100 to 2,000. It is preferable that the aspect ratio of the cellulose fiber is 30 or more because high mechanical properties can be obtained. 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). The “width of cellulose fiber” of pulp and synthetic fiber is usually 10 μm or more, preferably 10 to 50 μm, more 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 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).

  In addition, the defibrated material contained in the mixture is usually prepared by separately performing a defibrating treatment in advance. At this time, the defibrating treatment 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 resin composition is produced (for example, when melt kneading).

  These defibrated materials 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 group, imidazolyl group, imidazolidinyl group, pyrazolyl group, pyrazolidinyl group, thiazolyl group, thiazolidinyl group, isothiazolyl group, isothiazolidinyl group, oxazolyl group, oxazolidinyl group, isoxazolyl group, isoxazolidinyl group, furazanyl group, benzofuranyl group 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.

  In one Embodiment, it is preferable that a cellulose fiber is a pulp and a synthetic fiber, and it is more preferable that it is a pulp.

  In one embodiment, the cellulose fiber is preferably unmodified cellulose or partially modified cellulose (having 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 0.1-50 mass% with respect to the total mass of a thermoplastic resin and a cellulose fiber, It is more preferable that it is 0.1-30 mass%, More preferably, it is 5-25 mass%. A cellulose fiber content of 0.1% by mass or more is preferable because high mechanical properties can be obtained. On the other hand, when the content of the cellulose fiber is 50% by mass or less, the melt viscosity can be lowered and the handleability is excellent, which is preferable.

(Dispersant)
The mixture may further contain a dispersant. The dispersant has a function of suitably dispersing cellulose fibers in the 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, or the choline compound, more preferably the second copolymer, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N, N-dimethyl (meta ) Acrylamide, N, N-diethyl (meth) acrylamide, and a copolymer containing N, N-dipropyl (meth) acrylamide, and more preferred are lauryl (meth) acrylate, stearyl (meth) acrylate, and (meth ) Acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) a Riruamido, and particularly preferably a copolymer containing N- propyl (meth) acrylamide.

  The addition amount of the dispersant is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and further preferably 20 to 100 parts by mass with respect to 100 parts by mass of the cellulose fiber. preferable. It is preferable that the added amount of the dispersant is 1 part by mass or more because cellulose fibers can be finely dispersed. On the other hand, when the addition amount of the dispersant is 200 parts by mass or less, it is preferable because performance deterioration of the resin composition due to thermal deterioration or bleed-out can be suppressed.

(solvent)
In one embodiment, the mixture 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 mixture, and it is more preferable that it is 200 parts or less. In the present specification, the “solid content of the mixture” means the total mass of the components excluding the solvent in the mixture. Therefore, when a mixture does not contain a solvent, the total mass of a composition becomes solid content.

(Additive)
In one embodiment, the mixture may include an additive.

  The additive is not particularly limited, but is a defibrillation aid such as urea, urea derivatives, sugars, sugar alcohols, organic acids, organic acid salts, etc .; a decomposition product of the above defibration aid; talc, mica, scumite, graphite , Graphene and other fillers; phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc .; plasticizers; antioxidants; UV absorbers; Antistatic agent; Conductivity imparting agent; Stress relaxation agent; Release agent; Crystallization accelerator; Hydrolysis inhibitor; Lubricant; Impact imparting agent; Sliding property improving agent; Agents; Flow modifiers; Dyes; Sensitizers; Coloring pigments; Rubber polymers; Thickeners; Anti-settling agents; Anti-sagging agents; Antifoaming agents; Coupling agents; Antifouling agent; conductive polymer and the like. These additives may be used alone or in combination of two or more.

[Ionic liquid]
The ionic liquid has a function of facilitating fibrillation and dispersion of the cellulose fibers in the thermoplastic resin. In the present specification, the “ionic liquid” means a salt that exists in a liquid at 100 ° C. or lower and has a cation and an anion as basic constituent elements.

  Although it does not restrict | limit especially as a cation of an ionic liquid, An aromatic cation and an aliphatic cation are mentioned. That is, in one embodiment, the ionic liquid includes an ionic liquid having a cation selected from the group consisting of an aromatic cation and an aliphatic cation.

  Although it does not restrict | limit especially as an aromatic cation, A pyridinium cation, an imidazolium cation, an aromatic ammonium cation, an aromatic sulfonium cation, etc. are mentioned.

  Examples of the pyridinium cation include 1-methylpyridinium cation, 1-ethylpyridinium cation, 1-propylpyridinium cation, 3-methyl-1-propylpyridinium cation, 1-butylpyridinium cation, 1-butyl-3-methylpyridinium cation, Examples thereof include 1-butyl-4-methylpyridinium cation and 1- (3-cyanopropyl) pyridinium cation.

  Examples of the imidazolium cation include 1-methylimidazolium cation, 1,3-dimethylimidazolium cation, 1,2,3-trimethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-ethyl-2. , 3-dimethylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-3-methyl Imidazolium cation, 1-methyl-3-octylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-allyl-3-methylimidazolium cation, 1- Benzyl-3-methylimida 1,3-bis (cyanomethyl) imidazolium cation, 1,3-bis (3-cyanopropyl) imidazolium cation, 1- (3-cyanopropyl) -3-methylimidazolium cation, 1,3- Dihydroxyimidazolium cation, 1,3-dimethoxyimidazolium cation, 1,3-dimethoxy-2-methylimidazolium cation, 1- (2-hydroxyethyl) -3-methylimidazolium cation, 1-methyl-3- ( 4-sulfobutyl) imidazolium cation, 1-vinylimidazolium cation and the like.

  Examples of the aromatic ammonium cation include benzylethyldimethylammonium cation, ethyldimethyl (2-phenylethyl) ammonium cation, and benzyldimethyltetradecylammonium cation.

  Examples of the aromatic sulfonium cation include cyclopropyldiphenylsulfonium cation.

  The aliphatic cation is not particularly limited, and examples thereof include an aliphatic ammonium cation, a pyrrolidinium cation, a piperidinium cation, a morpholinium cation, a phosphonium cation, an aliphatic sulfonium cation, and a choline cation.

  Examples of the aliphatic ammonium cation include tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, trimethylpropylammonium cation, ethyldimethylpropylammonium cation, diethylmethylpropylammonium cation, tetrabutylammonium cation, butyltrimethylammonium cation, and tributyl. Methylammonium cation, tetrapentylammonium cation, triethylpentylammonium cation, tetrahexylammonium cation, tetraoctylammonium cation, methyltrioctylammonium cation, tetradecylammonium cation, tetradodecylammonium cation, cyclohexyltrimethyla Monium cation, dimethyl (2-methoxyethyl) methylammonium cation, ethyl (2-methoxyethyl) dimethylammonium cation, ethyl (3-methoxypropyl) dimethylammonium cation, tris (2-hydroxyethyl) methylammonium cation, 2-hydroxy An ethyl trimethyl ammonium cation etc. are mentioned.

  Examples of the pyrrolidinium cation include 1-butyl-1-methylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-allyl-1-methylpyrrolidinium cation, 1-methyl-1- Examples thereof include propylpyrrolidinium cation and 1- (2-methoxyethyl) -1-methylpyrrolidinium cation.

  Examples of the piperidinium cation include 1-butyl-1-methylpiperidinium cation and 1-methyl-1-propylpiperidinium cation.

  Examples of the morpholinium cation include 4-ethyl-4-methylmorpholinium cation.

  Examples of the phosphonium cation include a triethylmethylphosphonium cation, a tetrabutylphosphonium cation, a tributylmethylphosphonium cation, and a trihexyltetradecylphosphonium cation.

  Examples of the aliphatic sulfonium cation include a trimethylsulfonium cation, a triethylsulfonium cation, and a tributylsulfonium cation.

  Examples of the choline cation include a choline cation, an acetylcholine cation, a fluorocholine cation, and a chlorocholine cation.

  Among the above, the cation of the ionic liquid is preferably an aromatic cation, more preferably a pyridinium cation or an imidazolium cation, still more preferably an imidazolium cation, and 1-ethyl-3- Methylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-butyl-2,3-dimethylimidazole It is particularly preferable that the cation is 1-allyl-3-methylimidazolium cation.

In addition, the anion of the ionic liquid is not particularly limited, but halide ion, borate anion, carboxylate anion, sulfonate anion, sulfate anion, sulfonimide anion, phosphate anion, phosphate anion, phosphonate anion, diion Examples include cyanamide anion ((NC) ₂ N ⁻ ), thiocyanate anion (SCN ⁻ ), tricyanomethanide anion (C (CN) ₃ ⁻ ), and nitrate anion (NO ₃ ⁻ ). That is, in one embodiment, the ionic liquid comprises a halide ion, borate anion, carboxylate anion, sulfonate anion, sulfate anion, sulfonimide anion, phosphate anion, phosphate anion, phosphonate anion, dicyanamide anion, thiol. An ionic liquid having an anion selected from the group consisting of a cyanate anion, a tricyanomethanide anion, and a nitrate anion.

Examples of the halide ion include chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ), iodide ion (I ⁻ ), tribromide ion (Br ₃ ⁻ ), and triiodide ion (I ₃ ⁻ ). Can be mentioned.

Examples of the borate anion include tetrafluoroborate anion (BF ₄ ⁻ ), trifluoro (trifluoromethyl) borate anion (CF ₃ BF ₃ ⁻ ), and the like.

Examples of the carboxylate anion include formate anion (HCOO ⁻ ), acetate anion (CH ₃ COO ⁻ ), trifluoroacetate anion (CF ₃ COO ⁻ ), lactate anion (CH ₃ CH (OH) COO ⁻ ), and thiosalicylate anion. _{(HS-C 6 H 4 -COO} -) , and the like.

Examples of the sulfonate anion, methanesulfonate anion _{(CH 3} SO 3 ^-), trifluoromethanesulfonate anion ^{_{(CF 3 SO 3 -),}} p- toluenesulfonate anion _{(CH 3 -C 6 H 4 -SO} 3 - ) And the like.

Examples of the sulfate anion include methyl sulfate anion (CH ₃ SO ₄ ⁻ ), ethyl sulfate anion (C ₂ H ₅ SO ₄ ⁻ ), and the like.

Examples of the sulfonimide anion include bis (trifluoromethanesulfonyl) imide anion ((CF ₃ SO ₂ ) ₂ N ⁻ ), bis (fluorosulfonyl) imide anion ((FSO ₂ ) ₂ N ⁻ ), and the like.

Examples of the phosphate anion include hexafluorophosphate anion (PF ₆ ⁻ ).

Examples of the phosphate anion include dimethyl phosphate ((CH ₃ O) ₂ P (═O) O ⁻ ), diethyl phosphate anion ((C ₂ H ₅ O) ₂ P (═O) O ⁻ ), dibutyl phosphate anion (( C ₄ H ₉ O) ₂ P (═O) O ⁻ ) and the like.

Examples of the phosphonate anion include methyl phosphonate anion (HP (═O) (— OCH ₃ ) —O ⁻ ), ethyl phosphonate anion (HP (═O) (— OC ₂ H ₅ ) —O). ^-), butyl phosphonate anion (H-P (= O) (- OC 4 H 9) -O -) , and the like.

  Among the above, the anion of the ionic liquid is preferably a halide ion, borate anion, sulfonate anion, sulfate anion, sulfonimide anion, phosphate anion, phosphate anion, phosphonate anion, and halide ion. , Borate anion and phosphonate anion are more preferable, halide ion is more preferable, and chloride ion is particularly preferable.

  The ionic liquid may contain neutral molecules for the purpose of lowering the melting point. The neutral molecule is not particularly limited, but ethylene glycol, 1,4-butanediol, hexanediol, resorcinol, glycerin, triethylene glycol, isosorbide, levulinic acid, benzoic acid, phenylacetic acid, 3-phenylpropionic acid, Cinnamic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, itaconic acid, 1,2,3-propanetricarboxylic acid, tartaric acid, lactic acid, ascorbic acid, citric acid, 4-hydroxybenzoic acid, caffeic acid , Coumaric acid, gallic acid, glucose, sucrose, xylose, xylitol, sorbitol, urea, thiourea, 1-methylurea, 1,3-dimethylurea, 1,1-dimethylurea, acetamide, benzamide, 2,2, Examples include 2-trifluoroacetamide and imidazole.Of these, the neutral molecule is preferably ethylene glycol, glycerin, benzoic acid, or urea.

  The ionic liquid is a combination of the above-mentioned cation and anion and is not particularly limited. Specific examples of the ionic liquid include 1-butylpyridinium chloride, 1-butylpyridinium bromide, 1-butyl-3-methylpyridinium chloride, 1-butyl-3-methylpyridinium bromide, and 1-butyl-3-methylpyridinium. Bis (trifluoromethylsulfonyl) imide, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium bromide, 1,3-dimethylimidazolium chloride, 1,3-dimethylimidazolium bromide, 1,3-dimethylimidazolium methyl sulfate, 1,3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide, 1,3-dimethylimidazolium dimethyl phosphate 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl- 3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium methyl Phosphonate, 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanes Honate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium bis (trifluoro) Lomethanesulfonyl) imide, benzylethyldimethylammonium bis (trifluoromethanesulfonyl) imide, ethyldimethyl (2-phenylethyl) ammonium bis (trifluoromethanesulfonyl) imide, cyclopropyldiphenylsulfonium tetrafluoroborate, tetrabutylammonium chloride, tetrabutylammonium Bromide, tetrabutylammonium tetrafluoroborate, tetrapentylammonium chloride, tetrapentylammonium bromide, Trahexyl ammonium chloride, tetrahexyl ammonium bromide, dimethyl (2-methoxyethyl) methylammonium bis (fluorosulfonyl) imide, 1-butyl-1-methylpyrrolidinium chloride, 1-butyl-1-methylpyrrolidinium bromide, 1-butyl-1-methylpyrrolidinium bis (fluorosulfonyl) imide, 1-butyl-1-methylpiperidinium bromide, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl -1-propylpiperidinium bromide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 4-ethyl-4-methylmorpholinium bromide, triethylmethylphosphonium bromide, tetrabutyl Suphonium chloride, tetrabutylphosphonium bromide, trihexyltetradecylphosphonium chloride, trimethylsulfonium iodide, tributylsulfonium iodide, choline chloride, acetylcholine chloride, chlorocholine chloride, fluorocholine bromide, choline acetate, choline formate, choline propionate Etc.

  The ionic liquid may be a mixture of cations and anions and neutral molecules. The ionic liquid includes a mixture of choline chloride and ethylene glycol, a mixture of choline chloride and glycerin, a mixture of choline chloride and urea, a mixture of tetramethylammonium chloride and ethylene glycol, a mixture of tetramethylammonium chloride and glycerin, and tetramethyl chloride. Examples include a mixture of ammonium and urea, a mixture of tetrabutylammonium chloride and ethylene glycol, a mixture of tetrabutylammonium chloride and glycerin, a mixture of tetrabutylammonium chloride and urea, and the like.

  Among these, ionic liquids are 1-butylpyridinium chloride, 1-butylpyridinium bromide, 1-butyl-3-methylpyridinium chloride, 1-butyl-3-methylpyridinium bromide, 1-butyl-3-methylpyridinium bis ( Trifluoromethylsulfonyl) imide, 1-butyl-4-methylpyridinium tetrafluoroborate, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium bromide, 1,3-dimethylimidazolium chloride, 1, 3-dimethylimidazolium bromide, 1,3-dimethylimidazolium methyl sulfate, 1,3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide, 1,3-dimethylimidazolium dimethyl phosphate, 1-d Ru-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3- Methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium methylphosphonate 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate 1-butyl-3-methylimidazolium hexafluorophosphate, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium bis (trifluoromethane Sulfonyl) imide, preferably 1-butylpyridinium chloride, 1-butylpyridinium bromide, 1-butyl-3-methylpyridinium chloride, 1-butyl-3-methylpyridinium bromide, 1-butyl-4-methylpyridinium tetra Fluoroborate, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridinium bromide, 1,3-dimethylimidazolium chloride, 1,3-dimethylimidazolium bromide, 1-ethyl-3-methylimidazo 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium methylphosphonate, 1-butyl-3-methylimidazolium chloride 1-butyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide More preferably, 1-butylpyridinium chloride, 1-butylpyridinium bromide, 1-butyl-3-methylpyridinium chloride, 1-butyl-3-methylpyridinium bromide, 1-butyl-4-methylpyridinium chloride, 1-butyl-4 -Methylpi Dinium bromide, 1,3-dimethylimidazolium chloride, 1,3-dimethylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-butyl-3- More preferred are methylimidazolium chloride, 1-butyl-3-methylimidazolium bromide, 1-allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide, and 1,3-dimethylimidazole Rium chloride, 1,3-dimethylimidazolium bromide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-butyl-3 -Methylimidazolium bromide, -Allyl-3-methylimidazolium chloride, 1-allyl-3-methylimidazolium bromide are particularly preferred, 1,3-dimethylimidazolium chloride, 1-ethyl-3-methylimidazolium chloride, 1-butyl Most preferred are -3-methylimidazolium chloride and 1-allyl-3-methylimidazolium chloride.

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

  The molecular weight of the ionic liquid is preferably 400 or less, more preferably 100 to 400, even more preferably 100 to 300, particularly preferably 100 to 250, and preferably 100 to 200. Is very preferred, most preferably 130-200. It is preferable that the molecular weight of the ionic liquid is 400 or less because the tensile elastic modulus of the obtained molded article can be increased.

  The addition amount of the ionic liquid is less than 20 parts by mass with respect to 100 parts by mass of the cellulose fiber, preferably 0.01 parts by mass or more and less than 20 parts by mass, more preferably 0.3 to 18 parts by mass. More preferably, it is 3-15 mass parts, Most preferably, it is 4-12 mass parts. It is preferable for the amount of ionic liquid added to be less than 20 parts by mass because the production cost is excellent and the tensile modulus of the resulting molded article can be increased.

  In addition, in another one Embodiment, it is preferable that the addition amount of an ionic liquid is 0.3-18 mass parts with respect to 100 mass parts of cellulose fibers, and it is more preferable that it is 0.75-15 mass parts. The amount is preferably 1 to 12.5 parts by mass, particularly preferably 2 to 7.5 parts by mass. When the addition amount of the ionic liquid is within the above range, it is preferable because the manufacturing cost is excellent and the tensile strength of the obtained molded body is high.

[Melting and kneading]
A resin composition can be obtained by melt-kneading the above-mentioned mixture in the presence of an ionic liquid. At this time, the composition of the resin composition can be adjusted by adding a thermoplastic resin, cellulose fiber, a dispersant, an ionic liquid or the like during the melt-kneading as necessary.

  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 30 minutes, and more preferably 3 to 20 minutes.

[Resin composition]
The resin composition obtained by the above method is excellent in mechanical properties (tensile elastic modulus, tensile strength, etc.) because cellulose fibers are suitably defibrated and dispersed.

  The resin composition includes a thermoplastic resin, cellulose fiber and / or a defibrated material thereof, and an ionic liquid. In this case, the resin composition may contain at least one of a dispersant, a solvent, and an additive. As described above, the resin composition may contain cellulose fibers, that is, those that have not been defibrated during the melt-kneading process, those that have been defibrated but have a low degree of defibration, and the like. .

  The thermoplastic resin in the resin composition is as described above.

  Cellulose fibers in the resin composition are as described above. However, at least a part of the cellulose fibers can be defibrated during the melt-kneading process. That is, the cellulose fiber in the mixture and the cellulose fiber in the resin composition may have different cellulose fiber width, fiber length, aspect ratio, and the like.

  The width of the cellulose fiber in the resin composition is 100 μm or less, preferably 20 μm or less, more preferably 4 nm to 10 μm, and further preferably 4 nm to 5 μm.

  In addition, the cellulose fiber for a measurement prepared by the following method is used for the measurement of the width | variety of the cellulose fiber which exists in a resin composition, and the measurement of fiber length. 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.

  In principle, the ionic liquid, the dispersant, the solvent, the additive, and the like in the resin composition are also as described above. Also in these cases, the shape, average particle diameter, and the like may be different depending on the case in the mixture before melt-kneading and in the obtained resin composition.

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

  The molding method of the composition is not particularly limited, and a known method can be appropriately employed. Specific examples of the t-type 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.

  In addition, a physical property may be adjusted by further adding a thermoplastic resin, cellulose fiber and / or a defibrated material, a dispersant or the like to the resin composition before or during molding.

  The molded body thus obtained has excellent mechanical properties, so it can be used for interior materials, exterior materials, structural materials, etc. for automobiles, trains, ships, airplanes, etc .; personal computers, televisions, watches, telephones, mobile phones, portable music It can be suitably applied to housings such as playback equipment, video playback equipment, printing equipment, copying equipment, sports equipment, structural materials, internal parts, etc .; building materials; office equipment such as stationery, containers, containers, and the like.

  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.

[Synthesis example]
A four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube was charged with 123 parts by mass of isopropyl alcohol (IPA) and heated to 80 ° C. To this, 135.3 parts by mass of acrylamide, 108.2 parts by mass of lauryl methacrylate, 2.5 parts by mass of methyl acrylate, 246 parts by mass of IPA, 4 parts by mass of azo initiator (manufactured by Wako Pure Chemical Industries, Ltd.) And the melt | dissolution mixture of 10 mass parts of methyl ethyl ketone (MEK) was dripped over 2 hours, and reaction was performed at 73-77 degreeC. Subsequently, the inside of reaction container was maintained at 73-77 degreeC for 2 hours, and superposition | polymerization reaction was complete | finished. After removing the solvent from the obtained resin solution under the conditions of 0.08 to 0.095 MPa and 60 ° C. using a vacuum pump, it was dried by heating at 80 ° C. for 30 minutes using a dryer. A dispersant was obtained. The weight average molecular weight (Mw) of the dispersant was measured by gel permeation chromatography (GPC). Specifically, at this time, the measurement conditions of the gel permeation chromatography are as follows. That is, using a high-speed GPC HLC-8220 (manufactured by Tosoh Corporation) and a column (TSK-GELGMHXL × 2), 200 mL of a solution in which 5 mg of a sample was dissolved in 10 g of tetrahydrofuran (THF) was injected into the apparatus, and the flow rate: Measurement was performed with a differential refraction (RI) detector at 1 mL / min (THF), thermostatic bath temperature: 40 ° C.

  As a result, the weight average molecular weight of the dispersant was 15,000.

[Example 1]
335 parts of high-density polyethylene (HDPE) which is a thermoplastic resin, 100 parts of softwood bleached kraft pulp (NBKP) which is a cellulose fiber (width: 50 μm, fiber length: 2 mm, manufactured by Howe Sound Pulp and Paper), 30 parts of a dispersant , And 0.05 part of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1), which is an ionic liquid, was mixed. The obtained mixture was melt-kneaded for 10 minutes at 140 ° C. and 200 rpm in a small kneading apparatus (manufactured by Leo Lab Co., Ltd.) as a kneading apparatus to produce a resin composition.

  The structural formula of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) is as follows.

[Example 2]
A resin composition was produced in the same manner as in Example 1 except that the addition amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) was changed to 0.25 parts.

[Example 3]
A resin composition was produced in the same manner as in Example 1 except that the addition amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) was changed to 0.5 part.

[Example 4]
A resin composition was produced in the same manner as in Example 1 except that the addition amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) was changed to 2.5 parts.

[Example 5]
A resin composition was produced in the same manner as in Example 1 except that the addition amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) was changed to 5 parts.

[Example 6]
A resin composition was produced in the same manner as in Example 1 except that the addition amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) was changed to 10 parts.

[Example 7]
A resin composition was produced in the same manner as in Example 5 except that the dispersant was not added.

[Example 8]
A resin composition was produced in the same manner as in Example 5 except that 1-ethyl-3-methylimidazolium methylphosphonate (ionic liquid 2) was used as the ionic liquid.

  The structural formula of 1-ethyl-3-methylimidazolium methylphosphonate (ionic liquid 2) is as follows.

[Example 9]
A resin composition was produced in the same manner as in Example 5 except that 1-ethyl-3-methylimidazolium chloride (ionic liquid 3) was used as the ionic liquid.

  The structural formula of 1-ethyl-3-methylimidazolium chloride (ionic liquid 3) is as follows.

[Example 10]
A resin composition was produced in the same manner as in Example 5 except that 1-butyl-3-methylimidazolium chloride (ionic liquid 4) was used as the ionic liquid.

  The structural formula of 1-butyl-3-methylimidazolium chloride (ionic liquid 4) is as follows.

[Example 11]
A resin composition was produced in the same manner as in Example 5 except that 1-allyl-3-methylimidazolium chloride (ionic liquid 5) was used as the ionic liquid.

  The structural formula of 1-allyl-3-methylimidazolium chloride (ionic liquid 5) is as follows.

[Example 12]
A resin composition was produced in the same manner as in Example 5 except that 1-butyl-3-methylpyridinium chloride (ionic liquid 6) was used as the ionic liquid.

  The structural formula of 1-butyl-3-methylpyridinium chloride (ionic liquid 6) is as follows.

[Example 13]
A resin composition was produced in the same manner as in Example 5 except that tetrabutylphosphonium chloride (ionic liquid 7) was used as the ionic liquid.

  The structural formula of tetrabutylphosphonium chloride (ionic liquid 7) is as follows.

[Example 14]
A resin composition was produced in the same manner as in Example 5 except that 1-ethyl-3-methylimidazolium bromide (ionic liquid 8) was used as the ionic liquid.

  The structural formula of 1-ethyl-3-methylimidazolium bromide (ionic liquid 8) is as follows.

[Example 15]
A resin composition was produced in the same manner as in Example 5 except that 1-ethyl-3-methylimidazolium tetrafluoroborate (ionic liquid 9) was used as the ionic liquid.

  The structural formula of 1-ethyl-3-methylimidazolium tetrafluoroborate (ionic liquid 9) is as follows.

[Comparative Example 1]
A resin composition was produced in the same manner as in Example 1, except that the addition amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) was changed to 20 parts.

[Comparative Example 2]
A resin composition was produced in the same manner as in Example 1 except that the addition amount of 1-ethyl-3-methylimidazolium acetate (ionic liquid 1) was changed to 30 parts.

[Performance evaluation]
The physical properties of the molded bodies obtained from the resin compositions obtained in Examples 1 to 15 and Comparative Examples 1 and 2 were evaluated.

(Method for producing molded body)
The resin composition is injection-molded using a small injection molding machine (manufactured by Leo Lab Co., Ltd.) under conditions of a mold temperature of 50 ° C. and a cylinder temperature of 150 ° C., and a tensile test specimen (molded body) 74 mm in length, 5 mm in width, and 2 mm in thickness) were manufactured.

(Tensile modulus)
Using the tensile tester “AUTOGRAPH AGS-X” (manufactured by Shimadzu Corporation), the tensile test specimen manufactured as described above, tensile speed: 50 mm / min, distance between chucks: 50 mm, temperature: 23 degrees, humidity: The tensile elastic modulus was measured under the condition of 50%. The obtained results are shown in Table 1 below.

(Tensile strength)
Using the tensile tester “AUTOGRAPH AGS-X” (manufactured by Shimadzu Corporation), the tensile test specimen manufactured as described above, tensile speed: 50 mm / min, distance between chucks: 50 mm, temperature: 23 degrees, humidity: The tensile strength was measured under the condition of 50%. The obtained results are shown in Table 1 below.

  From the results shown in Table 1, according to the production method of the example, defibration and dispersion are performed in the process of melt-kneading, so steps such as dissolution and reprecipitation of cellulose are unnecessary, and the amount of ionic liquid added is small. Therefore, the manufacturing cost is excellent.

  Moreover, it turns out that the molded object obtained from the resin composition manufactured by the said method has the outstanding mechanical characteristic in high tensile elasticity modulus, tensile strength, etc.

Claims (6)

A method for producing a resin composition, comprising melt-kneading a mixture containing a thermoplastic resin and cellulose fibers in the presence of an ionic liquid,
The manufacturing method whose addition amount of the said ionic liquid is less than 20 mass parts with respect to 100 mass parts of cellulose fibers.   The production method according to claim 1, wherein the ionic liquid includes an ionic liquid having a cation selected from the group consisting of an aromatic cation and an aliphatic cation.   The ionic liquid is halide ion, borate anion, carboxylate anion, sulfonate anion, sulfate anion, sulfonimide anion, phosphate anion, phosphate anion, phosphonate anion, dicyanamide anion, thiocyanate anion, tricyano. The production method according to claim 1, comprising an ionic liquid having an anion selected from the group consisting of a methanide anion and a nitrate anion.   The manufacturing method of any one of Claims 1-3 whose molecular weight of the said ionic liquid is 400 or less.   The manufacturing method of any one of Claims 1-4 with which the said mixture further contains a dispersing agent.   The manufacturing method of a molded object including shape | molding the resin composition manufactured by the method of any one of Claims 1-5.